Adsorption behavior and corrosion inhibitive potential of xanthene on mild steel/sulphuric acid interface

The inhibition of xanthene (XEN) on the corrosion of mild steel in 0.5 M H₂SO₄ was studied by gravimetric and UV–visible spectrophotometric methods at 303–333 K. Results obtained show that XEN act as inhibitor for mild steel in H₂SO₄ solution. The inhibition efficiency was found to increase with increase in XEN concentration but decreased with temperature. Activation parameters and Gibbs free energy for the adsorption process using Statistical Physics were calculated and discussed. The corrosion process in 0.5 M H₂SO₄ in the absence and presence of XEN follows zero-order kinetics. The UV–visible absorption spectra of the solution containing the inhibitor after the immersion of mild steel specimen indicate the formation of a XEN–Fe complex. Quantum chemical calculations using DFT were used to calculate some electronic properties of the molecule in order to ascertain any correlation between the inhibitive effect and molecular structure of xanthene.     

Xanthione: A new and effective corrosion inhibitor for mild steel in sulphuric acid solution

The adsorption and inhibition effect of xanthione (XION) on mild steel in 0.5 M H₂SO₄ at 303–333 K were studied using gravimetric and UV–visible spectrophotometric methods. The results obtained show that XION acts as an effective corrosion inhibitor for mild steel in sulphuric acid and inhibition efficiency reaches 98.0% at a very low inhibitor concentration of 10 μM. Inhibition efficiency was found to increase with increase in XION concentration but decreased with temperature suggesting physical adsorption mechanism. Arrhenius law and its transition equation lead to estimate the activation parameters of the corrosion process. XION inhibits the corrosion of mild steel effectively at moderate temperature and adsorbs according to the Langmuir isotherm. Thermodynamic parameters governing the adsorption process have been calculated and discussed. The UV–visible absorption spectra of the solution containing the inhibitor after the immersion of mild steel specimen indicate the formation of a XEN–Fe complex. Attempt to correlate the molecular structure to quantum chemical indices was made using density functional theory (DFT).     

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.     

An acidic cellulose–chitin hybrid gel as novel electrolyte for an electric double layer capacitor

A novel acidic cellulose–chitin hybrid gel electrolyte including binary ionic liquids (ILs) with an aqueous H₂SO₄ solution was prepared for an electric double layer capacitor (EDLC). Its electrochemical characteristics were investigated by galvanostatic charge–discharge measurements. The test cell with a hybrid gel electrolyte shows a specific capacitance of 162 F g^?1 at room temperature, which is higher than that for a cell with an H₂SO₄ electrolyte, 155 F g^?1. This hybrid gel electrolyte exhibits excellent high-rate discharge capability in a wide range of current densities as well as an aqueous H₂SO₄ solution. The discharge capacitance of the test cell can retain over 80% of its initial value in 100,000 cycles even at a high current density of 5000 mA g^?1.     

Essential oil of Salvia aucheri mesatlantica as a green inhibitor for the corrosion of steel in 0.5 M H2SO4

Essential oil of aerial parts of Salvia aucheri Boiss. var. mesatlantica was obtained by hydrodistillation and analyzed by GC and GC/MS. The oil was predominated by camphor (49.59%). The inhibitory effect of this essential oil was estimated on the corrosion of steel in 0.5 M H₂SO₄ using electrochemical polarization and weight loss measurements. The corrosion rate of steel is decreased in the presence of natural oil. The inhibition efficiency was found to increase with oil content to attain 86.12% at 2 g/L. Polarization curves revealed that the oil of S. aucheri mesatlantica acts as mixed type inhibitor with a strong predominance of anodic character. The temperature effect on the corrosion behavior of steel in 0.5 M H₂SO₄ without and with the inhibitor at 2 g/L was studied in the temperature range from 303 to 343 K, the associated activation energy have been determined. The adsorption of oil on the steel surface was found to obey Langmuir’s adsorption isotherm.     

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.     

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.     

The experimental and DFT studies of 1,3-dimethyl-2-[4-chloro-styryl]-benzimidazolium iodide

1,3-Dimethyl-2-[4-chloro-styryl]-benzimidazolium iodide (1) was synthesized and characterized by X-ray diffraction, ¹H NMR, MS, IR, UV–vis spectra and elemental analysis. The crystals are monoclinic, space group P2₁/c, with a = 12.507(3) Å, b = 7.3259(19) Å, c = 36.705(9) Å, V = 3358.9(15) Å³, and Z = 4 (at 296(2) K). Crystal stacking scheme indicates the face-to-face π?π aromatic stacking interactions. Molecular geometries, frequencies, IR, ¹H NMR and UV–vis were calculated at DFT/TD-DFT level using two hybrid exchange–correlation functionals, B3LYP and PBE1PBE. The stability of the molecule arising from hyperconjugative interaction and charge delocalization had been analyzed using natural bond orbital (NBO) analysis. These calculations on (1) provide deep insight into its electronic structure and properties.     

Interaction parameters and (solid + liquid) equilibria calculation for KCl–H2O–HCl–C2H5OH,K2SO4–H2O–H2SO4 and K2SO4–H2O–C2H5OH mixed solvent-electrolyte systems

This work deals with the prediction and experimental measurements of the (solid + liquid) equilibrium (SLE) in acid medium for industrial purposes. Specific systems including KCl–ethanol–water–HCl and K₂SO₄–water–H₂SO₄ were analyzed. At first, a critical discussion of SLE calculations was given, based on the well-known UNIQUAC extended and LIQUAC models. Two new proposals were derived, considering the explicit necessity of a new reference state for SLE calculations for the studied (solvents + acid) mixtures. The solubility of KCl in water–ethanol–HCl mixed solvents was measured in the temperature range of 300.15 to 315.15 K using an analytical gravimetric method. These results combined with some other experimental data reported in the open literature let us to propose a set of parameters for the new models. They included the interaction parameters between ethanol and the H⁺ ion. The prediction capability of the new models, for calculations in acid medium, was illustrated. Experimentally, it was observed that the (K₂SO₄ + water + H₂SO₄) system presented the unusual behavior of increasing K₂SO₄ solubility with an increase in the sulfuric acid concentration. This was accurately predicted by the newly proposed models.     

Synthesis,spectroscopic studies and structures of square-planar nickel(II) and copper(II) complexes derived from 2-{(Z)-[furan-2-ylmethyl]imino]methyl}-6-methoxyphenol

Two new nickel(II) [Ni(L)₂] and copper(II) [Cu(L)₂] complexes have been synthesized with bidentate NO donor Schiff base ligand (2-{(Z)-[furan-2-ylmethyl]imino]methyl}-6-methoxyphenol) (HL) and both complexes Ni(L)₂ and Cu(L)₂ have been characterized by elemental analyses, IR, UV–vis, ¹H, ¹³C NMR, mass spectroscopy and room temperature magnetic susceptibility measurement. The tautomeric equilibria (phenol-imine, O–H?N and keto-amine, O?H–N forms) have been systemetically studied by using UV–vis absorption spectra for the ligand HL. The UV–vis spectra of this ligand HL were recorded and commented in polar, non-polar, acidic and basic media. The crystal structures of these complexes have also been determined by using X-ray crystallographic techniques. The complexes Ni(L)₂ and Cu(L)₂ crystallize in the monoclinic space group P2₁/n and P2₁/c with unit cell parameters: a = 10.4552(3) Å and 12.1667(4) Å, b = 8.0121(3) Å and 10.4792(3) Å, c = 13.9625(4) Å and 129.6616(3)Å, V = 1155.22(6) Å³ and 1155.22(6) Å³, D_x = 1.493 and 1.476 g cm^?3 and Z = 2 and 2, respectively. The crystal structures were solved by direct methods and refined by full-matrix least squares to a find R = 0.0377 and 0.0336 of for 2340 and 2402 observed reflections, respectively.     

(Solid + liquid) metastable equilibria in quaternary system (Li2SO4 + K2SO4 + Li2B4O7 + K2B4O7 + H2O) at T = 288 K

Metastable equilibrium solubilities and properties such as densities, conductivity, pH, refractive index, and viscosity of the solution were determined experimentally. According to the experimental data, the metastable equilibrium phase diagram was plotted. In the phase diagram, there are three invariant points, seven univariant curves, five fields of crystallization: Li₂SO₄ · H₂O, K₂SO₄, Li₂B₄O₇ · 3H₂O, K₂B₄O₇ · 4H₂O, and K₂SO₄ · Li₂SO₄. The double salt K₂SO₄ · Li₂SO₄ was found in the quaternary system metastable equilibria. Lithium sulfate (Li₂SO₄) has the highest concentration and strong salting-out effects on other salts.Also, the relationship diagram between the properties and the ion concentration of solution was constructed. It can be seen from the relationship diagram that the equilibrium solution density values, viscosity values, and refractive index values are increased apparently with the rise of sulfate ion concentration, reaching the maximum values at eutonic point F3. Electrical conductivity values and pH values, however, fall down with the rise of ion concentration on the whole.     

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.     

One-dimensional MoO2 nanorods for supercapacitor applications

One-dimensional (1D) MoO₂ nanorods were prepared by thermal decomposition of tetrabutylammonium hexamolybdate (((C₄H₉)₄N)₂Mo₆O₁₉) in an inert atmosphere. The synthesized nanorods have been characterized by XRD, TEM and HRTEM. The capacitive behaviour of 1D MoO₂ nanorods was studied by galvanostatic charge–discharge studies in 1 M H₂SO₄ solution at different current densities. The results indicate that the MoO₂ nanorods show good capacitive behaviour with a specific capacitance of 140 Fg^?1.     

Growth and characterization of 2-amino-4-picolinium 4-aminobenzoate single crystals

The organic material of 2-amino-4-picolinium 4-aminobenzoate (C₆H₉N₂⁺·C₇H₆NO₂^?) was synthesized and grown as single crystals at room temperature by slow evaporation solution growth technique in the constant temperature bath (±0.01 °C) using ethanol as solvent. The grown crystals were characterized by XRD and FT-IR spectral analyses. The melting point, density, UV–visible spectral studies were carried out for the grown crystals. The theoretical factor group analysis predicts 372 internal modes of vibration and optical modes in the grown title compound. The second harmonic generation (SHG) output of 2-amino-4-picolinium 4-aminobenzoate was recorded by Kurtz–Perry powder technique and it is found to be 355 mV at a given pulse energy of 1.45 mJ/s and for urea the SHG output was 525 mV. The dielectric behaviour of 2-amino-4-picolinium 4-aminobenzoate was investigated with different frequencies and temperatures.     

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.     

(Solid + liquid) isothermal evaporation phase equilibria in the aqueous ternary system (Li2SO4 + MgSO4 + H2O) at T = 308.15 K

The solubility and the density in the aqueous ternary system (Li₂SO₄ + MgSO₄ + H₂O) at T = 308.15 K were determined by the isothermal evaporation. Our experimental results permitted the construction of the phase diagram and the plot of density against composition. It was found that there is one eutectic point for (Li₂SO₄ · H₂O + MgSO₄ · 7H₂O), two univariant curves, and two crystallization regions corresponding to lithium sulphate monohydrate (Li₂SO₄ · H₂O) and epsomite (MgSO₄ · 7H₂O). The system belongs to a simple co-saturated type, and neither double salts nor solid solution was found. Based on the Pitzer ion-interaction model and its extended HW models of aqueous electrolyte solution, the solubility of the ternary system at T = 308.15 K has been calculated. The predicted solubility agrees well with the experimental values.     

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.     

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.     

Gas phase dissociation of H2SO4: A computational study

The decomposition of gaseous sulfuric acid has been investigated computationally. In particular the role of the hydrated gaseous coordination adducts of SO₃(g) and H₂SO₄(g) in the (dissociation + decomposition) process has been evaluated. A first principles study of the gaseous coordination complexes SO₃(H₂O)_n (n = 1 to 3) and H₂SO₄(H₂O)_m (m = 1 to 2) has been carried out deriving equilibrium ground state structures, vibrational frequencies and energetic stabilities by the Moller–Plesset perturbation approximation. These results have been used to derive the enthalpy of formation at 0 K and the Gibbs energy functions of these molecules. A new thermodynamic modeling of the decomposition of H₂SO₄(g) has been therefore performed considering the effect of temperature, pressure and initial composition of the gas (hydration conditions).     

Ternary non-noble metal chalcogenide (W–Co–Se) as electrocatalyst for oxygen reduction reaction

In this study, a catalyst based on a novel ternary non-noble metal chalcogenide, W–Co–Se, was synthesized for the oxygen reduction reaction (ORR) in acidic medium. The non-noble metal chalcogenide catalyst was electrochemically stable in the potential range of 0.05–0.8 V versus NHE in 0.5 M H₂SO₄ aqueous solution. This catalyst demonstrated significant catalytic activity towards the ORR, showing the ORR onset potential at 0.755 V versus NHE in 0.5 M H₂SO₄ at 25 °C. Such high activity might be attributed to the electronic structure of non-noble metals modified by chalcogen.