The effect of potential on the gold dissolution in cyanide solutions in the presence of sulfide ions

The effect of potential on the rate of gold dissolution in the cyanide solutions in the presence of sulfide ions is studied. The dependences of current on the time after the electrode surface renewal were measured under the potentiostatic conditions. The majority of experiments were performed in the solution of the following composition, M: 0.1 KCN, 0.1 KOH, 0.01 KAu(CN)₂, (1.5–2) × 10^?5 Na₂S at 23°C. It is shown that, at the potentials more positive than ?0.1 V (NHE), the rate of gold dissolution starts to increase as soon as the surface is renewed, which is associated with high-rate chemisorption of catalytically active sulfide ions. At E < ?0.1 V, the chemisorption proceeds slowly, and a considerable increase in the current takes much time. Therefore, in the potentiodynamic measurements, at E < ?0.1 V, no catalytic effect of sulfide ions is observed. When the ratio between the concentrations of sulfide and cyanide ions is decreased, the potential, which, by convention, bounds the aforementioned ranges, shifts in the positive direction. Plausible explanations for these regularities are proposed.     

Chemical and electrochemical behavior of metallic technetium in acidic media

The chemical and electrochemical properties of technetium metal were studied in 1–6 M HX and in 1 M NaX (pH 1 and 2.5), X = Cl, NO₃. The chemical dissolution rates of Tc metal were higher in HNO₃ than in HCl (i.e. 8.63 × 10^?5 mol cm^?2 h^?1 in 6 M HNO₃ versus 2.05 × 10^?9 mol cm^?2 h^?1 in 6 M HCl). The electrochemical dissolution rates in HNO₃ and HCl were similar and mainly depended on the electrochemical potential and the acid concentration. The optimum dissolution of Tc metal was obtained in 1 M HNO₃ at 1 V/AgAgCl (1.70 × 10^?3 mol cm^?2 h^?1). The dissolution potentials of Tc metal in nitric acid were in the range of 0.596–0.832 V/AgAgCl. Comparison of Tc behavior with Mo and Ru indicated that in HNO₃, the dissolution rate followed the order: Mo > Tc > Ru, and for dissolution potential the order: E _diss(Ru) > E _diss(Tc) > E _diss(Mo). The corrosion products of Tc metal were analyzed in HCl solution by UV–Visible spectroscopy and showed the presence of TcO₄ ^?. The surface of the electrode was characterized by microscopic techniques; it indicated that Tc metal preferentially corroded at the scratches formed during the polishing and no oxide layer was observed.     

The effect of thallium ions on the gold dissolution rate in thiosulfate electrolytes

The effect of TlNO₃ additions in the concentration (c ₁) range from 5 × 10^?6 to 1 × 10^?4 M on the anodic dissolution of gold in sodium thiosulfate solutions with the concentration (c ₂) from 0.005 to 0.2 M is studied by voltammetry on the electrode surface renewed by cutting off a thin metal layer immediately in solution and also by the quartz-crystal microbalance method. For c ₂ = 0.2 M, as c ₁ increases from 5 × 10^?6 to 1 × 10^?4 M, the gold anodic dissolution rate is observed to increase from 0.02 (in the absence of TlNO₃) to 0.75 mA/cm² for c ₁ = 7.5 × 10^?5 M according to a nearly linear law. The dissolution accelerates because the effective values of the transfer coefficient and the exchange current density increase from 0.2 and 4 ??A/cm² (in the absence of TlNO₃ admixtures) to 0.47 and 35 ??A/cm² (for c ₁ = 1 × 10^?4), respectively. Experiments with the renewal of the electrode surface in the course of electrolysis suggest that the gold dissolution is catalyzed in the presence of thallium ions by the adsorption mechanism and also as the result of the mixed kinetics of their adsorption on the electrode surface.     

Bis[2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulpho propylamino)phenolato]cobaltate(III) as a counter ion for the extraction and spectrophotometric determination of long-chain quaternary ammonium salts and tertiary alkylamines in the presence of each other

The singly charged complex anion bis[2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulphopropylamino)phenolato]cobaltate(III) is intensely purple-violet and is stable over the pH range 1–13. Its absorption spectrum remains the same over this pH range. At pH2, it forms extractable ion pairs with long-chain quaternary ammonium ions and protonated alkylamines. Only the quaternary ammonium ions are extracted into chloroform at pH 11, hence separate extractions allow both types to be determined. The absorbance of the organic phase is measured at 594 nm. The apparent molar absorptivity is 7.0 × 10⁴ l mol^?1 cm^?1. Calibration graphs for zephiramine, benzethonium and hexadecylpyridinium ions are linear over the range 0.1–2 × 10^?6 M. The only interference found was from anionic surfactants. The method is applied to hair and fabric conditioners.     

Electrochemical study and polarographic determination of ranitidine

In the polarographic reduction of ranitidine, an H₂-antagonist of histamine, three waves are observed; their half-wave potentials and limiting currents depend strongly on the pH of the solution. The first and second waves are due to reduction of teh protonated, CHNO₂H⁺, and unprotonated, CHNO₂, nitroethene group of ranitidine, respectively; the origin of the third wave is unknown. The characteristics of the second and third waves are studied in acetic acid/acetate buffer at pH 5.5; the first wave does not appear at this pH. The second wave (E_{$\text{1}\text{2}$} = ?0.90 V, vs. Ag/AgCl) is useful for determining ranitidine in the range 2.4–4.9 × 10^?4 M by direct current polarography and in the range 2.5 × 10^?7?2.05 × 10^?5 M by differential pulse polarography.     

Determination of trace amounts of nickel by differential pulse adsorptive cathodic stripping voltammetry using calconcarboxylic acid as a chelating agent

A method for the determination of nickel(II) by stripping voltammetry is described. The method is based on the adsorptive accumulation of nickel(II) calconcarboxylic acid complex onto a hanging mercury drop electrode (HMDE), followed by the reduction of the adsorbed complex using differential pulse voltammetry. The optimum operating conditions and parameters were found to be 0.05 M NH₃/NH₄Cl buffer (pH = 9.5) as the supporting electrolyte, a ligand concentration of 1 × 10^?6 M, accumulation potential of ?0.5 V (vs. Ag/AgCl) and accumulation time of 60 s. At the optimized conditions, the peak current is proportional to the concentration of nickel in the range of 1.7 × 10^?9 to 4.7 × 10^?7 M (0.1–28 ng ml^?1) with a detection limit of 0.05 ng ml^?1. The relative standard deviation (n = 10) at nickel concentrations of 2, 10 and 15 ng ml^?1 varies in the range 0.76 to 2.1%. Possible interferences by metal ions, which are of great significance in real matrices, have been studied. The method was successfully applied to the determination of nickel content in a chocolate sample.     

Kinetics of silver electrodeposition from thiocarbamide solutions at a regular surface coverage with sulfide ions

Kinetics of silver electrodeposition in the presence of sulfide ions is studied on electrodes renewed by cutting off a thin surface layer, at a controlled time of contact of the “fresh” surface with the electrolyte. Solutions containing 10^?2 M AgNO₃, 0.1 M thiocarbamide, 0.5 M HClO₄, and from 2 × 10^?6 to 1.5 × 10^?5 M Na₂S are studied. It is shown that under the studied conditions, the effect of silver electrodeposition on the surface concentration of sulfide ions is insignificant. As the concentration of sulfide ions in solution and their coverage on the electrode surface θ increase, the cathodic polarization decreases. Tafel curves plotted for θ = const are used in estimating the exchange current i ₀ and the transfer coefficient α. It is shown that α ≈ 0.5 and weakly depends on θ, whereas the exchange current increases with the increase in θ by an approximately linear law from 10^?5 A/cm² at θ ? 0 to 10^?4 A/cm² at θ = 0.43. The obtained data are compared with the results of kinetic studies of silver anodic dissolution in similar solutions.     

Iron(III) selective fluorescence probe based on perylene tetracarboxylic diimide

Responses of organic fluorophore, perylenediimide derivative N,N′-di[3-[2-(3-thienyl)ethyl]phenyl]perylene-3,4,9,10-bis-(dicarboxyimide) (PDI1) was investigated in polymer matrix of polyvinyl chloride (PVC) by emission spectrometry. Its response to Fe(III) ions was evaluated in terms of the effect of pH. The properties of time dependent response, reversibility, limit of detection, linear concentration range for the metal ion and repeatability characteristics of the sensing element also have been studied. The offered sensor exhibited remarkable fluorescence intensity quenching at pH 6.0 in the concentration range of 1 × 10^?6 to 2.5 × 10^?3 M Fe(III) ions. The reproducibility of the sensor membrane was investigated by alternately changing the solution between 1 × 10^?4 M Fe(III) in Na₂HPO₄ (4 × 10^?2 M) and NaH₂PO₄ buffer (2 × 10^?3 M).     

The kinetics of reduction of palladium (II) complexes with β-alanine at dropping mercury electrode and the complexes’ stability constants

By using dc and ac polarography, the kinetics of electroreduction of the palladium (II) complexes with β-alanine at a dropping mercury electrode was studied in solutions with the palladium (II) concentration from 2 × 10^?5 to 2 × 10^?4 M and variable β-alanine and sodium perchlorate concentrations (pH 6–12). One polarographic wave was observed in solutions with pH 9 and 10 at the β-alanine overall concentration of c _βala = 1 × 10^?3 to 5 × 10^?2 M; two waves, at lower pH or higher c _βala. It was concluded on the formation of different forms of palladium (II) complexes in the studied solutions; the complexes contained two to four β-alanine coordinated anions. Using the limiting diffusion currents for the two waves at pH 9–11 and c _βala = 0.1 and 0.5 M, the stepwise stability constant for the Pd(βala) ₄ ^2? complex was calculated. Using two ac peaks observed at pH 7–8 and c _βala = 1 × 10^?2 to 0.1 M, the stepwise stability constant for the Pd(βala) ₃ ^? . was calculated. The perchlorate ions adsorbed at the dropping mercury electrode, as well as βala^? anions at their higher concentrations, hamper the electroreduction of the palladium (II) complexes with β-alanine.     

Gold Dissolution Electrocatalysis in Thiourea Electrolytes in the Presence of Chemisorbed Sulfide Ions

Adding a microscopic quantity of sodium sulfide (～10^?5 M) into acid solutions of thiourea leads to a dramatic acceleration of anodic dissolution of gold. The acceleration effect is greater at larger thiourea concentrations (c) and longer times of the electrode contact with solution (Δt) before the beginning of measurements. The effect diminishes after a polarization curve passes through a maximum at E ? 0.5 V. Regularities of the gold dissolution in a solution containing 0.1 M thiourea and 0.5 M H₂SO₄ at given values of c and Δt are studied with use made of the technique of renewing the electrode surface by cutting off a thin surface layer of metal. The discovered regularities are given an explanation which is based on the assumption that the dissolution process is catalyzed by sulfide ions adsorbed on the electrode surface.     

Electrochemistry of triphenyltin acetate at a mercury-film glassy carbon electrode

The electrochemical behaviour of triphenyltin acetate was investigated by cyclic voltammetry, differential-pulse voltammetry and controlled potential electrolysis at a mercury-film glassy carbon electrode. Effects on the electrochemical response of the composition of supporting electrolytes, pH, electrode rotation speed and triphenyltin acetate concentration were determined. The electrochemical reduction of this compound was found to involve a preliminary adsorption process (E_peak ≈ ?0.7 V vs. SCE), the reduction of triphenyltin acetate to the triphenyltin radical (E_peak ≈ ?1.0 V) and reduction of the radical to the triphenyltin anion (E_peak ≈ ?1.4 V). A procedure for the determination of trace amounts of this compound by differential-pulse anodic stripping voltammetry in 50% (v/v) ethanol with 0.1 M acetic acid + 0.1 M ammonia solution was developed and applied to the analysis of a commercial powder formulation and water and fish samples. The limit of detection was 2.5 × 10^?9 M triphenyltin acetate.     

Polarographic determination of picolinaldehyde in the presence of some related compounds

A d.c. polarographic method is described for the determination of picolinaldehyde (1.5 × 10^?5–2.9 × 10^?4 M), based on the in situ formation of its Girard-P derivative in aqueous solution. A mechanism of reduction (E_1/2 = ?0.71 V at pH 3.5) is proposed. The applicability of this method is checked in synthetic samples containing pyridine, picoline and pyridine carboxylic acids.     

Electrochemical investigation and determination of ceftazidime in pharmaceutical dosage forms and human urine

A voltammetric study of the oxidation of Ceftazidime (CEFT) has been carried out at the glassy carbon electrode by cyclic, differential pulse (DPV) and square wave (SWV) voltammetry. The oxidation of CEFT was irreversible and exhibited diffusion controlled process depending on pH. The oxidation mechanism was proposed and discussed. According to the linear relationship between the peak current and concentration, DPV and SWV voltammetric methods for CEFT assay in pharmaceutical dosage forms and human urine were developed. For analytical purposes, a well resolved diffusion controlled voltammetric peak was obtained in 0.1 M H₂SO₄ at 1.00 and 1.02 V for differential pulse and square wave voltammetric techniques, respectively. The linear response was obtained within the range of 4 × 10^?6?8 × 10^?5 M with a detection limit of 6 × 10^?7 M for differential pulse and 4 × 10^?6–2 × 10^?4 M with a detection limit of 1 × 10^?6 M for square wave voltammetric technique. The determination of CEFT in 0.1 M H₂SO₄ was possible over the 2 × 10^?6–1 × 10^?4 M range in urine sample for both techniques. The standard addition method was used for the recovery studies.     

Trace Analysis of Al (III) Ions Based on the Redox Current of a Conducting Polymer

A conducting polymer was electrochemically prepared on a Pt electrode with newly synthesized 3′‐(4‐formyl‐3‐hydroxy‐1‐phenyl)‐5,2′ : 5′,2″‐terthiophene (FHPT) in a 0.1 M TBAP/CH₂Cl₂ solution. The polymer‐modified electrode exhibited a response to proton and metal ions, especially Al(III) ions. The poly[FHPT] was characterized with cyclic voltammetry, EQCM, and applied to the analysis of trace levels of Al(III) ions. Experimental parameters affecting the response of the poly[FHPT] were investigated and optimized. Other metal ions in low concentration did not interfere with the analysis of Al(III) ions in a buffer solution at pH 7.4. The response was linear over the concentration range of 5.0×10^?8–7.0×10^?10 M, and the detection limit was 5.0×10^?10 M using the linear sweep voltammetry (LSV). Employing the differential pulse voltammetry (DPV), the response was linear over the 1.0×10^?9–5.0×10^?11 M range and the detection limit was 3.0×10^?11 M. The relative standard deviation at 5.0×10^?11 M was 7.2% (n=5) in DPV. This analytical method was successfully verified for the analysis of trace amounts of Al(III) ions in a human urine sample.     

Application de la radiopolarographie a l'étude dequelques éléments à l'échelle des indicateurs

Basic equations of classical polarography are transposed and tested withmanganese and europium at tracer scale. Using the previously presented automatic system, standard dispersion for experimental points is about 3% and residual activity before the wave 3±2% compared with diffusion activity A_d. Results with manganese in 10^?3M ≤[LiCl]≤10^?1M and 2≤pH≤4 solutions, give an experimental yield about 100%, E_1/2=?1.47 V/SCE and α?0.85. The last values agree with results achieved at a weighable scale. For potentials <?2.00 V/SCE a screening effect with supporting electrolyte ions is observed. The screening effect influence on the diffusion coefficient is taken into consideration and results for europium (R?100%, E_1/2??1.95 V/ECS, α=1 at pH 2.7) are in good agreement with the literature. Radiopolarograms for Mn and Eu and mixtures of both are similar. Thus the range of polarographic analysis is enlarged.     

Voltammetric determination of selenosulfate ions at a mercury-film electrode

A procedure is proposed for the voltammetric determination of selenium as selenosulfate (SO₃Se^2?) ions at a mercury-film electrode (MFE). Selenosulfate ions are determined in the range from 2 × 10^?4 to 1.0 × 10^?3 M without analyte accumulation, using peak current at ?0.92 ± 0.02 V and in the range from 1 × 10^?7 to 2 × 10^?4 M after analyte accumulation with the open circuit, using peak current at ?1.18 ± 0.03 V as the analytical signal. The mechanisms of SO₃Se^2? reduction at an MFE under the conditions of direct voltammetry and stripping voltammetry with accumulation are proposed and discussed.     

Electrochemical Behavior of Apigenin at a Glassy Carbon Electrode and its Analytical Application

The electrochemical behavior of the antitumor herbal drug apigenin was studied in 0.1 mol L^?1 B‐R buffer solutions (50% ethanol, pH 3.0) by cyclic voltammetry (CV) at a glassy carbon electrode. In CV, two oxidation peaks (P₁ and P₂) with E_p1 = 1.03V and E_p2 = 1.23 V appeared at a scan rate of 0.05 V s^?1, and a new electroanalytical method for this herbal drug was established according to the oxidation peak P2. The peak currents have a linear relationship with apigenin concentration in a range from 9.0 × 10^?7 to 2.0 × 10^?5 mol L^?1. Using the established method, apigenin in a herbal drug was determined without pre‐separation with satisfactory results. Moreover, the electrode dynamics parameters were also investigated by electrochemical techniques and the possible electrode reaction mechanism was deduced.     

Kinetic studies on the metal(II) tartarate–peroxomonosulfate reaction

The kinetics of oxidation of tartaric acid (TAR) by peroxomonosulfate (PMS) in the presence of Cu(II) and Ni(II) ions was studied in the pH range 4.05–5.20 and also in alkaline medium (pH ～12.7). The rate was calculated by measuring the [PMS] at various time intervals. The metal ions concentration range used in the kinetic studies was 2.50 × 10^?5 to 1.00 × 10^?4 M [Cu(II)], 2.50 × 10^?4 to 2.00 × 10^?3M [Ni(II)], 0.05 to 0.10 M [TAR], and µ = 0.15 M. The metal(II) tartarates, not TAR/tartarate, are oxidized by PMS. The oxidation of copper(II) tartarate at the acidic pH shows an appreciable induction period, usually 30–60 min, as in classical autocatalysis reaction. The induction period in nickel(II) tartarate is small. Analysis of the [PMS]–time profile shows that the reactions proceed through autocatalysis. In alkaline medium, the Cu(II) tartarate–PMS reaction involves autocatalysis whereas Ni(II) tartarate obeys simple first‐order kinetics with respect to [PMS]. The calculated rate constants for the initial oxidation (k₁) and catalyzed oxidation (k₂) at [TAR] = 0.05 M, pH 4.05, and 31°C are Cu(II) (1.00 × 10^?4 M): k₁ = 4.12 × 10^?6 s^?1, k₂ = 7.76 × 10^?1 M^?1s^?1 and Ni(II) (1.00 × 10^?3 M): k₁ = 5.80 × 10^?5 s^?1, k₂ = 8.11 × 10^?2 M^?1 s^?1. The results suggest that the initial reaction is the oxidative decarboxylation of the tartarate to an aldehyde. The aldehyde intermediate may react with the alpha hydroxyl group of the tartarate to give a hemi acetal, which may be responsible for the autocatalysis. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 620–630, 2011     

Quartz crystal microbalance measurements of kinetic parameters of anodic dissolution of gold in thiocarbamide electrolytes in the presence of sulfide ions

As shown by quartz-crystal microbalance measurements, in the potential range from 0.0 to 0.55 V (NHE), sulfide ions adsorbed on the gold electrode surface accelerate the electrode reaction of anodic dissolution of gold in acidic thiocarbamide solutions. The microbalance determination of kinetic parameters at a constant electrode surface coverage with sulfide ions includes a special procedure developed for the determination of the gold dissolution rate. The conditions (the potential range and the potential scan rate) of independence of the dissolution rate from the diffusion limitations associated with the ligand delivery is determined. Under these conditions, the polarization curve is shown to be linear on semilogarithmic coordinates and correspond to the Tafel equation. In this potential range, the transfer coefficient α and the reaction order with respect to the ligand p are determined at a constant electrode surface coverage θ with adsorbed sulfide ions. It is shown that with the transition from the surface coverage with sulfide ions θ = 0.1 to θ = 0.8, the transfer coefficient α changes from 0.25 to 0.55, the exchange current (i ₀) changes from 10^?5 to 5 × 10^?5 A/cm², and the effective reaction order p with respect to the ligand changes from 0.2 to 1.3. The mentioned changes are associated not only with the acceleration of gold dissolution in the presence of chemisorbed sulfide ions but also with the changeover in the mechanism of this process. Quartz-crystal microbalance data on the gold dissolution rate qualitatively agree with the results of voltammetric measurements of a renewable gold electrode. A possible version of explanation of the catalytic effect of sulfide ion adsorption on the gold dissolution is put forward.     

Direct electrochemistry and electrochemical biosensing of glucose oxidase based on CdSe@CdS quantum dots and MWNT-modified electrode

The direct electron transfer of glucose oxidase (GOx) was achieved based on the immobilization of CdSe@CdS quantum dots on glassy carbon electrode by multi-wall carbon nanotubes (MWNTs)-chitosan (Chit) film. The immobilized GOx displayed a pair of well-defined and reversible redox peaks with a formal potential (E ^θ’) of ?0.459 V (versus Ag/AgCl) in 0.1 M pH 7.0 phosphate buffer solution. The apparent heterogeneous electron transfer rate constants (k _s) of GOx confined in MWNTs-Chit/CdSe@CdS membrane were evaluated as 1.56 s^?1 according to Laviron's equation. The surface concentration (Γ*) of the electroactive GOx in the MWNTs-Chit film was estimated to be (6.52?±?0.01)?×?10^?11?mol?cm^?2. Meanwhile, the catalytic ability of GOx toward the oxidation of glucose was studied. Its apparent Michaelis–Menten constant for glucose was 0.46?±?0.01 mM, showing a good affinity. The linear range for glucose determination was from 1.6?×?10^?4 to 5.6?×?10^?3?M with a relatively high sensitivity of 31.13?±?0.02 μA?mM^?1?cm^?2 and a detection limit of 2.5?×?10^?5?M (S/N=3).