Measurement of Temperature and Concentration of OH Radicals in Combustion of Hydrogen and Ethanol by the Laser‐Induced Fluorescence Technique

Diffusion combustion of ethanol and hydrogen and homogeneous combustion of hydrogen–oxygen mixtures are studied by the laserinduced fluorescence technique in the linear regime and with signal saturation. Data on the flame temperature and OH concentration are obtained. The burning temperature of 3090 K for a stoichiometric O₂–H₂ mixture is in agreement with the known value. It is shown that the maximum concentrations of radicals in the hydrogen–air and stoichiometric hydrogen–oxygen flames are close to each other (4.4· 10¹⁶ cm^-3).     

Volumetric and Transport Properties of Aqueous NaB（OH）4 Solutions

Density, pH, viscosity, conductivity and the Raman spectra of aqueous NaB（OH）4 solutions precisely measured as functions of concentration at different temperatures （293.15, 298.15, 303.15, 313.15 and 323.15 K） are presented. Polyborate distributions in aqueous NaB（OH）4 solution were calculated, covering all the concentration range, B（OH）4 is the most dominant species, other polyborate anions are less than 5.0%. The volumetric and the transport properties were discussed in detail, both of these properties indicate that B（OH）4 behaves as a struc- ture-disordered anion.     

Degradation of Methyl β-D-Ribopyranoside and Methyl β-D-Xylopyranoside by Oxygen in Aqueous Sodium Hydroxide Solution

Methyl β-D-ribopyranoside (1) and methyl β-D-xylopyranoside (2) were degraded by oxygen (0.682 MPa partial pressure) in 1.25 M sodium hydroxide at 120°C. The degradations of 1 and 2 were similar to the previously reported degradations of 1,5-anhydroribitol (3) and 1,5-anhydroxylitol (4), respectively.⁴ Both hydrogen peroxide and stable organic peroxides were detected in the reactions of 1 and 2. The riboside 1 degraded faster than the xyloside 2. This difference in reactivity is proposed to be a function of the relative acidity of the glycosides. Ionization of hydroxyl groups is postulated to be favored in 1, thus facilitating the initiation of the free radical degradation. The degradations of both 1 and 2 exhibited complex kinetics indicating autoinhibited reactions. In spite of the differences in reactivity, glycosidic bond cleavage occurred in approximately 60% of the degradations for both 1 and 2. C-1 radicals, resulting from abstraction of the anomeric hydrogen atom, are proposed to cause the observed autoinhibition via termination reactions with α-hydroxyhydroperoxyl radicals. However, decomposition of the glycosides via C-1 radicals is not believed to constitute a major degradation pathway since the reactivities of 1 and 2 were essentially the same as the analogous 1,5-anhydroalditols, i.e. 3 and 4, respectively. The major acidic degradation products of 1 and 2 were identical, but were formed in different relative ratios. The major acidic products were methoxyacetic acid, lactic acid, glycolic acid, glyceric acid, a methyl 3-C-carboxyfuranoside, and two isomeric 2-C-carboxyfuranosides.     

Synthesis of the Precursor of Aluminum–Calcium Oxide Systems by Anodic Oxidation of Aluminum in Aqueous Solutions

An aluminum oxide system is obtained by electrolysis with a soluble anode and by the subsequent thermal treatment of the precipitate. It is shown that this system can be modified with calcium oxide in the process of synthesis. The influence of the synthesis conditions (the anodic current density and the electrolyte composition) on the formation of finely dispersed particles of the aluminum–calcium systems is studied. The structure and properties of the powder particles obtained by the electrochemical method are studied using the methods of laser diffraction, X-ray diffraction analysis, and electron microscopy.     

The Effect of Cobalt on the Degradation of Methyl β-D-Gluco-Pyranoside by Oxygen in Aqueous Sodium Hydroxide Solution

Abstract

The effect of Co(II) (0 to 0.25 mW CoSO₄) on the degradation of methyl β-D-glucopyranoside (MBG) at 120°C in 1.25M NaOH with 0.68 MPa oxygen pressure was studied. When the Co(II) was increased from 0.00 to 0.01 to 0.05 mM the MBG half-life decreased from 12 to 6 to 1.5 hours, reflecting approximately a 0.5 order kinetic dependence on cobalt. An oxidation-reduction cycle between Co(II) and Co(III) involving oxidation of Co(II) by oxygen and oxidation of the glucoside by Co(III), hydroxyl radical, or superoxide is proposed for the degradation. At the 0.25 mM Co(II) addition level highly adsorptive Co(OH)₂ formed prior to reaction initiation with oxygen and removed otherwise soluble cobalt from solution. This resulted in lower rates of MBG degradation than obtained even at 0.01 mM Co(II) addition. However, Co(II) solubility could be enhanced if silicate anions or polyols (including MBG) were added to the alklaine medium prior to the Co(II) addition. In reactions initially containing 0.25 mM soluble Co(II), an adsorptive precipitate, presumably CoO(OH), gradually formed after reaction initiation with oxygen. Precipitation of the Co(III) solid coincided with a rapid decline in the rate of MBG degradation. Cobalt had little effect on the products of MBG degradation.     

Solar Photocatalytic Degradation of Textile Dyes in TiO2 Suspended Solutions

The degradation and decolourization of direct dye (Everdirect supra turguoise blue, FBL), acidic dye (Isolan orange S-RL) and vat dye (Indanthren red FBB) have been investigated by solar/TiO2 process. The effects of solution pH, dye concentration, dosage of TiO2 and nano-size of TiO2 have been studied. The increase in initial pH (3, 5 and 11) and dye concentration decrease the removal rate. The treatment for FBB and FBL dye solutions is more efficient than that of S-RL.Under optimum conditions, the color removal is found to be almost complete for FBB and FBL while that of S-RL also reaches 95%. Langmuir adsorption isotherm and modified Langmuir-Hinshelwood kinetic model (L-H model) have been fitted to the experimental data and found to correlate the adsorption patterns as well as the kinetics of the dyes studied.     

Mechanisms of Oxidative Degradation of Carbohydrates During Oxygen Delignktcation. I. Reaction of Methyl β-D-Glucopyranoside with Photochemically Generated Hydroxyl Radicals

Abstract

Hydroxyl radical is considered to be the major species causing degradation of carbohydrates during oxygen delignification. In this study, reactions involving a carbohydrate model compound and either photochemically generated hydroxyl radical or superoxide from potassium superoxide were carried out to investigate the cleavage of glycosidic linkages. Experiments show that hydroxyl radicals are responsible for the degradation of glycosidic linkages in methyl β-D-glucopyranoside by a substitution reaction displacing D-glucose. Once the glycosidic linkage is broken, reducing carbohydrates undergo a series of reactions forming aldonic acids and lower order aldoses. Control experiments established that no reaction occurs in the absence of UV light under otherwise identical conditions.     

Imazalil Degradation upon Applying Ozone—Transformation Products,Kinetics, and Toxicity of Treated Aqueous Solutions

The elimination of the pesticide imazalil (IMZ) spiked into ultrapure water as well as into wastewater applying ozone (O₃) and the identification of transformation products was investigated. O₃ under hydroxyl radical suppression conditions reacted rapidly with the aliphatic double bond or the imidazole ring in IMZ, yielding several transformation products by partial oxidation. The structures of four oxidation products not yet described were characterized and identified after liquid chromatography coupled with high resolution, high mass accuracy, mass and tandem mass spectrometry (LC/MS and -MSⁿ) in ultrapure water. For two identified transformation products, generated via direct ozone attack on IMZ, formation pathways were proposed. In wastewater, only two of those transformation products were observed. Kinetics studies for the reaction of IMZ with O₃, evaluated by the competition kinetic method, resulted in a second-order rate constant k_O3,IMZ ～ (1.02 ± 0.03)?×?10⁵ M^?1 s^?1 at pH 6.6 ± 0.2, indicating that IMZ is completely transformed during the ozonation process. Tests of acute toxicity were performed applying a solution of IMZ in ultrapure water or treated wastewater to Daphnia magna. In both cases the decrease of toxicity was observed after ozone treatment.     

Phenylalanine Residues Are Very Rapidly Damaged by Nitrate Radicals (NO3⋅) in an Aqueous Environment

Kinetic studies revealed that nitrate radicals (NO₃⋅), which are formed through reaction of the noxious air pollutants nitrogen dioxide (NO₂⋅) and ozone (O₃), very rapidly oxidize phenylalanine residues in an aqueous environment, with overall rate coefficients in the 10⁸–10⁹ M⁻¹ s⁻¹ range. With amino acids and dipeptides as model systems, the data suggest that the reaction proceeds via a π-complex between NO₃⋅ and the aromatic ring in Phe, which subsequently decays into a charge transfer (CT) complex. The stability of the π-complex is sequence-dependent and is increased when Phe is at the N terminus of the dipeptide. Computations revealed that the considerably more rapid radical-induced oxidation of Phe residues in both neutral and acidic aqueous environments, compared to acetonitrile, can be attributed to stabilization of the CT complex by the protic solvent; this clearly highlights the health-damaging potential of exposure to combined NO₂⋅ and O₃.     

Micellization and Clouding Behavior of EO–PO Block Copolymer in Aqueous Salt Solutions

Aqueous solution properties of polyethylene oxide–block-polypropylene oxide–block-polyethylene oxide TBP [(PEO)₁₀₃(PPO)₃₉(PEO)₁₀₃] were studied in the presence of sodium salts with different anions (NaI, NaBr, NaCl, NaF, Na₂SO₄, Na₃PO₄) to investigate unimer-to-micelle transition [critical micelle concentration (CMC), critical micellization temperature (CMT)], micelle size and the phase separation (cloud point). This TBP, due to its very hydrophilic (80% PEO) nature does not form micelles at ambient temperatures. Micellization can be induced much below its CMT in water on addition of sodium salts having different anions. Analytical methods viz. fluorescence, FTIR and dynamic light scattering (DLS) were used to monitor the salt-induced micellization. The hydration of respective anion and resultant contribution to its salting-out effect was found to be the governing factor in promoting micellization. The presence of salt decreases the CMC, CMT and phase separation temperature. The salts affect the aggregation process in agreement with an order mentioned in Hofmeister series.     

Separation of Arsenic from Aqueous Solutions by Amino-Functionalized γ-Fe2O3-β-Zeolite

In this research, γ-Fe₂O₃-β-zeolite nanocomposite was synthesized and functionalized by 3-amino propyl trimethoxysilane. The magnetic functionalized adsorbent was characterized by FTIR, X-ray diffraction, thermal analysis, vibrating sample magnetometry, scattering electron microscopy, and N₂ adsorption-desorption techniques. The adsorbent was then used for adsorption of arsenic from aqueous solutions. At optimized conditions the adsorption capacity of 30 mg.g^?1 was obtained, which was higher than the previously reported values. The loaded adsorbent was easily separated from the solution by applying an external magnetic field. Regeneration of the adsorbent by NaOH solution indicated that 97% of the initial capacity was remained after four adsorption-regeneration cycles.     

Ozone-activated Carbon Mineralization of 17-α-Ethynylestradiol Aqueous Solutions

Ozone and activated carbon (AC) have been used on the removal of 17α-ethynylestradiol (ETOL), a pharmaceutical compound, and its oxidation by-products. Although single ozonation is not able to totally remove the by-products formed from the degradation of the parent compound (about 65% of TOC removal at pH 7 after 2-hour reaction), the ozone/AC system led not only to higher TOC removal at the same conditions (about 90% in the case of P110 Hydraffin AC) but also to lower ozone consumption. In addition, samples treated with the catalytic process presented ecotoxicity values lower than those resulting from the application of single ozonation.     

Distribution of Hydrogen Isotopes between Phases at Vapor–Liquid Equilibrium in Aqueous Salt Solutions

Theoretical Foundations of Chemical Engineering - A single separation effect between deuterium and protium was studied experimentally under phase equilibrium conditions in a water vapor–water...     

Synthesis of Novel Chelating Adsorbents for Boron Uptake from Aqueous Solutions

Two kinds of novel chelating adsorbents have been synthesized to separate boron from aqueous solutions. One is the boron-specific chelating resin, synthesized by the functionalization of macroporous poly (glycidyl methacrylate-co- trimethylolpropane trimethacrylate), with N-methylglucamine. The other is the organic-inorganic hybrid mesoporous SBA-15 with polyol functional groups, prepared by a two-step post-grafting method. The resin can adsorb boron in almost all pH range, and its maximum uptake capacity reaches 1.15 mmol/g. The present study of the polyol-functionalized SBA-15 shows that the post-grafting is successful and the resulting adsorbent has the uptake capacity of 0.63 mmol/g.     

Ultrafiltration of Aqueous Solutions of PVA‐Cu(II) Macromolecular Complex

Abstract

The hydrodynamic behavior of aqueous solutions of poly(vinyl alcohol) and poly(vinyl alcohol)–cupric complex and its effect on the performance in the concentration of the macromolecular cupric complex by ultrafiltration is considered in this study which implements various synthetic membranes in polyethersulfone. The polyelectrolyte–like behavior of poly(vinyl alcohol) is highlighted. This behavior disappears in the case of the macromolecular complex. The disappearance of the polyelectrolyte–like effect is explained by the modification of the macromolecular conformation induced by the formation of the complex which takes up a tightly packed conformation. The study of the effect of the variation of the pH and the ionic strength made it possible to observe that the increase of the pH is accompanied by the reduction of the medium viscosity and the increase of the flux through the ultrafilters and the increase of the ionic strength of the medium is accompanied by the increase of the thickness of the adsorbed solute layer. The study of the effect of the nature of the ionic species in solution on the hydrodynamic behavior of the aqueous solutions of the macrocomplex leads to the conclusion that the use of the cupric chloride salt, instead of the nitrate or the sulphate salts, in the preparation of the macrocomplex improves the hydrodynamic properties of the solution and enhances the performance of its treatment by means of the ultrafiltration process.     

Pseudo‐Hydroxide Extraction in the Separation of Sodium Hydroxide from Aqueous Solutions Using Alkyl Phenols

Abstract

Pseudo‐hydroxide extraction of sodium hydroxide from aqueous solution using four alkyl phenols of nearly identical molecular weight in 1‐octanol at 25°C was examined to understand the effect of alkyl substituents. The order of extraction strength among the four alkyl phenols tested was 4‐tert‐octylphenol>3,5‐di‐tert‐butylphenol>2,4‐di‐tert‐butylphenol>2,6‐di‐tert‐butyl‐4‐methylphenol. A good correlation with phenol pK _a was observed, indicating that extraction strength is determined by phenol acidity, as modified by steric effects in proximity to the phenol –OH group. The effective partition ratios (P _eff) of two phenols from 1 M NaOH solution were determined, showing that the phenols remain predominantly in the 1‐octanol phase even when converted to their sodium salts. However, the hydrophobicity of the tested phenols may not be sufficient for process purposes. The equilibrium constants for the governing extraction equilibria were determined by modeling the data using the program SXLSQI, supporting the cation‐exchange extraction mechanism. The proposed mechanism consists of two simple sets of equilibria for

1. Ion‐pair extraction to give Na⁺OH^? ion pairs and corresponding free ions in 1‐octanol the phase and

2. Cation exchange by monomeric phenol molecules (HAs) to form monomeric organic‐phase Na⁺A^? ion pairs and corresponding free organic‐phase ions.

Extraction of Piperine from Piper Nigrum (Black Pepper) by Aqueous Solutions of Surfactant and Surfactant + Hydrotrope Mixtures

Abstract

The effect of combining butyl benzene sulfonate as hydrotrope with a surfactant in aqueous solutions is investigated for isolation of piperine, an alkaloid, from black pepper. The standard free energy change associated with piperine solubilization in the aqueous solutions of surfactant and hydrotrope individually and in their mixtures is determined from the solubility of piperine in these solutions. A combination of sodium dodecyl sulfate (SDS) and the hydrotrope gives increased percentage extraction of piperine as compared to the hydrotrope alone. The piperine purity recovered from aqueous solutions was higher as compared to the purity of piperine recovered using organic solvents. The piperine crystallized from aqueous solutions of surfactants and hydrotrope also showed cleaner surfaces and uniform structures with sharp edges, unlike the particles crystallized from organic solvents.     

Low-Temperature NOX (x = 1, 2) Removal with •OH Radicals from Catalytic Ozonation over α-FeOOH

FeOOH(H), FeOOH(P) and FeOOH(O) prepared by hydrothermal, precipitant-hydrolysis and oxidation-hydrolysis methods were tested as ozonation catalysts for the low-temperature NO_X (x = 1, 2) removal. FeOOH(H) exhibits higher catalytic activities than FeOOH(P) and FeOOH(O), achieving 85.6% of NO_X removal efficiency with a low ozone concentration. Compared to FeOOH(P) and FeOOH(O), FeOOH(H) shows much higher BET surface areas and higher density of surface -OH, both of which are critical for the ?OH radical generation over the catalysts. These radicals can be successfully transferred into the duct under the coupling effect of hydroxyl radicals and O₃, oxidizing and removing the NO_X (x = 1, 2). Results of ion chromatography (IC) indicate that the oxidation products are all NO₃^? without any NO₂^? in the tail solutions.     

What Are Reactive Oxygen Species,Free Radicals,and Oxidative Stress in Skin Diseases?

Oxygen in the atmosphere is a crucial component for life-sustaining aerobic respiration in humans. Approximately 95% of oxygen is consumed as energy and ultimately becomes water; however, the remaining 5% produces metabolites called activated oxygen or reactive oxygen species (ROS), which are extremely reactive. Skin, the largest organ in the human body, is exposed to air pollutants, including diesel exhaust fumes, ultraviolet rays, food, xenobiotics, drugs, and cosmetics, which promote the production of ROS. ROS exacerbate skin aging and inflammation, but also function as regulators of homeostasis in the human body, including epidermal keratinocyte proliferation. Although ROS have been implicated in various skin diseases, the underlying mechanisms have not yet been elucidated. Current knowledge on ROS-related and oxidative stress-related skin diseases from basic research to clinical treatment strategies are discussed herein. This information may be applied to the future treatment of skin diseases through the individual targeting of the ROS generated in each case via their inhibition, capture, or regulation.