Saturated calomel electrode electron-transfer

Electrochemical (DMF, 0.2 M [NBu4][BF4]), two reversible mono-electronic waves (— 1.02 and - 1.60 V versus saturated calomel electrode). Electronic spectrum in CH3CN strong charge-transfer bands at 322 nm... 

Examination of the behaviour of a dilute solution of the substrate at a small electrode is a preliminary step towards electrochemical transformation of an organic compound. The electrode potential is swept in a linear fashion and the current recorded. This experiment shows the potential range where the substrate is electroactive and information about the mechanism of the electrochemical process can be deduced from the shape of the voltammetric response curve [44]. Substrate concentrations of the order of 10 molar are used with electrodes of area 0.2 cm or less and a supporting electrolyte concentration around 0.1 molar. As the electrode potential is swept through the electroactive region, a current response of the order of microamperes is seen. The response rises and eventually reaches a maximum value. At such low substrate concentration, the rate of the surface electron transfer process eventually becomes limited by the rate of diffusion of substrate towards the electrode. The counter electrode is placed in the same reaction vessel. At these low concentrations, products formed at the counter electrode do not interfere with the working electrode process. The potential of the working electrode is controlled relative to a reference electrode. For most work, even in aprotic solvents, the reference electrode is the aqueous saturated calomel electrode. Quoted reaction potentials then include the liquid junction potential. A reference electrode, which uses the same solvent as the main electrochemical cell, is used when mechanistic conclusions are to be drawn from the experimental results. 

The cyclic voltammograms of thiadiazole fused [2,5-(l,3-dithiol-2-ylidene)-l,3,4,6-tetrathiapentalenes], BDT-TTPs 88, in benzonitrile exhibited four pairs of redox waves corresponding to one-electron transfer processes at 4-0.60, 4-0.81, 4-1.30, and 4-1.47 V (vs. saturated calomel electrode (SCE)). The El values are a little higher than that of 4,5-bis(methylthio)-BDT-TTP (4-0.49 V). The difference is attributed to the electron-withdrawing character of the fused thiadiazole ring on the bicycle <1997SM(86)1821>. 

Hale et al. reported the use of an enzyme-modified carbon paste for the determination of acetylcholine [21], The sensor was constructed from a carbon paste electrode containing acetylcholineesterase and choline oxidase, and the electron transfer mediator tetrathiafulvalene. The electrode was used for the cyclic voltammetric determination of acetylcholine in 0.1 M phosphate buffer at +200 mV versus saturated calomel electrode. Tetrathiafulvalene efficiently re-oxidized the reduced flavin adenine dinucleotide centers of choline oxidase. The calibration graph was linear up to 400 pM acetylcholine, and the detection limit was 0.5 pM. 

Nevertheless, CO2 reduction does not take place easily, and the actual electrolysis potentials for CO2 reduction are much more negative in most cases than the equilibrium ones. The reason is that the intermediate species CO2, formed by an electron transfer to a CO2 molecule, proceeds as the first step at highly negative potential, such as -2.21 V vs. saturated calomel electrode (SCE) measured in dimethyl fonnamide (DMF), as discussed later in detail. 

Reoxidation of the cosubstrate at an appropriate electrode surface will lead to the generation of a current that is proportional to the concentration of the substrate, hence the coenzyme can be used as a kind of mediator. The formal potential of the NADH/NAD couple is - 560 mV vs. SCE (KCl-saturated calomel electrode) at pH 7, but for the oxidation of reduced nicotinamide adenine dinucleotide (NADH) at unmodified platinum electrodes potentials >750 mV vs. SCE have to be applied [142] and on carbon electrodes potentials of 550-700 mV vs. SCE [143]. Under these conditions the oxidation proceeds via radical intermediates facilitating dimerization of the coenzyme and forming side-products. In the anodic oxidation of NADH the initial step is an irreversible heterogeneous electron transfer. The resulting cation radical NADH + looses a proton in a first-order reaction to form the neutral radical NAD, which may participate in a second electron transfer (ECE mechanism) or may react with NADH (disproportionation) to yield NAD [144]. The irreversibility of the first electron transfer seems to be the reason for the high overpotential required in comparison with the enzymatically determined oxidation potential. 

Electrochemistry is an analytical tool that can be used to determine redox potentials of an analyte as well as the fate of a molecule upon addition or removal of electrons. Of particular importance to photochemists is the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Cyclic voltammetry is one of the most commonly used electrochemical techniques and is based on the change in potential as a linear function of time. An electrochemical reaction is reversible if = 1 and AEp = 59/n mV, where ip is the anodic peak current, ip is the cathodic peak current, and A p (AE), = A p — Ep ") is the potential peak separation for the anodic ( ), ) and cathodic Ep ) peaks. The oxidation or reduction potential for a reversible electrochemical process is given by 1/2 = Ep + Ep jl and is recorded vs. a reference electrode. All electrochemical data provided herein are converted to V vs. saturated calomel electrode (SCE) to make the comparison more facile. A reversible redox couple implies that the complex undergoes facile electron transfer with the electrode and that no chemical reaction follows the electrochemical step. 

NCS, NH3, PR, py, CNR,...) have reversible potentials ranging from -0.3 to +2.0 V in acetonitrile vs. the saturated sodium chloride calomel (SSCE) reference electrode (2) and electron transfer involving such couples is known to be facile (3). Ru(IV) is also an accessible oxidation state at relatively low potentials by loss o grotons from bound water following oxidation, Ru(bpy)2(py)... 

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