A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO_4-H_2O and NaF-H_2O binary solutions and NaClO_4-NaF-H_2O ternary solution

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO4-H2O and NaF-H2O binary solutions and NaClO4-NaF-H2O ternary strong electrolyte aqueous solutions was developed based on the ion and molecule coexistence theory (IMCT). A transformation coefficient was needed to compare the calculated mass action concentration and the reported activity, because they were usually obtained at different standard states and concentration units. The results show that transformation coefficients between the calculated mass action concentrations and the reported activities of the same components change in a very narrow range. The transformed mass action concentrations of structural units or ion couples in NaClO4-H2O and NaF-H2O binary solutions agree well with the reported activities. The transformed mass action concentrations of structural units or ion couples in NaClO4-NaF-H2O ternary solution are also in good agreement with the reported activities in a total ionic strength range from 0.1 to 0.9 mol/kg H2O by the 0.1 mol/kg step with different ionic strength fractions of 0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1, respectively. The results indicate that the developed thermodynamic model can reveal the structural characteristics of binary and ternary strong electrolyte aqueous solutions, and the calculated mass action concentrations of structural units or ion couples also strictly follow the mass action law.     

Electrostatic Self-Assembled Multilayers from Side Chain Azo Polyelectrolytes

IntroductionRecently,a new self- assembly technique has beenintroduced by Decher based on the electrostaticattraction of counter- charged polyelectrolytes[1,2 ] .Through a layer- by- layer ( LBL) adsorptionprocess,two oppositely charged components canbe built up on a substrate to form a nano-composite multilayer film. This techniquesignificantly enriches the methods of thin filmproduction and is promising for variousapplications[3 8] .　With more understanding on the self- assemblymechanism,…     

5—磺基水杨酸存在下两相合成二茂钛氨基酸配合物

在两相体系（H2O／CHCl3)中,利用二氯二茂钛与5－磺基水杨酸形成的水溶液和N－（取代苯基）氨基乙酸反应,简便全盛了三种二茂钛氨基酸配合物,采用元素分析、IR及^1H NMR等对其进行了表征。结果表明,氨基酸的羧基以单齿氧原子与钛配位,形成了双分子取代的二茂钛配合物。     

水溶液中产生(O_2)~·的机理及其自旋捕获研究

研究了氧饱和碱性连二亚硫酸钠（Ｎａ２Ｓ２Ｏ４）水溶液中超氧负离子基（Ｏ２－）产生的机理，ＥＳＲ和ＵＶ光谱结果表明该反应可能经历Ｏ２与ＳＯ２－间单电子转移；体系中Ｏ２－处于产生－消失的动态过程，其稳定性依赖于溶液ｐＨ值；一次充氧饱和条件下，［Ｏ２－］应不超过１０－３ｍｏｌＬ－１；连续充氧条件下Ｏ２－的累积量与ＳＯ２－的累积量有关     

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO4-H2O and NaF-H2O binary solutions and NaClO4-NaF-H2O ternary solution

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO₄-H₂O and NaF-H₂O binary solutions and NaClO₄-NaF-H₂O ternary strong electrolyte aqueous solutions was developed based on the ion and molecule coexistence theory (IMCT). A transformation coefficient was needed to compare the calculated mass action concentration and the reported activity, because they were usually obtained at different standard states and concentration units. The results show that transformation coefficients between the calculated mass action concentrations and the reported activities of the same components change in a very narrow range. The transformed mass action concentrations of structural units or ion couples in NaClO₄-H₂O and NaF-H₂O binary solutions agree well with the reported activities. The transformed mass action concentrations of structural units or ion couples in NaClO₄-NaF-H₂O ternary solution are also in good agreement with the reported activities in a total ionic strength range from 0.1 to 0.9 mol/kg H₂O by the 0.1 mol/kg step with different ionic strength fractions of 0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1, respectively. The results indicate that the developed thermodynamic model can reveal the structural characteristics of binary and ternary strong electrolyte aqueous solutions, and the calculated mass action concentrations of structural units or ion couples also strictly follow the mass action law.     

四氮杂卟啉铁(II)催化降解水中有机污染物

详细介绍了利用一种新的铁四氮杂卟啉作为催化剂活化氧降解水中染料如酸性品红、甲基橙、罗丹明 B( Rh B)和有毒有机分子对硝基苯甲酸 ( NBA)的初步研究结果 .用紫外可见光谱 ( U V- Vis)、高效液相色谱 ( HPL C)和红外光谱 ( FRIR)检测表明 :铁四氮杂卟啉 / H2 O2 体系有很好的氧化性 ,能使酸性品红、甲基橙褪色 ,但氧化效率下降较快 .发现了铁四氮杂卟啉 / O2 体系有很好的氧化性能且效率高 ,此体系能使有毒有机分子对硝基苯甲酸 NBA氧化开环 ,氧化率达 85 % ,在酸性、中性和碱性环境中都具有一定的氧化性 .7h内 ,在中性和酸性水中罗丹明 B降解近2 0 % ,尤其在碱性水中的降解达 5 2 % .     

KBr-H2O、NH4Br-H2O和ZnBr2-H2O作用浓度计算模型

建立了强电解质水溶液KBr-H2O、NH4Br-H2O和ZnBr2-H2O作用浓度的计算模型,计算了上述三个溴化物二元水溶液体系在温度为298.15K、质量摩尔浓度达到饱和前的作用浓度.热力学模型计算的组元作用浓度以纯物质为标准态和摩尔分数为浓度单位,与文献报道的组元活度以无限稀为标准态和质量摩尔浓度为浓度单位经过活度的标准态转换后可良好地吻合,且转换系数在计算的浓度范围内基本守恒.以上热力学模型计算的组元作用浓度能反映出强电解质水溶液的结构本质;在本模型的假设下电解质水溶液呈现理想溶液特征,组元的作用浓度在计算的浓度范围内严格遵守质量作用定律.     

Bonding and reactivity at oxide mineral surfaces from model aqueous complexes

The kinetic stability of oxide surfaces affects a broad range of physical phenomena, including mineral dissolution and sorption reactions, stable-isotope fractionation, and catalyst support degradation. Our knowledge of the rates of these processes derives mostly from the rates of net mass transfer between the bulk solid and fluid phases. But from such data it is difficult to determine rates of elementary steps that are needed to test theoretical models. Here we determine the rates of oxygen exchange between an aqueous fluid and specific sites on the 'Al13' polyoxocation--AlO4Al12(OH)24(H2O)12(7+)--the structure of which closely resembles the surfaces of some Al-(hydr)oxide minerals in soils and catalyst supports. Extrapolation of these data to 298 K (and near pH 5.3) yields half-lives for oxygen on the complex that range from approximately 0.6 milliseconds for bound water to 41 seconds and 13 hours for the two distinct, but structurally similar, bridging hydroxyls. This surprisingly large range of labilities (approximately 10(7)) indicates that reactivity is very sensitive to molecular structure. Moreover, these results indicate that well chosen aqueous complexes provide important information to relate bonding to reactivity at mineral surfaces.     

环氧化物溶胶凝胶路线制备近单分散尺寸可控Fe3O4纳米粒子

以二价铁盐为原料,利用环氧化物的胶凝或沉淀作用,以乙醇或水作为反应介质,在较低的温度下制备Fe3O4纳米粒子.表征结果表明,以H2O为溶剂可得到粒径在25～83 nm之间粒度分布较宽的Fe3O4纳米颗粒,而以乙醇为介质时,可得到粒度分布窄近单分散Fe3O4纳米粒子.由于该路线在制备纳米氧化物方面具有反应条件温和、工艺简单、原料价廉和易于规模化制备等优点,显示出其具有工业化前景.     

不同Li/Mn摩尔比尖晶石型锰酸锂中锂离子的酸处理抽出

采用熔融盐法合成了2种不同Li/Mn摩尔比的尖晶石型锰酸锂.在水溶液中用稀盐酸、(NH4)S2O8介质对其进行处理,旨在观察这2种化合物中的Li+离子抽出行为.结果表明对于Li+来说,2种酸溶液的抽出效果相似;Li+离子抽出表现为离子交换反应和氧化还原反应.HCl对于Mn的溶出率大,但是(NH4)2S2O8溶液几乎不溶解这2种锰酸盐.Mn的平均氧化态低的尖晶石被氧化性酸处理时,有更多的Mn3+转化成Mn4+.     

二乙酰丙酮桥联双核铜(Ⅱ)配合物的合成,EPR谱与热分析

以高氯酸铜、二苯甲酰甲烷、二乙酰丙酮为原料合成了新型固态三元配合物[Cu2(C10H12O4)(C15H11O2)2,并用元素分析、电导率、红外光谱、电子光谱和电喷雾质谱对其进行了表征,确定了配合物的组成,研究了配合物在氮气气氛中的热分解行为.对配合物测量了室温固体电子顺磁共振谱,定性探讨了配合物的电子结构,得到了其波谱参数(g=2.0892).     

碱性水溶液中的单线态氧电致化学发光

研究发现：当在碱性无机盐（如K2HPO4,Na2CO3或Na2B4O7）水溶液中施加适当调制的双脉冲电信号时,可以在电极表面观察到发光．通过研究发光光谱以及各种单线态氧抑制／增强剂对化学发光强度的影响规律,确定该体系的发光体为单线态氧．其发光机理为负电位下溶解氧被电还原为过氧化氢,在随后的正脉冲下产生超氧基阴离子,两者以Haber-Weiss反应机理生成单线态氧并产生光发射．     

二棕榈酰磷脂酰胆碱LB膜诱导下草酸钙晶体生长的SEM研究

目的：利用二棕榈酰磷脂酰胆碱（DPPC）的Langmiur-Blodgett膜（简称LB膜）作为模板诱导草酸钙晶体的生长,进而模拟生物体内尿结石的形成和抑制。方法：采用扫描电子显微镜（SEM）,对磷脂DPPC的L膜诱导过饱和溶液中生长的草酸钙晶体的密度增加、尺寸增大。但很小（π=1mN/m)时,几科没有草酸钙晶体,随着膜压增大,草酸钙晶体的密度增加、尺寸增大。但当膜压增加到35mN/m时,晶体却特别稀少。结论：作为模板的DPPC的LB膜的膜压不同时,可以诱导生成具有不同形状、不同密度和尺寸的CaC2O4晶体。LB膜中DPPC分了间的距离与CaC2O4晶体的结构相匹配是CaC2O4晶体定向生长的主要原因。     

盐酸在氨基酸水溶液中热力学性质的研究2丙氨酸、缬氨酸＋盐酸＋水体系

本文测定了电池Ｐｔ，Ｈ２（ｇ，ｌａｔｍ）｜ＨＣｌ（ｍ）十氨基酸（ｍＡ）＋Ｈ２Ｏ｜Ａｇ－ＡｇＣｌ在２９８．１５，３０３．１５，３０８．１５．３１３．１５，３１８．１５Ｋ时的电动势，这里氨基酸分别为丙氨酸（Ａｌａ）和缬氨酸（Ｖａｌ），求出了Ａｇ—ＡｇＣｌ电极在不同氨基酸水溶液中的标准电极电势Ｅｍ０，计算了ＨＣＩ从水到不同氨基酸溶液中的迁移热力学函数．着重讨论了溶剂结构的变化情况．提出了在氨基酸水溶液中存在着两种不同的结构形式，并从理论上进行了讨论．     

HNO_3-UO_2(NO_3)_2-H_2O体系活度系数的关联和预测

用Ｃｌｅｇｇ－Ｐｉｔｚｅｒ方程关联了ＨＮＯ３－Ｈ２Ｏ和ＵＯ２（ＮＯ３）２－Ｈ２Ｏ单一电解质水溶液离子 平均活度系数。在此基础上考察了有无混合参数对ＨＮＯ３－ＵＯ２（ＮＯ３）２－Ｈ２Ｏ非对称混合电解质 水溶液体系的关联和预测功能的影响，并与原Ｐｉｔｚｅｒ方程进行了比较。结果表明，Ｃｌｅｇｇ－Ｐｉｔｚｅｒ 方程在电解质浓度适用范围及预测精度方面均优于原Ｐｉｔｚｅｒ方程。     

In situ cryogenic Raman spectroscopic studies on the synthetic fluid inclusions in the systems H2O and NaCl-H2O

Fluid inclusions of the H2O-salt systems constitute the major fluid inclusion types preserved in the nature. The salts commonly present in the fluid inclusions are NaCl, KCl, CaCl2 and MgCl2[1,2]; among them NaCl is the dominant species. The most powerful…     

超临界水氧化法处理硫化铵废水

超临界水氧化法可以快速处理硫化铵废水,其反应产物包括S2O32-、SO32-和SO42-。S2-的去除速率随反应时间、温度、压力、氧气浓度的增大而升高。     

Pt/HPW/ZrO2催化甘油脱氧制取1,3-丙二醇

以磷钨杂多酸为钨前驱体用浸渍法制备系列具有不同Pt含量和不同HPW/ZrO2焙烧温度的Pt/HPW/ZrO2催化剂。通过BET比表面积、红外光谱和X线衍射方法表征催化剂的结构,在连续流动固定床反应器中考察其对甘油水溶液催化脱氧制取1,3-丙二醇(1,3-PDO)反应催化性能的影响。结果表明:ZrO2负载磷钨杂多酸经500℃以上温度处理,磷钨杂多酸分解为相应的氧化物,单斜相WO3和磷氧化物分散在ZrO2表面。Pt/HPW/ZrO2催化剂对甘油脱氧反应具有较高的催化活性。铂负载量、HPW/ZrO2焙烧温度、反应温度、压力及甘油浓度等因素的变化,对甘油转化率和1,3-PDO收率的影响较大。在4 MPa、130℃、液体体积空速(LHSV)为0.25 h-1的反应条件下,2.0%Pt/HPWZ10(700)催化剂上60%甘油水溶液催化脱氧反应可得到53.4%甘油转化率和44.5%的1,3-PDO选择性,产物中1,3-PDO与1,2-丙二醇(1,2-PDO)摩尔比值达到14.3。100 h稳定性实验表明催化剂性能稳定。     

A novel cancer imaging method using chemiluminescence-mediated sonosensitization

In this paper, we introduce a novel method named chemiluminescence mediated sono dynamic diagnosis (SDD), which is designed as follows: sonosensitizer is used to localize the cancer tissue, and is sonosensitized by the ultrasound field to produce oxygen free radicals. Then, another agent, FCLA (fluoresceinyl cypridina luciferin analog), reacts with IO2 to efficiently transform the chemical energy of 1O2 to photons, thus a strong chemiluminescence is emitted.One can then detect this emission with a high sensitive CCD imaging system to localize the tumor. Based on the principle of chemiluminescence mediated SDD, we obtained a clear diagnostic image of a transplanted tumor in a nude mouse in the experiments. This method could have potential applications in clinics for early stage tumor diagnosis.