On the role of C<Subscript>2</Subscript>O radicals in the prompt-NO mechanism

The measurements of NO concentrations in the post-flame zone of different hydrocarbon + O₂ + N₂ flames at standard temperature and atmospheric pressure available in the literature are compared with predictions of the original Konnov reaction mechanism and with the same mechanism extended by the reaction of C₂O with N₂. The goal was to investigate the possible role of this reaction proposed by Williams and Fleming [Proc. Combust. Inst., Vol. 31 (2007), pp. 1109–1117]. This new reaction of C₂O with N₂ seems to be a reasonable explanation of the deficiencies in the prompt-NO route. Direct comparisons of the experimental measurements performed in different flames with the modeling strongly suggests that the upper limit of this reaction rate constant is k = 7 · 10¹¹ exp(−17,000/RT) [cm³/(mole · sec)]. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 5, pp. 3–7, September–October, 2008.     

Electrocatalytic oxidation of ethanol on Sn<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Ir<Subscript>(<Emphasis Type="Italic">x</Emphasis>)</Subscript>O<Subscript>2</Subscript> electrodes in acid medium

The electrochemical oxidation of ethanol at Sn_(1−x)Ir _x O₂ electrodes (with x = 0.01, 0.05, 0.1 and 0.3) was studied in 0.1 mol L⁻¹ HClO₄ solution. Electrolysis experiments were carried out and the reaction products were analyzed by Liquid Chromatography. It was found that the amounts of the reaction products depended on the composition of the electrode. In situ infrared reflectance spectroscopy measurements were performed to identify the adsorbed intermediates and to postulate a reaction mechanism for ethanol electrooxidation on these electrode materials. As evidence, acetaldehyde and acetic acid were formed through a successive reaction process. Carbon dioxide was also identified as the end product, showing that the cleavage of the carbon–carbon bond occurred. These results indicate that the synthesized catalysts are able to lead to the total combustion of organic compounds. Analysis of the water bending band at different potentials illustrated its role at the electrode interface.     

Low-temperature anti-icing reagents in the Ca(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-Mg(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-CO(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>-H<Subscript>2</Subscript>O system and their properties

The polytherms of ice melting in sections of the Ca(NO₃)₂-Mg(NO₃)₂-CO(NH₂)₂-H₂O system with different component ratios were studied in the temperature interval from 0 to −40°C. A series of nitrate and nitrate-carbonate reagents that are promising for the creation of anti-acing reagents were found, which form eutectics with ice at temperatures from −25 to −39°C. Their properties, viz., melting properties with respect to ice and corrosiveness on metals and alloys, were determined. An effective corrosion inhibitor was selected.     

Mitigation of N<Subscript>2</Subscript>O and CH<Subscript>4</Subscript> Emission from Rice and Wheat Cropping Systems Using Dicyandiamide and Hydroquinone

Agriculture contributes considerably to the emission of greenhouse gases, such as N₂O and CH₄. Here we summarize results from previous pot experiments assessing the effectiveness of urease and nitrification inhibitors reducing both N₂O and CH₄ emissions from wheat and rice cropping systems fertilized with urea (U). For the wheat cropping system, using a cambisol, we observed that the application of U with hydroquinone (HQ, a urease inhibitor), U with dicyandiamide (DCD, a nitrification inhibitor) and U with HQ plus DCD decreased the N₂O emissions by 11.4, 22.3 and 25.1%, respectively. For the rice copping system, using a luvisol, we found that the application of U with HQ, U with DCD and U with HQ plus DCD decreased N₂O emissions by 10.6, 47.0 and 62.3%, respectively, and CH₄ emissions by 30.1, 53.1 and 58.3%, respectively. In terms of total global warming potential (GWP) a reduction of 61.2% could be realized via the combined addition of HQ and DCD. The addition of wheat straw reduced the activity of HQ and DCD in the rice cropping experiments. In terms of total GWP only a reduction of 30.7% could be achieved. In general, both in upland and flooded conditions, the application of HQ and DCD alone was less effective than HQ in combination with DCD, but not significantly for U plus DCD treatment. Our observations may be further constrained, however, by practical, economic or social problems and should therefore be tested at the scale of a region (e.g. a watershed) and related to an integrated abatement of agricultural N losses.     

Synthesis and characterization of zeolite mazzite analogue in Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–Piperazine–H<Subscript>2</Subscript>O

Zeolite Mazzite (MAZ) analogue was synthesized directly using piperazine as a structure directing agent. The reactive gel composition used was (5.0–7.0) piperazine:(6.0–7.0) Na₂O:Al₂O₃:20.0SiO₂:400H₂O. Using this composition, the reaction time was shortened greatly to 4 days and the crystallization time was reduced as well. The DTA data showed that piperazine, in as-synthesized zeolite omega decomposed easily. The decomposition of the piperazine occurred at 400–480°C. NH₃-TPD analysis proved that zeolite H-omega from piperazine had strong surface acidity with ammonia desorption temperature up to 590°C.     

Combustion and structure formation in the Ti-Ta-C-Ca<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> system

Biocompatible composites (Ti, Ta)C _x + Ca₃(PO₄)₂ for deposition of nanofilms onto load-bearing implants by ion-plasma sputtering were prepared from Ti + Ta + C + Ca₃(PO₄)₂ mixtures by forced SHS compaction. The effect of Ta + C addition to green mixtures (characterized by parameter z) on the structure/phase formation in combustion products was explored. The addition of tantalum and carbon was found to have little or no influence on the burning velocity U and combustion temperature T _c. Two thermal spikes exhibited by thermograms were associated with the occurrence of two consecutive reactions leading to formation of titanium and tantalum carbides. With increasing z, the grain size of (Ti, Ta)C was found to diminish, its relative density to decrease, while the hardness to markedly grow.      

Impacts of Water Table Management on N<Subscript>2</Subscript>O and N<Subscript>2</Subscript> from a Sandy Loam Soil in Southwestern Quebec,Canada

Nitrous oxide (N₂O) is primarily produced as intermediate in denitrification and, to a lesser extent, through nitrification processes. Nitrous oxide emission and, consequently, its atmospheric impacts depend on the extent to which N₂O is reduced to dinitrogen gas (N₂) by denitrifiers. Field experiments were conducted from 1998 through 2000 growing seasons at St. Emmanuel, Quebec, Canada, to investigate the combined impact of water table management (WTM) and N fertilization rate on the soil denitrification (N₂O + N₂) rate, rate of N₂O production, and the N₂O:N₂O + N₂ ratio. Water table treatments included subirrigation (SI) with a target water table depth of 0.6 m and free drainage (FD) with open drains. The tile drains (75 mm diameter) were laid at a 1.0 m depth from the soil surface. Nitrogen fertilizer was applied at two rates:120 and 200 kg N ha⁻¹ as ammonium nitrate (34-0-0). The N₂O + N₂ evolution rates were greater in SI (12.9 kg N ha⁻¹) than in FD (5.8 kg N ha⁻¹) plots. The percentages of N₂O relative to overall N₂O + N₂ evolution were 35 and 11% for 1998, 29 and 8% for 1999, and 37 and 20% for 2000, under FD and SI, respectively. The reduced N₂O production under SI was due to a greater reduction of N₂O to N₂. Results indicate that greater N₂O + N₂ evolution under shallow water tables are not necessarily accompanied by higher N₂O emissions.     

Electrochemical oxidation of 4-chlorophenol and its by-products using Ti/Ru<Subscript>0.3</Subscript>M<Subscript>0.7</Subscript>O<Subscript>2</Subscript> (M = Ti or Sn) anodes: preparation route versus degradation efficiency

The electrochemical degradation of 4-chlorophenol and its main by-products was investigated in acid medium using binary oxides electrodes of nominal composition Ti/Ru_0.3Ti_0.7O₂ and Ti/Ru_0.3Sn_0.7O₂ prepared by thermal decomposition through two different routes: inorganic precursors dissolved in isopropanol and polymeric precursors (PPM). The aim of this study was to investigate the influence of both the composition and preparation methodology of these electrodes in the electrooxidation of the organic pollutants 4-chlorophenol and its by-products. Electrolyses were carried out using a filter press-type flow cell and monitored by high performance liquid chromatography (HPLC), total organic carbon (TOC), and chloride analyses. Besides CO₂, the by-products formed in the reactions were 1,4-benzoquinone, 4-chlorocatechol, and hydroquinone, as well as oxalic, maleic, malic, malonic, and succinic acids. The electrocatalytic efficiency with respect to the degradation of by-products was evaluated through the electrooxidation of 1,4-benzoquinone and oxalic acid (OA). The anodes investigated in this work are very promising for the degradation of pollutants because of their excellent efficiency concerning the consumption of 4-chlorophenol and its by-products, although the mineralization of the starting material is not complete. The cleavage of the aromatic ring occurs preferentially in the case of electrodes prepared by decomposition of inorganic precursors due to their larger electrochemically active area and electrocatalytic activity for oxygen evolution reaction (OER). However, OA oxidation is favored on Ti/Ru_0.3Sn_0.7O₂ prepared through decomposition of PPM.     

Conversion of CH<Subscript>4</Subscript> and CO<Subscript>2</Subscript> to syngas and higher hydrocarbons using dielectric barrier discharge

The conversion of methane to syngas and other hydrocarbons in dielectric barrier discharge plasma under the presence of CO₂ was investigated. Effects of the input voltage on the conversion of methane and CO₂ and the ratio of syngas were analyzed experimentally. The results of numerical simulations showed good quantitative agreement with those of experiments.     

Synergism Between Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Au/TiO<Subscript>2</Subscript> in the Low Temperature Oxidation of Propene

CO impedes the low temperature (<170 °C) oxidation of C₃H₆ on supported Pt. Supported Au catalysts are very effective in the removal of CO by oxidation, although it has little propene oxidation activity under these conditions. Addition of Au/TiO₂ to Pt/Al₂O₃ either as a physical mixture or as a pre-catalyst removes the CO and lowers the light-off temperature (T ₅₀) for C₃H₆ oxidation compared with Pt catalyst alone by ~54 °C in a feed of 1% CO, 400 ppm C₃H₆, 14% O₂, 2% H₂O.     

Kinetics of the nanocrystal formation in the ZrO<Subscript>2</Subscript>-In<Subscript>2</Subscript>O<Subscript>3</Subscript>-H<Subscript>2</Subscript>O system under hydrothermal conditions

The hydrothermal synthesis of nanocrystals in the ZrO₂-In₂O₃-H₂O system is investigated kinetically. The presence of indium hydroxide results in an increase in the dehydration temperature of this system. The size of nanocrystals is equal to 20–30 nm and virtually does not depend on the temperature and time of hydrothermal treatment or on the type of crystalline modification of ZrO₂. An increase in the synthesis temperature leads to an increase in the fraction of the monoclinic zirconia modification.Original Russian Text Copyright © 2005 by Fizika i Khimiya Stekla, Artamonova, Almjasheva, Mittova, Lavrushina, Gusarov.     

Subsoil <Superscript>15</Superscript>N-N<Subscript>2</Subscript>O Concentrations in a Sandy Soil Profile After Application of <Superscript>15</Superscript>N-fertilizer

Studies on emissions of nitrous oxide (N₂O) from agricultural soils mostly focus on fluxes between the soil and the atmosphere or are limited to the atmosphere in the topsoil. However, in soils with shallow water tables, significant N₂O formation may occur closer to the groundwater. The aims of this study were (i) to determine the importance of subsoil N₂O formation in a sandy soil; and (ii) to obtain a quantitative insight in the contribution of subsoil N₂O to the overall losses of N₂O to the environment. We applied ¹⁵N labeled fertilizer at a rate of 5.22 kg ¹⁵N ha⁻¹; 50% as Ca(NO₃)₂ and 50% as NH₄Cl, on a mesic typic Haplaquod seeded with potatoes (Solanum tuberosum L.), and traced soil N₂O concentrations and fluxes over a one-year period. Throughout the year, total N₂O and the amount of ¹⁵N recovered in soil N₂O were highest in the subsoil, with a maximum concentration at 48 cm depth in mid-February of 19900 μl m⁻³ and 24 μg ¹⁵N m⁻³, respectively. The maximum concentration coincided with the highest water-filled pore space of 71%. The cumulative flux of N₂O was 446 g N₂O-N ha⁻¹, the recovery of ¹⁵N in this flux was 0.06%. During the summer, maximum fluxes followed high soil N₂O concentrations. During winter, no such relation was found. We concluded that the formation of N₂O was the highest in the subsoil, largely controlled by water-filled pore space rather than NO₃⁻ concentration or temperature. Although high subsoil N₂O concentrations did not lead to high surface fluxes of N₂O in the winter, artificial draining may lead to high indirect N₂O emissions through supersaturated drainage water.     

Hydrolysis of titanium(IV) in the TiO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript>-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-H<Subscript>2</Subscript>O system during the preparation of a titanium silicate pigment

The hydrolysis of titanium(IV) sulfate during boiling in the presence of silica gel particles is considered. The scenario of solid-phase formation involves the sedimentation of hydrated titanium(IV) onto reactive silica gel particles; and individual phases of silicon(IV) and titanium(IV) hydroxides are formed. The quantitative ratio between the phases of the hydrated composition dictates the properties of its thermolysis products. Composition-property diagrams are plotted to determine the optimum parameters at which the titanium silicate product has high pigment properties.     

Separation characteristics of tetrapropylammoniumbromide templating silica/alumina composite membrane in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>, CO<Subscript>2</Subscript>/H<Subscript>2</Subscript> and CH<Subscript>4</Subscript>/H<Subscript>2</Subscript> systems

Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al₂O₃/ α-Al₂O₃ composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO₂/N₂, CO₂/H₂ and CH₄/H₂ systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al₂O₃ support and nanoporous unsupport (TPABr templating SiO₂/ γ-Al₂O₃ composite layer without α-Al₂O₃ support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al₂O₃ support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO₂ and CH₄. While the adsorption rates in the unsupport showed in the order of H₂> CO₂> N₂> CH₄ at low pressure range, the permeate flux in the membrane was in the order of H₂≫N₂> CH₄> CO₂. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO₂/H₂ and CH₄/H₂ systems. Although light and non-adsorbable molecules, such as H₂, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO₂ and CH₄, showed a higher separation factor (CO₂/H₂=5-7, CH₄/H₂=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Determination of the Diffusion Coefficient of H<Subscript>2</Subscript>O in Polyacrylonitrile Fiber Formation

An H₂O/dimethyl sulphoxide (DMSO) mixture was used as the coagulation bath of a wet-spun process. The diffusion coefficient of H₂O in the protofibers prepared by acrylonitrile homopolymers was determined. It was found that the diffusion coefficient of H₂O in the protofibers prepared by homopolymers synthesized by solution polymerization was highest compared with those of homopolymers synthesized by H₂O/DMSO mixture suspension polymerization and aqueous suspension polymerization. With an increase of polyacrylonitrile concentration in the dope, the diffusion coefficient of H₂O decreased continuously. The diffusion coefficient of H₂O increased along with the bath temperature, but the changes of diffusion coefficient values were less prominent as the temperature went beyond 60^○C. When the DMSO concentration in the coagulation bath was 55%, the value of the diffusion coefficient of H₂O was minimal. The diffusion coefficient of H₂O increased with increasing jet stretch minus ratio. When the protofiber radius was increased, there was a corresponding increase of the diffusion coefficient of H₂O.     

Electrical conductivity and structure of glasses in the Na<Subscript>2</Subscript>O-Na<Subscript>2</Subscript>S-P<Subscript>2</Subscript>O<Subscript>5</Subscript> and Na<Subscript>2</Subscript>S-P<Subscript>2</Subscript>S<Subscript>5</Subscript> systems

The glasses, in which oxygen was partially replaced with sulfur, have been synthesized in the Na₂O-P₂O₅-Na₂S system. The chemical and chromatographic analyses of the glasses synthesized have been performed. The temperature-concentration dependences of electrical conductivity of the glasses have been studied over a wide temperature range; the glass transition temperatures and the nature of charge carriers have been determined. The IR spectra and Raman spectra have been recorded at room temperature; the density and microhardness of the glasses and ultrasound velocity have been measured. A comparison of the electrical conductivities of the investigated glasses with those of the earlier studied glasses in the Na₂O-P₂O₅ system has shown their fair coincidence. The introduction of sodium sulfide into the Na₂O-P₂O₅ system is accompanied by an approximately threefold increase in electrical conductivity, although the concentrations of charge carriers (sodium ions) in the glasses amount to ∼17 and ∼26 mmol/cm³, respectively. The rise in electrical conductivity has been assumed to be caused by the increase in the degree of dissociation of polar structural chemical units including sulfide ions and by the higher mobility of sodium ions in the oxygen-free matrix.     

Crystallization and thermal transformations in nanocrystals of the YPO<Subscript>4</Subscript>-LuPO<Subscript>4</Subscript>-H<Subscript>2</Subscript>O system

Nanocrystals of yttrium lutetium phosphates of the general formula Y_1?x Lu_xPO₄ · nH₂O are synthesized. The temperature dependence of the nanocrystal size is investigated in the range 200–1100°C. The formation of a series of continuous solid solutions belonging to the tetragonal crystal system is revealed, and the limits of their thermal stability are determined.     

Preparation and thermal transformations of nanocrystals in the LaPO<Subscript>4</Subscript>-LuPO<Subscript>4</Subscript>-H<Subscript>2</Subscript>O system

Powders of nanosized particles of individual and mixed lanthanum and lutetium orthophosphates are synthesized. The grain growth process is studied in the temperature range of 200–1100°C. Temperature and concentration regions of existence of the solid solutions based on hexagonal and monoclinic forms of LaPO₄ as well as on tetragonal LuPO₄ are determined.     

The Oxidative Polycondensation of Benzylidene-4′-hydroxyanilene using Air O<Subscript>2</Subscript>, NaOCl and H<Subscript>2</Subscript>O<Subscript>2</Subscript>: Synthesis and Characterization

In this work, the oxidative polycondensation reaction conditions of benzylidene-4′-hydroxyanilene (B-4′-HA) were studied using oxidants such as air O₂, H₂O₂ and NaOCl in an aqueous alkaline medium between 40 and 95 ^○C. Oligo-benzylidene-4′-hydroxyanilene was characterized by ¹H-NMR, FT-IR, UV-Vis, size exclusion chromatography (SEC) and elemental analysis techniques. The solubility of oligomer using organic solvents such as DMF, THF, DMSO, methanol, ethanol, CHCl₃, CCl₄, toluene, acetonitrile, ethyl acetate was investigated. According to air O₂ oxidant (flow rate 8.5 L/h), the conversion of B-4′-HA was 82.0% in optimum conditions such as [B-4′-HA]₀=[KOH]₀=0.1015 mol/L at 50 ^○C for 25 h. According to the SEC analysis, the number-average molecular weight (M_n), weight-average molecular weight (M_w) and polydispersity index (PDI) values of O-B-4′-HA were found to be 1852 g mol⁻¹, 3101 g mol⁻¹ and 1.675; 2123 g mol⁻¹, 4073 g mol⁻¹ and 1.919; 2155 g mol⁻¹, 4164 g mol⁻¹ and 1.932, using air oxygen, NaOCl and H₂O₂ oxidants, respectively. Also, Thermo gravimetric analysis (TGA) showed oligo-benzylidene-4′-hydroxyanilene to be unstable against thermo-oxidative decomposition. The weight loss of O-B-4′-HA was found to be 95.87% at 1000 ^○C.