Heterogeneous reaction of NO2 on the surface of montmorillonite particles

The studies on heterogeneous reactions over montmorillonite, which is a typical 2:1 layered aluminosilicate, will benefit to the understanding of heterogeneous reactions on clay minerals. Montmorillonite can be classified as sodium montmorillonite or calcium montmorillonite depending on the cation presented between the different layers. Using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the heterogeneous reaction mechanism of NO₂ on the surface of montmorillonite was firstly investigated. Results showed that the reaction of NO₂ on the surface of sodium and calcium montmorillonite fit a first-order kinetics, and the reaction duration of calcium montmorillonite was longer than that of sodium montmorillonite under the dry condition. For either sodium or calcium montmorillonite, the uptake coefficient decreased as humidity increased.     

零价铁降解4-氯硝基苯动力学研究

实验采用无氧条件下不同浓度零价铁降解硝基芳香烃代表物4-氯硝基苯,研究4-氯硝基苯的降解速率及各产物的反应速率.根据化学反应计量学,通过准一级动力学方程对实验结果进行拟合,得到生成各产物反应速率,并利用穆斯堡尔技术检测零价铁的产物.结果表明,4-氯硝基苯的还原转化速率与零价铁浓度有关,中间产物4-氯亚硝基苯和4-氯苯基羟胺的生成和转化速率可通过拟合各反应速率得到.当零价铁浓度为1.04 g.L-1时4-氯硝基苯反应速率最快,反应速率常数为0.189min-1.反应过程中生成的亚铁离子在反应初期吸附在零价铁表面,各物质的生成和还原速率取决于零价铁表面的活性位点和各物质与零价铁之间的质量传递.     

流变相法制备包覆型CMC-Fe0及降解水中TCE的研究

以廉价环保的羧甲基纤维素钠(CMC)为表面修饰剂,采用流变相反应法制备包覆型纳米零价铁(CMC-Fe0),用XRD、SEM和TEM、氮气吸附-脱附手段对样品进行表征,并利用合成的零价铁粒子对三氯乙烯(TCE)进行还原脱氯反应.结果表明,当CMC-Fe0投加量为6 g·L-1,TCE初始浓度为5 mg·L-1时,反应40 h去除率达100%.包覆型CMC-Fe0对TCE的还原反应符合准一级反应动力学.最后,对反应产物进行了简单易行的回收.     

Spectrophotometric analyses of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in water

A simple and accurate spectrophotometric method for on-site analysis of royal demolition explosive(RDX) in water samples was developed based on the Berthelot reaction. The sensitivity and accuracy of an existing spectrophotometric method was improved by:replacing toxic chemicals with more stable and safer reagents; optimizing the reagent dose and reaction time; improving color stability; and eliminating the interference from inorganic nitrogen compounds in water samples. Cation and anion exchange resin cartridges were developed and used for sample pretreatment to eliminate the effect of ammonia and nitrate on RDX analyses. The detection limit of the method was determined to be 100 μg/L. The method was used successfully for analysis of RDX in untreated industrial wastewater samples. It can be used for on-site monitoring of RDX in wastewater for early detection of chemical spills and failure of wastewater treatment systems.     

On the explosion and flammability behavior of mixtures of combustible dusts

In the work presented in this paper, the explosion and flammability behavior of combustible dust mixtures was studied. Lycopodium, Nicotinic acid and Ascorbic acid were used as sample dusts.In the case of mixtures of two dusts, the minimum explosive concentration is reproduced well by a Le Chatelier's rule-like formula, whereas the minimum ignition energy is a linear combination of the ignition energies of the pure dusts.An unexpected behavior has been found in relation to the explosion behavior and the reactivity. When mixing Lycopodium and Nicotinic acid or Ascorbic acid, the rate of pressure rise of the mixture is much higher than the rate of pressure rise obtained by linearly averaging the values of the pure dusts (according to their weight proportions), thus suggesting that strong synergistic effects arise; but it is comparable to that of the most reactive dust in the mixture.The observed behavior seems to be linked to the presence of minerals in the Lycopodium particles which catalyze oxidation reactions of Nicotinic acid and Ascorbic acid, as suggested by TG analysis.In the case of mixtures of three dusts, a similar behavior is observed when the concentration of Lycopodium is twice that of the other two dusts.     

真空紫外光降解瓦斯反应动力学规律

为了研究真空紫外光降解瓦斯过程的反应动力学规律,在自制的真空石英光化学反应器中以含甲烷标准气体模拟矿井瓦斯,运用Langmuir-Hinshelwood(L-H)拟一级反应动力学模型对不同光照强度、氧气体积分数、甲烷初始体积分数和水分子体积分数下瓦斯(甲烷)的降解过程进行拟合.结果表明:真空紫外光降解瓦斯反应动力学规律符合一级反应动力学特性;光照强度、甲烷初始体积分数、氧气体积分数和水分子体积分数是影响真空紫外光降解瓦斯的主要因素;瓦斯(甲烷)降解的反应速率随光照强度和氧气体积分数增大而增大,随甲烷初始体积分数增大而减小,随水分子体积分数增大而先增大后减小.     

Total cobalt determination in human blood and synovial fluid using inductively coupled plasma-mass spectrometry: method validation and evaluation of performance variables affecting metal hip implant patient samples

Inductively coupled plasma with mass spectrometric detection (ICP-MS) has been used for clinical analysis of cobalt (Co) due to its sensitivity and specificity; however, media-specific validation studies are lacking. This study provides data on performance variables affecting differences between selected analytical platforms (Perkin Elmer and Agilent), tissue sample preparation, storage, and interferences affecting measurements in whole blood, serum, and synovial fluid. The limits of detection (LOD) range from 0.2–0.5 µg/L in serum and synovial fluid, and 0.6–1.7 µg Co/L in whole blood. The Agilent platform with collision reaction cell is more sensitive, while the Perkin Elmer platform with dynamic reaction cell demonstrates more polyatomic interferences near the LOD for serum and whole blood. Split sample analysis showed good accuracy, precision, and reproducibility between serum Co measurements using acid digestion or detergent dilution preparations for persons with metal hip implants or following supplement intake. The results demonstrated reliability of the ICP-MS methodology across the two analytical platforms and between two commercial laboratories for Co concentrations above 5 µg Co/L, but digestion procedures and polyatomic interferences may affect measurements in some media at lower concentrations. These studies validate the described ICP-MS methodology for clinical purposes with precautions at low cobalt concentrations (<5 µg Co/L).     

Chemical self-organization in self-assembling biomimetic systems

Far-from-equillibrium oscillating chemical reactions are among the simplest systems showing complex behaviors and emergent properties. This class of reactions is often employed to mimic and understand the mechanisms of a great variety of biological processes. In this context, pattern formation due to the coupling between reaction and transport phenomena represent an active and promising research area. In this paper, we present results coming from experiments where we tried to blend the structural properties of self-assembled matrixes (sodium dodecyl sulphate micelles and phospholipid bilayers) together with the evolutive peculiarities of the Belousov–Zhabotinsky reaction. A series of interesting dynamical behaviors, like spatio-temporal chaos, stationary patterns and segmented waves, were found in reaction–diffusion and reaction–diffusion–convection experiments.     

Aniline removal by Photocatalytic reaction of iron(iii) mediated with dissolved organic matter

When light (> 370 nm) was allowed to interact with an aqueous solution containing dissolved organic matter (DOM) and Fe(III), removal of aniline (AN) was observed. This was due to the photocatalytic reaction of Fe(III) mediated by DOM. Syringic acid (SYA) and humic acid (HA) were used as DOM in the present study. The ¹⁵N‐NMR spectrum of the product mixture from the light irradiation of the SYA/Fe(III) system demonstrated that AN was covalently bound to SYA. The kinetics of AN removal were, therefore, interpreted by assuming covalent binding between DOM and AN. The amounts of covalent binding sites and the apparent second‐order rate constants could be evaluated, and the amounts of covalent binding sites decreased with the increases of the concentration of DOM. This is attributed that the polymerization of DOM by the photo‐oxidation competed with the covalent binding between AN and DOM.     

Analytical solutions for multiple species reactive transport in multiple dimensions

Many numerical computer codes used to simulate multi-species reactive transport and biodegradation have been developed in recent years. Such numerical codes must be validated by comparison of the numerical solutions with an analytical solution. In this paper, a method for deriving analytical solutions of the partial differential equations describing multiple species multi-dimensional transport with first-order sequential reactions is presented. Although others have developed specific solutions of multi-species transport equations, here a more general analytical approach, capable of describing any number of reactive species in multiple dimensions is derived. A substitution method is used to transform the multi-species reactive transport problem to one that can be solved using previously published single-species solutions for various initial and boundary conditions. One- and three-dimensional examples are presented to illustrate the steps involved in extending single-species solutions to a four-species system with sequential first-order reactions.