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.     

Properties of low power spark ablation in aqueous solution for dissolution of precious metals and alloys

Spark ablation or electric dispersion of metal samples in aqueous solution can be a useful approach for sample preparation. The ablated metal forms a stable suspension that has been described as colloidal, which is easily dissolved with a small amount of concentrated (16 M) HNO₃. In this study, we have examined some of the properties of the spark ablation process for a variety of metals (Rh and Au) and alloys (stainless steel) using a low power spark (100–300 W). Particle size distributions and conductivity measurements were carried out on selected metals to characterize the stable suspensions. A LASER diffraction particle size analyzer was useful for showing that ablated particles varied in size from 1 to 30 μm for both the silver and the nickel alloy, Inconel. In terms of weight percent most of the particles were between 10 and 30 μm. Conductivity of the spark ablation solution was found to increase linearly for approximately 3 min before leveling off at approximately 300 S cm³. These measurements suggest that a significant portion of the ablated metal is also ionic in nature. Scanning electron microscope measurements revealed that a low power spark is much less damaging to the metal surface than a high power spark. Crater formation of the low power spark was found in a wider area than expected with the highest concentration where the spark was directed. The feasibility of using spark ablation for metal dissolution of a valuable artifact such as gold was also performed. Determinations of Ag (4–12%) and Cu (1–3%) in Bullion Reference Material (BRM) gave results that were in very good agreement with the certified values. The precision was ± 0.27% for Ag at 4.15% (RSD = 6.5%) and ± 0.09% for Cu at 1% (RSD = 9.0%).     

Effects of an applied magnetic field on the anodic dissolution of nickel in HNO3 + Cl− solution

All types of the magnetic field effects on the anodic dissolution of metallic materials have been found in one electrochemcial system: the Ni/0.40 M HNO₃ + 5.0 mM NaCl system. The effects are similar to those of a stirring on all occasions. With the presence of the magnetic field, the current decreases in the active region. However, the current oscillations are changed to active dissolution in the prepassive region and induced in the transitive potential from the prepassive region to the passive region by the magnetic field. In the passive region, the magnetic field has little influence. Those effects are discussed with different rate-determining steps. The study of the effects of the magnetic field on this system may help us understand why the magnetic field enhances the corrosion rates in some conditions while suppressing them in others.     

Electrochemical and XPS studies of a Nb-containing Ti-based glass-forming alloy system in H2SO4 solution

The corrosion behaviors of Ti₄₀Zr₂₅Ni_12 -xNb_xCu₃Be₂₀ (x = 0, 4, 8, and 12 at.%) alloys in 0.5 mol/L H₂SO₄ solution were studied, aiming to establish the relationship between Nb content and corrosion resistance. The addition of Nb element gives rise to a clear microstructural evolution, from a completely amorphous structure for the alloys without Nb and with 4% Nb alloys to an amorphous/crystalline composite structure for the alloys with 8% and 12% Nb. The alloy with higher Nb content exhibits better corrosion resistance, which can be attributed to the formation of Ti^4 +-, Zr^4 +-, and Nb^5 +-enriched highly protective surface film in corrosive solutions.     

Electrochemical deposition of PbTe onto n-Si(1 0 0) wafers

Electrochemical deposition of PbTe from 50 mM Pb(NO₃)₂ + 1 mM TeO₂ + 0.1 M HNO₃ solution onto n-Si(1 0 0) wafers was studied using cyclic voltammetry (CV), chronoamperometry, ex situ SEM, XRD and EDX. Electrochemical behavior of n-Si(1 0 0) electrode in electrolytes 50 mM Pb(NO₃)₂ + 0.1 M HNO₃ and 1 mM TeO₂ + 0.1 M HNO₃ was also studied. No underpotential deposition (UPD) of Pb and Te onto n-Si was observed in the investigated systems indicating weak Pb–Si and Te–Si interactions. Deposition of Pb and Te on n-Si occurred with overvoltage via 3D island growth. Electrosynthesis of PbTe (NaCl-like structure, a = 0.650 nm) takes place due to codeposition of Pb and Te at potentials E > E_{Pb²⁺/Pb⁰} (lead UPD onto tellurium). Cathodic deposition of PbTe onto n-Si(1 0 0) is irreversible – there is no anodic current in the CV curve. Oxidation of PbTe on n-Si is observed only under illumination, when photoelectrons and photoholes are generated in silicon substrate.     

Cyclometallated ruthenium(III) complexes: Synthesis,structure and properties

Reactions of Schiff bases (H₂apahR) derived from acetophenone and acid hydrazides, triethylamine and [Ru(PPh₃)₃Cl₂] (1:2:1 mole ratio) in methanol provide cyclometallated ruthenium(III) complexes of formula trans-[Ru(apahR)(PPh₃)₂Cl] in 74–81% yields. The complexes have been characterized by elemental analysis, magnetic susceptibility, spectroscopic (infrared, electronic and EPR) and electrochemical measurements. X-ray crystal structures of two representative complexes have been determined. In each complex, the metal centre is in distorted octahedral CNOClP₂ coordination sphere assembled by the C,N,O-donor meridionally spanning apahR^2?, the chloride and the two mutually trans-oriented PPh₃ molecules. All the complexes are one-electron paramagnetic (μ_eff. = 1.85–1.98 μ_B) and display rhombic EPR spectra in frozen (120 K) dichloromethane-toluene (1:1) solution. Electronic spectra of the complexes display several absorptions within 470–270 nm due to ligand-to-metal charge transfer and ligand centred transitions. The complexes are redox active and display a Ru(III) → Ru(II) reduction and a Ru(III) → Ru(IV) oxidation in the potential ranges ?0.66 to ?0.70 V and 0.75 to 0.80 V (vs. Ag/AgCl), respectively.     

The effect of temperature oscillation on the passive corrosion properties of Alloy 22

A temperature-oscillating heated electrode technique (TOHET) was developed for investigating the temperature effect on the passive corrosion properties of Alloy 22 (UNS N06022, Ni–22Cr–13Mo–3W–3Fe), which has been selected as the corrosion-resistant material (CRM) of the waste package outer barrier for the high level nuclear waste (HLNW) repository at Yucca Mountain, NV, USA. Cyclic and potentiostatic polarization tests were conducted on a temperature-controlled hot surface of Alloy 22, which was immersed in simulated Yucca Mountain ground waters. The current recorded during cyclic polarization tests was sensitive to temperature changes when the temperature amplitude was greater than 2 °C. Corrosion potential increased from −293 mV to −256 mV (Ag/AgCl) when temperature was decreased from 102 °C to 72 °C. Current variation was also observed during a potentiostatic test at −150 mV over which temperature oscillated between 65 °C and 95 °C. The log–linear plot of passive current density vs. temperature exhibited a linear relationship. In summary, the TOHET method is a valuable technique for studying the effects of temperature on the corrosion rate of passive alloys.     

Signal enhancement in solution-cathode glow discharge — optical emission spectrometry via low molecular weight organic compounds

HCOOH, CH₃COOH, and CH₃CH₂OH were used as chemical modifiers in a solution-cathode glow discharge. Emission was measured directly from the discharge, without a gas–liquid separator or a secondary excitation source. Emission from Ag, Se, Pb, and Hg was strongly enhanced, and the detection limits (DL) for these elements were improved by up to an order of magnitude using a combination of HCOOH and HNO₃ compared to using HNO₃ alone. The DL was measured for Mg (1 μg/L), Fe (10 μg/L), Ni (6 μg/L), Cu (6 μg/L), Pb (1 μg/L), Ag (0.1 μg/L), Se (300 μg/L), and Hg (2 μg/L). Coefficients of determination (R²) were between 0.9986 and 0.9999. A voltage of 1 kV was used, which produced a current of approximately 70 mA.     

Photocatalytic activity of TiO2 nanotube layers loaded with Ag and Au nanoparticles

Ag and Au nanoparticles were found to significantly enhance the photocatalytic activity of self-organized TiO₂ nanotubular structures. The catalyst systems are demonstrated to be highly efficient for the UV-light induced photocatalytic decomposition of a model organic pollutant – Acid Orange 7. The metallic nanoparticles with a diameter of ∼10 ± 2 nm (Ag) and ∼28 ± 3 nm (Au) were attached to a nanotubular TiO₂ layer that consists of individual tubes of ∼100 nm of diameter, ∼2 μm in length and approx. 15 nm of wall thickness. Both metal particle catalyst systems enhance the photocatalytic decomposition significantly more on the nanotubes support than placed on a compact TiO₂ surface.     

Inhibition of cold rolled steel corrosion in sulphuric acid solution by 2-mercapto-1-methylimidazole: Time and temperature effects treatments

2-Mercapto-1-methylimidazole (MMI) has been evaluated as a corrosion inhibitor for cold rolled steel in aerated 2 M H₂SO₄ by gravimetric method. The effect of MMI on the corrosion rate was determined at various immersions time and concentrations. The effect of the temperature on the corrosion behaviour with addition of different concentrations of MMI was studied in the temperature range 30–60 °C. The MMI acts as an effective corrosion inhibitor for cold rolled in sulphuric acid medium. The inhibition process is attributed to the formation of an adsorbed film of MMI on the metal surface which protects the metal against corrosion. The protection efficiency increased with increase in inhibitor concentration at various immersions time and decreased with increase in temperature. Adsorption of MMI on the cold rolled steel surface is found to obey the Langmuir adsorption isotherm. Some thermodynamic functions of dissolution and adsorption processes were also determined.     

The influence of chloride on the initial anodic dissolution of Cu3Au(1 1 1)

We report a detailed in situ X-ray diffraction study of the influence of chloride on the atomic structure evolution at the solid-electrolyte interface during the selective dissolution of Cu from a Cu₃Au(1 1 1) surface immersed in 0.1 M H₂SO₄. We disclose that the formation of the initial ultrathin Au-rich (1 1 1) with an inverted stacking sequence, as recently observed at Cu₃Au(1 1 1) in contact with pure 0.1 M H₂SO₄, is strongly influenced by adding 5 mM HCl. The main finding is a negative shift of about 150 mV of the critical potential at which the ultra-thin Au-rich layer transforms into thicker Au islands. The presented results support the view that it is not a thermodynamic driving force, but rather the rate of surface diffusion that dominates the formation of the structures of the metallic layer.     

Structural and spectroscopic properties of Ru(II) complexes of 4-(aryl)thiosemicarbazones of thiophen-2-carbaldehyde

Six Ru(II) complexes of formula [Ru(L)₂(PPh₃)₂] have been prepared where LH = 4-(aryl)thiosemicarbazones of thiophen-2-carbaldehyde. X-ray crystal structures of five of the complexes are reported. In all the complexes ruthenium is six coordinate with a distorted octahedral cis-P₂, cis-N₂, trans-S₂ donor environment, and each of the two thiosemicarbazone ligands are coordinated in a bidentate fashion forming a four membered chelate ring. The complexes undergo a one-electron oxidation at ～0.5 V vs. Ag/AgCl. The EPR spectrum of the electrochemically oxidized solution at 100 K shows a rhombic signal, with transitions at g₁ = 2.27, g₂ = 2.00 and g₃ = 1.80. DFT calculations on one of the complexes suggest that there is 35% ruthenium and 17% sulfur orbital contribution to the HOMO. These results suggest that the assignment of metal atom oxidation states in these compounds is not unambiguous.     

Enhanced electrochemiluminescence based on Ru(bpy)32+-doped silica nanoparticles and graphene composite for analysis of melamine in milk

A sensitive electrochemiluminescence (ECL) sensor for melamine analysis was fabricated based on Ru(bpy)₃²⁺-doped silica (Ru(bpy)₃²⁺@SiO₂) nanoparticles and graphene composite. Spherical Ru(bpy)₃²⁺@SiO₂ nanoparticles with uniform size about 55 nm were prepared by the reverse microemulsion method. Since per Ru(bpy)₃²⁺@SiO₂ nanoparticle encapsulated a great deal of Ru(bpy)₃²⁺, the ECL intensity has been greatly enhanced, which resulted in high sensitivity. Due to its extraordinary electric conductivity, graphene improved the conductivity and accelerated the electron transfer rate. In addition, graphene could work as electronic channel improving the efficient luminophor amount participating in the ECL reaction, which further enhanced the ECL signal. This proposed sensor was used to melamine analysis and the ECL intensity was proportional to logarithmic melamine concentration range from 1 × 10⁻¹³ M to 1 × 10⁻⁸ M with the detect limit as low as 1 × 10⁻¹³ M. In application to detect melamine in milk, satisfactory recoveries could be obtained, which indicated this sensor having potential application in melamine analysis in real samples.     

The electrochemical reduction of carbon dioxide (CO2) to methanol in the presence of pyridoxine (vitamin B6)

Experiments aimed at ameliorating carbon dioxide (CO₂) into methanol were explored using pyridoxine, a member of the vitamin B₆ family, to enhance the reduction process. At a platinum electrode, an aqueous solution (pH ≈ 5) of pyridoxine showed a quasi-reversible redox couple with the cathodic peak detected at ca. − 0.55 V vs. Ag/AgCl (3 M KCl) in the presence of CO₂ and argon. An increase in the corresponding cathodic peak current was observed following saturation of the solution with CO₂ using a Pt electrode, but with no detectable reduction current recorded at a glassy carbon electrode for the same system. Confirmation of methanol formation during the pyridoxine-assisted CO₂ reduction was conducted by using gas chromatography analysis of the electrolyzed solutions and faradic yields of ca. 5% were afforded. A combination of the results from the cyclic voltammetry and constant current chronopotentiometry experiments revealed an overpotential of ≤ 200 mV was required. The results indicate a potential utility of pyridoxine as an alternative reagent to the more toxic pyridine during the electrochemical reduction of CO₂.     

In situ scanning tunneling microscopy imaging of mercury film electrodeposited on Ir(1 1 1)

In situ scanning tunneling microscopy (STM) was used to examine multilayer Hg film electrodeposited on a well-ordered Ir(1 1 1) single crystal electrode in 0.1 M HClO₄ + 1 mM Hg(ClO₄)₂. Topography STM scans showed that the Ir(1 1 1) – supported Hg film electrode contained well-defined terraces separated by monatomic steps (Δz = 2.3 Å). The STM’s tip could be used to induce local dissolution of the Hg deposit under proper operating conditions and the depth of the etched pit informed directly the thickness of Hg deposit. Although in situ STM imaging with a tungsten tip could not result in atomic structure of bare Hg film in 0.1 M HClO₄, it discerned highly ordered iodine adlayers, represented by a (2 × 8√3)rect – I structure, on the Hg film in solution containing potassium iodide. These STM results suggested that the Hg substrate could have an ordered atomic structure.     

Inhibitive action of ethanol extracts from Nauclea latifolia on the corrosion of mild steel in H2SO4 solutions and their adsorption characteristics

The inhibitive action of ethanol extracts from leaves (LV), bark (BK) and roots (RT) of Nauclea latifolia on mild steel corrosion in H₂SO₄ solutions at 30–60 °C was studied using weight loss and gasometric techniques. The extracts were found to inhibit the corrosion of mild steel in H₂SO₄ solutions and the inhibition efficiencies of the extracts follow the trend: RT > LV > BK. The inhibition efficiency increased with the extracts concentration but decreased with temperature rise. Physical adsorption of the phytochemical components of the plant on the metal surface is proposed as the mechanism of inhibition. The adsorption characteristics of the inhibitor were approximated by the thermodynamic-kinetic model of El-Awady et al.     

Synthesis,characterization and spectroscopic studies of pyrazinamide metal complexes

The present paper deals with the synthesis and characterization of Schiff base complexes of pyrazinamide an antitubercular drug. Metals selected for complexation are copper, silver, gold, zinc, mercury, iron and cobalt. The complexes have been suitably synthesized and isolated in pure powdered form. Analytical data agrees with the compositions M(L), M′(L)₂ and M″(L)₂·2H₂O, respectively where M = Ag, M′ = Cu, Au, Zn and Hg and M″ = Fe and Co, ligand metal ratios were also confirmed by monovariation method and Job’s method of continuous variation. Molar conductance values suggest the non ionic nature of the complexes. The tentative structure assigned to the complexes on the basis of stoichiometry and analytical data were further supported by spectral studies viz; IR, NMR, magnetic susceptibility and electronic spectra. A preliminary attempt has also been made to compare the potencies of metal complexes with parent drug. The Cu and Ag complexes are giving encouraging results. Particle size studies further suggest that the drug molecule undergoes reduction in size on complexation.     

Selective and rapid detection of triacetone triperoxide by double-step chronoamperometry

A selective detector for the improvised explosive, triacetone triperoxide is proposed. This is based on the rapid redox reaction of peroxides (hexamethylene triperoxide diamine, benzoyl peroxide, t-butyl peroxide, triacetone triperoxide and H₂O₂) with bromide at 55 °C. Consumption of bromide is indicative of the reduction of the R–O–O–R moiety, the appearance of Br₂ was found for all except for triacetone triperoxide. The latter was found to breakdown to acetone which rapidly reacts with Br₂ producing bromoacetones. The lack of Br₂ production is unique to triacetone triperoxide. Double step chronoamperometry (E₁ = 700 mV, E₂ = 960 mV (vs. Ag/AgCl)) allows for the quantitation of bromine (Br₂ + 2e^? ? 2Br^?) and bromide (2Br^? ? Br₂ + 2e^?) respectively. The results yielded a detection limit of 8.5 µM for triacetone triperoxide with a sensitivity of 0.026 µA µM^? 1. The detection limits of 16.3 µM and 14.9 µM were found respectively for HMTD and H₂O₂ based on the appearance of Bromine. These results indicate a possibility to develop a handheld sensor for TATP dermination.     

Decomposition Studies of Aqueous Phase Ligands Used in Advanced Reprocessing Flowsheets

Two potential methods for decomposing organic ligands in nitric acid have been studied using acetic acid and diethylenetriaminepentaacetic acid (DTPA) as examples; these methods were oxidation by nitric acid at elevated temperatures (70-110 °C) and electrochemical oxidation, both direct and mediated electrochemical oxidation. Based on total carbon measurements, acetic acid proved to be rather stable against nitric acid oxidation whereas 60-80% of DTPA was decomposed at 100-110°C. Electrochemical oxidation methods were generally more effective in decomposing acetic acid and DTPA with mediated electrochemical oxidation using Ag(II) ions the most effective method under the conditions tested, with ∼80 and >90% loss of carbon from acetic acid and DTPA solutions respectively, at ambient temperature in 6 M HNO₃.     

DFT study of group 8 catalysts for the hydrophenylation of ethylene: Influence of ancillary ligands and metal identity

Computational methods are used to investigate catalytic hydrophenylation of ethylene using complexes of the type [(Y)M(L)(CH₃)(NCMe)]ⁿ⁺ [Y = Mp, n = 1; Y = Tp, n = 0; M = Ru or Os; L = PMe₃, PF₃, or CO; Mp = tris(pyrazolyl)methane; Tp = hydrido-tris(pyrazolyl)borate]. The conversion of ethylene and benzene to ethylbenzene with [(Y)M(L)(Ph)]ⁿ⁺ as catalyst involves four steps: (1) ethylene coordination, (2) ethylene insertion into the M–Ph bond, (3) benzene coordination, and (4) benzene C–H activation. DFT calculations form the basis to compare stoichiometric benzene C–H activation by [(Y)M(L)(CH₃)(NCMe)]ⁿ⁺ complexes to yield methane and [(Y)M(L)(Ph)(NCMe)]ⁿ⁺. In addition, starting from the 16-electron species [(Y)M(L)(Ph)]ⁿ⁺, potential energy surfaces for the formation of ethylbenzene are calculated to reveal the impact of modifications to the scorpionate ligand (Mp or Tp), co-ligand (L) and metal center (M).