Rapid and simple spectrophotometric determination of persulfate in water by microwave assisted decolorization of Methylene Blue

A rapid and simple method for determination of persulfate in aqueous solution was developed. The method is based on the rapid reaction of persulfate with Methylene Blue(MB) via domestic microwave activation, which can promote the activation of persulfate and decolorize MB quickly. The depletion of MB at 644 nm(the maximum absorption wavelength of MB) is in proportion to the increasing concentration of persulfate in aqueous solution. Linear calibration curve was obtained in the range 0–1.5 mmol/L, with a limit of detection of 0.0028 mmol/L. The reaction time is rapid(within 60 sec), which is much shorter than that used for conventional methods. Compared with existing analytical methods, it need not any additives, especially colorful Fe2+, and need not any pretreatment for samples, such as p H adjustment.     

Effect of electron beam irradiation on the degradation of monochlorophenols in aqueous solution

Electron beam was successfully used for the degradation of 2-chlorophenol (2-CP) and 4-chlorophenol (4-CP) in aqueous solutions in this research. The effect of radiation dose on substrate degradation and dechlorination of solutions with concentration of 50mg/L was investigated. The effect of initial concentration, pH and presence of oxygen was also investigated. The concentration of 2-CP and 4-CP remaining in solution after irradiation were measured by HPLC. The results showed that increased radiation dose led to increased degradation of the chlorophenols and increased CI^- yield. Deaeration was also found to significantly increase the rate of degradation of chlorphenols in water while degradation and dechlodnation under alkaline condition was lower than at low to neutral pH.     

Detection of hydroxyl radical in plasma reaction on toluene removal

A new method was introduced to detect the concentration of OH radical in dielectric barrier discharge(DBD)reaction.A film, which was impregnated with salicylic acid,was used to detect OH radical in plasma reaction at room temperature and atmospheric pressure.Salicylic acid reacts with OH radical and produces 2,5-dihydroxybenzoic acid(2,5-DHBA).Then,a high performance liquid chromatography(HPLC)was carried out to detect the concentration of 2,5-DHBA.Therefore,OH radical in nonthermal plasma reaction could be...     

Effects of amine, amine salt and amide on the behaviour of carbon dioxide absorption into calcium hydroxide suspension to precipitate calcium carbonate

The amount of carbon dioxide （CO2） absorption and calcium ion （Ca^2＋） concentration besides the pH of aqueous solution were observed during the COz absorption to precipitate calcium carbonate （CaCO3） from calcium hydroxide （Ca（OH）2）. A reaction rate-limiting effect of an amount of CO2 absorption without any organic additives in the early stage of the precipitation was observed, which was attributed to an interruption effect of bicarbonate ion （HCO3） on the precipitation of CaCO3. The improvement for the reaction rate was achieved not only by amine additives but also by neutral additives such as ε-caprolactam or amine salt. When the hexamethylene diamine was dissolved in the solution, successive change of crystal forms of CaCO3 aragonite to calcite in aqueous suspensions, confirmed by Ca^2＋ concentration change and X-ray diffraction, was concluded that a local environment around the amine group in aqueous solution and an interaction of the diamine with precipitated CaCO3 particles were important factors for these reactions.     

Radiation-induced reduction of chromium(Ⅵ) in aqueous solution by γ-irradiation in a laboratory-scale

Radiation-induced reduction of chromium（Ⅵ）（Cr（Ⅵ） by ,γ-irradiation was studied with an initial concentration of 42 mg/L in aqueous solutions. Several factors which might affect the reduction of Cr（Ⅵ） to Cr（Ⅲ） were examined, pH of aqueous solution affects the reduction efficiency significantly. Acidic condition of aqueous solution accelerates the process. At pH 2, a reduction of 86.2% was achieved with the absorbed dose of 15 kGy, while, with the same dose, at pH 5 and 7, the reduction ofCr （Ⅵ） were only 36.3% and 22.2%, respectively. Ethanol （0.1% in V：V） and sodium carbonate （1 mmol/L） were added into the solution respectively as relatively non-toxic hydroxyl radical scavengers. Reduction rate increased greatly in the presence of ethanol at each pH. Reduction efficiency of Cr（Ⅵ） was enhanced in neutral condition with the addition of sodium carbonate, however, no enhancement was found in acidic condition. The reduction of Cr（Ⅵ） was restrained when the solution was saturated with oxygen; however, the restraint was not significant.     

Sensitized effect of β-cyclodextrin on the fluorescence in the determination of carbaryl

Based on the significant enhancement of fluorescence intensity of carbaryl in inclusion complex, a spetrofluorimetdc method with high sensitivity was developed for the determination of carbaryl in aqueous solution. Under the optimum conditions, the complex had excitation and emission maxima at 278 nm and 332 nm, respectively. The linear range of the method was 7.0 ng/ml-1500 ng/ml with a detection limit of 1.2 ng/ml. The proposed method was successfully used to determine quantitativelv of carbarvl in cottonseeds.     

Determination of hydroxyl radicals with salicylic acid in aqueous nitrate and nitrite solutions

The qualitative and quantitative analyses of reactive oxygen species are essential to determine their steady-state concentration and related reaction mechanisms in environmental aquatic systems. In this study, salicylic acid was employed as an innovative molecular probe of hydroxyl radical(OH) generated in aqueous nitrate and nitrite solutions through photochemical reactions. Kinetic studies showed that the steady-state concentrations of OH in aqueous NO3^-(10 mmol/L, pH=5) and NO2^ (10 mmol/L, pH=5) solutions under ultraviolet irradiation were at a same magnitude, 10v-15 mol/L. Apparent quantum yields of OH at 313 nm were measured as 0.011 and 0.07 for NO3^- and NO2^ respectively, all comparable to the results of previous studies.     

Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere

The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin(2,3,7,8-TCDD) is an efcient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2 O are introduced in detail at the method of MPWB1K/6-31+G(d,p)//MPWB1K/6-311+G(3df,2p) level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus(RRKM) theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and O3 is 4.80 × 10 20cm3/(mole·sec) at 298 K and 760 Torr. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.     

2-Chlorophenol oxidation kinetic by photo-assisted Fenton process

Experimental data are presented to test and validate a kinetic model for the oxidation of 2-chlorophenol wastewater by photo-assisted Fenton process. The data showed that this process had produced good effects under acidic conductions. Up to 90% 2-chlorophenol was removed after 90-minute reaction time with H2O2 of 25% CODCr. in, while in UV/H2O2 system ordy 16.8% 2-chlorophenol was removed after one hour treatment. The optimal pH in this reaction occurred between pH 3.0 and pH 4.0. The reaction kinetics for photo-assisted Fenton process experimented in this research was investigated. Kinetic models were proposed for the treatment of 2-chlorophenol wastewater. The reaction was found to follow the 2nd order. The equations of reaction kinetics are as follows:-d[RH]/dt=KRH[RH][H2O2]0exp(-KH2o2t);-d[CODCr]/dt=KCODCr[CODCr][H2O2]0exp(-K′t).The prediction of the models was found to be in a good agreement with experimental results, thus confimfing the proposed reaction mechanism.     

Heterogeneous Fenton-like degradation of 4-chlorophenol using iron/ordered mesoporous carbon catalyst

Ordered mesoporous carbon supported iron catalysts(Fe/OMC) were prepared by the incipient wetness impregnation method and investigated in Fenton-like degradation of 4-chlorophenol(4CP) in this work. XRD and TEM characterization showed that the iron oxides were well dispersed on the OMC support and grew bigger with the increasing calcination temperature. The catalyst prepared with a lower calcination temperature showed higher decomposition efficiency towards 4CP and H2O2, but more metals were leached. The effect of different operational parameters such as initial pH, H2O2 dosage, and reaction temperature on the catalytic activity was evaluated. The results showed that 96.1% of 4CP and 47.4% of TOC was removed after 270 min at 30°C, initial pH of 3 and 6.6 mmol/L H2O2. 88% of 4CP removal efficiency was retained after three successive runs, indicating Fe/OMC a stable catalyst for Fenton reaction. 4CP was degraded predominately by the attack of hydroxyl radical formed on the catalyst surface and in the bulk solution due to iron leaching. Based on the degradation intermediates detected by high performance liquid chromatography, possible oxidation pathways were proposed during the 4CP degradation.     

Reaction mechanism of 3-chlorophenol with OH, H in aqueous solution

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平行板双介质阻挡放电处理水相中氯酚的脱氯机理

用平板介质阻挡放电等离子体技术和脉冲辐解方法研究了等离子体条件下水相中的4 氯酚脱氯的机理.研究结果表明,4 氯酚在等离子体中的脱氯近似为表观一级反应;4 氯酚的脱氯率与等离子体的电压和电极间距呈线性关系;溶液的pH值随着处理时间的增加而下降.用脉冲辐解方法得到的瞬态吸收光谱显示,在近中性和酸性条件下,4 氯酚主要经由4 氯酚的OH加合物进一步转化而脱氯;在碱性条件下,4 氯酚直接经过氯代酚氧自由基而进一步脱氯,脱氯率比中性或酸性的高.在等离子体条件下,水相中4 氯酚的脱氯主要是与·OH自由基作用的结果.4 氯酚在等离子体中脱氯后的产物为较易生物降解的酚类和有机酸类.     

电解对氯苯酚稀水溶液中脱氯降解机理研究

利用石墨电极进行了多种条件下对氯苯酚水溶液的电解研究。研究结果表明,CODCr去除率和脱氯率随电压的升高呈先升高后下降的趋势、随对氯苯酚质量浓度的升高呈指数下降、随溶液pH的升高而升高。碱性条件下电解效果明显优于中性和酸性条件。在电压为10V,pH≈12,电解100mg L的对氯苯酚溶液2h后,CODCr去除率可达52 94%,脱氯率达52 8%。由脉冲辐解瞬态吸收光谱可知,中性、酸性条件下降解机制均为OH·自由基的作用,经过瞬态分子OH-adducts(OH加合物)的中间产物进一步氧化降解;碱性条件下通过OH·自由基和对氯苯酚氧基负离子的阳极直接失电子氧化作用2种降解机制,经过瞬态分子氯代酚氧自由基中间产物氧化降解对氯苯酚,产物分析结果显示生成了对苯二酚和苯醌等中间产物。      

臭氧氧化水中2,4,6-三氯酚的反应机理研究

研究了臭氧氧化对2,4,6-三氯酚的去除效果,以及氧化过程中过氧化氢、氯离子、甲酸和乙二酸的变化情况,探讨了臭氧氧化2,4,6-三氯酚的反应机理和反应途径.实验结果表明,如果溶液中没有自由基清除剂,在臭氧投加量为24mg·L~(-1)时,0·1mmol·L~(-1)的2,4,6-三氯酚在6min内,去除率可达99%.臭氧分子氧化2,4,6-三氯酚的过程中产生过氧化氢,检测到的过氧化氢的最大摩尔浓度为初始2,4,6-三氯酚摩尔浓度的22·5%.中间产物过氧化氢随后和臭氧反应生成大量的羟基自由基,此时2,4,6-三氯酚是被臭氧和羟基自由基联合氧化,生成甲酸和乙二酸.当溶液中含有大量的自由基清除剂时,2,4,6-三氯酚首先被臭氧分子氧化成黄色的氯代对苯醌,然后氧化成甲酸和乙二酸.臭氧氧化2,4,6-三氯酚存在臭氧分子氧化以及O3/OH·联合氧化两种反应途径.     

蜂窝陶瓷催化臭氧化降解水中痕量硝基苯的机理研究

实验考察了HCO3-、CO32-、HPO42-、H2PO4-和叔丁醇等羟基自由基抑制剂存在条件下,单独臭氧氧化和臭氧/蜂窝陶瓷氧化对水中硝基苯降解效果的影响规律,初步推测了反应机理.结果表明,2种工艺对硝基苯的去除率都随着HCO3-浓度的增加(0～200 mg·L-1)先增高再降低,在浓度为50 mg·L-1时去除率达到最大值;单独臭氧氧化和臭氧/蜂窝陶瓷对硝基苯的去除率随着CO32-浓度的增加(0～20 mg·L-1)分别降低了16.57%和27.52%,随着HPO42-浓度的增加(0～12 mg·L-1)分别降低了13.61%和17.52%,随着H2PO4-浓度的增加(0～120 mg·L-1)分别降低了6.61%和12.52%,随着叔丁醇浓度的增加(0～10mg·L-1)硝基苯去除率降低了30.06%和46.09%.证明单独臭氧氧化和臭氧/蜂窝陶瓷氧化对硝基苯的降解遵循·OH氧化机理,叔丁醇更适合作为自由基抑制剂用来推断单独臭氧氧化和臭氧/蜂窝陶瓷氧化降解硝基苯的反应机理.单独臭氧氧化对硝基苯的去除率随着pH值的升高(3.02～10.96)而增大,臭氧/蜂窝陶瓷氧化对硝基苯的去除率在pH=9.23时达到最大值.     

光照下铜离子对水中氢氧自由基生成量的影响

研究了水溶液中铜离子与抗坏血酸、柠檬酸盐及藻等配合体系在高压汞灯光照下产生氢氧自由基的情况,其中铜与抗坏血酸系统反应最强,高压汞灯光照增强了铜与抗坏血酸反应产生氢氧自由基的过程,高压汞灯光照时所产生的自由基量为不光照时的6～7倍。同时铜(或抗坏血酸)单一的水溶液在光照条件下也能产生氢氧自由基。铜离子与柠檬酸钠溶液混合在光照下能产生氢氧自由基;铜离子与藻液混合能加倍藻液中氢氧自由基的产生。     

克百威光催化降解动力学的研究

采用TiO2光催化技术对克百威的降解进行了研究,并系统地考察了催化剂用量,溶液初始pH值,底物浓度,活性氧物种和各种阴阳离子对其降解动力学的影响.用Langmuir-Hinshelwood动力学模型对克百威的光催化降解进行了研究,结果表明,克百威在弱碱性条件下降解速率最快,×OH对克百威降解贡献比约为93.4%,h+和其他ROSs的贡献则相对较小.而水溶液中的阴离子BrO3-和S2O82-对克百威的光催化降解有促进作用,I-则有明显的抑制作用,并且水溶液中的K+,Ca2+,Na+,Mg2+和Cu2+等金属阳离子对克百威的降解也均体现了一定程度的抑制作用.     

邻-氯酚在TiO_2膜上光催化降解及反应动力学特征

以钛酸四丁酯为原料采用Sol Gel法制备了玻璃负载TiO2 膜光催化剂 ,应用XRD表征了不同实验条件下薄膜中TiO2 的晶相结构和粒度。分析了不同层数TiO2 膜的光催化活性和溶液 pH值对邻 氯酚 (2 CP)的影响。结果表明 :处理温度为 50 0℃时不同厚度薄膜中TiO2 均为锐钛矿晶型 ,粒径 8～ 33nm ,5层涂膜光催化活性最高。在高 pH值和低pH值区域 2 CP ,在TiO2 膜上的光催化降解速率较大。 2 CP初始浓度 (C0 )与反应速率 (r0 )的关系符合Langmuir Hinshelwood方程 ,当C0 ≤ 0 .6mmol·L- 1 时 ,降解反应可用一级动力学模式来描述。