Determination of the constants of affinity of FeCl3, CuCl2, and ZnCl2 for a nitrogen-containing organosilane bonded on Al2O3-cellulose acetate hybrid material surface from ethanol solution

This work describes the preparation and characterization of a cellulose acetate fiber coated with Al(2)O(3), resulting in the organic-inorganic hybrid Cel/Al(2)O(3). Furthermore, the hybrid was modified by attaching organofunctional groups by reaction with the precursor reagents (RO)(3)Si(CH(2))(3)L (L=NH(2), NH(CH(2))(2)NH(2), NH(CH(2))(2)NH(CH(2))(2)NH(2), and N(2)C(3)H(3) (imidazole)), resulting in Cel/Al(2)O(3)/Si(CH(2))(3)NH(2) (1), Cel/Al(2)O(3)/Si(CH(2))(3)NH(CH(2))(2)NH(2) (2), Cel/Al(2)O(3)/Si(CH(2))(3)NH(CH(2))(2)NH(CH(2))(2)NH(2) (3), and Cel/Al(2)O(3)/Si(CH(2))(3)N(2)C(3)H(3) (4). The amounts of attached organofunctional groups were (in mmol per gram of the material) 1=1.90, 2=1.89, 3=1.66, and 4=1.35. The isotherms of adsorption of FeCl(3), CuCl(2), and ZnCl(2) by Cel/Al(2)O(3)/Si(CH(2))(3)L from ethanol solutions were obtained at 298 K. Accurate estimates of the specific sorption capacities and the heteregeneous stability constants of the immobilized metal complexes were determined with the aid of several computational procedures. It is shown that the sorptional capacities are much less than the concentrations of the attached organofunctional groups. As all sorption isotherms are fitted properly with the Langmuir isotherm equation, the effects of the energetic heterogeneity and the lateral interactions do not affect the chemisorption equilibria. The heterogeneous stability constants of the immobilized complexes are fairly high, which provides efficient removal of the metal ions from solutions by the hybrid materials.     

Adsorption of metal halides from ethanol solutions by a 3-n-propylpyridiniumsilsesquioxane chloride-coated silica gel surface

3-n-propylpyridiniumsilsesquioxane chloride polymer, abbreviated as SiPy+Cl-, was used to coat a porous silica gel, SiO2, surface to form the chemically modified solid SiO2/SiPy+Cl-. The resulting polymer film was well adhered to the surface and presented an ion exchange capacity of 0.74 mmol g(-1). Metal halides, MClz [M=Fe(III), Cu(II), and Zn(II)], were adsorbed by the modified solid from ethanol solutions as neutral species by forming the surface anionic complexes described by the equation: mSiO2/SiPy+Cl-+ MClz <=> (SiO2/SiPy+)m[MCl(z+m)]m-, where the [MCl(z+m)]m- species adsorbed on the surface are FeCl4-, ZnCl4(2-), and CuCl4(2-). Accurate estimates of the specific sorption capacities and the heterogeneous stability constants of the immobilized metal complexes were determined with the aid of computational procedures.     

n-Propylpyridinium chloride-modified poly(dimethylsiloxane) elastomeric networks: preparation, characterization, and study of metal chloride adsorption from ethanol solutions

An n-propylpyridinium chloride-modified PDMS elastomeric network, PDMS/Py(+)Cl(-), was prepared from linear PDMS chains containing Si(CH(3))(2)OH end-groups cross-linked by 3-chloropropyltrimethoxysilane and posterior reaction with pyridine. PDMS/Py(+)Cl(-) material was structurally characterized by infrared spectroscopy (IR) and solid state (13)C and (29)Si NMR. Thermogravimetric analysis of the product showed good thermal stability, with the initial temperature of weight loss at 450 K. The ion-exchange capacity of the PDMS/Py(+)Cl(-) was 0.65 mmol g(-1). Metal halides, MCl(z) [M=Fe(3+), Cu(2+), and Co(2+)], were adsorbed by the modified solid from ethanol solutions as neutral species by forming the surface anionic complexes MCl(z+n)(n-). The nature of the anionic complex structure was proposed by UV-vis diffuse reflectance spectra. The species adsorbed were FeCl(-)(4), CuCl(2-)(4), and CoCl(2-)(4). The specific sorption capacities and the heterogeneous stability constants of the immobilized metal complexes were determined with the aid of computational procedures. The trend in affinities of PDMS/Py(+)Cl(-) for the metal halides were found to be FeCl(3)>CuCl(2) approximately CoCl(2).     

Composition,structure, and functional properties of organomineral composite sorbents KU-2×8-ZnS and KU-2×8-PbS

Organomineral composite sorbents KU-2×8-ZnS and KU-2×8-PbS were synthesized on the basis of the matrix of a strongly acidic KU-2×8 cation exchanger. Scanning electron microscopy and elemental analysis were used to study their microstructure and chemical composition. With the use of potentiometric titration, their bifunctional nature was revealed and the dissociation constants and the total exchange capacities of the ionogenic groups were determined. The sorption of copper(II), zinc, and cadmium by KU-2×8-ZnS and KU-2×8-PbS sorbents from 0.005 M solutions of their salts was examined. The total dynamic sorption capacity of the composite sorbents for the above metals, found in the study, exceeds similar values for the individual KU-2×8 cation exchanger by a factor of 1.6–2.0 and that in 0.001–0.050 M solutions of potassium and calcium chlorides, by a factor of 1.3–4.5. An explanation is suggested for the sorption process of heavy nonferrous metals on composite sorbents with an active sulfide component by the mechanism of coordination copolymerization.     

Tuning Hydrogen Sorption Properties of Metal–Organic Frameworks by Postsynthetic Covalent Modification

Postsynthetic modification is presented as a means to tune the hydrogen adsorption properties of a series of metal–organic frameworks (MOFs). IRMOF‐3 (isoreticular metal–organic framework), UMCM‐1‐NH₂ (University of Michigan crystalline material), and DMOF‐1‐NH₂ (DABCO metal–organic framework) have been covalently modified with a series of anhydrides or isocyanates and the hydrogen sorption properties have been studied. Both the storage capacities and isosteric heats of adsorption clearly show that covalent postsynthetic modification can significantly enhance the sorption affinity of MOFs with hydrogen and in some cases increase both gravimetric and volumetric uptake of the gas as much as 40 %. The significance of the present study is illustrated by: 1) the nature of the substituents introduced by postsynthetic modification result in different effects on the binding of hydrogen; 2) the covalent postsynthetic modification approach allows for systematic modulation of hydrogen sorption properties; and 3) the ease of postsynthetic modification of MOFs allows a direct evaluation of the interplay between MOF structure, hydrogen uptake, and heat of adsorption. The findings presented herein show that postsynthetic modification is a powerful method to manipulate and better understand the gas sorption properties of MOFs.     

Biosorption of Ni(II) from aqueous solutions by living and non-living ureolytic mixed culture

The present study explores the ability and the comparison of living and non-living ureolytic mixed culture (UMC) to remove Ni(II) from aqueous solution. Time dependency experiments for the Ni(II) uptake showed that adsorption equilibrium was reached almost 110 and 60 min after addition Ni(II) of 100mg/L. The kinetic data were analyzed in term of pseudo-first-order and pseudo-second-order expressions. Ni(II) sorption of living UMC was appropriate with pseudo-first-order kinetic (k(1)=2.15 h(-1), R(2)=0.93) while non-living UMC sorbed Ni(II) with respect to second-order kinetics (k(2)=1.64 g/mgh, R(2)=0.98). Also, comparison between the biosorption capacity of untreated living and non-living biomass was conducted for removal of Ni(II). The biosorption process was investigated in equilibrium batch tests for Langmuir, Freundlich and Temkin isotherm models. The data pertaining to the sorption dependence upon Ni(II) ion concentration ranged from 5 to 320 mg/L could be fitted to a Freundlich isotherm model. The capacity constants K of Freundlich model for living and non-living UMC were 1.55 and 0.38 mg/g, respectively; the affinity constants 1/n were 0.47 and 0.75, respectively. Based on the results, the UMC appear to be a potential biosorbent for removal of Ni(II) from wastewater.     

Removal of Trace Contaminants from Water Using New Chelating Resins

Abstract

The modification of cross‐linked polyacrylamide (CPAAm) and incorporation of methyl thiourea (MeTU) or phenyl thiourea (PhTU) group were utilized in the preparation of two new chelating resins CPAAm‐EDA‐MeTU (resin I) and CPAAM‐EDA‐PhTU (resin II), [EDA=ethylenediamine]. The prepared resins were characterized by elemental analysis and IR spectroscopy. The sorption behaviors of Cd(II), Pb(II), and Zn(II) ions on the prepared resins were studied and the optimum sorption conditions for the tested metal ions were determined. The optimum pH value for the sorption of Cd(II) and Zn(II) ions on both resins I and II was ranged between 7–8. The prepared new resins show very little affinity towards Pb(II) ion. The maximum experimental sorption capacities of resin I towards Cd(II) and Zn(II) ions were 3.2 and 0.6 mmol g^?1, respectively, and that of resin II were and 0.6 mmol g^?1 in the same prescribed order. Langmuir and Freundlich isotherm constants and correlation coefficients for the present system were calculated and compared. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) for cadmium and zinc sorption on the prepared resins were also determined from the temperature dependence.     

Removal of Mn(II) and Cd(II) from wastewaters by natural and modified clays

The adsorption capacities of commercial and Brazilian natural clays were evaluated to test their applications in wastewater control. We investigated the process of sorption of manganese(II) and cadmium(II) present in synthetic aqueous effluents, by calculating the adsorption isotherms at 298 K using batch experiments. The influence of temperature and pH on the adsorption process was also studied. Adsorption of metals was best described by a Langmuir isotherm, with values of Q ₀ parameter, which is related to the sorption capacity, corresponding to 6.3 mg g^{− 1} for K-10/Cd(II), 4.8 mg g^{− 1} for K-10/Mn(II), 11.2 mg g^{− 1} for NT-25/Cd(II) and 6.0 mg g^{− 1} for NT-25/Mn(II). We observed two distinct adsorption mechanisms that may influence adsorption. At the first 5 min of interaction, a cation exchange mechanism that takes place at exchange sites located on (001) basal planes is predominant. This process is inhibited by low pH values. After this first and fast step, a second sorption mechanism can be related to formation of inner-sphere surface complexes, which is formed at edges of the clay. The rate constants and the initial sorption rates correlate positively with temperature in all studied systems, denoting the predominance of a physisorption process. The addition of complexing agents that are incorporated within the K10 structure, enhance metal uptake by the adsorbent. The results have shown that both Cd(II) and Mn(II) were totally retained from a 50 mg L^{− 1} solution when K10 grafted with ammonium pyrrolidinedithiocarbamate (APDC) was used as adsorbent.     

Sorption of perfluorochemicals to granular activated carbon in the presence of ultrasound

Perfluorochemicals (PFCs) are emerging pollutants of increasing public health and environmental concern due to their worldwide distribution, environmental persistence, and bioaccumulation potential. Activated carbon adsorption is an effective method to remove PFCs from water. Herein, we report on the sorption of four PFCs: perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), and perfluorobutanoate (PFBA), from deionized water (MQ) and landfill groundwater (GW) by granular activated carbon (GAC) in the absence and presence of 20 kHz ultrasound. In all cases, the adsorption kinetics were found to be well-represented by a pseudosecond-order model, with maximum monolayer sorption capacity and initial sorption rate values following the orders q(e)(PFOS) > q(e)(PFOA) > q(e)(PFBS) > q(e)(PFBA) and v(0)(PFOS) > v(0)(PFBS) > v(0)(PFOA) > v(0)(PFBA), respectively. The equilibrium adsorption was quantified by the BET multilayer absorption isotherm, and the monolayer sorption capacity increased with increasing PFC chain length: q(m)(PFOS) > q(m)(PFOA) > q(m)(PFBS) > q(m)(PFBA). The equilibrium PFC sorption constants, q(e) and q(m), and the sorption kinetic constants, v(0) and k(2), were greater in Milli-Q water than in landfill groundwater with or without pretreatment, indicating competition for sorption sites by natural and cocontaminant groundwater organics. Ultrasonic irradiation significantly increased the PFC-GAC sorption kinetics, 250-900%, and slightly increased the extent of PFC equilibrium adsorption, 5-50%. The ultrasonic PFC-GAC sorption kinetics enhancement increased with increasing PFC chain length, suggesting ultrasound acts to increase the PFC diffusion rate into GAC nanopores.     

A chelating resin containing 1-(2-thiazolylazo)-2-naphthol as the functional group; synthesis and sorption behavior for trace metal ions

A new polystyrene-divinylbenzene resin containing 1-(2-thiazolylazo)-2-naphthol (TAN) functional group was synthesized and its sorption behavior for 19 metal ions including Zr(IV), Hf(IV) and U(VI) was investigated by batch and column experiments. The chelating resin showed a high sorption affinity for Zr(IV) and Hf(IV) at pH 2. Some parameters affecting the sorption of the metal ions are detailed. The breakthrough and overall capacities were measured under optimized conditions. The overall capacities of Zr(IV) and Hf(IV) that were higher than those of the other metal ions were 0.92 and 0.87 mmol/g, respectively. The elution order of metal ions at pH 4 was evaluated as: Zr(IV)>Hf(IV)>Th(IV)>V(V)>Nb(V)>Cu(II)>U(VI)>Ta(V)>Mo(VI)>Cr(III)>Sn(IV)>W(VI). Quantitative recovery of most metal ions except Zr(IV) was achieved using 2 M HNO₃. Desorption and recovery of Zr(IV) was successfully performed with 2 M HClO₄ and 2 M HCl.     

Single, binary, and multicomponent sorption of iron and manganese on lignite

Acid mine drainage (AMD) has long been a significant environmental problem resulting from the microbial oxidation of iron pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. The main objective of this study was to remove metal ions [Fe(II), Fe(III), Mn(II), Zn(II)] from AMD using lignite, a low-cost adsorbent. The lignite sorbent was utilized for the sorption of ferrous, ferric, manganese, zinc, and calcium ions in aqueous solutions. Studies were performed at different pH to find optimum pH. Equilibrium isotherms were determined to assess the maximum adsorption capacity of lignite for different metal ions. Sorption capacities were compared in single, binary, ternary, and multicomponent systems. The sorption data are correlated with Freundlich and Langmuir isotherms in each system. Both Freundlich and Langmuir isotherms fit the data reasonably well in terms of regression coefficients. Sorption studies were also performed at different temperatures to obtain the thermodynamic parameters of the process. The maximum lignite adsorption capacities at 25 degrees C were 34.22, 25.84, and 11.90 mg/g for Fe(II), Mn(II), and Fe(III), respectively. Adsorption of Fe(2+) (24.70 mg/g at 10 degrees C and 46.46 mg/g at 40 degrees C) increased with increased temperature, while Mn(2+) adsorption (28.11 mg/g at 10 degrees C and 7.70 mg/g at 40 degrees C) decreased with increased temperature.     

Effect of Complex-Former Ion Concentration on the Selectivity of Metal Ion Sorption on Cross-Linked <Emphasis Type="Italic">N</Emphasis>-2-Sulfoethylchitosan

Copper(II), silver(I), cobalt(II), nickel(II), zinc(II), manganese(II), and magnesium(II) sorption isotherms on cross-linked sulfoethylated chitosan with the degree of sulfoethylation DS = 0.7 (SEC 0.7) have been plotted for the individual or collective presence of these ions in solution have been constructed. The capacities of the studied sorbents for the studied metal ions have been calculated by processing the sorption isotherms. SEC 0.7 is found to have the greatest affinity to copper(II) and silver(I); their presence almost completely suppresses the sorption of associated metal ions. The Redlich–Peterson model gives the best fit to the sorption isotherms for collectively present metal ions, indicating the chemical inhomogeneity of the sorbent surface.     

Aluminum Oxide Coated Cellulose Fibers Modified with n-Propylpyridinium Chloride Silsesquioxane Polymer: Preparation, Characterization, and Adsorption of Some Metal Halides from Ethanol Solution

Aluminum oxide coated cellulose fibers were modified, by an impregnation procedure, with n-propylpyridinium chloride silsesquioxane polymer. Good adherence of the polymer to the surface of modified cellulose fibers was obtained due to the Al-O-Si bond formation. The metal X-ray mapping showed that aluminum oxide and the silsequioxane polymer (Al and Si mapping) are highly dispersed on the fiber's surface. The ion exchange capacity of the material, determined on basis of exchangeable chloride ions, was 1.1 mmol g-1. The adsorption isotherms of FeCl3, CuCl2, and ZnCl2 from ethanol solutions were determined for each metal. The adsorption capacities were (in mmol g-1): FeCl3 = 0.82, CuCl2 approximately ZnCl2 = 0.37. The metal ions are adsorbed as anionic complex species by the following equilibrium reaction: + MCln right arrow over left arrow Copyright 1999 Academic Press.     

Dye-ligand immobilized IPNs membrane for removal heavy metal ions

We have developed a novel approach to obtain high metal sorption capacity utilizing a membrane containing chitosan and an immobilized reactive dye (i.e. Reactive Yellow-2). The composite membrane was characterized by SEM, FT-IR, swelling test, and elemental analysis. The membrane has uniform small pores distribution and the pore dimensions are between 5 and 10 μm, and the HEMA:chitosan ratio was 50:1. The reactive dye immobilized composite membrane was used in the removal of heavy metal ions [i.e., Pb(II), Hg(II) and Cd(II)] from aqueous medium containing different amounts of these ions (5-600 mg l⁻¹) and at different pH values (2.0-7.0). The maximum adsorption capacities of heavy metal ions onto the composite membrane under non-competitive conditions were 64.3 mmol m⁻² for Pb(II), 52.7 mmol m⁻² for Hg(II), 39.6 mmol m⁻² for Cd(II) and the affinity order was Pb(II) > Hg(II)>Cd(II).     

Heavy metals and adsorbents effects on activated sludge microorganisms

The sorption of Cu(II) and Cd(II) from synthetic solution by powdered activated carbon (PAC), biomass, rice husk (RH) and activated rice husk (ARH) were investigate under batch conditions. After activated by concentrated nitric acid for 15 hours at 60-65 degrees C, the adsorption capacity for RH was increased. The adsorbents arranged in the increasing order of adsorption capacities to the Langmuir Q degree parameter were biomass > PAC > ARH > RH. The addition of adsorbents in base mix solution had increased the specific oxygen uptake rate (SOUR) activated sludge microorganisms with and without the presence of metals. The increased of SOUR were due to the ability of PAC and RH in reducing the inhibitory effect of metals on microorganisms and provide a reaction site between activated sludge microorganisms and substrates.     

Sorption of proton and heavy metal ions on a macroporous chelating resin with an iminodiacetate active group as a function of temperature

A macroporous resin containing iminodiacetic groups (Lewatit) was investigated for its sorption properties towards proton and nickel(II) and cadmium(II). Different compositions of the aqueous phase, and different temperatures were examined. The stoichiometry, the exchange coefficients and the intrinsic constants of the sorption equilibria were obtained from the experimental data by using the Gibbs-Donnan model for the ion exchange resin. The intrinsic constants were found to be independent of the composition of the solution, so that they were used for characterizing the sorption equilibria. While the first intrinsic protonation constant of the active groups in the resin was found to depend on the temperature, the second one was independent. The sorption equilibrium of nickel in the resin was different from that of cadmium, being ascribable respectively to the formation of the complexes NiL and Cd(HL)(2). inside the resin. Their intrinsic complexation constants were found to be 10(-1.84) and 10(-3.64) at 25 degrees C. Compared to those of another resin with the same active groups, but not macroporous, they are higher. The dependence of the intrinsic constant on the temperature was also different for the two metals, allowing to evaluate a DeltaH degrees of +30.9 and of +13.7 kJ mol(-1) respectively. When a comparison is possible, these values are near to those in aqueous solution for the complexation with ligands of similar structure. These results can be used to achieve metal ion separation based on temperature variations.     

Ethyleneimine Anchored on Thiol-Modified Silica Gel Surface-Adsorption of Divalent Cations and Calorimetric Data

Activated silica gel was previously modified by the silylant agent 3-mercaptopropyltrimethoxysilane. The organofunctionalized silica gel containing pendant groups ended with the -SH functions reacted with the three-member cyclic ethyleneimine molecules to yield the new ligand attaching sulfur and nitrogen basic centers available to complex cations. This final anchored surface adsorbs MX(2) (M=Co(2+), Ni(2+), Cu(2+), and X=Cl(-), NO(3)(-)) at 298+/-1 K. A considerable increase in adsorption capacity was observed for nitrate counteranions. This process of extraction was followed by the batch method and the order of the maximum capacities found was Ni(2+)>Cu(2+)>Co(2+) for both series of salts. The pendant immobilized groups-cation interaction processes showed exothermic enthalpies. Those values are more pronounced for chlorides, with the largest values obtained for cobalt. The calculated DeltaG values are in agreement with the spontaneity of the proposed reactions and the complexation is entropically favored. Copyright 2000 Academic Press.     

Adsorption of methylene blue and orange II onto unmodified and surfactant-modified zeolite

Adsorption of cationic methylene blue and anionic orange II onto unmodified and surfactant-modified zeolites was studied using a batch equilibration method. The effects of equilibrium time, solution pH, and sorption temperature were examined. The results suggested that 2% sodium dodecyl benzenesulfonate (SDBS)- and 3% sodium dodecyl sulfate (SDS)-modified zeolites had higher adsorption capacities for methylene blue than the unmodified zeolite, while 2% cetylpyridinium bromide hexadecyl (CPB)- and 2% hexadecylammonium bromide (HDTMA)-modified zeolites were the best adsorbents for orange II. The adsorption conditions were optimized, and the mechanisms of adsorption are briefly discussed.     

Solid phase extraction of copper(II) by fixed bed procedure on cation exchange complexing resins

The efficiency of the metal ion recovery by solid phase extraction (SPE) in complexing resins columns is predicted by a simple model based on two parameters reflecting the sorption equilibria and kinetics of the metal ion on the considered resin. The parameter related to the adsorption equilibria was evaluated by the Gibbs–Donnan model, and that related to the kinetics by assuming that the ion exchange is the adsorption rate determining step. The predicted parameters make it possible to evaluate the breakthrough volume of the considered metal ion, Cu(II), from different kinds of complexing resins, and at different conditions, such as acidity and ionic composition.