Effect of the Addition of Zero Valent Iron (Fe0) on the Batch Biological Sulphate Reduction Using Grass Cellulose as Carbon Source

Mineral mining generates acidic, saline, metal-rich mine waters, often referred to as acid mine drainage (AMD). Treatment of AMD and recovering saleable products during the treatment process are a necessity since water is, especially in South Africa, a scarce commodity. The aim of the study presented here was to investigate the effect of zero valent iron (Fe⁰) on the biological removal of sulphate from AMD in batch reactors. The performance of the reactors was assessed by means of sulphate reduction, chemical oxygen demand (COD), volatile fatty acid (VFA) utilisation and volatile suspended solids (VSS) concentration. To this end, three batch reactors, A, B and C (volume 2.5 L), were operated similarly with the exception of the addition of grass cuttings and iron filings. Reactors A and B received twice as much grass (100 g) as C (50 g). Reactor A received no iron filings to act as a control, while reactors B and C received 50-g iron filings for the experimental duration. The results showed that Fe⁰ appears to provide sustained sulphate removal when sufficient grass substrate is available. In reactors A and C, sulphate removal efficiency was higher when the COD concentration was lower due to utilisation. In reactor B, sulphate removal efficiency was accompanied by an accumulation of COD as hydrogen (H₂) provided by the Fe⁰ was utilised for sulphate reduction. Furthermore, these results showed the potential of Fe⁰ to enhance the participation of microorganisms in sulphate reduction.     

Microcalorimetric analysis of methylcellulose influence on the hydration process of tricalcium aluminate,alite and their mixture

In the paper, the results of investigation concerning the influence of 0.3% addition of hydroxypropyl methylcellulose (MC) of 40 and 70 Pa s viscosity on the hydration process of main clinker phases C₃S and C₃A are presented. The course of hydration is documented using microcalorimetry, and formed phases were identified by XRD. The research indicated that methylcellulose inhibited the hydration process of clinker phases, analysed both, separately and in their mixture. Moreover, it was found that the presence of MC admixture also led to the reduction in calcium sulphate dihydrate reactivity in the system.     

铅及铅锑合金阳极膜中硫酸铅的氧化过程

应用电位阶跃和交流阻抗法分别研究铅和Pb-5wt% Sb合金在4.5mol·dm^-^3H~2SO~4(30℃)中于1.3V(vs. Hg/Hg~2SO~4, 下同)生长20min后的阳极膜在0.9V还原5min后再在1.4V将膜中硫酸铅氧化的过程。实验结果表明在0.9V还原二氧化铅而得到的硫酸铅能在1.4V于1min内氧化为二氧化铅。这是由于此种硫酸铅处于硫酸铅颗粒表层的缘故。至于颗粒内部由铅直接生成的硫酸铅的氧化为二氧化铅就要缓慢得多。合金中的锑能使二氧化铅晶核形成和生长速率显著降低。     

Fundamentals of lead-acid cells: Part XII. The reduction of lead sulphate

The reduction of lead sulphate grown anodically on planar and porous electrodes has been studied by a potentiostatic step technique. Both “planar” and “porous” electrodes behave in a similar manner and indicate that the electrode reduction reaction has a finite depth of penetration into the electrode. The kinetics of the formation of metallic lead on both electrodes appear to be instantaneous nucleation and two-dimensional growth processes with subsequent current limitations due to overlap and lead sulphate depletion. The current limitation processes are very complex and it has not been found possible to fit a satisfactory mathematical model.     

Size-Controlled Synthesis of Palladium Nanoparticles

Palladium nanoparticles protected by PVP were obtained first by reducing PdCl₂ with NaBH₄ solution. Then different size palladium nanoparticles with a large size range (1.49 nm ～ 23.26 nm) were prepared by the multi-step reduction of PdCl₂ by hydrogen adsorbed on the surface of palladium nanoparticles. Transmission electron microscopy (TEM) and x-ray diffraction (XRD) were used to characterize the nanoparticles. The increasing value of average diameter from the first to the eighth reduction reaction is about 0.58 nm, from the ninth to the fifteenth reduction reaction the value is about 2.44 nm.     

Electrocatalysis and pH (a review)

The factors determining pH effects on principal catalytic reactions in low-temperature fuel cells (oxygen reduction, hydrogen oxidation, and primary alcohols oxidation) are analyzed. The decreasing of hydrogen oxidation rate when passing from acidic electrolytes to basic ones was shown to be due to the electrode surface blocking by oxygen-containing species and changes in the adsorbed hydrogen energy state. In the case of oxygen reduction, the key factors determining the process’ kinetics and mechanism are: the O₂ adsorption energy, the adsorbed molecule protonation, and the oxygen reaction thermodynamics. The process’ high selectivity in acidic electrolytes at platinum electrodes is caused by rather high Pt-O₂ bond energy and its protonation. The passing from acidic electrolytes to basic ones involves a decrease in the oxygen adsorption energy, both at platinum and nonplatinum catalysts, hence, in the selectivity of the oxygen-to-water reduction reaction. The increase in the methanol and ethanol oxidation rate in basic media, as compared with acidic ones, is due to changes in the reacting species’ structure (because of the alcohol molecules dissociation) on the one hand, and active OH_ads species inflow to the reaction zone, on the other hand. In the case of ethanol, the above-listed factors determine the process’ increased selectivity with respect to CO₂ at higher pHs. Based on the survey and valuation, priority guidelines in the electrocatalysis of commercially important reactions are formulated, in particular, concepts of electrocatalysis at nonplatinum electrode materials that are stable in basic electrolytes, and approaches to the practical control of the rate and selectivity of oxygen reduction and primary alcohols oxidation over wide pH range.     

Synthesis and inclusion properties of pillar[n]arenes

A detailed study of the reaction conditions revealed that a quantitative cyclocondensation of 1,4-dialkoxy-2,5-bis(alkoxymethyl)-benzenes to pillar[n]arenes can be achieved by catalysis of p-toluenesulfonic acid in CH₂Cl₂. Major product of this new reaction is in each case a cyclopentamer (n = 5), but small amounts of the pillar[n]arenes with n = 6, 7 and 10 can be obtained as well. Different alkoxy groups in 1- and 4-position lead to regioisomers. All cyclooligomers exist in pillar structures as pair of enantiomers, which show a racemisation at room temperature, which is fast in terms of the NMR time scale. The racemisation process occurs by rotation of the 1,4-phenylene segments in the macrocyclic rings. Pillar[n]arenes exhibit novel host–guest behavior.     

Reduction of Oxide Minerals by Hydrogen Plasma: An Overview

Carbothermic reduction of oxide minerals is one of the major routes to obtain the corresponding metals. This process produces a lot of CO₂, which is responsible for greenhouse effect. Alternatively, hydrogen plasma containing hydrogen in atomic, ionic, and excited states can reduce almost every metal oxide even at lower temperatures. Besides this advantage, plasma processing also offers kinetic advantages. Further, hydrogen-water cycle does not pose any environmental problems. However, reduction of metal oxides in hydrogen plasma is not so straightforward—there are issues relating to introduction of material into the plasma zone, residence time, reverse reaction, and scale-up that must be resolved—yet, it holds the key to future environmental challenges particularly with respect to CO₂ emission. This paper provides an overview of reduction of oxide minerals by hydrogen plasma. The influences of various reaction conditions particularly with respect to reduction of oxides are discussed and some aspects of both thermal and non-thermal cold plasma linking oxidative as well as dissociative reduction are presented.     

Crystal hydration and vacancy enhanced isotopic exchange reactions in heterogeneous solid-liquid systems

The rate of some heterogeneous isotopic exchange reactions can be enhanced by the simultaneous hydration of the solid participating in the exchange process. The results presented here show that the concomitant hydration of anhydrous sodium sulphate enhances the Na₂SO₄–²²Na⁺ isotopic exchange reaction in a water-acetone medium. The reaction rate is further enhanced by creating a controlled number of vacancies in the crystal lattice of sodium sulphate by doping.     

Facile and green solvothermal synthesis of palladium nanoparticle-nanodiamond-graphene oxide material with improved bifunctional catalytic properties

We developed a selective solvothermal synthesis of palladium nanoparticles on nanodiamond (ND)–graphene oxide (GO) hybrid material in solution. After the GO and ND materials have been added in PdCl₂ solution, the spontaneous redox reaction between the ND–GO and PdCl₂ led to the creation of nanohybrid Pd@ND@GO material. The resulting Pd@ND@GO material was characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared (FTIR) spectrometry, scanning electronic microscopy (SEM), and atomic absorption spectrometry methods. The Pd@ND@GO material has been used for the first time as a catalyst for the reduction for 2-nitrophenol and the degradation of methylene blue in the presence of NaBH₄. GO plays the role of 2D support material for Pd nanoparticles, while NDs act as a nanospacer for partly preventing the re-stacking of the GO. The Pd@ND@GO material can lead to high catalytic activity for the reduction reaction of 2-nitrophenol and degradation of methylene blue with 100% conversion within ~15 s for these two reactions even when the content of Pd in it is as low as 4.6 wt%.     

Use of surfactant in aniline polymerization with TiO2 to PANI-TiO2 for supercapacitor performance

Polyaniline sulphate salt titanium dioxide composite (PANI-H₂SO₄·TiO₂) was synthesized by chemical in situ polymerization of aniline in the presence of TiO₂. The effect of anionic surfactant (sodium lauryl sulphate) in this reaction was also assessed. During the polymerization reaction, sodium lauryl sulphate (SLS) is converted to dodecyl hydrogen sulphate (DHS) in the presence of acidic medium and gets doped onto polyaniline along with sulphuric acid dopant, i.e. formation of polyaniline-sulphate-dodecyl hydrogen sulphate-titanium dioxide composite (PANI-H₂SO₄-DHS·TiO₂). In the PANI-H₂SO₄-DHS·TiO₂ composite, the presence of DHS is confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and energy-dispersive X-ray analysis (EDAX) and TiO₂ is confirmed by XRD and EDAX results. In PANI-H₂SO₄-DHS·TiO₂ system, the nanoparticle of TiO₂ (10–20 nm) is uniformly embedded on nanofibres (20–60 nm) of PANI-H₂SO₄-DHS, and some part of PANI-H₂SO₄-DHS·TiO₂ forms core–shell morphology, wherein TiO₂ is in core and PANI-H₂SO₄-DHS in shell forms. Stability of PANI-H₂SO₄-DHS increases due to the incorporation of stable TiO₂. Utility of PANI-TiO₂ composite was carried out in supercapacitor cell system by performing cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopic techniques in 1 M H₂SO₄ solution. Very low values of solution resistance, charge transfer resistance and time constant are obtained between 0.2 and 0.6 V. Initial specific capacitance values for the cell carried out at low and high current densities are found to be 280 and 205 F g^?1, respectively, and after 1,700 charge–discharge cycles, its retention in the specific capacitance values is found to be the same (65–66 %) with coulombic efficiency of 98–100 %. A capacitor can work even at a high discharge rate. The efficiency of oxidizing and doping power increases with the use of a surfactant. Moreover, the use of a long chain surfactant dopant containing polyaniline as an electrode material plays an important role to increase the performance of the supercapacitor by allowing the electrolyte to easily enter and come out from PANI electrodes.     

Temperature-programmed reduction of lightly yttrium-doped Au/CeO<Subscript>2</Subscript> catalysts

The reducibility of Au catalysts on CeO₂ supports doped with 1 and 2.5 mass% Y₂O₃ by two types of preparation methods (impregnation and co-precipitation) has been studied by temperature-programmed reduction and compared with that of pure Au/CeO₂. The kinetic parameters of reduction were determined simulating each reduction process. The capacities of these catalysts to retain oxygen have been evaluated by temperature-programmed desorption. The catalytic activities in water gas shift reaction were determined measuring CO conversion between 413 and 623 K. The catalytic performances of all these catalysts were explained in terms of mobility of the oxygen ions of the CeO₂ lattice.     

Viscosity reduction of cellulose + 1-butyl-3-methylimidazolium acetate in the presence of CO2

Viscosities of microcrystalline cellulose + 1-butyl-3-methylimidazolium acetate ([bmIm][Ac]) solutions (0.6–1.2 wt%) in contact with CO₂ were measured at 312 K with a resonant vibrational viscometer. At 4 MPa and 312 K, the CO₂ could reduce the viscosity of 1.2 wt% cellulose + [bmIm][Ac] solution by about 80 %, whereas N₂ at the same conditions gave less than a 10 % reduction in viscosity. The viscosity-averaged degree of polymerization and IR spectrum showed that cellulose did not decompose during experiments and that [bmIm][Ac] acted as a non-derivatizing solvent during the dissolution and viscosity reduction process. Further, although CO₂ does react with [bmIm][Ac] to form 1-butyl-3-methylimidazolium-2-carboxylate, the reaction seems to be reversible and it does not affect the cellulose. Thus, [bmIm][Ac] with CO₂ provides an effective solvent for cellulose and the solvent system can probably be recycled or reused.     

Determination of Sulphur in Solid and Liquid Samples by Potentiometric Titration with Ion Selective Electrode.

Abstract

This paper describes a potentiometric method for the determination of sulphur in solid and liquid samples, using a sulphide ion selective electrode after the reduction distillation step. The determination of sulphide in solid and liquid samples without prior treatment was carried out by direct and titration potentiometric methods.

The reproducibility of the method and the recovery of sulphate in solid samples was investigated using analytical reagent grade 99% sodium sulphate. Portions of aproximately 100 mg of reagent were subjected to the reduction distillation process. After the ion selective electrode showed a stable value of the potential, indicating that all the sulphate had been reduced to sulphide, the potentiometric titration with lead nitrate solution was performed. A mean recovery of 98% of sulphate was found. The potentiometric titration method described in this work, can be applied to determine S⁼ in solid samples with the advantage that it does not require sample solubilization or extraction prior to the determination. The method yields an almost total reduction of sulphur and also a good precision.     

Kinetics and Mechanism of Cr(VI) Reduction in a Water Cathode Induced by Atmospheric Pressure DC Discharge in Air

The process of reduction of Cr⁶⁺ ions (solution of potassium dichromate, K₂Cr₂O₇) in a water cathode was studied during a DC discharge in air. The concentration range of Cr⁶⁺ was (5.7–19) ×10^?5 mol/l and discharge current range was 20–80 mA. Cr⁶⁺ ions were shown to be reversibly reduced under a discharge action. The equilibrium degree of reduction increased with increasing initial concentration of the solution at fixed discharge current. At fixed initial concentration the reduction degree increased with increasing discharge current. The reduction degrees so obtained were 0.34–0.84. A kinetic scheme of the processes taking place in a solution was proposed. The calculated data obtained as a result of application of this scheme described well the experimental results on Cr⁶⁺ kinetics. The main processes of Cr⁶⁺ reduction and Cr³⁺ oxidation were revealed. HO ₂ ^· radicals and hydrogen peroxide were shown to be responsible for Cr⁶⁺ reduction whereas ^·OH radicals and O₂ molecules provide the reverse process of Cr³⁺ oxidation to Cr⁶⁺. The mechanism of action of phenol additives improving the process efficiency is discussed. The efficiency of phenol action as a radical scavenger was shown to be determined with its mass-transfer to the reaction area rather than chemical reaction rate.     

Theoretical study on the radical–radical reaction mechanism of CH2I + NO2

The mechanisms of CH₂I with NO₂ reaction were investigated on the singlet and triplet potential energy surfaces (PESs) by the UB3LYP method. The energetic information is further refined at the UCCSD(T) and UQCISD(T) levels of theory. Our results indicated that the title reaction is more favorable on the singlet PES thermodynamically, and less competitive on the triplet one. On the singlet PES, the title reaction is most likely to be initiated by the carbon-to-oxygen approach forming the adduct IM1 (H₂ICONO-trans) without any transition state, which can isomerizes to IM2 (H₂ICNO₂) and IM3 (H₂ICONO-cis), respectively. The most feasible pathway is the 1, 3-I shift with C–I and O–N bonds cleavage along with the N–I bond formation of IM1 lead to the product P1 (CH₂O + INO), which can further dissociate to give P3 (CH₂O + I + NO). The competitive pathway is 1, 3-H shift associated with O–N bond rupture of IM1 to form P2 (CHIO + HNO). The theoretically obtained major product CH₂O and adducts IM1 and IM2 are in good agreement with the kinetic detection in experiment. The similarities and discrepancies between CH₂I + NO₂ and CH₂Br + NO₂ reactions are discussed in terms of the electronegativity of halogen atom and the barrier height of the rate-determining process. The present study may be helpful for further experimental investigation of the title reaction.     

Electrocatalytic activity of carbon-supported metallophthalocyanine catalysts toward oxygen reduction reaction in alkaline solution

Carbon-supported metallophthalocyanine catalysts, composed of a transition central metal M (M = Co, Mn, Ni, Fe) in the phthalocyanine ring, were synthesized in this work. As cathodic reaction in a fuel cell, the oxygen reduction reaction (ORR) was investigated in alkaline medium with linear scanning voltammetry at the surface of these electrocatalysts deposited onto a rotating disk electrode (RDE). It was found that the number of electrons transferred depended on the nature of the metallic cation in the catalyst. Evidences provided with Koutecky-Levich approach showed that iron phthalocyanine (FePc) exhibited the better electrocatalytic ability toward the ORR with four electrons exchanged and low activation overpotential. Among these different as-prepared materials, MnPc and FePc led to a four-electron pathway, while CoPc and NiPc proceeded by a two-electron route. The latter reaction process was also determined with a rotating ring-disk electrode (RRDE), which allowed the determination of hydrogen peroxide formed as O₂ reduction intermediate in a small amount, i.e., less than 1.2 %.     

Reduction Reaction of the Copper(II) Complex Bearing 1,3-Di(pyridine-2-carboxaldimino)propane (pitn) by Decamethylferrocene in Acetonitrile

The reduction reaction of the Cu(II)–pitn complex (pitn = 1,3-di(pyridine-2-carboxaldimino)propane) by decamethylferrocene [Fe(Cp*)₂] was examined in acetonitrile. The observed pseudo-first-order rate constants exhibited saturation kinetics with increasing excess amount of [Fe(Cp*)₂]. Detailed analyses revealed that the reaction is controlled by a structural change prior to the electron transfer step, rather than a conventional bimolecular electron transfer process preceded by ion pair (encounter complex) formation. The rate constant for the structural change was estimated to be 275 ± 13 s^?1 at 298 K (?H* = 33.3 ± 1.0 kJ·mol^?1, ?S* = 86 ± 5 J·mol^?1·K^?1), which is the fastest among gated reactions involving CuN₄ complexes. It was confirmed by EPR measurement and Conflex calculations that the dihedral angle between the two N–N planes is significantly large (40°) in solution whereas it is merely 17.14° in the crystal.     

Determination of Riboflavin Using the Polarographic Reduction Wave of Its Photochemical Reaction Products

Abstract

A new, simple, and sensitive method for the determination of riboflavin based on the single-sweep polarographic reduction wave of the photolysis products of riboflavin has been developed. Under the irradiation of an iodine-tungsten lamp, the photolysis reaction of riboflavin in pH 9.3 NH₃-NH₄Cl buffer solution can be complete in about 20 min. The reaction products yield a single adsorptive reduction wave at ?0.63 V (vs. SCE) negative to the reduction wave of riboflavin by 0.18 V. The derivative wave height is linearly proportional to the concentration of riboflavin in the range of 0.01–17.5 µg/mL (correlation coefficient 0.996). The detection limit is 0.00 5µg/mL. The proposed method has been applied to the determination of multivitamin tablets with satisfactory results. In comparison with the methods directly using the reduction wave of riboflavin for the determination, this method eliminates the effect of the degradation of riboflavin on the determination accuracy and is much more sensitive. The new method could be useful in many fields.