The stabilization of nanodisperse silver in a sulfo cation exchanger

Silver-ion exchanger (electron ion exchanger, EI) composites with equivalent silver and hydrogen counterion contents were prepared by chemical deposition. Microscopic and X-ray data showed that silver nanoparticles and their ensembles isolated from each other and stabilized by a polymeric matrix were formed. Contact of Ag⁰-EI in the H⁺ form with solutions of silver salts caused the occurrence of two processes, ion exchange and metal recrystallization. These processes were interrelated because they involved one common particle, the silver counterion. Recrystallization proceeded by the electron-ion mechanism, but, because of matrix isolation of silver particles, electron transfer occurred inside separate structural elements (ensembles of particles) rather than over the whole composite volume. The transfer of silver ions largely occurred over ionogenic matrix centers, which substantially decreased their mobility. The low electronic conductivity of the composite and limited mobility of counterions were charge stabilization factors, which hindered recrystallization and, along with matrix stabilization, contributed to the retention of nanosized silver particles.     

Formation of silver bromide precipitate of nanoparticles in a single microemulsion utilizing the surfactant counterion

Silver bromide precipitate of nanoparticles was prepared by addition of silver nitrate aqueous solution to a single microemulsion system consisting of dioctyldimethylammonium bromide, n-decanol, and water in isooctane. The silver ion reacted readily with the surfactant counterion, bromide, to form the precipitate of nanoparticles, which was stabilized in the water pools. The use of the surfactant counterion as a reactant is a new approach to nanoparticle preparation in microemulsions. It is characterized by high reactivity and less dependency on the intermicellar exchange of solubilizate. The effects of the surfactant and the cosurfactant concentrations, the amount of silver nitrate, and the water to surfactant mole ratio, R, were evaluated. Increasing the surfactant concentration at fixed R and amount of silver nitrate enhanced the role of intermicellar nucleation and resulted in the formation of larger particles, while increasing the amount of silver nitrate at fixed values of all the other variables enhanced the direct nucleation and resulted in the formation of smaller particles. Particle aggregation and flocculation took place when the concentration of n-decanol or the value of R was increased. Particle aggregation and flocculation were attributed to the decrease in the interaction between the surfactant protective layer and the nanoparticles in the water pools.     

快速测定CODcr的研究

对以往经典的测定水样ＣＯＤｃｒ的方法进行了改进，研究了消解时间与酸度的关系，确定了最佳条件，并确定了用硝酸银沉淀氯离子，消除氯离子的干扰取有毒的硫酸汞是可行的。     

银诱导大鼠肝脏金属硫蛋白的提纯与鉴定

Ｗｉｓｔａｒ公鼠经腹腔注射ＡｇＮＯ３后可诱导肝脏合成ＭＴ。经匀浆、乙醇沉降、Ｓｅｐｈａｄｅｘ－７５、ＤＥＡＥ－５２两次柱层析，可得到两个亚型。原子吸收测定结果表明：该蛋白分别含７份Ａｇ、２份Ｚｎ和２份Ｃｕ，具有与Ｃｄ５Ｚｎ２－ＭＴ并不相同的二级、三级结构。进一步研究表明，蛋白中伴随Ｃｕ和Ｚｎ的含量与所用诱发剂的种类、数量均有关，且Ｃｕ和Ｚｎ（通过ＭＴ）具有某种微妙的联系。     

Nucleophilic substitution at sulphonyl sulphur part 3. Hydrolysis of substituted thiophene-2-sulphonyl chlorides catalysed by silver nitrate and silver nitrite salts

Hydrolysis reactions of substituted thiophene-2-sulphonyl chlorides (5-methyl, 5-H, 5-chloro, 5-nitro) catalysed by silver nitrate and silver nitrite salts have been studied in water at 25°. Salt effects by potassium nitrate, sodium perchlorate and mercuric bromide have also been investigated. For the catalysis effected with silver nitrate, the pseudo-first order rate constants depend on the first power of silver ion concentration, while nitrate anion is not involved in the transition state. The corresponding curved Hammett plot suggests a transition state with a partially developed sulphonylium character. With silver nitrite, the rate dependence on both silver and nitrite ion concentrations would indicate that silver is involved in the transition state as well as nitrite. Also, in this case the curved Hammett plot obtained suggests a partial positive charge on the sulphur atom in the transition state. A comparison with uncatalysed hydrolysis reactions would support a previous interpretation that thiophene-2-sulphonyl chlorides hydrolyze by an S_N2 type mechanism which can shift toward an S_N1 or an S_AN process depending on the ring substituent.     

Continuous preconcentration system for nitrate ions using anionic reverse osmosis tubes coupled to an ion chromatograph

A continuous preconcentration system for nitrate ions was developed using cation exchange tubing made from Nafion perfluorosulfonic acid membrane. This method is based on ion exclusion effects and reverse osmosis phenomena. The system was evaluated by connecting it to an ion chromatograph. The concentration ratios could be increased by raising the pressures between the two sides of the cation exchange tubing. Twenty-fold concentration of nitrate ion was achieved when the pump pressure was 20 x 10(5) Pa. The relative standard deviations of the preconcentration ratio at four different pump pressures, 5, 10, 15 and 20 x 10(5) Pa were 1.2-2.8% (n = 5).     

Transference numbers of silver perchlorate in water at 25°C

The cation and anion transference numbers of aqueous silber perchlorate at 25°C have been determined by the direct moving boundary method from 0.01 to 0.2 M. The cation constituent transference numbers rise in a monotone fashion with increasing concentration contrary to the expectations, of the limiting Debye-Hückel-Onsager theory. The results can be fitted by the revised 1963 Fuoss-Onsager theory only by the assumption of unrealistically large distances of closest approach. The behavior of aqueous silver perchlorate closely parallels that of aqueous silver nitrate and suggests that some property of the silver ion is responsible. To whom correspondence should be addressed.     

活性碳纤维对银离子还原吸附能力的改进

活性碳纤维不仅对有机物有高的吸附容量,对贵金属离子也具有强的还原吸附能力,可将Pd(Ⅱ）,Ag（Ⅰ）,Au（Ⅲ）等离子还原为金属单质。因而可用于提取矿液或加收废液中的贵金属。由此,提高或改善贵金属在活性碳纤维上的还原吸附容量或分布形成,显得非常重要。本文研究了活性碳纤维制备条件、表面氧化改性、以有负载有机物等对活性碳纤维还原能力的影响。结果表明,（1）制备条件对剑麻基活性碳纤维的还原能力有很大的影响。用H3PO4或ZnCl2活化的活性碳纤维对银离子具有更高的还原吸附容量,分别可达250和700mg/g,约为水蒸汽活化剑麻基活性碳纤维对银离子还原吸附容量的2倍和5倍。（2）过氧化氢、高锰酸钾、或硝酸等无机氧化剂对活性碳纤维进行表面改性,也能提高活性碳纤维的还原能力。结果表明,虽然改性活性碳纤维的比表面积和孔体积下降10-20%左右,但基表面含氧量及含氧基团的种类发生了改变。这些改性活性碳纤维对Ag(NH3)2^ 的还原吸附量大幅度提高,可达550mg/g以上。推断表面改性在活性碳纤维表面创造了更多有利于碱性条件下发生氧化还原的活性点。（3）在活性碳纤维表面负载适当的有机物如亚甲基蓝、苯胺或对硝基苯酚,也能显著提高活性碳纤维对Ag(NH3)2^ 的还原吸附能力。     

On the Chemical Processes Accompanying Silver Reduction from Solutions of Its Salts in Organic Media

Silver reduction from its nitrate has been studied in the media of DGEBA-based and aliphatic epoxy resins. It has been found that, under the experimental conditions that were employed, silver ions can be reduced without chemical interaction with the medium only due to photochemical processes. The reduction rate is determined by the rate of dissolution of the initial silver salt in an organic medium and the possibility of the formation of solvates by the system components. Refractometry has been proposed for use in monitoring the kinetics of silver nitrate dissolution in epoxy resins and the formation of silver nanoparticles. Stable dispersions of silver nanoparticles in epoxy resins have been obtained.     

显影机理的正电子化学研究

采用正电子湮没技术(PAT)研究了照相明胶中的自由体积空穴在显影过程中的作用机理,为显影过程中银丝的生成机理探讨了一个新的模式,并为感光科学的研究拓展了一种新的研究技术和手段.结果表明:明胶的自由体积空穴的平均尺寸在显影过程中基本保持不变.照相明胶的自由体积空穴在电子密度空间限制了银离子还原为银原子的过程,并使得银原子的沉积生长以丝状的形式进行.照相明胶大分子结构和组份的复杂性导致了其自由体积空穴在空间分布无序混乱性,可能正是这种无序混乱性导致了银丝缠绕成团的松散空间结构.     

Titration of cyanide and hexacyanoferrate(II) with silver nitrate-II Determination of sodium cyanide and sodium hexacyanoferrate(II) in a complexing agent

Cyanide and hexacyanoferrate(II) can be titrated with silver nitrate in the presence of a complexing agent masked with a suitable metal ion. A method for determination of sodium cyanide and sodium hexacyanoferrate(II) in the presence of sodium nitrilotriacetate masked with magnesium ions is given as an example.     

Continuous preconcentration system for nitrate ions using anionic reverse osmosis tubes coupled to an ion chromatograph

A continuous preconcentration system for nitrate ions was developed using cation exchange tubing made from Nafion perfluorosulfonic acid membrane. This method is based on ion exclusion effects and reverse osmosis phenomena. The system was evaluated by connecting it to an ion chromatograph. The concentration ratios could be increased by raising the pressures between the two sides of the cation exchange tubing. Twenty-fold concentration of nitrate ion was achieved when the pump pressure was 20 × 10⁵ Pa. The relative standard deviations of the preconcentration ratio at four different pump pressures, 5, 10, 15 and 20 × 10⁵ Pa were 1.2 ～ 2.8% (n = 5).     

Titration of cyanide and hexacyanoferrate(II) with silver nitrate-I Calculation of titration curves for potentiometric and conductometric titration

Stepwise potentiometric titration of cyanide and hexacyanoferrate(II) with silver nitrate is possible in the absence of potassium ions. At an initial concentration below 5.00 x 10(-4)M, cyanide can be titrated with silver nitrate (Ag:CN = 1:2) and the end-point indicated by precipitation of silver hexacyanoferrate(II); hexacyanoferrate(II) can be titrated with silver nitrate (Ag: Fe(CN)(6) = 4:1) and the end-point indicated by precipitation of silver dicyanoargentate. The hexacyanoferrate(II) reacts with silver to form two poorly soluble salts, Ag(4)Fe(CN)(6), KAg(3)Fe(CN)(6). The formation of these salts has been confirmed by conductometric titration of hexacyanoferrate(II) with silver nitrate in solutions containing varying concentrations of potassium nitrate.     

The mechanism of the platinum indicator electrode in argentometry

A study has been made of the behaviour of platinum and some other inert electrodes in silver nitrate titrations. Where the metal surface has been subjected to a reducing treatment, such as cathodic polarization, before use, the electrode will often function as a silver indicator electrode throughout the titration. It has been shown experimentally that this is due to the formation of a layer of metallic silver upon the electrode by interaction of the surface with silver ions in solution. If the metal surface undergoes such pretreatment that it is oxidized, then its potential normally remains at the oxide value during a silver nitrate titration until the silver ion concentration is sufficiently great for this value to be exceeded by the silver silver ion potential; formation of metallic silver then again takes place and from this point onwards the electrode behaves as a silver electrode. A detailed interpretation of the behaviour of platinum after various pretreatments has been made along these lines.     

隔膜电解法测定离子水化数

在电解质溶液中,离子往往以水化离子形式存在,水化离子的形成影响溶液的静态和动态性质。离子水化数的测定有助于了解电解质溶液的结构,也为电解质溶液理论所需要。在已经提出的测定离子水化数的方法中,被引用得较多的几种经典方法和近代方法,或者由于方法本身的限制,或者在处理数据时所作的假设不尽合理,因此这些方法尚未满意地解决离子水化数的测定。迄今人们仍在不断寻求各种新的方法。本文将离子交换膜作为电解池的隔膜,电解时测量通过电解池的电量和阴极室或阳极室溶液体积的变化,并作必要的体     

几种固态芳烃与银离子配合物形成常数的测定

作者曾报道用溶质蒸气循环方式制备液态芳烃的饱和溶液,测出苯、甲苯、二甲苯、卤代苯等液态芳烃在水和硝酸银体系中的溶解度,并计算了上述芳烃与Ag~+配合物的形成常数。 具有C=C双键的许多固态芳烃也象液态芳烃一样可与银离子形成配合物,我们设计了溶质蒸气循环方式制备固态芳烃的装置,该法的最大特点是固态溶质和溶剂不直接接触,可以避免固态溶质颗粒在溶剂中的分散和容器壁上的吸附现象,因此用本法测定的溶解度和配合物的形成常数数据可靠、精确。     

Uptake of silver from AgNO3 salt by Zeolite-13X

Isotherms of silver uptake by zeolite-13X from AgNO₃ at temperatures /323-563 K/ around the melting point of the nitrate are reported. Measurements of silver uptake have been carried out by a neutron activation method. At temperatures below the melting point the Ag⁺ uptake is exchange dominant while above the melting point the exchange accompanies substantial AgNO₃ inclusion. The overall process of Ag⁺ uptake from both the powder and the melt is endothermic within the temperature range employed.     

Size control and catalytic activity of highly dispersed Pd nanoparticles supported on porous glass beads

This paper presents a novel in situ method to prepare monodispersed palladium nanoparticles supported on porous glass beads with an egg-shell structure at room temperature. This method integrates two processes of ion exchange and reduction in one step just by changing the solvent from water to alcohol. The monodispersed Pd nanoparticles around 3.75 nm in diameter with a face-centered cubic structure have been successfully prepared. The adsorption capacity for palladium reached 55.00 ± 0.55 mg/g in ethanol, which was 26 times larger than that in water. These Pd nanoparticles supported on porous glass beads showed an excellent catalytic performance through the hydrogenation of cyclohexene. In addition, this in situ method was also successfully applied to prepare monodispersed silver and gold nanoparticles supported on porous glass beads. Overall, this facile method provided an alternative for preparing a supported nanoparticle catalyst in a green way.     

自动电位滴定法测定炼油工业污水中的氯离子

介绍自动电位滴定法测定炼油工业污水中氯离子含量。炼油工业污水样品经加热煮沸、双氧水氧化等预处理后,通过调节使其pH=2～6,以硝酸银标准溶液为滴定剂,在自动电位滴定仪上进行电位滴定。试验表明,本方法可以用来测定带色度的炼油工业污水样品,且对样品的酸碱度无苛刻要求,过量的双氧水不影响测定结果,不同浓度的标准样品其测定结果与其标称浓度无显著性差异。     

菁染料与溴化银相互作用性质的研究

本文用计时电位法及电位滴定研究了十六种不同染料与溴化银之间的相互作用,进一步证明了具有离域π-电子的菁染料才能与卤化银形成络合物的论点。从得到的平衡常数K表明,固体表面上的卤化银-染料与溶液中银离子-染料具有相同键性质,都是银离子与染料离域π-电子作用的结果。