Determination of nickel by direct automatic potentiometric titration with EDTA and a chemically modified electrode based on a strong acid ion exchanger containing 4-(3,5-dichloro-2-pyridylazo)-1,3-diaminobenzene

A chemically modified electrode (CME) was constructed and evaluated for use as an end-point indicator in the automatic titration of Ni(II) with EDTA. The CME consisted of a graphite paste prepared by mixing a strong acid ion exchanger containing 4-(3,5-dichloro-2-pyridylazo)-1,3-diaminobenzene and graphite powder-Nujol paste. This mixture showed high mechanical resistance in strongly acidic and alkaline solutions (6 M HCl-pH 12). The CME did not require any special conditioning prior to use. It could be used over long periods (5-6 months) of continuous work without renewing either the electroactive surface or paste. In buffered solutions (pH 3-4.5), automatic direct potentiometric titrations could be carried out over a wide interval of Ni(II) concentrations, ranging from 3 to 6000 ppm, with satisfactory accuracy and precision. For practical analysis, the electrode was applied to the determination of nickel in two certified composition alloys. Interferent ions were previously separated by applying an ion-exchange procedure.     

4-(3,5-dichloro-2-pyridylazo)-1,3-diaminobenzene as a metallochromic indicator for the complexometric determination of Cu(II) with EDTA

In slightly acid solutions Cu(II) and 4-(3,5-dichloro-2-pyridylazo)-1,3-diaminobenzene (3,5-C12PADAB) form a red-purple complex( = 5.0 x 10(4)1.mole(-). cm(-1) at 547 nm). The complex is readily broken by EDTA, with a sharp change of colour to the yellow of the free reagent (Deltalambda(max) = 110 nm at pH 3.5). This colour contrast and the reversibility of the formation reaction, together with the solubility of the complex in water, make the pyridylazo reagent useful as a metallochromic indicator for copper titration, at pH 2.7-5.5. The Cu(II)-3,5-C12PADAB indicator system has been satisfactorily applied to the determination of sulphur in cast iron, "useful oxides" (Al(2)O(3) + Fe(2)O(3)) in samples of commercial aluminium sulphate, and total phosphorus in a synthetic mixed fertilizer.     

Determination of vanadium(V) by direct automatic potentiometric titration with EDTA using a chemically modified electrode as a potentiometric sensor

A chemically modified electrode (CME) was prepared and studied as a potentiometric sensor for the end-point detection in the automatic titration of vanadium(V) with EDTA. The CME was constructed with a paste prepared by mixing spectral-grade graphite powder, Nujol oil and N-2-naphthoyl-N-p-tolylhydroxamic acid (NTHA). Buffer systems, pH effects and the concentration range were studied. Interference ions were separated by applying a liquid-liquid extraction procedure.The CME did not require any special conditioning before using. The electrode was constructed with very inexpensive materials and was easily made. It could be continuously used, at least two months without removing the paste.Automatic potentiometric titration curves were obtained for V(V) within 5 × 10⁻⁵ to 2 × 10⁻³ M with acceptable accuracy and precision. The developed method was applied to V(V) determination in alloys for hip prothesis.     

铑（Ⅲ）与2—（3,5—二氯—2—吡啶偶氮）—5—二甲氨基苯胺络合物的催化氢波

本文提出一种新的测定铑的催化氢波体系.先使Rh(Ⅲ)与3,5-diCl-PADMA在HAc-NaAc缓冲溶液中生成稳定的络合物,再以适量HclO_4将溶液酸化后进行极谱测定。利用正交试验法确定体系的最佳分析条件为:0.05 mol/L pH5.0的HAc-NaAc,1.6×10~(-5)mol/L3,5-diCl-PADMA,沸水浴加热15min.,4.4 mol/L HCIO4酸化。在此条件下的线性范围为1.9×10~(-11)～3.9×10~(-9)mol/L,检出限达5.8×10~(-12)mol/L。大量Cu(Ⅱ)、Ni(Ⅱ)、Fe(Ⅲ)及Co(Ⅱ)对体系的干扰可用EDTA消除。研究了催化波的性质,表明该波为Rh(Ⅲ)与3,5-diClPADMA络合物的催化氢波。     

Synthesis and characterization of 2-(3,5-Dichloro-2-pyridylazo)-5-dimethylaminophenol as a reagent for determination of lanthanum

2-(3,5-Dichloro-2-pyridylazo)-5-dimethylaminophenol (3,5-diCIDMPAP) has been synthesized and its spectral properties, acid-base equilibria, physical constants, and solubility and stability are presented. This reagent is highly promising for the determination of lanthanides. The influence of Triton X-100 on the dissociation constant has been investigated and the association constant between the reagent and the surfactant determined. Analytical data for the 3,5-diCIDMPAP complexes with La(III), Eu(III), Gd(III), Er(III) and Yb(III) are given, La(III) in synthetic samples has been determined with 3,5-diCIDMPAP.     

Spectrophotometric determination of zinc with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol in the presence of anionic surfactant

A sensitive spectrophotometric method for zinc has been established by reacting zinc with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol (3,5-diBr-PADAP) in the presence of an anionic surfactant, sodium lauryl sulphate. The molar absorptivity is 1.3 x 10(5) l.mole(-1).cm(-1) at 570 nm. The molar ratio of zinc to 3,5-diBr-PADAP is 1:2. Beer's law is obeyed up to 0.7 ppm of zinc. With preseparation of zinc by extraction of its thiocyanate complex, the method has been applied to the determination of zinc in waste water.     

A non-ionic surfactant as a new solvent for liquid-liquid extraction of zinc(II) with 1-(2-pyridylazo)-2-naphthol

A new method for extracting zinc(II) with 1-(2-pyridylazo)-2-naphthol (PAN) has been developed, based on the fact that a micellar solution of a non-ionic surfactant separates into two phases above a certain temperature, defined as the cloud point. Polyoxyethylene nonyl phenyl ether, (PONPE-7.5; average number of ethylene oxide units 7.5) was used as the surfactant. The cloud point of a 0.40% PONPE-7.5 solution is 1 degrees , and hence the solution is turbid at room temperature. The two phases can be separated by centrifuging for 8 min at room temperature. The zinc chelate of PAN is quantitatively extracted from 50g of the solution into a small volume (about 1 ml) of the lower (surfactant-rich) phase over the pH range 8.0-11.5. After most of the supernatant solution has been removed, the amount of final solution is adjusted to 2.00 g with 0.5 g of 10% of PONPE-20 solution and water. This mixture is transparent at room temperature. The absorbance is measured as 535 nm. Concentration factors of up to 25 can be obtained by choosing appropriate amounts of final ( 2.0 g) and initial solution ( 50 g). This new technique has been applied to the determination of zinc(II) in tap water.     

Determination of sulfide with chloranilic acid by biamperometric and automatic potentiometric end-point detection with a lead chloranilate selective electrode

A titrimetric method for determination of sulfide and of sulphur in steels with chloranilic acid by biamperometric and automatic potentiometric end-point detection is described. The construction of the sensor for potentiometric indication is also described. The results obtained agree with those of the iodine-thiosulfate method and with the certified values for the steels.     

Chemically modified carbon paste electrode for determination of copper(II) by potentiometric method

The utility of carbon paste electrode modified with DTPT (3,4-dihydro-4,4,6-trimethyl-2(1H)-pyrimidine thione) for the potentiometric determination of Cu(II) in aqueous medium is demonstrated. The electrode exhibits linear response to Cu(II) over a wide concentration range (9.77x10(-7)-7.6x10(-2)) with Nernstian slope of 30+/-2 mV per decade. It has a response time of about 45 s and can be used for a period of two months with good reproducibility. The detection limit of this electrode was 7.0x10(-7) M. The proposed electrode shows a very good selectivity for Cu(II) over a wide variety of metal ions. This chemically modified carbon paste electrode was successfully used for the determination of Cu(II) in electronics waste sample solution.     

Cyclic flow-injection analysis for the repetitive determination of zinc with 2-(5-bromo-2-pyridylazo)-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol and EDTA.

A circulatory flow-injection method (cyclic FIA) for the repetitive determination of zinc has been proposed. The procedure involves the use of 2-(5-bromo-2-pyridylazo)-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol (5-Br-PAPS) together with EDTA as a reagent carrier solution, which is recycled in a single-line flow system via a reservoir. The formed 5-Br-PAPS-Zn(II) complex was measured spectrophotometrically at 552 nm, and the signal intensity corresponded to the zinc concentration. After passing through a flow-through cell, the carrier stream then returned to the reservoir, and the main reagent, 5-Br-PAPS, was successfully regenerated by a ligand-exchange reaction with EDTA, allowing the repetitive determination of zinc. The calibration curve for zinc was linear in the concentration range from 0.4 to 10.0 mg dm(-3) with a correlation coefficient of 0.9995 (n = 6). The detection limit of this method was 0.02 mg dm(-3) (S/N= 3). This method allowed as many as 300 repetitive determinations of 2.0 mg dm(-3) zinc solution with only 100 cm3 of the circulating carrier solution, providing a reduction in the consumption of reagents and an elimination of waste, an important approach towards clean chemistry.     

Compleximetric titration of chromium (III) with catalytic end-point detection

Chromium (III) (2–20 mg) is determined by reaction with excess of EDTA and backtitration with a standard copper(II) solution to a catalytic end-point. The indicator reaction is the copper (II) -catalyzed autodecomposition of hydrogen peroxide, which is observed biamperometrically. For 10 mg of chromium (III) , the relative standard deviation was < 0.5 % (n=10).     

Simultaneous spectrophotometric determination of Zinc(II) and Nickel(II) with 1-(2-pyridylazo)-2-naphthol

A new procedure for the simultaneous spectrophotometric determination of Zn(II) and Ni(II) with 1-(2-pyridylazo)-2-naphthol as chromogenic reagent has been developed. It is based on resolution of the mixed spectrum over the wavelength range 530–590 nm by applying a least-squares fitting program to standard spectra from each component. The spectra are recorded at an apparent pH of 5.0, provided by an acetate buffer in a mixed 6040 v/v 2-ethoxyethanol/water medium. The relative standard deviations for determination of 13.7 g of Ni and 31.0 g of Zn were 1.9 and 1.0%, respectively (8 replications). The method has been applied to the analysis of iron surfaces coated with a Zn-Ni alloy. The results are compared with those obtained by atomic-absorption spectrophotometry.