Selective determination of trace copper(II) by cathodic adsorptive stripping voltammetry with a naphthol-derivative Schiff's base

A selective and sensitive stripping voltammetric method for the determination of trace amounts of copper(II) with a recently synthesized naphthol-derivative Schiff's base (2,2'-[1,2-ethanediylbis(nitriloethylidyne)]bis(1-naphthalene)) is presented. The method is based on adsorptive accumulation of the resulting copper-Schiff's base complex on a hanging mercury drop electrode, followed by the stripping voltammetric measurement at the reduction current of adsorbed complex at -0.15 V (vs. Ag/AgCl). The optimal conditions for the stripping analysis of copper include pH 5.5 to 6.5, 8 microM Schiff's base and an accumulation potential of -0.05 V (vs. Ag/AgCI). The peak current is linearly proportional to the copper concentration over a range 2.3-50.8 ng ml(-1) with a limit of detection of 1.9 ng ml(-1). The accumulation time and RSD are 90 s and (3.2-3.5)%, respectively. The method was applied to the determination of copper in some analytical grade salts, tap water, human serum and sheep's liver.     

Determination of Trace Amounts of Copper by Adsorptive Stripping Voltammetry

ABSTRACT

A technique is presented for the determination of trace amounts of copper(II) by adsorptive cathodic stripping voltammetry. The procedure is based on adsorptive accumulation of copper(II)-Alizarin Red S (ARS) complex on a hanging mercury drop electrode, followed by a stripping voltammetric measurement of the reduction current of the adsorbed complex at -0.16 V (vs. Ag/AgCl). The height of the copper -ARS reduction peak is linearly dependent upon the copper(II) concentration between 0.2-15 and 15-500 ng.ml^?1. The detection limit of the technique is 0.05 ng.ml^?1 copper(II) for a collection time of 1 minute. The method is free from most interferences. The procedure has been successfully applied to the determination of trace amounts of copper(II) in some analytical grade salts.     

Differential pulse adsorption stripping voltammetric determination of copper(II) with 2-mercaptobenzimidazol at a hanging mercury-drop electrode.

Copper(II) was selectively accumulated on a hanging mercury-drop electrode by using 2-mercaptobenzimidazole. Ensuing measurements were carried out by differential pulse adsorption stripping voltammetry. Factors affecting the accumulation, reduction, and stripping steps were investigated and a procedure was developed. The optimum conditions for the analysis of copper were pH 5.0, 5.33 x 10(-5) M 2-mercaptobenzimidazole and an accumulation potential of -0.10 V (vs. Av/AgCl). A linear range was obtained in the concentration range 0.2-100 ng/ml with a 90 s accumulation time and a scan rate of 16 mV/s. For ten successive determinations of 1.0, 20.0 and 70.0 ng/ml copper(II), relative standard deviations of 4.2, 3.5 and 2.8%, respectively, were obtained. The developed method was applied to the determination of copper in commercial salts and aluminium alloys.     

Determination of alprazolam in serum by adsorptive stripping voltammetry

The surface-active properties of alprazolam at a hanging mercury drop electrode allow their sensitive determination by differential-pulse adsorptive stripping voltammetry. Detection limits are 0.07 ng/ml for accumulation in water (accumulation time 240 s) and 0.3 ng/ml for accumulation in serum extract (accumulation time 30 s). Coefficients of variation at 5 ng/ml (10 determinations) were typically <2%.     

Galvanic stripping determination of trace amounts of lead

A galvanic stripping procedure for rapid determination of trace amounts of lead with a glassy-carbon electrode is described. The method is useful for determining lead at 1-200 ng/ml concentration.     

Cyclopentanone thiosemicarbazone, a new complexing agent for copper determination in biological samples by adsorptive stripping voltammetry.

A selective and sensitive stripping voltammetric method for the determination of trace amounts of copper(II) with cyclopentanone thiosemicarbazone (CPTSC) is presented. The method is based on the adsorptive accumulation of the resulting copper-CPTSC complex on a hanging mercury drop electrode, followed by the stripping voltammetric measurements at the reduction current of the adsorbed complex at -0.37 V vs. Ag/AgCl. The optimal conditions for the stripping analysis of copper include pH 9.3, deposition time of 120 s, and a deposition potential of -0.1 V (vs. Ag/AgCl). The peak current is linearly proportional to the copper concentration over a range 3.14 x 10(-9) M to 1.57 x 10(-6) M with a limit of detection of 1.57 x 10(-9) M. The technique has been applied to the determination of copper in biological samples, like urine and whole blood.     

Adsorptive stripping voltammetric determination of dimenhydrinate at a hanging mercury drop electrode

Dimenhydrinate exhibits a single adsorptive stripping peak at a hanging mercury drop electrode after accumulation at 0.0V vs Ag/AgCl electrode at pH 3.8 (acetate buffer). The addition of trace amounts of copper ions enhanced the dimenhydrinate peak and its height depends on the concentration of each dimenhydrinate and Cu²⁺. The adsorptive stripping response was evaluated with respect to accumulation time and potential, concentration dependence, electrolyte, the presence of other purines, surfactants and other metal ions, and some variables. The calibration graph for dimenhydrinate determination is linear over the range 2.0×10^–8–2.0×10^–7 M (pre-concentration for 60s). The correlation factor is found to be 0.985 and RSD is 3.2% at 1.0×10^–7 M. Detection limit is 1.0×10^–8 M after 5 min accumulation. The determination of dimenhydrinate in pharmaceutical formulations by the proposed method is also reported.     

Determination of Copper by an Adsorption Differential Pulse Stripping Method with Naphthol Derivative

ABSTRACT

A simple, sensitive and selective method is proposed for the determination of copper(II) by adsorption-differential pulse stripping method. This method is based on the selective accumulation of the complexes of Cu(II) with l-(2-pyridylazo)-2-Naphthol and then reduction of the complex on a HMDE. The reduction current of the complex is about 0.0V vs. Ag/AgCl reference electrode at p8543146=4.0. The influences of various experimental parameters on the current peak were completely studied. The calibration graph was linear up to 50.0 ng/ml for a deposition time of 60 sec. The relative standard deviation was 2.3% (n=5) for Cu(II) concentration of 10.0 ng/ml, with a limit of detection of 0.2 ng/ml. The influence of potentially interfering ions was completely studied. The method has been applied for the determination of Cu(II) in water samples.     

Kinetic determination of thiocyanate on the basis of its catalytic effect on the oxidation of methylene blue with potassium bromate.

This study reports a sensitive kinetic spectrophotometric method for the determination of trace amounts of thiocyanate. In acidic solution, Methylene Blue (MB) is oxidized by bromate to form a colorless compound. The reaction is accelerated by trace amounts of thiocyanate and can be followed by measuring the absorbance at 664 nm. The absorbance of the reaction decreased with an increase in the reaction time. Under the optimum experimental conditions (0.56 M of sulfuric acid, 3.9 x 10(-5) M of MB, 3.0 x 10(-3) M of bromate, 180 s, 25 degrees C), thiocyanate can be determined in the range 5.0 - 180 ng/ml. The relative standard deviations (n = 8) are 2.81 and 1.43% for 10.0 and 150 ng/ml thiocyanate, respectively. The detection limit of this method is (3sigma) 3.8 ng/ml. This method was successfully applied to the determination of thiocyanate in real samples.     

卟啉在分析化学中的应用(Ⅰ)——四-(4-三甲铵苯基)卟啉吸光光度法测定痕量铜

本文提出以水溶性卟啉α、β、γ、δ-四-(4-三甲铵苯基)叶啉[简称T-(4-TAP)P]作显色剂并研完了T-(4-TAP)P与铜(Ⅱ)的显色反应。试验了21种金属离子及8种盐的干扰,影响均小。提出了吸光光度测定ppb级痕量铜的方法。应用于测定高纯稀土及水样中痕量铜,操作简便快速,结果满意。     

A Selective Film Based on Poly(3‐octylthiophene) Doped with Dihydroxyanthraquinone Sulfonate

A stable film of poly(3‐octylthiophene)–dihydroxyanthraquinone sulfonate has been synthesized electrochemically in non‐aqueous solution. The incorporation of dihydroxyanthraquinone sulfonate as an anionic complexing ligand into poly(3‐octylthiophene) film during electropolymerization was achieved and copper ions were accumulated by reduction on the electrode surface. The presence of dihydroxyanthraquinone sulfonate during the electrochemical polymerization of 3‐octylthiophene is shown to impact the sensitivity and the stability of the organic conducting film electrode response. The electroanalysis of copper(II) ions using conducting polymer electrode was achieved by differential pulse anodic stripping voltammetry with remarkable selectivity. The analytical performance was evaluated and linear calibration graphs were obtained in the concentration range of 50–400 ng mL^?1 copper(II) ion for 240 seconds accumulation time and the limit of detection was found to be 7.8 ng mL^?1. To check the selectivity of the proposed stripping voltammetric method for copper(II) ion, various metal ions as potential interferents were tested. The developed method was applied to copper(II) determination in certified reference material, NWRI‐TMDA‐61, trace elements in fortified water.     

Über die Anwendung der Kohlepaste-Elektrode zur inversvoltammetrischen Bestimmung kleiner Quecksilbermengen

The applicability of the carbon paste electrode to the determination of trace quantities of mercury has been investigated in a base electrolyte of 0.1 N KSCN + 0.025 N HCl containing 25 ng/ml copper. The detection limit of the mercury determination has a value near 2.5 ng/ml (1.25×10^?8 M), if pre-electrolysis is carried out 10 min at ?1.0 V and the current voltage curve is registered with a scan rate of 16.7 mV/sec between ?0.5 and +0.5 V. The peak height is directly proportional to the concentration in the range from 1.25×10^?8 to 1.25×10^?6 M. With appropriate preconditioning the carbon paste electrode can be used for several measurements without renewing the surface.     

Simultaneous determination of copper, bismuth and lead by adsorptive stripping voltammetry in the presence of thymolphthalexone.

A novel, sensitive and selective adsorptive stripping procedure for simultaneous determination of copper, bismuth and lead is presented. The method is based on the adsorptive accumulation of thymolphthalexone (TPN) complexes of these elements onto a hanging mercury drop electrode, followed by reduction of adsorbed species by voltammetric scan using differential pulse modulation. The influences of control variables on the sensitivity of the proposed method for the simultaneous determination of copper, lead and bismuth were studied using the Derringer desirability function. The optimum analytical conditions were found to be TPN concentration of 4.0 microM, pH of 9.0, and accumulation potential at -800 mV vs. Ag/AgCl with an accumulation time of 80 s. The peak currents are proportional to the concentration of copper, bismuth and lead over the 0.4-300, 1-200 and 1-100 ng mL(-1) ranges with detection limits of 0.4, 0.8 and 0.7 ng mL(-1), respectively. The procedure was applied to the simultaneous determination of copper, bismuth and lead in the tap water and some synthetic samples with satisfactory results.     

Nafion修饰电极预富集-石墨炉原子吸收法测定痕量银的研究

本文报道了用Nafion修饰电极预富集-石墨炉原子吸收法测定痕量银的方法。采用不加电位的离子交换富集方法,将痕量银富集在Nafion修饰钨丝电极上,然后用石墨炉原子吸收法测定,检出限为0.04ng/ml,线性范围为0.08～12ng/ml,RDS为4.2%,回收率为88～100%。方法简便、灵敏,选择性好,适用于测定复杂体系中的痕量银。     

Adsorption voltammetry of the copper(II) 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex

The voltammetric determination of copper(II), based on adsorptive accumulation of the Cu(II)-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (S-Br-PADAP) complex on a hanging mercury drop electrode, is reported. The complex can be accumulated at the electrode at constant potential in 0.1M ammonium nitrate/ammonia buffer solution, and its reduction wave observed by scanning the potential in the negative direction, in the differential pulse mode. The calibration graph for copper is linear over the range 0.05-0.5muM, with accumulation for 5 min at -0.20 V. The adsorption of the complex is discussed and compared with that of copper complexes with several other pyridylazo derivatives.     

Determination of trace amounts of thallium by adsorptive cathodic stripping voltammetry with xylenol orange.

Trace amounts of thallium(I) can be determined using adsorptive cathodic stripping voltammetry in the presence of Xylenol Orange (XO). The reduction current of the thallium(I)-XO complex ion was measured by square-wave cathodic stripping voltammetry. The peak potential was at -0.44 V vs. Ag/AgCl. The effect of various parameters (pH, ligand concentration, accumulation potential and collection time) on the response are discussed. The response was linearly related to the thallium concentration in the range 0.5-110 ng ml(-1) and 110-2000 ng ml(-1). The limit of detection was 0.2 ng ml(-1). The relative standard deviation for the determination of 80 ng ml(-1) thallium was 2.8%. Many common anions and cations did not interfere with the determination of thallium. The interference of lead was reduced by the addition of 0.003 M sodium carbonate. The voltammetric procedure was then successfully applied to the determination of thallium in various complex samples.     

Novel monohydrogenphosphate sensor based on vanadyl salophen

A novel PVC-based membrane sensor based on vanadyl salophen (VNSP) for determination of trace amounts of monohydrogenphosphate (MHP) ions is introduced. The electrode revealed Nernstian response towards monohydrogenphosphate over the wide concentration range from 1.0×10⁻¹ to 1.0×10⁻⁶ M at the pH of 8.2. The effect of solvent mediator, cationic additives and amount of ion-carrier on the behavior of the sensor was investigated. The sensor shows a short response time (<20 s) in the whole concentration ranges. The selectivity of the electrode is very high, and it can be used for detection of trace amounts of monohydrogenphosphate in the presence of large amounts of other anions. The detection limit of the electrode was 5.0×10⁻⁷ M (48 ng/ml) and it could be used for 14 weeks without any measurable changes in the slope. The potentiometric selectivity coefficients data revealed negligible interference from 16 common anions. It was successfully applied for the direct determination of monohydrogenphosphate in fertilizer samples and, as an indicator electrode, in potentiometric titration of HPO₄²⁻ ion with barium nitrate.     

Determination of Trace Copper by Adsorptive Voltammetry Using a Multiwalled Carbon Nanotube Modified Carbon Paste Electrode

A new method for the determination of trace copper was described. A multiwalled carbon nanotube modified carbon paste electrode was prepared and the adsorptive voltammetric behavior of copper‐alizarin red S (ARS) complex at the modified electrode was investigated. By use of the second‐order derivative linear sweep voltammetry, it was found that in 0.04 mol/L acetate buffer solution (pH 4.2) containing 4×10^?6 mol/L ARS, when accumulation potential is 0 mV, accumulation time is 60 s and scan rate is 100 mV/s, the complex can be adsorbed on the surface of the electrode, yielding one sensitive reduction peak at ?172 mV (vs. SCE). The peak current of the complex is proportional to the concentration of Cu(II) in the range of 2.0×10^?11–4.0×10^?7 mol L^?1 with a detection limit (S/N=3) of 8.0×10^?12 mol/L (4 min accumulation). The proposed method was successfully applied to the determination of copper in biological samples with satisfactory results, the recoveries were found to be 96%–102%.     

Simultaneous Determination of Iron,Copper, and Cadmium by Adsorptive Stripping Voltammetry in the Presence of Thymolphthalexone

A novel, sensitive and selective adsorptive stripping procedure for simultaneous determination of iron, copper and cadmium is presented. The method is based on the adsorptive accumulation of thymolphthalexone (TPN) complexes of these elements onto a hanging mercury drop electrode, followed by reduction of adsorbed species by voltammetric scan using differential pulse modulation. The influences of control variables on the sensitivity of the proposed method for the simultaneous determination of iron, copper and cadmium were studied using the Derringer desirability function. The optimum analytical conditions were found to be TPN concentration of 2.0 μM, pH of 9.5, and accumulation potential at ?0.4 V vs. Ag/AgCl with an accumulation time of 60 s. The peak currents are proportional to the concentration of iron, copper and cadmium over the 1–80, 0.5–100 and 1–100 ng mL^?1 ranges with detection limits of 0.5, 0.4 and 0.9 ng mL^?1_, respectively. The R.S.D. at a concentration level of 20 ng mL^?1 of iron, copper and cadmium were 2.5%, 0.9% and 1.5% (n=6), respectively. The procedure was applied to the simultaneous determination of iron, copper and cadmium in the tap water and some synthetic samples with satisfactory results.     

Determination of palladium(II) with alpha-(2-benzimidazolyl)-alpha',alpha'-(N-5-nitro-2-pyridylhydrazone)-toluene by adsorptive cathodic stripping voltammetry

The determination of palladium(II) complexed with alpha-(2-benzimidazolyl)-alpha',alpha'-(N-5-nitro-2-pyridylhydrazone)-Toluene (BINPHT) was investigated by adsorptive cathodic stripping voltammetry using hanging mercury drop electrode. Palladium(II) in the sample solution can be determined in BINPHT and ethylenediaminetetraacetic acid (EDTA). Accumulation is achieved by adsorption of Pd(II)-BINPHT complex on a hanging mercury drop electrode. Optimal conditions were found to be: supporting electrolyte; 0.01 M sodium acetate buffer at pH 5.0, accumulation potential; -590 mV versus Ag/AgCl, accumulation time; 180 s, scan rate; 50 mV s(-1), concentration of BINPHT; 2x10(-5) M. The linear range of Pd(II) was observed over the concentration range 20-100 ng ml(-1) The detection limit (S/N=3) is 2 ng ml(-1). A good reproductivity shows RSD of 2.0% (n=7). This procedure offers high selectivity with the presence of EDTA masking some metallic ions. River water sample spiking with palladium was determined.