Polarographic study of composition and stability constants of Pb(II) N-(2-acetamido) imino diacetate complexes

Summary The complexation of Pb(II) by N-(2-acetamido) imino diacetate (ADA) has been studied polarographically (dc and ac polarographic techniques). Ac polarographic studies have been particularly helpful in deciding the reversibility of the reduction of both simple and complexed metal ions and for confirmation of the overall stability constants. A weighted least squares numerical technique has been applied for the calculation of the overall stability constants using both dc and ac techniques. The reduction of Pb(II) in N-(2-acetamido) iminodiacetate solutions has been found to be reversible and diffusion controlled, involving a two electron transfer process. Potential vs. concentration data at =0.1 mol dm^–3 (KNO₃) are interpreted on the basis of the formation of two complex species PbADA and Pb(ADA)^2– in thepH range 6.85–8.50. The logarithms of the stability constants (calculated from ac measurements) of these complexes are 8.73±0.12, 10.86±0.18 at 25°C, 8.31±0.28, 10.31±0.09 at 35°C and 7.61±0.20, 10.10±0.11 at 45°C, respectively. The thermodynamic parameters G, H and S have been calculated at 35°C.

---

Polarographische Untersuchung von Zusammensetzung und Stabilitätskonstanten von Pb(II) N-(2-Acetamido)iminodiacetat-Komplexen

Zusammenfassung Es wurde die Komplexierung von Pb(II) mit N-(2-Acetamido)iminodiacetat (ADA) polarographisch mittels DC- und AC-Techniken untersucht. Insbesonders AC-Polarographie ergab eine klare Entscheidung bezüglich der Reversibilität der Reduktion von einfachen und komplexierten Metallionen und für die Bestätigung der Stabilitätskonstanten. Zur Bestimmung der Gesamtstabilitätskonstanten wurde eine gewichtete mittlere Fehlerquadrat-Methode auf Basis von DC- und AC-Messungen herangezogen. Die Reduktion von Pb(II) in N-(2-Acetamido)iminodiacetat-Lösung stellte sich als ein reversibler und diffusionskontrollierter Zweielektronen-Transferprozess heraus. Die Abhängigkeit des Potentials von der Konzentration bei =0.1 mol dm^–3 (KNO₃) läßt sich mit der Bildung von zwei Komplex-Spezies PbADA und Pb(ADA)^2– impH-Bereich 6.85–8.50 erklären. Die Logarithmen der Stabilitätskonstanten dieser Komplexe (aus AC-Messungen) sind 8.73±0.12 und 10.86±0.18 bei 25°C, 8.3 ±0.28 und 10.31±0.09 bei 35°C bzw. 7.61±0.20 und 10.10±0.11 bei 45°C. Die thermodynamischen Parameter G, H und S wurden für eine Temperatur von 35°C berechnet.

     

Behavior of Copper (II) Ion to Inosine

Abstract

The DC polarographic behavior of the Cu(II)-inosine complex was investigated, in aqueous solutions of inosine in Britton Robinson buffer solutions at pH's from 1.0 to 4.0. At low concentrations of free inosine ion, only one polarographic wave was found corresponding to a two-electron reduction.

Anisotropy of g/ = 2,039, g// = 2,287 and A// = 172G, A/= OG, was observed in the ESR spectrum of the Cu(II)/inosine complex. When the composition ratio of the complex was obtained by both polarography and ESR, it was found that the ratio Cu(II) to inosine was 1:2. The polarographic wave showed a two electron reduction wave.     

Polarographic behaviour of salicylaldehyde-2-pyridylhydrazone and its copper(II) complex

The polarographic behaviour of salicylaldehyde-2-pyridylhydrazone (SAPH) has been studied in aqueous buffer solution containing 40% ethanol using DC and DP polarographic methods. In the pH range 1.8–7.5 the observed single irreversible reduction wave is assigned to the splitting of the N-N bond and reduction of C=N centre. In alkaline medium, a second wave appears at a more negative potential due to the reduction of the salicylaldehyde which is formed by hydrolytic decomposition of the SAPH molecule. The effect of pH on the limiting current andE _1/2 as well as the reduction mechanism are discussed and compared with similar compounds. The kinetic parameters of the electrode reaction have been calculated.The analytical properties of the copper(II)-SAPH system is described. The complex gave rise to a single irreversible well-defined wave (E _1/2=–0.58 V at pH=5.2). The reaction process is diffusion controlled. A method is suggested for the determination of Cu(II) in presence of different metal ions as the difference in theirE _1/2 values is sufficient for the purpose.This work is taken partly from the M. Sc. Thesis of Jamal S. Shalabi     

Simultaneous kinetic spectrophotometric determination of Cu(II), Co(II) and Ni(II) using partial least squares (PLS) regression

A partial least squares (PLS-1) calibration model based on kinetic—spectrophotometric measurement, for the simultaneous determination of Cu(II), Ni(II) and Co(II) ions is described. The method was based on the difference in the rate of the reaction between Co(II), Ni(II) and Cu(II) ions with 1-(2-pyridylazo)2-naphthol in a pH 5.8 buffer solution and in micellar media at 25°C. The absorption kinetic profiles of the solutions were monitored by measuring the absorbance at 570 nm at 2 s intervals during the time range of 0–10 min after initiation of the reaction. The experimental calibration matrix for the partial least squares (PLS-1) model was designed with 30 samples. The cross-validation method was used for selecting the number of factors. The results showed that simultaneous determination could be performed in the range 0.1-2 μg mL⁻¹ for each cation. The proposed method was successfully applied to the simultaneous determination of Cu(II), Ni(II) and Co(II) ions in water and in synthetic alloy samples.      

Electroanalytical Study of the Reduction of Sb(III) in Tartrate Medium

Abstract

A systematic study on the reduction of Sb(III) on a mercury electrode in aqueous solution of tartrate ion has been carried out. The nature of the electrode reactions has shown to be a function of the acidity of the solution. Results from polarographic, coulometric and voltammetric experiments allow us to outline a model of electrode reaction according to which different Sb-tartrate complex ions can be reduced. Sensitivity and detection limits for the polarographic determination of Sb(III) in tartrate medium are given using several polarographic waves obtained at different pH. In this way, the selection of the basic medium is vindicated.     

Differential pulse polarographic behaviour of copper(II)-ethyleneglycol-bis-(2-aminoethylether)-tetraacetate and copper(II)-ethylenediaminetetraacetate chelates in the presence of Lanthanum(III)

Summary The substitution reduction waves of copper(II)-EGTA and copper(II)-EDTA chelates were investigated with differential pulse and tast polarographic methods. The reduction wave of copper(II)-EGTA chelate shifts to more positive potential in the presence of lanthanum(III) and a new differential pulse peak appears. The peak height increases linearly with increasing concentration of lanthanum(III) between 5 and 25 M. When the copper(II)-EDTA chelate is reduced in a supporting electrolyte containing no buffer solution, lanthanum(III) gives a substitution reduction peak, but in acetate buffer solution the lanthanum(III) peak disappears.

---

Differential-Puls-Polarographisches Verhalten des Kupfer(II)-Ethylenglykol-bis-(2-aminoethylether)-tetraacetat-Chelats und des Kupfer(II)-Ethylendiamintetraacetat-Chelats in Gegenwart von Lanthan(III)

Zusammenfassung Die Substitutionsreduktionswellen des Kupfer(II)-EGTE- und des Kupfer(II)-EDTE-Chelats wurden mit Hilfe der Differential-Puls- und der Tast-Polarographie untersucht. Die Reduktionswelle des Kupfer(II)-EGTE-Chelats verschiebt sich in Gegenwart von Lanthan(III) zu positiverem Potential und ein neuer Differential-Puls-Peak erscheint. Die Peakhöhe nimmt mit steigender Lanthanionkonzentration zwischen 5 und 25 M linear zu. Wenn Kupfer(II)-EDTE-Chelat im pufferfreien Leitelektrolyt reduziert wird, gibt Lanthan(III) einen Substitutionsreduktions-Peak, in Acetat-Pufferlösung jedoch verschwindet der Lanthan(III)-Peak.

     

Differential pulse polarography of germanium(IV), tin(IV), arsenic(V), antimony(V), selenium(IV) and tellurium(VI) at the static mercury drop electrode in catechol—perchlorate media

The differential pulse polarography of Ge(IV), Sn(IV), As(V), Sb(V), Se(IV) and Te(VI) has been investigated in perchlorate media containing catechol using a static mercury drop electrode. Under optimum conditions, Ge(IV), Sn(IV), As(V), and Sb(V) undergo reduction to yield well-defined peaks; detection limits of 82 ppb, 28 ppb, 4 ppm, and 25 ppb, respectively, have been calculated. Few electrolytes are known for which these ions exhibit a quantitatively useful polarographic response. While Se(IV) and Te(VI) may be detected at levels of 115 ppb and 17 ppb, respectively, addition of catechol does not enhance the peak current relative to that observed in simple perchlorate solutions, as was the case for the other ions studied. The determination of germanium, arsenic and antimony in samples is described.     

Gravimetric Determination of Mercury(II) and Vanadium(IV) with Benzoylacetanilide

Abstract

Gravimetric methods for the determinations of mercury(II) and vanadium(IV) with benzoylacetanilide have been described. These metals have been separated from commonly associated ions and a procedure for the determination of vanadium content of steel has been developed. By these methods, 14 to 50 mg. of mercury and 5 to 20 mg. of vanadium have been estimated with relative standard deviations of 0.18% and 0.10%, respectively.     

Nucleophilic attack by bromide ions as a first step of conversion of Se(VI) to Se(IV)

Numerous commonly used analytical methods allow only determination of a total amount of selenium in a given sample. Electroanalytical methods as well as those based on hydride generation or on formation of piazselenol allow only determination of Se(IV). To determine Se(VI) by these procedures, present alone or in mixtures with Se(IV), it is first necessary to convert Se(VI) to Se(IV). Such conversion is effective in the presence of excess of halides in acidic media or by photoreduction. In the often used conversion of Se(VI) in the presence of chlorides or less frequently of that of bromides, it has been assumed that the halide ion acts as a reducing agent. Kinetic studies of conversion of Se(VI) in acidic solutions containing an excess of bromide ions indicated that the rate determining first step of the reaction with Se(VI) is a nucleophilic substitution of the OH₂⁺ group in the protonated form of H₂SeO₄ by bromide ions. For the overall reaction with rate −d[Se(VI)]/dt = k₁[H⁺][Br⁻]^1.15[Se(IV)] the rate constant 1 × 10⁻³ L² mol⁻² s⁻¹ was found. The following formation of Se(IV) from the bromo derivative is a fast reaction probably resulting in elimination of HBrO.     

Determination of selenium(IV) and tellurium(IV) by differential pulse polarography

Differential pulse polarographic methods for the determination of selenium(IV) and tellurium(IV) in nitric acid medium are described. The peak current is maximal when 0.25M nitric acid medium is used, the DPP peaks for Se(IV) and Te(IV) being at -0.54 and -0.8 V vs. Ag/AgCl respectively. The peak current is a linear function of selenium concentration over three ranges, 5.1 x 10(-6)-1.3 x 10(-5), 1.27 x 10(-5)-1.27 x 10(-4) and 1.27 x 10(-4)-7.60 x 10(-4)M Se(IV), with different slopes. The plot for Te(IV) is linear over the range 0.78 x 10(-6)-9.40 x 10(-5)M.     

Differential Pulse Polarographic Determination of Cd(II) and Pb(II) in Milk Samples after Solid‐Phase Extraction Using Amberlite XAD‐2 Resin Modified with 2,2′‐DPED3P

In the present paper novel column solid phase extraction procedure was developed for the determination of Cd(II) and Pb(II) in cows', goats', ewes', buffalos' and humans' milk samples using newly synthesized reagent 2,2′‐DPED₃P (2,2′‐{[1,2‐diphenylethane‐1,2‐diylidene]dinitrilo}diphenol) for preconcentration and separation prior to differential pulse polarography using amberlite XAD‐2 in the ranges of pH 4.0–5.0. The sorbed elements were subsequently eluted with 10 mL of 2 M HCl elutes were analysed by differential pulse polarography (DPP). The interference of foreign ions has also been studied. Effects of various instrumental parameters are investigated and received conditions are optimized. The total metal concentration of the milk samples in the study area were in the following ranges 0.030–0.090 μg L^?1 of Cd(II), 0.009–0.026 μg L^?1 of Pb(II) respectively. The limits of detections were found to be 0.020 and 0.024 μg L^?1 for Cd(II) and Pb(II) respectively by applying a preconcentration factor ～40. The proposed enrichment method was applied successfully for the determination of metal ions in cows', goats', ewes', buffalos' and humans' milk samples.     

Polarographic Determination of Pb(II) and Cd(II) with Selective Removal of Se(IV) Using Ionic Poly(<Emphasis Type="Italic">N,N</Emphasis>-dimethylacrylamide-co-allylthiourea)

Hydrogels based on N,N-dimethylacrylamide (DMAAm), allylthiourea (ATU), and maleic acid (MA) were synthesized by free-radical cross-linking copolymerization in water with N,N-methylene-bis(acrylamide) (BAAm) as the cross-linker, ammonium persulfate (APS) as the initiator, and N,N,N′,N′-tetramethylenediamine (TEMED) as the activator. Since Se(IV) is the most serious interfering element in the electroanalytical (polarographic or voltammetric) determination of lead and cadmium, a new method for their correct determination after selective separation of the interfering ion (selenite) was developed by using poly(N,N-dimethylacrylamide-co-allylthiourea) [P(DMAAm-co-ATU)] hydrogels containing reducing pedant groups like allylthiourea. The proposed method showed good reproducibility and accuracy with relative standard deviations of 8.5 and 3.4% and relative errors of ?6.0 and ?5.4% for the determination of 5.0 × 10^?5 M Pb(II) and Cd(II), respectively, next to 3.0 × 10^?5 M Se(IV).     

Silica gel surface modified with sulfanilamide for selective solid-phase extraction of Cu(II), Zn(II) and Ni(II)

A new chelating matrix has been prepared by immobilising sulfanilamide (SA) on silica gel (SG) surface modified with 3-chloropropyltrimethoxysilane as a sorbent for the solid-phase extraction (SPE) Cu(II), Zn(II) and Ni(II). The determination of metal ions in aqueous solutions was carried out by inductively coupled plasma optical emission spectrometry (ICP-OES). Experimental conditions for effective sorption of trace levels of Cu(II), Zn(II) and Ni(II) were optimised with respect to different experimental parameters using the batch and column procedures. The presence of common coexisting ions does not affect the sorption capacities. The maximum sorption capacity of the sorbent at optimum conditions was found to be 34.91, 19.07 and 23.62 mg g^?1 for Cu(II), Zn(II) and Ni(II), respectively. The detection limit of the method defined by IUPAC was found to be 1.60, 0.50 and 0.61 µg L^?1 for Cu(II), Zn(II) and Ni(II), respectively. The relative standard deviation (RSD) of the method under optimum conditions was 4.0% (n = 8). The method was applied to the recovery of Cu(II), Zn(II) and Ni(II) from the certified reference material (GBW 08301, river sediment) and to the simultaneous determination of these cations in different water samples with satisfactory results.     

Tropaeolin OO as a Chemical Sensor for a Trace Amount of Pd(II) Ions Determination

The selective determination of metals in waste solutions is a very important aspect of the industry and environmental protection. Knowledge of the contents and composition of the waste can contribute to design an efficient process separation and recovery of valuable metals. The problematic issue is primarily the correct determination of metals with similar properties such as palladium and platinum. Thus this paper focuses on the development of a selective method that enables Pd(II) determination in the presence of Pt(IV) ions using the azo-dye tropaeolin OO (TR). For this purpose, the process of the metalorganic complex formation and Pd(II) ions determination were studied by using UV–Vis spectrophotometry under different conditions: solvents (water and B-R buffer), pH (2.09–6.09), temperature (20–60 °C), anions and cations concentrations. The formed metalorganic complex between Pd and tropaeolin OO allows for distinguishing Pd(II) ions from both platinum complexes, i.e. Pt(II), Pt(IV). Moreover, the proposed method can be applied to solutions containing both chloride and chlorate ions. The obtained characteristic spectrum with two maxima allows the determination of palladium even in the presence of other cations (Na, K, Mg, Zn, Co, Ni, Al) and changed concentrations of Pt(IV) ions. Furthermore, the developed spectrophotometric method for the Pd(II) ions determination using tropaeolin OO is characterized by high selectivity towards palladium ions.     

Spectrophotometric study of Cd(II), Pb(II), Hg(II) and Zn(II) complexes with 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin

The reaction of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) with Cd(II), Pb(II), Hg(II) and Zn(II) was studied spectrophotometrically and kinetics, equilibrium constants as well as photodecomposition of complexes were determined. It was verified that these metal ions with large radius accelerate the incorporation reaction of zinc into TCPP. On the basis of the mechanism and kinetics of this reaction, a sensitive method for the spectrophotometric determination of trace amounts of Zn(II) has been developed. The molar absorptivity of examined Zn-TCPP complex and Sandell's sensitivity at 423 nm were 3.5×10⁵ M⁻¹ cm⁻¹ and 18.3 ng cm⁻². The detection limit for the recommended procedure was 1.4×10⁻⁹ M (0.9 ng ml⁻¹) and precision in range 20-100 ng ml⁻¹ not exceeds 2.7% RSD. The proposed method applied for zinc determination in natural waters and nutritional supplement was compared with AAS results and declared value.     

Hetero-binuclear chelates of Mn(II), Co(II) and Cu(II) o-cresolphthalein complexonates with other metal ions

Heterobinuclear metal chelates of Mn²⁺, Co²⁺ or Cu²⁺ and some transition metal ions with o-cresolphthalein complexone have been prepared and characterized. Elemental analyses are in agreement with proposed formulae. Thermal analyses (TGA and DTA) were used to determine the degradation products; some thermodynamic parameters were calculated. IR and UV-Vis spectra identified the mode of bonding between the metal ions and the ligand as well as its geometry. Magnetic moment determination and ESR spectra of the heterobinuclear complex revealed some antiferromagnetic interaction between the metal ions, which depends mainly on the two metal ions forming the chelate. Electrochemical studies of the complexes [DC-polarography and cyclic voltammetry (CV)] confirmed the existence and the nature of the metal ions in the chelate.     

Simultaneous Polarographic Determination of Lead (II) and TIN (II) by Multivariate Calibration

ABSTRACT

The polarographic waves of lead (II) and tin (II) overlap due to their similar reductive potentials and it is difficult to determine these two components simultaneously without a pre-separation. In this paper, differential pulse polarography (DPP) combined with multivariate calibration approaches, such as classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS), were successfully applied to the resolution of overlapping polarographic waves of these two components in the concentration range of 0.05-3.50 mg 1^?1. Satisfactory quantitative results were obtained.     

Polarographic behaviour of phenyl-2-picolylketone-2-pyridylhydrazone and its copper (II) complexes

The polarographic behaviour of phenyl-2-picolylketone-2-pyridylhydrazone, PPKPyH, has been studied in aqueous-ethanol mixtures of different pH's using DC and DP polarographic method. In the pH range 3.7–6.2, the observed single irreversible reduction wave is assigned to the splitting of the N—N bond and reduction of C=N centre. In alkaline medium, a second wave appears at more negative potential due to the reduction of the phenyl-2-picolylketone which is formed from the hydrolysis of PPKPyH. The optimum conditions for the analytical determination of PPKPyH was reported. Differential pulse polarography have been used to elucidate the complexation reaction between PPKPyH and copper(II) in unbuffered solutions. Two complexes are formed with log ₁ = 4.42 and log ₂ = 8.87.     

Differential pulse polarographic determination of Co(II) using moxifloxacine

The polarographic reduction of Co(II) in the presence of moxifloxacin (1-cyclopropyl-7-[(S,S)-2.8-diazabicyclo[4.3.0]non-8-yl]-6-fluoro-8-methoxy-1.4-dihydro-4-oxo-3-quinolinecarboxylic acid) gives rise to an additional adsorption peak corresponding to the reduction of Co(II)-moxifloxacin complex on the mercury drop electrode at −1.17 V. This new peak is applicable to Co(II) determination with the linearity proportional to the Co(II) concentration in the range of 4.93 × 10⁻⁷−6.90 × 10⁻⁵ M and can be attributed to an adsorption-controlled process with an irreversible reduction. Without using moxifloxacin, the polarographic determination of 2.50 × 10⁻⁶ M Co(II) is impossible under the given conditions due to very poor sensitivity at −1.38 V. The proposed method showed good precision and accuracy with a relative standard deviation of 3.01% and relative error of +6.40% for the determination of 2.50 × 10⁻⁶ M Co(II) next to 5.0 × 10⁻⁶ M of Zn(II), Ni(II), and Cd(II). The accuracy of the method was also checked by the determination of Co(II) spiked with tap water and certified sea water, and the percentage recoveries were 97.5 and 96.7%, respectively (n = 4 at 95% confidence interval). The text was submitted by the authors in English.     

Polarographic Determination of Famotidine through Complexation with Nickel(II) Chloride

The present investigation describes the development of a sensitive, rapid polarographic method for the determination of famotidine in pure form and in certain dosage forms. The proposed method depends upon studying the polarographic activity of Nickel(II)‐famotidine complex in Britton Robinson buffer over the pH range 4–8 and its usefulness in the analysis of famotidine using direct current (DC_t), differential pulse (DPP), and alternating current (AC_t) polarography. The different experimental parameters affecting the cathodic waves were carefully investigated and optimized. Moreover, to check the validity of the proposed method, the standard addition method was applied by adding famotidine to the previously analyzed tablets. The recovery of the drug was calculated by comparing the concentration obtained from the spiked mixtures with those of the pure drug. The results of analysis of commercial tablets and the recovery study suggested that there is no interference from any excipients, which are present in tablets. Statistical comparison of the results was performed with regard to accuracy and precision using student's t‐test and F‐ratio at 95% confidence level. There is no significant difference between the comparison and proposed method with regard to accuracy and precision.