Showing papers on "Cyclic voltammetry published in 1975"
TL;DR: In this article, the authors applied convolution potential sweep voltammetry to the analysis of charge transfer kinetics and found that the postfactum experimental kinetics deviate significantly from the Butler-Volmer behavior, involving a dependence of the transfer coefficient α upon the electrode potential.
212 citations
TL;DR: In this paper, a strongly bound (poisoning) intermediate which adsorbs only on the Pt atoms and a direct oxidation path which involves an intermediate occupying a single site and a second intermediate occupying two sites.
137 citations
TL;DR: In this paper, a theoretical study of Brdicka's adsorption waves and of the corresponding i-E curves in cyclic voltammetry and E-t curves in chronopotentiometry is presented under the following conditions: (a) the electrochemical reaction 0+ne⇌R is reversible; (b) both the oxidized and the reduced forms are strongly adsorbed; (c) the adorption is rapid; and (d) allowance is made in the isotherm for interactions between the molecules (Frumkin type isother
114 citations
TL;DR: The anodic behavior of iridium in the oxide layer region has been investigated using conventional electrochemical techniques such as cyclic voltammetry as discussed by the authors, and the mechanism of charge storage is discussed in terms of both an expanded lattice theory for oxide growth on noble metals and a more recent theory of irreversible oxide formation with subsequent stoichiometry changes.
Abstract: The anodic behaviour of iridium in the oxide layer region has been investigated using conventional electrochemical techniques such as cyclic voltammetry. Applying a triangular voltage sweep at 10 Hz, 0.01 to 1.50 V increases the amount of electric charge which the surface can store in the oxide region. This activation effect and the mechanism of charge storage is discussed in terms of both an expanded lattice theory for oxide growth on noble metals and a more recent theory of irreversible oxide formation with subsequent stoichiometry changes. The lack of hysteresis between the anodic and cathodic peaks at ca. 0.9 V suggests that the process involved here is proton migration in a relatively thick surface layer, i.e. that the reaction involved is some type of oxide-hydroxide transition. Lack of chloride ion inhibition in the anodic region also supports the irreversible oxide formation theory; however, to account for the hydrogen region of the potential sweep a compromise theory involving partial reduction of the outer regions of iridium oxide film is proposed. The loss of charge storage capacity when the activated iridium surface is anodized for a short time above ca. 1.60 V is attributed to loss by corrosion of the outer active layer from the metal surface.
109 citations
TL;DR: In this article, the capacity of carotenes to accept or donate electrons reversibly was revealed, and the kinetics of the reactions with the participation of these particles were studied.
88 citations
TL;DR: In this paper, the formation of the unstable species (CH3)3Si(NCCH3n)n from the electrochemical oxidation of (CH 3)3 SiSiSi(CH 3 n) in acetonitrile was investigated.
77 citations
TL;DR: In this article, the relationship between structure and the formal electrode potential, E0, for the oxidation of substituted metal carbonyls of the type [M(CO)6−xLx]y+ has been investigated.
60 citations
TL;DR: In this article, the electrochemical behavior of electroless cobalt in 1N NaOH was studied at 35, 60 and 85°C by cyclic voltammetry, and three anodic peaks corresponding to the formation of Co(OH) 2 /CoO, Co 3 O 4, Co OOH were observed.
57 citations
TL;DR: In this paper, cyclic voltammetry was used to study the mechanisms of electron transfer and peak potentials of eleven alkenes, propylene oxide and propylene sulfide, and carbon disulfide.
Abstract: We have studied by cyclic voltammetry the mechanisms of electron transfer and peak potentials of eleven alkenes, propylene oxide, propylene sulfide, and carbon disulfide. We have also studied the cationic polymerization of styrene in acetonitrile solution initiated by controlled potential electrolysis at the anodic peak potential of styrene. The electrolyte used was tetrabutylammonium fluoborate, which was not electroactive at the electrolysis potential, and the reference electrode was a Ag0/Ag+ electrode. The electrochemical studies show that direct electron transfer from styrene is the initiation steps. Plots of reacted monomer concentrations versus time are sigmoidal curves. The propagation rate constant was found from a kinetic relationship based on an autocatalytic reaction. The activation energy is 15.6 kcal/mole at 20°C. The current behavior and effect of stirring on polymerization rate suggest that the growth of polymer takes place partially on the electrode surface.
48 citations
TL;DR: The electrochemical behavior of triphenyltin and bis(tri-n-butyltin) oxide (TBTO) in 50% (v/v) ethanol solution has been investigated by various electrochemical techniques including d.c. polarography, cyclic voltammetry and controlled potential coulometry as mentioned in this paper.
36 citations
TL;DR: In this article, a mechanism which involves a rapid adsorption equilibrium between the bulk and adsorbed nickel(II)-thiocyanate complex and oxidation of electroreduced metallic nickel with thiocalyanate ion has been presented and discussed.
TL;DR: In this article, a mechanism for cyclic regeneration of cobalt(II) by the oxidation of electrodeposited metallic cobalt with thiocyanate ion has been presented.
TL;DR: The reduction potentials for 1-chloropermethylpolysilanes are in all cases, including the hexasilanes, less negative than those for the corresponding α, ω-dichloropermethyl polysilanes as mentioned in this paper.
TL;DR: In this paper, the general feaures about the electrochemical oxidation of diphenylamines and the compounds derived from them in acetonitrile medium were investigated by voltammetry with the rotating disc electrode and cyclic voltammetric on platinum in acidic, neutral and basic medium.
TL;DR: In this paper, cyclic voltammetry, controlled potential coulometry and ESR have been used to examine the mechanisms of the redox chemistry of vanadium(IV), chromium(III), molybdenum(V), tungsten(V) tetraphenylporphyrins (TPP).
TL;DR: In this article, the electrochemical properties of lead electrodes in aqueous chloride solutions were experimentally investigated over a range of 0.1 to 6.0 mM HCl with the aim of extending previous work carried out only at 1.0 M HCl concentration.
Abstract: The electrochemical properties of lead electrodes in aqueous chloride solutions were experimentally investigated over a range of 0.1 to 6.0 M HCl with the aim of extending previous work carried out only at 1.0 M HCl concentration. Experimental results using the rotating disc electrode technique, cyclic voltammetry, galvanostatic and potentiostatic charging conditions were employed in conjunction with spectroscopic studies of the electrolyte and X-ray powder diffraction analyses of electrode surface products. Experiments were also carried out in simulated sea water (3% NaCl) at different pH and compared with results obtained using HCl at the same molar concentration. At all chloride concentrations the overall reaction led to the formation of PbCl2 on the electrode surface, with the exception that in NaCl solutions where pH ≥ 6.5, Pb(OH)Cl was found to be one of the products. For concentrations of less than 0.4 M HCl, our results indicated that the diffusion of chloride ions to the electrode surface was the...
TL;DR: In this article, the diamagnetic bis(tetramethylthiophene)iron(II) cation was isolated and characterized as its hexafluorophosphate salt and studied by differential pulse polarography and cyclic voltammetry.
TL;DR: In this paper, the influence of proton donors and methyl iodide on the reduction behavior of azobenzene in DMF and in HMPA was investigated by cyclic voltammetry.
TL;DR: In this article, the pKA of hydrido-cobalamin was determined from the E-pH diagram obtained from cyclic voltammetry of vitamin B 12r, adjusting the sweep rate to eliminate the effect of hydrogen evolution and the kinetic influence of the base-on/base-off reaction.
Abstract: The pKA of hydrido-cobalamin is determined from the E–pH diagram obtained from cyclic voltammetry of vitamin B 12r, adjusting the sweep rate to eliminate the effect of hydrogen evolution and the kinetic influence of the base-on/base-off reaction.
TL;DR: In this paper, a procedure has been developed for determining dialkyltin compounds down to ppb level, which involves the formation of an ion-radical which is further reduced in the second step to the dibutyltin diradical.
TL;DR: The reduction mechanism of bis 2,2′,2″-terpyridine complexes of manganese, cobalt, nickel, and europium was investigated in acetonitrile by means of DC and AC polarograph and Kalousek polarograph at DME and cyclic voltammetry at an HDME as discussed by the authors.
Abstract: The reduction mechanism of bis 2,2′,2″-terpyridine complexes of manganese(II), cobalt(II), nickel(II) and europium (III) were investigated in acetonitrile by means of DC and AC polarograph and Kalousek polarograph at DME and cyclic voltammetry at an HDME. It was found that univalent metal complex anions, such as [M-(terpy)2]− (M=manganese and nickel), were formed at the electrode surface in acetonitrile. For the europium(III) complex, the standard rate constant of the second reduction step was estimated.
TL;DR: In this paper, the first kind (thin layers on Pt) have been investigated in tetrafluorborate solutions with the aid of slow (40 mV min −1 ) cyclic voltammetry.
TL;DR: In this paper, the preparation of diindenyliron and cyclopentadienyl(Indenyl)iron species was reported, and their relative eases of oxidation was determined by cyclic voltammetry to be: Ind 2 Fe > (Ind)(Cp)Fe > Cp 2 Fe; and (1,3-Me 2 Ind) 2Fe > (1-MeInd) 2 Fe> Ind 2Fe.
TL;DR: The electrochemical reduction on mercury of P + φ 4 in low acidity solvents is studied using polarography, cyclic voltammetry, coulometry and preparative-scale electrolysis as mentioned in this paper.
TL;DR: In this article, the catalytic activity of the substoichiometric tungsten trioxide electrodes for the oxidation of hydrogen has been investigated, using simultaneous EPR spectroscopy and linear-sweep voltammetry measurements.
TL;DR: In this paper, the dehalogenation of aromatic compounds at a mercury cathode in dimethylformamide containing 1% deuterium oxide with tetra-n-propylammonium perchlorate as supporting electrolyte may or may not result in deuteriam incorporation, depending on the substrate.
Abstract: Reductive dehalogenation of aromatic compounds at a mercury cathode in dimethylformamide containing 1% deuterium oxide with tetra-n-propylammonium perchlorate as supporting electrolyte may or may not result in deuterium incorporation, depending on the substrate. Compounds giving a radical anion intermediate which is detectable by cyclic voltammetry do not incorporate deuterium. The radical anion decomposes away from the electrode to a σ-radical which abstracts a hydrogen atom from the organic solvent. Compounds which give no detectable radical anion accept one electron in the initial step and fragment to a σ-radical at the electrode surface. This radical is reduced further to a carbanion which reacts with incorporation of deuterium into the product. Evidence for σ-radical intermediates in the latter cases comes from isolation of dimers or products of intramolecular radical cyclisation of appropriate substrates.
TL;DR: In this paper, cyclic voltammetry of antimony was studied in aqueous media (HCl-LiCl) and in nonaqueous media after extraction with 20% tri-n-butylphosphate in toluene, with a rotating glassy carbon disc electrode.
TL;DR: In this article, a cyclic voltammetry of AuCl 4 − was studied in the medium of aqueous hydrochloric acid and in non-aqueous media using the rotating disc electrode made from glassy carbon.