An alternative Avrami equation to evaluate kinetic parameters of the interaction of Hg(II) with thin chitosan membranes

In this work, thin chitosan membranes were utilized as an adsorbent for the removal of Hg(II) from aqueous solutions. A rise of temperature accelerates the mass transfer of Hg(II) to the membranes, surfaces. The kinetic data did not present a good fitting to the traditional Lagergren adsorption kinetic equations. An alternative Avrami kinetic equation was employed and successfully fitted to the kinetic adsorption quantities. From this new equation, two regions presenting distinct kinectic parameters were found, and the use of the parameter n was also relationed to the determination of the kinetic order. Variations of the adsorption kinetic rate in relation to the time, the initial Hg(II) concentration, and the temperature were also calculated and are discussed.     

Multistep adsorption of anionic dyes on silica/chitosan hybrid. 1. Comparative kinetic data from liquid- and solid-phase models

In this work, a hybrid silica/chitosan was synthesized and characterized by nitrogen elemental analysis and thermal analysis (TG, DTG, DTA, and DSC) and BET surface area. The hybrid was used in adsorption studies of two anionic dyes from aqueous solutions. A rise of temperature accelerates mass transfer of dyes into the hybrid. However, the maximum adsorption capacities reach similar values from 25 to 55 degrees C. The kinetic data were first evaluated in relation to the decrease of the time-related residual concentration of the dyes in solution, where the second-order model has presented the best fitting. The solid-phase interaction of dye data presents a rough fitting to the traditional first-order Lagergren kinetic model. However, a modified Avrami kinetic equation was successfully fitted to the kinetic quantities, where from five to seven kinetic regions were found. A pore-diffusion model has also demonstrated that the diffusion is the rate-controlling interaction mechanism. However, the experimental-calculated comparative values are the best way to evaluate a specific aqueous- or solid-phase kinetic model.     

Determination of kinetic parameters of Cu(II) interaction with chemically modified thin chitosan membranes

In this work, vanillin-modified thin chitosan membranes were utilized as adsorbents for the removal of Cu(II) from aqueous solutions. A rise of temperature accelerates mass transfer of Cu(II) to the membranes surfaces. The kinetic data did present a rough fit to the traditional Lagergren adsorption kinetic equations. An alternative Avrami kinetic equation was successfully fitted to the kinetic adsorption quantities. From this new equation, from one to three regions presenting distinct kinetic parameters were found, and the use of the parameter n was also related to the determination of the kinetic orders. Variations of the adsorption rate in relation to the contact time and the temperature were also calculated and are discussed.     

Thermodynamic assessment of Hg(II)-gibbsite interactions

As discrete particles and/or as surface coatings on other minerals in natural systems, aluminum hydroxides are efficient sinks for Hg(II). The Hg(II) adsorption on gibbsite was determined as a function of temperature (T), pH, and the type of background electrolytes, i.e., NaNO(3), NaClO(4), and NaCl. When the equilibration time t(E) approximately 2 h, the Hg(II) retention on gibbsite was found to be a reversible process, which was ascribed to adsorption. The Hg(II) adsorption capacity, i.e., Gamma(Hg(II)), varied with the type of electrolyte used in accordance with the following order: Gamma(NO(3))(Hg(II)) > or = Gamma(ClO(4))(Hg(II)) > or = Gamma(Cl)(Hg(II)). In all cases, the estimated thermodynamic parameters showed that the Hg(II) adsorption on gibbsite was endothermic and spontaneous. The Hg(II) adsorption data were quantified with the Langmuir or Hill, and Dublin-Radushkevick (DR), isotherms at all temperatures and acidity levels examined. Always, the Hg(II) adsorption data were in compliance with the DR model. However, the Hg(II) adsorption in NaNO(3) or NaClO(4) was interpreted in terms of the Langmuir model. When NaCl was used as electrolyte, the Hg(II) adsorption was modeled well with the Hill equation. The mean free energy values calculated from DR plots concluded that Hg(II)-gibbsite interactions are a result of chemical bonding.     

Kinetics of adsorption and proteolytic cleavage of a multilayer ovalbumin film by subtilisin Carlsberg

Adsorption and proteolytic activity of the enzyme subtilisin Carlsberg have been studied on an immobilized, multilayer ovalbumin film. The cross-linked multilayer substrate permits protease adsorption to be examined unencumbered by the surface inhomogeneity typically observed in monolayer studies of protease surface kinetics. Decline of the protein film was measured over time using ellipsometry. Resulting kinetic data as a function of aqueous enzyme concentration and temperature were well fit by a Langmuir-Michaelis-Menten model for surface proteolysis. We observed that both the protein degradation kinetics and the in situ adsorption data were well described by the proposed model. The temperature dependence of the kinetic rate parameter yielded an activation energy of 12 kcal/mol. Further, the apparent Langmuir adsorption equilibrium constant of the enzyme at the protein/aqueous interface was 0.11 L/mg at 22 degrees C, 0.034 L/mg at 36 degrees C, and 0.011 L/mg at 50 degrees C. Although enzyme adsorption at a given aqueous enzyme concentration decreased at higher temperature, the enzyme cleaved the substrate more rapidly, leading to a net increase in the ovalbumin film degradation rate. We observed that the maximum enzyme coverage on the immobilized protein surface was approximately 40% of a close-packed monolayer at ambient temperature (22 degrees C).     

Adsorption of aqueous Hg (II) by a novel poly(aniline‐co‐o‐aminophenol)/mesoporous silica SBA‐15 composite

A novel poly(aniline‐co‐o‐aminophenol) (PAOA)/mesoporous silica SBA‐15 nanocomposite was synthesized and investigated for adsorption of Hg (II) from aqueous solutions of wide pH range. A chemical oxidation method was employed for polymerization of aniline and o‐aminophenol on an ordered SBA‐15 template to obtain a significantly enlarged BET surface area of the adsorbent. Efficiency study revealed that the PAOA/SBA‐15 could reach a maximum Hg (II) adsorption capacity of over 400 mg/g. Kinetic study showed that the Hg (II) adsorption by the PAOA/SBA‐15 fitted a pseudo‐second‐order kinetic model, indicating that the mercury adsorption process was predominantly controlled by chemical process. The results of this study also proved that the adsorbed Hg (II) could be effectively desorbed from the PAOA/SBA‐15 in 0.1M HCl and 5% sulfocarbonide solutions. Associated adsorption mechanism was also investigated by means of Fourier transform infrared (FTIR) and X‐ray photoelectron spectroscopy (XPS) techniques. Copyright © 2010 John Wiley & Sons, Ltd.     

The Influence of Temperature on the Adsorption of Cadmium(II) and Cobalt(II) on Goethite

The adsorption of Cd(II) and Co(II) onto goethite was measured at five temperatures between 10 and 70 degrees C. For both cations the amount adsorbed at any given pH increased as the temperature was increased. Cd(II) adsorbed at a slightly lower pH at each temperature than Co(II). Adsorption isotherms at pH 7.00 for Cd(II) could be fitted closely by a simple Langmuir model, but a two-site Langmuir model was needed for Co(II). Potentiometric titrations of goethite suspensions in the presence and absence of added cation could be modeled closely by a constant-capacitance surface complexation model that assumed the adsorption reactions M2+ + SOH ⇋ SOM+ + H+ and M2+ + SOH + H2O ⇋ SOMOH + 2H+, where M represents Cd or Co. This model also fitted the experimental data from the adsorption edge and adsorption isotherm experiments. Thermodynamic parameters estimated from both Langmuir and surface complexation models showed that the adsorption of both metals was endothermic. Values obtained for the adsorption enthalpies from both modeling schemes were similar for both cations. Estimates of the adsorption entropies were model-dependent: Langmuir parameters yielded positive entropies, while some of the surface complexation parameters generated negative adsorption entropies. Copyright 1999 Academic Press.     

Adsorption of atrazine on soils: model study

The adsorption of the widely used herbicide atrazine onto three model inorganic soil components (silica gel, gamma-alumina, and calcite (CaCO(3)) was investigated in a series of batch experiments in which the aqueous phase equilibrated with the solid, under different solution conditions. Atrazine did not show discernible adsorption on gamma-alumina (theta=25 degrees C, 3.8相似文献   

Adsorption of Pb(II) and Ni(II) From Aqueous Solution by a High-Capacity Industrial Sewage Sludge-Based Adsorbent

In the present study, adsorption of Ni(II) and Pb(II) from aqueous solution was investigated using activated carbon synthesized with industrial wastewater sludge. The synthesized adsorbent was analyzed using nitrogen adsorption–desorption and Fourier transfer infrared (FTIR) techniques. Batch adsorption mode was used to evaluate the effect of solution pH, contact time, adsorbent dose, initial metal ion concentration, and temperature on the adsorption capacity of the synthesized adsorbent. The kinetic data were analyzed using different kinetic models. The pseudo-second-order equation gave the best fit to the experimental data for both metal ions. The equilibrium isotherm data were analyzed using the Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) isotherm models. The results showed that the data obtained for the Ni(II) and Pb(II) adsorption are in good agreement with the Langmuir model. The Langmuir mono-layer maximum adsorption capacities for Ni(II) and Pb(II) ions were estimated to be 74.06 and 88.76 mg g^?1 at 25°C, respectively. In addition, the thermodynamic studies proved that the adsorption process of both metals could be considered endothermic.     

Single, binary and multi-component adsorption of copper and cadmium from aqueous solutions on Kraft lignin--a biosorbent

A new biosorbent for removing toxic metal ions from water/industrial wastewater has been investigated using by-product lignin from paper production. Lignin was extracted from black liquor waste, characterized and utilized for the removal of copper and cadmium from aqueous solutions in single, binary and multi-component systems. Adsorption studies were conducted at different temperatures, lignin particle sizes, pHs and solid to liquid ratios. All the studies were conducted by a batch method to determine equilibrium and kinetic parameters. The Langmuir and Freundlich isotherm models were applied. The Langmuir model fits best the equilibrium isotherm data. The maximum lignin adsorption capacities at 25 degrees C were 87.05 mg/g (1.37 mmol/g) and 137.14 mg/g (1.22 mmol/g) for Cu(II) and Cd(II), respectively. Adsorption of Cu2+ (68.63 mg/g at 10 degrees C and 94.68 mg/g at 40 degrees C) and Cd2+ (59.58 mg/g at 10 degrees C and 175.36 mg/g at 40 degrees C) increased with an increase in temperature. Copper and cadmium adsorption followed pseudo-second order rate kinetics. From kinetic studies, various rate and thermodynamic parameters such as effective diffusion coefficients, activation energy, and activation entropy were evaluated. Adsorption occurs through a particle diffusion mechanism at temperatures 10 and 25 degrees C while at 40 degrees C it occurs through a film diffusion mechanism. The sorption capacity of black liquor lignin is higher than many other adsorbents/carbons/biosorbents utilized for the removal of Cu(II) and Cd(II) from water/wastewater in single and multi-component systems.     

Equilibrium,kinetic and thermodynamic biosorption studies of Hg(II) on red algal biomass of Porphyridium cruentum

Among a variety of microbial materials employed for biosorption, algae have added advantages of non-toxic and autotrophic nature. In this study, biosorption of Hg(II) was studied with red algal biomass of Porphyridium cruentum. The parameters affecting biosorption such as dosage of biosorbent, pH, contact time, initial metal concentration, temperature and effect of foreign metal cations in binary system were evaluated. Kinetic data were described with the help of pseudo-first-order and pseudo-second-order kinetic models. Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models were applied to adsorption equilibrium data. According to the results, the maximum removal capacity (q_max) was 2.62?mg/g observed at pH 7 with 0.25?g/L of biosorbent dosage for Hg(II) solution containing 10?mg/L of metal ions. The Langmuir isotherm model fits best to the adsorption data while the kinetic data followed the pseudo-second-order model. Thermodynamics studies showed that the biosorption process of Hg(II) on P. cruentum was exothermic in nature.     

Adsorption of an endoglucanase from the hyperthermophilic Pyrococcus furiosus on hydrophobic (polystyrene) and hydrophilic (silica) surfaces increases protein heat stability

The interaction of an endoglucanase from the hyperthermophilic microorganism Pyrococcus furiosus with two types of surfaces, that is, hydrophobic polystyrene and hydrophilic silica, was investigated, and the adsorption isotherms were determined. The adsorbed hyperthermostable enzyme did not undergo loss of biological activity. A model was proposed for the mechanism of interaction of the enzyme with the surface based on the shape of the adsorption isotherm, the morphological characteristics of the enzyme, and the thermodynamic parameters of the system. The enzyme was irreversibly immobilized at the solid/liquid interface even at high temperatures, and most interestingly, it acquired further heat stabilization upon adsorption. The denaturation temperature increased from 108 degrees C in solution to 116 degrees C upon adsorption on hydrophilic silica particles. Adsorption on the hydrophobic polystyrene surface even shifted the denaturation temperature to 135 degrees C, the most extreme experimentally determined protein denaturation temperature ever reported. Maintenance of the biological function particularly at high temperatures is important for the development of solid substrate immobilized enzymes for applications in biocatalysis and biotechnology. This also presents an additional stabilization mechanism employed by nature where the extracellular hyperthermostable enzyme remains folded and active at the extreme temperatures of its natural environment by adsorption on the surface of rocks and other materials appearing in the surroundings of the microorganism.     

Selective Adsorption of Co(Ⅱ)by Mesoporous Silica SBA-15-Supported Surface Ion Imprinted Polymer:Kinetics,Isotherms,and Thermodynamics Studies

A novel surface ion imprinted adsorbent [Co(II)‐IIP] using polyethyleneimine (PEI) as function monomer and ordered mesoporous silica SBA‐15 as support matrix was prepared for Co(II) analysis with high selectivity. The prepared polymer was characterized by Fourier transmission infrared spectrometry, scanning electron microscopy, X‐ray diffraction and nitrogen adsorption‐desorption isotherm. Bath experiments of Co(II) adsorption onto Co(II)‐IIP were performed under the optimum conditions. The experimental data were analyzed by pseudo‐first‐order and pseudo‐second‐order kinetic models. It was found that the pseudo‐second‐order model best correlated the kinetic data. The intraparticle diffusion and liquid film diffusion were applied to discuss the adsorption mechanism. The results showed that Co(II) adsorption onto IIP was controlled by the intraparticle diffusion mechanism, along with a considerable film diffusion contribution. Langmuir, Freundlich and Dubinin‐Radushke‐ vich adsorption models were applied to determine the isotherm parameters. Langmuir model fitted the experiment data well and the maximum calculated capacity of Co(II) reached 39.26 mg/g under room temperature. The thermodynamic data were indicative of the spontaneousness of the endothermic sorption process of Co(II) onto Co(II)‐IIP. Co(II)‐IIP showed high affinity and selectivity for template ion compared with non imprinted polymer (NIP).     

Modification of silica nanoparticles with 1-hydroxy-2-acetonaphthone as a novel composite for the efficient removal of Ni(II), Cu(II), Zn(II), and Hg(II) ions from aqueous media

In this paper, a novel composite based on the formation of Schiff base on silica nanoparticles was facilely synthesized. Firstly, silica nanoparticles, which contain silanol groups (Si-OH), were modified with (3-aminopropyl)trimethoxysilane. Then, the modified silica reacted with 1-hydroxy-2-acetonaphthone to form a novel Schiff base/silica composite. The synthesized composite was characterized using several tools such as XRD, FT-IR, FE-SEM, N₂ adsorption/desorption analyzer, and CHN analyzer. The considerable reduction at 2θ = 21.9° in the intensity of the XRD peak of the composite is owing to the formation of the Schiff base. Also, the observed FT-IR bands in the composite at 3440 and 1604 cm^?1 are owing to the stretching and bending vibrations of OH and/or CN, respectively. The FE-SEM images confirmed that the silica includes irregular shapes whereas the composite possesses a flaky surface owing to the formation of the Schiff base. Elemental analysis of the composite demonstrated that the % C, % H, and % N are 15.26, 3.24, and 1.65 %, respectively. The BET surface area and total pore volume of the composite were reduced because the formed Schiff base blocks the pores of silica. The synthesized composite was employed for the efficient removal of Ni(II), Cu(II), Zn(II), and Hg(II) ions from aqueous media. The maximum uptake capacity of the composite toward Cu(II), Hg(II), Zn(II), and Ni(II) ions is 68.630, 50.942, 45.126, and 40.420 mg/g, respectively. The adsorption processes of the studied metal ions were spontaneous, chemical, and well described using the pseudo-second-order kinetic model and Langmuir equilibrium isotherm. The synthesized composite can be successfully regenerated and utilized various times in the removal of studied metal ions from aqueous media.     

Bioconversion of cellulose into ethanol by nonisothermal simultaneous saccharification and fermentation

The kinetic characteristics of cellulase and beta-glucosidase during hydrolysis were determined. The kinetic parameters were found to reproduce experimental data satisfactorily and could be used in a simultaneous saccharification and fermentation (SSF) system by coupling with a fermentation model. The effects of temperature on yeast growth and ethanol production were investigated in batch cultures. In the range of 35-45 degrees C, using a mathematical model and a computer simulation package, the kinetic parameters at each temperature were estimated. The appropriate forms of the model equation for the SSF considering the effects of temperature were developed, and the temperature profile for maximizing the ethanol production was also obtained. Briefly, the optimum temperature profile began at a low temperature of 35 degrees C, which allows the propagation of cells. Up to 10 h, the operating temperature increased rapidly to 39 degrees C, and then decreased slowly to 36 degrees C. In this nonisothermal SSF system with the above temperature profile, a maximum ethanol production of 14.87 g/L was obtained.     

Adsorption of phenylacetylene on Si(100)-2 x 1: kinetics and structure of the adlayer

Direct adsorption of phenylacetylene on clean silicon surface Si(100)-2 x 1 is studied in ultrahigh vacuum (UHV). The combination of scanning tunnel microscopy (STM) and surface differential reflectance spectroscopy (SDRS) with Monte Carlo calculations are put together to draw a realistic kinetic model of the evolution of the surface coverage as a function of the molecular exposure. STM images of weakly covered surfaces provide evidence of two very distinct adsorption geometries for phenylacetylene, with slightly different initial sticking probabilities. One configuration is detected with STM as a bright spot that occupies two dangling bonds of a single dimer, whereas the other configuration occupies three dangling bonds of adjacent dimers. These data are used to implement a Monte Carlo model which further serves to design an accurate kinetic model. The resulting evolution toward saturation is compared to the optical data from surface differential reflectance spectroscopy (SDRS). SDRS is an in situ technique that monitors the exact proportion of affected adsorption sites and therefore gives access to the surface coverage which is evaluated at 0.65. We investigate the effect of surface temperature on this adsorption mechanism and show that it has no major effect either on kinetics or on structure, unless it passes the threshold of dissociation measured at ca. 200 degrees C. This offers a comprehensive image of the whole adsorption process of phenylacetylene from initial up to complete saturation.     

Copper (II) adsorption from aqueous solution by herbaceous peat

In this research, the herbaceous peat collected from Gavurgolu peatlands, one of the biggest Turkish peatlands, was utilized as an adsorbent for the removal of copper (II) ions from aqueous solution. Adsorption experiments were conducted under various conditions, i.e., initial concentration, temperature, and pH. While the amount of Cu (II) adsorbed on the peat increased with increasing concentration of Cu (II) ions, it was not markedly affected by temperature and pH. Percentage removal was higher at lower concentration. For example, the maximum percentage removal of Cu (II) ions for initial concentration of 3 x 10(-4) M was 97.04% at 21 degrees C and pH 5.5. The adsorption capacity (Q(0)) of the peat was 4.84 mgg(-1) from Langmuir adsorption isotherm for the concentration range of 3 x 10(-4)-6 x 10(-4) M at 21 degrees C and pH 5.5. The equilibrium time of adsorption of Cu (II) ions was 150 min and independent of concentration and temperature. The amount of Cu (II) adsorbed at equilibrium time did not considerably change with temperature and pH. It was also determined that adsorption isotherm followed both Freundlich and Langmuir. Uptake mechanism of Cu (II) ions by the peat occurs via cation exchange (especially by means of Ca(2+) and Mg(2+)) as well as copper/peat complexation. Adsorption kinetic was consistent with the pseudo-second-order model.     

Effective adsorption of Hg(II) ions by new ethylene imine polymer/β-cyclodextrin crosslinked functionalized magnetic composite

A new effective magnetic composite material was prepared successfully for adsorption Hg(II) ions by introducing β-cyclodextrin/ethylene imine polymer to the mesoporous silica. The morphology and structure of EIP-β-CD magnetic adsorbents were characterized by FT-IR, XR, DTG, XPS and SEM technologies. The effect of many factors were discussed detailedly such as adsorption time, initial concentration, pH, different composition of adsorbent and adsorption temperature. It was found that EIP-β-CD showed excellent adsorption capacity, high selectivity, good reutilization and fast adsorption rate. The maximum adsorption capacity was 248.72 mg/g and the best removal rate was 99.49 % under the optimized experimental conditions. The kinetic and thermodynamic study showed typical characteristic of chemical adsorption, exothermic and spontaneous. The best mass proportion of β-cyclodextrin, ethylene imine polymer and glutaraldehyde was 1.0:0.4:0.2, and proper β-cyclodextrin can develop the adsorption capacity for Hg(II) ions in this adsorbent. The possible adsorption mechanism was investigated in detail. After the fifth cycle experiment, this new adsorbent still showed excellent adsorption capacity which indicated that it has great potential for Hg(II) ions cleanup in water solution.     

Adsorption of Acid Blue 193 from aqueous solutions onto Na-bentonite and DTMA-bentonite

Dodecyltrimethylammonium bromide-modified bentonite (DTMA-bentonite) was prepared and tested as an adsorbent for an acid dye (Acid Blue 193, AB193) removal from aqueous solution in comparison with Na-bentonite. The effect of various experimental parameters was investigated using a batch adsorption technique. In this manner, the adsorption isotherms, adsorption kinetics, and temperature and pH effects upon Acid Blue 193 adsorption on Na-bentonite and DTMA-bentonite were thoroughly examined. Results show that a pH value of 1.5 is favorable for the adsorption of Acid Blue 193. The isothermal data could be well described by the Freundlich equation. The dynamical data fit well with the pseudo-second-order kinetic model. The adsorption capacity of DTMA-bentonite (740.5 mg g(-1)) was found to be around 11 times higher than that of Na-bentonite (67.1 mg g(-1)) at 20 degrees C. Thermodynamic parameters such as activation energy (E(a)) and change in the free energy (DeltaG(0)), the enthalpy (DeltaH(0)), and the entropy (DeltaS(0)) were also evaluated. The overall adsorption process was exothermic but it is only spontaneous at 20 degrees C. The results indicate that Na-bentonite and DTMA-bentonite could be employed as low-cost alternatives to activated carbon in wastewater treatment for the removal of color which comes from textile dyes.