Removal of Cr(VI) From Aqueous Solution by Turkish Vermiculite: Equilibrium,Thermodynamic and Kinetic Studies

Abstract

The adsorption of Cr(VI) from aqueous solution by Turkish vermiculite were investigated in terms of equilibrium, kinetics, and thermodynamics. Experimental parameters affecting the removal process such as pH of solution, adsorbent dosage, contact time, and temperature were studied. Equilibrium adsorption data were evaluated by Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models. Langmuir model fitted the equilibrium data better than the Freundlich model. The monolayer adsorption capacity of Turkish vermiculite for Cr(VI) was found to be 87.7 mg/g at pH 1.5, 10 g/L adsorbent dosage and 20°C. The mean free energy of adsorption (5.9 kJ/mol) obtained from the D–R isotherm indicated that the type of sorption was essentially physical. The calculated thermodynamic parameters (ΔG ^o , ΔH ^o and ΔS ^o ) showed that the removal of Cr(VI) ions from aqueous solution by the vermiculite was feasible, spontaneous and exothermic at 20–50°C. Equilibrium data were also tested using the adsorption kinetic models and the results showed that the adsorption processes of Cr(VI) onto Turkish vermiculite followed well pseudo-second order kinetics.     

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.     

Selective Adsorption of Mo(VI) From Re(VII) Containing Effluent on Orange Waste Gel Modified by Ethylenediamine,Diethylamine, and Triethylamine

New adsorption gels were prepared by chemically immobilizing functional groups of ethylenediamine, diethylamine and/or triethylamine on orange waste, named OW-en, OW-DEA, and OW-TEA, respectively. By comparing with the adsorption of other coexisting metals, such as Re(VII), Pb(II), Fe(III), Zn(II), Mn(VII), Ca(II), and Cu(II), the novel gels exhibited selectivity only for Mo(VI) and the adsorption behavior obeys the Langmuir model. The maximum adsorption capacity for molybdenum was in the order, OW-en (2.17 mol/kg) > OW-TEA (1.26 mol/kg) > OW-DEA (0.88 mol/kg). A kinetic study for the adsorption of molybdenum at various temperatures confirmed that the endothermic adsorption process followed pseudo-second order kinetics. In addition, its excellent adsorption characteristics for Mo(VI) were confirmed by the adsorption and elution tests using a column packed with the OW-en gel, especially by separation of Mo(VI) from Mo-Re containing industrial effluent.     

A comparative study of removal of Cu(II) from aqueous solutions by locally low-cost materials: marine macroalgae and agricultural by-products

In this study, adsorption of Cu(II) onto the five locally abundantly low-cost biosorbents (Laminaria japonica, P. yezoensis Ueda, rice bran, wheat bran and walnut hull) was investigated depending on initial solution pH, contact time, adsorbent concentration and reaction temperature. Cu(II) removal was pH-dependent for various biosorbents investigated. For P. yezoensis Ueda, rice bran, wheat bran and walnut hull, the batch equilibrium data were correlated to Langmuir and Freundlich isotherms and the data fitted better to the Langmuir isotherm equation and yielded Langmuir monolayer capacity of 5.04, 10.41, 6.85 and 3.52 mg/g at the temperature of 20°C, respectively. In the case of Laminaria japonica, the equilibrium data obeyed the Hill-der Boer equation for the whole initial concentration ranges of 0–200 mg/L examined, but only to Langmuir and Freundlich equations for the initial concentration less than 120 mg/L at various temperatures. The apparent thermodynamic parameters were calculated for each of the five biosorbents (ΔH = 9.25–40.04 kJ/mol; ΔG = –17.60 to –24.16 kJ/mol and ΔS = 85.81–228 J/mol K). The numerical values obtained showed that Cu(II) adsorption is a spontaneous, entropy-driven and endothermic process. The batch kinetic data were correlated to the pseudo-first order and pseudo-second order models and the data fitted better to the pseudo-second order equation (the pseudo-second order rate constants, k_2,e = 0.1059–0.9453 g/(mg min); the correlation coefficients, r = 0.9816–0.9993).     

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.     

Adsorption studies of Cr(VI) and Cu(II) metal ions from aqueous solutions by synthesized Ag and Mg co-doped TiO2 nanoparticles

ABSTRACT

This communication provides the eliminating of heavy metals from water resources using Ag-Mg/TiO₂ nanoparticles. The nanoparticles with a size of 15 nm were prepared using sol-gel technique and used for the removal of Cr(VI) and Cu(II) from waste waters. Batch sorption studies were carried out to investigate the adsorption of the above metal ions for a concentration range of 0.1–10 mg/L. The maximum sorption capacity values were found to be 2.42 mg/g for Cr(VI) and 2.03 mg/g for Cu(II) at a concentration of 0.1 ppm. The mechanism of adsorption was also investigated. The results showed that both Freundlich and Dubinin–Radushkevitch isotherms were found to be the best fit for the adsorption of metals. The results from kinetic data reveal that the pseudo-second-order and Reichenberg film diffusion models were found to be well fit for the experimental data. The value of the thermodynamic parameter ΔH° revealed the endothermic adsorption process and negative value of ΔG° shows the feasibility and spontaneity of material–anion interaction. In addition, the method is considered to be simple and cost-effective, and shows excellent adsorption removal properties on heavy metals for industrial applications.     

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.     

EQUILIBRIUM,KINETICS, AND BREAKTHROUGH STUDIES FOR ADSORPTION OF Cr(VI) ON CHITOSAN

Wastewater containing low levels of pollutants can be effectively treated by the adsorption technique. In the present work, an adsorption study was carried out using chitosan as adsorbent in a fixed-bed column for the removal of Cr(VI) from wastewater solutions. The column performance of Cr(VI) adsorption onto chitosan was studied at different bed heights (3–9 cm), flow rates (50–200 mL/min), initial metal concentrations (2–10 mg/L), pH values (2–7), and temperatures (30°–60°C). The equilibrium data for the batch adsorption of Cr(VI) on chitosan were tested using the Langmuir, Freundlich, and BET isotherm models. The Langmuir model was found to be the most suitable, with a maximum adsorption capacity of 35.7 mg/g and a correlation coefficient (R ²) = 0.952. The experimental data were found to fit well with the pseudo-second-order kinetic model, with R ² = 0.999. The dynamics of the adsorption process was modeled using the Adams-Bohart, Thomas, and mass transfer models. The models were used to predict the breakthrough curves of adsorption systems and to determine the characteristic design parameters of the column. The adsorption data were observed to fit well with all three models. The model parameters were derived using MATLAB software. In order to compare quantitatively the applicability of adsorption dynamic models in fitting to experimental data, the percentage relative deviation (P) was calculated and found to be less than 5, confirming that the fit is good for all three models.     

Study on adsorption of Cu(II)–Cr(VI) binary system by carbonized Eupatorium adenophorum

We first report a mechanism study on the adsorption of Cu(II)-Cr(VI) binary mixture by a novel low-cost adsorbent, carbonized Eupatorium adenophorum. The influences by pH value, dosage, initial concentration, temperature, and adsorption time on its performance to absorb copper and chromium were investigated. The experimental data were fitted according to the Langmuir and Freundlich adsorption isotherm models, the pseudo-first-order kinetics, the pseudo-second-order kinetics, and the intra-particle diffusion model. The results indicated that when the reaction system was with its pH = 5, the dosage of carbonized Eupatorium adenophorum was 0.1 g, the adsorption time was 30 min, and the temperature was 25°C; the adsorption capacities for Cu(II) and Cr(VI) reached 27.62 mg/g and 9.68 mg/g, respectively. The process of carbonized Eupatorium adenophorum to absorb Cr(VI) is also accompanied by redox reactions. The Langmuir model and the pseudo-second-order model can better ?t the experimental data. Observation by fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) found no significant change of functional groups before and after the adsorption by carbonized Eupatorium adenophorum, and this adsorption process is mainly a physical adsorption.     

Study on adsorption behavior between Cr(VI) and crosslinked amphoteric starch

Crosslinked amphoteric starches (CASs) with quaternary ammonium cationic and carboxymethyl anionic groups were prepared by a hemidry reaction. Their adsorption behavior for Cr(VI) was investigated, and was found to follow the Langmuir isotherm. The adsorption process was found to be dependent on initial pH, concentration of Cr(VI), dose of CAS, and temperature. The adsorption capacity decreased with increasing degree of substitution of anionic groups. The thermodynamic study indicated that the adsorption process was exothermic, and the enthalpy changes (ΔH^θ), the entropy changes (ΔS^θ), and free energy changes (ΔG^θ) for CASs were determined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 263–267, 2003     

Surface modification of rubber (Hevea brasiliensis) leaves for the adsorption of copper ions: kinetic,thermodynamic and binding mechanisms

BACKGROUND: This research describes the adsorption of copper ions from aqueous solutions following the modification of rubber (Hevea brasiliensis) leaves with formaldehyde solution. The main objectives of this research were to identify the binding mechanisms of copper ions on the chemically modified rubber leaves by spectroscopic techniques and to investigate the effects of several important physicochemical parameters such as pH, copper concentration, contact time, adsorbent dose and temperature on copper removal. RESULTS: Based on a kinetic study, the pseudo‐second‐order model was found to fit the experimental results well, while the Boyd kinetic model indicated that the rate‐determining step was due to film diffusion. Adsorption isotherms were modelled by the Langmuir and Freundlich isotherm equations, with the former providing a better fit for the data. Based on the Langmuir model, the maximum adsorption capacities of Cu(II) ions at 300, 310 and 320 K were 8.36, 8.61 and 8.71 mg g^?1, respectively. Thermodynamic parameters such as the Gibbs free energy (ΔG°), enthalpy (ΔH°) and entropy changes (ΔS°) were calculated. The adsorption process was spontaneous as the values of ΔG° were negative, and endothermic as higher adsorption capacities were recorded at higher temperatures. More than 80% of copper ions bound on the adsorbent were able to be desorbed using 0.02 mol L^?1 HCl, HNO₃ and EDTA solutions. Besides ion exchange, surface complexation could also play a major role in copper binding. CONCLUSION: Due to its relative abundance and satisfactory adsorption capacity, the modified rubber leaves can be considered as a good low‐cost adsorbent for removing copper ions from dilute aqueous solutions. Copyright © 2008 Society of Chemical Industry     

Equilibrium,kinetics, and thermodynamics of Pd(II) adsorption onto poly(m‐aminobenzoic acid) chelating polymer

This study describes the equilibrium, kinetics, and thermodynamics of the palladium(II) (Pd(II)) adsorption onto poly(m‐aminobenzoic acid) (p‐mABA) chelating polymer. The p‐mABA was synthesized by the oxidation reaction of m‐aminobenzoic acid monomer with ammonium peroxydisulfate (APS). The synthesized p‐mABA chelating polymer was characterized by FTIR spectroscopy, gel permeation chromatography (GPC), thermal analysis, potentiometric titration, and scanning electron microscopy (SEM) analysis methods. The effects of the acidity, temperature, and initial Pd(II) concentration on the adsorption were examined by using batch adsorption technique. The optimum acidity for the Pd(II) adsorption was determined as pH 2. In the equilibrium studies, it was found that the Pd(II) adsorption capacity of the polymer was to be 24.21 mg/g and the adsorption data fitted better to the Langmuir isotherm than the Freundlich isotherm. The kinetics of the adsorption fitted to pseudo‐second‐order kinetic model. In the thermodynamic evaluation of the adsorption, the ΔG° values were calculated as ?16.98 and ?22.26 kJ/mol at 25–55°C temperatures. The enthalpy (ΔH°), entropy (ΔS°), and the activation energy (E_a) were found as 35.40 kJ/mol, 176.05 J/mol K, and 61.71 kJ/mol, respectively. The adsorption of Pd(II) ions onto p‐mABA was a spontaneous, endothermic, and chemical adsorption process which is governed by both ionic interaction and chelating mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42533.     

Fabrication of a copolymer flocculant and application for Cr(VI) removal

A copolymer flocculant (CATCS) derived from starch and chitosan was fabricated and used as eco‐friendly adsorbent for removal of Cr(VI) from aqueous solution. The CATCS flocculant was characterized by scanning electron microscope, thermogravimetic analysis, and Fourier transform infrared spectroscopy. The effects of CATCS dosage, initial Cr(VI) concentration, pH, and reaction time on removal of Cr(VI) were discussed. The results showed CATCS removed Cr(VI) effectively and the adsorption isotherm agreed well with the Freundlich isotherm and R–P isotherm models. The enthalpy change (ΔH) of the process was 16.75 kJ/mol suggesting the existence of chemisorption and the reaction was endothermic. Moreover, the negative free energy change (ΔG) indicated the adsorption process was feasible and spontaneous. The positive entropy change (ΔS) showed there was an increase of disorder in the system during the adsorption process. The adsorption kinetics results showed that the adsorption could be described by the pseudo‐second‐order kinetics mechanism. The activation energy (E_a) of the adsorption reaction was 29.16 kJ/mol. POLYM. ENG. SCI., 56:1213–1220, 2016. © 2016 Society of Plastics Engineers     

Equilibrium,Thermodynamic, and Kinetic Studies on Trichoderma viride Biomass as Biosorbent for the Removal of Cu(II) from Water

Equilibrium, thermodynamic, and kinetic studies on the biosorption of Cu(II) using biomass, Trichoderma viride were carried out. The biosorbent was characterized by Fourier transform infrared spectroscopy and Scanning Electron Microscopy. The Langmuir and Freundlich isotherm models were applied to describe the biosorption process. The influence of pH, the biomass dosage, the contact time, the initial metal ion concentration, and the temperature of the solution on the biosorption was studied. The maximum Cu(II) biosorption was attained at pH 5. The equilibrium data were better fit by the Langmuir isotherm model than by the Freundlich isotherm. The maximum biosorption capacity of T. viride biomass was found to be 19.6 mg/g for Cu(II). The kinetic studies indicated that the biosorption of Cu(II) followed the pseudo-second-order model. The calculated thermodynamic parameters, Gibbs-free energy (ΔG^o), enthalpy (ΔH^o), and entropy (ΔS^o) showed that the biosorption of Cu(II) onto T. viride biomass was spontaneous and endothermic. It can be concluded that the T. viride biomass has the potential as an effective and low-cost biosorbent for Cu(II) removal from aqueous solutions.     

Synergistic removal of Cu(II) and nitrazine yellow dye using an eco‐friendly chitosan‐montmorillonite hydrogel: Optimization by response surface methodology

A comprehensive feasibility study on adsorption of Cu(II) and a water‐soluble nitrazine yellow (NY) dye by chitosan‐montmorillonite (CS‐MMT) hydrogel as the biosorbent was investigated as a function of biosorbent dosage, initial concentration, pH, temperature, and the presence of salts. Box–Behnken methodology was applied to optimize the adsorption experiments. Maximum adsorption values were determined as 132.74 mg/g and 144.41 mg/g at pH = 5.0, for Cu(II) and NY dye, respectively. Equilibrium isotherms of Langmuir and Freundlich were analyzed by the non‐linear regression model. The equilibrium data were well described by Freundlich model and the adsorption process well fitted pseudo‐second order kinetics. The enthalpy change of adsorption (ΔH°) were calculated as ?3.78 kJ/mol and ?5.75 kJ/mol for Cu(II) and NY dye, respectively, indicating that the adsorption processes were exothermic. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43664.     

Removal of Chromium(VI) and Chromium(III) from Aqueous Solution by Grainless Stalk of Corn

Abstract

Grainless stalk of corn (GLSC) was tested for removal of Cr(VI) and Cr(III) from aqueous solution at different pH, contact time, temperature, and chromium/adsorbent ratio. The results show that the optimum pH for removal of Cr(VI) is 0.84, while the optimum pH for removal of Cr(III) is 4.6. The adsorption processes of both Cr(VI) and Cr(III) onto GLSC were found to follow first-order kinetics. Values of k _ads of 0.037 and 0.018 min^?1 were obtained for Cr(VI) and Cr(III), respectively. The adsorption capacity of GLSC was calculated from the Langmuir isotherm as 7.1 mg g^?1 at pH 0.84 for Cr(VI), and as 7.3 mg g^?1 at pH 4.6 for Cr(III), at 20°C. At the optimum pH for Cr(VI) removal, Cr(VI) reduces to Cr(III). EPR spectroscopy shows the presence of Cr(V) + Cr(III)-bound-GLSC at short contact times and adsorbed Cr(III) as the final oxidation state of Cr(VI)-treated GLSC. The results indicate that, at pH ≈ 1, GLSC can completely remove Cr(VI) from aqueous solution through an adsorption-coupled reduction mechanism to yield adsorbed Cr(III) and the less toxic aqueous Cr(III), which can be further removed at pH 4.6.     

Kinetics,equilibrium and thermodynamic studies on biosorption of hexavalent chromium by dead fungal biomass of marine Aspergillus niger

Quite a number of reports are available on metal binding capacity of different groups of microorganisms. However, reports on the equilibrium studies on biosorption by marine fungi are quite inadequate. The present study was carried out in a batch system using dead biomass of marine Aspergillus niger for the sorption of Cr(VI). The removal rate of Cr(VI) was increased with a decrease in pH and an increase in Cr(VI) and biomass concentration. A. niger exhibited the highest Cr(VI) uptake of 117.33 mg g^?1 of biomass at pH 1.0 in the presence of 400 mg l^?1 Cr at 50 °C. Kinetics studies based on fractional power, zero order, first order, pseudo-first order, Elovich, second order and pseudo-second order rate expressions have also been carried out. The experimental data were analyzed using five, two-parameter isotherms (Langmuir, Freundlich, Dubinin–Radushkevich, Temkin and Halsey). It was observed that Langmuir model exhibited the best fit to experimental data. Thermodynamic parameters of the biosorption (ΔG°, ΔH° and ΔS°) were also determined.     

Fe2+-modified Vermiculite for the Removal of Chromium (VI) from Aqueous Solution

A novel adsorbent: Fe²⁺-modified vermiculite was prepared in a two-step reaction. Adsorption experiments were carried out as a function of pH, contact time, and concentration of Cr(VI). It was found that Fe²⁺-modified vermiculite was particularly effective for the removal of Cr(VI) at pH 1.0. The adsorption of Cr(VI) reached equilibrium within 60 min, and the pseudo-second-order kinetic model best described the adsorption kinetics. The adsorption data follow the Langmuir model more than the Freundlich model. At pH 1.0, the maximum Cr(VI) sorption capacity (Q _max ) was 87.72 mg · g^?1. Desorption of Cr(VI) from Fe²⁺-modified vermiculite using NaOH treatment exhibited a higher desorption efficiency by more than 80%. The sorption mechanisms including electrostatic interaction and reduction were involved in the Cr (VI) removal. The results showed that Fe²⁺-modified vermiculite can be used as a new adsorbent for Cr(VI) removal which has a higher adsorption capacity and a faster adsorption rate.     

Heterocyclic modification of chitosan for the adsorption of Cu (II) and Cr (VI) ions

A heterocyclic modification of chitosan has been attempted for development of an effective adsorbent material for removal of metal ions. The modified polymer was characterized using infrared (IR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS) and x-ray diffraction (XRD) techniques. The adsorption capacity exhibited for Cu (II) and Cr (VI) were 83.75 and 85.0 mgg^?1, respectively, which is a significant improvement over chitosan. The adsorption on the modified polymer was a second-order kinetic process and followed Langmuir isotherm model. The thermodynamic analysis indicated exothermic and spontaneous nature of adsorption. About 80% of the adsorbed metal ions were desorbed in appropriate stripping solutions indicating reusability.