The application of the ph-stat method to metal ion-catalyzed reactions

The pH-stat method, which is well known in organic chemistry and biochemistry, is used for the kinetic determination of metal ion catalysts. Indicator reactions that involve protons can be followed by controlled addition of standard base or acid. This is illustrated by the following examples: determination of copper(II) (0.03–0.3 μg ml^-1) with the indicator reaction ascorbic acid—peroxydisulphate; determination of molybdenum(VI) (0.2–2.5 μg ml^-1) with the indicator reaction thiosulphate—hydrogen peroxide; determination of zirconium(IV) (0.2–2 μg ml^-1) with the indicator reaction iodide—hydrogen peroxide; and determination of vanadium(V) (0.2–2 μg ml^-1) with the indicator reaction iodide—bromate. For one example, the copper—ascorbic acid—peroxydisulphate reaction, it is shown that the pH-stat method has distinct advantages over closed systems, giving considerably better sensitivity for the determination of copper (0.5–5 ng ml^-1 ).     

离子阱串联质谱法检测鱼肉中指示性多氯联苯

建立了使用离子阱串联质谱技术和同位素稀释技术准确测定鱼肉中的7种指示性多氯联苯（PCB）单体的方法。方法的检出限为0．025—0．068ng／g,6个加标鱼样（添加水平1ng／g）中7个单体的回收率为87.2％～103.7％,RSD为3．2％-8．7％（n=6）。本方法定量准确可靠,可用于食品中指示性PCB的测定。     

Applications involving oxidation with ethanolic iodine. Rapid potentiometric method for some reductants

Rapid potentiometric method was adopted for the determination of small amounts of hexacyanoferrate(II), thiosulfate, thiocyanate, and ascorbic acid, based on oxidation with ethanolic iodine at different pH values and subsequently titration of iodide with mercury(II) using silver amalgam as indicator electrode. The potential breaks at the vicinity of the endpoints were sharp enough for their accurate detection. The method provides for accurate determination of small amounts of some reductants of analytical importance.     

Benzohydroxamic acid as a reductometric titrant: Determination of manganese, chromium and vanadium in steels

A method has been developed for the rapid determination of manganese and chromium by direct stepwise reductometric titration with benzohydroxamic acid, and of vanadium by titration with ascorbic acid (with benzohydroxamic acid as indicator) in the same aliquot. The method is free from the interference of common alloying elements present in steels. Some BCS steel samples have been analysed with good precision and accuracy.     

Titrations using an apparatus for recording the antilogarithm of pH or pM

A titration apparatus plotting either the concentration of sample ion or the concentration of titrant ion has been tested. An antilog apparatus, converting measured e.m.f. values into concentrations is connected to ordinary titration equipment. The instrument has been tested by means of acid—base titrations (titrations of mixtures of weak acids and of a weak and a strong acid), precipitation titrations (determination of the chloride concentration in tap-water, titration of mixtures of halides), titrations with ion-selective electrodes (determination of the fluoride content of toothpaste) and complexometric titrations (determination of copper with EDTA, using mercuric ion as indicator ion and amalgamated silver rod as indicator electrode, or using a copper-selective indicator electrode). The method considerably simplifies the evaluation of the results as compared to conventional potentiometric titrations.     

三乙撑四胺六乙酸在络合返滴定测定钯中的研究

提出了在不同ｐＨ值下,络合返滴定三乙撑四胺六乙酸（ＴＴＨＡ）以测定钯的六个灵敏新指示剂体系;建立了以镧－ＤＢＳ－偶氮氯膦作为络合物滴定指示剂体系,研究了ＴＴＨＡ－Ｐｄ络合物的特性及反应机理。     

Determination of insoluble azides by thermometric titrimetry

A method for determination of azide, based on the thermometric titration of this anion with hydrochloric acid, is described. Although this reaction has a large enthalpy change (DeltaH = -3.6 kcal/ mole), sulphate is added as an endothermic thermometric indicator to improve the end-point. The application of the method to the analysis of insoluble azides has been studied.     

A new volumetric method for the determination of molybdenum(VI)

Summary A new volumetric method has been developed for the determination of molybdenum(VI). The method consists in the reduction of molybdenum(VI) by heating with a slight excess of hydrazine sulphate in 1 to 2 M hydrochloric acid medium for ten minutes on a water bath. The mixture is cooled and the molybdenum(V) obtained determined by titration with a standard solution of ceric sulphate at an overall acidity of 4 N hydrochloric acid, using diphenyl benzidine as indicator and adding 5 ml of syrupy phosphoric acid for 50 ml of the mixture. Alternately the molybdenum(V) can be titrated with a standard solution of ceric sulphate at an overall acidity of 3 N hydrochloric acid using ferroin as indicator and adding 5 ml of syrupy phosphoric acid for 50 ml of the titration mixture. The molybdenum(V) can also be titrated with a standard solution of sodium vanadate in 8 N sulphuric acid medium, using N-phenyl anthranilic acid as indicator. Alternately, the titration with sodium vanadate can be made with diphenyl benzidine as indicator in 4 N acid medium, adding 5 ml of syrupy phosphoric acid and 1 ml of 1.0 M oxalic acid to catalyse the indicator action. The method now proposed is much more convenient than the methods currently available. It is simple because it does not require any costly chemicals or complicated apparatus. Furthermore, it has the advantages of great rapidity and excellent precision.     

Determination of iron in the presence of large amounts of phosphate by titration with disodium dihydrogen ethylenediaminetetraacetate

Ferric iron, even in the presence of comparatively large amounts of phosphate, can be determined by titrating with the disodium salt of ethylenediaminetetraacetic acid (Versenate, Complexone III), using ammonium thiocyanate as indicator and extracting the red ferric thiocyanate into amyl alcohol, provided the pH is controlled at 2.0—2.4 at the end-point. The method has been successfully used for the determination of iron in phosphate-containing deposits from steam boilers.     

葡萄糖氧化酶催化荧光测定的非酶体系研究

多数氧化酶及其底物都是重要的临床检验指标[1]，目前普遍采用酶荧光法或酶显色法，通过氧化酶催化氧化底物生成H刃。，过氧化物酶（HRP）催化H刃2氧化生成荧光／生色底物，实现间接测定［’j．酶法测定的缺点是体系不稳定、反应条件苛刻、费用较高．最近Mitani等［’j报道了非酶法化学发光测定葡萄糖氧化酶，灵敏度高，但需要特殊试剂，且测定时间较长．我们用Fenton反应［‘j将H。O。转化为羟基自由基（“OH），进而氧化对苯二甲酸生成荧光物质，建立了荧光测定葡萄糖氧化酶的非酶法，详细研究了荧光指示剂的选择、Fenton试剂的改进…     

重铬酸钾容量法测定铁矿石中全铁的方法改进

选用三氯化钛-重铬酸钾-中性红指示剂容量法,通过对方法的改进,对温度、溶样酸、酸介质、指示剂及共存离子消除的不同条件实验的对比研究,优化了无汞测定全铁的分析方法,实验表明,方法的相对标准偏差(RSD)为0.16%,对国家标准物质测定结果与推荐值基本一致,参加中实国金比对Z比分数小于2,测定结果满意。     

Two-parameter determination in vinegar by a flow injection-pervaporation system

A flow injection method (FI) for the sequential determination of ethanol and acetic acid in vinegar is reported. The determination of ethanol is based on the oxidation of the pervaporated ethanol by K2Cr2O7. The acetic acid is determined by an acid-base reaction with Thymol Blue as the indicator. Both reactions are monitored photometrically at 600 nm using a single detector. Optimisation studies and assessment of the sequential Fl method are also reported. The linear determination range is 0-12% v/v for ethanol and 0-10% (grams of acetic acid in 100 ml) for acetic acid. The sample throughput of the sequential manifold is seven per hour. The new method was applied to vinegar samples and the results obtained were in excellent agreement with those from reference methods used in Spain.     

EDTA滴定法测定分银渣中的铅含量

采用氟化铵-盐酸-硝酸-高氯酸溶解样品,加入氢溴酸除去样品中的砷、锑、锡等共存元素,加入硫酸将样品中的铅转化为硫酸铅沉淀,通过过滤与其它元素分离,滴定前加入巯基乙酸掩蔽铋,在乙酸-乙酸钠缓冲体系下,以二甲酚橙为指示剂,建立了采用EDTA络合滴定法测定分银渣中铅含量的方法。实验方法用于测定分银渣中的铅含量,测定结果的相对标准偏差(RSD,n=11)为0.32%～0.90%,加标回收率为100%～102%。能够满足日常测定需求。     

EDTA络合滴定法快速测定矿石中钙、镁

试样用盐酸、硝酸、氢氟酸、高氯酸分解,在pH值为6～9时,经六次甲基四胺-铜试剂分离铁、铝、镍、钴、铅、锌、铜、镉、锰等干扰元素后,在pH=10的氨水和氯化铵缓冲溶液中,以酸性铬蓝K-萘酚绿B为指示剂,用EDTA络合滴定法测定钙镁合量;另在氢氧化钾溶液中,用钙试剂为指示剂,以EDTA络合滴定法测定钙量,从而计算镁的含量。当样品钙高镁低或者镁高钙低时,低含量的镁量或钙量(<5%)可用电感耦合等离子体原子发射光谱(ICP-AES)法准确测定,使结果更准确。实验中对三个标准样品中的钙和镁进行多次测定,结果与认定值相符,相对标准偏差在0.69%～1.3%(n=7),加标回收率在99%～102%。方法实用性强,已经成功应用于各类矿石中钙镁的检测。     

Spectrophotometric and volumetric molybdenum determination with 2,2'-biquinoxalyl

Volumetric and spectrophotometric methods for molybdenum determination based on reaction with 2,2'-biquinoxalyl (2,2'-BQx) in concentrated hydrochloric acid media have been developed. Absorption spectra of the 1,1'-dihydro 2,2'-biquinoxalylene complex shows the most intensive absorption band at 685 nm with molar absorptivity = 3.3 x 10(4) 1. mole(-1). cm(-1). The compound is characterized by good durability to high temperatures and concentrated acid media. The mentioned indicator gives distinct colour changes at the titration end-point. The spectrophotometric method for molybdenum determination is based on the use of the difference in absorbance between the oxidized and reduced forms of 2,2'-BQx. The indicator is reduced with Sn(II) and then part of it is reoxided as a result of addition of Mo(VI). The difference in absorbance between the blank determination and molybdenum sample increases linearily in the concentration range 0.2-2.0 mug Mo/cm(3). 2,2'-Biquinoxalyl was used as an indicator in the volumetric method for the determination of molybdenum concentrations in steel alloy. The interfering ions FE(III) and Cr(III) are easily eliminated as the precipitate of hydroxides. The mineral acids, hydrochloric sulphuric and perchloric acids, have been tested as reaction media.     

Über die Eigenschaften eines neuen Chromogens für die Blutzuckerbestimmung nach der GOD/POD-Methode

A method is described which uses the ammonium salt of 2,2′-azino-di-[3-ethyl-benzothiazoline-(6)-sulphonic acid] as a redox indicator for the photometric determination of glucose with glucose oxidase and peroxidase. The sensitivity of this method is more than four times better than the method using o-dianisidine. The test solution including all reagents necessary for the determination of glucose is highly stable.     

Analysis of hypobromite solutions by indicator titrations

A rapid titrimetric method is described for the determination of the three oxidizing components in 10^-1 N hypobromite solutions with only arsenic(III) as the standard reagent. Hypobromite is determined by titration with arsenic(III) in alkaline medium, with bromothymol blue, quinoline yellow or epsilon blue as reversible indicator. Bromite is determined by reaction with an excess of iodide in weakly alkaline medium, followed by titration of the formed triiodide with arsenic(III) solution and starch as indicator. Total hypobromite, bromite and bromate is determined by titration of arsenic(III) in hydrochloric acid medium, with quinoline yellow as reversible indicator. Bromate is calculated by difference.     

Selective determination of altertoxins by high-performance liquid chromatography with electrochemical detection with dual "in-series" electrodes

A selective method for the determination of altertoxin-I and altertoxin-II by high-performance liquid chromatography with electrochemical detection is described. Altertoxins were separated on a reversed-phase column with methanol-water containing 0.1 M sodium nitrate and 1 mM nitric acid (60:40) as eluent and detected with dual in-series electrodes operating in the "redox" mode (generator electrode +1.0 V, indicator electrode -0.1 V). The method was applied successfully to the determination of sub-ppm levels of altertoxins in samples of maize, rice and tomatoes infected by Alternaria alternata.     

Potentiometric titration of Co(II) in presence of Co(III)

A potentiometric titration for cobalt(II) determination in the presence of Co(III) based on the oxidation of Co(II) with Na₂CrO₄ in ethylenediamine medium and back-titration of the oxidant excess with (NH₄)₂Fe(SO₄)₂ in acid medium is described. The titration is monitored with a Pt indicator electrode and carried out until the greatest jump of potential from one drop of titrant appears. A RSD smaller than 1.5% has been obtained for 50–300 μmol Co(II). The method proposed was applied in the analysis of a new type electroless copper plating solutions containing Co(II)-ethylenediamine complex compounds as reducing agents. Cu(II), Co(III) and Cr(III) do not interfere in the determination of Co(II).     

EDTA络合滴定法测定选铁尾矿中CaF2含量

采用EDTA络合滴定法测定选铁尾矿中的氟化钙含量。选用稀乙酸浸取试样中的碳酸钙,分离过滤氟化钙,用锆-二甲酚橙褪色分光光度法测定浸取液中的氟含量,折算为在稀乙酸中微溶的氟化钙的量;同时沉淀部分用氯化铝溶液在沸水浴中溶解浸取氟化钙,以三乙醇胺掩蔽干扰离子,在KOH介质中,以钙指示剂为指示剂,用EDTA标准滴定溶液测定沉淀中氟化钙的量,两者之和为试样中氟化钙的含量。用此法对试样进行11次平行测定,相对标准偏差（RSD）小于1.0%。在选铁尾矿试样中加入萤石标准物质进行加标回收实验,加标回收率在99%-102%。方法流程短,操作简单。精密度和加标回收率均能满足要求。