Iron adsorption on SiO2/Si(111)

The adsorption of ferric and ferrous iron onto the native oxide of the SiO₂/Si(111) surface has been evaluated using X‐ray photoelectron spectroscopy (XPS). Through a series of immersion experiments, performed at room temperature and pH 1, it has been shown that the ferric species is strongly adsorbed onto the hydrophilic surface, while ferrous iron remains in solution. Dehydroxylation of the silica surface by etching with hydrofluoric acid reduces the concentration of receptive Si‐OH groups, thereby limiting iron adsorption. The experiments were reproduced in a combined ultrahigh vacuum‐electrochemical system (UHV‐EC), which allowed a carbon‐free surface to be prepared before contacting the iron solutions, and confirmed the strong affinity of ferric iron towards the SiO₂/Si(111) surface. Copyright © 2007 John Wiley & Sons, Ltd.     

Grafting polymerization of acrylic acid onto preirradiated polypropylene fabric

Acrylic acid (AAc) was grafted onto polypropylene (PP) fabric by a preirradiation method using a Co-60 gamma ray. The effect of absorbed dose, AAc concentration, reaction temperature, reaction time, storage time, as well as the effect of ferrous ion and sulfuric acid on the degree of grafting were determined. It has been shown that the synergistic effect of sulfuric acid with the ferrous sulfate can not only increase the grafting yield, but also decrease the apparent activation energy for the grafting. It leads to the possibility of getting a particular grafting yield at a lower absorbed dose. In this experiment, It has also been shown that the grafting activity of preirradiated PP fabric in AAc aqueous solution could be well kept at room temperature for a long period.     

Experimental and First‐Principles Characterization of Functionalized Magnetic Nanoparticles

Magnetic iron oxide nanoparticles synthesized by coprecipitation and thermal decomposition yield largely monodisperse size distributions. The diameters of the coprecipitated particles measured by X‐ray diffraction and transmission electron microscopy are between approximately 9 and 15 nm, whereas the diameters of thermally decomposed particles are in the range of 8 to 10 nm. Coprecipitated particles are indexed as magnetite‐rich and thermally decomposed particles as maghemite‐rich; however, both methods produce a mixture of magnetite and maghemite. Fourier transform IR spectra reveal that the nanoparticles are coated with at least two layers of oleic acid (OA) surfactant. The inner layer is postulated to be chemically adsorbed on the nanoparticle surface whereas the rest of the OA is physically adsorbed, as indicated by carboxyl O? H stretching modes above 3400 cm^?1. Differential thermal analysis (DTA) results indicate a double‐stepped weight loss process, the lower‐temperature step of which is assigned to condensation due to physically adsorbed or low‐energy bonded OA moieties. Density functional calculations of Fe–O clusters, the inverse spinel cell, and isolated OA, as well as OA in bidentate linkage with ferrous and ferric atoms, suggest that the higher‐temperature DTA stage could be further broken down into two regions: one in which condensation is due ferrous/ferrous– and/or ferrous/ferric–OA and the other due to condensation from ferrous/ferric– and ferric/ferric–OA complexes. The latter appear to form bonds with the OA carbonyl group of energy up to fivefold that of the bond formed by the ferrous/ferrous pairs. Molecular orbital populations indicate that such increased stability of the ferric/ferric pair is due to the contribution of the low‐lying Fe³⁺ t_2g states into four bonding orbitals between ?0.623 and ?0.410 a.u.     

Thermal treatment of whewellite—a thermal analysis and Raman spectroscopic study

Thermal transformations of natural calcium oxalate monohydrate known in mineralogy as whewellite have been undertaken using a combination of thermal analysis and Raman microscopy with the use of a thermal stage. High resolution thermogravimetry shows that three mass loss steps occur at 162, 479 and 684 °C.Evolved gas mass spectrometry shows that water is evolved in the first step and carbon dioxide in the second and third mass loss steps. The changes in the molecular structure of whewellite can be followed by the use of the in situ Raman spectroscopy of whewellite at the elevated temperatures. The whewellite is stable up to around 161 °C, above which temperature the anhydrous calcium oxalate is formed. At 479 °C, the oxalate transforms to calcium carbonate with loss of carbon dioxide. Above 684 °C, calcium oxide is formed.     

A radioactive tracer and radiation study of the stability of ferric and ferrous ions and ascorbic acid

A preliminary liquid-liquid extraction study of ferric and ferrous ions has been undertaken using the radioactive tracer technique with⁵⁹Fe as an indicator of iron. Various solvents were studied and suitable media and solvents were selected for the separation of the two oxidation states of iron. Such separation was used to study the effect of ascorbic acid and other reducing agents on the reduction of ferric ions. The oxidation of ferrous ions to the ferric state under the effect of gamma radiation from⁶⁰Co has also been investigated in the absence and presence of ascorbic acid, using spectrophotometry. In addition, a calculation of the amount of iron oxidized by gamma radiation is given with a discussion of its mechanism and possible effects on the metabolism of iron in the human body.     

Acrylonitrile - alkyl acrylate copolymers containing ferric chloride: A Mössbauer study

Acrylonitrile (AN)-methyl acrylate (MA), acrylonitrile (AN)-ethyl acrylate (EA), acrylonitrile (AN)-butyl acrylate (BA) copolymers with and without doping with ferric chloride were prepared by free radical polymerization at 70°C. Mössbauer spectrum shows no reduction of ferric species to ferrous during the copolymerization. TGA studies show that the addition of ferric chloride changes the thermal decomposition pattern of the copolymer. TGA analysis shows that the inclusion of ferric chloride stabilizes the copolymers by 20–25°C. Mössbauer studies of the copolymers heated at 300°C and 500°C for 15 min showed that during the thermal degration, Fe³⁺ species was reduced to Fe²⁺ and then finally it formed -Fe₂O₃.     

Heterogeneous-catalytic fischer reaction

The catalytic synthesis of 7-azaindole and its 2-methyl derivative has been accomplished for the first time by cyclization of acetaldehyde and acetone 2-pyridylhydrazones in the presence of -Al₂O₃ and fluorinated aluminum oxide. The temperature dependence of the yields of reaction products — azaindoles and 2-aminopyridine — was studied. The cyclization of acetaldehyde 2-pyridylhydrazone proceeds under more severe conditions. The maximum yield of 7-azaindole is 15% at 450° on fluorinated aluminum oxide. The yield of 2-methyl-7-azaindole reaches 50% at 315°. Fluorinated aluminum oxide displays higher catalytic activity.See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 656–658, May, 1972.     

Mössbauer study of ferric oxide particles as products of thermal decomposition of iron/III/benzoate

The products of the thermal decomposition in air of iron/III/benzoate [Fe₃/C₆H₅COO/₆/OH/₂]OH.H₂O have been studied using conventional thermal analysis, X-ray diffraction measurements and mainly Mössbauer spectroscopy. The decomposition occurs in the temperature range 200–350°C. It was possible to identify benzoic acid and ferric oxide as final products. Above 300°C, the observed ferric oxide showed a particle size distribution, which depends on the heating temperature and the heating time interval, as evidenced by the following detected phases: superparamagnetic -Fe₂O₃ and magnetically ordered state with crystal structure of the phases -Fe₂O₃ and -Fe₂O₃. Also, two iron/III/ benzoate complexes having four and three ligands within the coordination sphere are suggested as intermediate products.     

Computational study of the catalytic synthesis of 5‐nitro‐1,2,4‐triazol‐3‐one

In this study, 5‐nitro‐1,2,4‐triazol‐3‐one (NTO) was theoretically synthesized from urea via chlorination followed by amination, formylation, and nitration under aqueous and gaseous environments based on experience of experimental methods, and metal chlorides and metal oxides were used as catalysts to promote reaction. Reaction routes closely related to experimental processes were successfully constructed, and the corresponding energy barriers were estimated for each elementary reaction. Reaction conditions distinct from those reported in the literature (including the adoption of aluminum chloride, ferric chloride, aluminum oxide, ferrous oxide, and chromium oxide catalysts, the use of nitric acid and dinitrogen pentoxide as nitration agents, and adjustment of the reaction temperature) were used in corresponding reaction systems, and the modeling results suggested that ferric chloride is a good catalyst for the chlorination reaction, ferrous oxide is suitable for catalyzing amination, formylation, and nitration, and nitric acid is the better agent for nitration. Estimates of the comparable energy barriers for each reaction stage were considered to imply more feasible pathways for NTO synthesis. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Spectrophotometric determination of anions by reextraction through the exchange of ligands: The determination of traces of oxalate using ferric indol-2-carboxylate in isoamyl alcohol

In this paper an indirect spectrophotometric method is proposed to determine oxalate, by a new technique called “reextraction through the exchange of ligands.” This new method is based on the decoloration produced in organic solutions of colored complexes when mixed with aqueous solutions of complexing anions.The established procedure for the preparation of solutions of ferric indole-2-carboxylate in isoamyl alcohol is given, as well as a discussion of the variables which influence the reextraction through the exchange of ligands.Finally, the technique was applied in determining traces of oxalate in an aqueous solution. The decoloration varies linearly with the oxalate concentration between 1 and 6 ppm. The error and reproducibility of the method were calculated. Also studied were the value of the constant of exchange and the interferences caused by various ions.     

Radiation synthesis of superabsorbent polyethylene oxide/tragacanth hydrogel

A new superabsorbent hydrogel has been prepared from tragacanth and polyethylene oxide (PEO) by gamma radiation at room temperature. Tragacanth solutions with different concentrations (1%, 3% and 5%) have been blended with 5% aqueous solution of PEO at a ratio of 1:1 and irradiated at doses 5–20 kGy. The properties of the prepared composite hydrogels were evaluated in terms of the gel fraction and the swelling behavior. An unexpected growth of the gel fraction was observed in PEO/tragacanth hydrogels irradiated at 5 kGy. Incorporation of 5% tragacanth into the aqueous PEO increased significantly the swelling percent of the hydrogels to more than 14,000% and thus makes it a superabsorbent material.     

Sol-Gel Preparation of Coating Films Containing Noble Metal Colloids

Coating films containing Au, Ag, Pt and Pd metal colloids have been prepared by sol-gel processing. It is shown that for oxide films the temperature where the metal particles are precipitated by heating in air depends on metal species: 200°C for Au, 600°C for Ag, 800°C for Pt and 1000°C for Pd. The use of reducing atmosphere lowers the temperature for formation of noble metal colloids. This procedure can be used for direct formation of metal colloids from metal ions in the film as well as reduction of oxide particles to metal particles in the film. For an organic-inorganic matrix, noble metal colloids are precipitated by thermal reduction or photo-reduction. Thermal reduction occurs as a result of reduction by decomposing organic matter. Photo-reduction occurs as a result of UV irradiation.     

Dielectric behavior of polyaniline synthesized by different techniques

Polyaniline doped with dodecylbenzenesulfonic acid (Pani.DBSA) was synthesized by different procedures: by a dedoping-redoping process, by one step inverted emulsion polymerization and by one step aqueous dispersion polymerization. The effect of these different techniques on the electric properties (dielectric constant, dielectric losses, and complex electric modulus) of the corresponding emeraldine base has been studied by thermal dielectric analyzer (DETA) in the temperature range −130 °C to 200 °C and in frequency range 0.03-10⁵ Hz. It was found that the preparation technique has significant influence on the dielectric properties of Pani. The different synthetic routes give rise to polyaniline with different distribution of electric relaxation process, indicating different chain structure. Emeraldine base from Pani.DBSA prepared by one step aqueous dispersion polymerization exhibits one single relaxation peak with narrow distribution whereas that prepared by inverted emulsion polymerization exhibits two relaxation peaks, indicating two-phase structure as indicated by a bimodal distribution of relaxation process. Emeraldine base from Pani.DBSA prepared by dedoping-redoping process presents an intermediary behavior. Percentage crystallinity of Pani.DBSA samples has also been investigated using wide-angle X-ray diffraction analysis. Pani.DBSA prepared by aqueous dispersion exhibited higher crystallinity degree, which agrees with the higher conductivity.     

Reactions of Elemental Phosphorus and Phosphine with Electrophiles in Superbasic Media: XI.1 Phosphorylation of 4-Methoxybenzyl Chloride with Elemental Phosphorus and Phosphine

4-Methoxybenzyl chloride reacts with elemental (red or white) phosphorus under the conditions of phase-transfer catalysis (concentrated aqueous KOH, dioxane, benzyltriethylammonium chloride, 85-90°C, argon) to give as major product tris(4-methoxybenzyl)phosphine oxide in up to 45% yield. With white phosphorus at lower (70°C) temperature this reaction yields mainly bis(4-methoxybenzyl)phosphine oxide. Phosphine reacts with 4-methoxybenzyl chloride in superbasic KOH-DMSO suspension, and under definite conditions bis(4-methoxybenzyl)phosphine oxide is predominantly formed.     

Effect of Different Treatments on the Reducibility of NiO—Y2O3 Mixed Oxides by Hydrogen

Some physico-chemical properties and reactivity in their reduction with hydrogen of NiO—Y₂O₃ mixed oxides prepared in a dry way have been studied using isothermal thermogravimetry in the range of 320–410°C and temperature-programmed reduction. It was found that addition of small amounts of chloride and acetate anions retarded the reduction of nickel oxide and accelerated the reduction of mixed oxides. The presence of oxalate and formate ions manifests itself by a small positive effect. Introduction of platinum activator or heat treatment of the samples in various atmospheres led to a pronounced increase in the reduction rate. The efficiency of the spill-over effect increases with increasing proportion of non-reducible Y₂O₃. The pre-irradiation of the samples by accelerated electrons and gamma rays at a dose of 1 MGy results in a negative kinetic effect only with the samples containing an excess of nickel oxide.This revised version was published online in November 2005 with corrections to the Cover Date.     

Combustion Derived Ultrafine γ-Fe2O3 Structure,morphology and thermal studies

A novel combustion method of employing poly(ethylene glycol) with the precursor in a fixed ratio for the synthesis of ultrafine γ-Fe₂O₃ through a self-propagating combustion synthesis is reported. Four different precursors viz. ferrous hydroxide, ferrous oxalate dihydrate, ferric 8-hydroxyquinoline and ferric acetylacetonate are employed in this study for the conversion of these precursors to ultrafine g-Fe₂O₃ particles. The as synthesized γ-Fe₂O₃ samples are characterized by XRD, SEM and thermal techniques. A case study for the synthesis of γ-Fe₂O₃ employing ferric acetyl acetonate as precursor is reported. The importance of employing thermal analysis techniques in understanding the combustion synthesis is envisaged. This revised version was published online in July 2006 with corrections to the Cover Date.     

Reverse micellar based synthesis of ultrafine MgO nanoparticles (8-10 nm): characterization and catalytic properties

Anisotropic nanostructures of magnesium oxalate dihydrate were synthesized using cationic surfactant based microemulsion method. The cationic surfactant plays an important role in forming the anisotropic structures. The oxalate nanostructures acts as an excellent precursor for the synthesis of fine magnesium oxide nanoparticles (~10 nm). Both the precursor and the oxide were characterized by using PXRD, IR, surface area and HRTEM. The surface area of these surfactant free oxide nanoparticles was found to be 108 m(2)/g. The catalytic activity of this basic oxide was examined for the Claisen-Schmidt condensation reaction and was found to be comparable to the best reported for the conventionally prepared MgO. Chalcone formation was found to increase with time as observed using gas chromatography-mass spectrometry (GC-MS). The reusability of the catalyst was checked by using the same catalyst twice which showed a reduced percentage (50% compared to first cycle) conversion.     

Extraction of cobalt by the AOT microemulsion system

The extraction of cobalt by Winsor II microemulsion system was studied. In the bis (2-ethylhexyl) sulfosuccinate sodium salt (AOT)/n-pentanol/n-heptane/NaCl system, AOT was used as a anionic surfactant to form microemulsion in n-heptane, n-pentanol was injected in the microemulsion as a cosurfactant. Co(II) was found to be extracted into the microemulsion phase due to ion pair formation such as Co²⁺(R–SO₃ ⁻)Cl. The influence of different parameters such as the volume ratio of aqueous phase to microemulsion, surfactant concentration, pH of the feed solutions, cosurfactant concentration as well as temperature on the extraction yield (E%) were investigated. The results showed that it was possible to extract 95% of cobalt by the AOT Winsor II microemulsion.     

Synthesis of a new smart temperature responsive glycopolymer via click-polymerisation

A novel temperature responsive water-soluble glycopolymer was synthesised via copper wire-catalysed click-polymerisation. Di-hydroxyl terminated poly(ethylene glycol) was quantitatively alkyne end-capped to yield di-alkyne terminated poly(ethylene glycol) (DAT-PEG). 2,3,4,2′,3′,4′-hexa-O-acetyl-6,6′-diazido-6,6′-dideoxy-α,α-D-trehalose (HADADT) was prepared from the di hydrated α,α-D-Trehalose by tosylation/acetylation followed by azidation. Click-polymerisation reaction between DAT-PEG and HADADT was successfully carried out to produce an alternating glycopolymer with triazole rings as linkers in high yield. All the intermediates as well as the glycopolymer were fully characterised by NMR, MS, IR, SEC, TGA and DSC. The cloud point of the aqueous solution of glycopolymer was investigated by optical microscopy and UV–vis spectroscopy. The LCST was found to be within physiological range of about 39 °C, known as fever temperature.