A study of dimethylferrocene diffusion and electrode kinetics using microelectrode voltammetry in poly(ethylene glycol) solvent

The heterogeneous electron transfer rate constant (k(s)) of dimethylferrocene (DMFc) was estimated using cyclic voltammetric peak potential separations taken typically in a mixed diffusion geometry regime in a polyelectrolyte, and the diffusion coefficient (D) of DMFc was obtained using a steady-state voltammogram. The heterogeneous electron transfer rate constant and diffusion coefficient are both smaller by about 100-fold in the polymeric solvent than in the monomeric solvent. The results are in agreement with the difference of longitudinal dielectric relaxation time (tau(L)) in the two kinds of solvents, poly(ethylene glycol) (PEG) and CH3CN, indicating that k(s) varies inversely with tau(L); k(s), is proportional to D of DMFc. Both D and k(s) of DMFc in PEG containing different supporting electrolytes and at different temperatures have been estimated. These results show that D and k(s) of DMFc increase with increasing temperature in the polyelectrolyte, whereas they vary only slightly with changing the supporting electrolyte.

A novel electrochemical method for simultaneously measuring diffusion coefficient and ion transference number

This paper introduces a new method to estimate the diffusion coefficient and transference number of a salt or an electroactive ion in a solution with little or no supporting electrolyte. The above two parameters can be obtained from a single potential step experiment without previous knowledge of either one. It would appear that the method could also be used in the study of ion transport in a high viscosity solvent or a solid electrolyte. (C) 1998 Elsevier Science S.A.

A study on the diffusion of quinhydrone in polymer electrolyte

The diffusion coefficients (D) of quinhydrone were estimated in polymer electrolytes by using non-steady-state chronoamperometry and steady-state current voltammetry. The D values have been estimated in polyethylene glycol (PEG) containing different concentrations, and cations of supporting electrolytes, and in different solvents over a range of temperatures. The dependencies of electroactive probe diffusion coefficients on temperature, supporting electrolyte concentration and polymer chain length are discussed. The results show that D increases with increasing temperature and decreasing concentration of supporting electrolyte. The diffusion coefficient depends strongly on the length of polymer chain and decreases sharply with increasing polymer chain length. The contribution of electron self-exchange has been explored and it seems to be negligible here. (C) 1998 Elsevier Science S.A.

Studies of ferrocene derivative diffusion and heterogeneous kinetics in polymer electrolyte by using microelectrode voltammetry

The heterogeneous electron transfer rate constants (k(s)) of seven ferrocene derivatives were estimated using cyclic voltammograms under mixed spherical/semi-infinite linear diffusion and steady-state voltammetry at a microdisk electrode in polymer electrolyte. The k(s) and diffusion coefficient (D) are both 100 to 1000-fold smaller in polymer solvent than in monomeric solvents, and the D and k(s) decrease with increasing polymer chain length. The results conform to the difference of viscosity (eta) or relaxation time (tau(L)) for these different solvents. The k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction are obtained. The influences of the substituting group in the ferrocene ring on k(s) and D are discussed. The k(s) are proportional to the D of the ferrocene derivatives, which indicates that solvent dynamics control the electrode reaction. (C) 1998 Elsevier Science S.A.

Hydrazines probe of interaction of horseradish peroxidase with cryo-hydrogel

The interaction between horseradish peroxidase (HRP) and the cryo-hydrogel was probed by using hydrazines which show high specificity of the reaction of the edge in the prosthetic heme of horseradish peroxidase. For comparison, the interaction of hydrazine with the horseradish peroxidase adsorbed on graphite electrode was also carried out by using steady-state response of the enzyme electrode and cyclic voltammetry. In order to obtain a proper explanation of the kinetic parameters for the enzymatic reaction, the theoretical expressions of I-max and K-M' in the Michaelis-Menten equation for the experimental system were provided. (C) 1997 Elsevier Science B.V.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .2. Effect of the ionic size of supporting electrolytes

The diffusion coefficients(D-app) and the heterogeneous electron-transfer rate constants(k(s)) for ferrocene in MPEG/salt electrolytes were determined by using steady-state voltammetry. The temperature dependence of the two parameters obeys the Arrhenius equation. The effect of the ionic size of six supporting electrolytes on diffusion and electron transfer dynamics of ferrocene was discussed.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .3. Effect of the polymer solvents

The diffusion coefficients(D-app) and the heterogeneous electron transfer rate constants(k(s)) for ferrocene in several polymer solvents were determined by using steady-state voltammetry. The temperature dependence of the two parameters indicates Arrhenius behavior, The polymer solvent effects on diffusion and electron transfer dynamics of ferrocene were discussed.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .1. Effect of the nature of electroactive solutes

The diffusion coefficients(D-app) and the heterogeneous electron-transfer rate constants(k(s)) for ferrocene and its seven derivatives in MPEG/LiClO4 electrolyte were determined by using steady-state voltammetry. The two parameters increase with increasing temperature, indicating Arrhenius behavior. The effects of the nature of electroactive solute molecules on D-app, k(s), and the half-wave potentials(E-1/2) are discussed.

An ultramicroelectrode study of ferrocene diffusion and heterogeneous electron transfer rate in polyelectrolyte

Steady-state voltammograms at a microdisk electrode are used to measure the diffusion coefficient (D) and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG.MClO(4). The diffusion coefficient and standard heterogeneous rate constant of ferrocene are both smaller in polymer solvents than in monomeric solvents. The D and k(s) of ferrocene have been estimated in PEG containing different concentrations and cations of supporting electrolytes, and the dependencies of D and k(s) on temperature have been observed. These results show that the D and k(s) of ferrocene increase with increasing temperature in polyelectrolyte, and with increasing cation radius of supporting electrolyte, eg D and k(s) increase in the order Bu(4)NClO(4) > NaClO4 > LiClO4. On the other hand, D and k(s) increase with decreasing concentration of supporting electrolyte. The dependence of the half-wave potential (E(1/2)) on the concentration of the supporting electrolyte is also observed. E(1/2) shifts in the negative direction as the concentration of supporting electrolyte increases. (C) 1997 Elsevier Science Ltd.

Study on diffusion of electroactive species in polyelectrolyte polyethylene glycol lithium perchlorate by chronoamperometry at a microdisk electrode

The mass transport dynamics of Ferrocene in polyelectrolyte polyethylene glycol lithium perchlorate (PEG . LiClO4) was studied by using chronoamperometry at a microdisk electrode. Chronoamperometry is a powerful method for the study of mass transport in polyelectrolyte, it has many advantages over the conventional methods at a microelectrode and the steady-state method at an ultramicroelectrode. By using this method the apparent diffusion coefficient D-app and concentration C-a of the electroactive species, can be estimated from a single experiment without previous knowledge of either one. We have estimated D-app and C-a of ferrocene in PEG . LiClO4 polyelectrolyte from 25 degrees C to 75 degrees C. The dependence on the concentration of electroactive species was observed. The diffusion coefficients decrease with increasing ferrocene concentration and decreasing temperature. The mass transport mechanism is explained, by using a free volume model.

A study of the dependence of ferrocene diffusion on chain length in polymer electrolytes

The diffusion rates of ferrocene have been estimated in five kinds of poly(ethylene glycol) solution, containing the electrolyte LiClO4, by using non-steady-state chronoamperometry. The D-app of ferrocene increases with increasing temperature, and the dependency of D-app on temperature obeys the Williams-Landel-Ferry equation. The D-app of ferrocene decreases with increasing polymer chain length. Both the chain length and temperature dependence conform to a simple free volume model. A relation between current and polymer chain length is suggested at room and high temperatures.

STUDY ON ELECTROCATALYTIC OXIDATION OF NADH BY FERROCENE DERIVATIVES AND DETERMINATION OF CATALYTIC RATE-CONSTANT AT MICRODISK ELECTRODE

The electrocatalytic oxidation of NADH by ferrocene derivatives and the influence of complexation with beta-cyclodextrin (beta-CD) were investigated at a microdisk electrode in a buffer solution. The cyclic voltammetric behavior of the ferrocene derivatives on the microdisk electrode was used to determine the electron-transfer rate constant from NADH to the ferricinium species. The heterogeneous rate constants and the diffusion coefficient of ferrocene derivatives were determined with the microdisk electrode. The effect of temperature and pH on the electrocatalytic oxidation of NADH were assessed.

ATTEMPTS TO MODIFY AN ELECTRODE WITH A CONDUCTING PLATINUM CLUSTER COMPOUND

A conducting platinum cluster compound K1.64Pt(C2O4)(2) was electrochemically synthesized on a glassy carbon electrode through the electrooxidation of K2Pt(C2O4)(2) in an aqueous medium using single potential step and cyclic voltammetry methods. The precursor K2Pt(C2O4)(2) was prepared by a ligand exchange reaction between C2O42- and PtCl42-. During single potential step experiments, the electrolytic current corresponding to the oxidation of K2Pt(C2O4)(2) increased dramatically after a sharp decrease at the beginning (due to the formation of conducting K1.64Pt(C2O4)(2) on the surface of the working electrode). Two kinds of mechanism account for the current transients at the different applied potentials. Cyclic voltammetry was conducted with K1.64Pt(C2O4)(2) on the surface of the working electrode and a steady-state diffusion current was observed. Since the material grew in a fibrous manner, each conducting fiber which was in contact with the electrode could serve as an ultramicroelectrode. The behavior of the working electrode was thus changed from a plain to an ultramicroelectrode array.

AN INTEGRATED CALCIUM-FLUORIDE CRYSTAL IR THIN-LAYER CELL AND ITS APPLICATION TO IDENTIFICATION OF ELECTROCHEMICAL REDUCTION PRODUCT OF BILIRUBIN

An integrated CaF2 crystal optically transparent infrared (ir) thin-layer cell was designed and constructed without using any soluble adhesive materials. It is suitable for both aqueous and nonaqueous systems, and can be used not only in ir but also in uv-vis studies. Excellent electrochemical and spectroelectrochemical responses were obtained in evaluating this cell by cyclic voltammetry and steady-state potential step measurements for both ir and uv-vis spectrolectrochemistry with ferri/ferrocyanide in aqueous solution, and with ferrocene/ferrocenium in organic solvent as the testing species, respectively. The newly designed ir cell was applied to investigate the electrochemical reduction process of bilirubin in situ, which provided direct information for identifying the structure of the reduction product and proposing the reaction mechanism.

HIGHLY SENSITIVE AND SELECTIVE DETERMINATION OF RIBOFLAVIN BY FLOW-INJECTION ANALYSIS USING PARALLEL DUAL-CYLINDER MICROELECTRODES

A novel wall-jet cell with parallel dual cylinder (PDC) microelectrodes was constructed and used for flow injection analysis (FLA). The detector takes the advantages of ''redox recycling'' between bipotentiostated microcylinder electrodes (- 0.4 V/SCE an