稀土掺杂对氯化氢氧化制氯气CuO-CeO2-SiO2催化剂结构和性能的影响

采用模板法制备了CuO-CeO₂-SiO₂和稀土掺杂的CuO-Ce_0.9M_0.1O₂-SiO₂ (M=La, Pr, Nd)催化剂. 运用X射线衍射(XRD), N₂吸附-脱附, 透射电镜(TEM), 拉曼(Raman)光谱, X射线光电子能谱(XPS)和氢气-程序升温还原(H₂-TPR)等手段对催化剂的结构进行表征, 并考察稀土掺杂对氯化氢催化氧化制氯气性能的影响. 结果表明, 稀土掺杂进入CeO₂晶格中形成良好的固溶体结构, 获得更小的晶粒尺寸和更高的比表面积, 并且显著提高了固溶体的表面氧空位浓度. 稀土掺杂显著影响了催化剂的氯化氢催化氧化活性, 活性顺序为: CuOCe_0.9La_0.1O₂-SiO₂>CuO-Ce_0.9Nd_0.1O₂-SiO₂>CuO-Ce_0.9Pr_0.1O₂-SiO₂>CuO-CeO₂-SiO₂, 固溶体氧空位浓度的高低与氯化氢氧化活性直接相关. 通过与Ce_0.9M_0.1O₂-SiO₂催化剂的结构和性能的对比, 发现氧空位浓度的提高并不能增强在固溶体表面发生的氯化氢氧化反应. 动力学测试显示, 稀土掺杂后, 氧分子的吸附成为反应过程的决速步骤. 但在V(O₂):V(HCl)=1 条件下, 更高的氧空位浓度导致了固溶体更低的氯化氢氧化反应速率. 结合机理分析认为, CuO-Ce_0.9M_0.1O₂-SiO₂催化剂更高的氧空位浓度增强了固溶体表面的“氧溢流”, 加快了氯化氢氧化的整体反应速率, 这是CuO-Ce_0.9M_0.1O₂-SiO₂具备高活性的关键.     

高浓度二氧化氯气体的在线检测研究

在40℃下,高浓度ClO2气体在盘管中迅速溶解于水中达到平衡,使用分光光度法检测平衡溶液的浓度,从而间接测定出ClO2气体的浓度。该方法可检测体积分数大于0.14%的ClO2,响应时间为15~30s,相对标准偏差为0.3%,与连续碘量法相比测定结果没有显著性差异(P<0.01),全过程中未使用化学试剂,操作简便,干扰小,适用于的高浓度ClO2气体在线检测。     

Critical considerations for the accelerated ageing of high-density polyethylene potable water materials

Accelerated ageing conditions with chlorinated water were identified that minimize variations in solution chemistry and water sorption, and that also enable the interpretation of HDPE physical and chemical changes during 20 week (3884 h) immersion periods. Of the ten conditions tested, three conditions with an alkalinity concentration of 50 ppm as CaCO₃ at pH 6.5 and at 23 and 37 °C performed best. These three conditions exhibited stable pH, free available chlorine, and alkalinity concentration during 20 weeks of HDPE immersion with 72 h changes of ageing solution. HDPE was periodically characterized using differential scanning calorimetry, thermogravimetric analysis, tensile analysis, a density gradient column, moisture analysis, and optical and infrared spectroscopy. Formation of surface carbonyl bonds and gradual reductions in oxidation induction time were detected, as well as water sorption into HDPE. Ageing solution and water sorption monitoring recommendations from this work should be incorporated into accelerated ageing protocols and considered when characterizing aged PE drinking water pipe.     

Theoretical investigation of the kinetics for the hydrogen abstraction reaction of 1,1,1,2-tetrafluoroethane (HFC-134a) by chlorine radical

The hydrogen abstraction reaction of 1,1,1,2-tetrafluoroethane (HFC-134a) by chlorine radical is investigated by theoretical calculations. Equilibrium geometries and harmonic vibrational frequencies of the reactants, transition state, and products are calculated using high-level ab initio methods. Rate constants of forward and backward reactions for the temperatures from 200 to 1000 K are calculated using classical transition state theory with Eckart tunneling correction, fitted in the expressions k_f (T) = 1.19 × 10⁻²³T^3.93exp (−1110/T), and k_b (T) = 8.86 × 10⁻²⁴T^3.32exp (−959/T) cm³ molecule⁻¹ s⁻¹ for forward and backward reactions, respectively, and are in reasonable agreement with the available experimental values.     

Liquid-phase microextraction and fibre-optics-based cuvetteless CCD-array micro-spectrophotometry for trace analysis

Liquid-phase microextraction (LPME) has been investigated for trace analysis in the present work in conjunction with fibre-optic-based micro-spectrophotometry which accommodates sample volume of 1 μL placed between the two ends of optical fibres. Methods have been evolved for the determination of (i) 1-100 μM and 0.5-20 μM of thiols by single drop microextraction (SDME) and LPME in 25 μL of the organic solvent, respectively, involving their reaction with the Ellman reagent and ion pair microextraction of thiolate ion formed; (ii) 70 μg to 7 mg L⁻¹ of chlorine/chlorine dioxide by headspace in-drop reaction with alternative reagents, viz., mixed phenylhydrazine-4-sulphonic acid and N-(1-naphthyl)ethylenediamine dihydrochloride, o-dianisidine, o-tolidine, and N,N-diethyl-p-phenylenediamine; (iii) 0.2-4 mg L⁻¹ of ammonia by reaction with 2,4-dinitro-1-fluorobenzene to give 2,4-dinitroaniline which was diazotized and coupled with 1-naphthylamine, the resulting dye was subjected to preconcentration by solid-phase extraction and LPME; and (iv) 25-750 μg L⁻¹ of iodide/total iodine by oxidation of iodide by 2-iodosobenzoate, microextraction of iodine in organic solvent, and re-extraction into aqueous starch-iodide reagent drop held in the organic phase. LPME using 25-30 μL of organic solvent was found to produce more sensitive results than SDME. The cuvetteless spectrophotometry as used in combination with sample handling techniques produced limits of detection of analytes which were better than obtained by previously reported spectrophotometry.     

Formation of halogenated by-products of parabens in chlorinated water

Chemical transformations of four alkyl esters of p-hydroxybenzoic acid, parabens, in chlorinated water samples are investigated. Quantification of the parent species and identification of their reaction by-products were performed using gas chromatography in combination with mass spectrometry. Experiments were accomplished considering free chlorine and paraben concentrations at the mg L⁻¹ and μg L⁻¹ level, respectively. Concentration of water samples, using solid-phase extraction, and silylation of the target species were carried out in order to improve the detectability of parent species and their possible transformation products, achieving quantification limits at the low ng L⁻¹ level. Under employed experimental conditions, the decrease in the concentrations of parabens followed pseudo-first-order kinetics. Half-lives values obtained for model ultrapure water solutions were in good agreement with those observed in tap water samples. For the first type of sample, only two by-products were detected for each paraben. They corresponded to chlorination of the aromatic ring in one or two carbons situated in ortho-positions to the hydroxyl group. Both species were also generated after the addition of parabens to chlorinated tap water. Moreover, three new transformation products were noticed for each parent compound. They were identified as bromo- and bromochloro-parabens, formed due to the existence of traces of bromide in tap water sources. Experiments carried out by mixing paraben-containing personal care products with tap water, containing free chlorine, confirmed the formation of all above described halogenated by-products. In addition, the presence of the di-chlorinated forms of methyl and propyl paraben has been detected for first time in raw sewage water samples.     

Calix[4]quinones. Part 4: The ClO2 oxidation of calix[4]arene dialkyl ethers

Except for the special case of calix[4]arene diethyl ether 1, the chlorine dioxide oxidation of dialkyl ethers 2-5 yielded only the corresponding calix[4]diquinone dialkyl ethers 8-11. Chlorine dioxide oxidation of calix[4]arene diethyl ether 1 produced two isomeric products 6 and 7, which were stable enough to be isolated by column chromatography. However, a slow conformational interconversion between isomeric pair 6 and 7 was observed at room temperature, and the equilibrium was reached after 400 h at 18 °C with an amount of 5:3 in favor of syn-isomer.     

烟用有机肥中氯离子含量测定方法的比较

为科学指导烟草栽培中有机肥的施用,以保证烟叶氯含量在适宜范围内,保障烟叶质量,研究比较了离子色谱法、连续流动分析法、硝酸银滴定法和佛尔哈德法测定烟用有机肥中氯离子含量.几种测定氯离子含量的方法比较结果为:离子色谱法和连续流动分析法测定烟用有机肥中氯离子含量的结果均较好,且方法不存在显著差异;硝酸银滴定法对低含量样品的检测偏差较大;佛尔哈德法不适宜用于测定烟用有机肥中氯离子含量.离子色谱法和连续流动分析法的平均回收率分别为102.4％、103.1％,方法检出限分别为0.05mg/L、0.30mg/L,对样品测定的平均相对标准偏差分别为2.41％和2.77％.     

Determination of Trace Chlorine in Fine Ceramics by ICP-AES Using Tungsten Boat Furnace Vaporizer and Exchangeable Sample Cuvette System as a Direct Solid Sampler

A new approach to simple solid sample digestion, subsequent vaporization, and introduction into an inductively coupled plasma was developed for the direct determination of chlorine in fine ceramic materials by atomic emission spectrometry. To each small sample cuvette made of tungsten, a powder sample was placed and weighed accurately. Following an addition of modifier solution, the cuvette was positioned on the tungsten boat furnace incorporated an electrothermal vaporizer. Then, the analyte in the sample cuvette was vaporized and introduced into the plasma; the major components of ceramic being retained. The solid ceramic samples were analyzed by using an external calibration curve prepared with the aqueous standard solutions. The detection limit of chlorine was estimated to be 0.71 ng, which corresponds to 59 ng g^?1 of the chlorine concentration in solid ceramic materials. The relative standard deviation was calculated to be 3.2%. The analytical results in various ceramic materials are described.