新显色剂2-(2-噻唑偶氮)-5-二乙氨基苯甲酸分光光度法测定微量钴

近年来,杂环偶氮苯甲酸类显色剂取得了较快的发展。由于氨基取代结构对试剂性能有较大的影响^[1],因此本文合成了新显色剂2-(2-噻唑偶氮)-5-二乙氨基苯甲酸,(TAEB)并研究了它与钴的显色反应。     

Complexing Properties of Uranium and Lanthanoids With 4-(2-Thiazolylazo)-6-Chlororesorcinol

Abstract

4-(2-Thiazolylazo)-6-chlororesorcinol (TAR-Cl) reacts sensitively with uranyl(II) and lanthanoids(III), and forms reddish-brown 1:1 and 1:2 complexes. The complexing behaviors were examined spectrophotometrically. The absorption maxima of the complexes are focused near 553 nm and the optimum pH for complexation lies between 6.5–8.8. Beer's law holds up to about 2 × 10^?5 mol 1^?1, with a molar absorptivity of 3.00 × 10⁴ 1 mol^?1 cm^?1 for uranium and 6 × 10⁴ 1 mol^?1 cm^?1 level for each lanthanoid. The absorptivities are increased with the atomic number, especially in light lanthanoids, that are correlative both to the lanthanoid contraction and the basicity of ortho hydroxyl group in the resorcinol ring, but such effects are not clearly recognized in heavy lanthanoids. Effect of masking agents was also examined, and uranium could be determined selectively in the presence of lanthanoid mixtures by the addition of CyDTA.     

4—（2—噻唑偶氮）—2,4—二氨基甲苯与铑显色反应的研究

本研究了４－（２－噻唑偶氮）－２，４－二氨基甲苯（简称ＴＡＤＡＴ）与铑的显色反应。在ｐＨ＝３．７～４．９的酸度范围内试剂与铑形成红色络合物，加入无机酸后色泽加深，络合物的最大吸收位于５９０ｎｍ，表观摩尔吸光系数为１．１×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，其组成为Ｒｈ：ＴＡＤＡＴ＝１：３。铑浓度在０～１２μｇ／２５ｍｌ范围内服从比尔定律。该方法用于模拟样中铑的测定，结果满意。     

Selective Spectrophotometric Determination of Palladium (II) With 2-(5-Bromo-2-Pyridylazo)-5-(Diethylamino)-Phenol

Abstract

A spectrophotometric study of the Pd(II) complex of a reagent 2-(5-Bromo-2-Pyridylazo)-5-(diethylamino)-Phenol (5-Br-PADAP) is presented. A violet complex is formed at pH 3.53, and shows maximal absorbance at 585 nm with molar absorptivity of 3.86 × 10⁴ 1. mol^?1 cm^?1. Beer's law is obeyed up to 50 μ of Pd(II). The method offers the advantages of simplicity, high precision, requires no extraction and is very selective, where 5.0 mg Pt(VI) and 0.3 mg Au(III) ions do not interfere.     

2-(2-Thiazolylazo)-p-cresol as a spectrophotometric reagent for vanadium determination in the presence of ascorbic acid

The present work describes the use of 2-(2-thiazolylazo)-p-cresol (TAC) as a spectrophotometric reagent for vanadium determination. TAC reacts with vanadium(IV) in the presence of ascorbic acid, forming a red complex with absorption maximum at 525 nm. The following parameters were studied: complex stability, pH effect, amount of TAC, amount of acetate buffer, HEDTA effect, order of addition of reagents and Beer's law validity. TAC can be used for vanadium determination in the pH range 4.6–6.0, with molar absorptivity of 2.11 × 10⁴Lmole^–1 cm^–1 (at525nm). Beer's law is obeyed up to 2.0 g mL^–1. Many cation interferences can be easily eliminated by using HEDTA as a masking agent. Steel reference standards were used to test the proposed procedure and the accuracy and precision obtained were satisfactory.     

2-(2-Thiazolylazo)-pcresol (TAC) as a reagent for the spectrophotometric determination of titanium (IV)

The reaction between titanium(IV) and 2-(2-thiazolylazo)-p-cresol-(TAC) in aqueous methanol media at apparent pH 4.0–5.6 results in a intensely coloured complex that is stable for at least 2 h. The combining ratio is 1 1 cation TAC. Beer's law is obeyed up to 5.0 g/ml titanium(IV) at 580 nm. The apparent molar absorptivity at 580 nm is 9.82.10³ l.mole^–1.cm^–1 and the detection limit obtained was 5 ng/ml titanium (IV). A spectrophotometric method for the simultaneous determination of titanium and iron with TAC is proposed.     

4－（2－氨基噻唑）－间苯二酚为柱前衍化剂液相色谱／电化学检测Fe、Co、Ni

４－（２－氨基噻唑）－间苯二酚为柱前衍化剂液相色谱／电化学检测Ｆｅ、Ｃｏ、Ｎｉ格日勒，李惠梅，李南强，汪尔康（中国科学院长春应用化学研究所电分析化学开放实验室，北京大学化学系，长春，１３００２２）关键词液相色谱，Ｆｅ，Ｃｏ，Ｎｉ，４－（２－氨基噻唑）...     

Determination of Lead Using a New Chromogenic Reagent 2-(2-Sulfo-4-acetylphenylazo)-7-(2,4,6-trichlorophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic Acid

A novel chromogenic reagent, 2-(2-sulfo-4-acetylphenylazo)-7-(2,4,6-trichlorophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid 1, was prepared by diazo coupling of 4-acetylaniline-2-sulfonic acid and 2,4,6-trichloroaniline to chromotropic acid through –N=N– groups. Based on this reagent, a simple, sensitive and selective spectrophotometric method was developed for the determination of lead. In 0.20M phosphoric acid medium, lead reacts with 1 to form a 1:2 blue complex with an absorption maximum of 654nm. Beers law is obeyed in the range of 0–0.6mgL^–1 of lead. The apparent molar absorptivity is 1.25×10⁵Lmol^–1cm^–1. The detection limit and quantification limit were found to be 0.63µgL^–1 and 2.1µgL^–1, respectively. The relative standard deviation for eleven replicate measurements was of 2.6%. The interference of foreign ions was also investigated. All the other foreign ions studied did not interfere with lead determination except for Ca(II) and Ba(II). The interference caused by Ca(II) and Ba(II) can be eliminated by prior extraction of lead with potassium iodide-methylisobutylketone (KI-MIBK). The proposed method was applied to the determination of lead in certified samples with satisfactory results.     

Simultaneous First Derivative Spectrophotometric Determination of Palladium and Nickel Using 2-(2-Thiazolylazo)-5-Dimethylaminobenzoic Acid as an Analytical Reagent

 A simple, rapid, selective, sensitive and economical method has been developed for the simultaneous determination of trace amounts of palladium and nickel in aqueous methanolic medium using 2-(2-thiazolylazo)-5-dimethylam inobenzoic acid as an analytical reagent by first derivative spectrophotometr y. Palladium is determined by measuring base to peak distance at λ=695.0 nm while nickel is estimated by zero crossing method in the mixture. The linearity is maintained between 0.12–1.75 μg mL⁻¹ for palladium and 0.07–1.60 μg mL⁻¹ for nickel in the pH range 2.8–7.2 and 3.4–8.8 respectively. Seven replicate determinations of 1.0 μ g mL⁻¹ of palladium and 0.8 μg mL⁻¹ of nickel in a mixture give a mean signal height of 0.391 for Pd and 0.541 for Ni with relative standard deviations of 0.9% and 1.2%, respectively. The sensitivity of the proposed method is 0.391 (dA/dλ)/(μg mL⁻¹) for palladium and 0.685 (dA/dλ)/(μg mL⁻¹) for nickel. Various parameters have been optimised for the simultaneous determination of palladium and nickel in various complex samples. Received March 30, 1999. Revision November 25, 1999.     

Determination of Trace Amounts of Cobalt in Natural Water Samples as 4-(2-Thiazolylazo) Recorcinol Complex After Adsorptive Preconcentration

ABSTRACT

A chromatographic method has been established for the determination of trace amounts of cobalt by preconcentration on Amberlite XAD-16 resin as cobalt/4-(2-Thiazolylazo) resorcinol (TAR) complexes. The conditions (e.g. pH, resin amounts, matrix ions) affecting the recovery of cobalt from aqueous solution were studied. The method has been employed for the determination of cobalt in natural water samples.     

Erbium(III) PVC Membrane Ion-Selective Sensor based on 4-(2-Thiazolylazo)resorcinal

Abstract

4-(2-Thiazolylazo)resorcinol (TR) was used as a new compound to play the role of an excellent ion carrier in the fabrication of an Er(III) membrane electrode. The electrode shows a very good selectivity toward Er(III) ions over a wide variety of cations, including alkali, alkaline earth, transition, and heavy-metal ions. The proposed sensor exhibits a Nernstian behavior (with slope of 19.6 ± 0.6 mV per decade) over a wide concentration range (1.0 × 10^?6 to 1.0 × 10^?2 M). The detection limit of the sensor is 6.6 × 10^?7 M. It has a very short response time, in the whole concentration range (～10 s), and can be used for at least 12 weeks in the pH range of 2.8–9.3. The proposed sensor was successfully applied as an indicator electrode for the potentiometric titration of a Er(III) solution, with EDTA. It was also successfully applied to the F^? ion determination in some mouthwashing solutions.     

Cloud Point Extraction Simultaneous Spectrophotometric Determination of Zn(II), Co(II) and Ni(II) in Water and Urine Samples by 1-(2-Pyridylazo)2-Naphthol Using Partial Least Squares Regression

A cloud-point extraction (CPE) process using the nonionic surfactant Triton X-114 to simultaneous extraction and spectrophotometric determination of Zn(II), Co(II) and Ni(II) from aqueous solution using partial least squares (PLS) regression is investigated. The method is based on the color reaction of these cations with 1-(2-pyridylazo)2-naphthol and subsequent micelle-mediated extraction of products. The optimum extraction and reaction conditions such as pH, reagents concentration and effect of time have been studied. Linearity was obeyed in the range 2–150, 5–250 and 2–150 ng mL⁻¹ of Zn(II), Co(II) and Ni(II) respectively. The relative standard error (RSE) for the simultaneous determination of 15 test samples of different concentrations of Zn(II), Co(II) and Ni(II) was 4.38%;, 1.18% and 2.42%, respectively. The total relative standard error (RSE_t) for applying the PLS method to 15 synthetic samples in the linear ranges of these metals was 2.36%. The interference effect of some anions and cations was also tested. The method was applied to the simultaneous determination of Zn(II), Co(II) and Ni(II) in water and human urine samples.     

Spectrophotometric Simultaneous Determination of Zinc(II), Manganese(II) and Iron(II) in Pharmaceutical Preparations Using OSC-PLS

The purpose of this paper is to develop a fast and sensitive spectrophotometric method for the simultaneous determination of zinc(II), manganese(II) and iron(II) in pharmaceutical preparations. The method presented in this work is based on the well-known reaction of these ions with 4-(pyridylazo)resorcinol (PAR)1. The application of quantitative chemometric methods, particularly PLS to multivariate chemical data is becoming more widespread owing to the availability of digitized spectroscop…     

Solid Phase Extraction and Spectrophotometric Determination of Silver with 2-(2-Quinolylazo)-5-diethylaminoaniline as Chromogenic Reagent

 A new chromogenic reagent, 2-(2-quinolylazo)-5-diethylaminoaniline(QADEAA), was synthesized. A highly sensitive, selective and rapid method for the determination of silver was developed. It is based on the rapid reaction of silver (I) with QADEAA and the solid phase extraction of colored chelate using reversed-phase separation cartridge. At pH 6.5 in the presence of sodium dodecyl sulfonate (SDS), QADEAA reacts with silver to form a violet chelate in a molar ratio of 1:2 (silver to QADEAA). This chelate was enriched by solid phase extraction. The retained chelate can be eluted from the cartridge with ethanol. In ethanol medium, the molar absorptivity of the chelate is 1.36×10⁵ L·mol⁻¹·cm⁻¹ at 590 nm. Beer’s law is obeyed in the range 0.01–0.6 μg L⁻¹. The relative standard deviation for eleven replicate samples of 0.01 μg L⁻¹ level is 1.9%. The detection limit reaches the 0.02 μg L⁻¹ level. This method shows satisfactory results when used for the determination of silver in water. Correspondence: Department of Chemistry, Yuxi Teacher’s College, Yuxi, 653100, P.R. China. e-mail: hugiufena@163.com Received 19 August 2002; accepted 20 October 2002     

Spectrophotometric Determination of Palladium(II) with n-Hydroxy-N,N-Diphenylbenzamidine and 1 -(2-Pyridylazo)-2-Naphthol

A spectrophotometric method to determine palladium(II) at trace levels is based on the extraction of palladium(II) as a binary complex with N-hydroxy-N,N′-diphenylbenzamidine (HDPBA) in chloroform at pH 5.0 ± 0.2. The complex shows maximum absorbance at 400 nm with molar absorptivity 6.4 × 10³ L mol^?1 cm^?1. The sensitivity of the Pd(II)-HDPBA complex was enhanced by the addition of l-(2-pyridylazo)-2-naphthol (PAN). The green coloured complex shows maximum absorbance at 620 nm with molar absorptivity 1.58 × 10⁴ L mol^?1 cm^?1. Sandell's sensitivity and the detection limit of the method are 0.0067 μg cm^?2and 0.1 μg Pd(II) mL^?1, respectively. Most common metal ions associated with palladium metal do not interfere. The effects of various analytical parameters on the extraction of the metal are discussed.     

Simple,Selective, and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel（Ⅱ）, Copper （Ⅱ）, Cobalt （Ⅱ）, and Iron （Ⅲ） with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.     

Some Arylidene-2-Pyridylhydrazone Derivatives as Reagents for Spectrophotometric Determination of Palladium (II)

Abstract

A method for spectrophotometric determination of palladium by complexation with Arylidene-2-pyridylhydrazone derivatives in 50% (V/V) ethanolic solution are described-Pd(II) forms a 1:1 complex with the reagents. Beer's law is obeyed over the range 0.2-6.5 μg ml^?1. The effect of pH, effect of excess reagent, stability of complexes as well as the tolerance amount of many metal ions have been reported. The method is applied, with fair accuracy, to the determination of pd(II) in synthetic solutions.     

Lead(II) Siloxides

Although Pb^II-siloxides have been known until now to decompose to oxoclusters, here [{RO^F}PbOSi(SiMe₃)₃] (RO^F=fluoroalkoxide) and, most importantly, [Pb₂{OSi(SiMe₃)₃}{μ₂-OSi(SiMe₃)₃}₃], are presented. The unusual bonding pattern in the latter thermally stable dinuclear complex was investigated by crystallographic and computational methods. Its stability is much higher than that of the simple, yet elusive “[Pb(OSiPh₃)₂]”, for which decomposition pathways towards [Pb₄(μ₄-O)(μ₂-OSiPh₃)₆] have been clearly established.