Effects of a homogeneous chemical reaction preceding electron transfer on the current-time curves and current integrals obtained in controlled-potential electrolysis

1969 ◽  
Vol 73 (12) ◽  
pp. 4348-4350 ◽  
Author(s):  
Robert S. Rodgers ◽  
Louis Meites
Keyword(s):  
Electron Transfer ◽  
Chemical Reaction ◽  
Current Time ◽  
Homogeneous Chemical Reaction ◽  
Controlled Potential Electrolysis ◽  
Controlled Potential ◽  
Homogeneous Chemical

Interaction of a homogeneous chemical reaction and mass transfer in a single moving droplet

2013 ◽  
Vol 104 ◽  
pp. 260-268 ◽  
Author(s):  
Alexander Pawelski ◽  
Sang Jun Jeon ◽  
Won Hi Hong ◽  
Anja R. Paschedag ◽  
Matthias Kraume
Keyword(s):  
Mass Transfer ◽  
Chemical Reaction ◽  
Homogeneous Chemical Reaction ◽  
Homogeneous Chemical

Electrochemical reduction of the nickel(II) dithiocarbamates at the mercury electrode

1976 ◽  
Vol 29 (6) ◽  
pp. 1191 ◽  
Author(s):  
TH Randle ◽  
TJ Cardwell ◽  
RJ Magee
Keyword(s):  
Electron Transfer ◽  
Chemical Reaction ◽  
Mercury Electrode ◽  
Electrode Reaction ◽  
Reduction Mechanism ◽  
Ece Mechanism ◽  
Controlled Potential ◽  
Nickel Species ◽  
Electron Transfers ◽  
Potential Conditions

The reduction mechanism of a series of nickel(11) dithiocarbamates has been investigated in dimethyl sulphoxide at the mercury electrode. Under controlled-potential conditions, the reduction proceeds initially by an ECE mechanism (electron transfer-chemical reaction-electron transfer) with n = 1 for both electron transfers. The chemical reaction involves a dissociation to produce a nickel species more easily reduced than the nickel(11) dithiocarbamate. However, for some derivatives, rate constants for the chemical step show a time dependence, at electrolysis times above 5 s, consistent with an ECCE mechanism of the type where the product of the first chemical reaction reacts further to produce a nickel species more difficult to reduce than nickel(11) dithiocarbamate. Exhaustive reduction of nickel(11) diethyldithiocarbamate at the mercury-pool electrode gave non-integral n-values (2 > n > 1) consistent with the ECCE mechanism, and demonstrated that the product of the second chemical reaction is reoxidized to nickel(11) diethyldithiocarbamate by oxygen. The nature of the complete electrode reaction suggests a metal-centred reduction.

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