埋葬土壤中阴离子含量分布特征及对金属文物的影响

金属文物在埋葬土壤环境中腐蚀情况比较复杂,使得保护金属文物方面受到一定的限制。采用离子色谱法测定墓地土壤中水浸取液的F^-、Cl-、Cl^-、SO_4-、SO_4^(2-)和NO_3(2-)和NO_3^-的含量,探讨阴离子含量随土壤深度的分布特征及对金属文物的影响。结果表明,F-的含量,探讨阴离子含量随土壤深度的分布特征及对金属文物的影响。结果表明,F^-、NO_3-、NO_3^-含量随着深度的增加整体呈升高趋势;而SO_4-含量随着深度的增加整体呈升高趋势;而SO_4^(2-)、Cl(2-)、Cl^-作为腐蚀金属文物的主要阴离子,含量整体呈现出波浪状。其中SO_4-作为腐蚀金属文物的主要阴离子,含量整体呈现出波浪状。其中SO_4^(2-)含量在距地面3 m处达到最大,并且在5.5 m处又出现小峰值;Cl(2-)含量在距地面3 m处达到最大,并且在5.5 m处又出现小峰值;Cl^-在距地面2 m左右出现小峰值,之后一直递增,在距地面5.5 m处含量达到最大。阴离子对金属文物的影响体现在地下环境使得金属与阴离子发生电化学反应,进而加速金属文物的腐蚀。阴离子对土质文物的影响主要表现在SO_4-在距地面2 m左右出现小峰值,之后一直递增,在距地面5.5 m处含量达到最大。阴离子对金属文物的影响体现在地下环境使得金属与阴离子发生电化学反应,进而加速金属文物的腐蚀。阴离子对土质文物的影响主要表现在SO_4^(2-)、Cl(2-)、Cl^-的破环性较强,这可能是由于地下环境的复杂使得土质文物出现酥碱、霉变等盐害。     

纳滤膜对浓海水中溴离子的截留影响研究

采用国产纳滤膜N40、N70对海水淡化浓海水中溴离子的截留行为进行研究,考察不同的运行通量、回收率、温度、运行方式对纳滤分离过程中溴离子透过率的影响。结果显示：纳滤膜对离子的截留顺序为 SO₄^2->Mg²⁺>Ca²⁺>F^->Cl^->Br^-;N70 纳滤膜对溴离子具有高的透过率,N40 纳滤膜对溴离子无截留作用,但其对浓海水的软化作用和脱盐效果较 N70差。溴离子透过率随运行通量增加先降低后趋缓,而水回收率对溴离子截留的影响较小;溴离子透过率随温度升高而增加,且恒通量运行时相比恒压力运行条件下透过率增加更为明显;恒通量运行且温度为35 °C 时,N70 纳滤膜对溴离子的透过率为 95.3%。     

分子结构对阳离子双子表面活性剂性能的影响

以十六烷基二甲基叔胺、棕榈酰胺丙基二甲基胺、1,4-二氯丁烷和1,4-二溴丁烷为原料合成了四种阳离子双子表面活性剂(CG-C、CG-PC、CG-B和CG-PB)。产物结构经红外光谱和核磁共振氢谱进行确认,并通过对表面张力、油水界面张力、泡沫性和乳化性等性能的测定来阐述分子结构(疏水碳链和无机反离子)对阳离子双子表面活性剂效能的影响。结果表明,含Br^-的表面活性剂的表面活性优于含Cl-的表面活性剂的表面活性优于含Cl^-的,碳链上酰胺基团的引入导致表面活性降低;反离子对降低界面张力的能力影响不大,未带有酰胺基团的降低界面张力的能力较强;含有Cl-的,碳链上酰胺基团的引入导致表面活性降低;反离子对降低界面张力的能力影响不大,未带有酰胺基团的降低界面张力的能力较强;含有Cl^-(未带酰胺基团)的乳化性能强于含有Br-(未带酰胺基团)的乳化性能强于含有Br^-(酰胺基团)的;含Br-(酰胺基团)的;含Br^-的泡沫性能稍强于含Cl-的泡沫性能稍强于含Cl^-的,含酰胺基团的起泡能力较差,但泡沫稳定性好。     

催化湿式氧化处理头孢氨苄废水

采用催化湿式氧化处理头孢氨苄废水,考察反应温度、进水pH及Cl-含量对RCT催化剂性能的影响,并对液体样品及催化剂进行了HPLC、TOC/TN、GC-MS、N2物理吸附-脱附及XRF表征。通过正交实验,得出最佳的工艺条件为:进水pH=4.8,Cl-浓度1 500 mg·L-1,反应温度260℃;对催化剂进行300 h连续寿命考察,废水TOC及TN去除率均超过90%,催化剂稳定性高,活性组分流失较少;废水经催化湿式氧化处理,水中残留的主要有机物均可生化降解。     

硫代杯[4]冠-4在硝酸体系中对Sr2+的萃取

乏燃料后处理的高放废液分离过程中,发展新型分离材料实现对锶的高效萃取至关重要。合成了1,2交替构象的硫代杯[4]冠-4(TCACE),利用FT-IR、¹H NMR和MS对目标产物进行了表征。研究不同稀释剂对萃取的影响,优化得出CH₂Cl₂为稀释剂,在硝酸浓度为3 mol·L^-1,有机相中硫代杯[4]冠-4浓度为1×10^-3 mol·L^-1,水相中Sr²⁺浓度为5×10^-4 mol·L^-1,萃取温度为25℃,萃取80 min条件下,平均传质系数为1.36×10^{-5 m}·s^-1,Sr²⁺的分配比为0.69。分析了不同条件对硫代杯[4]冠-4对Sr²⁺的萃取影响,研究了萃取计量方程式,实验结果表明萃合物为{Sr(NO₃)₂}·{TCACE}。研究了TCACE对其他金属离子Mo⁶⁺、Ni²⁺、Ag⁺、Sn⁴⁺等的萃取效果,表明对Sr²⁺具有较好的选择性。     

共存物质对UV/PS降解莠灭净的影响及降解路径

采用紫外（UV）激活过硫酸盐（PS）生成活性极强的自由基（·SO₄^-、·OH）降解莠灭净（AMT）,考察了UV/PS工艺对AMT降解效果及反应动力学模型。研究了水中不同浓度的无机阴离子（Cl^-、HCO₃^-、NO₃^-）、天然有机质（腐植酸）对反应效果及速率的影响,比较了超纯水、自来水和锡东水厂不同工艺出水作为不同水质背景时AMT的去除效率,并推测了UV/PS降解AMT的降解产物及可能的降解路径。结果表明：UV/PS对AMT的降解符合准一级反应动力学模型（R²≥0.94）。水中Cl^-浓度为5mmol/L时,会抑制AMT的降解,而其他浓度的Cl^-对反应的影响并不明显;随着HCO₃^-浓度的增加,准一级反应速率常数k_obs逐渐减小;NO₃^-会加快AMT的去除,当其浓度为200mmol/L时对AMT降解的促进作用变弱;随着腐植酸质量浓度的增加,k_obs逐渐减小。AMT在超纯水中的降解率高于其他实际水体中的降解率。UV/PS系统降解AMT过程中主要的降解产物可能是2-甲硫基-4,6-二氨基-1,3,5-三嗪和2-羟基-4-乙氨基-6-异丙氨基-1,3,5-三嗪。     

改性纳米零价铁去除地下水硝酸盐的研究

采用提纯凹凸棒土(ATP)负载纳米零价铁(nZVI)制备得到改性材料ATP-nZVI,将其用于对地下水硝酸盐的去除研究。通过静水实验考察了溶液中共存阴离子和反应温度对ATP-nZVI去除NO₃^--N的影响,通过模拟可渗透反应墙(PRB)考察了溶液初始pH、初始NO₃^--N浓度、材料装填方式、流速对ATP-nZVI去除NO₃^--N的影响,并通过更换PRB装填材料将ATP-nZVI与石英砂、ATP、铁粉、nZVI等材料对NO₃^--N的去除效果进行了比较。结果表明：共存阴离子对ATP-nZVI去除NO₃^--N具有抑制作用,其抑制作用的顺序为PO₄^3->CO₃^2->SO₄^2->Cl^-;ATP-nZVI对NO<...     

双通道离子色谱法测定陶质文物表面结晶盐中有机酸根和无机阴阳离子

对双通道离子色谱同时测定陶质文物表面结晶盐中的CH₃COO^-、HCOO^-、F^-、Cl^-、SO₄^2-、NO₃^-等9种阴离子和Li⁺、Na⁺、K⁺等6种阳离子的测定方法进行优选。通过优化色谱条件,确定采用Metrosep A Supp7色谱柱为阴离子分析柱,3 mmol/L碳酸钠为阴离子淋洗液,流速为0.7 mL/min;Metrosep C4型色谱柱为阳离子分析柱,0.8 mmol/L吡啶二羧酸-1.6 mmol/L硝酸为阳离子淋洗液,流速为0.7 mL/min。在此方法下,净化后的滤液一次进样,电导检测器检测,各离子峰形好,分离时间适中,分离效果很好。各离子的标准曲线相关系数R>0.999,具有良好的线性关系,检出限在0.005～0.05 mg/L之间,加标回收率在96%～106%之间,相对标准偏差为0.1%～4%(n=...     

高温水解-离子色谱法同时测定固体生物质燃料中有害元素的研究

建立高温水解-离子色谱法测定生物质燃料中有害元素(F、Cl、N、S)含量的方法,考察了水解温度、水解时间、氧气流量和水蒸气流量对测定效果的影响。结果表明,水解温度900℃和水解时间25 min,样品完全燃烧;氧气流量40 mL/min和水蒸气流量3 mL/min时,有害元素含量达到最大值。各离子(F^-、Cl-、Cl^-、NO_3-、NO_3^-、NO_2-、NO_2^-、SO_4-、SO_4^(2-))含量在0～10μg/g范围内,峰面积和离子浓度线性关系良好,相对标准偏差0. 54%～4. 63%,加标回收率99. 32%～100. 40%。该方法操作简单,可以同时测定几种有害元素,大大缩短了检测周期,而且该检测方法稳定性和精密度高。     

城市中水对湿法烟气脱硫工艺的影响

以湛江电力有限公司工业原水由地下水改为城市中水为例,分析和讨论了中水对湿法烟气脱硫工艺三方面的影响:(1)抑制吸收塔内CaCO_3的转化及CaSO_3·1/2H_2O的氧化过程;(2)导致脱硫石膏Cl^-含量和含水率升高,石膏品级降低。真空过滤不同Cl-含量和含水率升高,石膏品级降低。真空过滤不同Cl^-含量的石膏浆液,发现随着石膏浆液Cl-含量的石膏浆液,发现随着石膏浆液Cl^-含量的升高,过滤得到的石膏滤饼含水率升高,即Cl-含量的升高,过滤得到的石膏滤饼含水率升高,即Cl^-的存在不利于石膏浆液的脱水;(3)Cl-的存在不利于石膏浆液的脱水;(3)Cl^-含量升高加剧了脱硫系统中碳钢及不锈钢的腐蚀,特别是碳钢在高浓度Cl-含量升高加剧了脱硫系统中碳钢及不锈钢的腐蚀,特别是碳钢在高浓度Cl^-溶液中会发生剧烈全面腐蚀。     

卤离子调控的镍钴基电极材料生长及电容影响研究

超级电容器是很有发展潜力的电化学储能器件,其性能主要取决于电极材料。利用水热法,通过改变加入的卤离子（F^-、Cl^-、Br^-）种类,可以简便地对镍钴（NiCo）基超级电容器电极材料的形貌、物相以及化学组成进行调控。由X射线衍射（XRD）和扫描电镜（SEM）等表征结果可知,F^- 诱导生成纳米片支撑纳米线阵列,成分为稳定的NiCo LDH结构;Cl^-/Br^- 诱导生成纳米线,成分为碱式碳酸钴。从电化学测试结果可知,形貌和晶型对电化学性能有显著的影响。其中Cl^- 调控的电极在120 ℃下反应3 h时,其形貌为纳米线,晶型偏向无定形,此时性能最优;在2 mA/cm²电流密度下不仅具有最大的面积比电容2 940 mF/cm²,且该电极与负极活性炭组装的器件具有1.8 V的大电压窗口和优异的循环稳定性。     

镍铝层状双金属氢氧化物的亲油改性及其吸油性能

Ni^(2+)与Al^(3+)物质的量比为3∶1,尿素为沉淀剂,通过水热合成技术制备镍铝层状双金属氢氧化物层状材料(Ni^(2+)-Al^(3+)-CO_3^(2-)-LDHs)。以Ni^(2+)-Al^(3+)-CO_3^(2-)-LDHs为前驱体,分别与Na Cl和十二烷基磺酸钠[CH_3(CH_2)_(11)SO_3Na]进行离子交换反应得到Ni^(2+)-Al^(3+)-CH_3(CH_2)_(11)SO_3^--LDHs新型吸附剂材料。将CH_3(CH_2)_(11)SO_3^-亲油客体负载到Ni^(2+)-Al^(3+)-LDHs层状材料层间,实现镍铝层状双金属氢氧化物的亲油改性。利用Ni^(2+)-Al^(3+)-CH_3(CH_2)_(11)SO_3^--LDHs复合材料对含油污水进行处理,结果表明,镍铝层状双金属氢氧化物亲油改性后增强了LDHs的亲油吸附性能。     

Empirical correlation of flow properties of poly(vinyl chloride)

Empirical correlations of flow properties of poly(vinyl chloride) were made using data reported by a number of investigators. Correlation was made by plotting the reduced variable viscosity η/η₀ versus \documentclass{article}\pagestyle{empty}\begin{document}$ (\eta _0 \dot \gamma \bar M_w )/(_\rho RT) $\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$ (\eta _0 \dot \gamma \bar M_w ^{0.5} )/(_\rho RT) $\end{document} for unplasticized PVC and versus \documentclass{article}\pagestyle{empty}\begin{document}$ (\eta _0 \dot \gamma \bar M_w ^{0.5} )/(_\rho RTW_2 ^a ) $\end{document} with polymer concentration, W₂, for PVC containing plasticizer.     

Influence of electrolytes on the absorption of nitrogen oxide components N2O4 and N2O3 in aqueous absorbents

The influence of electrolytes, which are dissolved in the aqueous absorbent and do not react with nitrogen oxides, on the absorption kinetics of both these components was investigated experimentally. In addition to demineralized water, various salt solutions of different concentrations as well as sodium hydroxide solution were used as absorbents. The term H \documentclass{article}\pagestyle{empty}\begin{document}$ H\sqrt {k_1 D} $\end{document} for N₂O₄ and N₂O₃, which is important for the design of industrial absorbers, was determined as a function of composition and concentration of the absorbents. In the case of N₂O₄, the chosen measuring and evaluation methods permitted a separate determination of the rate constant k of the pseudo first order reaction and of the solubility H. The diffusion coefficient D of the gas in the absorbent can be obtained only by calculation. Experimental results showed that \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 4} } $\end{document} decreases with increasing ionic strength I, however, without a clear indication of any ion-specific effects. This decrease does not appear to be caused simply by a reduction in solubility (salting out effect), or in diffusion coefficient, but at least, to the same extent, through a decrease of the rate constant k with increasing electrolyte content in the absorbent. The measurements permitted the determination of the gas-based salting out parameter for N₂O₄. The investigations on the absorption of N₂O₃ in water and in an Na₂SO₄ solution showed no experimentally detectable influence of dissolved salts on \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 3} } $\end{document}. The numerical value of \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 3} } $\end{document} is six times that of \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 4} } $\end{document}.     

The Radiation Chemistry of Cytochrome c

The literature on the reaction of cytochrome c with the radiolytically generated radicals \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm e}_{{\rm eq}}^ -,^. {\rm OH,}^{\rm .} {\rm H,CO}_2^ -,{\rm O}_{\rm 2}^ -,{\rm Br}_{\rm 2}^ - $\end{document} and various organic radicals is reviewed. It would appear that negatively charged radicals, aided by the electric field of cytochrome c, react at the exposed haem edge. Uncharged organic radicals also react at this site. \documentclass{article}\pagestyle{empty}\begin{document}$ ^. {\rm H} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ ^. {\rm OH} $\end{document} are likely to reduce the prosthetic group indirectly by a tunnelling mechanism.     

Cu-Ce-O/γ-Al_2O_3的CO氧化性能

采用柠檬酸络合法制备一系列不同铜铈比的Cu-Ce-O/γ-Al_2O_3催化剂,用XRD、H2-TPR对其进行表征,采用连续固定床微反装置对Cu-Ce-O/γ-Al_2O_3催化剂CO催化氧化活性进行评价。结果表明,Cu-Ce-O/γ-Al_2O_3催化剂的XRD图谱中除归属于γ-Al_2O_3的晶相峰外,还出现CuO和CeO_2的晶相峰。高温水热引起活性组分CeO_2的晶粒聚集、长大和尖晶石结构CuAl2O4物质的生成;CuO-CeO_2之间的共生共存与相互作用,使得Cu-Ce-O/γ-Al_2O_3催化剂中具有非完整结构的[Cu2+1-xCu+x][O1-12x12x]增多,Cu+离子和氧空位增多,有利于其H2-TPR还原峰温度向低温区偏移,有利于提高其CO的催化氧化活性,使得Cu-Ce-O/γ-Al_2O_3催化剂的TCO50和TCO90降低。Cu与Ce物质的量比为5∶5制备的Cu-Ce-O/γ-Al_2O_3-55催化剂的TCO50和TCO90分别降至最低的162℃和199℃,表明此时的Cu-Ce-O协同效应最佳;CuO-CeO_2二相的共生共存与相互作用有利于减少高温水热环境下活性组分的聚集和晶粒长大,有利于Cu-Ce-O/γ-Al_2O_3催化剂能够保持较高的CO催化氧化活性。     

Polymerization of cyclohexene oxide by methyl-4-[bis(4-bromophenyl)amino]benzoate cation radical salts

Methyl-4-[bis(4-bromophenyl)amino]benzoate cation radical salts having non-nucleophilic anions such as $ {\text{SbF}}^{ - }_{6} $ , $ {\text{PF}}^{ - }_{6} $ and $ {\text{AsF}}^{ - }_{6} $ were newly prepared and found to be very active initiators for the polymerization of cyclohexene oxide at room temperature, in dichloromethane without any external stimulation. The effects of counter ion structure, salt and monomer concentration on the polymerization yield and molecular weight, and the mechanism of initiation are presented.     

Characterization of polyvinyl chloride part II. The unperturbed end to end distance values obtained from a new GPC method and viscometry

A new gel permeation chromatography (GPC) method is proposed for determining the unperturbed end-to-end distance, \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2 }}{M}} \right)^{0.5} $\end{document}, of polymers of known molecular weights, Mn and Mw. This method requires the value of \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2 }}{M}} \right)^{0.5} _{{\rm ps}} $\end{document} of polystyrene which was determined through viscometry to be 0.735 \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{{\rm {\AA}}^2-{\rm mole}}}{{gm}}} \right)^{0.5} $\end{document} Polyvinyl chloride (PVC) was chosen to illustrate the method and \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2}}{M}} \right)^{0.5} _{pvc} $\end{document} was found to be 0.99 from GPC data which is in agreement with the result obtained from viscometry, \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2}}{M}} \right)^{0.5} _{pvc} $\end{document} = 1.01. All \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2 }}{M}} \right)^{0.5} $\end{document} values were determined at 30°C. The advantage to this method lies in its speed and economy of materials.     

Magnetic cobalt-zinc ferrite/PVAc nanocomposite: synthesis and characterization

Metal oxide nanoparticles are the subject of current interest because of their unusual optical, electronic, and magnetic properties. In this work, cobalt zinc ferrite ( $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ ) nanoparticles have been synthesized successfully through redox chemical reaction in aqueous solution. The synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles have been used for the preparation of homogenous polyvinyl acetate-based nanocomposite ( $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} /{\text{PVAc}} $ ) via in situ emulsion polymerization method. Structural, morphological and magnetic properties of the products were determined and characterized in detail by X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The XRD patterns of the $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ confirmed that the formed nanoparticles are single crystalline. According to TEM micrographs, the synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles had nano-needle morphology with an average particle size of 20 nm. The calculated coefficient of variation (CV) of nanoparticles diameters obtained by TEM micrographs was 16.77. The $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles were dispersed almost uniformly in the polymer matrix as was proved by SEM technique. The magnetic parameters of the samples, such as saturation magnetization (M _s) and coercivity (H _c) were measured, as well. Magnetization measurements indicated that the saturation magnetization of synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} /{\text{PVAc}} $ nanocomposites was markedly less than that of $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ magnetic nanoparticles. However, the nanocompoites exhibited super-paramagnetic behavior at room temperature under an applied magnetic field.