EDTA滴定法连续测定铅精矿中铅和锌

建立了EDTA滴定法连续测定铅精矿中铅和锌的方法。试样用盐酸、硝酸、硫酸和氯酸钾分解。铅通过硫酸铅沉淀与其他干扰元素分离,沉淀溶解于乙酸-乙酸钠溶液中。在滤液中加入氨水、氟化钾使铁等干扰元素沉淀并与锌溶液分离。用二甲酚橙作指示剂,EDTA分别滴定溶液中的铅和锌。研究中测定了能力验证NILPT(2010)-0211铅精矿样品10-1和10-2中铅和锌,结果满意。     

Colloidal and Chemical Processes during the Interaction between Polyacrylic Acid and Zinc Oxide Dispersion

The kinetics of the accumulation of zinc ions in a solution during the interaction between polyacrylic acid and an aqueous dispersion of zinc oxide is investigated. It is shown that the concentration of zinc ions in solution reaches its maximum within 1.5–5 min after the onset of the process, depending on the concentration of the acid and zinc oxide. The initial rate of a process and the maximum concentration of zinc ions in the solution depend on the initial concentration of reagents in the system. The dissolution rate of zinc oxide is affected by the flocculation of dispersion particles and the concentration of zinc ions in the solution. The adsorption isotherm of polyacrylic acid on zinc oxide particles is of a step-wise type.     

用废电池锌片制备硫酸锌的实验改进

用废电池锌片制备硫酸锌的学生实验,因锌的酸溶解过程所需时间太长而影响实验教学质量。本文采取加热、加入稀CuSO4溶液"催化"并实施锌的"部分溶解"等措施较好地解决了这一问题。     

An atomic absorption spectrophotometric method for the determination of trace amounts of zinc in canned juices after ion exchange separation

An atomic absorption spectrophotometric method is described for the determination of microgram quantities of zinc in canned juices. After sample digestion in concentrated nitric acid, the solution is evaporated till near dryness, and then a solution of 2 M HCl is added to form tetrachlorozincate (II) ion. This acid solution, containing the zinc complex is passed through an ion-exchange column (anion exchange resin, chloride form, which is preconditioned by passing 1 M HCl solution). Zinc is eluted from the column with 0.01 M HCl solution. After evaporation to dryness, the residue is dissolved in 1% (v/v) HNO3, and then atomized into an air-acetylene flame. The limit of detection of the method is 0.15 micrograms ml-1 Zn. The analytical aspects of the proposed method, including the standard addition technique are discussed.     

A rapid turbidimetric method for the determination of total sulphur in zinc concentrate

A rapid, simple and reliable routine method for the determination of total sulphur in zinc concentrates, roasted products and leached residues from zinc smelters is described. The method involves the fusion of the ample with sodium peroxide and sodium carbonate or routine acid decomposition and dissolution to give soluble compounds. The absorbance of the barium sulphate suspension produced by the addition of barium chloride powder to a dilute hydrochloric acid solution of the sample, containing cetyltrimethylammonium bromide solution as a dispersing agent, is measured at 420 nm. The results obtained for some zinc concentrates and other products are compared with those obtained by the conventional gravimetric barium sulphate method. Results for a reference zinc concentrate and other samples with various matrices and the results obtained with standard additions to the samples are good.     

The use of naphthidine as indicator in the determination of zinc in metallurgical analysis

Using naphthidine as an internal indicator in the titration of zinc with standard potassium ferrocyanide solutions, suitable procedures are recommended for the determination of zinc in various non-ferrous alloys and in rubber ashes. With aluminium alloys, aluminium bronzes and white metals the zinc is separated from interfering elements by hydrogen sulphide procedures, whereas with tin bronzes the separation is best accomplished by an 8-hydroxyquinoline procedure. After the solution of rubber ashes in hydrochloric acid, the major interfering elements are removed from the zinc by filtration after making the solution ammoniacal. With samples giving large precipitates with ammonia, it is necessary to redissolve them and determine the entrained traces of zinc.     

锌汞齐还原法测定二硫代二乙酸

将锌汞齐能还原二硫代二乙酸(DTDGA)成巯基乙酸(TGA)的原理和碘量法滴定相结合,对电还原DTDGA合成TGA反应液中的DTDGA进行定量分析,测定结果的相对标准偏差为0.37%,加标平均回收率100.6%。     

Complexometric determination of aluminium in iron ore,sinter, concentrates and agglomerates

A method for the complexometric determination of aluminium in iron ore, sinter, concentrates and agglomerates encountered in international trade is described. The sample is fused in a zirconium crucible with a mixed flux of sodium carbonate and sodium peroxide. The fused mass is completely soluble in hydrochloric acid. The R₂O₃ oxides are then precipitated with ammonia and redissolved in hydrochloric acid. Elements such as iron, titanium and zirconium are separated from aluminium by solvent extraction with cupferron and chloroform. After removal of traces of organic matter from the aqueous phase, the solution is treated with an excess of EDTA, which is then back-titrated with zinc solution (Xylenol Orange as indicator). Addition of ammonium fluoride then releases EDTA equivalent to the aluminium and this is titrated with zinc solution. The method is rapid. The precision and accuracy are excellent, and the results comparable with those obtained by the referee method.     

Die Verteilungsenthalpie als Maß für die Donatorstärke eines Extraktionsmittels

The enthalpy which appears during the extraction of a metal ion with an organic solvent can be determined by calorimetric measurements. This measurements were based on the distribution of bismuth, mercury, zinc and cadmium from a solution containing lithium iodide and the extraction of iron, zinc, and uranium from a solution containing potassium thiocyanate. Uranyl nitrate was also investigated. The organic phase consisted of various esters of phosphoric and phosphonic acid and tri-n-octylphosphine oxide in i-octane. The calculated enthalpies are in accordance with the extraction behaviour of the metal ions observed by analytical methods.     

Extraction separation of cadmium and zinc with tetra-n-butylammonium iodide

Tetra-n-butylammonium iodide (TBAI) forms associations in chloroform and aqueous solutions. A TBAI solution in chloroform extracts hydroiodic acid by addition. From 0.5M hydroiodic acid medium cadmium is quantitatively extracted into a TBAI solution in chloroform. Under these conditions zinc is not extracted. This makes possible the extractive separation of cadmium from zinc in micro-or macroamounts.     

Surface treatment of zinc by Schiff’s bases and its corrosion study

The zinc metal surface is chemically modified by newly synthesized Schiff’s bases and its corrosion protection is investigated. The influence of concentration of Schiff’s bases on modification of zinc surface and immersion time in treatment bath are investigated and optimized for maximum corrosion protection efficiency. The electrochemical studies of treated zinc specimens are performed in aqueous acid solution using galvanostatic polarization technique. The treated zinc samples show good corrosion resistance. The recorded electrochemical data of chemically treated samples indicate a basic modification of the zinc surface. The protection efficiency of organic layer formed on zinc surface is tested by varying the acid concentration and temperature of the corrosive medium. The corrosion protection efficiency increases with the concentration of Schiff’s bases and immersion time. This is due to a strong interaction between zinc and the organic molecules, which results in the formation of a protective layer. This layer prevents the contact of aggressive medium with the zinc surface. The surface modification is confirmed by the scanning electron microscopy images. The interaction between metal atoms and Schiff’s bases is also established by IR studies. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 7, pp. 886–892. The text was submitted by the authors in English.     

New iodometric methods for the microdetermination of arsenic in organic compounds

New methods are described for the iodometric microdetermination of arsenic in organic compounds after wet digestion or oxygen flask combustion. After evaporation of the arsenic solution to dryness and dissolution of the residue in water, acetone is added and the solution is treated with iodide-iodate and the iodine liberated (by the interfering acids and the first dissociation step of arsenic acid) is reduced with thiosulphate. The KH(2)AsO(4) left is then reacted with zinc sulphate in presence of excess of KI and KIO(3). Acetone is added and the liberated iodine is titrated with thiosulphate. This titration corresponds to the second and third dissociation steps of arsenic acid and is used to calculate the arsenic content of the compound. When arsenicals not containing sulphur are decomposed by the oxygen flask method, the arsenic acid solution obtained is reacted directly with zinc sulphate in presence of KI and KIO(3) and the iodine released is titrated with thiosulphate. In this case, the titration corresponds to all three dissociation steps of arsenic acid. The average recoveries obtained by the two methods are 99.5 and 99.9%, respectively.     

柠檬酸中锌防蚀剂（1,3-Dioxolan-2-ylmethyl）三苯基溴化磷和碘离子的协同效应研究

采用称重法、动电位极化法和电化学交流阻抗技术研究了30 ^oC时(1,3-Dioxolan-2-ylmethyl)三苯基溴化磷（DTPB）对0.5 mol·L^-1柠檬酸中锌腐蚀行为的影响. 通过在环保型电解槽中对锌进行酸洗,这在文献中是不常用的. 结果表明,DTPB作为一种有效的防蚀剂,添加浓度仅为3×10^-3 mol·L^-1时,锌在柠檬酸溶液中的防蚀效率可达98.9%. 由于DTPB和碘化钾存在协同效应,两者联用时的防蚀效果要比单独使用DTPB强,防蚀参数为1.2,并随温度升高而减小. 本文提出了碘化钾作为吸附媒介,可使金属表面与DTPB结合的防蚀机制.     

Xylan hydrolysis in zinc chloride solution

Xylan is the major component of hemicellulose, which consists of up to one-third of the lignocellulosic biomass. When the zinc chloride solution was used as a pretreatment agent to facilitate cellulose hydrolysis, hemicellulose was hydrolyzed during the pretreatment stage. In this study, xylan was used as a model to study the hydrolysis of hemicellulose in zinc chloride solution. The degradation of xylose that is released from xylan was reduced by the formation of zinc-xylose complex. The xylose yield was >90% (w/w) at 70°C. The yield and rate of hydrolysis were a function of temperature and the concentration of zinc chloride. The ratio of zinc chloride can be decreased from 9 to 1.3 (w/w). At this ratio, 76% of xylose yield was obtained. When wheat straw was pretreated with a concentrated zinc chloride solution, the hemicellulose hydrolysate contained only xylose and trace amounts of arabinose and oligosaccharides. With this approach, the hemicellulose hydrolysate can be separated from cellulose residue, which would be hydrolyzed subsequently to glucose by acid or enzymes to produce glucose. This production scheme provided a method to produce glucose and xylose in different streams, which can be fermented in separated fermenters.     

EDTA滴定法测定再生锌原料中的锌含量

采用氟化铵-盐酸-硝酸-硫酸分解样品,氨水沉淀分离铁、锰、铅等共存元素,滤液中加入掩蔽剂掩蔽少量干扰元素,在pH=5～6的乙酸-乙酸钠缓冲溶液中,以二甲酚橙为指示剂,用EDTA标准滴定溶液滴定。测得结果为锌、镉合量,扣除镉量,即为锌量。方法用于测定再生锌原料中锌,结果的相对标准偏差(RSD,n=11)为0.15%～1.0%。按照实验方法对再生锌原料样品进行加标回收实验,回收率为99.1%～102%。能满足日常对再生锌原料中锌含量的检测要求。     

微分脉冲伏安法测定硫酸锌溶液中铊

研究了微分脉冲伏安法测定复杂硫酸锌溶液体系中的铊。讨论了伏安图的形成、测定底液和pH值的选择。结果表明:在醋酸介质(pH=4.5±0.2)中,加入适量EDTA、聚乙二醇6000和抗坏血酸的测定体系,采用微分脉冲伏安法可直接测定铊。方法检出限为1.0×10-8g/L,千倍浓度的8种阳离子共存或单独存在时均不干扰测定。方法用于湿法炼锌中上清、一段净化后液、二段净化后液、电积新液、电积废液中铊的测定,相对标准偏差RSD分别为1.6%,2.5%,3.3%,8.3%,4.9%,铊加标回收率为98.4%～102.2%。方法灵敏、简单、快速,用来测定湿法炼锌各阶段硫酸锌溶液中的铊,结果满意。     

Compleximetric titration of aluminum and zirconium in siliceous materials after alkali fusion of samples

Rapid methods for the determination of zirconium and aluminum in siliceous materials are described. Samples are decomposed by sodium carbonate—sodium borate fusion and dissolved in perchloric acid. The zirconium is titrated directly with standard EDTA solution at 90–95 ° C in 1 M perchloric acid solution with xylenol orange as the indicator. Aluminum is then complexed by boiling with an excess of EDTA and the free EDTA is back-titrated potentiometrically with standard zinc solution. Interference of titanium in the aluminum determination is prevented by lactic acid masking. The methods have been applied successfully to a wide variety of glass-ceramics, refractories and NBS minerals.     

Determination of sulphide, polysulphide, thiocarbonates and sulphur by extraction with tributyltin hydroxide, and of thiosulphate by hydrogenation

The methods presented involve the separation of sulphur compounds by means of a hexane solution of tributyltin hydroxide (TBT), followed by titration with o-hydroxymercuribenzoic acid in the presence of dithizone as indicator. Free sulphide is selectively extracted from strongly alkaline solution, whereas the polysulphides and thiocarbonates are extracted at pH 9-10. The polysulphide and thiocarbonate extracts decompose to form TBT-sulphide, sulphur and carbon disulphide. Treatment with sulphite, stannate(II), copper, vinyl cyanide and ethylenediamine, and hydrogenation with zinc and hydrobromic acid have been applied in the course of the analysis. The sulphur is determined by its attack on copper to form copper(I) sulphide which is subsequently dissolved in aqueous potassium cyanide solution and the sulphide separated by extraction.     

EDTA滴定法测定含锌物料中氧化锌

采用氯化铵-氨水体系溶解试样,干过滤后,向移取的滤液中加入氯化钡和硫酸共沉淀铅离子,过滤分离硫酸铅沉淀,向滤液中加人抗坏血酸、氟化钾、硫代硫酸钠等掩蔽剂掩蔽少量干扰元素。在pH=5~6的乙酸-乙酸钠缓冲溶液中,以二甲酚橙为指示剂,用EDTA标准滴定溶液滴定测得结果为氧化锌、水溶性锌和镉合量,扣除由原子吸收光谱法测得的水溶性锌量和镉量,即为氧化锌量。对总氨浓度、氯化铵-氨水浓度比、溶液加入量、搅拌时间、共存离子干扰、精密度等进行了实验,建立了EDTA滴定法测定含锌物料中氧化锌物相的分析方法。实验证明,氧化锌含量在24%~83%时,方法精密度(RSD)为0.25%~0.54%,加标回收率在99%~104%,完全满足含锌物料中氧化锌的测定要求。     

Determination of nitrate in sea water

Nitrate in sea water is determined by reduction to nitrite with zinc metal in ammoniacal solution in the presence of manganese (IV) as catalyst. The effects of hydrogen ion concentration, reduction temperature, reaction time and the order of reagent addition are discussed. The nascent nitrite diazotizes with sulfanilamide and is then coupled by N-1-naphthylethylenediamine in acid medium forming a diazo-dye which is measured spectrophotometrically.