Solvent extraction-spectrophotometric determination of trace amounts of ammonium, barium and potassium in a mixture by dicyclohexyl-18-crown-6 and orange II

A simple and sensitive extraction-spectrophotometric method for the determination of ammonium, barium and potassium in a mixture solution is reported. The DC18C6-ammonium-Orange II (DC18C6-NH(4)-OR II), DC18C6-Barium-Orange II (DC18C6-Ba-(OR II)(2)) and DC18C6-Potassium-Orange II (DC18C6-K-OR II) ternary complexes are quantitatively extracted into dichloromethane and their absorbances are measured at 483 nm. Linear calibration graphs were obtained over the concentration ranges of 0.05-3.00, 0.05-2.00 and 0.05-6.00 mug ml(-1) for ammonium, barium and potassium, respectively. The relative standard deviations for 1.0 mug ml(-1) of ammonium, barium and potassium are, respectively, 1.1, 1.6 and 2.50%. The limit of detection, LOD, for these three ions is reported to be 0.02, 0.01 and 0.02 mug ml(-1), respectively. The interfering effect of a large number of diverse ions on the determination of these three ions was studied. The method was applied to the Karon river raw water contaminated with industrial and house sewages. The results showed high potential of the recommended method for the determination of NH(4)(+), Ba(2+) and K(+) in water samples.     

Differential Pulse Anodic Stripping Voltammetric Determination of Lead (II) Using Poly Xylenol Orange Modified Electrode

In this work a method for sensitive anodic stripping voltammetric determination of Pb(II) ions using a poly xylenol orange film modified electrode (PXOFME) has been proposed. Poly xylenol orange film (PXOF) was formed on a paraffin impegrenated graphite electrode (PIGE) using electro polymerization method by scanning the potential between −0.5 V to 1.3 V, at a scan rate of 50 mV/s for 30 segments in 0.1 M phosphate buffer solution (PBS) of pH 7. The PXOFME was characterized by scanning electron microscopy (SEM), ATR‐IR spectroscopy, cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). The modified electrode has been used to develop a sensitive method for the determination of Pb(II) ions by anodic stripping voltmmetry (ASV). The PXOFME was used to preconcentrate Pb(II) ions through complexation, the complexed metal ions were reduced electrochemically and then stripped anodically from the surface of the electrode. A linear range of 5 μg/L to 413 μg/L with a limit of detection (S/N=3) of 1.6 μg/L was observed for the determination of Pb(II) ions. The method was applied to lead determination in sea water and tap water samples and the results were found to be satisfactory.     

Highly Sensitive Differential Pulse Voltammetric Determination of Cd,Zn and Pb Ions in Water Samples Using Stable Carbon‐Based Mercury Thin‐Film Electrode

A new carbon‐based mercury thin‐film electrode consisting of screen‐printed carbon on a low temperature co‐fired ceramic substrate was made. Ex‐situ mercury deposition in a potassium thiocyanate solution was used. This approach an electrode with high long‐term stability (>500 measurement cycles) and reproducibility (≤2 %) for sensitive determination of ultra trace heavy metals, using differential pulse anodic stripping voltammetry. The detection limits were 0.25, 0.08 and 5.5 ng mL^?1 for Cd(II), Pb(II), and Zn(II), respectively. The method was applied to the determination of the analytes in water, wastewater, lake water, and certified reference material samples with satisfactory results.     

Reversed flow injection spectrophotometric determination of trace amount of ammonia in natural water by oxidation of ammonia to nitrite

A new sensitive flow injection method for determination of ammonia in natural water samples have been developed, based on the oxidation of ammonia to nitrite by hypochlorite in the presence of large amount of potassium bromide. The oxidant solution obtained by on-line mixing of hypochlorite and potassium bromide was injected into a water carrier stream, and then mixed with sample stream. Ammonia in the sample solution was oxidized to nitrite. Nitrite was then determined by spectrophotometry with sulfanilamide and N-1-naphthylethylenediamine. By reversed injection of the oxidant solution, the interference of nitrite and turbidity of the sample can be removed. The linear range of the method for ammonia is 0.2-12 muM. The proposed method is simple and sensitive. It had been applied to the determination of ammonia in lake water samples. Recoveries of 95-104% were obtained.     

Overoxidized polypyrrole doped with 4,5-dihydroxy-3-(p-sulfophenylazo)-2,7-naphthalene disulfonic acid as a selective and regenerable film for the stripping detection of copper(II).

A conducting polymer modified electrode based on the incorporation of 4,5-dihydroxy-3-(p-sulfophenylazo)-2,7-naphthalene disulfonic acid, SPADNS, as an anionic complexing ligand into polypyrrole film during electropolymerization was prepared. The electroanalysis of copper(II) in this modified electrode was achieved by medium exchange and differential pulse voltammetry. Copper ions were accumulated from ammonia buffer on the electrode surface by the formation of a chemical complex at open circuit. The resulting electrode with complexed Cu(2+) was then transferred to an acetate buffer and subjected to anodic stripping voltammetry. The analytical performance was evaluated and, finally, linear calibration graphs were obtained in the concentration range of 2 - 250 ng ml(-1) for Cu(II). The detection limit was found to be 1.1 ng ml(-1) and RSD was obtained at 3.1 and 1.9% for two different concentrations. Many coexisting metal ions had little or no effect on the determination of copper. The developed method was applied to Cu(II) determination in natural water and human hair samples. Also, the rapid and convenient regeneration of electrode allows the use of a single modified electrode in multiple analyses.     

Determination of potassium in sea-water by capillary isotachophoresis

Summary A new analytical procedure for the determination of potassium in sea-water was developed using capillary isotachophoresis and ion-exchange. After the sea-water sample was passed through the column packed with an ammonium form cation-exchange resin, sodium ion was removed with 2×10^–2 mol/l ammonium chloride solution and then potassium ion was eluted with 3×10^–1 mol/l ammonium chloride solution. Simultaneous determination of potassium and sodium ions was performed with a newly developed electrolyte system; the leading electrolyte was 5 mmol/l cesium hydroxide containing 2 mmol/l 18-crown-6, 0.01% hydroxypropyl methylcellulose (HPMC) and 70% methanol; the terminating electrolyte was 5 mmol/l tetrabutylammonium bromide containing 0.01% HPMC and 70% methanol. A large amount of ammonium in the eluate did not interfere with the isotachophoretic measurement of potassium and sodium ions. A linear working curve was obtained for artificial sea-water samples containing up to 700 mg/l potassium ion. The proposed method was applied to the determination of potassium in surface and bottom sea-water samples.

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Kaliumbestimmung in Meereswasser durch Capillar-Isotachophorese

     

Determination of Ammonium by Stripping Voltammetry

The behavior of ammonium ions at amalgam electrodes was studied by cyclic and stripping voltammetry. It was found that the oxidation peak of an ammonium hydride amalgam can be used as the analytical signal. Conditions were selected for the determination of ammonium ions in aqueous solutions at a mercury film electrode by stripping voltammetry using potassium chloride as the supporting electrolyte. The determination limit for ammonium ions was found to be 2 × 10^–7M (0.004 mg/L). The procedure was tested in river waters of the Ob' basin and in the atmospheric air.     

Square‐Wave Adsorptive‐Stripping Voltammetric Detection in the Quality Control of Fluoxetine

ABSTRACT

A simple and sensitive extraction-spectrophotometric method for the determination of barium and potassium is reported. The 18C6-Barium-Orange II (18C6-Ba-(OR II)₂) and 18C6-Potassium-Orange II (18C6-K-OR II) ternary complexes are quantitatively extracted into dichloromethane and their absorbances are measured at 483 nm. Linear calibration graphs were obtained over the barium concentration range of 0.1-5 μg ml^?1 and potassium concentration range of 1-8 μg ml^?1. The relative standard deviation for 2.0 μg ml^?1 barium and pottasium are, respectively, 4.16% and 3.60%. The interfering effect of a large number of diverse ions on the determination of barium and potassium was studied. The method was applied to a synthetic sample with natural matrix effects of tap water and the results showed high potential of the recommended method for the determination of Ba and K in water samples.     

流动注射多元校正-络合滴定法同时测定混合金属离子

将流动注射应用于电位络合滴定分析法,建立了一种可同时测定混合金属离子的电位滴定方法。在该方法中,用EDTA与氟化钠的混合溶液作为滴定剂,在流通池中同时插入汞膜电极和氟离子指示电极,在滴定过程中的任一滴定点,流出液的汞电位和反应物的混合比例可由两个电极的电位测定值同时获得,从而可应用多元校正法由相应的滴定曲线求得混合金属离子中每一种组分的含量。应用该方法对混合样品中的Cu2+、Pb2+、Zn2+进行了同时测定,测定结果的相对标准偏差均在0.14%~0.48%(n=5)之间,回收率均在97.3%~103.9%之间。     

Characterization of an ion-selective polypyrrole coating and application to the joint determination of potassium, sodium and ammonium by electrochemical impedance spectroscopy and partial least squares method

A stable immobilization of ionophores (INPHs) was achieved by selectively electropolymerizing overoxidized pyrrol on the working electrode surface. The optimal conditions found allowed the immobilization of a huge amount of INPH which remained its recognition properties. A single sensing chip, containing a generic INPH or an INPH mixture, was employed to the joint quantification of potassium, ammonium and sodium in fertilizer samples. Electrochemical impedance spectroscopy (EIS) and partial least square (PLS) regression were used to obtain and process the data, respectively. The sensing element (INPH) and the exposure time were optimized. The best results were obtained by using the dibenzo-18-crown-6 INPH after waiting for 60 s, the time required to stabilize the impedimetric measurement. Taking into account that a single chip was employed, acceptable relative errors were obtained in the determination of potassium and ammonium (17% and 9%, respectively) in real fertilizer samples, also containing sodium. Although sodium concentration could not be estimated with precision, it had to be introduced into the calibration set data in order to model its interference with the other two ions.     

多壁碳纳米管修饰玻碳电极伏安法测定氯霉素

研究了氯霉素(CAP)在多壁碳纳米管修饰玻碳电极上的电化学行为.发现在pH=2.0的0.1 mol/LKCl-HCl底液中,CAP在该修饰电极上有一灵敏的还原峰(Ep=-0.36 V vs.Ag/AgCl),峰电流与CAP浓度成正比,线性范围为6.0×10-6~2.7×10-4mol/L,检测限达3.0×10-6mol/L.该方法灵敏、准确,用于模拟样品和实际样品的测定,结果满意.     

Synergy of glutathione, dithiothreitol and N-acetyl-L-cysteine self-assembled monolayers for electrochemical assay: sensitive determination of arsenic(III) in environmental and drinking water

A simple and efficient electrochemical assay based on self-assembled monolayers (SAMs) was developed for the highly sensitive determination of arsenic(III) in water samples. The synergy of glutathione (GSH), dithiothreitol (DTT) and N-acetyl-L-cysteine (NAC) mixed SAMs enhanced the detection specificity and sensitivity of As(III) in water samples, resulting from the immobilization of a large number of As(III) moieties on the gold electrode surface via As-O and As-S linkages. After accumulating As(III), anodic stripping voltammetry (ASV) was performed, and linear sweep voltammetry (LSV) was employed for signal recording. Several main voltammetric parameters were optimized as follows: supporting electrolyte, 1 mol L(-1) HCl; deposition potential, -0.35 V; deposition time, 150 s. A good linear relationship (R = 0.9980) was attained between the concentration of the As(III) standard and peak current, in the range of 3-100 μg L(-1). The limit of detection (LOD) of this sensing system was determined to be 0.5 μg L(-1) at a signal-to-noise ratio of 3. A variety of common coexistent ions in water samples were examined, showing no obvious interferences on the As(III) determination. The amenability of this method to the analyses of water samples was also investigated. High recovery of 90.5% with the precision of 5.1% at spiked 10 μg L(-1), and low LOD of 0.3 μg L(-1) were obtained in seawater. The synergy effect of GSH, DTT and NAC provided the possibility for the rapid and sensitive LSV determination of As(III) in complicated water samples.     

Determination of ammonium in river water and sewage samples by capillary zone electrophoresis with direct UV detection

We developed capillary zone electrophoresis (CZE) with direct UV detection for determination of ammonium in environmental water samples. Ammonium in the samples was partly converted into ammonia in the alkaline background electrolyte (BGE) during migration and was detected by molecular absorption of ammonia at 190 nm in approximately 7 min. The limit of detection (LOD) for ammonium was 0.24 mg/l (as nitrogen) at a signal-to-noise ratio of three. The respective values of the relative standard deviation (RSD) of peak area, peak height, and migration time for ammonium were 2.1, 1.8, and 0.46%. Major alkali and alkaline earth metal ions coexisting in the samples did not interfere with ammonium determination by the proposed method. The proposed method determined ammonium in surface water and sewage samples. The results were compared to those obtained using ion chromatography (IC).     

Determination of mercury in table salt samples by on-line medium exchange anodic stripping voltammetry

A new method for the determination of traces of total mercury by using a gold film electrode in salt samples was developed. Table salts are known to contain mercury at ultra-trace level as well as a high quantity of chloride ions that cause severe disturbance during the stripping step when gold is used as the electrode material in voltammetric measurements. The interference of high chloride content in the determination of mercury was eliminated by reducing its concentration down to 3 x 10(-3) mol L(-1) level which is optimum for the determination by using on-line medium exchange procedure immediately after the deposition step. The deposition potential applied to the electrode was maintained at 0.2 V (vs. Ag/AgCl double junction electrode) while the cell content was sucked by a pump and replaced with fresh electrolyte simultaneously. The analyte loss resulted from the air contact of the electrode was prevented by this means. The mercury ions present in the salt samples were collected at +0.2 V for 60 s, the electrolyte was replaced by 0.1 mol L(-1) HClO4 and the potential was scanned, attaining a detection limit of 0.17 microg L(-1), with R.S.D. of 1.2% (S/N=3). The recovery of the method was 94.6%. The performance and accuracy of the method was compared with that of atomic fluorescence spectrometry (AFS). Consequently, this developed method can offer a wide range of application in saline samples.     

纳米二氧化钛膜光催化分解-电化学法联用测定水体中的总磷

利用电化学方法制备了磷钼酸修饰电极,该修饰电极对溶液中的PO43-有很好的电流响应,继而提出了一种用纳米TiO2-K2S2O7共存体系光催化氧化有机磷生成正磷,然后以磷钼酸修饰电极进行测定的新方法。实验中以有机膦酸为标准物质,研究了测定机理,优化了测定条件。实验表明,本方法操作简单、快速、准确。PO43-在0.04~16 mg/L浓度范围内,与修饰电极上的电流响应呈线性关系,检出限为0.02 mg/L。用本方法测定实际水样与标准分析方法所得结果相近。     

Amperometric sensor for nitrite based on copper tetrasulphonated phthalocyanine immobilized with poly-L-lysine film

In this work, an amperometric sensor for nitrite detection based on a glassy carbon electrode modified with copper tetrasulphonated phthalocyanine immobilized by polycationic poly-L-lysine film is presented. The modified electrode showed an excellent catalytic activity toward nitrite oxidation. A linear response range from 0.12 up to 12.20 micromol L(-1) was obtained with a sensitivity of 0.83 microA L micromol(-1). The detection limit for nitrite was 36 nmol L(-1). The repeatability of the proposed sensor, evaluated in terms of relative standard deviation, was 1% for 10 measurements of 10 micromol L(-1) nitrite solution. Finally, the developed sensor was applied for nitrite determination in water samples and the results were in agreement to the comparative method. The average recovery for the samples was 101 (+/-4)%.     

Ammonium Determination in Water Samples by Using Opa-Nac Reagent: A Comparative Study with Nessler and Ammonium Selective Electrode Methods

A selective and sensitive method based on the ammonium derivatisation with o -phthaldialdehyde (OPA) and N -acetyl-cysteine (NAC) has been developed for ammonium determination in real water samples. The proposed procedure has been compared with ammonium reference methods such as Nessler reagent method and ammonium selective electrode. All procedures have been chemometrically tested and compared in terms of the main analytical properties. These procedures have been used to determine ammonium in unknown water samples. The OPA-NAC reagent method does not present any systematic error (proportional or constant), while Nessler reagent presents both of them for some samples assayed. The ammonium selective electrode is free of corrigible systematic errors, however presents amine interference. The OPA-NAC ammonium method is able to achieve a detection limit (LOD) of 0.07 mg/L in the sample, with a linear dynamic range up to 1.4 mg/L of ammonium.     

EDTA滴定法测定含锌物料中氧化锌

采用氯化铵-氨水体系溶解试样,干过滤后,向移取的滤液中加入氯化钡和硫酸共沉淀铅离子,过滤分离硫酸铅沉淀,向滤液中加人抗坏血酸、氟化钾、硫代硫酸钠等掩蔽剂掩蔽少量干扰元素。在pH=5~6的乙酸-乙酸钠缓冲溶液中,以二甲酚橙为指示剂,用EDTA标准滴定溶液滴定测得结果为氧化锌、水溶性锌和镉合量,扣除由原子吸收光谱法测得的水溶性锌量和镉量,即为氧化锌量。对总氨浓度、氯化铵-氨水浓度比、溶液加入量、搅拌时间、共存离子干扰、精密度等进行了实验,建立了EDTA滴定法测定含锌物料中氧化锌物相的分析方法。实验证明,氧化锌含量在24%~83%时,方法精密度(RSD)为0.25%~0.54%,加标回收率在99%~104%,完全满足含锌物料中氧化锌的测定要求。     

Septonex-tetraphenylborate screen-printed ion selective electrode for the potentiometric determination of Septonex in pharmaceutical preparations

A screen-printed electrode (SPE) was fabricated for the determination of 1-(ethoxycarbonyl)pentadecyltrimethylammonium bromide (Septonex) based on the use of Septonex-tetraphenylborate as the electroactive substance, and o-nitrophenyloctylether (o-NPOE) as the plasticizing agent. The electrode passes a near-Nernstian cationic slope of 59.33 ± 0.85 mV from activity between pH values of 2 to 9 with a lower detection limit of 9×10(-7) M and response time of about 5 s and exhibits an adequate shelf-life of 6 months. The method was applied for the determination of Septonex in pharmaceutical preparations. A percentage recovery of 99.88% was obtained with RSD=1.24%. The electrode was successfully applied in the determination of Septonex in laboratory-prepared samples by direct potentiometric, calibration curve and standard addition methods. Potentiometric titration of Septonex with sodium tetraphenylborate and phosphotungstic acid as a titrant was monitored with the modified screen-printed electrode as an end-point indicator electrode. Selectivity coefficients for Septonex relative to a number of potential interfering substances were determined. The sensor was highly selective for Septonex over a large number of compounds. Selectivity coefficient data for some common ions show negligible interference; however, cetyltrimethylammonium bromide and iodide ions interfere significantly. The analytical usefulness of the proposed electrode was evaluated by its application in the determination of Septonex in laboratory-prepared pharmaceutical samples with satisfactory results. The results obtained with the fabricated sensor are comparable with those obtained by the British Pharmacopeia method.     

Aluminum electrode modified with manganese hexacyanoferrate as a chemical sensor for hydrogen peroxide

A chemically modified electrode was fabricated based on manganese hexacyanoferrate (MnHCF) film. The MnHCF was used as a modifier immobilized onto an aluminum electrode. Stability of the electroactive film formed on the Al electrode surface indicated that MnHCF is a suitable material for the preparation of modified electrodes. The analytical applicability of the modified electrode for the determination of hydrogen peroxide was examined. A linear response in concentration range of 6.0x10(-7)-7.4x10(-3) M (r=0.9997) was obtained with detection limit of 2.0x10(-7) M for the determination of hydrogen peroxide. The modified electrode exhibited a good selectivity for H(2)O(2) in real samples. The mentioned electrode has advantages of being highly stable, sensitive, inexpensive, ease of construction and use.