Study of a bis-furaldehyde Schiff base copper(II) complex as carrier for preparation of highly selective thiocyanate electrodes

A new highly selective thiocyanate electrode based on N,N-bis-(furaldehyde)-1,2-phenylenediamine-dipicolyl copper(II) complex [Cu(II)-BFPD] as neutral carrier is described. The electrode has an anti-Hofmeister selectivity sequence: SCN^–>I^–>Sal^–>ClO₄ ^–>Br^–>NO₂ ^–>Cl^–>NO₃ ^–>SO₄ ^2–>SO₃ ^2–>H₂PO₄ ^– and a near-Nernstian potential linear range for thiocyanate from 1.0×10^–1 to 5.0×10^–6 mol L^–1 with a detection limit 2.0×10^–6 mol L^–1 and a slope of 57.5 mV decade^–1 in pH 5.0 of phosphate buffer solution at 20 °C. The response mechanism is discussed on the basis of results from A.C. impedance measurement and UV spectroscopy. The anti-Hofmeister behavior of the electrode results from a direct interaction between the central metal and the analyte ion and a steric effect associated with the structure of the carrier. The electrode has the advantages of simplicity, fast response, fair stability and reproducibility, and low detection limit. The selectivity of electrodes based on [Cu(II)-BFPD] exceeds that of classical anion-sensitive membrane electrodes based on ion exchangers such as lipophilic quaternary ammonium or phosphonium salts. Application of the electrode for determination of thiocyanate in waste water samples from a laboratory and a gas factory, and in human urine samples, is reported. The results obtained were fair agreement with the results obtained by HPLC.     

Voltammetric copper(II) determination with a montmorillonite-modified carbon paste electrode

The clay mineral montmorillonite has been tested as modifier for the carbon paste electrode with a novel electrode modification technique. The differential pulse voltammetric determination of copper(II) by means of this modified carbon paste electrode has been studied. A detection limit of 4×10^-8 mol/l has been achieved after 10 min preconcentration under open circuit conditions with subsequent anodic stripping voltammetry. The calibration curve for Cu(II) is linear in the range of 4×10^-8–8×10^-7 mol/l. Pb interferes in a 10-fold molar and Cd and Hg in a 100-fold molar excess. The interference by humic ligands is significant.     

Determination of Selenium(IV) by Stripping Voltammetry at a Mercury-Film Electrode

A procedure was proposed for the determination of selenium(IV) by stripping voltammetry on a mercury-film electrode at an electrolysis potential of +0.4 V versus the saturated silver–silver chloride reference electrode in a 1 M H₂SO₄ solution. The current of the cathodic peak is a linear function of the selenium(IV) concentration in the range from 5 × 10^–3 to 3 × 10^–1 mg/L (6.3 × 10^–8 to 3.8 × 10^–6 M) at a time of electrolysis of 30 s (t _el). The detection limit for selenium is 1 × 10^–4 mg/L (1.3 × 10^–9 M) at t _el = 300 s. It was shown that selenium(IV) can be determined in the presence of 10 mg/L Zn(II), 1 mg/L Cd(II), 0.5 mg/L Pb(II), and 0.2 mg/L Cu(II). A procedure for the determination of selenium in natural, mineral, and potable water was proposed.     

Complexation of copper(I) by thiourea in acidic aqueous solution

The interaction of copper(II) and copper(I) with thiourea(Tu) has been investigated by UV and visible spectrophotometry. Over the range of concentrations of copper(I) and Tu(0.1–20)×10^–3 mol-dm^–3 in acid aqueous solutions there are two complexes, CuTu₂ ⁺ (log ₂=11.1) and the other has the ratio Cu/Tu=1/1 with the likely composition Cu₂Tu₂ ²⁺ with log ₂₂=18.5. By the determination of copper(0) solubility in acid thiourea solution and potentiometric measurements it was shown that the potential of the copper electrode is that of a non-equilibrium (corrosive) electrode.     

Kinetics of alkaline chloramine-T oxidation of arginine monohydrochloride with and without catalytic action of Cu(II) ion

The kinetics of uncatalysed and Cu(II) catalysed oxidation of arginine monohydrochloride was investigated. Both reactions follow a singular order dependence each in oxidant and substrate. An inverse order dependence is reported with the alkali concentration. A plot of observed rate constant versus Cu(II) concentrations Cu(II)2.0×10^–5 M is linear; from the intercept the rate constant for the uncatalysed pathway was calculated. However, at high copper ion concentrations i.e. Cu(II)>2.0×10^–5 M a fixed value of rate constant was found for all catalyst concentrations. Added neutral salts show an insignificant effect on the reaction rate. Mechanisms were proposed for both cases and rate expressions were derived by applying steady state assumptions.

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Die Kinetik der alkalischen Chloramin-T-Oxidation von Arginin-monohydrochlorid mit und ohneCu(II) als Katalysator

Zusammenfassung Die Oxidation erfolgt sowohl mit als auch ohne Cu(II)-Katalysator in erster Ordnung bezüglich des Oxidationsmittels und des Substrats; inverse Ordnung wird bezüglich der Alkalikonzentration beobachtet. Bis zu einer Cu(II)-Konzentration von2×10^–5 M ist die Geschwindigkeitskonstante der Katalysatorkonzentration proportional; darüber wird eine konstantbleibende Geschwindigkeit beobachtet, die nun von der Cu(II)-Konzentration unabhängig ist. Neutralsalze haben keinen Effekt auf die Geschwindigkeitskonstante. Es wird für den katalysierten und unkatalysierten Reaktionsablauf ein Mechanismus vorgeschlagen und ein mathematischer Ansatz präsentiert.

     

Preconcentration and voltammetric determination of the herbicide metamitron with a silica-modified carbon paste electrode

A carbon paste electrode incorporating silica (Si-MCPE) was fabricated to accumulate Metamitron at the electrode surface. Several electroanalytical techniques were used to explore its reductive behaviour. The results indicate that the system is irreversible and fundamentally controlled by adsorption. The adsorptive stripping response has been evaluated with respect to accumulation time, deposition potential, scan rate, pH and other variables, using differential pulse voltammetry (DPV) and square wave voltammetry (SWV) as redissolution techniques. In both cases a voltammetric peak is obtained, at –0.542 V (DPV) and –0.421 V (SWV) in Britton-Robinson buffer (pH 1.9). The detection limits were 3.66 × 10^–1 M and 4.22 × 10^–9 M for AdS-DPV and AdS-SWV, respectively. Under optimum conditions the Metamitron reduction peak gave two linear regions in the range from 4.0 × 10^–9 M to 8.0 × 10^–8 M by means of AdS-DPV, with a coefficient of variation of 2.19% (n = 10) for 1 × 10^–8 M herbicide solution. A method was developed for determination of Metamitron in soils, with a recovery of 98.8% and a coefficient of variation of 5.26% (0.01 g/g of soil).     

Mechano-elektrochemische Effekte,VI. Einfluß der Elektrodengeometrie auf Potentialverschiebungen bei der plastischen Deformation von Kupfer und Hinweise auf die Systemorganisationen

Summary Plastic deformation of a copper electrode in an aqueous 10^–4 M Cu(ClO₄)₂ solution leads to greater potential shifts, to smaller post strain effects and to greater relaxation rates as the ratio interfacial area: volume of copper is increased. It is suggested that its system organization is improved, as the interfacial area is increased. The system organization appears also to be improved as oxidic superstructures are developing at the interface, where the highest hierarchic levels of both electrode and electrolyte are in immediate contact. Further hints as to the system organization of the whole system Cu/CuSO₄ solution are obtained from the fact that atpH=2 andc _Cu + +=10^–1 mol/l the redox potential is independent of the pretreatment of the electrode and independent of the presence of oxidic superstructures. It is underlined that the passivity due to the presence of an oxidic superstructure is maintained only atpH >2, whereas at lowerpH-values copper is more readily dissolved. It is suggested that atpH=2 the system is in an optimal state of system organization (OSO), similar to those reported in the course of phase transformations, in extremely thin metal films and in solutions at the isokinetic temperature.

     

Catalytic determination of ultratrace amounts of Cu(II) by the oxidative coupling reaction of 3-methyl-2-benzothiazolinone hydrazone with N,N-dimethylaniline

Summary Copper (II) catalyzes the coupling reaction of 3-methyl-2-benzothiazolinone hydrazone (MBTH) with N,N-dimethylaniline (DMA) to form an intensely colored dye (_max=590 nm) in the presence of hydrogen peroxide and ammonia as an activator. On the basis of this reaction, a highly sensitive and selective catalytic method for Cu(II) has been developed. As little as 10^–9 M Cu(II) can be determined by measuring the absorbance of the reaction product at a fixed time (20 min at 40°C). Sandell's sensitivity calculated from the working curve is 1.3×10^–3 ng cm^–2. The method was applied to water analysis and some comments on the analysis of copper in river water were added.Presented at the 1st International Symposium on Kinetics in Analytical Chemistry, Córdoba, Spain, September 28th, 1983.     

Adsorptive accumulation voltammetry of copper(II) using complex formation reaction with salicylideneamino-2-thiophenol

Summary The cathodic stripping voltammetry of copper(II) was investigated with a method, based on the adsorptive accumulation of the Cu(II)-salicylideneamino-2-thiophenol (SATP) complex on a hanging mercury drop electrode. The copper(II)-SATP complex could be accumulated on the electrode at –0.20 V in 0.01 mol/l nitric acid. The reduction peak of the copper complex was observed by scanning the potential in a negative direction in the differential pulse mode. The calibration curve for copper was linear over the range 5×10^–9–1×10^–7 mol/l. This method was applied to determine copper(II) in GSJ (Geological Survey of Japan) standard rock reference materials.     

Voltammetric determination of N-acetylcysteine using a carbon paste electrode modified with copper(II) hexacyanoferrate(III)

The preparation and electrochemical characterization of a carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) as well as its behavior as electrocatalyst toward the oxidation of N-acetylcysteine were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of N-acetylcysteine were explored using sweep linear voltammetry. The best voltammetric response was observed for a paste composition of 20% (w/w) copper(II) hexacyanoferrate(III) complex, acetate buffer solution at pH of 6.0 as the electrolyte and scan rate of 10 mV s^− 1. A linear voltammetric response for N-acetylcysteine was obtained in the concentration range from 1.2 × 10^− 4 to 8.3 × 10^− 4 mol L^− 1, with a detection limit of 6.3 × 10^− 5 mol L^− 1. The proposed electrode is useful for the quality control and routine analysis of N-acetylcysteine in pharmaceutical formulations.     

Synthesis,crystal structure and magnetic properties of the first dinuclear copper(II)–iron(II) complex [Cu(L)Fe(CN)5NO] based on nitroprusside

The nitrosyl cyanide [Cu(L)Fe(CN)₅NO] was prepared by the reaction of [Cu(L)]Cl₂ [L = 3, 10-bis(2-hydroxymethyl)-1,3,5,8,10,12-hexaazacyclotetradecane] with Na₂[Fe(CN)₅NO]·2H₂O in aqueous solution. Single-crystal analysis revealed that the title complex is the first structurally characterized dinuclear copper(II)–iron(II) complex based on the nitroprusside. Variable temperature magnetic susceptibility measurements (4.0–180.0 K) show the occurrence of very weak antiferromagnetic interactions between the copper(II) ions with zJ = –0.410 cm^–1.     

Determination of copper(I)-ethylene complexes, [Cu(C2H4)]+ and [Cu(C2H4)2]+, with aid of EDTA titration of copper(I) and copper(II) ions

Summary Volumetric measurements of ethylene and simple EDTA titration of copper(I) and copper(II) ions confirm that [CuL]⁺ and [CuL₂]⁺ are formed when an aqueous solution of copper(II) is reduced by copper metal in the presence of ethylene, (L). The formation constants,K ₁=[CuL⁺]²[Cu²⁺]^–1[L]^–2 andK ₂=[CuL ₂ ⁺ ]^–1[L]^–1, have been estimated. The formation of [CuL]⁺ is accompanied by an enthalpy change, H, of –25 kJ mol^–1, and a positive entropy change, S, of 13 J mol^–1 K^–1.     

Oxidation of bis[2-(2-pyridyl)benzimidazole]copper(II) by molecular oxygen in acetonitrile solution

Summary The complex bis[2-(2-pyridyl)benzimidazole]copper(I) perchlorate, [Cu(PBIM)₂]ClO₄, has been prepared and its oxidation with molecular oxygen in acetonitrile studied. Dependence of the rate constant, k₀, upon an excess of ligand was not observed. The rate constant for the oxidation of this complex was found to be 30 M^–2s^–1. The corresponding copper(II) compound behaves as a 11 electrolyte, commensurate with one of the complexed ligands losing a hydrogen.     

Semi-automatic catalytic titration of some aminopoly-carboxylic acids,copper(II), and cobalt(II)

Summary A semi-automatic potentiometric method is described for the catalytic titrimetric determination ofg amounts of some aminopolycarboxylic acids. The method is based on their inhibitory effect on the copper(II)-catalyzed periodate-thiosulfate reaction. Amounts of EDTA in the 0.7–600g range (10^–6–8×10^–5 M), of DCTA in the 7–7000g range (10^–6–10^–3 M), of EGTA in the 0.8–800g range (10^–7–10^–4 M), and of DTPA in the 4–800g range (5×10^–7–10^–4 M) were determined with average relative errors and coefficient of variation of about 0.4–1%. The method has also been used for the indirect catalytic titrimetric determination ofg amounts of Cu²⁺ and Co²⁺ ions with about the before mentioned accuracy and precision.

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Halbautomatische katalytische Titration einiger Aminopolycarbonsäuren sowie von Cu(II) und Co(II)

Zusammenfassung Eine halbautomatische potentiometrische Methode zur katalytischen Maßanalyse von Mikrogrammengen einiger Aminopolycarbonsäuren wurde angegeben. Sie beruht auf dem Hinderungseffekt gegenüber der Cu(II)katalysierten Perjodat-Thiosulfatreaktion. EDTA in Mengen von 0,7–600g, DCTA in Mengen von 7–7000g, EGTA in Mengen von 0,8–800g und DTPA in Mengen von 4–800g wurden mit einem mittleren relativen Fehler von etwa 0,4–1% bestimmt. Das Verfahren wurde auch zur Bestimmung von Cu(II) und Co(II) mit der angeführten Genauigkeit verwendet.

     

Synthesis and Crystal Structure of a Novel Polymeric Thiocyanato-Bridged Heteronuclear Complex of Copper(II) and Cadmium(II)

The title polymeric complex of Cu(II) and Cd(II) bridged by thiocyanate, Cu(en)₂[Cd(SCN)₃]₂, has been prepared and its structure determined by X-ray diffraction (XRD) methods. The crystal structure reveals that the Cu(II) atom is in an elongated octahedral coordination formed by two SCN^– anions and two en molecules. The Cd(II) atom is in a distorted octahedral coordination formed by six bridging SCN^– anions. Two different bridging thiocyanate anions exist in the complex. Both 1,1--SCN^– and 1,3--SCN^– anion act a role of bridge ligand and link Cu(II), Cd(II) atoms, and adjacent Cd(II). Cd(II) atoms form the three-dimensional (3-D) network polymeric structure. The IR and UV-Vis spectra have also been investigated.     

A calorimetric study ofN,N-dimethylformamide complexes of copper(II) in acetonitrile

Complex formation of copper(II) with N,N-dimethylformamide(DMF) has been investigated calorimetrically in acetonitrile at 25°C. Calorimetric titration curves obtained are explained in terms of formation of [Cu(dmf) _n ]²⁺ (n=1–4, 6) and their formation constants, enthalpies and entropies were determined. Formation of [Cu(dmf)₅]²⁺ is uncertain. The stepwise enthalpies S ₃ ⁰ and entropies S _n ⁰ at each consecutive step are all negative except for S ₃ ⁰ . The overall enthalpies of formation of [Cu(dmf)₆]²⁺ is –(77.8±5.4) kJ-mol^–1, which is compared with the enthalpy of transfer of copper(II) ion, H _t ^o =–79.7 kJ-mol^–1, from acetonitrile to DMF.     

Bis-(tetraethylammonium)[tetraazidocuprate(II)] and catena-di-μ-1,1-azido-[di-μ-1,1-azido-bis-(2,4-dimethylpyridine)dicopper(II)]

Two new copper(II) azido complexes, namely bis-(tetraethylammonium)[tetraazidocuprate(II)] (1) and catena-di--1,1-azido-[di--1,1-azido-bis-(2,4-dimethylpyridine)dicopper(II)] (2), have been prepared and characterized by spectroscopic and crystallographic methods. Complex (1) consists of isolated NEt⁺ ₄ cations and [Cu(N₃)₄]^2– anions. The site symmetry around the copper atom in the anion is 4/m. Complex (2) features a 1 D chain structure, five coordinated square pyramidal copper(II) atoms with both azides functioning as -1,1-bridges. The i.r. spectra reveal that both complexes contain asymmetric azido ligands. The solid and solution electronic spectra of (1) and (2) show very strong absorption bands in the visible region associated with N^– ₃ Cu^II charge-transfer transitions. The e.p.r. spectra of powder samples and solutions at room temperature were recorded and discussed.     

Amperometric nitrite sensor based on hemoglobin/colloidal gold nanoparticles immobilized on a glassy carbon electrode by a titania sol-gel film

A novel amperometric nitrite sensor was developed based on the immobilization of hemoglobin/colloidal gold nanoparticles on a glassy carbon electrode by a titania sol-gel film. The sensor shows a pair of well-defined and nearly reversible cyclic voltammogram peaks for Hb Fe(III)/Fe(II) with a formal potential (E°) of –0.370 V, and the peak-to-peak separation at 100 mV s^–1 was 66 mV vs. Ag/AgCl (3.0 M KCl) in a pH 6.9 phosphate buffer solution. The formal potential of the Hb Fe(III)/Fe(II) couple shifted linearly with pH with a slope of –50.0 mV/pH, indicating that electron transfer accompanies single-proton transportation. The sensor exhibited an excellent electrocatalytic response to the reduction of nitrite. The reduction overpotential was 0.45 V below that obtained at a colloidal gold nanoparticles/TiO₂ sol-gel film-modified GCE. The linear range for nitrite determination for the sensor was 4.0×10^–6 to 3.5×10^–4 M, with a detection limit of 1.2×10^–6 M. The stability, repeatability and selectivity of the sensor were also evaluated.     

Effect of substituents,solute–solute–non-polar solvent interactions and temperature on the spectral properties of bis(dithiophosphato)copper(II) complexes

Extended studies by e.p.r. and electronic spectroscopy on the effect of different non-polar solvents, temperature and disulfide concentration on the spectral properties of bis(dithiophosphato)copper(II), Cu[(RO)₂PS₂]₂, complexes [R = Me, Et and i-Pr] are reported. The molar absorptivity and e.p.r. intensity are very sensitive to the shape and size of the remote ligand substituents and increase in the order: Me < Et < i-Pr. The nature of the solvent and time after dissolution are also important regarding the magnitude of the e.p.r. intensity and molar absorptivity which, 1 h after dissolution, do not follow Beer's law. The molar absorptivities obtained at a given Cu^II(R₂–dtp)₂ concentration increase in the solvent order: n-hexane < n-heptane < CCl₄ < PhMe < PhH < CHCl₃. Twenty-four hours after dissolution the same samples exhibit: (i) linearity between absorbance and concentration of Cu^II(R₂–dtp)₂; (ii) a significant increase in molar absorptivity which is not equal for all the complexes studied and follows the same substituent and solvent orders. Beer's law is satisfied above 5 × 10^–4 M for [(RO)₂PS₂]₂Cu (R = Et, i-Pr) and above 3 × 10^–3 M for [(MeO)₂PS₂]Cu. A significant additional increase, ca. 30–40%, of molar absorptivity, is obtained by increasing the solution temperature from 20 to 50 °C. The molar absorbtivity remains unchanged during 2–3 days after reducing the temperature. Further increase of molecular absorbtivity appears after addition of the corresponding disulfide of dithiophosphate [(RO₂)PS₂–S₂P(RO)₂] to Cu^II[(RO)₂PS₂]₂. The molar absorptivity of Cu[(i-PrO)₂PS₂]₂ increases from 4.8 × 10³ cm^–1 M^–1, 1 h after dissolving the complex up to 2 × 10⁴ cm^–1 M^–1 after addition of the corresponding disulfide. The observed effects are explained on the basis of a self-redox reaction taking place in this type of sulfur containing copper(II) complexes.     

Enhanced sensitivity for Cu(II) by a salicylidine-functionalized polysiloxane carbon paste electrode

A new approach for decreasing the detection limit for a copper(II) ion-selective electrode (ISE) is presented. The ISE is designed using salicylidine-functionalized polysiloxane in carbon paste. This work describes the attempts to develop the electrode and measurements of its characteristics. The new type of renewable three-dimensional chemically modified electrode could be used in a pH range of 2.3–5.4, and its detection limit is 2.7 × 10⁻⁸ mol L⁻¹ (1.2 μg L⁻¹). This sensor exhibits a good Nernstian slope of 29.4 ± 0.5 mV/decade in a wide linear concentration range of 2.3 × 10⁻⁷ to 1.0 × 10⁻³ mol L⁻¹ of Cu(II). It has a short response time (8 s) and noticeably high selectivity over other Cu(II) selective electrodes. Finally, it was satisfactorily used as an indicator electrode in complexometric titration with EDTA and determination of copper(II) in miscellaneous samples such as urine and various water samples.