Direct-current,normal-pulse and reverse-pulse polarography of some heavy metal—polycarboxylate complexes

Complex formation of Zn(II) and Cd(II) with polymethacrylic acid (PMA) andpolyacrylic acid (PAA) is studied by sampled direct-current, normal-pulse and reverse-pulse polarography. The combined use of these techniques serves a twofold purpose: to cover different time windows and to eliminate interferences from adsorption of the metal ion induced by the ligands. The two Zn(II) systems appear to be labile on the different time scales. The association constants (K) evaluated from potential data and those from current data show good consistency. The dependence of K on the degree of neutralization (α_n) is much stronger for PAA complexes than it is for those of PMA. With the Cd(II)—PMA system complications from induced Cd(II) adsorption are completely removed by using reverse-pulse polarography. The system is not liable and stabilities derived from potential data differ from those obtained from current data. The remaining discrepancy cannot be attributed to simple association and dissociation kinetics.     

Removal of cationic methylene blue and malachite green dyes from aqueous solution by waste materials of Daucus carota

In present study adsorption capacity of waste materials of Daucus carota plant (carrot stem powder: CSP and carrot leaves powder: CLP) was explored for the removal of methylene blue (MB) malachite green (MG) dye from water. The morphology and functional groups present were investigated by scanning electron microscope (SEM) and Fourier transform infrared (FTIR) spectroscopy. The operating variables studied were pH, adsorbent dose, ionic strength, initial dye concentration, contact time and temperature. Equilibrium data were analysed using Langmuir and Freundlich isotherm models and monolayer adsorption capacity of adsorbents were calculated. Kinetic data were studied using pseudo-first and pseudo-second order kinetic models and the mechanism of adsorption was described by intraparticle diffusion model.Various thermodynamic parameters such as enthalpy of adsorption ΔH°, free energy change ΔG° and entropy ΔS° were estimated. Negative value of ΔH° and negative values of ΔG° showed that the adsorption process was exothermic and spontaneous. Negative value of entropy ΔS° showed the decreased randomness at the solid–liquid interface during the adsorption of MB and MG onto CSP and CLP.     

Insight from adsorption properties of Xylidyl Blue embedded hydrogel for effective removal of uranyl: Experimental and theoretical approaches

Applications of a hybrid material consisting of polyacrylamide (PAA) and Xylidyl Blue (XB) for the removal of uranyl ions from aqueous solutions has been investigated with all details. Adsorption experiments were performed at batch mode and constant temperature. Experimental parameters affecting adsorption process such as pH, initial uranyl concentration, time and temperature were studied on the removal of the uranyl ions. The isotherms assays were carried out with synthetic solutions and adsorption data were evaluated by using Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models. Morphological and chemical characterizations of new synthesized material were investigated by UV-VIS-NIR spectroscopy and SEM/EDX techniques and pH_pzc experiments. The results of the kinetic experiments are consistent with pseudo-second-order models and intra-particle diffusion models with a slightly better fit to the latter. Equilibrium was achieved within 3 h. The value of rate constant for adsorption process was calculated as 1.055 mol⁻¹ kg min⁻¹ at 318 K. The calculated thermodynamic parameters (ΔG°, ΔH° and ΔS°) indicated that the adsorption of uranyl ions onto XB@PAA was feasible, spontaneous and endothermic nature under the studied temperature. The developed material has also a potential as a sensor because its color turn from pink to red by adsorption of uranyl ions.     

A study of the factors affecting the adsorption of cobalt ions onto Pakistani coal powder from solutions

Large deposits of coal are abundantly available in Pakistan. An attempt has been made to check its efficacy for the cobalt ions from aqueous solutions in order to exploit the locally available naturally occurring cheaper material for the decontamination/removal of metal ions from nuclear and industrial effluents. The adsorption behavior of cobalt ions on coal powder has been studied as a function of various physicochemical parameters i.e., stirring speed, shaking time, pH, concentration of cobalt ions, temperature, etc. Conditions for the uptake of cobalt ions were established. Adsorption dynamics models such as intra-particle diffusion model, pseudo-first order kinetic model (Lagergren’s equation) and pseudo-second order kinetic model were applied to the adsorption data to elucidate the adsorption process and its mechanism. Results reveal that the adsorption mechanism is predominantly diffusion and both intra-particle and boundary layer diffusion seem significant in the rate controlling step. The adsorption process is best accounted for using pseudo second order kinetic model and the overall rate of adsorption process appears to be controlled by more than one step, namely the external mass transfer and intra-particle diffusion mechanism. The existence of two slopes in the Freundlich plot also confirms the surface diffusion and intra-particle diffusion modes of adsorption. The Langmuir isotherm equation was obeyed well in the whole range of cobalt ions concentration with high value of correlation coefficient (r ²  = 0.999). The adsorption energy (E _a) calculated from D–R isotherm was 6.756 kJ/mol indicating physical nature of adsorption. The adsorption of cobalt ions increased with the increase of temperature and thermodynamic parameters such as ΔH, ΔS and ΔG were calculated. Results suggested that the cobalt ions adsorption on coal powder is endothermic (ΔH 33.90 kJ/mol) and spontaneous (negative ΔG values) process. The adsorption of other metal ions on coal powder was studied at optimized condition for cobalt ions to check its selectivity. Consequently, cobalt ions can be removed from Zr, Ru Eu, Er, Sm, Gd, Dy, Ce, U, and Th ions, where as Cs, Cr and Sr ions reduces the adsorption of cobalt ions by co-adsorption and their reducing affect is in the order of Sr > Cr > Cs.     

Concentration effects associated with the kinetics of ruthenium ions adsorption on activated charcoal

The batch kinetics of ruthenium ions adsorption on activated charcoal has been investigated over a wide range of ruthenium ions concentration (0.05–0.40 g/L) at room temperature of 23 ± 1 °C in 3 M HNO₃ solution. The adsorption process of ruthenium ions proceeds via two stages: the first stage is rather fast, followed by slower one, indicative of boundary layer and intra-particle diffusion effects respectively. The mechanism of the adsorption is predominantly diffusion and the intra-particle diffusion played a significant role in rate determining, but it was not the only main rate determining step throughout the adsorption process. Both intra-particle and boundary layer diffusion seem significant in the rate controlling step. It was also observed that the adsorption of ruthenium ions adsorption process is best accounted for using pseudo second order kinetic model and the overall rate of adsorption process appears to be controlled by more than one step, namely the external mass transfer and intra-particle diffusion mechanism. Moreover, the adsorption of ruthenium ions obeys the Freundlich and the Langmuir isotherms in the concentration range studied.     

Chelating Properties of γ-Aminobutyrohydroxamate Resin toward Lanthanides

γ-Aminobutyrohydroxamate resin that simulate siderophore analogues was prepared. The structure and conversion of functional groups of the resin were confirmed with IR spectra and elemental analysis. The influence of pH on adsorption of metal ions to the resin was examined. Uptake of metal ions increased with pH and was quantitative in the pH range of 4 to 6 for most of the lanthanides. These metal ions showed high exchange rates towards the resin. The complexation behavior of the resin was also investigated by means of IR and potentiometry. The dissociation constant, pK_a of the hydroxamic hydroxyl group is 9.36. Stability constants of the insoluble lanthanide complexes on the resins were measured potentiometrically at 25 ± 0.1 °C and ionic strength of 0.1 M KCl. The results were compared with those of the corresponding soluble lanthanide complexes. It was found that a higher stability of the resin resulted in an increase of the stability constants. The phenomena might be due to the length of the spacer in providing the proper geometry of the resin ligand for intramolecular metal complexation.     

Evaluation of the rate parameters from i-E polarographic characteristics—kinetic study of oxidation of the Mo(V)—EDTA complex by vanadyl chelate

The kinetics of the oxidation of Mo(V)—EDTA by vanadyl chelate has been studied by the catalytic current technique of dc polarography. The reaction order appears to be first order in both chelates and EDTA. The kinetic analysis of the current-potential curves combined with the current ratio technique has been successfully applied to interpretation of the data obtained from polarographic measurements. Agreement between theory and experiment obtained is quite satisfactory as regards the effect of the following catalytic reaction in the polarographic wave. The rate constant for oxidation of the Mo(V) chelate is log k=4.30±0.02 obtained by the catalytic to non-catalytic current ratio method, and log k=4.45±0.07 obtained from the half-wave potential shifts at t^o=25.0±0.1°C. The mechanism of the electrochemical reaction considered is also discussed.     

Differential Pulse Polarographic Study of Ternary Complexes of Copper (Ii) With Pyruvate and Some Amino Acids

Abstract

The ternary complexes of copper (II) with glycine, alanine, aspartate or glutamate as primary ligand and pyruvate as secondary ligand have been investigated using differential pulse polarography. the reversible diffusion controlled reduction of the complexed ion reveals two mixed complexes to be formed with stoichiometries 1:1:1 and 1:2:1. Their overall formation constants in a sodium perchlorate supporting electrolyte have been calculated at μ =0.1 and 25°C.     

The effect of ligand donor atoms on ternary complex stability

Formation constants of mixed ligand complexes of Cu²⁺, Zn²⁺, Ni²⁺, Co²⁺, and Mn²⁺,with cyadine-5′-monophosphoric acid (CMP) and various primary ligands such as 1,10-phenanthroline(phen), glycylglycine(glygly) and salicylic acid (sal) have been determined in aqueous solution at 35°C and 0.1 M (KNO₃) by potentiomeric measurements. The acid dissociation constants of all the above mentioned ligands together with their 1 : 1 binary metal complex formation constants were also measured at 35°C. In general all the 1 : 1 binary complexes follow the Irving-Williams order of stability. Further the binary metal complexes of primary ligands are more stable than their ternary complexes with CMP. For ternary complexes, Δ(log K) values seem to change from positive to highly negative as the coordinating atoms of the primary ligands were varied from N,N to N,O^? to O^?O^?. The higher stability of ternary complexes involving phen is due to its Π-bonding interaction with the above metal ions and the relative decrease in the stability of other ternary systems is due to the coulombic repulsion of donor oxygen atoms of primary and secondary ligands. Thus for ternary complexes the stabilities follow a decreasing order of M-phen-CMP > M-glygly-CMP > M-sal-CMP.     

Complex formation of uranyl ions with polyaminopolycarboxylic acids

The complex formation of uranyl ions with ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and triethylenetetraminehexaacetic acid has been studied by pH titrations, with computer evaluation of the titration data. For each ligand, the formation constants of a series of mono- and di-nuclear complexes were determined in 0.1 M KNO₃ at 25.0°C. The hydrolysis constants for uranyl ions and the dissociation constants of the ligands were also calculated. A novel approach was used to obtain realistic estimates of the uncertainties in the respective constants. Certain likely structures of the complexes are suggested.     

Ternary complexes: Equilibrium study of mixed complexes of uranyl ion with thiodicarboxylic and simple dicarboxylic acids in aqueous medium

The potentiometric studies of the mixed-ligand complexes of uranyl ion with dicarboxylic acids such as thiodiglycolic, thiodipropionic, malonic, succinic, itaconic, glutaric and adipic acids have been made at a temperature of 30±0.1°C and μ =0.1 M (NaClO₄). Uranyl forms 1:1 complexes with all the ligands except malonic and glutaric acids with which it forms both 1:1 and 1:2 chelates.Ternary chelates of uranyl - thiodiglycolic - dicarboxylic and uranyl - thiodipropionic - dicarboxylic acid systems have been studied. The mixed-ligand chelate formation is also discussed on the basis of the calculated concentrations of simple and mixed species in the uranyl - thiodipropionic - malonic acid system. The equilibrium constant K_2YX is dependent on the product of acid dissociation constants of the secondary ligands. The overall stability constant (β_XY) is found to depend on the 1:1 binary stabilities of the metal chelates.     

Complexation Kinetics of N‐Alkyl‐Substituted Diamino Diamides with Nickel (II) in Aqueous Solution

Equilibrium constants are deter mined for the protonation and metal complexation of the nickel(II) complexes with 4‐methyl‐4,7‐diazadecanediamide (4‐Me‐L‐2,2,2), 4,7‐dimethyl‐4,7‐diazadecanediamide (4,7‐N,N′‐Me₂‐L‐2,2,2), 4‐ethyl‐4,7‐diazadecanediamide (4‐Et‐L‐2,2,2), and 4‐methyl‐4,8‐ diazaundecane diamide (4‐Me‐L‐2,3,2), in 0.10 M KCl at 25.0°C. The formation kinetics of these nickel (II) complexes have been studied under the same conditions with use of the stopped‐flow technique. The possible path ways for the complexation reaction of nickel (II) with these ligands are discussed. The first metal‐nitrogen bond formation is proposed as the rate‐determining step for the reactions of nickel (II) with the unprotonated ligands; proton loss is the rate‐limiting step in the reactions of nickel (II) with the monoprotonated ligands. Similarly, in dissociation reactions of these nickel (II) complexes, the rate‐determining step for the water dissociation pathway is the break age of the second nickel‐nitrogen bond; the rate‐determining step for the proton‐assisted path way is the protonation of the released amino group. The important factors determining the reactivity of these complexes are considered. The kinetic results of the formation and dissociation reactions of these complexes are consistent with dissociative mechanism.     

Electrochemical Behaviour Study of Mixed Ligand Complexes of Diaminopropane and Phthalate with Cd(II) Using Differential Pulse Polarography and Cyclic Voltammetry Techniques

Abstract

Differential pulse(d. p.)polarography has been used to study the simple and mixed ligand complexes of 1, 3 diaminopropane (DAMP) and phthalate(PHLT) with Cd(II) at constant ionic strength (u= 1.0 M NaNO₃) at 25°C The overall formation constants of simple and mixed complexes were calculated. The reduction of the simple and mixed species is reversible and diffusion controlled. The postive values of the mixing constants for the mixed-ligand complexes indicate that the mixed-ligand complexes are more stable than simple binary complexes. The equilibria between the various mixed-ligand species in the solution and their equilibrium are given.     

Kinetic of Patent Blue VF Adsorption from Aqueous Solution on Activated Bone Charcoal

The effect of temperature of activation on bone charcoal, used as adsorbent for the removal of Patent Blue VF from water solutions was studied. The adsorbent was characterized by FTIR, XRD, SEM and EDS. The kinetic of adsorption of dye was carried out at 10 °C and 45 °C. Carbonization temperature (600–1000 °C) of the adsorbent has significant effect on the removal of dye from water solutions. The first order kinetic, Elovich, Bangham, parabolic diffusion and power function equations were found to fit the kinetic data. Activation energies of adsorption (Δ≠) have higher values for the charcoal activated at high temperatures and the other thermodynamic parameters like ΔH≠, ΔS≠ and ΔG≠ were also found.     

Electrode reaction of zinc ions at a dropping mercury electrode in ammonium sulphate solutions

The electrode reaction of Zn(II) at a DME in aqueous solutions of (NH₄)₂SO₄ has been studied by d.c. and square-wave polarography at 25.0±0.1°C. The electrochemical kinetic parameters for the reaction are determined. The appearance of the second wave in the square-wave polarogram has been attributed to the low values of the rate parameter and the transfer coefficient.     

Potentiometric characterisation of cyclodextrin inclusion complexes of local anaesthetics

The complexation of several local anaesthetics by β and γ-cyclodextrins was studied by potentiometry with glass electrode. Tetracaine and dibucaine complexation constants were determined at 25°C in the presence of 0.1 M of NaCl. It was found that prilocaine and lidocaine complexes cannot be detected.     

Thermodynamic characteristics of the formation of complexes of nickel(II) with L-homoserine

The formation of complexes of nickel(II) with L-homoserine at 298.15 K and ionic strengths I = 0.5, 1.0, and 1.5 (KNO₃) are investigated by potentiometry and calorimetry. Standard characteristics of studied equilibria (log K°, Δ_rG°, Δ_rH°, and Δ_rS°) are determined.     

Kinetics of zinc and cadmium dissociation of metallothionein in the presence of chelating agents

The dissociation kinetics of metal ions from native metallothionein (Cd₅Zn₂-MT) of rat liver has been studied in the presence of external ligands including amino acids, peptide and polyamino polycarboxylic acids at 25°C. The study shows that the solution pH affects the metal dissociation process. Different ligands present different multiphasic kinetics. The possible mechanism of metal dissociation from metallothionein has been proposed.     

The determination of crown–cation complexation behavior in dioxane/water mixtures by conductometric studies

Using conductance measurements, an attempt has been made to gain detailed information about the specific molecular interactions of crown compounds with metal ions in a 1,4-dioxane/water binary system. Analyses of the transport data of dioxane/water mixtures yielded the mobility of the crown compound action complexes and the ion-pair dissociation constant of the crown compound–electrolyte complex. Binary mixed aqueous solvents are frequently employed in broad areas of chemistry. Their applicability ranges from synthetic and mechanistic studies in organic chemistry to biophysical chemistry, with emphasis on molecular interactions in biologically significant structures. Stability constants of crown compound complexes are determined by various methods, such as potentiometry (with ion selective electrodes), polarography, voltammetry, spectrophotometry, nuclear magnetic resonance, calorimetry and solubility. In this study the conductometry measurements have been carried out with high precision at optimal concentrations in dioxane/water systems. Structures of crown–cation complexes in dioxane/water mixtures are estimated from the conductance parameters (κ, Λ and α) as well as the complex formation constant, K_e = (Λ_MAm − Λ) / (Λ − Λ_MaLbAm) [L]. The conductance behavior of Na⁺, K⁺ chlorides and Na⁺ perchlorates with 18-crown-6, 15-crown-5, and 12-crown-4 have been studied in various dioxane/water systems (50%, 80%, and 85%) at 25°C. The all experimental studies have been made by the ratio 1 : 1 of the metal-ion and the crown ether, K_e. For the calculations, Excel. 5.0 was used as an application program. Copyright © 1998 John Wiley & Sons, Ltd.     

Competitive Adsorption of Methylene Blue and Rhodamine B on Natural Zeolite: Thermodynamic and Kinetic Studies

A batch system was applied to study the adsorption behavior of methylene blue (MB) and rhodamine B (RB) in single and binary component systems on natural zeolite. In the single component systems, the zeolite presents higher adsorption capacity for MB than RB with the maximal adsorption capacity of 7.95×10^?5 and 1.26×10^?5 mol/g at 55°C for MB and RB, respectively. Kinetic studies indicated that the adsorption followed pseudo‐second‐ order kinetics and could be described by a two‐step diffusion process. For the single component systems, the adsorption isotherm could be fitted by the Langmuir model. In the binary component system, MB and RB exhibit competitive adsorption on the zeolite. The adsorption is approximately reduced to 50% and 60% of single component adsorption systems of MB and RB, respectively at an initial concentration of 6×10^?6 mol·L^?1 at 25°C. In the binary component system, kinetic and adsorption isotherm studies demonstrate that the experimental data are following pseudo‐second‐order kinetics and Langmuir isotherm and kinetic data are fairly described by a two‐step diffusion model. Effect of solution pH on adsorption of MB and RB in both single and binary component systems was studied and the results were described by electrostatic interactions.