Equilibrium,thermodynamics and kinetics study on Au(III) extraction by gemini surfactant with different spacer length

The effect of spacer lengths of imidazolium gemini surfactant [C₁₄-n-C₁₄im]Br₂ (n = 2, 4, 6) on the equilibrium, thermodynamics and kinetics of Au(III) extraction from hydrochloric acid medium were investigated in this article. The thermodynamic parameters, including the changes in enthalpy (ΔH*), entropy (ΔS*) and Gibbs free energy (ΔG*) were determined. The values of ΔH* demonstrated that the extraction of Au(III) by [C₁₄-n-C₁₄im]Br₂ was endothermic at first and exothermic at last. The kinetics study found that extraction rate became faster when the spacer lengths were increased. Moreover, kinetics results demonstrated that the diffusion is the controlling step, and the mass transfer coefficients of Au(III) in the investigated systems indicated that the resistance of mass transfer was smaller when the spacer lengths was longer. The studies of interfacial tension further confirmed the better extractability of [C₁₄-n-C₁₄im]Br₂ with longer spacer lengths. Our results reveal efficient and sustainable gold separation.     

A Comparative Study of the Biosorption of Iron(III)—Cyanide Complex Anions to Rhizopus arrhizus and Chlorella vulgaris

ABSTRACT

In this study a comparative biosorption of iron(III)—cyanide complex anions from aqueous solutions to Rhizopus arrhizus and Chlorella vulgaris was investigated. The iron(III)—cyanide complex ion-binding capacities of the biosorbents were shown as a function of initial pH, initial iron(III)—cyanide complex ion, and biosorbent concentrations. The results indicated that a significant reduction of iron(III)—cyanide complex ions was achieved at pH 13, a highly alkaline condition for both the biosorbents. The maximum loading capacities of the biosorbents were found to be 612.2 mg/g for R. arrhizus at 1996.2 mg/L initial iron(III)—cyanide complex ion concentration and 387.0 mg/g for C. vulgaris at 845.4 mg/L initial iron(III)—cyanide complex ion concentration at this pH. The Freundlich, Langmuir, and Redlich-Peterson adsorption models were fitted to the equilibrium data at pH 3, 7, and 13. The equilibrium data of the biosorbents could be best fitted by all the adsorption models over the entire concentration range at pH 13.     

Kinetics of Eu(III) extraction in macroporous bifunctional phosphinic acid resin

The rate of ion exchange of Eu(III) from semi-infinite bath containing dilute nitric acid solution was studied on a macroporous bifunctional phosphinic acid resin. The influence of particle size, concentration of nitric acid and temperature on the uptake of Eu(III) was examined. The kinetic data were fitted into the Reichenberg approximate solution, based on the Nernst–Planck resin diffusion model, that relates the fractional attainment of equilibrium (U_t) and internal diffusion coefficient (D_A). The measured D_A was of the order of 10^?13 m²/s, and it was found to increase with the increase of temperature, and decrease with the increase of particle size of the resin and concentration of nitric acid.     

Grafting of vinyl monomers onto silk fibers: Trivalent-manganese-initiated graft copolymerization of acrylamide onto silk fibers

Graft copolymerization of acrylamide (AM) onto silk fibers, using Mn(III)–sulphate as initiator, has been investigated, in aqueous sulphuric acid in the temperature range of 30–55°C. Grafting reaction has been studied by varying the concentration of monomer, Mn(III), sulphuric acid, temperature, and also with the modified silk. The graft yield increases significantly with increase of monomer concentrations to the extent of 0.85M, after which the rate falls. With increase in Mn(III) concentration and H⁺ ion concentration the graft yield increases, but after an optimum concentration a depression in the graft yield is noticed. The rate of the reaction is temperature-dependent; with increase of temperature the graft-on increases. Among the solvent composition studied a solvent/water mixture containing 10% of the solvent seems to constitute the most favorable medium for grafting, and a further increase of solvent composition decreases the graft yield. The effect of various additives such as transition metal salts, aromatic and heterocyclic amines on grafting reaction has been studied. A suitable mechanism for grafting has been proposed. Finally physical characterization such as thermal analysis (TGA) of the grafted samples has been carried out in order to ensure grafting and to study the change in the properties of the fibers.     

Biosorption Characteristics of Indigenous Plant Material for Trivalent Arsenic Removal from Groundwater: Equilibrium and Kinetic Studies

A biomass derived from plant A. nilotica (leave) has been used for efficient removal of trivalent arsenic (As(III)) from aqueous media. The experiments were carried out to study the effects of different parameters i.e., biomass dosage, As(III) concentration, pH, temperature, and contact time. The equilibrium biosorption data were analyzed by the Langmuir and Freundlich isotherm models and satisfactorily both isotherm models could be fitted well. The biosorption mean free energy based on the D-R isotherm model was calculated in the range of 7.50–8.21 kJ mol^?1. The data of thermodynamic parameters [enthalpy (ΔH°), Gibbs free energy (ΔG°), and entropy (ΔS°)] were identified that biosorption of As(III) onto studied biomass was spontaneous, feasible, and exothermic under the optimum experimental conditions. Kinetic estimations based on the experimental data demonstrated that the biosorption of As(III) followed the pseudo-second-order kinetics. The studied biomass was successfully applied for the removal of As(III) from contaminated groundwater samples of Jamshoro district.     

Adsorption of Cu(II) and Cr(VI) onto Treated Shorea dasyphylla Bark: Isotherm,Kinetics, and Thermodynamic Studies

The efficacy of treated Shorea dasyphylla bark for Cu(II) and Cr(VI) adsorption was assessed in a batch adsorption system as a function of pH, agitation period, and initial metal concentration. The equilibrium nature of Cu(II) and Cr(VI) adsorption was described by the Freundlich, Langmuir, and Dubinin-Radushkevich isotherms. The maximum monolayer capacities of treated Shorea dasyphylla bark, estimated from the Langmuir equation were 184.66 and 42.72 mg/g for Cu(II) and Cr(VI), respectively. The experimental results were fitted using pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models; the pseudo-second order showed the best conformity to the kinetic data. Thermodynamic parameters such as enthalpy change (ΔH°), free energy change (ΔG°) and entropy change (ΔS°) were determined by applying the Van't Hoff equation. The adsorption of Cu(II) and Cr(VI) onto treated Shorea dasyphylla bark was found to be spontaneous and exothermic. The adsorption mechanism was confirmed by means of Fourier transform infrared (FTIR) and Energy dispersive X-ray (EDX) spectroscopy. The dimensionless constant separation factor (R _L), indicated that treated Shorea dasyphylla bark was favorable for Cu(II) and Cr(VI) adsorption.     

Adsorption of Furfural from Aqueous Solution onto Activated Carbon: Kinetic,Equilibrium and Thermodynamic Study

Abstract

The present study aims to evaluate the influence of various experimental parameters viz. initial pH (pH ₀), adsorbent dose, contact time, initial concentration and temperature on the adsorptive removal of furfural from aqueous solution by commercial grade activated carbon (ACC). Optimum conditions for furfural removal were found to be pH ₀ ≈ 5.9, adsorbent dose ≈ 10 g/l of solution and equilibrium time ≈ 6.0 h. The adsorption followed pseudo‐second‐order kinetics. The effective diffusion coefficient of furfural was of the order of 10^?13 m²/s. Furfural adsorption onto ACC was found to be best represented by the Redlich‐Peterson isotherm. A decrease in the temperature of the operation favorably influenced the adsorption of furfural onto ACC. The positive values of the change in entropy (ΔS ⁰); and the negatived value of heat of adsorption (ΔH ⁰) and change in Gibbs free energy (ΔG ⁰) indicated feasible, exothermic, and spontaneous nature of furfural adsorption onto ACC.     

Preparation and characterization of selective phenyl thiosemicarbazide modified Au(III) ion‐imprinted cellulosic cotton fibers

In this study, a novel selective Au(III) chelating surface ion imprinted fibers based on phenyl thiosemicarbazide modified natural cotton (Au‐C‐PTS) has been synthesized, and applied for selective removal of Au(III) from aqueous solutions. Batch adsorption experiments were performed with various parameters, such as contact time, pH, initial Au(III) concentration, and temperature. The kinetic studies revealed that the adsorption process could be described by pseudo‐second‐order kinetic model, while the adsorption data correlated well with the Langmuir and Freundlich models. The maximum adsorption capacities calculated from the Langmuir equation are 140 ± 1 mg g^?1 and 72 ± 1 mg g^?1 at pH 5 for both Au‐C‐PTS and NI‐C‐PTS, respectively. The estimated thermodynamic parameters (Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy change (ΔS°)) indicated the spontaneity and exothermic nature of the adsorption process. Furthermore, the selectivity study revealed that the ion imprinted fibers was highly selective to Au(III) compared with Cu(II), Cd(II), Hg(II), and Fe(III). The adsorbent was successfully regenerated with a 0.1M HNO₃ solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40769.     

Removal of Basic Blue 3 by sorption onto a weak acid acrylic resin

A weak acid acrylic resin was used as an adsorbent for the investigation of Basic Blue 3 (BB3) adsorption kinetics, isotherms, and thermodynamic parameters. Batch adsorption studies were carried out to evaluate the effect of pH, contact time, initial concentration (28–100 mg/g), adsorbent dose (0.05–0.3 g), and temperature (290–323 K) on the removal of BB3. The adsorption equilibrium data were analyzed by the Langmuir, Temkin, and Freundlich isotherm models, with the best fitting being the first one. The adsorption capacity (Q_o) increased with increasing initial dye concentration, adsorbent dose, and temperature; the highest maximum Q_o (59.53 mg/g) was obtained at 323 K. Pseudo‐first‐order and pseudo‐second‐order kinetic models and intraparticle diffusion models were used to analyze the kinetic data; good agreement between the experimental and calculated amounts of dye adsorbed at equilibrium were obtained for the pseudo‐second‐order kinetic models for the entire investigated concentrations domain. Various thermodynamic parameters, such as standard enthalpy of adsorption (ΔH^o = 88.817 kJ/mol), standard entropy of adsorption (ΔS^o = 0.307 kJ mol^?1 K^?1), and Gibbs free energy (ΔG^o < 0, for all temperatures investigated), were evaluated and revealed that the adsorption process was endothermic and favorable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Removal of Cr (VI) from aqueous solution by newspapers

The potential to remove Cr (VI) ions from aqueous solution using newspapers was investigated in the present study. The effects of relevant parameters such as solution pH, adsorbent concentration, and reaction temperature on Cr (VI) adsorption were examined. The adsorption of Cr (VI) ions onto newspapers was found to be highly pH-dependent and the highest uptake occurred at pH 1.0. The sorption equilibrium data were correlated to the Langmuir, Freundlich, Redlich-Peterson and Dubinin-Radushkevich equations. Five different non-linear error functions were examined and the result indicated that the Freundlich and Redlich-Peterson equations better fitted the equilibrium data than Langmuir isotherm. The maximum sorption capacity was found to be 55.06 mg/g at pH 1.0, adsorbent concentration 4 g/L and reaction temperature of 30 °C. Different thermodynamic parameters viz., changes in standard free energy (ΔG⁰), enthalpy (ΔH⁰) and entropy (ΔS⁰) were also evaluated and the results show that the sorption process was spontaneous and endothermic in nature. The kinetic experimental data were well fitted by the pseudo-second order, external film diffusion and diffusion models allowing the corresponding parameters to be evaluated. The sorption capacity increased with the decrease of adsorbent concentration.     

Polymerization of acrylamide and methacrylamide initiated by a potassium peroxydiphosphate/Mn(II) system

The kinetics of aqueous polymerization of acrylamide (AM) and methacrylamide (MAM) have been studied using a potassium peroxydiphosphate (PDP/Mn(II) system in an inert atmosphere at 40°C and at constant pH (1·30). The polymerization rate R_p has been found to be proportional to the half power of PDP and Mn(II) concentrations. The overall energy of activation (ΔE) was found to be 40·2±0·1kJmol^-1 and 45·0±0.1kJmol^-1 for AM and MAM, respectively. Intrinsic viscosity [η], viscometric average molecular weight (M_v) and number average degree of polymerization (P_n) at different concentrations of PDP, Mn(II) and monomer are reported. © 1998 SCI.     

Studies on the reduction of birnessite thin layers: Influence of medium

This paper describes studies on the reduction of birnessite thin layers electrodeposited onto a cheap transparent semiconductor substrate, tin dioxide (SnO₂), in neutral sulphate solutions. A coupled approach based on electrochemical measurements (cyclic voltammetry and chronoamperometry) and X-ray diffraction (XRD) characterisation allowed us to give information about reduction mechanism of birnessite in presence or absence of Mn(II) in solution. In absence of Mn(II), birnessite is reduced only at low potential (E = −0.6 V) into β-MnOOH (feitkneichtite), if Q_reduction is lower than Q_synthesis, and in amorphous Mn(II) compound, if Q_reduction is equal to Q_synthesis. In presence of Mn(II) in solution, hausmannite (Mn₃O₄) was detected, and even at high potentials (E = 0.15 V). These results signify that a complex between Mn(III), coming from the reduction of Mn(IV) species, and Mn(II) present in solution, can be formed near the surface and leads to the formation of Mn₃O₄, a very resistive compound. These results are important for studies devoted to environmental applications, chemical sensors and also for energy storage.     

Electrochemical removal of boron from water: Adsorption and thermodynamic studies

The present work provides an electrochemical removal of boron from water and its kinetics, thermodynamics, isotherm using mild steel and stainless steel as anode and cathode respectively. The various operating parameters on the removal efficiency of boron were investigated, such as initial boron ion concentration, initial pH, current density and temperature. The results showed that the optimum removal efficiency of 93.2% was achieved at a current density of 0.2 A dm^?2 at pH of 7.0. First‐, second‐order rate equations, Elovich and Intraparticle models were applied to study adsorption kinetics. Adsorption isotherms of boron on Fe(OH)₃ were determined and correlated with isotherm equations such as Langmuir, Freundlich and D‐R models. Thermodynamic parameters, such as standard Gibb's free energy (ΔG°), standard enthalpy (ΔH°) and standard entropy (ΔS°), were also evaluated by Van't Hoff equation. The adsorption process follows second‐order kinetics. The adsorption of boron preferably fits with Langmuir adsorption isotherm suggesting monolayer coverage of adsorbed molecules. The adsorption of boron onto Fe(OH)₃ was found to be spontaneous and endothermic. © 2011 Canadian Society for Chemical Engineering     

Adsorption of Cu(II) ions from aqueous solutions on modified chrysotile: Thermodynamic and kinetic studies

The adsorption of Cu(II) ions by modified chrysotile from aqueous solution was investigated under different experimental conditions. The Langmuir and Freundlich equations were introduced to describe the linear forms about the adsorption of Cu(II) ions on the surface of modified chrysotile, and it was found that the adsorption equilibrium process was well described by the Langmuir isotherm model with the maximum adsorption capacity of 1.574 mmol/g at 333 K. The thermodynamic parameters (ΔG⁰, ΔH⁰ and ΔS⁰) for adsorption on modified chrysotile were also determined from the temperature dependence. The influences of specific parameters such as temperature, pH value and initial concentration for the kinetic studies were also examined. The adsorption follows a pseudo-second order rate law.     

Mechanism of potentiostatic deposition of MnO2 and electrochemical characteristics of the deposit in relation to carbohydrate oxidation

Cyclic voltammetric (CV) and chronoamperometric (CA) studies on potentiostatic deposition of MnO₂ on Pt from Mn(II) solution in very weakly alkaline media show the process to be controlled by a one-electron transfer step, which means that the deposition proceeds through the generation of Mn(III). The electrocatalytic activity of the deposited electrode towards carbohydrate oxidation is found to be maximum at an optimum amount of deposition. Chronopotentiometric (CP) and CV measurements show that the oxidation of carbohydrates on the deposited electrodes follows a catalytic EC (electrochemical-chemical) mechanism via electrolytic formation of Mn(V) and its subsequent consumption either by disproportionation or by chemical reaction in the presence of carbohydrates. The rate constants of the reaction of Mn(V) with dextrose and fructose have been obtained from CA results. The relative order of the oxidation currents for dextrose and fructose as well as their dependence on carbohydrate concentration has been discussed. Replacement of Pt by carbon as the electrode support material does not affect the electrocatalytic activity of the MnO₂ deposit. The observed linear variation of the steady state oxidation currents with carbohydrate concentration can be exploited for analytical application.     

Ozonation of 1,3,6‐naphthalenetrisulfonic acid in presence of heavy metals

A study was conducted of the mechanisms by which heavy metals, commonly present in industrial effluents, increase the purification effectiveness of ozone in the removal of organic contaminants of low biodegradability. For this purpose, the ozonation of 1,3,6‐naphthalenetrisulfonic acid (NTS) in the presence of Ni(II), Fe(II), Mn(II), Zn(II), Sr(II), Cr(III), Cd(II), Hg(II), and Cu(II) was examined. The presence of small amounts of Mn(II), Fe(II), Ni(II), Zn(II), and Cr(III) was observed in the system, increasing the degradation rate of the NTS and transforming the dissolved organic matter into CO₂. The mineralization of the organic matter was highly favored, especially in the first minutes of treatment. The results obtained appear to indicate that the activity of the metals in the NTS ozonation process is related to their reduction potential. Thus, metals susceptible to oxidation by ozone are potential promoters of NTS ozonation. The presence of Fe(II) or Mn(II) during NTS ozonation increased its degradation rate by 79% and 72% respectively. Moreover, the reaction kinetics of metal oxidation with ozone controls the increase in the purification effectiveness of these systems. The presence of radical scavengers (tert‐butanol or bicarbonate) in the medium during the promoted ozonation of NTS showed a negative effect on this process, and the NTS degradation rate decreased with an increasing concentration of these inhibitors in the system. These results confirm that the degradation of NTS by ozone in the presence of heavy metals occurs by a radical mechanism. O₃/Zn(II) and O₃/Fe(II) systems were applied to the decontamination of urban waste waters. The presence of Zn(II) or Fe(II) during the ozonation produced a reduction during the first 5 min of treatment of 20% or 44%, respectively, in the concentration of dissolved organic matter present in the system. These results show that ozonation in the presence of heavy metals is a highly promising system for the purification of waste waters and industrial effluents. Copyright © 2004 Society of Chemical Industry     

Selective Extraction and Separation of Ce (IV) and Th (IV) from RE(III) in Sulfate Medium using Di(2-ethylhexyl)-N-heptylaminomethylphosphonate

The extraction and separation of Ce(IV) and Th(IV) from trivalent rare earths (RE, including scandium) in sulfate medium using di(2-ethylhexyl)-N-heptylaminomethylphosphonate (DEHAMP, L) were studied. The effects of H₂SO₄ concentration, extractant concentration, and temperature on the metal extraction were investigated systematically. It was found that the extraction of metal ions by DEHAMP decreases in the following order: Ce(IV) > Th(IV) > Sc(III) > other RE(III). A possible extraction mechanism was proposed and the extracted complexes as Ce(SO₄)₂·2L and Th(HSO₄)₂SO₄·L were determined by the slope analysis method. Thermodynamic parameters (ΔH, ΔG, and ΔS) were calculated. The extraction reactions of Ce(IV) and Th(IV) were each exothermic processes. The loaded Ce(IV) and Th(IV) can be stripped efficiently by 3% H₂O₂ and 4 mol/L HCl, respectively. The extraction capacity of 0.63 mol/L DEHAMP is 30.0 g/L CeO₂ and 24.4 g/L ThO₂, respectively. Furthermore, a solvent extraction process to selectively extract and recover cerium and thorium from bastnaesite leaching was proposed, by which the purities of cerium and thorium products reached 97.2% and 96.5% with a yield of 85.4% and 98.8%, respectively.     

Functionalized sepiolite for heavy metal ions adsorption

Surface modification of clays has become increasingly important due to the practical applications of clays such as fillers and adsorbents. The surface modification of sepiolite with [3-(2-aminoethylamino)propyl]trimethoxysilane has been employed. The modified sepiolite surface was investigated by FTIR, XRD and DTA/TG analysis. It was found that the chemical bonding takes place between the hydroxyl groups and/or oxygen atoms within the structure of sepiolite and methoxy groups of [3-(2-aminoethylamino)propyl]trimethoxysilane. The changes on electrokinetic properties of modified sepiolite particles were studied by measuring the zeta potential of particle as a function of metal concentration and equilibrium pH of solution. It was found that the zeta potential of the clay particles was always negative independent of the metal concentration in solution. This study also provides some evidence for the adsorption of metal ions on modified sepiolite. The adsorption of metal ions onto modified sepiolite has varied with the type of metal cations. The available basic nitrogen centers covalently bonded to the sepiolite skeleton were studied for Co(II), Cu(II), Mn(II), Zn(II), Fe(III) and Cd(II) adsorption from aqueous solutions. It was found that the amount of metal ion adsorbed onto modified sepiolite increases with increase in solution equilibrium pH and temperature, whereas it generally decreases with the ionic strength. The experimental data were correlated reasonably well by the Langmuir adsorption isotherm and the isotherm parameters (q_m and K) were calculated. The ability to adsorb the cations gave a capacity order of Zn(II) > Cu(II) ~ Co(II) > Fe(III) > Mn(II) > Cd(II) with affinities of 2.167×10⁻⁴, 1.870×10⁻⁴, 1.865×10⁻⁴, 1.193×10⁻⁴, 0.979×10⁻⁴ and 0.445×10⁻⁴ mol g⁻¹, respectively.     

Electrochemical evaluation of the a carbon-paste electrode modified with spinel manganese(IV) oxide under flow conditions for amperometric determination of lithium

The participation of cations in redox reactions of manganese oxides provides an opportunity for development of chemical sensors for non-electroactive ions. This paper describes the amperometric determination of lithium ions using carbon-paste electrode modified with spinel manganese(IV) oxide under flow conditions. Systematic investigations were made to optimize the experimental parameters for lithium sensor by flow injection analysis. The detection was based on the measurement of anodic current generated by oxidation of Mn(III) to Mn(IV) at the surface of the electrode and consequently the lithium ions extraction into the spinel structure. An operating potential of 0.50 V (vs. Ag/AgCl/3 KCl mol/L) was exploited for amperometric monitoring. The amperometric signal was linearly dependent on the lithium ions concentration over the range 4.0 × 10⁻⁵ to 1.0 × 10⁻³ mol L⁻¹. The equilibrium constant of insertion/extraction of the lithium ion in the spinel structure, apparent Gibbs energy of insertion, and surface coverage of the electrode with manganese oxide, were calculated by peak charge (Q) in different concentration under flow conditions. Considering selectivity, the peak charge of the sensor was found to be linearly dependent on the ionic radius of the alkaline and earth-alkaline cations.