Electrochemical studies of amine salts of monothiocarbamates

1982 ◽  
Vol 35 (12) ◽  
pp. 2465
Author(s):  
RJ Magee ◽  
B Annuar
Keyword(s):  
Electrochemical Behaviour ◽  
Mercury Electrode ◽  
Compact Layer ◽  
Cyclic Voltammetric ◽  
Reactive Material ◽  
Anodic Wave ◽  
Diffusion Controlled ◽  
Controlled Potential ◽  
Controlled Potential Coulometry ◽  
Amine Salts

The electrochemical behaviour of the amine salts of morpholyl-, pyrrolidyl-�and piperidyl-mono- thiocarbamates (morpholinium morpholine-4-carbothioate, piperidinium piperidine-1-carbothioate and pyrrolidinium pyrrolidine-1-carbothioate) at the mercury electrode has been studied by means of d.c. polarography and cyclic voltammetry. All three exhibited a well defined anodic wave, but the pyrrolidyl derivative (pymtc) gave an additional wave. The main wave in each case was found to be diffusion-controlled. Temperature coefficients showed erratic behaviour at higher temperatures which was thought to be due to decreasing availability of reactive material because of decomposition. Controlled potential coulometry gave n = 1 per mole for the main wave of each compound. The behaviour was similar to that of the dithiocarbamate ligands under the same conditions and the small pre-wave in the polarograms of pymtc is attributed to the formation of a mercuric pyrrolidyl monothiocarbamate, which, unlike the mercuric complex of the other two ligands is structurally ordered and able to form a compact layer with the electrode. Cyclic voltammetric results supported the findings of polarography and confirmed the following mechanism: mtc- + Hg → Hg(mtc) + e' (1) 2Hg(mtc) → Hg(mtc)2 + Hg (2)

scholarly journals Electrochemical Behaviour of N′-(p-toluenesulphonyl)-3-methyl-4-(4′-substituted arylhydrazono) pyrazolin-5-ones

2012 ◽  
Vol 9 (4) ◽  
pp. 1864-1874
Author(s):  
V. Nagaraju ◽  
R. Sreenivasulu ◽  
P. Venkata Ramana
Keyword(s):  
Electrochemical Behaviour ◽  
Reduction Process ◽  
Effect Of Solvent ◽  
Buffer Solutions ◽  
Diffusion Controlled ◽  
Controlled Potential Electrolysis ◽  
Dc Polarography ◽  
Controlled Potential ◽  
Ph Range ◽  
And Diffusion

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.

Behaviour of disubstituted dithiocarbamates at the mercury electrode

1975 ◽  
Vol 28 (1) ◽  
pp. 21 ◽  
Author(s):  
TH Randle ◽  
TJ Cardwell ◽  
RJ Magee
Keyword(s):  
Surface Film ◽  
Electrochemical Behaviour ◽  
Mercury Electrode ◽  
Alkyl Substituent ◽  
Electrode Reaction ◽  
Anodic Wave ◽  
Alkyl Groups ◽  
Product Film ◽  
Triton X ◽  
General Method

The electrochemical behaviour at the mercury electrode of a series of sodium dithiocarbamates in aqueous solution has been investigated. Although the overall electrode reaction mechanism is the same as that for sodium diethyldithiocarbamate in each case, the current flowing in the main anodic wave is determined by the nature of the film of the particular insoluble mercury(II) dithiocarbamate deposited on the electrode and varies with the alkyl substituent group in the dithiocarbamate. A porous, loosely bound film which periodically bursts, causing localized stirring and large irregular currents, was indicated for large bulky alkyl groups (e.g. butyl) while for small or planar alkyl groups (e.g. methyl, tetramethylene) current inhibition was observed, suggesting a compact surface film. The influence of the surfactant Triton X-100 on the product film has also been examined. Linear sweep chronoamperometry is recommended as a general method of analysis for dithiocarbamates as the electrolysis time (and therefore the film thickness) can be selected to avoid the above interferences.

Polarography of n-butylthioglycolate in aqueous media, methanol, and acetonitrile

1984 ◽  
Vol 62 (9) ◽  
pp. 1817-1821
Author(s):  
K. C. Gupta ◽  
Kalpana K. Sharma
Keyword(s):  
Aqueous Media ◽  
Mercury Electrode ◽  
Wave Characteristics ◽  
Anodic Wave ◽  
Diffusion Controlled ◽  
Dropping Mercury Electrode ◽  
Drop Time ◽  
And Diffusion ◽  
Mechanism Of The Reaction

The polarographic behaviour of n-butylthioglycolate (RSH) at the DME in aqueous media, methanol, and acetonitrile has been investigated in the presence of 0.1 M KNO3 and 0.01% thymol. The effect of pH, concentration of RSH, and drop time on the wave characteristics and the mechanism of the reaction occurring at the surface of the mercury drop have been studied. Well-defined reversible and diffusion-controlled anodic waves were obtained in aqueous media (pH 4.2), 40% methanol (pH 3.22), and 40% acetonitrile (pH 2.96). Mathematical and analytical evidence was obtained to show that the anodic wave of RSH at a dropping mercury electrode in aqueous media, 40% methanol, and 40% acetonitrile is due to the formation of the mercury complex RSHg. The dissociation constant (pK) of the mercapto group in n-butylthioglycolate is 9.6 and the diffusion coefficient in the different media are 1.17 × 10−6 cm2 s−1 (in aqueous media) 1.23 × 10−6 cm2 s−1 (in 40% methanol), and 2.43 × 10−6 cm2 s−1 (in 40% acetonitrile). The linearity of id with RSH concentration provides a rapid and precise method for the determination of RSH, down to 0.4 mM in aqueous media, methanol, and acetonitrile.

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
Keyword(s):  
Oxidation Process ◽  
Electrochemical Behaviour ◽  
Mercury Electrode ◽  
The Other ◽  
Hanging Mercury Drop Electrode ◽  
Dihydroxybenzoic Acid ◽  
Current Function ◽  
Controlled Potential Electrolysis ◽  
Controlled Potential ◽  
Ph Range

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.

Voltammetric studies of the electrochemical behaviour of salicylidene-2-aminopyridine at a hanging-mercury-drop-electrode

1986 ◽  
Vol 64 (4) ◽  
pp. 702-705 ◽  
Author(s):  
Refat Abdel-Hamid
Keyword(s):  
Chemical Reaction ◽  
Electrochemical Behaviour ◽  
Order Rate Constant ◽  
Potential Sweep ◽  
Cyclic Voltammetric ◽  
Diffusion Controlled ◽  
Voltammetric Characteristics ◽  
Irreversible Chemical Reaction ◽  
Voltammetric Studies ◽  
Tetraethylammonium Perchlorate

Electrochemical behaviour of salicylidene-2-aminopyridine has been investigated in 0.1 M tetraethylammonium perchlorate–dimethylformamide solutions by cyclic voltammetric and convolution potential sweep voltammetric methods. It was found that the depolarizer exhibits two well-defined diffusion-controlled irreversible one-electron waves. The cyclic voltammetric characteristics and the convolution, deconvolution, and logarithmic convolution analyses reveal that salicylidene-2-aminopyridine in such conditions follows a set of two one-electron transfer reactions each followed by an irreversible chemical reaction. The values of the first-order rate constant of the irreversible chemical reaction and E1/2 were computed.

An electrochemical investigation on mononuclear and dinuclear copper(I) aminocarbonyl complexes

1985 ◽  
Vol 63 (4) ◽  
pp. 922-927 ◽  
Author(s):  
Piero zanello ◽  
Piero leoni
Keyword(s):  
Carbon Monoxide ◽  
Electrochemical Behaviour ◽  
Platinum Electrodes ◽  
Electron Charge ◽  
Electrochemical Investigation ◽  
Carbonyl Derivatives ◽  
Dimethyl Sulfoxide Solution ◽  
Controlled Potential ◽  
Cathodic Processes ◽  
Controlled Potential Coulometry

The electrochemical behaviour of some copper(I) aminocarbonyl derivatives, namely, [Cu(dien)(CO)]+ (dien = diethylenetriamine), [Cu(Medpt)(CO)]+ (Medpt = N,N-bis(3-aminopropyl)methylamine), [Cu2(tmen)2(μ-PhCO2)(μ-CO)]+ (tmen = N,N,N′,N′-tetramethylethylenediamine), has been studied in dimethyl sulfoxide solution at platinum electrodes by cyclic and dc voltammetry, and controlled potential coulometry. In all studied complexes each copper(I) centre undergoes one-electron charge transfers in both anodic and cathodic processes. The electrogenerated copper(II) complexes, fully characterized, can be reversibly reduced to the starting copper(I) carbonyl derivatives in the presence of carbon monoxide. The electron-transfer sequences in which these copper(I) complexes may be involved have been elucidated.

Determination of titanium by controlled-potential coulometry

1971 ◽  
Vol 43 (6) ◽  
pp. 747-751 ◽  
Author(s):  
Lester P. Rigdon ◽  
Jackson E. Harrar
Keyword(s):  
Controlled Potential ◽  
Controlled Potential Coulometry

Real-time computer prediction of end points in controlled-potential coulometry

1970 ◽  
Vol 42 (7) ◽  
pp. 764-774 ◽  
Author(s):  
Frederick B. Stephens ◽  
Fredi. Jakob ◽  
L. P. Rigdon ◽  
Jackson E. Harrar
Keyword(s):  
Real Time ◽  
Computer Prediction ◽  
End Points ◽  
Controlled Potential ◽  
Controlled Potential Coulometry

The behaviour of copper(II) dithiocarbamates at the mercury electrode

1976 ◽  
Vol 29 (1) ◽  
pp. 85 ◽  
Author(s):  
TH Randle ◽  
TJ Cardwell ◽  
RJ Magee
Keyword(s):  
Propylene Carbonate ◽  
Electrochemical Techniques ◽  
Mercury Electrode ◽  
Alkyl Substituent ◽  
Reduction Step ◽  
Electron Diffusion ◽  
Reduction Potentials ◽  
Diffusion Controlled

The reduction at the mercury electrode of a series of copper(11) dithiocarbamates [CU(S2CNR2)2] in propylene carbonate has been investigated by a variety of electrochemical techniques. Thecomplexes undergo reduction in two successive one-electron diffusion-controlled steps, with associated adsorption of the complexes and the reduction products. Exhaustive reduction at a mercury-pool electrode shows the completely reduced species [CU(S2CNR2)2]2- to undergo slowdissociation. The alkyl substituent influences the strength of adsorption of the reduction products, the reduction potentials of the complexes and the reversibility of the first reduction step, thesecond step being quasi-reversible in all cases. The electroactive centre appears to be the metal.

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