On the use of electrochemical techniques to monitor free oxide content in molten fluoride media

The electrochemical behaviour of oxide ions has been studied in fluoride melts(LiF/NaF eutectic) by cyclic voltammetry, square wave voltammetry and chronopotentiometry. The purpose is to determine whether these techniques can be used for titration of free oxide ions (O2-) in molten fluorides released by lithium oxide additions. Cyclic voltammetry is shown to be unsuitable for this purpose due to oxygen bubbling disturbing the oxidation peak, while square wave voltammetry is far more appropriate because the observed signal is a well defined oxidation peak with a height proportional to the oxide content. Thus, the present work is focused on a strategy of oxide ions titration by square wave voltammetry. In addition, this work allows assessing that the electrochemical reduction of oxide ions proceeds by diffusion of these species, and the O2- diffusion coefficient is estimated by chronopotentiometry

Electrochemical study of the Eu(III)/Eu(II) system in molten fluoride media

The electrochemical behaviour of the Eu(III)/Eu(II) system was examined in the molten eutectic LiF-CaF2 on a molybdenum electrode, using cyclic voltammetry, square-wave voltammetry and chronopotentiometry. It was observed that EuF3 is partly reduced into EuF2 at the operating temperatures (1073-1143 K). The electrochemical study allowed to calculate both the equilibrium constant and the formal standard potential of the Eu(III)/Eu(II) system. The reaction is limited by the diffusion of the species in the solution; their diffusion coefficients were calculated at different temperatures and the values obey Arrhenius' law. The second system Eu(II)/Eu takes place out of the electrochemical window on an inert molybdenum electrode, which inhibits the extraction of Eu species from the salt on such a substrate

Electrochemical behaviour of carbamazepine in acetonitrile and dimethylformamide using glassy carbon electrodes and microelectrodes

The electrochemical reduction of carbamazepine in acetonitrile (ACN) and dimethylformamide (DMF) using a glassy carbon electrode and microelectrodes has been studied. The reduction process is consistent with an Electrochemical-Chemical mechanism (EC) involving a two electron transfer followed by a first order reaction, as shown by the cyclic voltammetry and differential pulse voltammetry. Half-wave potential, number of electron transfer, diffusion coefficient and rate constant of the associated chemical reaction are reported. Detection limits are in DPV: LoD=0.92 and 0.76 μg mL-1 in ACN and DMF, respectively. Precision (%RSD) and recovery (%) values when pharmaceutical compounds (200mg carbamazepine tablets) and spiked plasma samples were tested ranged from 1.09 to 9.04% and % recoveries ranged from 96 to 104.1%

Voltammetric determination of the critical micellar concentration of surfactants by using a boron doped diamond anode

The electrochemistry of three surfactants has been studied by voltammetry at boron doped diamond (BDD) electrode in sodium sulphate solutions. The electrochemical behaviour of these surfactants is characterized by an oxidation signal (peak or wave) situated before the electrolyte oxidation. The anodic current is found to follow a linear relation with the concentration of the surfactants; the slope decreases abruptly above the critical micellar concentration (CMC) of the surfactants. The CMC values obtained for an anionic (sodium dodecylbenzenesulfonate, SDBS), a cationic (polyoxyethylene-23-dodecyl ether, BRIJ 35) and a neutral (1-(hexadecyl)trimethylammonium bromide, CTAB) surfactant are found in good agreement with those measured by the classical technique of surface tension. This voltammetric method has the advantage not to require the use of a redox active electrochemical probe

A combined "electrochemical-frustrated Lewis pair" approach to hydrogen activation: surface catalytic effects at platinum electrodes

Herein, we extend our “combined electrochemical–frustrated Lewis pair” approach to include Pt electrode surfaces for the first time. We found that the voltammetric response of an electrochemical–frustrated Lewis pair (FLP) system involving the B(C6F5)3/[HB(C6F5)3]− redox couple exhibits a strong surface electrocatalytic effect at Pt electrodes. Using a combination of kinetic competition studies in the presence of a H atom scavenger, 6-bromohexene, and by changing the steric bulk of the Lewis acid borane catalyst from B(C6F5)3 to B(C6Cl5)3, the mechanism of electrochemical–FLP reactions on Pt surfaces was shown to be dominated by hydrogen-atom transfer (HAT) between Pt, [Pt[BOND]H] adatoms and transient [HB(C6F5)3]⋅ electrooxidation intermediates. These findings provide further insight into this new area of combining electrochemical and FLP reactions, and proffers additional avenues for exploration beyond energy generation, such as in electrosynthesis

A mechanistic study of the EC′ mechanism – the split wave in cyclic voltammetry and square wave voltammetry

In this paper, a detailed investigation of electrochemical reactions coupled with homogenous chemical steps using cyclic voltammetry (CV) and square wave voltammetry (SWV) was carried out to study the electrocatalytic (EC’) mechanism. In CV, parameters including scan rate, electrode material and redox reactant were investigated while in SWV, parameters including substrate concentrations and frequencies were altered to demonstrate EC’ mechanism. Mechanistic studies focused on the EC’ mechanism using L-cysteine with ferrocenecarboxylic acid and 1,1 ′-ferrocenedicarboxylic acid respectively. Voltammetric responses were recorded and under conditions of high chemical rate constant and low substrate concentration, a split wave was observed in both CV and SWV studies

Electrochemistry of ferrocenylphosphines FcCH₂PR₂ (Fc=(η⁵-C₅H₅)Fe(η⁵-C₅H₄); R=Ph, CH₂OH and CH₂CH₂CN), and some phosphine oxide, phosphine sulfide, phosphonium and metal complex derivatives

Electrochemical studies of the free ferrocenylphosphine ligands FcCH₂PR₂ (Fc=(η⁵-C₅H₅)Fe(η⁵-C₅H₄); R=Ph, CH₂OH and CH₂CH₂CN) and some phosphine oxide, phosphine sulfide, phosphonium and metal derivatives are described. The free ligands exhibit complex voltammetric responses due to participation of the phosphorus lone pair in the redox reactions. Uncomplicated ferrocene-based redox chemistry is observed for PV derivatives and when the ligands are coordinated in complexes cis-PtCl₂[FcCH₂P(CH₂OH)₂], PdCl₂[FcCH₂P(CH₂OH)₂], [Au{FcCH₂P(CH₂OH)₂}₂]Cl, RuCl₂(η⁶-C₁₀H₁₄)[FcCH₂P(CH₂OH)₂] and RuCl₂(η⁶-C₁₀H₁₄)(FcCH₂PPh₂). The reaction pathways of the free ligands after one-electron oxidation have been examined in detail using voltammetry, NMR spectroscopy and electrospray mass spectrometry. Direct evidence for formation of a P---P bonded product is presented

First direct evidence of N-heterocyclic carbene in BMIm acetate ionic liquid. An electrochemical and chemical study on the role of temperature

Cyclic voltammetry provides the first direct evidence of N-­heterocyclic carbene (NHC) presence in neat 1-‐butyl-­3-­methylimidazolium acetate ionic liquid (BMImAcO) at 120°C. The NHC existence, proved by its oxidation current in cyclic voltammetry, was confirmed by the formation of a PhCHO-­NHC adduct in pure ionic liquid. The role of the temperature was considered