Removal of Reactive Yellow 84 from aqueous solutions by adsorption onto hydroxyapatite

The adsorption of a reactive dye, Reactive Yellow 84, from aqueous solution onto synthesized hydroxyapatite was investigated. The experiments were carried out to investigate the factors that influence the dye uptake by the adsorbent, such as the contact time under agitation, absorbent dosage, initial dye concentration, temperature and pH of dye solution. The experimental results show that the amount of dye adsorbed increases with an increase in the amount of hydroxyapatite. The maximum adsorption occurred at the pH value of 5. The equilibrium uptake was increased with an increase in the initial dye concentration in solution. The experimental isotherm data were analyzed using Langmuir isotherm equation. The maximum monolayer adsorption capacity was 50.25 mg/g. The adsorption has a low temperature dependency and was endothermic in nature with an enthalpy of adsorption of 2.17 kJ mol⁻¹.     

Isotherms of poly(ethylene glycol) adsorption from aqueous solutions by carbon adsorbents

Isotherms of adsorption of poly(ethylene glycols) PEG300, PEG6000, and PEG15 000 from aqueous solutions on graphitized carbon black and active carbon were measured at 25°C. Isotherms of excess adsorption of PEG6000 and PEG15 000 from aqueous solutions on both adsorbents were characterized by a distinct maximum. Comparison of adsorption isotherms for PEG6000 and PEG15 000 on a mesoporous AU-87 carbon testified to the existence of a sieve effect upon the adsorption of large PEG15 000 macromolecules in the accessible pores of this adsorbent. The analysis of the dependence of maximal adsorption values on the PEG molecular mass indicated a possible unfolding of macromolecular coils in the field of adsorption forces. As a result, all oxygen and carbon atoms of PEG macromolecules in a monolayer tend to approach active sites on the surface of a carbon adsorbent. The calculated values of thickness of dense adsorption monolayers of PEG300, PEG6000, and PEG15 000 lie within 0.36–0.63 nm for both adsorbents. PEG300 adsorption monolayers also contain, in addition to macromolecules, molecules of a solvent (water).Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 856–859.Original Russian Text Copyright © 2004 by Eltekov, Eltekova, Roldughin.     

Phenol removal from aqueous solution by adsorption and ion exchange mechanisms onto polymeric resins

The removal of phenol from aqueous solution was evaluated by using a nonfunctionalized hyper-cross-linked polymer Macronet MN200 and two ion exchange resins, Dowex XZ (strong anion exchange resin) and AuRIX 100 (weak anion exchange). Equilibrium experimental data were fitted to the Langmuir and Freundlich isotherms at different pHs. The Langmuir model describes successfully the phenol removal onto the three resins. The extent of the phenol adsorption was affected by the pH of the solution; thus, the nonfunctionalized resin reported the maximum loading adsorption under acidic conditions, where the molecular phenol form predominates. In contrast both ion exchange resins reported the maximum removal under alkaline conditions where the phenolate may be removed by a combined effect of both adsorption and ion exchange mechanisms. A theoretical model proposed in the literature was used to fit the experimental data and a double contribution was observed from the parameters obtained by the model. Kinetic experiments under different initial phenol concentrations and under the best pH conditions observed in the equilibrium experiments were performed. Two different models were used to define the controlling mechanism of the overall adsorption process: the homogeneous particle diffusion model and the shell progressive model fit the kinetic experimental data and determined the resin phase mechanism as the rate-limiting diffusion for the phenol removal. Resins charged after the kinetic experiments were further eluted by different methods. Desorption of nonfunctionalized resin was achieved by using the solution (50% v/v) of methanol/water with a recovery close to 90%. In the case of the ion exchange resins the desorption process was performed at different pHs and considering the effect of the competitive ion Cl⁻. The desorption processes were controlled by the ion exchange mechanism for Dowex XZ and AuRIX 100 resins; thus, no significant effect for the addition of Cl⁻ under acidic conditions was observed, while under alkaline conditions the total recovery increased, specially for Dowex XZ resin.     

Adsorption kinetics and isotherm parameters of naphthalene onto natural- and chemically modified bentonite from aqueous solutions

Polycyclic aromatic hydrocarbons (PAHs) have widely been studied and a special concern because of their mutagenic and carcinogenic activities. In this study, natural- and chemically modified-bentonite were characterized by means of N₂ adsorption method, XRD, SEM, FT-IR, elemental and thermal analysis and zeta potential techniques and their adsorption behavior were then investigated toward naphthalene, which is the first member of the PAHs. The effects of various experimental parameters such as pH, contact time and temperature on adsorption were tested in the experiments. The optimum pH values for naphthalene adsorption onto natural bentonite (NB) and hexadecyltrimethylammonium bromide modified bentonite (HB) were found to be as 4.00 and 5.97, respectively. The equilibrium contact time was 60 min for both of the adsorbent. A comparison of the linear and nonlinear method of three widely used kinetic models, which are Lagergren-first order, the pseudo-second-order and Elovich kinetics, and the most popular isotherms, which are Langmuir and Freundlich, were examined to the experimental data of the adsorption of naphthalene onto NB and HB. The kinetic results indicated that the pseudo-second-order kinetic model with high correlation coefficients was more suitable than the other kinetic models e.g. Lagergren first-order and Elovich. All results showed that the modified bentonite can be used as an adsorbent to remove PAHs from aqueous solutions by using adsorption method due to its effectiveness, simplicity and low-cost than the other conventional methods.     

Isotherm analysis of phenol adsorption on polymeric adsorbents from nonaqueous solution

Macroporous poly(methyl methacrylate-co-divinylbenzene) (PMMA), interpenetrating polymer adsorbent based on poly(styrene-co-divinylbenzene) (PS) and poly(methyl methacrylate-co-divinylbenzene) (PMMA/PS), and macroporous cross-linked poly(N-p-vinylbenzyl acetylamide) (PVBA) were prepared for the adsorption of phenol from cyclohexane. The sorption isotherms of phenol on the three polymeric adsorbents were measured and fitted to Langmuir and Freundlich isotherms. It is shown that the Langmuir isotherm, which is based on a homogeneous surface model, is unsuitable to describe the sorption of phenol on the adsorbents from nonaqueous solution and the Freundlich equation fits the tested three adsorption systems well. The isosteric enthalpy was quantitatively correlated with the fractional loading for the sorption of phenol onto the three polymeric adsorbents. The surface energetic heterogeneity patterns of the adsorbents were described with functions of isosteric enthalpy. The results showed that the tested three polymeric adsorbents exhibited different surface energetic heterogeneity patterns. The initial isosteric enthalpy of phenol sorption on polymeric adsorbent has to do with the surface chemical composition and is free from the pore structure of the polymeric adsorbent matrix. Forming hydrogen bonds between phenol molecules and adsorbent is the main driving force of phenol sorption onto PVBA and PMMA adsorbent from nonaqueous solution. When phenol is adsorbed on PMMA/PS, pi-pi interaction resulting from the stacking of the benzene rings of the adsorbed phenol molecules and the pendant benzene ring of adsorbent is involved.     

Modeling synergistic adsorption of phenol/aniline mixtures in the aqueous phase onto porous polymer adsorbents

The adsorption equilibria of phenol and aniline on nonpolar polymer adsorbents (NDA-100, XAD-4, NDA-16 and NDA-1800) were investigated in single- and binary-solute adsorption systems at 313 K. The results showed that all the adsorption isotherms of phenol and aniline on these adsorbents can be well fitted by Freundlich and Langmuir equations, and the experimental uptake of phenol and aniline in all binary-component systems is obviously higher than predicted by the extended Langmuir model, arising presumably from the synergistic effect caused by the laterally acid-base interaction between the adsorbed phenol and aniline molecules. A new model (MELM) was developed to quantitatively describe the synergistic adsorption behavior of phenol/aniline equimolar mixtures in the binary-solute systems and showed a marked improvement in correlating the binary-solute adsorption of phenol and aniline by comparison with the widely used extended Langmuir model. The newly developed model confirms that the synergistic coefficient of one adsorbate is linearly correlated with the adsorbed amount of the other, and the larger average pore size of adsorbent results in the greater synergistic effect of phenol/aniline equimolar mixtures adsorption.     

Regularities of adsorption of zinc acetate from aqueous solutions onto the surface of modified activated carbons

The dependence of the characteristics of Zn(OAc)₂/C catalysts for vinyl acetate synthesis on the solution circulation rate, on the temperature and initial concentration of zinc acetate solution, and on the procedures for modification of activated carbons with oxidants was studied with the aim to achieve uniform distribution of the supported active component (zinc acetate). Oxidation of activated carbons with hydrogen peroxide and nitric acid increases the adsorption rate and the amount of adsorbed zinc acetate. Treatment of the support with acetic acid leads to an increase in the adsorption capacity for zinc acetate, to more uniform distribution of the active component over the surface, and to enhancement of the catalyst activity. The hydrodynamic regime of stirring in the two-phase system consisting of the support and zinc acetate solution is an important factor determining the activity and stability of the zinc acetate catalyst for vinyl acetate synthesis.     

Kinetic models applied to erbium adsorption on activated charcoal from aqueous solutions

The adsorption of erbium (Er) ions on activated charcoal (AC) is investigated at temperatures 10–40 °C from aqueous solutions to understand the kinetics behavior. The intra-particle diffusion, the pseudo-first order kinetic and pseudo-second order kinetic models were used to describe the kinetic data. Results shows that the adsorption of Er ions on AC occurs in two stages and the surface adsorption and diffusion phenomena are operative in the adsorption process. The result also reveals that intra-particle diffusion is not only the main rate determining step through out the adsorption process, but the boundary layer diffusion also play significant role in rate determination. Values of the intra-particle diffusion rate constant and the extent of the boundary layer diffusion were calculated. A comparison of the kinetics models on the overall adsorption rate indicates that the Er/AC system is best described by the pseudo-second order kinetic model than the pseudo-first order model, and the overall rate of the Er ions adsorption on AC appears to be controlled by more than one step, i.e., external mass transfer and diffusion mechanism.     

Adsorption of benzethonium chloride from aqueous solutions on dispersed adsorbents

The adsorption of benzethonium chloride from aqueous solutions on the surface of finely dispersed particles of aluminum oxide, titanium dioxide, and zirconium dioxide is investigated. The ratio of the amount of adsorbed benzethonium chloride molecules to the amount of surface hydroxyl groups as potential adsorption sites is proposed to be used for characterizing the structure of adsorption layers. It is shown that the formation of supramolecular structures of benzethonium chloride molecules on solid surfaces begins when its concentrations in suspensions is significantly lower than the critical micellization concentration. It is established that benzethonium chloride is adsorbed via simultaneous interaction of the surfactant molecules with the surface hydroxyl groups and hydrophobic interaction of their hydrocarbon tails; the amounts of molecules adsorbed as a result of these interactions depend on both benzethonium chloride concentration in a solution and the density of the hydroxyl groups on an oxide surface.     

Investigation into adsorption mechanisms of sulfonamides onto porous adsorbents

The presence of sulfonamide antibiotics in aquatic environments poses potential ecological risks and dangers to human health. In this study, porous resins as adsorbents for the removal of two sulfonamides, sulfadiazine and sulfadimidine, from aqueous solutions were evaluated. Activated carbon F-400 was included as a comparative adsorbent. Despite the different surface properties and pore structures of the three resins, similar patterns of pH-dependent adsorption were observed, implying the importance of sulfonamide molecular forms to the adsorption process on the resins. Sulfonamide adsorption to the three resins exhibited different ionic strengths and temperature dependence consistent with sulfonamide speciation and the corresponding adsorption mechanism. Adsorption of sulfadiazine to F-400 was relatively insensitive to pH and ionic strength as micropore-filling mainly contributed to adsorption. The adsorption mechanism of sulfadiazine to the hypercrosslinked resin MN-200 was similar to that of the macroporous resin XAD-4 at lower pH values, whereas it was almost identical to the aminated resin MN-150 at higher pH. This work provided an understanding of adsorption behavior and mechanism of sulfonamide antibiotics on different adsorbents and should result in more effective applications of porous resin for antibiotics removal from industrial wastewater.     

Structure in aqueous solutions of nonpolar solutes from the standpoint of scaled-particle theory

Underlying assumptions have been examined in scaled-particle theory for the case of a rigid-sphere solute in liquid water. As a result, it has been possible to improve upon Pierotti's corresponding analysis in a way that explicitly incorporates measured surface tensions and radial-distribution functions for pure water. It is pointed out along the way that potential energy nonadditivity should create an orientational bias for molecules in the liquid-vapor interface that is peculiar to water. Some specific conclusions have been drawn about the solvation mode for the nonpolar rigid-sphere solute.This paper is substituted for the talk given at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.Editor's note     

Thermodynamics of Pb2+ and Ni2+ adsorption onto natural bentonite from aqueous solutions

Removal of Pb2+ and Ni2+ from aqueous solutions by sorption onto natural bentonite was investigated. Experiments were carried out as a function of particle size, the amount of bentonite, pH, concentration of metals, contact time, and temperature. The adsorption patterns of metal ions onto followed the Langmuir, Freundlich, and Dubinin-Radushkevich isotherms. This included adsorption isotherms of single-metal solutions at 303 K by batch experiments. The thermodynamic parameters (DeltaH,DeltaS,DeltaG) for Pb2+ and Ni2+ sorption onto bentonite were also determined from the temperature dependence. The adsorptions were endothermic reactions. The results suggested that natural bentonite is suitable as a sorbent material for recovery and adsorption of metal ions from aqueous solutions.     

Modeling adsorption of copper (II) onto fly ash and bentonite complex from aqueous solutions

Transportation of copper (II) ions from aqueous solutions to a fly ash and bentonite complex amorphous heterogeneous oxides (AHO: CaO-SiO(2)-Al(2)O(3)-MgO-FeO) system was studied. The particles of the fly ash and bentonite complex AHO system were highly porous and composed of platelike grains. They provide the physical basis for establishing a liquid-solid reaction model applicable to mesoporous solids. The main innovation of this model was in simplifying the powder granules to aggregates of close particles, while the particles act in accordance with the model better. The calculated curves from the models were well in line with the experimental results.     

Paraquat adsorption onto clays and organoclays from aqueous solution

Clays were compared with organoclays for the sorption of paraquat from aqueous solution. Sepiolite (S), bentonite (B), and illite (I) were used as clay samples. Organoclays were prepared by the modification of the clays with nonyl- and dodecylammonium chlorides, denoted as NS, DS, NB, DB, NI, and DI, respectively. Specific surface area and pore size distribution of the samples were determined by N2 adsorption-desorption at 77 K using the BET method. X-ray powder diffraction analysis of the samples was used to determine the effects of modifying agents on the layer structure of the clays. In the adsorption experiments, C(m) values increased from 0.038 mmol/g for DS to 0.223 mmol/g for NI. Kd0.3 values ranged from 0.177 for DS to 0.843 for NI. The adsorption data indicated that illite and NI are the most effective adsorbents among these clays and organoclay samples, respectively.     

Thermodynamics and kinetics of adsorption of Cu(II) from aqueous solutions onto multi-walled carbon nanotubes

Release of heavy metals into water as a result of industrial activities may pose a serious threat to the environment. The objective of this study is to assess the uptake of Cu²⁺ from aqueous solutions onto multi-walled carbon nanotubes (MWCNT). The potential of the t-MWCNT to remove Cu²⁺ cations from aqueous solutions was investigated in batch reactor under different experimental conditions. The processing parameters such as initial concentration of Cu²⁺ ions, temperature, and adsorbent mass were also investigated. Copper uptake was quantitatively evaluated using the Langmuir, Freundlich and Dubinin–Kaganer–Radushkevich (DKR) models. In addition, the adsorption equilibrium was described well by the Langmuir isotherm model with maximum adsorption capacity of 12.34 mg/g of Cu²⁺ cations on t-MWCNT. Various thermodynamic parameters, such as ΔG⁰, ΔH⁰ and ΔS⁰ were calculated. The thermodynamics of Cu²⁺ cations adsorption onto t-MWCNT system pointed at spontaneous and endothermic nature of the process. Using the second-order kinetic constants, the activation energy of adsorption (E_a) was determined as 27.187 kJ/mol according to the Arrhenius equation.     

Adsorption of CTAB onto perlite samples from aqueous solutions

In this study, the adsorption properties of unexpanded and expanded perlite samples in aqueous cetyltrimethylammonium bromide (CTAB) solutions were investigated as a function of ionic strength, pH, and temperature. It was found that the amount of cetyltrimethylammonium bromide adsorbed onto unexpanded perlite was greater than that onto expanded perlite. For both perlite samples, the sorption capacity increased with increasing ionic strength and pH and decreasing temperature. Experimental data were analyzed by Langmuir and Freundlich isotherms and it was found that the experimental data were correlated reasonably well by the Freundlich adsorption isotherm. Furthermore, the isotherm parameters (KF and n) were also calculated. The adsorption enthalpy was determined from experimental data at different temperatures. Results have shown that the interaction between the perlite surface and CTAB is a physical interaction, and the adsorption process is an exothermic one.