Determination and differentiation of nitrilotriacetic acid and ethylenediaminetetra-acetic acid

Ethylenediaminetetra-acetic acid (EDTA) and nitrilotri-acetic acid (NTA) can be differentiated and determined by titration with metal ions to visual metallochromic dye end-points. EDTA can be determined without interference from NTA, either by titrating with copper(II) at pH 5 using PAN indicator, or by titrating with iron(III) at pH 6 and 70 degrees using Tiron indicator. The total chelating power (EDTA + NTA) can be determined either by titrating with lead(II) at pH 4.4 using dithizone indicator, or by titrating with iron(III) at pH 3.5 using Tiron indicator ; NTA is determined by difference. The lowest concentration at which NTA can be determined in EDTA by titration to the iron(III)-Tiron end-point is about 1 wt.%. The apparent stability constants of the iron(III)-Tiron complexes under the conditions of the titration at pH 3.5 and pH 6 have been determined using the method of continuous variations.     

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.     

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。     

Potentiometric determination of NTA, EDTA and DTPA in mixtures

Consecutive potentiometric determination of EDTA and NTA or DTPA and NTA is described. The method is based on the titration with iron(III) chloride at pH 4-5 in the presence of a small amount of ferroin and 1,10-phenanthroline which keeps the concentration of free iron(II) ions constant, thus making the potential dependent only on the free iron(III) concentration.     

Détermination des constantes de stabilité des complexes de tl+ avec l'acide ethylénediaminotétracétique (edta) et avec l'acide nitrilotriacétique (nta)

The range of stability of the thallium complex with etylenediaminetetraacetic acid (EDTA) and with ammoniatriacetic acid (NTA) has been determined. In the presence of an excess (100 x ) of chelating agent, the formation of the complexes starts at pH = 6 Chelation of the metal with EDTA is practically complete at pH = 7, while completion of the chelation with NTA is reached merely at pH = 9.The cathodic reduction of thallium(I) at the dropping mercury electrode is reversible as well for the chelated metal as for free TI⁺ ions.The shift of the polarographic half wave potential of Tl+ by addition of the chelating agents was used for the calculation of the stability constants of the chelates The following values have been found: K^c(EDTA) = 10^{-5.81 ± 0.05} (25°C. μ = ± 1.0) between pH = 7 and pH = 10.5. K^c(NTA) = 10^{-3.44 ± 0.03} (25°C. μ = ± 1.4) between pH = 9 and pH = 10.5.     

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.     

Natural pyrite as an electrochemical sensor for potentiometric titrations with EDTA, mercury(II) and silver(I)

The results obtained in potentiometric titrations of copper(II), mercury(II) and iron(III) with standard EDTA solutions are presented. The titration of copper(II) at pH values in the range from 8.11 to 10.99 (ammonia buffer) and the titration of mercury(II) and iron(III) at pH values from 3.59 to 5.65 (acetate buffer) were performed. The titration end-point (TEP) was detected with an indicator electrode made from natural crystalline pyrite as an electrochemical sensor. The results obtained in potentiometric titration with the pyrite electrode were compared with those obtained using a platinum electrode (Fe³⁺), a Cu ion selective electrode (Cu²⁺) and a Hg electrode (Hg²⁺). Accurate and reproducible results with good agreement were obtained, but higher potential changes at the TEP were obtained using the pyrite electrode. In the course of the titration the potential was established within less than 1 min, whereas at the TEP it was within about 2–3 min. The potential changes at the TEP were in the range from 60 to 200 mV per 0.1 ml EDTA, according to the stability constant of the complex formed. The highest potential changes, ranging from 160 to 200 mV, were obtained in the titration of iron(III) at pH 3.59. Reverse titration was also performed and accurate and reproducible results were obtained. Moreover, titration of halogenide and thiocyanate with standard mercury(II) solutions, as well as cyanide with silver(I) solution, were performed and accurate and reproducible results were again obtained. Received: 20 February 1998 / Accepted: 19 November 1999     

Direct complexometric determination of magnesium in the presence of uranium, iron and aluminium

Conditions for the direct complexometric determination of magnesium in the presence of uranium, iron and aluminium are described. The method is based on the masking of uranium by hydroxylamine, and of iron and aluminium by triethanolamine. Methylthymol Blue is used as indicator for the EDTA titration of magnesium at pH 10.     

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。     

The coulometric generation of manganese(II) from a manganese electrode: : The Titration of EDTA

The anodic behavior of a manganese electrode is discussed. Manganese(II) can be generated with greater than 95% current efficiency over a limited current density range in neutral aqueous and methanolic chloride media. The current efficiency for the generation of manganese(II) as a function of current density, supporting electrolyte, solvent, pH, and generation time is given. Electrogenerated manganese(II) is useful in the coulometric titration of 4.460 × 10^-6–2.214 × 10^-5 mol of EDTA in 1.0 M sodium chloride buffered at pH 5.5. The end-point can be detected amperometrically by monitoring the anodic current from the oxidation of manganese(II) at platinum. The titration error is about 1% in replicate determinations. Permanganate can be generated in aqueous sodium hydroxide media but the current efficiencies are less than 20% and irreproducible.     

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。     

EDTA titration of calcium and magnesium with a calcium-selective electrode

Direct semi-automatic and automatic derivative potentiometric EDTA procedures for the determination of calcium and/or magnesium with a calcium-selective electrode are described. Calcium is titrated in the presence of magnesium at pH 12.0 and the total calcium and magnesium is determined at pH 9.7. Calcium in the range 1-8 mg and magnesium in the range 0.7-5 mg are determined semi-automatically with average errors of about 0.2 and 0.3% respectively and automatically with average errors of 0.4 and 0.7%. Titration times vary from a few seconds to a few minutes.     

Potentiometric Determination of Nitrilotriacetate in Water and Sewage

Abstract

A potentiometric titration of nitrilotriacetate in wastewater and sewage samples and a procedure of sample treatment to eliminate the interferences are described. T1³⁺ and Cu²⁺ solutions were the titrants and the potentiometric titrations were monitored with a platinum redox electrode. T1³⁺ :2NTA complex formation was found. The lower detection limit was 0. 1 ppm of NTA. The relative standard deviation in sewage samples was 5% and the recovery varied from 90–110%.     

Amperometric complex-formation titration of traces of alkaline earths

Alkaline earth metals were determined in microgram quantities by complexometric titration with EDTA, EGTA and DTPA. The end-point was detected by following the anodic wave of the chelating agent at the rotating mercury electrode. All the alkaline earths can be titrated at the microgram level with reasonable accuracy, and calcium may be titrated with EGTA in the presence of a 1000-fold excess of magnesium.     

Amperometry with Two Polarizable Electrodes. Chelometric Determination of Rare Earths

Abstract

The method of determining rare earths by chelometric EDTA titration with biamperometric end-point indication using two stationary platinum electrodes was studied. The convenient pH range for the determination of lanthanum is 5.0 – 8.0, for yttrium 3.5 – 8.0 and for ytterbium 3.0 – 8.0. Rare earths have been determined in the presence of iron and thorium. Iron and thorium can be titrated at pH 1.5 – 2.0 and rare earths of the lanthanum group can be determined by successive titration at pH 5.0. Large amounts of rare earths of the yttrium group interfere with the determination of iron and thorium.     

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.     

Back titration with mercuric nitrate in alkaline : medium volumetric analysis of binary mixtures of the alkaline earths,magnesium, zinc and cadmium

Mercuric nitiate has proved to be suitable for the back titration of the excess amount of EDTA remaining in solution when this compound has reacted quantitatively either with zinc or cadmium in the presence of one of the three elements barium, strontium and magnesium at pH 8 or 9, or with both cations at pH 11. Advantage is taken of this behaviour for analysing binary mixtures of the above mentioned cations by back titration at lower and higher pH's The end-points are detected potentiometrically, reasonable jumps being obtained; the agreement with the theoretical end-points is satisfactory.     

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.     

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.