A Novel Potentiometric Sensor for Thiocyanate Based on an Amide‐Linked Manganese Diporphyrin Xanthene

The synthesis of a new compound, amide‐linked manganese diporphyrin xanthene (Mn₂Cl₂ADPX), and its application for preparation of thiocyanate selective electrodes was described. The electrode was prepared with a PVC membrane combining Mn₂Cl₂ADPX as an electro active material, 2‐nitrophenyl octyl ether (o‐NPOE) as a plasticizer in the percentage ratio of 3 : 65 : 32 (Mn₂Cl₂ADPX: o‐NPOE: PVC, w : w : w). The electrode exhibited linear response within the concentration range of 2.4×10^?6 to 1.0×10^?1 M SCN^?, with a working pH range from 3.0 to 8.0 and a fast response time of less than 60 s. Several electroactive materials and solvent mediators have been compared and the experimental conditions were optimized. The Mn₂Cl₂ADPX based electrode shows obviously better response characteristics than that of monoporphyrin manganese in terms of working concentration range and slope. Selectivity coefficients for SCN^? relative to a number of interfering ions were investigated. The electrode exhibits anti‐Hofmeister selectivity toward SCN^? with respect to common coexisting anions. The electrode was applied to the determination of SCN^? in body urine with satisfactory results.     

A new copper(I) thiocyanato thiocyanogen complex

The reaction between Cu²⁺ and SCN^?, in glacial acetic acid at a Cu/SCN ratio, of 1:4, gave a dark red solution that exhibited an absorption band at 496 nm. The colour of the freshly prepared solution was bleached by water with concomitant production of SO₄^2? ion. On standing, the stability of the colour towards water is increased and the position of the absorption band shifts to a higher wavelength. It is inferred that the thiocyanogen produced on oxidation of SCN^? by Cu²⁺ is stable in the non-aqueous medium and is coordinated together with SCN^? in a Cu(I) complex. The bleaching action of water is attributed to the hydrolysis of thiocyanogen, mainly to SO₄^2?. The presence of thiocyanogen enhanced polymerization and subsequent deposition of an orange-brown solid complex. On the basis of chemical, spectral, and thermal analyses the formula K[Cu(SCN)₂(NCS—SCN)], is assigned to the new compound.     

Mechanism of electroreduction of cobalt(II) in thiocyanate solutions at mercury electrodes

The process of electroreduction of cobalt(II) in thiocyanate solutions at mercury electrodes has been investigated by cyclic voltammetric, chronoamperometric and polarographic methods. The influences of pH, the concentrations of Co(II) and SCN^?, and the reduction products of SCN^?, CN^? and S^2? on the reduction waves are described. The polarographic pre-wave is an autocatalytic in nature. A mechanism involving an initial reduction of Co(II)—SCN^? at a mercury electrode followed by the chemical reduction of thiocyanate ion with the electroreduced metallic cobalt, and taking into account cyanide, sulfide, and hydroxide ions, the latter being produced by the hydrolysis of cyanide ion, is presented. Cobalt sulfide adsorbed at the electrode surface stimulates further reduction of Co(II)—CN^? and —SCN^? complexes, and depresses the interfering influence of Co(OH)₂, which is reductively desorbed from the electrode surface with giving rise to an additional peak near ?1.08 V vs. SCE.     

Electrochemical kinetics of gold electrodes in SCN−/dimethylsulfoxide solutions

The electrochemical behaviour of the Au/SCN^? (DMSO) interface is studied at 25°C≤T≤65°C, by means of the triangular potential sweep technique and the RDE. Within a relatively limited potential range the main electrode process is:3 SCN^?=(SCN)₃^?+2e The kinetics of this reaction involves a mixed control. At higher potentials the electrodissolution of the base metal takes place. Side reactions occurring there make the overall process rather complex. The electrochemical behaviours of the Au/SCN^? (DMSO) and Au/SCN^? (ACN) are compared.     

A new iron(II) thiocyanato thiocyanogen complex

The reaction between Fe³⁺ and SCN^?, in glacial acetic acid medium, gave a dark red solution which differs from the classical FeSCN²⁺, prepared in aqueous medium, with regard to stability and composition. In contrast to [FeSCN]²⁺ which undergoes photochemical decomposition and is bleached by light and reduced by hydroxylammonium chloride, the new complex is stable towards these agents, but it reacts with water. In addition to the charge transfer band at 480 nm exhibited by both solutions, the new complex exhibits a sharp strong band at 253 nm characteristic of the trithiocyanate ion, [SCN^? + NCSSCN]; thiocyanogen being produced by oxidation of SCN^? by Fe³⁺. The reaction with water is attributed to the hydrolysis of thiocyanogen mainly into sulphate. The presence of thiocyanogen in the new complex enhanced polymerixation and subsequent deposition of solid complex. On the basis of chemical, spectral, and thermal analyses the formula K₂[Fe(SCN)₄(NCSSCN)], is assigned to the new compound.     

Novel Membrane Potentiometric Thiocyanate Sensor Based on Tribenzyltin(IV) Dithiocarbamate

A novel PVC membrane ion‐selective electrode based on tribenzyltin(IV) dithiocarbamate [Sn(IV)–TBDTB] as neutral carrier was developed for thiocyanate (SCN^?) determination. The electrode exhibits a near‐Nernstian response for SCN^? with a slope of 62.8±2.0 mV per decade over a wide concentration range 1.0×10^?1–2.0×10^?6 mol L^?1 and a detection limit of 1.0×10^?6 mol L^?1 in MES–NaOH buffer, pH 6.0, at 25 °C. The electrode prepared with 1.5 wt.% Sn(IV)–TBDTB, 32.5 wt.% PVC and 66.0 wt.% 2‐nitrophenyloctyl ether (o‐NPOE) shows optimal response characteristics. Anti‐Hofmeister selectivity sequence for a series of anions shown by the electrode was as follows: SCN^?>Sal^?>I^?>ClO >phCOO^?>CH₃COO^?>Br^?>Cl^?>NO >NO >Citrate>SO₄^2?. The useful pH range for the electrode was found to be 3–7 with a response time 30–40 s. The electrode has been used for direct determination of thiocyanate in wastewater with satisfactory results.     

Zum Einfluß von Kaliumtricyanmethanid und -dicyanamid auf das anodische Verhalten von Kupfer in wäßrigen Lösungen

On the Influence of Potassium Tricyanmethanide and Dicyanamide on the Anodic Behaviour of Copper in Aqueous Solutions Electrochemical measurements on copper anodes in aqueous solutions of potassium tricyanmethanide and dicyanamide show a strong tendency of passivation of copper. Comparative galvanostatic investigations of copper in aqueous solutions of the potassium halides and pseudo-halides KX (X: Cl, Br, J, SCN, N(CN)₂, N(CN)₂, C(CN)₃) are indicating a clear increase in the efficiency of the formation of a passivating layer in the series Cl^? ? Br^?<J^?<SCN^?<N(CN)₂^?<C(CN)₃^?. In solutions of halides the first anodic process is followed by the second one at few increased potential, whereas a broad passive areal appears in solutions of pseudohalides, for instance in the cases of tricyanmethanide and dicyanamide.     

Surface-enhanced Raman spectroscopy of 12CN− and 13CN− adsorbed at silver electrodes

Measurements are reported of the surface-enhanced Raman of ¹²CN and ¹³CN (and of isotopically labelled mixtures) adsorbed at silver electrodes. The spectra are shown to arise from a complex species whose coordination number does not change with electrode potential. This species is probably a [Ag(CN₂)]^? entity having C_2v symmetry; at very negative potentials a reduced form of this complex [Ag(CN)₂]^2? coexists with the formally Ag¹ species at the surface. The shifts in band position are interpreted in terms of changes in the bond character of the adsorbed CN^? species. The spectrum of water coadsorbed with CN^? is also markedly dependent on the charge density of the adsorbed CN^? groups.     

Medium effects: The adsorption of ions on a mercury electrode from mixed H2O-organic solvent systems

The problems met in the investigations of ionic adsorption at the mercury electrode from mixed solvent systems are discussed. An attempt is made to give such an interpretation of non-monotonic changes of the anion adsorption as function of solvent composition which could be equally well applied for interpreting the non-monotonic changes of the rate constants of electrode reactions. The practical difficulties of evaluating the surface excesses in the case of mixed solvents are discussed. Some experimental results for the adsorption of SCN^? ions from the system 0.2 M (NaSCN+NaF) in H₂O+acetone are presented. A suggestion for checking the consistency of the evaluated surface excesses is given.     

Salt Effects in the Cononsolvency of Poly(N‐isopropylacrylamide) Microgels

Poly(N‐isopropylacrylamide) (PNIPAM) is well known to exhibit reentrant behavior or cononsolvency in response to the composition of a mixed solvent consisting of water and a low‐chain alcohol. Since the solvent structure plays an important role in this phenomenon, the presence of structure‐breaking/structure‐making ions in solution is expected to have a dramatic effect on the cononsolvency of PNIPAM. The present work examines the way that the presence of different salts can modify the reentrant‐phase diagram displayed by a cationic PNIPAM microgel in the mixed ethanol/water solvent. The effects of four Hofmeister anions—SO₄^2?_, Cl^?, NO₃^? and SCN^?—with different abilities to modify the solvent structure are analyzed. The species with kosmotropic or structure‐making character show a clear competition with ethanol for the water molecules, intensifying the nonsolvency of the PNIPAM with the EtOH volume fraction (?_e). However, striking results are found with the most chaotropic or structure‐breaking anion, SCN^?. In contrast to what happens in water‐rich solutions, the presence of SCN^? in alcohol‐rich solvents enhances the solubility of the polymer, which macroscopically results in the microgel swelling. Moreover, this ion displays great stabilizing properties when ?_e> is 0.2. These results have been explained by considering how chaotropic or structure‐breaking ions interact with water and ethanol molecules.     

Electrocatalytic oxidation of nickel amalgam in aqueous solutions of halogen and pseudohalogen ions

The voltammetric oxidation of nickel amalgam from the hanging mercury drop electrode in aqueous solutions of F^?, Cl^?, Br^?, I^?, N₃^?, SCN^?, and ClO₄^? ions have been investigated. Concentrations of these anions were sufficiently low to depress the formation of complexes with nickel(II) in the bulk of the solution.An increase in the rate of anodic oxidation with increase of concentration of anions was observed both without and with correction for the φ₂ potential. This increase is explained as due to a catalytic effect of anions adsorbed on the electrode surface.Using the concept of changes of the activity coefficient of the activated complex it was possible to show that the oxidation of the nickel amalgam in thiocyanates and azides proceeds by the formation of the activated complex with bound SCN^? and N₃^? anions. These complexes form only in the activated state and decompose when products leave the double layer.In chlorides and bromides a similar mechanism is suggested only at larger surface concentration of anions. At lower surface concentration and in iodides the oxidation proceeds by the activated complex with no anions bound to the nickel, only long-range interactions of adsorbed anions with activated complex then exist.The order of these electrode reactions was calculated using the concept of the surface activity.The two-step mechanism of the charge transfer is also discussed.     

Electrochemical oxidation of thiocyanates on a boron-doped diamond electrode in acid media

The kinetics and selectivity of the oxidation of thiocyanate on a boron-doped diamond (BDD) electrode in a 0.5 M solution of H₂SO₄ were studied. An analysis of the cyclic voltammetry curves showed that the oxidation of SCN^? was irreversible and occurred with diffusion control in the range of water decomposition potentials. The obtained kinetic dependences can be described by the pseudo-first order equation. The apparent rate constant depends on the current density and initial concentration of the reagent. The main product of oxidation at low current density and high concentration of SCN^? was CN^?.     

Maßanalyse und Katalyse

The application of the therinometric method to the catalytic endpoint indication in volumetric determinations by precipitation reactions is discussed. The direct titration of silver, mercury(II) and palladium(II) as well as the determination of several anions (Cl^?, Br^?, J^?, SCN^?, CN^?, [Fe(CN)₆]^4? and S^2?) by backtitration with iodide standard solution is described. The well known reaction between cerium(IV) and arsenic(III), catalysed by iodide, serves as an indicator. The ions mentioned can thus be determined in the microgram range with good accuracy.     

Highly Selective Thiocyanate Electrode Based on Bis‐bebzion Schiff Base Binuclear Copper(II) Complex as Neutral Carrier

Abstract

A highly selective polyvinyl chloride (PVC) membrane electrode, based on N,N′‐(aminoethyl)ethylenediamide bis(2‐benzoideneimine) binuclear copper(II) complex [Cu(II)‐AEBB] as neutral carrier, was prepared for thiocyanate (SCN^?) determination, which displays an anti‐Hofmeister selectivity sequence for a series of anions in the following order: SCN^?>ClO₄ ^?>Sal^? > I^?>NO₃ ^?>Br^?> Cl^?>NO₂ ^?>SO₃ ^2?>F^?>H₂PO₄ ^?>SO₄ ^2?. The electrode exhibited near‐Nernst response for SCN^? with a slope of –59.0 mV/decade over a wide concentration range (8.5×10^?7～6.8×10^?1 mol/L) with a detection limit of –5.0×10^?7 mol/L in pH 5.0 phosphate buffer solution at 25°C. Alternating current (AC) impedance and equivalent circuits were used to investigate the thiocyanate response mechanism of the membrane doped with [Cu(II)‐AEBB].     

Characterization and Electrocatalytic Property of Cobalt Hexacyanoferrate Film on Carbon Nanotubes Modified Gold Electrode

Abstract

Cobalt hexacyanoferrate (CoHCF) film was formed on multiwalled carbon nanotubes (MWNTs) modified gold electrode by electrodeposition from 0.5 M KCl solution containing CoCl₂ and K₃Fe(CN)₆. The electrochemical behavior and the electrocatalytic property of the modified electrode were investigated. Compared with CoHCF/gold electrode, the CoHCF/MWNTs/gold electrode exhibits greatly improved stability and enhanced electrocatalytic activity toward the oxidation of thiosulfate. A linear range from 5.0×10^?5 to 6.5×10^?3 M (r=0.9990) for thiosulfate detection at the CoHCF/MWNTs/gold electrode was obtained, with a detection limit of 2.0×10^?5 M (S/N=3).     

Fast visualization of the mass transfer processes at the electrode/electrolyte interface with a Mach-Zehnder interferometer

A Mach-Zehnder interfeometer is employed to visualize the mass transfer processes at the electrode/electrolyte interface during the potentiodynamic sweep of the Pt electrode in 0.1 mol dm^?3 K₄Fe(CN)₆ with 0.5 mol dm^?3 KCl solution at 20 mV s^?1. The changes of solution??s refractive index, brought about by the mass transfer during the reaction, can be recorded in situ in interferograms. The distributions of the optical path difference are obtained by numerical reconstruction of interferograms to reflect changes of solution??s refractive index and the mass transfer processes. The mass transfer of [Fe(CN)₆]^4? and [Fe(CN)₆]^3? is presented visually. This method provides a new approach to detect the mass transfer processes at the electrode/electrolyte interface in real-time.     

Removal of thiocyanates and heavy metal ions from simulated wastewater solutions by electro- and peroxyelectrocoagulation

A procedure for treatment of simulated wastewater solutions to remove Cu²⁺, Ni²⁺, and SCN^? ions using various combinations of aluminum and iron electrodes in the electro- and peroxyelectrocoagulation processes was studied. The influence exerted by the current density, pH of solution, and concentrations of impurities and hydrogen peroxide on the efficiency of removal of these ions was analyzed. Electrocoagulation using aluminum anode does not lead to a significant decrease in the thiocyanate concentration. In the peroxyelectrocoagulation process, the efficiency of removal of SCN? ions increases with an increase in the [H₂O₂]: [SCN^?] ratio. The electrocoagulation efficiency with the Fe/Fe electrode pair reaches 87% for SCN^? and 99.5% for Cu²⁺ and Ni²⁺ at a current density of 20 mA cm^–2 and electrolysis time of 20 min.     

Improving the electrochemical performances of active carbon-based supercapacitors through the combination of introducing functional groups and using redox additive electrolyte

High-performance and low-cost electrochemical capacitors (ECs) are essential for large-scale applications in energy storage. In this work, the specific capacitance of active carbon (AC) electrode was significantly improved through the combination of introducing functional groups on the surface of AC and adding redox-active molecules (K₃Fe(CN)₆) into 2?M KOH aqueous electrolytes. The surface-oxygen functionalized AC (FAC) was synthesized using HNO₃ echoed as the electrode and 2?M KOH with 0.1?M K₃Fe(CN)₆ as the electrolyte. The surface functional groups of the AC not only contribute to the pseudocapacitance but also increase the active sites of the electrode/electrolyte interface, which enhances the electrochemical activity of the Fe(CN)₆^3?/Fe(CN)₆^4? redox pair, thus leading to high capacitance. In the redox electrolyte, the specific capacitance was much higher in 229.17?F?g^?1 (1?A?g^?1) achieved for those FAC than in raw AC (only 147.06?F?g^?1). Similarly, the FAC electrode suggested high energy density and extended cycling stability in the KOH?+?K₃Fe(CN)₆ electrolyte.     

Solubilities and Ksp Values of the Less Soluble Anion Salts of “Nitron” (1,4-Diphenyl-3-anilino-1,2,4-triazoline)

Abstract

The solubilities and K_sp values at 25°C for the following anion salts of nitron are reported: VO₄ ⁼, Cro₄ ⁼, Cr₂O₇ ⁼,WO₄ ⁼, MoO₄ ⁼, BF₄ ^?, NO₃ ^?, NO₂ ^?, SeO₃ ⁼, S₂O₈ ⁼, SCN^?, Fe(CN)₆ ^?3, Fe(CN)₆ ^?4, Fe(CN)₅NO⁼, I^?, IO₄ ^?, CIO₃ ^?, CIO₄ ^?, BrO₃ ^?, and picrate^?. A total of 58 anions were tested.     

Evaluation of GaN and In0.2Ga0.8N Semiconductors as Potentiometric Anion Selective Electrodes

The response of potentiometric anion selective electrodes consisting of undoped GaN or In_0.2Ga_0.8N films grown on Al₂O₃ (sapphire) was measured in electrolyte solutions of F^?, NO₃^?, Cl^?, SCN^?, ClO₄^? or Br^? anions at concentrations ranging from 10^?6 to 10^?1 M. The slope of the linear regions varied between ?32.8 and ?51.9 mV/decade for the GaN electrode and between ?31.0 and ?72.0 mV/decade for the In_0.2Ga_0.8N electrode. The drift of the GaN electrode reached 1.57 mV/day in KNO₃ solutions, whereas the drift of the In_0.2Ga_0.8N electrode could not be evaluated due to large drops in the slope of its linear range over time. Both electrodes were sensitive to pH variations over the pH range from 12.8 to 1.3. The GaN electrode surface could be electrochemically etched under anodic polarization; however, both GaN and In_0.2Ga_0.8N electrodes remained chemically stable and mechanically intact under open circuit conditions even after prolonged use.