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Adsorption: Journal of the International Adsorption Society (v.13, #1)

High pressure sorption isotherms via differential pressure measurements by John M. Zielinski; Charles G. Coe; Randy J. Nickel; Anthony M. Romeo; Alan C. Cooper; Guido P. Pez (pp. 1-7).

A differential pressure adsorption unit (DPAU) has been constructed which is capable of accurately measuring isotherm data up to 2000 psia with as little as 100 mg of sample. This non-traditional adsorption/desorption method has been benchmarked by comparing hydrogen and methane isotherms measured with standard volumetric and gravimetric instruments on a NaA (4A) zeolite and an activated carbon at near ambient temperatures. The results from stability tests and well as the details of the mathematical analysis for this differential pressure method are also provided.

Keywords: Adsorption; Differential pressure; Isotherm; Isotherm measurement; Hydrogen storage; Volumetric method

Experimental investigation of liquid chromatography columns by means of computed tomography by Dirk-Uwe Astrath; Florian Lottes; Duc Thoung Vu; Wolfgang Arlt; Erling H. Stenby (pp. 9-19).

The efficiency of packed chromatographic columns was investigated experimentally by means of computed tomography (CT) techniques. The measurements were carried out by monitoring tracer fronts in situ inside the chromatographic columns. The experimental results were fitted using the equilibrium dispersive model (EDM) and varying the so called apparent axial dispersion coefficient. The additivity of the first and second central moments was exploited to estimate column efficiency in different regions of the column. The results showed that the columns under investigation offered a higher column efficiency in the centre compared to the wall region. Furthermore the void fraction in the vicinity of the walls was lower than that in the column core. For this reason the bands were conveyed faster in the central region of the column where the permeability was higher. This result is in good agreement with earlier findings.

Keywords: Chromatography; Computed tomography (CT)

Simplified gauge-cell method and its application to the study of capillary phase transition of propane in carbon nanotubes by José P. B. Mota; Isabel A. A. C. Esteves (pp. 21-32).

A modification of the gauge-cell method for Monte Carlo studies of phase equilibrium in nano-confined systems is presented and employed for studying the capillary phase transition of propane in single-walled carbon nanotubes as a function of tube diameter. It is shown that if an analytical equation of state for the vapor phase is known, the acceptance rule for the trial move of particle exchange can be modified to reference the bulk system through its chemical potential. Under these conditions, the simulation procedure is simplified and acquires many characteristics of a Monte Carlo simulation conducted in the grand canonical ensemble. It is also shown that the critical temperature can be estimated by interpolation of sub- and supercritical values of the slope of the inverse isotherm at the inflection point. To enhance the sampling of propane molecules in the hollow space of the nanotubes the configurational-bias scheme is employed. The simulation results show that the confinement of propane increases its critical density, reduces the critical temperature and narrows the binodal curve with decreasing tube diameter until the system approaches one-dimensional behavior.

Keywords: Gauge-cell method; Molecular simulation; Single-walled carbon nanotubes; Capillary phase transition; Propane adsorption

Sorption of Cu(II) and Eu(III) ions from aqueous solution by olive cake by M. Konstantinou; K. Kolokassidou; I. Pashalidis (pp. 33-40).

The sorption of Cu(II) on olive cake, a biomass by-product of olive oil production, has been investigated by potentiometry at pH 6, I=0.1 M NaClO₄, 25 °C and under atmospheric conditions. Numerical analysis of the experimental data supports the formation of surface complexes and allows the evaluation of the corresponding formation constant, which is found to amount log β=5.1±0.4. This value is close to corresponding values given in literature for Cu(II)-humate complexes, indicating that the same type of active sites (e.g. carboxylic and phenolic groups) is responsible for the Cu(II) binding by olive cake. Addition of a competing metal ion (e.g. Eu(III) ion) in the system leads to replacement of the Cu(II) by Eu(III). Evaluation of the potentiometric data obtained from competition experiments indicates on a ionexchange mechanism. The formation constant of the Eu(III) species sorbed on olive cake is found to be log β=5.4±0.9. The results of this study are of particular interest with respect to waste water treatment technologies using biomass products as adsorbent material and environmental impact assessments regarding disposal of biomass by products in the geosphere.

Keywords: Olive cake; Copper; Europium; Surface complexes; Ionexchange; Formation constants

Removal of Cu(II), Zn(II) and Co(II) ions from aqueous solutions by adsorption onto natural bentonite by Ş. Kubilay; R. Gürkan; A. Savran; T. Şahan (pp. 41-51).

In this study, the removal of Cu(II), Zn(II) and Co(II) ions from aqueous solutions using the adsorption process onto natural bentonite has been investigated as a function of initial metal concentration, pH and temperature. In order to find out the effect of temperature on adsorption, the experiments were conducted at 20, 50, 75 and 90 °C. For all the metal cations studied, the maximum adsorption was observed at 20 °C. The batch method has been employed using initial metal concentrations in solution ranging from 15 to 70 mg L⁻¹ at pH 3.0, 5.0, 7.0 and 9.0. A flame atomic absorption spectrometer was used for measuring the heavy metal concentrations before and after adsorption. The percentage adsorption and distribution coefficients (K _d) were determined for the adsorption system as a function of adsorbate concentration. In the ion exchange evaluation part of the study, it is determined that in every concentration range, adsorption ratios of bentonitic clay-heavy metal cations match to Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich (DKR) adsorption isotherm data, adding to that every cation exchange capacity of metals has been calculated. It is shown that the bentonite is sensitive to pH changes, so that the amounts of heavy metal cations adsorbed increase as pH increase in adsorbent-adsorbate system. It is evident that the adsorption phenomena depend on the surface charge density of adsorbent and hydrated ion diameter depending upon the solution pH. According to the adsorption equilibrium studies, the selectivity order can be given as Zn²⁺>Cu²⁺>Co²⁺. These results show that bentonitic clay hold great potential to remove the relevant heavy metal cations from industrial wastewater. Also, from the results of the thermodynamic analysis, standard free energy ΔG ⁰, standard enthalpy ΔH ⁰ and standard entropy ΔS ⁰ of the adsorption process were calculated.

Keywords: Adsorption; Heavy metals; Bentonite; Removal; Wastewater

Hydrogen adsorption in defected carbon nanotubes by V. Gayathri; R. Geetha (pp. 53-59).

Recently there has been lot of interest in the development of hydrogen storage in various systems for the large-scale application of fuel cells, mobiles and for automotive uses. Hectic materials research is going on throughout the world with various adsorption mechanisms to increase the storage capacity. It was observed that physisorption proves to be an effective way for this purpose. Some of the materials in this race include graphite, zeolite, carbon fibers and nanotubes. Among all these, the versatile material carbon nanotube (CNT) has a number of favorable points like porous nature, high surface area, hollowness, high stability and light weight, which facilitate the hydrogen adsorption in both outer and inner portions. In this work we have considered armchair (5,5), zig zag (10,0) and chiral tubes (8,2) and (6,4) with and without structural defects to study the physisorption of hydrogen on the surface of carbon nanotubes using DFT calculations. For two different H₂ configurations, adsorption binding energies are estimated both for defect free and defected carbon nanotubes. We could observe larger adsorption energies for the configuration in which the hydrogen molecular axis perpendicular to the hexagonal carbon ring than for parallel to C–C bond configuration corresponding to the defect free nanotubes. For defected tubes the adsorption energies are calculated for various configurations such as molecular axis perpendicular to a defect site octagon and parallel to C–C bond of octagon and another case where the axis perpendicular to hexagon in defected tube. The adsorption binding energy values are compared with defect free case. The results are discussed in detail for hydrogen storage applications.

Keywords: Carbon nanotube; Hydrogen adsorption; Defects; Chiral; Achiral

Mixed silica and alumina hosted carboxylate oxide for removal of chromium species from wastewater by E. H. Borai; S. I. El-Dessouky; H. S. Hassan (pp. 61-71).

Increasing in the use of various chromium species over the past few decades has inevitably resulted in an increased flux of their metallic substances in aquatic life. Therefore, experimental work was developed to improve the physical and chemical characteristics of the prepared mesoporous SiO₂–Al₂O₃ mixed oxides via a sol–gel process. The effective key parameter on the properties of the materials was achieved by the addition of carboxylate functional group such as Alph-hydroxyl isobuteric acid (AHIBA) during the gelation process and prior the calcinations step. Better performance of these carboxylate resins are attributed to the complexing ability of the carboxylate groups toward polyvalent chromium species which is added to the normal sorption properties of the oxides. Urea has been used as a means of producing an aluminum precipitate that is easier to filter than that produced by rapid addition of base. Introduction of Al and Si salts together to form mixed oxide modified the way of their substitution in the hosting resin than when they were separately added. The data revealed that mesoporous materials with very narrow pore diameter distribution (micron-sized) and high surface area were obtained. The surface areas and pore size distributions were mainly depend on SiO₂ content. Systematic investigations were carried out on the set of the prepared mixed oxides with different porosity, cross-linking degree and exchange loading to find out the best sorbent for chromium removal. The final objective in all cases was aimed at determining feasible and economically reliable solution to the environmental problems related to the tannery industry.

Keywords: Modified silica and alumina; Cr(III); Cr(VI); Wastewater

Two-resistance mass transfer model for the adsorption of the pesticide deltamethrin using acid treated oil shale ash by Z. Al-Qodah; A. T. Shawaqfeh; W. K. Lafi (pp. 73-82).

Adsorption characteristics of the pesticides Deltamethrin were studied in aqueous solutions using acid treated Oil Shale Ash (ATOSA) in a series of batch adsorption experiments. The maximum loading capacity of the adsorbent and the rate of adsorption were found to increase with increasing the pesticide initial concentration, mixing speed and were found to decrease with temperature and particle size. Langmuir as well as Freundlich isotherm models fit the adsorption data with R ²>0.97 in all cases. The maximum adsorption capacity for Deltamethrin was 11.4 mg/g. The two-resistance mass transfer model based on the film resistance and homogeneous solid phase diffusion was used to fit the experimental data. A computer program has been developed to estimate the theoretical concentration-time dependent curves and to compare them with the experimental curves by means of the best-fit approach. The model predicts that the external mass transfer coefficient K was affected by varying the initial pesticide concentration, the agitation speed and temperature whereas the diffusion coefficient D was affected by the initial pesticide concentration, and temperature.

Keywords: Adsorption; Pesticides; Oil shale ash adsorption isotherms; Adsorption capacity; Langmuir isotherm; Freundlich isotherm; Adsorption modeling

Adsorption kinetics of fluoride on iron(III)-zirconium(IV) hybrid oxide by Krishna Biswas; Durjoy Bandhoyapadhyay; Uday Chand Ghosh (pp. 83-94).

Fluoride occurs in some drinking water sources at levels that are hazardous to health. Tests were conducted to assess the ability of a mineral-based adsorbent to take-up fluoride ion. Consequently, in search of novel adsorbent media, crystalline and hydrous iron(III)-zirconium(IV) hybrid oxide (IZHO) was synthesized, and tested to determine its capacity and kinetics for fluoride adsorption. The Fourier Transform Infrared (FTIR) spectrum of IZHO indicated the presence of Fe–O–Zr linkage which showed hybrid nature of the synthetic oxide. The optimum pH range for fluoride adsorption was ranged between 4.0 and 7.0. The analyses of the isotherm equilibrium data using the Langmuir and the Redlich–Peterson model equations by linear and non-linear methods showed that the data fitted better with latter model than the former. Thermodynamic analysis showed spontaneous nature of fluoride adsorption, and that took place with the increase of entropy. The kinetic data obtained for fluoride adsorption on IZHO at pH 6.8 (±0.1) and room temperature (303±2 K) described both the pseudo-first order and the reversible first-order equations equally well (r ²= ∼0.98–0.99), and better than pseudo second order equation (r ²= ∼0.96–0.98) for higher concentrations (12.5 and 25.0 mg/dm³) of fluoride. The kinetics of fluoride adsorption on the mixed oxide took place with boundary layer diffusion. External mass transport with intra-particle diffusion phenomena governed the rate limiting process, which has been confirmed from the Boyd poor non-linear kinetic plots.

Keywords: Adsorption; Fluoride; Kinetics; Isotherm; Iron(III)-zirconium(IV) oxide

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Adsorption: Journal of the International Adsorption Society (v.13, #1)

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Adsorption: Journal of the International Adsorption Society (v.13, #1)