Equilibrium and kinetics studies of Cu(II) ions adsorption on polyamidoamine dendrimer starch

A polyamidoamine dendrimer starch (PSt) was prepared with epichlorohydrin as cross-linking agent and characterized by FTIR and scanning electron microscopy. The adsorption behavior of PSt for Cu(II) ions was then studied. Effects of adsorption time, initial concentration of Cu(II) ions, and temperature on the adsorption of Cu(II) ions by PSt were researched, and the equilibrium, kinetics and thermodynamics of the adsorption process were further investigated. The results showed that PSt can effectively adsorb Cu(II) ions from the solution. The adsorption process can be well described by Langmuir isotherm and Freundlich isotherm, and the maximum adsorption capacities of G1PSt, G2PSt, and G4PSt were 3.0571, 3.4228, and 3.9527 mmol/g, respectively. The adsorption of Cu(II) ions on PSt was endothermic in nature. In addition, the pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The pseudo-second-order kinetic model provided a better correlation of the experimental data in comparison with the pseudo-first-order model.     

Adsorption dynamics and equilibrium studies of Zn (II) onto chitosan

Batch equilibration studies are conducted to determine the nature of adsorption of zinc (II) over chitosan. The factors affecting the adsorption process like particle size, contact time, dosage, pH, effects of chloride and nitrate are identified. The influence of temperature and co-ions on the adsorption process is verified. The fraction of adsorption,Y _t and the intraparticle diffusion rate constant,k _p are calculated at different environments and the results are discussed. The nature of adsorption of the zinc (II)-chitosan system is explained using Freundlich, Langmuir isotherms and thermodynamic parameters     

Kinetics and Equilibrium Models for Sorption of Cu(II) onto a Novel Manganese Nano-adsorbent

The studies of kinetics and equilibrium sorption of Cu(II) were undertaken using nanoscale zerovalent manganese (nZVMn) synthesized by chemical reduction in a single pot system. nZVMn was characterized using scanning electron microscopy, energy dispersive x-ray, and surface area determined by Brunauer–Emmett–Teller. The effect of pH, contact time, adsorbent dose, agitation speed, initial Cu(II) concentrations, temperature, and ionic strength on the sorption of Cu(II) onto nZVMn were investigated in a batch system. The kinetic data followed pseudo-second-order. The mechanism was governed by pore diffusion. The equilibrium sorption data were tested by Freundlich, Langmuir, Temkin, Dubinin–Kaganer–Raduskevich, and Halsey isotherm models. The Langmuir monolayer adsorption capacity (Q_max = 181.818 mg/g) is much greater compared to other nano-adsorbents used in sorption of Cu(II). The thermodynamic parameters (ΔH⁰, ΔS⁰, ΔG⁰) revealed a feasible, spontaneous, and endothermic adsorption process. nZVMn has a great potential for effective removal of copper (II) in aqueous solution.     

Removal of Cu(II), Zn(II) and Co(II) ions from aqueous solutions by adsorption onto natural bentonite

In this study, the removal of Cu(II), Zn(II) and Co(II) ions from aqueous solutions using the adsorption process onto natural bentonite has been investigated as a function of initial metal concentration, pH and temperature. In order to find out the effect of temperature on adsorption, the experiments were conducted at 20, 50, 75 and 90 °C. For all the metal cations studied, the maximum adsorption was observed at 20 °C. The batch method has been employed using initial metal concentrations in solution ranging from 15 to 70 mg L⁻¹ at pH 3.0, 5.0, 7.0 and 9.0. A flame atomic absorption spectrometer was used for measuring the heavy metal concentrations before and after adsorption. The percentage adsorption and distribution coefficients (K _d) were determined for the adsorption system as a function of adsorbate concentration. In the ion exchange evaluation part of the study, it is determined that in every concentration range, adsorption ratios of bentonitic clay-heavy metal cations match to Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich (DKR) adsorption isotherm data, adding to that every cation exchange capacity of metals has been calculated. It is shown that the bentonite is sensitive to pH changes, so that the amounts of heavy metal cations adsorbed increase as pH increase in adsorbent-adsorbate system. It is evident that the adsorption phenomena depend on the surface charge density of adsorbent and hydrated ion diameter depending upon the solution pH. According to the adsorption equilibrium studies, the selectivity order can be given as Zn²⁺>Cu²⁺>Co²⁺. These results show that bentonitic clay hold great potential to remove the relevant heavy metal cations from industrial wastewater. Also, from the results of the thermodynamic analysis, standard free energy ΔG ⁰, standard enthalpy ΔH ⁰ and standard entropy ΔS ⁰ of the adsorption process were calculated.     

The efficacy of nitrosonaphthol functionalized XAD-16 resin for the preconcentration/sorption of Ni(II) and Cu(II) ions

Amberlite XAD-16 resin has been functionalized using nitrosonaphthol as a ligand and characterized employing elemental, thermogravimetric analysis and FT-IR spectroscopy. The sorption of Ni(II) and Cu(II) ions onto this functionalized resin is investigated and optimized with respect to the sorptive medium (pH), shaking speed and equilibration time between liquid and solid phases. The monitoring of the influence of diverse ions on the sorption of metal ions has revealed that phosphate, bicarbonate and citrate reduce the sorption up to 10–14%. The sorption data followed Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) isotherms. The Freundlich parameters computed are 1/n = 0.56 ± 0.03 and 0.49 ± 0.05, A = 9.54 ± 1.5 and 6.0 ± 0.5 mmol g⁻¹ for Ni(II) and Cu(II) ions, respectively. D–R isotherm yields the values of X_m = 0.87 ± 0.07 and 0.35 ± 0.05 mmol g⁻¹ and of E = 9.5 ± 0.23 and 12.3 ± 0.6 kJ mol⁻¹ for Ni(II) and Cu(II) ions, respectively. Langmuir characteristic constants estimated are Q = 0.082 ± 0.005 and 0.063 ± 0.003 mmol g⁻¹, b = (4.7 ± 0.2) × 10⁴ and (7.31 ± 0.11) × 10⁴ l mol⁻¹ for Ni(II) and Cu(II) ions, respectively. The variation of sorption with temperature gives thermodynamic quantities of ΔH = −58.9 ± 0.12 and −40.38 ± 0.11 kJ mol⁻¹, ΔS = −183 ± 10 and −130 ± 8 J mol⁻¹ K⁻¹ and ΔG = −4.4 ± 0.09 and −2.06 ± 0.08 kJ mol⁻¹ at 298 K for Ni(II) and Cu(II) ions, respectively. Using kinetic equations, values of intraparticle transport and of first order rate constant have been computed for both the metal ions. The sorption procedure is utilized to preconcentrate these ions prior to their determination in tea, vegetable oil, hydrogenated oil (ghee) and palm oil by atomic absorption spectrometry using direct and standard addition methods.     

Equilibrium and kinetics studies on adsorption of Cu(II) from aqueous solutions onto a graft copolymer of cross-linked starch/acrylonitrile (CLSAGCP)

A synthetic graft copolymer of cross-linked starch/acrylonitrile was used as an adsorbent for the removal of Cu(II) ions from an aqueous solution of copper nitrate hexahydrate Cu(NO₃)₂ · 6H₂O at different temperatures and fixed pH. The amount adsorbed increased with increasing concentration of Cu(II) ions and decreasing temperature. The length of time taken to reach equilibrium of the adsorption of Cu(II) ions was the same at all temperatures tested. Kinetics studies showed that the adsorption process obeyed first-order reversible kinetics and the adsorption isotherms followed the Freundlich model. Furthermore, the thermodynamic parameters, i.e. standard free energy (ΔG^∘), standard enthalpy (ΔH^∘), and standard entropy (ΔS^∘), of the adsorption process were calculated and the results are discussed in detail.     

Adsorption of Cu(II) and Zn(II) ions from aqueous solutions onto fine powder of Typha latifolia L. root: kinetics and isotherm studies

Fine powder of Typha latifolia L. root was used for adsorption of copper and zinc ions from buffered and nonbuffered aqueous solutions. The adsorption reached equilibrium in 60 min. During this time, more than 90 % of the adsorption process was completed. The effect of initial pH, initial concentration of metal ion, and contact time was investigated in a batch system at room temperature. The optimum adsorption performance was observed at pH 5.00 and 4.25 for nonbuffered solutions of Cu(II) and Zn(II), respectively, while for buffered solutions it occurred at pH 6.00. The total metal uptake decreased on application of ammonium acetate buffer, from 37.35 to 17.00 mg g^?1 and 28.80 to 9.90 mg g^?1 for Cu(II) and Zn(II) solutions, respectively, with 100 mg L^?1 initial concentration. The pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models were used to describe the adsorption kinetics. The experimental data followed the pseudo-second-order kinetic model. The biosorption equilibrium was well described by Langmuir and Freundlich isotherm models.     

Biosorption kinetics, thermodynamics and isosteric heat of sorption of Cu(II) onto Tamarindus indica seed powder

Biosorption of Cu(II) by Tamarindus indica seed powder (TSP) was investigated as a function of temperature in a batch system. The Cu(II) biosorption potential of TSP increased with increasing temperature. The rate of the biosorption process followed pseudo second-order kinetics while the sorption equilibrium data well fitted to the Langmuir and Freundlich isotherm models. The maximum monolayer Cu(II) biosorption capacity increased from 82.97 mg g(-1) at 303 K to 133.24 mg g(-1) at 333 K. Thermodynamic study showed spontaneous and endothermic nature of the sorption process. Isosteric heat of sorption, determined using the Clausius-Clapeyron equation increased with increase in surface loading showing its strong dependence on surface coverage. The biosorbent was characterized by scanning electron microscopy (SEM), surface area and porosity analyzer, X-ray diffraction (XRD) spectrum and Fourier transform infrared (FTIR) spectroscopy. The results of FTIR analysis of unloaded and Cu(II)-loaded TSP revealed that -NH(2), -OH, -C=O and C-O functional groups on the biosorbent surface were involved in the biosorption process. The present study suggests that TSP can be used as a potential, alternative, low-cost biosorbent for removal of Cu(II) ions from aqueous media.     

Theoretical studies on magnetic interactions between Cu(II) ions in hydroxypyridone nucleobases

The origin of a ferromagnetic interaction between Cu²⁺ ions in the Cu²⁺–DNA system which reported by Tanaka et al. is examined by using DFT calculations. In order to consider effects of an entanglement and a dis-entanglement of the double helix chain, three types of structural disorders i.e. distance, rotation angle and discrepancy in XY-plane, are considered in the model dimer structure. All calculated results show that J_ab values are weak anti-ferromagnetic couplings. Boltzmann distribution simulation indicates that the high spin (HS) species exist 21% at 1.5 K by thermal excitation within the model structure.     

Theoretical studies on magnetic interactions between Cu(II) ions in salen nucleobases

The magnetic and other physical properties between Cu²⁺ ions coordinated by salen–base pairs (Cu²⁺–DNA) are examined by using DFT calculations. In order to consider effects of entanglement and dis-entanglement of the double helix chain, three types of structural disorders i.e. distance, rotation angle and discrepancy in XY-plane, are changed in the model dimer structure. All calculated results show that J_ab values are weak anti-ferromagnetic couplings. It is also found that the J_ab values strongly depend on the salen structure.     

Dynamic and Equilibrium Studies on Adsorption of Cu(II) Ions onto Biopolymeric Cross-Linked Pectin and Alginate Beads

Binary biopolymeric beads of alginate and pectin were prepared and characterized by FTIR spectra. On to the surfaces of the prepared beads were performed static and dynamic adsorption studies of Cu(II) ions at fixed pH and ionic strength of the aqueous metal ion solutions. The adsorption data were applied to Langmuir and Freundlich isotherm equations and various adsorption parameters were calculated. The influence of various experimental parameters such as effect of time, pH, temperature, solid to liquid ratio, and the presence of salts were investigated on the adsorption of copper ions.     

Utilization of olive pomace in nano MgO modification for sorption of Ni(II) and Cu(II) metal ions from aqueous solutions

Magnesium oxide nanoparticles were synthesized and modified by olive pomace (NMOOP700) as a novel sorbent and characterized using Fourier Transform Infrared Spectra, Scanning Electron Microscope, Transmission Electron Microscope, X-ray Diffraction, Differential Thermal Analysis and Thermal Gravimetric Analysis. Sorption of Cu (II) or Ni (II) ions were achieved taking into account important parameters including initial pH of the medium, contact time, initial metal ion concentration and temperature. A comparative study between Magnesium oxide nanoparticles and NMOOP700 material for the sorption of Cu (II) or Ni (II) ions was implemented. The obtained data revealed that the sorption process is significantly improved using NMOOP700. The monolayer capacity of Ni (II) and Cu (II) metal ions on NMOOP700 at pH 5 were found to be 149.93 ± 4.4 and 186.219 ± 6.3 mg/g, respectively. Findings of the present work highlight the potential use of NMOOP700 as a novel and effective sorbent material for the removal of Cu (II) or Ni (II) ions from the liquid phase.     

Impact of environmental conditions on the sorption behavior of Pb(II) onto attapulgite

This paper examined the application of attapulgite as an adsorbent for the removal of Pb(II) from heavy metal-contaminated water under various conditions. The sorption results indicated that the sorption of Pb(II) on attapulgite was strongly dependent on ionic strength at pH < 7.0. Outer-sphere surface complexation or ion exchange may be the main sorption mechanism of Pb(II) on attapulgite at low pH values. No drastic difference of Pb(II) sorption was observed at pH 7.0–10.0, and the sorption at pH > 10.0 was mainly dominated by inner-sphere surface complexation. The sorption of Pb(II) on attapulgite was affected by foreign ions in solution at pH < 7.0, and was not affected by foreign ions at pH > 7.0. The thermodynamic parameters (ΔH°, ΔS° and ΔG°) were evaluated from the temperature-dependent sorption isotherms, and the results indicated that the sorption process of Pb(II) on attapulgite was spontaneous and endothermic in nature.     

Adsorption/desorption of Cd(II), Cu(II) and Pb(II) using chemically modified orange peel: Equilibrium and kinetic studies

Waste materials from industries such as food processing may act as cost effective and efficient biosorbents to remove toxic contaminants from wastewater. This study aimed to establish an optimized condition and closed loop application of processed orange peel for metals removal. A comparative study of the adsorption capacity of the chemically modified orange peel was performed against environmentally problematic metal ions, namely, Cd²⁺, Cu²⁺ and Pb²⁺, from aqueous solutions. Chemically modified orange peel (MOP) showed a significantly higher metal uptake capacity compared to original orange peel (OP). Fourier Transform Infrared (FTIR) Spectra of peel showed that the carboxylic group peak shifted from 1637 to 1644 cm⁻¹ after Pb (II) ions binding, indicated the involvement of carboxyl groups in Pb(II) ions binding. The metals uptake by MOP was rapid and the equilibrium time was 30 min at constant temperature and pH. Sorption kinetics followed a second-order model. The mechanism of metal sorption by MOP gave good fits for Freundlich and Langmuir models. Desorption of metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after four cycles of adsorption-elution, the adsorption capacity was regained completely and adsorption efficiency of metal was maintained at around 90%.     

Thermodynamics of the Cu(II) adsorption on thin vanillin-modified chitosan membranes

In this work, low-density vanillin-modified thin chitosan membranes were synthesized and characterized. The membranes were utilized as adsorbent for the removal of Cu(II) from aqueous solutions. The experimental data obtained in batch experiments at different temperatures were fitted to the Langmuir and Freundlich isotherms to obtain the characteristic parameters of each model. The adsorption equilibrium data fitted well with the Langmuir model (average R² > 0.99). Interactions thermodynamic parameters (Δ_intH, Δ_intG, and Δ_intS), as well as the interaction thermal effects (Q_int) were determined from T = (298 to 333) K. The thermodynamic parameters, the Dubinin–Radushkevick equation and the comparative values of Δ_intH for some Cu(II)–adsorbent interactions suggested that the adsorption of Cu(II) ions to vanillin-chitosan membranes show average results for both the diffusional (endothermic) and chemical bonding (exothermic) processes in relation to the temperature range studied.     

Equilibrium studies of mercury(II) complexes with penicillamine

A solid-phase microextraction method coupled with a flame photometric detector was developed for the analysis of organophosphorus pesticides in water. Two kinds of fiber (100 mum polydimethyl siloxane (PDMS) and 85 mum polyacrylate (PA) fibers) were used and compared. Parameters that may affect the extraction, such as the duration of absorption and desorption, temperature of absorption, ionic strength, elutropic strength, and concentration of humic acid were investigated. Higher sensitivity and lower detection limits were achieved using a PA fiber than using a PDMS fiber. The detection limit is less than 0.3 mug l(-1) for most of the analytes, except for mevinphos (420 mug l(-1)). The precision is better than 9%.     

EDTA effect on the removal of Cu(II) onto TiO2

The adsorption of Cu(II) and Cu(II)-EDTA onto TiO2 with variations in the pH, concentration, and molar ratio of Cu(II) to EDTA has been studied. The adsorption of Cu(II) and Cu(II)-EDTA onto TiO2 showed typical cationic- and anionic-type behavior, respectively. The removal of Cu(II) in an EDTA-excess system was less than that in an equimolar Cu(II)/EDTA system due to the competitive adsorption of EDTA and Cu(II)-EDTA onto the TiO2. The removal of Cu(II) was favorable at low pH for both the equimolar and EDTA-excess systems, while significant Cu(II) removal was observed over the entire pH range in a copper-excess system. For model predictions, the MINTEQA2 program employing an inner-sphere complexation and a diffuse layer model was used; the surface complexes used included Ti(OH2)OCu+, Ti(OH)EDTAH2-(2), and Ti(OH)EDTACu2-.     

Magnetic,epr and SOD studies of some Cu(II)-Cu(II), Cu(II)-Ni(II) and Cu(II)-Zn(II) imidazolate bridged complexes

Magnetic, spectroscopic and superoxide dismutase activity of imidazolate bridged [(Salala)Cu-Im-Cu(Salala)]Na, [(Salala)Cu-Im-Zn(Salala)]Na and [(Salala)Cu-Im-Ni(Salala)]Na (Salala=Salicyledenealiniate, Im=Imdiazolate) are described. The epr and electronic spectra of related mononuclear complexes, viz., [(Salala)Cu-OH(2)] and [(Salala)Cu-ImH] also described. Appearance of a half-field signal in polycrystalline and decrease in mu(eff) per copper(II) ion indicate super exchange coupling between copper(II) ion in [(Salala)Cu-Im-Cu(Salala)]Na binuclear complex. A pH-dependent epr and UV-vis study of 50% aqueous DMSO solution of binuclear complexes suggest that the complexes are stable in narrow pH range.     

Influence of sorption on the catalytic activity of iron(III) and copper(II) ions

An analysis is made of earlier work by the authors in investigating the catalytic activity of Fe(III) and Cu(II) ions in solution and on different surfaces in certain redox reactions: the decomposition of H₂O₂, oxidation of ascorbic acid, etc. General principles have been established which provide a means of predicting one or another action of sorption on the catalytic activity: if the reaction proceeds within the ion exchanger phase as in a homogeneous (concentrated) solution, it is most probable to have a decrease (or cessation) of the catalytic activities of the ions. If the ion catalysts are included in a surface complex in whose coordination sphere there are places which the substrate may occupy the reaction is facilitated. The analysis carried out of the influence of sorption on the catalytic activity of the iron and copper ions shows a favorable change in the catalytic activity for these ions during their sorption on different types of surfaces.Translated from Teoreticheskie i Éksperimental'naya Khimiya, Vol. 22, No. 6, pp. 706–711, November–December, 1986.