金—钼酸盐—丁基罗丹明B体系显色反应研究

研究了在高氯酸和聚乙烯醇（ＰＶＡ）存在下，金与钼酸盐和丁基罗丹明Ｂ（ＢＲＢ）的显色反应。其适宜条件ＣＨＣｌＯ４＝１．５ｍｏｌ／Ｌ，ＣＭｏＯ２－４＝９．１×１０－４ｍｏｌ／Ｌ，ＣＢＲＢ＝３．８×１０－５ｍｏｌ／Ｌ及０．０８％ＰＶＡ。金钼杂多酸—丁基罗丹明Ｂ离子缔合物的最大吸收位于５７０ｎｍ，表观摩尔吸光系数为３．３６×１０６Ｌ·ｍｏｌ－１·ｃｍ－１，金量在０～４０μｇ／Ｌ范围内服从比尔定律，测定极限（Ｓ／Ｎ＝３）０．９０μｇ／Ｌ（ｎ＝１０），对于２８μｇＡｕ（Ⅲ）／Ｌ测定的相对标准偏差２．１％（ｎ＝７）。缔合物至少可稳定５ｈ，摩尔比Ａｕ∶ＢＲＢ＝１∶３。考察了４４种共存离子的影响，大多数常见离子不干扰，用活性炭分离富集金，对砂矿和炭粉中金的测定，结果满意。     

化学镀钴液中钴（Ⅲ）的分光光度测定

研究了钴－１－（２－吡啶偶氮）－２－萘酚及溴化十六烷基三甲铵体系测定钴。钴与ＰＡＮ二元配合物摩尔吸光系数可达９．４－１０＾３ｌ．ｍｏｌ＾－１．ｃｍ＾－１加入表面活性剂后，钴与ＰＡＮ生成三元配合物，摩尔吸光系数数值提高到２．１２－１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，钴含量０－２５μｇ／５０ｍｌ范围内经耳定律，方法应用于测定化学镀钴液中钴的测定。     

磷锑钼三元杂多酸光度法测定药品中的抗坏血酸

研究了少量抗坏血酸与磷锑钼三元杂多酸体系的显色特性，建立了借磷锑钼三元杂多蓝测定抗坏血酸的分光光度法。最佳显色条件为［ＰＯ３－４］＝３０×１０－４ｍｏｌ·Ｌ－１，［ＳｂⅢ］＝４５×１０－５ｍｏｌ·Ｌ－１，［ＭｏＯ２－４］＝７５×１０－３ｍｏｌ·Ｌ－１，Ｐ∶Ｓｂ∶Ｍｏ＝１∶０１５∶２５，［Ｈ加入］／［Ｍｏ］＝５７。测定波长为λｍａｘ＝７１０ｎｍ，线性范围为１～５０μｇ·ｍＬ－１，回归方程为Ａ＝３６８０Ｃ－００１４，线性相关系数ｒ＝０９９９８，表现摩尔吸光系数ε７１０＝３６８×１０３Ｌ·ｍｏｌ－１·ｃｍ－１，检出限为０２μｇ·ｍＬ－１，标准回收率为９５％～１００％，变异系数ｃｖ≤０３４％（ｎ＝６）。与二元磷钼杂多酸方法相比，省去了水浴加热的繁琐操作，而且由于锑（Ⅲ）的引入，显色在室温下３５ｍｉｎ便可完成，并可稳定５ｈ。     

新显色剂4—（2—苯并噻唑偶氮）邻苯二酚—钼（Ⅵ）—OP体系的分光光度研究

在ｐＨ５．０～５．７范围内，新显色剂４－（２－苯并噻唑偶氮）邻苯二酚（ＢＴＡＰＣ）与钼（Ⅵ）和非离子表面活性剂ＯＰ反应，形成稳定的、带负电荷的、紫红色三元胶束配合物。该配合物中Ｍｏ（Ⅵ）与ＢＴＡＰＣ的组成比为１∶２；其λｍａｘ为５６０ｎｍ，对比度（Δλ）为１２８ｎｍ；在２０℃、ｐＨ５．２和μ０．１时，配合物的表观稳定常数为３．０２×１０１０，表观摩尔吸光系数ε５６０为８．１１×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，真实ε５６０为７．６７×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。钼含量在０～０．７２ｍｇ／Ｌ范围内遵从比耳定律。建议了配合物的结构。本法简便、快速、准确，用于合金钢试样中痕量或小量钼的测定，取得了满意的结果。     

新显色剂甲氧基—茉并噻唑重氮氨基偶氮苯与汞的显色反应及应用研究

研究了新量色剂－６甲氧基－苯并噻唑重氮氨基偶氮苯与Ｈｇ（Ⅱ）的显色反应。在非离子表面活性剂存在下的ＰＨ１０．５Ｎａ２Ｂ４Ｏ７－ＮａＯＨ缓冲介质中,Ｈｇ（Ⅱ）与该试剂形成１：２的稳定络合物,其λｍａｘ＝５２５ｎｍ,ε５２５＝１．６×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１。汞含量在０－８μｇ／１０ｍＬ范围内遵守比尔定律,用于废水中汞的测定,得到满意的结果。     

5—Br—PADAP—乳化剂OP分光光度法测定电镀废水中微量锌

研究了在乳化剂ＯＰ存在下,利用５－Ｂｒ－ＰＡＤＡＰ测定电镀废水中微量锌的显色条件。实验表明,在Ｐ来７．５－１０．０硼酸－硼酸钠缓冲溶液中,锌与５－Ｂｒ－ＰＡＤＡＡＰ,乳化剂ＯＰ形成紫红色３元配合物,其λｍａｘ＝５５２ｎｍ,∑５５２＝１．３＊１０＾５Ｌ／ｍｏｌ ｃｍ配位比为１：２,在０－２５μｇ／５０ｍＬ服从朗伯－比一律。该方法应用于电镀废水微量锌的测定具有灵敏度高,准确度好,操作简便安全,快速的特     

5—（5—硝基—2—吡啶偶氮）—2,4—二氨基甲苯与铂（Ⅱ）显色反应的研究

报道了５－（５－硝基－２－吡啶偶氮）－２,４－二氨基甲苯（５－ＮＯ２－ＰＡＤＡＴ）与铂（Ⅱ）的显色反应。实验表明,在０．９～３．２ｍｏｌ／Ｌ的磷酸介质中,铂（Ⅱ）可与试剂形成稳定的１∶３绿蓝色配合物。该配合物的最大吸收波长为６１３ｎｍ,表观摩尔吸光系数为７．０２×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。铂（Ⅱ）浓度在０～１１μｇ／１０ｍＬ范围内符合比尔定律。大量的常见金属离子和除钌外的其他贵金属离子不干扰测定。所拟方法选择性好,可在不加任何分离的情况下,直接用于二次合金管理样－８８及催化剂中微量铂的测定,结果满意。     

Mo（Ⅵ）与Tiron的显色反应及应用研究

研究了Ｍｏ（Ⅵ）与Ｔｉｒｏｎ的反应，发现在ｐＨ４．０的ＨＡｃ－ＮａＡｃ介质中形成１：１配合物，该配合物在２５２ｎｍ、３１５ｎｍ有两个吸收峰，而在可见光区无吸收峰。测得ε２５２＝６．９×１０￣３Ｌ·ｍｏｌ－１·Ｃｍ－１，ε３１５＝３．５×１０３Ｌ·ｍｏｌ－１·Ｃｍ－１。据此建立了测定Ｍｏ（Ⅵ）的方法，在２５２ｎｍ和３１５ｎｍ处的线性范围分别为１．６×１０－６ｍｏｌ·Ｌ－１～２．Ｏ×１０－４ｍｏｌ·Ｌ－１和３．２×１０－４ｍｏｌ·Ｌ－１～２．０×１０－４ｍｏｌ·Ｌ－１。检出限分别为８．Ｏ×１０－７ｍｏｌ·Ｌ－１和１．６×１０－６ｍｏｌ·Ｌ－１．ＰＯ＿４￣３＋、ＳｉＯ＿３￣２－对测定无干扰，而Ｗ（Ⅵ）、Ｖ（Ⅴ）、Ｆｅ（Ⅲ）等有干扰。该法试用于有机磷合钼聚多酸盐样品的测定，结果满意，方法回收率９６％～１０２％，变异系数≤１．ｌ％（ｎ＝１２）。     

蒸汽冷凝液中微量PO4^3—的测定

探索了用氯化亚锡还原光度法代替原用分光光度法测定锅沪蒸汽冷凝液中的微量ＰＯ４３－。实验最大吸收λ＝７００ｎｍ，表观摩尔吸收系数ε＝１．８×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，ＰＯ４３－含量在２．５×１０－５～６．０×１０－４ｍｇ／ｍｌ内服从比尔定律，测定回收率为９３％～１０６％，标准偏差３．９（ｎ＝７）。已应用于实际生产中，结果满意     

分光光度法测定盐酸环丙沙星

研究了０．１ｍｏｌ·Ｌ＾－１的硫酸介质中，盐酸环丙沙星与三氯化铁的显色反应。盐酸环丙沙星浓度在３．３×１０＾－５￣７．３×１０＾－４ｍｏｌ·Ｌ＾－１（０．０１２￣０．２７ｍｇ·Ｌ＾－１）范围内符合比尔定律，ε＝１．８５×１０＾３Ｌ·（ｍｏｌ·ｃｍ）＾－１。测得络合物组成比为１：１。本方法简便准确，可用于片剂和胶囊中盐酸环丙沙星的测定。     

钕-铝系稀土色料的研制

通过钕-铝系列色料合成实验,分析不同配比及不同矿化剂等对色料呈色效果的影响,确定最佳工艺方法。对实验结果进行XRD及色度分析,确定其主晶相为钕酸铝,试样的明度均在70以上,色彩鲜艳亮丽。     

Phase equilibrium in binary La2O3-Dy2O3 and ternary CeO2-La2O3-Dy2O3 systems

Cerium oxide doped with oxides of rare earth elements is a multifunctional material, a wide range of uses which is associated with its unique physicochemical properties. Phase diagrams of multicomponent systems are the physicochemical basis for the creation of new materials with improved characteristics.In this work, phase equilibria in ternary CeO₂–La₂O₃–Dy₂O₃ and binary La₂O₃–Dy₂O₃ systems in the whole concentration range were studied. No new phases have been identified in these systems. An isothermal section of the phase diagram of the CeO₂–La₂O₃–Dy₂O₃ system at a temperature of 1500 °С is constructed. No new phases have been detected in the system. It was found that in the studied ternary system solid solutions are formed on the basis of (F) modification of CeO₂ with structure of fluorite type, monoclinic (B), cubic (C) and hexagonal (A) modifications of Ln₂O₃.In the La₂O₃–Dy₂O₃ binary system (1500–1100 °С) three types of solid solutions are formed: based on hexagonal modification A-La₂O₃, monoclinic modification B-Dy₂O₃ and cubic modification C-Dy₂O₃ separated by two-phase fields (A+B) and (B+C), respectively. The boundaries of the regions of homogeneity of solid solutions based on A-La₂O₃ are determined by compositions containing 35–40, 20–25, 15–20 mol% Dy₂O₃ at 1500, 1250, 1100 °C, respectively. From the obtained data it follows that the solubility of Dy₂O₃ in the hexagonal modification of lanthanum oxide is 39 mol% at 1500 °C, 23 mol. % at 1250 °C and 16 mol% at 1100 °C. The limits of existence of solid solutions based on monoclinic B-modification are determined by compositions containing 30–35, 65–60 (1250 °С), 35–40, 55–60 (1100 °С) 40–45, 70–75 (1500 °C) mol% Dy₂O₃.In the studied system, with a decrease in temperature from 1500° to 1100°C, there is a decrease in the solubility of La₂O₃ in the crystal lattice of cubic solid solutions of C-type from 16 to 10 mol%.     

Polycrystalline In2O3 and In2O3/Y2O3 photoanodes

Single crystal In₂O₃ shows promise as a photoanode for the decomposition of water. Because of various difficulties in the preparation of the single crystal material, two simple techniques were developed for the preparation of polycrystalline In₂O₃ anodes. One method involves the thermal decomposition of the nitrate while the other utilizes the chemical vapour deposition technique. Voltammograms and photoresponse spectra of these anodes are compared to the single crystal material. Among other observations, it is noted that the quantum efficiencies of the thermally decomposed films are comparable to the single crystal material. It is also shown that the on-set potential can be shifted to more negative values by forming the mixed oxide In₂O₃/Y₂O₃.     

Fe2+/H2O2体系O2生成路径

掌握Fe²⁺/H₂O₂体系O₂的生成路径,可为避免H₂O₂无效分解,开发经济高效的Fe²⁺/H₂O₂体系利用技术指明方向。采用添加自由基捕获剂的方法,探究Fe²⁺/H₂O₂体系内各种自由基对O₂生成速率的影响,进而确定O₂的生成路径。结果表明:Fe²⁺/H₂O₂体系内不会产生大量O₂^-·,O₂^-·不是生成O₂的主要反应物质;O₂^-·被全部捕获后,体系中仍产生大量O₂^-·,但此时无O₂生成,证明生成O₂的反应由·OH和HO₂·两种自由基直接参与。分析认为反应·OH+HO₂·-H₂O+O₂是体系内O₂生成的主要路径。控制Fe²⁺/H₂O₂体系定向生成·OH,抑制HO₂·的产生,是提高Fe²⁺/H₂O₂体系中H₂O₂利用率的有效手段。     

Na2O-Al2O3-Fe2O3系烧结过程中铝、铁的反应行为

以Al2O3, Fe2O3和Na2CO3为原料,对Na2O-Al2O3-Fe2O3系烧结过程中的反应行为进行了详细研究. 基于溶出率与时间、温度的关系,证明Na2O×Al2O3和Na2O×Fe2O3的生成反应动力学都服从Zhuralev-Lesokin-Tempelman模型,表观活化能分别为186.59和80.92 kJ/mol,表明Na2O×Fe2O3比Na2O×Al2O3在动力学上更易形成;Al2O3易与Na2O×Fe2O3反应形成Na2O×Al2O3和Fe2O3,在1273 K烧结30 min,所得熟料Al2O3溶出率达98.51%;Fe2O3对Na2O×Al2O3的形成有双重作用,在1273 K下可加速Na2O×Al2O3的形成,超过1323 K,促使Na2O×Al2O3分解成Na2O和b-Al2O3,且随着温度升高或时间延长,分解程度增高,从而导致熟料中Al2O3溶出率显著降低.     

H2O2 / O3, H2O2 / UV And H2O2 / Fe2+ Processes For The Oxidation Of Hazardous Wastes

Activated hydrogen peroxide produces very reactive OH-radicals which destroy hazardous contaminants in water. The principles and different methods of activation are described. Results from laboratory studies show the numerous applications of this new technology. A successful scaleup of laboratory tests to an industrial level is discussed. Finally, a cost estimate for treating different types of water with hydrogen peroxide is presented.     

Propylene metathesis over Re2O7/Al2O3-B2O3 catalysts

A series of alumina aluminum borate (AAB) with various Al/B molar ratios were prepared by the coprecipitation method. The supported rhenium oxide catalysts with various contents of Re₂O₇ were also prepared by the impregnation method with perrhenic acid. The catalytic activity and stability of Re₂O₇/AAB catalysts for the reaction of propylene metathesis were tested in a fixed-bed microreactor. It was found that Re₂O₇/AAB is more active, stable and regenerable than Re₂O₇/Al₂O₃ for propylene metathesis. The optimum Al/B molar ratio was found to be in the range of 4–10.