Masking of manganese in relation to stepwise complexometric determination of calcium, magnesium and manganese

A critical study has been made of the masking of manganese with potassium cyanide in alkaline medium for complexometric titration of calcium and magnesium. It has been found that there is incomplete oxidation to manganese(III) unless the solution is aged for a sufficient period or air is bubbled through the solution at 35 ± 5° for 10 min. The manganese(III) complex can be reduced with ascorbic acid for titration with EDTA. Procedures are given for stepwise titration of magnesium, manganese and calcium in silicate materials. Mixed indicators are used, to improve the end-points.     

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。     

A rapid complexometric scheme for analysis of iron, aluminium, calcium and magnesium in slags

A simple and rapid complexometric method has been developed for the simultaneous determination of iron, aluminium, calcium and magnesium in a single solution in slags. Phosphorous and small amounts of chromium (1.5 mg) and vanadium (1 mg) do not interfere in the titration. Titanium and manganese are suitably masked with lactic acid and tetra sodium pyrophosphate, respectively. In a suitable aliquot, iron is titrated at pH 2 with EDTA, using sulphosalicylic acid as indicator. To this solution, excess disodium 1,2-cyclohexane diamine tetra acetic acid (DCTA) is added and aluminium is titrated by titrating the excess DCTA with standard copper sulphate solution at pH 3.5, using 1-(2-pyridylazo)-2-naphthol (PAN) as an indicator. A known excess of EDTA is added, the pH is raised to 10 and calcium and magnesium are jointly titrated by titrating the excess EDTA with copper sulphate solution, using PAN indicator. The Ca-EDTA complex is demasked with ammonium oxalate at pH 5 and the released EDTA equivalent to calcium is titrated with copper sulphate solution at pH 10 with PAN indicator. Results of analysis compare favourably with certified values and values obtained by standard methods for BCS and other slags. A set of five samples can be analysed for iron, aluminium, calcium and magnesium in four hours as compared to three days by the classical conventional method.     

Application of potentiometric stripping analysis to compleximetric titrations

Samples that are 0.1–10 mM in lead(II) or 0.025–0.25 mM in bismuth(III) can be titrated with EDTA and the titrations monitored by means of computerized potentiometric stripping analysis. The coefficients of variation are 0.12–0.40%; systematic errors are estimated from computer-calculated titration curves using conditional constants obtained from the titration curves. The conditional stability constants for calcium(II), manganese(II) and lanthanum(II) in 0.5 M sodium chloride are determined from the exchange reaction with the lead—EDTA complex.     

偶氮胂-DCS作为钙镁络合滴定指示剂的研究及其应用

研究了利用光度显色剂偶氮胂－ＤＣＳ作为钙镁联合滴定指示剂的可能性及使用该指示剂滴定钙镁的准确性,与常用的钙镁络合滴定指示剂进行了比较,并成功地应用于水泥试样中钙镁含量测定。结果表明,偶氮胂－ＤＣＳ是一种良好的钙镁络合滴指示剂。     

Complexometric estimation of copper

Summary Copper(II) or Copper(II) and iron(III) in a mixture are determined by titration with EDTA (disodium salt) solution as complexometric reagent at p_H 4.0 using potassium thiocyanate-p-anisidine as an indicator.Fe^III is estimated in the mixture by titration with EDTA (disodium salt) solution using potassium thiocyanate-ether as an indicator.Cu^II present in the mixture is, therefore, equivalent to the difference in amounts of the EDTA (disodium salt) used for the two sets of titrations of the mixture using potassium thiocyanate-p-anisidine and potassium thiocyanate-ether as indicators respectively.Strontium, magnesium, manganese, calcium, barium and mercuric ions do not interfere in these estimations.

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Zusammenfassung Kupfer(II) oder Kupfer(II) und Eisen(III) zusammen werden komplexometrisch mit ÄDTA-Lösung bei p_H 4,0 unter Verwendung von Kaliumthiocyanat-p-Anisidin als Indicator titriert. Eisen(III) wird in dem Gemisch durch komplexometrische Titration gegen Kaliumthiocyanat-Äther als Indicator bestimmt. Der Kupfer(II)-gehalt ergibt sich aus der Differenz der beiden Titrationen. Strontium, Magnesium, Mangan, Calcium, Barium und Quecksilber(II) stören nicht.

     

镉离子选择电极电位滴定测定钙镁

建立了以镉离子选择电极极作指示电极ＥＤＴＡ、ＥＧＴＡ电位滴定测定钙、镁的方法，详细考察了电位滴定的适宜条件，干扰离子的影响及消除办法。在四硼酸钠－氢氧化钠缓冲介质中，ＥＧＴＡ滴定钙，ＥＤＴＡ滴定钙镁含量，测定矿泉水及硅酸盐样品中钙镁含量，结果符合要求。     

多元稀土薄膜的微量化学分析法(YSmLuCa)3(FeGe)5O12原子比值

本法解决了薄膜取样问题,以及稀土与非稀土元素的分离和测定,从而确定了薄膜组份的原子比值。方法的准确度与精密度都达到要求,并可为非破坏性测定提供校对数据。本法也适用于其他类型的多元稀土薄膜的测定。     

Arsenazo III as metallochromic indicator for complexometric determination of calcium in slightly alkaline medium

Arsenazo III is proposed as metallochromic indicator for calcium in slightly alkaline medium. The visual titration with EDTA was performed at pH 8 and 40 microg-12 mg of calcium were determined. The interference of some ions was considered and it was found that phosphate does not interfere appreciably. Spectrophotometric detection of the end-point was used for titration of calcium in the presence of magnesium at pH 9. For the estimation of the titration error, the conditional stability constants of the calcium-arsenazo III complex were found.     

Concentration and Thermodynamic Stability Constants of Magnesium(II) and Calcium(II) Tartrate Complexes in Aqueous Solutions

The formation of calcium and magnesium tartrate complexes was studied by potentiometric titration at ionic strengths of 0.1 and 0.3 (in the presence of tetraethylammonium chloride) at a temperature of 298.15 K. The composition and the stability constants of the complexes formed in the system were determined. The known stability constants were used to optimize the conditions of calorimetric determination of the heats of formation of calcium and magnesium tartrates in an aqueous solution.     

A micro-heterometric determination of traces of iron (III) in alloys and salts with α-nitroso β-naphthol

Ferric iron constituting approximately 0.01% — 0.1% may be determined by a heterometric titration with α-nitroso-β-naphthol. The solution may contain 99.9% or more of calcium, barium, magnesium, aluminium, chromium, manganese, nickel, cadmium or lead salts. No previous separation is necessary. The α-nitroso-β-naphthol is dissolved in alcohol. The analysed solution must be acidified. No complexing agents are necessary. Citrate or tartrate must be absent. The maximum optical density values which are obtained at the end of the titration are proportional to the amount of iron which is analysed. These maximum values are entirely unaffected by the concentrated salt solutions. The heterometric sensitivity of the reaction between iron and α-nitroso-β-naphthol is three times higher in 50% alcoholic solution than in water. The titration takes about one hour. The error is 0.0—4%.     

Comparative study of metomega chrome blue BBL, calcon, eriochrome blue S.E. and omega chrome black blue G as indicators in the complexometric titration of calcium and magnesium

Conclusion It can be concluded that for the determination of calcium and magnesium in mixtures two separate titrations are to be done in case of Calcon, Erio SE, BBG. Total calcium and magnesium was determined first and then calcium in a separate titration. Magnesium is found by differences whereas in the case of BBL, the mixture was first titrated for its calcium content, then the solution is made acidic with hydrochloric acid and then alkaline with ammonia buffer solution pH 10 and magnesium is determined in the same sample.It is also noticed that Erio SE can work in sodium hydroxide or potassium hydroxid medium as well as in diethyl amine; but its drawback is the red hue which can be overcome by the addition of a green component, whereas BBL is spoilt in sodium hydroxide or potassium hydroxide medium.In comparing the first 3 indicators (Calcon, Erio SE, BBG) we find that BBG is the best one in the titration of calcium and magnesium using either EDTA on Complexion IV, and its endpoint has no red hue as that found in Erio SE; also the recovery of calcium is quantitative in any ratio of magnesium.

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Vergleichende Untersuchung von Metomega Chromblau BBL, Calcon, EriochromblauS.E.und Omega-ChromschwarzblauG als Inidicatoren bei der komplexometrischen Bestimmung von Calcium und Magnesium

     

Determination of calcium in silicate rocks by potentiometric titration with ethyleneglycol-bis-(2-Aminoethylether)tetraacetic acid and a calcium-selective electrode

The method reported for the determination of calcium in silicate rocks involves titration with ethyleneglycol-bis(2-aminoethylether)tetraacetic acid (EGTA) to a potentiometric end-point. A Crytur calcium-selective electrode is used; the selectivity constants (K_ca,x) are less than 10^-3 for Mg, Ba, Sr, K and Na. The method can be used for calcium contents of 2% or higher (and exceptionally for lower contents), in the presence of up to 60% Mg, 33% AI, 17% Fe, 5% Ba, 5% Ti, and 2.5% Mn. Al, Fe and Ti are masked with sulphosalicylic acid, barium is precipitated as its sulphate, and manganese is bound as its cyanide complex. If the magnesium content is less than that of calcium, EDTA can be used as titrant, magnesium being masked with acetylacetone.     

Determination of calcium,magnesium, and phosphate in the presence of iron and each other

Excess EDTA and MgSO₄ solution is added to a mildly acidic solution of the sample containing calcium, magnesium, iron, and phosphate ions. Addition of NH₄OH to this solution results in the precipitation of MgNH₄PO₄·6H₂O and various iron compounds. Calcium ions and a portion of the magnesium ions stay in the solution as the respective EDTA chelates. The mixture is adjusted to a known volume and filtered. The EDTA content of the filtrate with the exception of the EDTA tied up as calcium-EDTA chelate, is titrated with standard CaCl₂ solution at pH 12.5–13.0 in the presence of hydroxy naphthol blue indicator. The calcium content of the sample can be calculated from the result of this titration.     

Non-destructive method for the analysis of gold(I) cyanide plating baths Complexometric determination of nickel and indium

A method is described for rapid determination of nickel and indium in gold(I) cyanide baths containing large amounts of citric acid and/or sodium citrate, without previous destruction of organic matter. Gold is removed by extraction with ethyl acetate. In one aliquot of the solution indium is masked with thioglycollic acid and nickel is precipitated with sodium diethyldithiocarbamate, extracted into chloroform, stripped into water and determined complexometrically. In a second aliquot indium and nickel are precipitated together with the same reagent and stripped into water, then nickel is masked with 1,10-phenanthroline, and indium is determined by direct titration with EDTA.     

Synthesis of o,o′-dihydroxyazo compounds and their application to the determination of magnesium and calcium by flow injection analysis

Seven _o,o′-dihydroxyazo dyes were synthesized and examined as spectrophotometric reagents for magnesium and calcium. These reagents are highly sensitive for magnesium (? = 47 000) and calcium (? = 39 000 l mol^?1 cm^?1). Of the reagents synthesized, 2-(2-hydroxy-3,6-disulfo-1-naphthylazo)-5-(N,N-diethylamino)phenol was the best because of its ease of preparation and purification, and its stability in alkaline solution. This dye was applied in the determination of magnesium and calcium by flow injection analysis. The total concentration of magnesium (0.1–1.2 mg 1^?1) and calcium (0.4–4.0 mg 1^?1) was determined by masking iron(III), aluminium(III), copper(II), zinc(II), manganese(II) and cadmium(II) with 2,3-dimercapto-1-propanol (DMP) and triethanolamine (TEA). Magnesium was determined by masking calcium and the other metal ions with a ligand buffer containing barium(II)—EGTA, DMP and TEA. The amount of calcium was obtained as the difference between the two peak heights. Results for the determination of magnesium and calcium in potable water and serum are presented.     

Omega Chrome Black PPV, a new metal indicator

Summary The use of Omega Chrome Black PPV for the EDTA titration of zinc, manganese, nickel, cadmium, magnesium and lead is described. The sensitivity limits of detection of the equivalence points are determined. The indicator has been found to be suitable in titrations of mixtures of manganese and zinc.     

The use of Metomega Chrome Blue BBL as a metal indicator and its application for the determination of calcium and magnesium in serum

Summary Metomega Chrome Blue BBL was used as a metal indicator for the detection and titration of calcium, magnesium, manganese, nickel and manganese. A displacement reaction was described for the titration of cadmium using Mn-EDTA. A stepwise titration was conducted for the direct titration of both calcium and magnesium in blood serum.Fenugreek mucilage was used as a media for increasing the sensitivity limits of detection of barium, cadmium, cerous, calcium, copper, cobalt, magnesium, manganese, nickel, lead and zinc.     

EDTA滴定法测定钢渣中游离氧化镁

以碘-乙醇溶液为催化剂,选择乙二醇作溶剂浸取钢渣中游离氧化镁,采用EDTA滴定法测定其中游离氧化镁的含量。试验中考察了碘-乙醇的最佳用量和K-B混合指示剂的最合适配比。结果表明:催化剂碘-乙醇溶液的添加量达碘与氧化镁的质量比为7.5比1,指示剂中酸性铬蓝K和萘酚绿B的比值为1比1.4时,滴定终点变色明显,滴定结果准确。在钢渣中加入纯氧化镁测定的平均回收率为96.5%,相对标准偏差(n=5)为1.3%。     

The use of Omega Chrome Black Blue G in chelatometric titrations

Summary The reactions of Omega Chrome Black Blue G with a large number of cations is studied. This study has shown in many cases high sensitivity limits of detection of metals. It also showed that this dye can be used as an indicator for EDTA titrations of zinc, cadmium, manganese and lead. It is also a suitable indicator for the step wise titration of calcium and magnesium in blood serum and water.