A study of mercury-cathode membrane cells for the electrolytic reduction of uranyl solutions

1960 ◽  
Author(s):  
J W Kim ◽  
R Simard
Keyword(s):  
Electrolytic Reduction ◽  
Mercury Cathode

Electrolytic reduction of o-nitrobenzyl thiocyanate in buffered solutions on mercury

1985 ◽  
Vol 50 (1) ◽  
pp. 33-41 ◽  
Author(s):  
Jaromír Hlavatý
Keyword(s):  
Acidic Medium ◽  
Reaction Path ◽  
Electrolytic Reduction ◽  
Buffer System ◽  
Height Ratio ◽  
Preparative Electrolysis ◽  
Clear Explanation ◽  
Ec Mechanism ◽  
Controlled Potential

The o-nitrobenzyl thiocyanate (I) behaves differently on the DME and on a large mercury pool electrode. Polarography did not give a sufficiently clear explanation of the reaction mechanism, only the preparative experiments yielded useful results. Whereas polarographic curves in solutions of Britton-Robinson buffer system with 50% by vol. ethanol exhibit two cathodic waves within the pH region 1-12, corresponding according to their height ratio to an uptake of 4 e and 2 e respectively, the controlled potential preparation electrolysis (CPE) and coulometry results indicate a more complicated reaction path. In the CPE carried out at the concentration of I 1 . 10 -2 mol/l the electroreductive splitting of CH2-SCN occurs as the first step. Nitrobenzyl radicals so formed react in the follow-up dimerization resulting in dibenzyl or toluene structures. Simultaneously or at a later stage the completion of the electrolytic reduction of the nitro group proceeds to the hydroxylamino group. In solution of 9 > pH > 1 the CPE of nitro compound I takes place by an ECEC mechanism yielding dibenzodiazocine III, its N-oxide IV and 2,2'-dimethylazoxybenzene (V). In course of preparative electrolysis in strongly acidic medium 2-amino-benzo(l,3)-thiazine-l-oxide (II) is formed by an EC mechanism.

On the electroreduction mechanism of halobenzenes: Detection of intermediates in reduction of monohalobenzenes

1989 ◽  
Vol 54 (4) ◽  
pp. 900-910 ◽  
Author(s):  
Juan Casado ◽  
Iluminada Gallardo
Keyword(s):  
Cyclic Voltammetry ◽  
Electrochemical Behaviour ◽  
Experimental Results ◽  
Disk Electrode ◽  
Rotating Ring Disk Electrode ◽  
Mercury Cathode

Experimental results from electrochemical behaviour of halobenzenes in DMF at a mercury cathode are used to discuss alternative mechanisms of reduction. Intermediates of these mechanisms, such as phenyl anion, phenylmercury radical and phenylmercury cation have been detected at the electrode by using cyclic voltammetry and a rotating ring-disk electrode.

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