Contributions to the basic problems of complexometry-XX Determination of calcium and magnesium

A new method for the determination of magnesium in the presence of calcium is described. Calcium is masked with EGTA whilst magnesium is titrated with DCTA with Methylthymol Blue as the indicator. Calcium can be determined in the same solution by back-titration of the excess EGTA with calcium chloride solution. The usual masking agents for iron, aluminium and other heavy metals can be used.     

Fluorometric titration of calcium, magnesium and iron using calcein blue as indicator

Calcium, magnesium and iron can be determined by successive fluorometric titration without separation. Calcium is titrated directly with EGTA at a pH 13; magnesium is determined by a substitution reaction with copper-EDTA complex at a pH of about 11 ; and iron is titrated directly with EDTA in the presence of hydrogen peroxide at a pH of 10.5, after destroying its triethanolamine complex. Calcein Blue serves as an indicator in all of the titrations and as a fluorescent standard. The end-points are sharp and the accuracy is good for various proportions of the metal ions. The method is simple, reproducible and inexpensive. Standard solutions of ions, limestone, cement and serum samples have been analysed by the proposed method.     

Amperometric complex-formation titration of traces of thorium

Thorium has been determined in the microgram range by complexometric titration with EDTA. The end-point was detected by following the anodic wave of EDTA at a rotating mercury electrode. It has been shown that thorium can be titrated in the presence of large amounts of other metals. Following electrolysis at a mercury pool electrode the titration is selective for thorium.     

Compleximetric determination of calcium in impure calcium carbonate and limestone

Calcium is determined in impure calcium carbonate and limestone samples by titrating with 0.01 M disodium EGTA at pH 12 in the presence of at least 0.6 mg of magnesium and a maximum of 500 μg of iron(III), using a pH 12.5 sodium hydroxide-potassium cyanide-sodium sulfide buffer and Calcon indicator. The results of such titrations are compared with those obtained by titrating at pH 10 the calcium perchlorate solutions derived from calcium oxalate, and with those of a modified LEWIS AND MELNICK method. The results for magnesium (% MgO) obtained by difference are in fair agreement. Magnesium can be titrated compleximetrically as magnesium perchlorate, but the reagent blank must be determined.     

Ethyleneglycol-bis(aminoethyl)tetraacetic acid in the amperometric titration of cadmium in the presence of zinc

Cadmium can be titrated amperometrically with EGTA in the presence of zinc; three modifications of the titration are described. The diffusion current of cadmium may be used to follow the titration at —0.90 or —0.70 V vs, the S.C.E, in ammoniacal or acetate-buffered medium respectively The titration may also be performed in ammoniacal solution at —0.30 V vs. the S.C.E., using copper as the amperometric indicator. The influence of iron, aluminium, magnesium, alkaline earths and lead was studied. Ascorbic acid could be used to mask iron and as an effective remover of oxygen. Under appropriate conditions cadmium could be titrated in the presence of 500-fold amounts of zinc. The titration error is approximately 0.002–0.003 ml of a 0.1 M titrant solution.     

Dosage electrochimique rapide,en une seule operation et sans separation,du calcium et du magnesium en presence lún de láutre: Application aux dosages de ces elements dans le serum sanguin et dans lúrine

An important simplification is proposed for the simultaneous electrochemical titration of calcium and magnesium in blood serum and urine. By using platinum wire and mercury electrodes, calcium can be titrated with EGTA and then magnesium with EDTA in the presence of a buffer (pH 10.5) and possibly a citrate-tartrate masking agent. A current due to oxidation of mercury in presence of EGTA or EDTA marks the end-point, and can be read directly or recorded. For blood serum, no preliminary operation is needed; for urine, prior addition of a little silver nitrate makes the method satisfactory.     

Semi-automatic catalytic titration of metal ion mixtures and its application to metallurgical samples

The semi-automatic catalytic titration of several metal ions and binary mixtures of iron(III) with copper(II), nickel or manganese(II) is described. The 4,4′-dihydroxybenzophenone thiosemicarbazone/hydrogen peroxide system was used in the presence of EDTA or EGTA as inhibitors with copper(II) as catalytic titrant. Two sample aliquots are necessary for the analysis of binary mixtures. In one, both metals are titrated in the presence of EDTA; in the other, only copper, nickel or manganese is titrated with EGTA or EDTA if a masking agent for iron(III) (triethanolamine or fluoride) is added. The iron/metal ratios tolerated range from 1:14 to 13:1 for the 0.2–3.0 μmol range, the relative standard deviation being 1–2%. The method was applied to metallurgical samples with good results.     

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。     

oxidmetric titration of triphenyl derivatives of phosphorus,arsenic, antimony and bismuth with N-bromosuccinimide

A simple direct titration for milligram and microgram amounts of triphenylphosphorus, -arsenic, -antimony, and -bismuth is described. The methanolic sample solution, with a little water, hydrochloric acid and bromide added, is titrated with N-bromosuccinimide to a methyl red end-point. All four compounds were titrated in the same way with recoveries of 99–100% and relative standard deviations of 1–5% were obtained.     

Rapid visual compleximetric titration of calcium in natural waters

Visual compleximetric methods for the titration of calcium in the presence of magnesium have been based either on masking the magnesium or using an indirect indicator procedure, e.g., the system Zn-EGTA-Zincon. In the proposed method these two approaches are combined. Zn-EGTA complex is added to the mixture and the zinc liberated in the calcium replacement reaction is titrated with EGTA after the magnesium has been masked with fluoride ion.     

Antilg i1-E曲线上的示波伏安滴定法

i_1-E曲线示波伏安滴定法是一种新的灵敏、准确的滴定分析方法。为进一步提高滴定终点指示的灵敏度,本文在产生i_1-E曲线的线路中,增加了正反馈电路和反对数电路,并提出了Antilg i_1-E曲线上的示波伏安滴定法。用EDTA或EGTA滴定了Ga~(3+)、Cd~(2+)、Zn~(2+)、Ni~(2+)、Co~(2+)等离子,并测定了铜锰合金中的锰,效果较好。     

Complexometric titration of calcium in the presence of larger amounts of magnesium

A simple and accurate titrimetric determination of calcium in the presence of larger amounts of magnesium is proposed. Calcium is extracted into a small volume of organic solvent as its glyoxal-bis(2-hydroxyanil) complex, and the calcium is titrated with EGTA. The end-point is sharp, and occurs when the red colour of the organic layer vanishes. This method has been successfully applied to the determination of calcium in sea-water with an error less than 0.1%.     

示波微分伏安滴定法

对示波伏安滴定装置进行了改进;提出了示波微分伏安滴定法;用EDTA及EGTA滴定了Zn~(2+)、Ga~(2+)、Cd~(2+)、Ni~(2+)和Co~(2+)等离子。实验结果表明:新方法灵敏度高、准确性好。     

Stepwise photometric titrations

Stepwise titrations of several metals with photometric end-point detection are described. The equivalence points when 2 metal ions are titrated compleximetrically, can be detected if the conditional stability constants are sufficiently high in value even if there are only slight differences between the colours of the different species of the indicator compounds.The following systems were analysed by stepwise photometric titration using either metalphthalein or eriochrome black T as indicator: manganese-calcium; manganese-magnesium; calcium-magnesium; manganese-calcium-magnesium; zinc-magnesium, EDTA, DTPA and EGTA were used as titrants. A satisfactory accuracy was attained in each case. The results agreed with conclusions drawn from the theory of stepwise photometric titrations based on equilibrium calculations and absorbance values.     

Successive substitution titration of calcium and magnesium with EGTA using thallium oxide electrode for indication

Summary It is demonstrated that magnesium can be titrated with EGTA in the presence of CaEDTA complex. On the basis of this substitution reaction, calcium and magnesium are successively titrated with EGTA, if an appropriate amount of CaEDTA is added after having reached the end point for calcium. Both end points are indicated amperometrically using a thallium oxide anode. The method has been tested for analysis of tap and mineral water. Larger amounts of manganese(II) render the calcium result too high. Moreover, the indication of both end points is affected by the electrode position of an inactive MnO₂-layer onto the Tl₂O₃-layer. Reducing agents destroy the Tl₂O₃-layer. These interferences can be overcome by addition of an appropriate amount of manganate(VII) to the sample.

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Sukzessive Substitutionstitration von Calcium und Magnesium mit ÄGTA, indiziert mit der Thalliumoxidelektrode

Zusammenfassung Magnesium kann mit ÄGTA in Gegenwart des CaÄDTA-Komplexes titriert werden. Auf der Grundlage dieser Substitutionstitration können Calcium und Magnesium nacheinander mit ÄGTA titriert werden, wenn nach dem Endpunkt für Calcium eine ausreichende Menge CaÄDTA zugesetzt wird. Beide Endpunkte werden amperometrisch mit Hilfe einer Thalliumoxidelektrode angezeigt. Die Methode wurde an Leitungswasser und Mineralwasser geprüft. Größere Mengen Mangan(II) bewirken zu hohe Calciumwerte. Darüber hinaus wird die Indikation beider Endpunkte dadurch beeinträchtigt, daß sich eine inaktive MnO₂-Schicht auf der Tl₂O₃-Schicht elektrolytisch abscheidet. Reduzierende Stoffe zerstören die Tl₂O₃-Schicht. Diese Störungen können durch Zugabe von Permanganat vermieden werden.

     

Simultaneous determination of microgram amounts of chlorine or bromine or iodine and sulfur in organic compounds

A general method for the simultaneous and rapid determination of microgram amounts of chlorine or bromine or iodine and sulfur in organic compounds is described.The procedure is based on the combustion of the sample, containing approximately 0.005 meq of Cl or Br or I and 0.005 meq of S. by the Schöniger flask technique, using potassium hydroxide and hydrazine hydrate as absorption solution. The excess of hydrazine is eliminated with hydrogen peroxide after combustion.This method allows complete reduction of halogens to halides and oxidation of sulfur to sulfate.The halide ions are titrated with mercuric perchlorate and diphenylcarbazone as indicator; the sulfate ions with barium perchlorate and dimethylsulfonazo(III) as indicator.The results obtained are in good agreement with calculated values.     

Consecutive indirect titration of periodate and iodate with EDTA

Periodate and iodate (μmol amounts) are determined successively in the same solution by their selective oxidation of iron(II) at pH 2.0 and in acetic acid, respectively. The resultant iron(III) is titrated with EDTA solution to a sulphosalicylic acid end-point. Bromate—iodate mixture can be titrated similarly.     

Rapid coulometric titrations with a new design of electrolytic cell

The construction of a compact coulometric titration cell with integrated injection valve and photometric and biamperometric flow-through detectors is reported. The lower part of the cell is designed as a magnetic centrifugal pump by means of which the supporting electrolyte is propelled through the other functional parte. Various rapid titration procedures were developed. The favourable flow conditions allow titration times between 10 and 100 s. The principle of continuous titration up to a preselected set-point is applied for both the photometric and biamperometric detectors. Microgram amounts of cyanide and thioglycolic acid are titrated directly with electro-generated iodine. Full advantage of the cell design is obtained in the implementation of back-titration procedures during which the sample and the reagent in excess are injected simultaneously into the circulating electrolyte. Back-titrations are implemented to determine microgram amounts of iodine, copper (II) and iron (III).     

Determination of nitrite and mixtures of bromide and iodide with o-iodosobenzoate

Nitrite diazotizes sulphanilamide, which then does not undergo 3,5-dibromination. Nitrite can therefore be determined by reaction with excess of sulphanilamide, the surplus of which is then titrated with o-iodosobenzoate or chloramine-T in the presence of potassium bromide, with Methyl Red as indicator. Mixtures of iodide and bromide can be analysed by oxidation of the iodide with excess of o-iodosobenzoate at pH 4-6, followed by extraction of the iodine (which is then titrated with thiosulphate) and then oxidation of the bromide in dilute sulphuric acid medium in the presence of sulphanilamide as bromine scavenger, the residual oxidant being evaluated iodometrically.     

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.