Electrochemical kinetics of the hydrogen reaction on platinum in concentrated HCl(aq)

The hydrogen reaction in concentrated HCl(aq) solutions is a key reaction for the CuCl(aq)/HCl(aq) electrolytic cell. Here, electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) were used to obtain new data for the hydrogen reaction on platinum submerged in highly concentrated acidic solutions at 25 °C and 0.1 MPa. LSV and EIS data were collected for Pt in 0.5 mol/L H₂SO₄(aq), 1 mol/L HCl(aq) and 7.71 mol/L HCl(aq) solutions. It was found that exchange current density (j₀) values varied between 1 and 2 mA/cm². An equivalent circuit model was used to obtain comparable j₀ and limiting current density values from EIS data relative to values obtained with LSV data. It was found that as the concentration of acid increased, a noticeable decrease in the performance was observed.     

Highly selective thiocyanate electrode based on bis-bebzoin-semitriethylenetetraamine binuclear copper(II) complex as neutral carrier

A novel selective thiocyanate PVC membrane electrode based on bis-bebzoin-semitriethylenetetraamine binuclear copper(II) [Cu(II)₂–BBSTA] as neutral carrier is reported, which displays an anti-Hofmeister selectivity sequence in following order: SCN⁻ > ClO₄⁻ > I⁻ >Sal⁻ >SO₃²⁻ >NO₃⁻ > H₂PO₄⁻ > Cl⁻ >NO₂⁻ > SO₄²⁻. The electrode exhibits Nernstian potential linear range to thiocyanate from 1.0 × 10⁻¹ to 9.0 × 10⁻⁷ mol/l with a detection limit 7.0 × 10⁻⁷ mol/l and a slope of −57.0 mV/decade in pH 5.0 of phosphorate buffer solution at 25 °C. The response mechanism is discussed in view of the AC impedance technique and the UV spectroscopy technique. From comparison of potentiometric response characteristics between the binuclear metallic complex copper(II) [Cu(II)₂–BBSTA] and mononuclear copper(II) metallic complex [Cu(II)–BBSDA], an enhanced response towards thiocyanate from the electrode based on binuclear metallic complex copper (II) [Cu(II)₂–BBSTA] was observed. The electrode based on binuclear copper(II) compound was used to determine the thiocyanate content in waste water with satisfactory results.     

Electrodeposited PbO2 thin film on Ti electrode for application in hybrid supercapacitor

PbO₂ thin films were prepared by pulse current technique on Ti substrate from Pb(NO₃)₂ plating solution. The hybrid supercapacitor was designed with PbO₂ thin film as positive electrode and activated carbon (AC) as negative electrode in the 5.3 M H₂SO₄ solution. Its electrochemical properties were determined by cyclic voltammetry (CV), charge–discharge test and electrochemical impedance spectroscopy (EIS). The results revealed that the PbO₂/AC hybrid supercapacitor exhibited large specific capacitance, high-power and stable cycle performance. In the potential range of 0.8–1.8 V, the hybrid supercapacitor can deliver a specific capacitance of 71.5 F g^?1 at a discharge current density of 200 mA g^?1(4 mA cm^?2) when the mass ratio of AC to PbO₂ was three, and after 4500 deep cycles, the specific capacitance remains at 64.4 F g^?1, or 32.2 Wh Kg^?1 in specific energy, and the capacity only fades 10% from its initial value.     

Mono- and dinuclear copper(II) complexes with meta-phenylene-bridging ligands: Synthesis,structure and magnetic properties

The new double-Schiff-base ligand H₆ipa-bhea has been synthesized by condensation of a 4,6-diformylresorcinol derivative (ipa) with two equivalents of N,N-bis-(2-hydroxyethyl)ethylenediamine (bhea). Reaction with copper(II) perchlorate leads to the formation of two different products depending on the reaction conditions. The directed synthesis of either a mononuclear or dinuclear copper(II) complex is reported. The reaction in methanol results in the formation of a dinuclear complex [Cu₂(H₄ipa-bhea)](ClO₄)₂ (1). Whereas in the presence of water as solvent for the reaction, one imine side chain of the ligand is hydrolyzed regenerating the formyl moiety with the mononuclear complex [Cu(H₃hyforsa-bhea)]ClO₄ · 2H₂O (2) as final product. Subsequent reaction of complex 2 with N,N-bis-(pyridin-2-ylmethyl)ethylenediamine (unspenp) as additional amine component results in the formation of the mononuclear complex [Cu(Hhyforsa-unspenp)]ClO₄ (3). All complexes are characterized by IR spectroscopy, elemental analysis and X-ray crystallography. Temperature-dependent magnetic measurements on the dinuclear complex indicate weak antiferromagnetic exchange interactions between the copper(II) ions with a coupling constant of J = ?16.4 cm^?1. Density functional calculations have been used to evaluate the magnetic properties. The exchange coupling constant can be nicely reproduced with the use of the broken symmetry approach. The exchange pathway through the meta-phenylene-linkage is discussed in terms of a competitive spin-polarization and superexchange mechanism as well as geometrical changes at the copper(II) ions.     

NMR and theoretical study on interactions between diperoxovanadate complex and pyrazole-like ligands

To understand the effects of pyrazole substitution on reaction equilibrium, the interactions between a series of pyrazole-like ligands and [OV(O₂)₂(D₂O)]^?/[OV(O₂)₂(HOD)]^? were explored by using multinuclear (¹H, ¹³C, and ⁵¹V) magnetic resonance, HSQC, and variable temperature NMR in 0.15 mol/L NaCl ionic medium mimicking physiological conditions. These results show that the relative reactivities among the pyrazole-like ligands are 3-methyl-1H-pyrazole ≈ 4-methyl-1H-pyrazole ≈ 1H-pyrazole > 1-methyl-1H-pyrazole. As a result, the main factor which affects the reaction equilibrium is the steric effect instead of the electronic effect of the methyl group of these ligands. A pair of isomers has been formed resulting from the coordination of 3-methyl-1H-pyrazole and a vanadium complex, which is attributed to different types of coordination between the vanadium atom and the ligands. Thus, the competitive coordination leads to the formation of a series of six-coordinate peroxovanadate species [OV(O₂)₂L]^? (L, pyrazole-like ligands). Moreover, the results of density functional calculations provided a reasonable explanation on the relative reactivity of the pyrazole-like ligands as well as the important role of solvation in these reactions.     

Dimethyl sulfoxide oxidation mediated by a copper(II) diamine complex: A possible source of problem in the synthesis of molecular magnetic compounds

In the present work we report a reaction in which dimethyl sulfoxide, initially used as solvent, undergoes oxidation to form sulfate, which then participates to the formation of a linear one-dimensional copper chain. Indeed, using [Cu(bipy)Cl₂], a building block largely applied in synthesis of molecular magnetic compounds, the coordination compound [Cu(bipy)(H₂O)₂(SO₄)]_n, where bipy = 2,2′-bipyridine was obtained. Magnetic characterization of complex shows a weak antiferromagnetic interaction between the copper(II) ions with J = ?0.53 cm^?1. DFT calculations demonstrate that the pathway for the weak antiferromagnetic interaction is through the sulfate bridge.     

Biological study and electrochemical characterization of Cu(II) and 1,8-bis-(2-pyridyl)-3,6-dithiaoctane (pdto) complex

Preliminary proliferation assays in human tumor cervix line HeLa, using the coordination compound [Cu(pdto)H₂O]²⁺ (pdto = 1,8-bis-(2-pyridyl)-3,6-dithiaoctane) and its precursors Cu(NO₃)₂ · 2.5H₂O and pdto, were carried out. The results showed that the copper complex has a behavior similar to that of the reference drug cis-platin. No biological activity for the non-coordinated ligand and the copper salt was found. It was established by cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy, that the complex [Cu(pdto)H₂O]²⁺ presents an electrochemical reversible Cu(II)/Cu(I) reduction, in acetonitrile solution, meanwhile, the copper salt Cu(NO₃)₂ · 2.5H₂O exhibited an electrochemical irreversible behavior. A comparison between biological and electrochemical results corresponding to [Cu(pdto)H₂O]²⁺ and Cu(NO₃)₂ · 2.5H₂O let us to proposed, the electrochemical reversibility, as one important factor in the antitumoral activity of the copper complex. Due to the nature of the studies presented in this work, other factors like intercalation properties with DNA cannot be neglected in the antitumoral activity of the complex.     

Synthesis and crystal structure of a new water-soluble sulfur-containing palladacyclic diaqua complex

A new water-soluble sulfur-containing palladacyclic diaqua complex [(SC)Pd^II(H₂O)₂]₂(SO₄) {[1]₂(SO₄), SC = C₆H₄-2-(CH₂S^tBu)} was synthesized from a reaction of Ag₂SO₄ with a water-insoluble palladacyclic dichloro complex [(SC)Pd^II(μ-Cl)]₂ (2) in water. Water-solubility of [1]₂(SO₄) at pH 7 at 25 °C is 9.4 mg/mL. NH₄PF₆ was added to the solution of [1]₂(SO₄) in water to give [1](PF₆). The structures of [1](PF₆) and 2 were unequivocally determined by X-ray analysis.     

Direct electrochemistry of myoglobin based on DNA accumulation on carbon ionic liquid electrode

Poly-anionic deoxyribonucleic acid (DNA) was accumulated on the positively charged surface of carbon ionic liquid electrode (CILE) with N-butylpyridinium hexafluorophosphate (BPPF₆) as binder, and then myoglobin (Mb) was immobilized onto the DNA film by electrostatic interaction to form Mb/DNA/CILE electrode. The direct electrochemistry of Mb was then investigated in detail. A pair of well-defined, quasi-reversible cyclic voltammetric peaks of Mb was obtained with the formal potentials (E⁰′) at ?0.304 V (vs. SCE) in phosphate buffer solution (PBS, pH 7.0). The Mb/DNA/CILE electrode showed excellent electrocatalytic activity to H₂O₂ and trichloroacetic acid (TCA) in the range of 1.0–160 μmol/L and 0.5–40.0 mmol/L, respectively. The apparent Michaelis–Menten constants (K_M) toward H₂O₂ and TCA were calculated as 0.42 and 0.82 mmol/L. So, the DNA/CILE had potential to study other proteins.     

Study on a single flow acid Cd–chloranil battery

This paper describes a novel redox flow battery–single flow acid Cd–chloranil battery. The electrolyte of this battery for both negative electrode and positive electrode is the aqueous intermixture of H₂SO₄–(NH₄)₂SO₄–CdSO₄, the negative electrode is inert metal such as copper foil, and the positive electrode is an insoluble organic material, tetrachloro-p-benzoquinone (chloranil). Typically, the electrolyte is continuously circulated to pass though the cells by means of a single pump as the battery is on duty. There is no requirement for a membrane. Tetrachloro-p-benzo-hydroquinone is oxidized to chloranil at positive electrode and the cadmium ions is reduced to cadmium and electroplated onto the negative electrode during charge. The reverse occurs during discharge. Results obtained with a small laboratory cell show that high efficiencies can be achieved with an average coulombic efficiency of 99% and energy efficiency of 82% over 100 cycles at the current density of 10 mA cm^?2.     

V2O5·0.6H2O nanoribbons as cathode material for asymmetric supercapacitor in K2SO4 solution

V₂O₅·0.6H₂O nanoribbons were prepared and their electrochemical behaviors in K₂SO₄ aqueous solution were investigated. Results show for the first time that K⁺ ions could intercalate/deintercalate reversibly in the V₂O₅·0.6H₂O lattice. An asymmetric supercapacitor activated carbon/0.5 mol/l K₂SO₄/V₂O₅·0.6H₂O was successfully assembled, which could be cycled reversibly in the voltage region of 0–1.8 V. This supercapacitor presents an energy density of 29.0 Wh/kg based on the total mass of the active electrode materials, a very good rate behavior with energy density of 20.3 Wh/kg at power density of 2 kW/kg, and also a rather good cycling performance.     

Catalytic cyclopropanation of olefins using copper(I) diphosphinoamines

Catalytic cyclopropanation reactions of olefins with ethyl diazoacetate were carried out using copper(I) diphosphinoamine (PPh₂)₂N(R) (R = ⁱPr, H, Ph and –CH₂–C₆H₄–CHCH₂) complexes at 40 °C in chloroform. High yields of the cyclopropanes were obtained in all cases. The rate of the reaction was influenced by the nuclearity of the complex and the binding mode of the ligand which was either bridging or chelating. Comparison of isostructural complexes shows that the rate follows the order R = ⁱPr > H > Ph, where R is the substituent on the N. However, cyclopropane formation versus dimerization of the carbene, and trans to cis ratios of cyclopropane was similar in all cases. The nearly identical selectivity for different products formed was indicative of a common catalytic intermediate. A labile “copper–olefin” complex which does not involve the phosphine or the counterion is the most likely candidate. The differences in the reaction rates for different complexes are attributed to differences in the concentration of the catalytically active species which are in equilibrium with the catalytically inactive copper–phosphinoamine complex. To test the hypothesis a diphosphinoamine polymer complexed to copper(I) was used as a heterogeneous catalyst. Leaching of copper(I) and deactivation of the catalyst confirmed the proposed mechanism.     

Nitrogen enriched mesoporous carbon spheres obtained by a facile method and its application for electrochemical capacitor

A kind of mesoporous carbon spheres (MCS) containing in-frame incorporated nitrogen has been prepared by a facile polymerization-induced colloid aggregation method. As the electrode material for electric double layer capacitor (EDLC) in 5 mol/L H₂SO₄, the MCS products present excellent specific capacitance as 211 F/g much larger than that of the most popularly applied activated carbon at a high discharge current density of 1 A/g. Its specific capacitance can still remain 200 F/g at 20 A/g. The superior electrochemical performance of MCS is associated with the following characteristics: high specific surface area (∼1330 m²/g) contributed mainly by the mesopores, uniform pore size as large as 29 nm and moderate content of nitrogen (10 wt%), which are the requirements for ideal supercapacitors.     

Dual-signal anodic stripping voltammetric determination of trace arsenic(III) at a glassy carbon electrode modified with internal-electrolysis deposited gold nanoparticles

A glassy carbon electrode (GCE) modified with internal-electrolysis deposited gold nanoparticles (AuNPs_ied) was applied to sensitively and selectively detect As(III) by anodic stripping linear sweep voltammetry (ASLSV). The AuNPs_ied/GCE was prepared based on the redox replacement reaction between a supporting-electrolyte-free aqueous HAuCl₄ and a copper sheet in saturated KCl separated by a salt bridge. Under optimum conditions (0.5 M aqueous H₂SO₄, 300-s preconcentration at − 0.4 V), the ASLSV peak current for the As(0)–As(III) oxidation responded linearly to As(III) concentration from 0.02 to 3 μM with a limit of detection (LOD) of 0.9 nM (0.07 μg L^− 1) (S/N = 3), while that for the As(III)–As(V) oxidation was linear with As(III) concentration from 0.02 to 1 μM with a LOD of 4 nM (0.3 μg L^− 1) (S/N = 3). An appropriate high-scan-rate for ASLSV can enhance both the sensitivity and signal-to-noise ratio. This method was applied for analyses of As(III) in real water samples.     

A new luminescent sulfate bridged dimeric copper(II) complex with DNA binding and SO2 fixation ability: Synthesis and structure

New luminescent mononuclear and dinuclear copper(II) (S = 1/2) complexes [Cu(HL)(H₂O)₂](ClO₄)₂ (1a) and [Cu₂(HL)₂(μ-SO₄)₂]·2H₂O (1b) were synthesized with the acyclic tridentate pyridine-2-carboxaldehyde-2-pyridylhydrazone ligand, HL (1). Interestingly, the mononuclear complex 1a can be converted into the disulfate bridged dimeric copper(II) complex 1b by passing freshly prepared SO₂ through the basic medium. On excitation at 290 nm, the ligand fluoresces at 364 nm due to an intraligand ¹(π–π1) transition. Upon complexation with copper(II), the emission peak is slightly blue shifted (356 nm, F/F₀ 0.76 for 1a and 354 nm, F/F₀ 0.89 for 1b) with a little quenching in the emission intensity. The association constants (K_ass (5.06 ± 0.004) × 10⁴ for 1a and K_ass (5.46 ± 0.006) × 10⁴ for 1b at 298 K) and the thermodynamic parameters have been determined by UV–Vis spectroscopy. The molecular structure of the complex 1b (Cu?Cu 4.456 Å) has been determined by single crystal X-ray diffraction studies. The complex 1b exhibits a strong interaction towards DNA as revealed from the K_b (intrinsic binding constant) 6.3 × 10⁴ M^?1 and K_sv (Stern–Volmer quenching constant) 2.93 values.     

Inhibition effect of hexadecyl pyridinium bromide on the corrosion behavior of some austenitic stainless steels in H2SO4 solutions

The inhibition effect of hexadecyl pyridinium bromide (HDPB) as a cationic surfactant on the corrosion behavior of some Egyptian austenitic stainless steel SS 304L, SS 316H and SS 304H in 0.5 M H₂SO₄ solutions was investigated by using potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The results indicate that HDPB is a good inhibitor for the samples under investigation in 0.5 M H₂SO₄ solutions. In addition, the inhibition efficiency η% increases with the inhibitor concentration while decreases with the increasing temperature referring to physical adsorption. The adsorption of the inhibitor obeys a Temkin adsorption isotherm. Polarization curves show that HDPB is a mixed inhibitor in H₂SO₄ solutions. The results obtained from polarization and impedance measurements are in good agreement. Activation-free energies, enthalpies, and entropies for the inhibition process of HDPB were determined.     

Simple analyzer for continuous monitoring of sulfur dioxide in gas streams

The construction, optimization and use of simple and inexpensive gas analyzer for real time measurement of sulfur dioxide in gas streams are described. The analyzer consisted of three main components (i) a custom fabricated hollow fiber membrane (HFM) gas contactor, (ii) carrier solution which absorbs SO₂ molecules from the gas stream in the HFM gas contactor and (iii) a flow-through detector placed downstream which continuously measures the changes occurred to the carrier solution upon absorption of SO₂ molecules. The significant acidic properties of the produced sulfurous acid suggested pH and conductivity detectors to monitor the decrease in pH or the increase in the conductivity which constituted the basis for quantification of SO₂ in the gas line. Aqueous potassium oxalate (10^? 1 mol/L) and hydrogen peroxide (10^? 3 mol/L) were used as carrier solutions in combination with pH and conductivity detectors, respectively. The analyzer equipped with pH detector provided linear potentiometric response to SO₂ concentration up to 1000 ppm with Nernstian slop of 61 mV/log[SO₂]. Excellent SO₂ recoveries (97–108%) were obtained in the presence of several folds of potentially interfering acidic gases, i.e., CO₂ and H₂S. The conductivity detector provided linear response up to 2500 ppm. Under optimized conditions, both detectors offered several favorable performance characteristics such as (i) fast response and recovery times, (ii) excellent signal stability and reproducibility (RSD = 0.5%), (iii) intrinsic high selectivity to most common neutral gases, e.g., CH₄, N₂, O₂, CO, etc. The suggested analyzer was applied successfully in monitoring the removal of SO₂ from SO₂–N₂ gas mixtures with hollow fiber membrane contactor using distilled water or aqueous sodium hydroxide as stripping solvents.     

(Liquid + liquid) equilibria of ternary and quaternary systems containing n-hexane,toluene, m-xylene,propanol, sulfolane,and water at T = 303.15 K

(Liquid + liquid) equilibrium data for ternary and quaternary systems containing n-hexane (C₆H₁₄), toluene (C₇H₈), m-xylene (C₈H₁₀), propanol (C₃H₈O), sulfolane (C₄H₈SO₂), and water (H₂O) were measured at T = 303.15 K. Phase diagrams of {w₁C₄H₈SO₂ + w₂C₇H₈ + (1 − w₁ − w₂)C₆H₁₄}, {w₁C₄H₈SO₂ + w₂C₈H₁₀ + (1 − w₁ − w₂)C₆H₁₄}, {w₁C₄H₈SO₂ + w₂C₃H₈O + w₃C₇H₈ + (1 − w₁ − w₂ − w₃)C₆H₁₄} and also systems containing water: {w₁C₄H₈SO₂ + w₂H₂O + w₃C₇H₈ + (1 − w₁ − w₂ − w₃)C₆H₁₄} and {w₁C₄H₈SO₂ + w₂H₂O + w₃C₈H₁₀ + (1 − w₁ − w₂ − w₃)C₆H₁₄} (w = mass fraction) were obtained at T = 303.15 K. The (liquid + liquid) equilibrium data of the systems were used to obtain interaction parameters in non-random two-liquid (NRTL) and universal quasi-chemical theory (UNIQUAC) activity coefficient models. These parameters can be used to predict equilibrium data of ternary and quaternary systems. The root mean square deviations (RMSDs) using these models were calculated and reported. The partition coefficients and the selectivity factors of solvents for extraction of toluene or m-xylene from n-hexane at T = 303.15 K are calculated and presented. The experimental selectivity factors of sulfolane for the system {w₁C₄H₈SO₂ + w₂C₇H₈ + (1 − w₁ − w₂)C₆H₁₄} at T = 298.15 K and T = 323.15 K were taken from the literature and the influence of temperature on the extraction of toluene was also investigated. The phase diagrams for the ternary and quaternary systems including both the experimental and correlated tie lines are presented. The tie-line data of the studied systems were also correlated using the Hand equation and the correlation parameters are calculated and reported.     

Study on electrochemical performance of activated carbon in aqueous Li2SO4, Na2SO4 and K2SO4 electrolytes

The electrochemical performances of activated carbon (AC) in 0.5 mol/l Li₂SO₄, Na₂SO₄ and K₂SO₄ aqueous electrolytes were investigated. The cyclic voltammetric results at different scan rates show that the rate behaviors of AC in the three electrolytes improve in the order of Li₂SO₄ < Na₂SO₄ < K₂SO₄. This improvement can be mainly ascribed to the following two reasons: (1) the decreasing equivalent series resistance in the order of Li₂SO₄ > Na₂SO₄ > K₂SO₄, which is the main factor influencing the maximum output power, and (2) the increasing migration speed of hydrated ions in the bulk electrolyte and in the inner pores of AC electrode in the order of Li⁺ < Na⁺ < K⁺. Their cycling behaviors do not show any differences in capacitive fading. The above results provide valuable information to explore new hybrid supercapacitors.     

Magnetostructural examination of Mn(III) complexes [Mn(cyclam)X2]+ with strong axial ligands

Three novel Mn(III) cyclam complexes, [Mn(cyclam)(NCBH₃)₂](CF₃SO₃), [Mn(cyclam)(NCBPh₃)₂](CF₃SO₃), and [Mn(cyclam)(NCSe)₂](CF₃SO₃) · H₂O, have been synthesized. These complexes are in the high-spin state between 4 and 350 K, and show large zero-field splittings. The crystal structure of [Mn(cyclam)(NCBH₃)₂](CF₃SO₃) was determined where the axial elongation of Mn–N bonds is found to be the largest among the homologue complexes. Ligand field in the [Mn(cyclam)X₂]⁺ complex series was examined by angular-overlap model calculation.