Surface imhomogeneity of platinum-metal electrodes in redox reactions

Investigation of the electrochemical behaviour of the redox systems I₂/I^2? and Fe(CN)^3?₆ Fe(CN)^4?₆ on electrodes from Pt, Pd, Ir and Au revealed anomalies in the dependence of the limiting currents i_d on the rotation rate of the disk electrode ω and in the dependence of faradaic impedance components R, 1/Cf on the ac frequency f. The anomalous

dependences are characterized either by deviation from linearity or by lesser slopes than those determined from Levich's equation. Such dependences are observed for the Ir electrode and also for Pt and Pd electrodes, non-activated and poisoned by chemisorbed substances. These anomalous dependences are also observed also for the Pt electrode near 0°C. The R/f^{?$\text{1}\text{2}$} and 1/C/f^{?$\text{1}\text{2}$} curves depend on the state of the surface in a similar manner.These experimental data can be explained if on Pt, Pd and Ir electrodes the redox reaction is assumed to proceed only on separate surface areas—active sites, the number and size of which depend on the metal, surface pretreatment, temperature, presence of surfactants in solution and other factors. This inhomogeneity is macroscopic since the linear dimensions of the active sites are of the order of 10^?5?10^?3 cm, depending on the metal and on the state of its surface.     

Electron-transfer reactions at semiconducting anodic niobium oxide films

Anodic niobium oxide in a n-type semiconductor due to an oxygen deficit. Electron donor densities and the dependence of excitation energies upon donor density were determined from measurements of space-charge capacitances as a function of electrode potential. Rates of Fe(III) reduction and of Fe(II) oxidation were measured at oxide films of different donor densities as functions of electrode potential and pH value. The results indicate electronic states in the space-charge layer below the oxide surface to participate in the electron-transfer reactions. Experimental polarisation curves are compared to curves calculated theoretically. From the shape of the polarisation curve flat-band potentials of the oxide are estimated. The observed polarisation curves are compatible with λ = 1·2 eV for the reorganisation energy of the Fe(CN)^3?₆/Fe(CN)^4?₆ redox couple.     

Oxidation of iodide ions by means of cyclic voltammetry

From chronovoltammetric and cyclovoltammetric polarization curves three mechanisms of iodide ions have been established: 3I^? = I^?₃ + 2e,2I^?₃ = 3I₂ + 2e and 2I^? = I₂ + 2e under certain conditions of scan rate, concentration of iodide ions and area of electrode in the aqueous solutions KI (background solution 1 N Na₂SO₄) with half-wave potentials of 0.428, 0.489 and 0.507 V by silver/silver chloride electrode.     

Cyanide detoxification by selective ion exchange with protonated poly(4-vinyl pyridine)

In order to explore the possibility of using cross-linked poly(4-vinyl pyridine), PVP, for selective removal of cyanide in waste water by complexation of the cyanide with ferrous ion followed by ion exchange, the sorption behaviour of the anionic ferrocyanide complex (Fe(CN)₆^4-) on the resin operating in an acid salt form has been studied. The results are compared with those obtained on a conventional gel-type weak base resin, Amberlite IRA-68. The ferrocyanide complex is selectively sorbed in preference to other common ions and is readily stripped with dilute sodium hydroxide. PVP has a high sorption capacity, fast sorption kinetics and a rapid rate of regeneration, being much superior to Amberlite IRA-68 in all these respects. The sorption rate is film-diffusion controlled at low solution concentrations (< 0.8 mmol litre^?1) and particle-diffusion controlled at higher concentrations (> 0.8 mmol dm^?3). Lowering pH to ～ 1 increases the sorption of Fe(CN)₆^4? on to protonated PVP by 75% over that at pH 7, a phenomenon explained by the formation of protonated ferrocyanide species, HFe(CN)₆^3- and H₂Fe(CN)₆^2-. From column operations with 156 mg dm^?3 cyanide waste stream a capacity of 73 mg CN^? g^?1 of protonated PVP to 1 mg dm^?3 breakthrough is determined, compared to 60 mg CN^? g^?1 of protonated IRA-68.     

Specific adsorption of formate ions at the mercury—aqueous solution interface

Adsorption on polarized Hg electrode of formate ions from aqueous solutions of pure HCOONa using differential capacity measurements was studied. Anion specific adsorption was indicated by the cathodic shift of potential of zero charge with increase in bulk-electrolyte activity. Variation of charge due to surface excess of sodium ions (Γ ₊ Z₊ F) and of charge due to specifically adsorbed formate ions (q¹), with electrode charge (q^M) indicated super-equivalent adsorption of formate ions at all positive charges and for all concentrations studied. Esin—Markov coefficient was found to be unreliable criterion of the occurence of specific adsorption. Logarithmic form of constant charge adsorption isotherms were found to be followed. The plots of φ^{M ? 2}vs q¹ at constant q^M were not linear and resembled those for F^?, BF₄^? and CH₃COO^? ions; which is attributed to relatively weak specific adsorption of anions.     

The potentiodynamic behaviour of iron in alkaline solutions

The potentiodynamic behaviour of iron in alkaline solutions under carefully controlled perturbation conditions reveals that the overall electrochemical process is more involved than was thought earlier. The electrochemical characteristics of the systems are explained through a series of successive conjugated redox couples principally involving Fe(OH), Fe(OH)₂ and FeOOH as limiting stoichiometric species. The yield of soluble species such as either FeO^2?₂ or HFeO^?₂ increases with the pH. Ageing effects of reactants and products are also distinguished through the potentiodynamic E/I records.     

Faradaic impedance titration and control of electron transfer of 1-(12-mercaptododecyl)imidazole monolayer on a gold electrode

In this work, we studied interfacial proton transfer of the self-assembled monolayer (SAM) of 1-(12-mercaptododecyl)imidazole on a gold electrode by faradaic impedance titration method with Fe(CN)₆³⁻ as an anionic redox probe molecule. The surface pK_1/2 was found to be 7.3, which was nearly the same as that of 1-alkylimidazole in solution. We also investigated the electrochemical properties of the SAM-modified electrode by cyclic voltammetry. Cyclic voltammetry was performed (1) in the solution containing Fe(CN)₆³⁻ with repeated alternation of pH values to investigate the electrostatic interaction of the protonated or deprotonated imidazole with Fe(CN)₆³⁻ and (2) in the acidic or basic electrolyte containing Ru(NH₃)₆³⁺ as a cationic redox probe to verify the effect of the polarity of a redox probe. We observed the reversible adsorption/desorption of Fe(CN)₆³⁻ and concluded that the adsorbed Fe(CN)₆³⁻ catalyzed the electron transfer of both Fe(CN)₆³⁻ itself and cationic Ru(NH₃)₆³⁺.     

Vertically aligned,polypyrrole encapsulated MoS2/graphene composites for high-rate LIBs anode

Ultrathin MoS₂ nanosheets were vertically anchored on the reduced graphene oxide (MoS₂/rGO) via hydrothermal method. To further engineering the surface conductivity, ultrathin polypyrrol (PPy) layer was coated on the MoS₂/rGO composite via in situ polymerization to form a bi-continuous conductive network with a sandwich-like structure. The graphene nanosheets and the PPy coating can facilitate the electrons transfer rate, while the ultrathin MoS₂ nanosheets can enhance the utilization efficiency of the active materials. The obtained MoS₂/rGO-10 composite exhibits high reversible specific capacity (970?mAh?g^?1 at 0.1?A?g^?1) and rate capability (capacity retention of 64% at 3.2?A?g^?1). Moreover, the PPy@MoS₂/rGO hybrids reveal lower specific capacity but better rate capability, and a “trade-off” effect between electrons and ions transfer resistance was observed. This easy-scalable PPy surface conductivity engineering strategy may be applied in the preparation of high-performance LIBs active materials.     

Voltammetric study of the cyanide complexes of osmium—II. The behaviour of lower oxidation state cyanide complexes of osmium on a platinum rde

It was found that the product of the reduction of the cyanide complex of hexavalent osmium, OsO₂(OH)₂(CN)^2?₂ is the Os(OH)₄(CN)^3?₄ complex and the product of the reduction of the OsO₂(CN)^2?₄ complex is the Os(OH)₂(CN)^2?₂ complex. Further reduction of the Os(OH)₄(CN)^3?₄ complex of trivalent osmium is complicated by a follow-up chemical reaction and the stable reduction product is a complex of divalent osmium, Os(OH)₂(CN)^4?₄ which forms a reversible redox system with the Os(OH)₂(CN)^3?₂ complex with a formal redox protential (1 M KOH, 0.1 M KCN) of ?760 mV/sce. The Os(OH)₄(CN)^3?₂ and Os(OH)₂(CN)^4?₄ complexes are stable only in solutions with at least a ten-fold excess of OH^? ions over the concentration of CN^t- ions. At greater cyanide concentrations, the chemical reactioins, Os(OH)₄(CN)^3?₂ → Os(OH)₂(CN)^3?₄ and Os(OH)₂(CN)^4?₄ → Os(CN)^4?₆, occur. The reaction rate for the latter reaction was found to be ?₄ = 1.87 × 10^t-4 l mol^?1 s^?1 in solutions with pH = 11.8. The characteristics of the individual forms of the cyanide complexes of osmium are also discussed.     

Electrochemical characterization of cetyltrimethyl ammonium bromide modified carbon paste electrode and the application in the immobilization of DNA

A cetyltrimethyl ammonium bromide modified carbon paste electrode (CTAB/CPE) was developed in this work based on the surface modification method. The improved electrochemical response of K₄Fe(CN)₆ at this electrode indicated that CTAB could change the surface property of carbon paste electrodes (CPEs), which was demonstrated by the electrochemical impedance spectroscopy (EIS). In 0.1 mM [Fe(CN)₆]^3−/4−, a low exchange current (i₀) of 2.72×10⁻⁷ A at bare CPE was observed while that at CTAB/CPE was 6.79×10⁻⁵ A. The effect of CTAB concentration on the electrode quality revealed that CTAB formed a compact monolayer on the electrode surface with high density of positive charges directed outside the electrode. This electrode showed strong accumulation ability toward Fe(CN)₆⁴⁻ and can also accumulate Co(phen)₃²⁺ by the adsorption of the organic ligands in the hydrophobic area of the monolayer. The electrode was applied to the immobilization of DNA, which was characterized by the isotherm adsorption of Co(phen)₃²⁺.     

The interrelation between the electrochemical behaviour of a polymer-coated electrode and the ion exchange properties of the coating

The Fe(CN)^3−/4−₆ charge-transfer reaction was studied with anion-exchange polymer-coated electrodes SO²⁻₄ and ClO⁻₄ were mainly used as the anions of the background electrolyte. The electrochemical results are correlated with the equilibrium distribution of the ions between the electrolyte and the coating. Since the considered anions are ir-active their concentration in the film could be determined by ir-reflection-absorption spectroscopy, after the coated electrodes had been withdrawn from the electrolyte. The strong influence of the films' ion-exchange selectivity on the electrode behaviour is demonstrated.     

Mesure de pO2− au moyen d'une electrode a membrane de zircone stabilisee et determination potentiometrique de constantes d'equilibre d'echange de O2− dans le melange equimolaire NaCl-KCl fondu

A galvanic cell with a Ag/AgCl reference electrode and a pO^2? indicating electrode—made of a solid-state membrane in zirconia stabilized by calcia and filled by a mixture of Ni + NiO—has been constituted for working in the molten mixture NaCl-KCl (1:1), from 700 to near 1000°C. The response of the zirconia electrode in the fused salt has been tested by known variations of pO^2?, due to coulometric titrations of free oxide ions, then of hydroxide ions, by means of metallic ions (Ni²⁺, Cu⁺) forming scarcely soluble metallic oxides. The results of measurements were in a good accordance with the variation laws theoretically established, giving the proof that measurements of pO^2?, between about 2 and 12, are possible in the electrolytic and temperature range considered, by means of this system. An alteration of the electrode can arise in media with too low a pO^2? value.Equilibrium constants have been determined: solubility products (K_s) of the oxides NiO and Cu₂O, constant values of the equilibria 2OH^? ? H₂O (g) + O^2? (K₁) and H₂O (g) + 2Cl^? ? O^2? + 2HCl (g) (K₂); as functions of the absolute temperature T/°K and in the molar fraction scale (partial pressure of the gazeous substances in atm):

The solubility product values (at 727°C) for a few metallic oxides have been calculated from the free enthalpy values of formation and experimental values of the activity coefficients of the metallic ions and O^2? dissolved in NaCl-KCl.Limitations to the ability of the membrane electrode for measuring pO^2? have been established by an analysis based on the chemical and electrochemical behaviour of zirconia. A potential-pO^2? diagram shows the area inside which one has to work.     

Electrochemical oxidation and determination of antiretroviral drug nevirapine based on uracil-modified carbon paste electrode

A novel uracil covalently grafted carbon paste electrode (Ura/CPE) based on electro-deposition of uracil on CPE was prepared for the quantitative determination of nevirapine. The records of electrochemical impedance spectroscopy (EIS) and cyclic voltammograms (CV) in K₃Fe(CN)₆/K₄Fe(CN)₆ solution illustrated that uracil grafted on CPE efficiently decreased the charge transfer resistance value of electrode and improved the electron transfer kinetic between analyte and electrode. The electrochemical properties of Ura/CPE towards the oxidation of nevirapine were investigated by cyclic voltammetry and differential pulse voltammetry (DPV) in 0.1 M NaOH. The effects of pH and scan rates on the oxidation of nevirapine were studied. The results indicated the participation of the same protons and electrons in the oxidation of nevirapine, and the electrochemical reaction of nevirapine on Ura/CPE is an adsorption-controlled process. Under optimized conditions, the linearity between the oxidation peak current and nevirapine concentration was obtained in the range of 0.1–70.0 μM with detection limit of 0.05 μM and the sensitivity of 2.073 μA mM^?1 cm^?2 (S/N = 3). The proposed method was also successfully applied to detect the concentration of nevirapine in human serum samples.     

Influence of crystal surface orientation on redox reactions at semiconducting MoS2

The redox system Cu(NH₃)^2+/1+_x, Fe(CN)^{$\text{3?}\text{4?}$}₆ and Fe^3+/2+ and oxygen reduction have been studied on MoS₂ surfaces normal to the C-axis and parallel to the C-axis, using rotating disc electrodes under potentiostatic conditions. Current—voltage curves were obtained and apparent exchange current densities (i₀) and rate constants (k⁰_app) have been evaluated. The i₀ and k^o_app values are one order of magnitude larger for the |-C surfaces than for the ⊥-C surfaces of MoS₂. Both forward and reverse reactions occurred readily in the case of Cu(NH₃)^2+/1+_x whereas the reverse reaction was partly or totally blocked in the case of Fe(CN)^{$\text{3?}\text{4?}$}₆ and Fe^{$\text{3+}\text{2+}$}, respectively. The results indicate that surface states and crystal imperfections play a very important role for all these redox reactions. These surface states seem to be connected with Mo-atoms at edges and steps on the surface where they are directly exposed to the electrolyte. The differences in the electron transfer rate between the two surfaces is attributed to the greater overlapping of the electron orbitals of the conduction band at the |-C surface of MoS₂ with the electron orbitals of the redox systems, than of those at the ⊥-C surface.     

A chromotropic acid modified SBA-15 as a highly sensitive fluorescent probe for determination of Fe<Superscript>3+</Superscript> and I<Superscript>−</Superscript> ions in water

A novel organic–inorganic hybrid nanomaterial (SBA-15-CA) was prepared by covalent immobilization of chromotropic acid onto the surface of mesoporous silica material SBA-15. Different techniques such as XRD, TEM, FT-IR, N₂ adsorption–desorption and TGA analyses were employed to characterize the grafting process. The data showed that the organic moiety (0.41 mmol g^?1) was successfully grafted to the SBA-15 and the primary hexagonally ordered mesoporous structure of SBA-15 was preserved after the grafting procedure. SBA-15-CA has been realized as a highly sensitive and selective fluorescent probe towards Fe³⁺ and I^? ions in aqueous media. SBA-15-CA exhibited a remarkable fluorescent quenching in the presence of Fe³⁺ ion over other competitive cations including Na⁺, Mg²⁺, Al³⁺, K⁺, Ca²⁺, Cr³⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺ as well as I^? ion among a series of anions including F^?, Cl^?, Br^?, CO₃^2?, HCO₃^?, CN^?, NO₃^?, NO₂^?, SCN^?, SO₄^2?, H₂PO₄^?, HPO₄^2?, and CH₃COO^?. A good linear response was observed between the concentration of the quenchers (Fe³⁺ and I^? ions) and fluorescence intensity of SBA-15-CA with detection limits of 1.5?×?10^?7 M for Fe³⁺ and 0.2?×?10^?7 M for I^?. Moreover, the effects of various pH values on the sensing ability of SBA-15-CA were investigated. Finally, the proposed method was successfully utilized for the determination of Fe³⁺ and I^? ions in river water, well water and tap water samples.     

Activated carbon adsorption of cyanide complexes and thiocyanate ion from petrochemical wastewaters

Experimental isotherms indicate that thiocyanate and nickel cyanide complex (tetracyanonicklate (II)) adsorb to an equal extent from synthetic and actual waste solutions at loadings below 10 mg/g carbon. Loading of nickel hexammine complex is an order of magnitude less. Adsorption of the divalent nickel cation is strongly pH dependent and is believed to be a chemisorption by precipitation or reaction on the carbon surface. In pure solution, ferrocyanide (hexacyanoferrate (II)) adsorption was comparable to that of thiocyanate or nickelocyanide, but adsorption from the waste liquor tested was negligible. This difference may be due to solvation of ferrocyanide with methanol in the wastewater to form a species with entirely different adsorption characteristics. Chemical oxygen demand (COD) values were obtained for several of the pure materials (SCN^?, 1.1; Fe(CN)₆^?4, 0.5; Ni(CN)₄^?2, 0.4 mg $\text{COD}\text{mg}$ ion) and the wastewater to monitor adsorption of organic background materials.     

Kinetics measurements on a stationary disk electrode in a uniformly rotating fluid (SDERF). II. The electron transfer reaction in the Fe(CN)4−6/Fe(CN)3−6-system

The operation of the SDERF-cell in the study of the electron transfer kinetics of the Fe(CN)^4?₆/Fe(CN)^3?₆-system in 1 M KCl and 1 M KNO₃-solutions at a stationary Pt-disk electrode is reported. The experimental current—overpotential curves are recorded by linear sweep voltammetry and analysed by two different methods using the theoretical relationship derived for a stationary disk electrode placed in a free rotating fluid. Both methods give the same value for the experimental rate constant k*. The effects of the temperature (0° to 40°C) and of the ratio of the rotor radius (r_r) to the electrode radius (r_e)(r_r/r_e = 0.50 to 0.81) have been studied. The activation energy for the redox process in 1 M KCl and 1 M KNO₃ are: E_a = 3.4 ± 0.6 kcal/mol and E_a = 3.7 ± 0.7 kcal/mol respectively, while the k*-values at 25°C are: k* = (5.67 ± 0.41) × 10^?3 cm.s^?1 and k* = (4.53 ± 0.29) × 10^?3 cm.s^?1 respectively. The difference from the standard rate constant k₀ ? 0.100 cm.s^?1 is explained by the effect of the cell-geometry characterized by the G-factor, so that k° = Gk*, where G ? 19 for our cell.     

Kinetic measurements on a stationary disk electrode in a uniformly rotating fluid (SDERF) — I. The limiting diffusion current in the Fe(CN)4−6-Fe(CN)3−6-system

The construction and operation of an electrochemical cell provided with a sde in a uniformly rotating fluid (SDERF-cell) are reported. The test of the SDERF-cell with respect to the diffusional kinetics is made with the Fe(CN)^4?₆-Fe(CN)^3?₆ system in 1 M solutions of NaOH, KCl and KNO₃, in potentiodynamic conditions. The linear relationship between the limiting diffusion current I_d and the square root of the angular velocity of the rotor, ω^{$\text{1}\text{2}$}_r holds, but the straight line does not intercept the coordinate axes in the origin. The square root of the angular velocity of fluid, ω^{$\text{1}\text{2}$}_f — calculated from I_d — depends only on the ω^{$\text{1}\text{2}$}_r — value irrespective of the concentration and the physical properties of the fluid. The diffusion coefficients and the activation energy of diffusion, E_a, in 1 M KNO₃ were measured; E_a = 3.15 kcal/mol for both Fe(CN)^4?₆ and Fe(CN)^3?₆-ions.     

Selectivity Coefficients for Zn(CN)4 2-, Cd(CN)4 2-, and Hg(CN)4 2- from Continuous Foam Fractionation with a Quaternary Ammonium Surfactant

Abstract

An experimental study is presented on the continuous flow, foam fractionation of cyanide complex anions. Zn(CN)₄ ^2-, Cd(CN)₄ ^2-, and Hg(CN)₄ ^2- form 7.5 × 10^?6 to 1.5 × 10^?5 M aqueous solutions with the quaternary ammonium surfactant, hexadecyltrimethylammonium iodide. The selectivity coefficients were determined for Zn(CN)₄ ^2- vs I^? equal to 8.86. for Cd(CN)₄ ^2- vs I^? equal to 21.79 and for Hg(CN)₄ ^2- vs I^? equal to 25.12. The surfactant ion-exchange reaction with the studied complex ions was also suggested.     

Voltammetric study of the cyanide complexes of osmium—I. The reduction of the cyanide complex of Os(VI) on a platinum rde

Two forms of cyanide complexes of hexavalent osmium were found in alkaline KCN solutions. The initially formed complex, OsO₂(OH)₂(CN)^2?₂, is stable only in solutions with at least a ten-fold excess of OH^? ions over CN^? ions. At higher cyanide concentrations it is converted into the OsO₂(CN)^2?₄ complex. Both these complexes are reduced to tervalent osmium. A more detailed study of complex OsO₂(OH)₂(CN)^2?₂ has shown that it is reduced electrochemically according to the scheme of a consecutive electrochemical reaction.OsO₂(OH)₂(CN)^2?₂ + 2e(k₁,α₁) → Os(IV) + e(k₂,α₂) → Os(OH)₄(CN)^3?₂The values α₁ = 0.65 and α₂ = 0.40 and the potential dependences of constants k₁ and k₂ were determined.