Complexometric determination of copper(II) in ores,alloys and complexes using 2-mercaptoethanol as indirect masking reagent

A complexo-titrimetric method for the determination of copper(II) in the presence of other metal ions is described, based on the selective masking ability of 2-mercaptoethanol towards copper(II). Copper and other ions in a given sample solution are initially complexed with an excess of EDTA and the surplus EDTA is titrated with zinc sulfate solution at pH 5.0–6.0 (hexamine), using xylenol orange as indicator. A known excess of 2-mercaptoethanol solution (10%) is then added, the mixture is shaken well and the released EDTA from the Cu-EDTA complex is titrated against standard zinc sulfate solution. The interferences of various ions are studied and the method is applied to the determination of copper in its ores, alloys and complexes. Reproducible and accurate results are obtained for 2.5–40 mg of Cu with relative errors 0.4% and standard deviations 0.04 mg.     

Ion-selective electrodes in organic functional group analysis: Microdetermination of hydrazines with the copper electrode

Summary A simple micromethod is described for the determination of hydrazines using the copper ion-selective electrode. The method is based on direct potentiometric titration of the sample in ammoniacal solution of pH 9.5±0.2 with copper(II) ions at room temperature. N-Shaped curves with well-defined inflections at 11 and 12 molar ratios are obtained. This is probably due to the formation of copper monohydrazinate and copper dihydrazinate complexes. Various alkyl and aryl hydrazines and hydrazine salts have been satisfactorily analyzed with an average recovery of 99.4% and a relative standard deviation of ±0.4%. The reaction of hydrazines with Fehling's solution followed by measuring the copper(I) oxide formed using the copper ion-selective electrode also has been investigated.

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Zusammenfassung Eine einfache Mikromethode zur Bestimmung von Hydrazinen mit einer kupferionen-selektiven Elektrode wurde beschrieben. Sie beruht auf der direkten potentiometrischen Titration in ammoniakalischer Lösung mit Cu(II)ionen bei pH 9,5±0,2 bei Zimmertemperatur. N-förmige Kurven mit gut ausgebildeten Spitzen bei Molverhältnissen 11 und 12 wurden erhalten, wahrscheinlich auf Grund der Bildung von Mono- bzw. Dihydrazinatkomplexen des Kupfers. Verschiedene Alkyl- und Arylhydrazine und deren Salze wurden zu 99,4% mit einer Standardabweichung von ±0,4% wiedergefunden. Die Reaktion der Hydrazine mit Fehlingscher Lösung wurde ebenfalls durch Messung des entstandenen Cu(I) mit der erwähnten Elektrode untersucht.

     

Studies on the kinetics and mechanism of dissociation of copper(II) and nickel(II) complexes of the macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene in perchloric acid media

Summary Acid catalysed dissociation of the copper(II) and nickel(II) complexes (ML²⁺ of the quadridentate macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene (L) has been studied spectrophotometrically. Both complexes dissociate quite slowly with the observed pseudo-first order rate constants (k_obs) showing acid dependence; for the nickel(II) complex (k_obs)=k_O+k_H[H⁺], the k_o path is however absent with the copper(II) complex. At 60°C (I=0.1M) the k_H values areca 10^–4 M^–1 s^–1 for both complexes; k _H ^Cu /k _H ^Ni =ca. 3.9, comparable to some other square-planar complexes of these metal ions. The rate difference is primarily due to H values [copper(II) complex, 29.4±0.5 kJ mol^–1; nickel(II) complex, 35.6±1.5 kJ mol^–1] with highly negative S values [for copper(II), –215.5 ±6.1 JK^–1 mol^–1 and for nickel(II), –208.1 ±5.6 JK^–1 mol^–1] which are much higher than the entropy of solvation of Ni²⁺ (ca. –160 JK^–1 mol^–1) and Cu²⁺ (ca. –99 JK^–1 mol^–1) ions; significant solvation of the released metal ions and the ligand is indicated.     

Complexing Power of Vitamin D3 Toward Various Metals. Potentiometric Studies of Vitamin D3 Complexes with Al3+, Cd2+, Gd3+, and Pb2+ Ions in Water–Ethanol Solution

This study reports the stability constants of complexes with vitamin D₃ and Al³⁺, Cd²⁺, Gd³⁺ and Pb²⁺ ions in a water–ethanol medium (30/70% v/v at 25.0°C). The logarithms of the overall stability constants are: ₁ = 12.4 ± 0.5, 7.6 ± 0.3, 9.33 ± 0.07, and 9.1 ± 0.5, respectively, whereas the logarithms of ₂ are 24.4 ± 0.5 (Al³⁺), 14.3 ± 0.3 (Cd²⁺), and 15.4 ± 0.5 (Pb²⁺). Gd³⁺ forms only the 1:1 complex. These values are compared to those reported previously and correlations are established between the stability constants and physical properties, such as the ionization energy.     

Preparation of uniform spherical aluminum hydrous oxide particles from acetylacetonato-aluminum solutions

Uniform spherical particles of amorphous aluminum hydrous oxide (0.45 m in diameter with a relative standard deviation of 0.09) were produced under a limited set of conditions in an aluminum sulfate/acetylacetone system at 100°C aged for 24 h. Grain-like crystalline -AlOOH particles (2.6 m in length with a relative standard deviation of 0.10) were also prepared in the absence of sulfate ions at 100°C for 42 h. Their morphology and size were sensitive to the total aluminum concentration, even though the initial pH was kept the same. The temperature dependence of the absorption spectra of acetylacetonato-aluminum complexes indicated their exothermic formation. These complexes release free aluminum ions at elevated temperatures, which subsequently hydrolyzed. The resulting polymerized hydroxo-aluminum species complexes with the sulfate ion act as precursors to particle formation.     

Complex equilibria of molybdenum(V) and molybdenum(VI) witho-hydroxybenzylamine-N,N,O-triacetic acid (HBATA)

Summary Complex reactions between Mo^V.VI ando-hydroxybenzylamine-N,N,O-triacetic acid (HBATA) have been investigated in the 1–3 and 2.8–6.5 pH range by potentiometric titration at 30° C in 0.5 mol dm^–3 NaCl. The equilibrium data were analyzed with the SCOGS2 and MINIQUAD programs, taking into account side reactions of Mo^V.VI and HBATA with hydrogen ion. The favorable reaction model comprises two complexes, (1,1,1)⁺ and (1,2,2)^–, with formation constants log ₁₁₁ = 14.85 ± 0.11 and log ₁₂₂ = 28.51 ± 0.08 for the Mo^V-HBATA system and the two complexes (1,1,2)^3– and (1,1,3)^2– with formation constants log ₁₁₂ = 17.36 ± 0.01 and log ₁₁₃ = 20.60 ± 0.01 for the Mo^VI-HBATA system. The numbers in brackets refer to the chemical stoichiometric coefficients of molybdenum, HBATA and hydrogen ion in the complexes. The structure and coordinating behaviours of Mo^V and Mo^VI complexes are discussed. The equilibria studied for the polymerization of Mo^V indicates that dimeric, trimeric and tetrameric species are present at pH 1–3.     

Study of the uptake of inorganic ions and organic acids at theα-alumina-electrolyte interface in a colloidal system by radiochemical techniques and microelectrophoresis

The interactions of the alumina-electrolyte in the presence of inorganic ions (copper, selenium) and/or organic acids (benzoic acid, glutamic acid, phenol) have been studied. The acid-based properties of-alumina have been determined in NaCl media (pzc=8.5±0.3). Three types of hydroxy groups with different acidity constants have been found. The adsorption of copper and selenium have been described by the formation of the surface complexes: (=Al¹–OH, CuCl) and (=Al¹, SeO₃)^–. The interaction of copper with the surface oxygen atoms is strong and so is the interaction of selenium with the surface aluminium atoms, which involves a shift of the iep of alumina. For the three organic acids studied (HX), the adsorption equilibrium is:=Alⁱ–OH+HX(=Alⁱ, X)+H₂O. The interaction of the X^– group and the aluminium atoms is strong following the order: glutamic acid > benzoic acid > phenol. The uptake of selenium is uninfluenced by the presence of organic acids with carboxylic, amino-acidic and phenolic groups. The uptake of copper is highly increased by the presence of organic acids but it is not influenced by the presence of the phenolic groups. Both of these behaviours can be extrapolated to inorganic ions of the same chemical structure.     

Complexation properties of phosphonocarboxylic acids in aqueous solutions

The concentration formation constants of phosphonoacetic acid (PAA) complexes with the Ca²⁺ and Mg²⁺ ions were determined in aqueous solution at 25°C by potentiometric and coulometric titrations at different ionic strengths and were extrapolated to I=0 in order to obtain thermodynamic values of the formation constants. Complexes were formed by the completely deprotonated K _f (ML) and monoprotonated K _f (MHL) forms of the PAA anion. The respective values for the complexes are: log K _f (CaL)=4.68±0.03, log K _f (CaHL)=2.61±0.08; log K _f (MgL)=5.58±0.09, log K _f (MgHL)=3.0±0.3. The enthalpy and entropy of complexation for the deprotonated Ca²⁺ and Mg²⁺ PAA species, determined from the temperature dependence of the log K _f (ML), are: H⁰(Ca) =0.6±0.2 kcal-mol^–1, S⁰(Ca)=21.4±0.6 cal-mol^–1-K^–1, H⁰(Mg)=3.0±0.7 kcal-mol^–1, and S⁰(Mg)=35±2 cal-mol^–1-K^–1. It is seen there-fore, that the complexes are entropy stabilized but enthalpy destabilized. Formation constants were also determined for Ca²⁺ and Mg²⁺ complexes with PAA analogs, phosphonoformic and 3-phosphonopropionic acids and the complexation of PAA was also studied at a single ionic strength, with Na⁺, Ag⁺, Tl⁺, Sr²⁺, Ba²⁺, Cd²⁺, Cu²⁺, and Pb²⁺ ions.     

Peroxide derivatives of molybdenum(VI) in neutral and alkaline media

Summary The peroxidation of molybdenum(VI) was investigated in neutral and alkaline media. The stability constants of the peroxo complexes were determined by spectrophotometric measurement as (9.12±0.67)×10^–7, (2.68±0.17) ×10⁵, (1.26±0.06)×10⁶ and (1.58±0.02) for the 11, 21 (yellow), 31 and 41 (red) species. The diperoxomolybdate disproportionates into the tetraperoxo derivative when treated with alkali. Formation of the tetraperoxo complex was found to be pH dependent according to a curve, with maximum at pH 10. Acidification of tetraperoxomolybdate solution results in the regeneration of hydrogen peroxide and the diperoxo complex is reformed.     

Potentiometric Investigation of Fluoride Complexes of Zirconium(IV) and Hafnium(IV) in 1 <Emphasis Type="Italic">M</Emphasis> (H,Na)ClO<Subscript>4</Subscript> Medium Using a Fluoride Ion Selective Electrode

The stability constants of zirconium(IV) and hafnium(IV) fluoride complexes in 1 M (H,Na)ClO₄ medium were measured potentiometrically at 293 K for the first time using a fluoride ion selective electrode (F-ISE). This technique has been recommended by IUPAC as the best tool for studying fluoride complexes. A number of precautions were taken to ensure the stabilization of zirconium or hafnium in 1 M (H,Na)ClO₄ medium and to prevent the formation of polynuclear hydroxo complexes. The formation of only mononuclear complexes was indicated. The average log values of the overall stability constants of zirconium(IV)-fluoride complexes, ₁, ₂, ₃ and ₄ were computed by varying the concentration of metal ion and were found to be 8.49 ± 0.11, 15.76 ± 0.15, 21.57 ± 0.10, and 26.68 ± 0.16, respectively, whereas the corresponding values for hafnium(IV)-fluoride complexes were 8.22 ± 0.06, 15.48 ± 0.15, 21.76 ± 0.14, and 27.42 ± 0.15, respectively. The thermodynamic stability constant, ₁, calculated for these complexes follows the same trend as expected from the linear correlation based on the Brown Sylva Ellies (BSE) model for metal-fluoride complexes provided the effective charge on Zr is taken as +4.1 instead of the formal charge of +4. Without considering this adjustment of formal charge, an attempt has also been made to explain the trend in ₁ values of group(IV) metal-fluoride complexes based on electronegativity values. A good linear correlation was obtained that could explain the ability of these group(IV) ions to form different fluoride complexes with varying number of fluoride ions.     

Sorption of Copper and Strontium Ions and Fulvinate and Citrate Complexes from Aqueous Solutions by Flocculating Microbocenosis

Sorption of copper and strontium ions and citrate and fulvinate complexes by the microorganisms of natural activated sludge is studied. It is shown that the latter contains charged hydrophilic and hydrophobic biocolloids and capable of active sorbing of copper and strontium ions, as well as their organic complexes, from aqueous solutions. It is established that metal ions possess a higher affinity for a given microbocenosis than their organic complexes and the limiting sorption of metal compounds within a concentration range of 0.1–1 mM is equal to (in mmol/g): 0.646 (Cu²⁺), 0.177 (Cu-fulvinate), 0.156 (Cu-citrate), 0.495 (Sr²⁺), 0.364 (Sr-fulvinate), and 0.292 (Sr-citrate). Copper ions and organocomplexes are bound to the activated sludge stronger than corresponding compounds of strontium.     

Study of monensin complexes with monovalent metal lons in anhydrous methanol solutions

Potentiometric and cyclo-voltammetric studies have been carried out on monensin anion (Mon^–) complexes with the alkali ions as well as with Tl⁺ and Ag⁺ in absolute methanol solutions. The log K_f values obtained for the complexity constants and corrected for the activity effects are: Li⁺, 3.3±0.1; Na⁺, 6.72±0.05; K⁺, 5.18±0.05; Rb⁺, 4.58±0.05; Cs⁺, 3.75±0.05; Tl⁺, 5.31±0.05; Ag⁺, 8.2±0.2. It is seen that for the alkali, the most stable complex is formed with Na⁺. The enthalpy and entropy of complexation with the sodium ion were found to be H^o=–5.47±0.24 kcal-mole^–1 and S^o=+12.4±0.7 e.u. The complex, therefore, is enthalpy and entropy stabilized.     

Complexation,solubilities and thermodynamic functions for cerium(III) fluoride-water system

The solubility, solubility product and the thermodynamic functions for the CeF₃–H₂O system have been measured using the radiometric, conductometric and potentiometric techniques. The radiometric values for the solubility and solubility product, the lowest and more acceptable for reasons cited in previous papers, are 3.14·10^–5 M and 2.17·10^–17 respectively. The enthalpy change measured by the conductometric method is almost twice as that obtained by potentiometric method due to abnormal conductances registered at higher temperatures. The average values for H^o and G^o and S^o at 298 K are 53.0±17.4, 91.7±4.0 and –129.7±58.2 KJ·mol^–1 respectively. The positive values for H^o and G^o and the negative value for S^o are indicative of the low solubility of this salt in water. The stability constants for the mono- and difluoride complexes of Ce(III) have been determined potentiometrically using unsaturated solution mixtures of Ce(III) and F^–. These values for CeF⁺ and CeF ₂ ⁺ are 997±98 and (1.03±0.44)·10⁵, respectively. Studies on pH dependence of the solubility shows that the solubility reaches a minimum value at a pH of about 3.2.     

Komplexbildung des Kupfer(II) mit Opioidpeptiden

Complex Formation of Copper(II) with Opioid Peptides Complex compounds of copper(II) with the neuropeptide enkephaline were detected as CuH_?(n?1)L + nLi⁺ ions by means of FAB mass spectrometry. Formation constants of proton and copper(II) complexes of four opioid peptides (L-I ? L-IV) were determined potentiometrically. Complexes with methionine-containing ligands show the highest stability. Under physiological pH values all brain-existent enkephaline may be bound by endogeneous copper provided that [Cu²⁺] > 10^?7 M.     

Spectrophotometric Determination of Acyclovir and Amantadine Hydrochloride through Metals Complexation1

A simple spectrophotometric method for determination of some antiviral drugs, such as acyclovir and amantadine hydrochloride in pure and dosage forms, have been developed. The proposed method is based on the reactions of the selected drugs and metals. Acyclovir was reacted with copper (II) and cobalt (II) using a borax/sodium pH 9 hydroxide buffer, and in a non-aqueous medium using 1% pyridine in methanol, respectively.The formed complexes were absorbed maximally at A, 290 nm and at X 287 nm. The method determined from 112–1620 g/mL of acyclovir, with a mean percentage of recovery of 99.32 ± 0.63 and of 98.77 ± 0.70 for copper (II) and cobalt (III), respectively.The suggested method was applied to a Novirus capsule, and its validity was ascertained by the standard addition technique. In addition, amantadine hydrochloride was allowed to react with iron (III) at pH 3 adjusted with 0.1 M ammonium hydroxide. The formed complex absorbed maximally at 295 nm. This method determined from 94–940 g/mL of amantadine hydrochloride with a mean percentage of recovery of 99.49 ± 0.57. The suggested method was applied to an Adamine capsule, and its validity was ascertained by the standard addition technique.     

Copper(II) complexes of thioarylazo-pentanedione: Structures,magnetism, redox properties and correlation with DFT calculations

Copper(II) complexes of 3-((2-(alkylthio)phenylazo)-2,4-pentanedione, tridentate O, N, S donor ligands, are described in this work. Chloride bridged copper(II) polymers (1) and thiocyanato bridged copper(II) dimmers (2) are characterized by a single crystal X-ray diffraction study. The complexes show antiferromagnetic interactions, with J = −0.5 ± 0.1 cm⁻¹ (1a) and −25.8 ± 0.5 cm⁻¹ (2b), which implies stronger coupling in the –SCN-bridging compound. The spectra, redox and magnetism are explained by DFT studies.     

The determination of thermodynamics of oxygen complexes of anions of sulfur dioxide and fluoronitrobenzenes using atmospheric pressure ionization mass spectrometry

The thermodynamic properties of oxygen complexes of the negative ions of 1-fluoro-2,4-dinitrobenzene (FDNB), 1,5-difluoro-2,4-dinitrobenzene (DFDNB), and sulfur dioxide have been determined by measuring the temperature dependence of the pertinent ion ratios by using a mass spectrometer equipped with a⁶³Ni atmospheric pressure ionization source. The values of -H° and -S°are SO ₂ ^–(O₂), 101 ± 2.1 kJ mole¹ and 121 ± 3.8 J/K-mole; FDNB^–(O₂), 51.5 ±3.4 kJ mole^–1 ± 9.2 J/K-mole; and DFDNB^–(O₂), 65.7 ± 0.4 kJ mole^–2 and 110 ± 5.0 J/K-mole.     

Complexometric determination of cadmium using 2-Mercaptoethanol as masking reagent

A complexometric method for the determination of cadmium(II) in presence of other metal ions is described based on the selective masking ability of 2-mercaptoethanol towards cadmium(II). Cadmium and other ions in a given sample solution are initially complexed with excess of EDTA and the surplus EDTA is titrated with lead nitrate solution at pH 5.0–6.0 (hexamethylentetramine), using xylenol orange as indicator. A known excess of 2-mercaptoethanol solution (10% alcoholic) is then added, the mixture is shaken well and the released EDTA from the Cd-EDTA complex is titrated against standard lead nitrate solution. The interferences of various ions are studied and the method is applied to the determination of cadmium in its complexes. Reproducible and accurate results are obtained for 3.5–25mg of Cd with relative errors 0.65% and standard deviations 0.06 mg.     

Determination of cobalt,nickel and copper in steel and in radioactive wastes using desferrioxamine “B”

A simple and sensitive spectrophotometric method for the determination of cobalt, nickel and copper with desferrioxamine-B (desferal) is described. The sensitivity of the colour reactions of cobalt, nickel and copper is increased by introducing desferal. The pH range for the formation of Co II, Ni II or Cu II-desferal. Chelates is 4.5–8.5, 5.5–9, and 6.5–9.5, respectively. The molar absorptivities of the chelates are 1.2·10⁵, 5.6·10⁴ and 4.8·10⁴ at 545 nm, 390 nm and 680 nm, respectively. Beer's law is obeyed up to 10 g/ml of metal ion. The effect of desferal concentration, pH, standing time and interfering ions are discussed. The method was applied to the determination of trace amounts of cobalt, nickel and copper in steel and simulated radioactive wastes.