Adsorption of binary hydrocarbon mixtures in carbon slit pores: A density functional theory study

Adsorption of binary hydrocarbon mixtures involving methane in carbon slit pores is theoretically studied here from the viewpoints of separation and of the effect of impurities on methane storage. It is seen that even small amounts of ethane, propane, or butane can significantly reduce the methane capacity of carbons. Optimal pore sizes and pressures, depending on impurity concentration, are noted in the present work, suggesting that careful adsorbent and process design can lead to enhanced separation. These results are consistent with earlier literature studies for the infinite dilution limit. For methane storage applications a carbon micropore width of 11.4 Angstrom (based on distance between centers of carbon atoms on opposing walls) is found to be the most suitable from the point of view of lower impurity uptake during high-pressure adsorption and greater impurity retention during low-pressure delivery. The results also theoretically confirm unusual recently reported observations of enhanced methane adsorption in the presence of a small amount of heavier hydrocarbon impurity.

Surface diffusion and adsorption of hydrocarbons in activated carbon

Adsorption and diffusion in a porous media were studied theoretically and experimentally with a differential transient permeation method. The porous medium is allowed to equilibrate at some specified loading, and then the time trajectory of the permeation process is followed after a small difference between the pressures at the end faces of the porous medium is introduced at time t = 0 +. Such a trajectory us. time would contain adsorption and diffusion characteristics of the system. By studying this for various surface loadings, pore and surface diffusions can be fully characterized. Mathematical modeling of transient permeation is detailed for pure gases or vapors diffusion and adsorption in porous media. Effects of nonlinearity of adsorption isotherm, pressure, temperature and heat effects were considered in the model. Experimental data of diffusion and adsorption of propane, n-butane and n-hexane in activated carbon at different temperatures and loadings show the potential of this method as a useful tool to study adsorption kinetics in porous media. Validity of the model is best tested against the transient data where the kinetics curves exhibit sigmoidal shape, which is a result of the diffusion and adsorption rate during the initial stage of permeation.

Effects of the solute ionization on the adsorption of aromatic compounds from dilute aqueous solutions by activated carbon

Adsorption of four dissociating aromatic compounds and one nondissociating compound on a commercial activated carbon is investigated systematically. All adsorption experiments were carried out in pH-controlled aqueous solutions. The adsorption isotherms are fitted to the binary homogeneous Langmuir model, where the concentrations of the molecular and the ionic species in the liquid phase are expressed in terms of the sum of the two and the degree of solute ionization. Examination of the relationships between the solution pH, the degree of ionization of the solutes, and the model parameters is found to give new insights into the adsorption process. Furthermore, this is used to correlate the variation of the monolayer capacity with the solution pH.

Adsorption of mixtures containing subcritical fluids on activated carbon

A theoretical analysis of adsorption of mixtures containing subcritical adsorbates into activated carbon is presented as an extension to the theory for pure component developed earlier by Do and coworkers. In this theory, adsorption of mixtures in a pore follows a two-stage process, similar to that for pure component systems. The first stage is the layering of molecules on the surface, with the behavior of the second and higher layers resembling to that of vapor-liquid equilibrium. The second stage is the pore-filling process when the remaining pore width is small enough and the pressure is high enough to promote the pore filling with liquid mixture having the same compositions as those of the outermost molecular layer just prior to pore filling. The Kelvin equation is applied for mixtures, with the vapor pressure term being replaced by the equilibrium pressure at the compositions of the outermost layer of the liquid film. Simulations are detailed to illustrate the effects of various parameters, and the theory is tested with a number of experimental data on mixture. The predictions were very satisfactory.

Effect of pore-network connectivity on multicomponent adsorption of large molecules

The effect of pore-network connectivity on binary liquid-phase adsorption equilibria using the ideal adsorbed solution theory (LAST) was studied. The liquid-phase binary adsorption experiments used ethyl propionate, ethyl butyrate, and ethyl isovalerate as the adsorbates and commercial activated carbons Filtrasorb-400 and Norit ROW 0.8 as adsorbents. As the single-component isotherm, a modified Dubinin-Radushkevich equation was used. A comparison with experimental data shows that incorporating the connectivity of the pore network and considering percolation processes associated with different molecular sizes of the adsorptives in the mixture, as well as their different corresponding accessibility, can improve the prediction of binary adsorption equilibria using the LAST Selectivity of adsorption for the larger molecule in binary systems increases with an increase in the pore-network coordination number, as well with an increase in the mean pore width and in the spread of the pore-size distribution.

Enzymatic phosphorylation of hair keratin enhances fast adsorption of cationic moieties

The current study describes the in vitro phosphorylation of a human hair keratin, using protein kinase for the first time. Phosphorylation of keratin was demonstrated by 31P NMR (Nuclear Magnetic Resonance) and Diffuse Reflectance Infrared Fourier Transform (DRIFT) techniques. Phosphorylation induced a 2.5 fold increase of adsorption capacity in the first 10 minutes for cationic moiety like Methylene Blue (MB). Thorough description of MB adsorption process was performed by several isothermal models. Reconstructed fluorescent microscopy images depict distinct amounts of dye bound to the differently treated hair. The results of this work suggest that the enzymatic phosphorylation of keratins might have significant implications in hair shampooing and conditioning, where short application times of cationic components are of prime importance.

Adsorption of arsenic from ammonia containing waste water by ferrous hydroxide waste

Arsenic is a toxic substance. The amount of arsenic in waste water is a raising problem because of increasing mining industry. Arsenic is connected to cancers in areas where arsenic concentration in drinking water is higher than recommendations. The main object in this master’s thesis was to research how ferrous hydroxide waste material is adsorbed arsenic from ammonia containing waste water. In this master’s thesis there is two parts: theoretical and experimental part. In theoretical part harmful effects of arsenic, theory of adsorption, isotherms modeling of adsorption and analysis methods of arsenic are described. In experimental part adsorption capacity of ferrous hydroxide waste material and adsorption time with different concentrations of arsenic were studied. Waste material was modified with two modification methods. Based on experimental results the adsorption capacity of waste material was high. The problem with waste material was that at same time with arsenic adsorption sulfur was dissolving in solution. Waste material was purified from sulfur but purification methods were not efficient enough. Purification methods require more research.

Adsorption of element 112 on a Au surface

Während der letzten 20 Jahre hat sich das Periodensystem bis zu den Elementen 114 und 116 erweitert. Diese sind kernphysikalisch nachgewiesen, so dass jetzt die chemische Untersuchung an erster Selle steht. Nachdem sich das Periodensystem bis zum Element 108 so verhält, wie man es dem Periodensystem nach annimmt, wird in dieser Arbeit die Chemie des Elements 112 untersucht. Dabei geht es um die Adsorptionsenergie auf einer Gold-Ober fläche, weil dies der physikalisch/chemische Prozess ist, der bei der Analyse angewandt wird. Die Methode, die in dieser Arbeit angwandt wird, ist die relativistische Dichtefunktionalmethode. Im ersten Teil wird das Vielkörperproblem in allgemeiner Form behandelt, und im zweiten die grundlegenden Eigenschaften und Formulierungen der Dichtefunktionaltheorie. Die Arbeit beschreibt zwei prinzipiell unterschiedliche Ansätze, wie die Adsorptionsenergie berechnet werden kann. Zum einen ist es die sogenannte Clustermethode, bei der ein Atom auf ein relativ kleines Cluster aufgebracht und dessen Adsorptionsenergie berechnet wird. Wenn es gelingt, die Konvergenz mit der Größe des Clusters zu erreichen, sollte dies zu einem Wert für die Adsorptionsenergie führen. Leider zeigt sich in den Rechnungen, dass aufgrund des zeitlichen Aufwandes die Konvergenz für die Clusterrechnungen nicht erreicht wird. Es werden sehr ausführlich die drei verschiedenen Adsorptionsplätze, die Top-, die Brücken- und die Muldenposition, berechnet. Sehr viel mehr Erfolg erzielt man mit der Einbettungsmethode, bei der ein kleiner Cluster von vielen weiteren Atomen an den Positionen, die sie im Festkörpers auf die Adsorptionsenergie soweit sichergestellt ist, dass physikalisch-chemisch gute Ergebnisse erzielt werden. Alle hier gennanten Rechnungen sowohl mit der Cluster- wie mit der Einbettungsmethode verlangen sehr, sehr lange Rechenzeiten, die, wie oben bereits erwähnt, nicht zu einer Konvergenz für die Clusterrechnungen ausreichten. In der Arbeit wird bei allen Rechnungen sehr detailliert auf die Abhängigkeit von den möglichen Basissätzen eingegangen, die ebenfalls in entscheidender Weise zur Länge und Qualität der Rechnungen beitragen. Die auskonvergierten Rechnungen werden in der Form von Potentialkurven, Density of States (DOS), Overlap Populations sowie Partial Crystal Overlap Populations analysiert. Im Ergebnis zeigt sich, dass die Adsoptionsenergie für das Element 112 auf einer Goldoberfläche ca. 0.2 eV niedriger ist als die Adsorption von Quecksilber auf der gleichen Ober fläche. Mit diesem Ergebnis haben die experimentellen Kernchemiker einen Wert an der Hand, mit dem sie eine Anhaltspunkt haben, wo sie bei den Messungen die wenigen zu erwartenden Ereignisse finden können.

Driving forces for the adsorption of cyclopentene on InP(001)

In this work the interaction of cyclopentene with a set of InP(001) surfaces is investigated by means of the density functional theory. We propose a simple approach for evaluating the surface strain and based on it we have found a linear relation between bond and strain energies and the adsorption energy. Our results also indicate that the higher the bond energy, the more disperse the charge distribution is around the adsorption site associated to the high occupied state, a key feature that characterizes the adsorption process. Different adsorption coverages are used to evaluate the proposed equation. Our results suggest that the proposed approach might be extended to other systems where the interaction of the semiconductor surface and the molecule is restricted to first neighbor sites. (C) 2011 Elsevier B.V. All rights reserved.

Degradation and adsorption of AZO RR239 dye in aqueous solution by nanoscale zerovalent iron particles immobilized on sawdust

Carra sawdust pretrated with formaldehyde was used to adsorb RR239 (reactive azo dye) at varying pH and zerovalent iron (ZVI) dosage. Modeling of kinetic results shows that sorption process is best described by the pseudo-second-order model. Batch experiments suggest that the decolorization efficiency was strongly enhanced with the presence of ZVI and low solution pH. The kinetics of dye sorption by mixed sorbent (5 g of sawdust and 180 mg of ZVI) at pH 2.0 was rapid, reaching more than 90% of the total discoloration in three minutes.

Adsorption of chromium(VI) by titanium(IV) oxide coated on a silica gel surface

Titanium(IV) oxide, coated on the surface of silica gel (surface area, 308 m2 g-1; amount of Ti(IV) per gram of modified silica gel, 1.8 x 10(-3) mol), was used to adsorb CrO4(2-) ions from acidic solutions. The exchange capacity increased at lower pH values and was affected to some extent by the acid used. The material was used to preconcentrate Cr(VI) from 0.5 ppm solutions of chromate very efficiently and virtually 100% recovery was achieved in every instance.

Adsorption of silanes bearing nitrogenated Lewis bases on SiO 2/Si (100) model surfaces

The present paper describes the one-pot procedure for the formation of self-assembled thin films of two silanes on the model oxidized silicon wafer, SiO2/Si. SiO2/Si is a model system for other surfaces, such as glass, quartz, aerosol, and silica gel. MALDI-TOF MS with and without a matrix, XPS, and AFM have confirmed the formation of self-assembled thin films of both 3-imidazolylpropyltrimethoxysilane (3-IPTS) and 4-(N- propyltriethoxysilane-imino)pyridine (4-PTSIP) on the SiO2/Si surface after 30 min. Longer adsorption times lead to the deposition of nonreacted 3-IPTS precursors and the formation of agglomerates on the 3-IPTS monolayer. The formation of 4-PTSIP self-assembled layers on SiO2/Si is also demonstrated. The present results for the flat SiO2/Si surface can lead to a better understanding of the formation of a stationary phase for affinity chromatography as well as transition-metal-supported catalysts on silica and their relationship with surface roughness and ordering. The 3-IPTS and 4-PTSIP modified SiO2/Si wafers can also be envisaged as possible built-on-silicon thin-layer chromatography (TLC) extraction devices for metal determination or N-heterocycle analytes, such as histidine and histamine, with on-spot MALDI-TOF MS detection. © 2005 Elsevier Inc. All rights reserved.

Adsorption of dihydrogen phosphate ion on platinum electrodes in aqueous media monitored by probe-beam deflection

Probe-beam deflection (PBD) was used to monitor concentration gradients of anions adjacent to the surface of a platinum electrode in acidic aqueous media containing H3PO4. PBD can measure the potential-dependent extent of adsorption of H2PO4- on the Pt electrode surface and permits the Langmuir isotherm to be fitted to the experimental data. The value thus obtained for the surface concentration was 1.3 × 10-11 mol mm -2, or 1.7 atoms of Pt per H2PO4-. Also, the electron transfer number obtained was 0.24, signifying an incomplete transfer of charge, and the equilibrium constant is 1.80 suggesting a reversible adsorption process. © 2005 Elsevier B.V. All rights reserved.

Adsorption of heavy metal ions and epoxidation catalysis using a new polyhedral oligomeric silsesquioxane

The objective of this research was the preparation of a silsesquioxane functionalized with eight chloropropyl chains (T8-PrCl) and of a new derivative functionalized with a pendant linear chain (2-amino-1,3,4-thiadiazole - ATD; T8-Pr-ATD). The two nanostructured materials were characterized by 13C and 29Si NMR, FTIR and elemental analysis. The new nanostructured material, octakis[3-(2-amino-1,3,4-thiadiazole)propyl] octasilsesquioxane (T8-Pr-ATD), was tested as a ligand for transition-metal ions with a special attention to adsorption isotherms. The adsorption was performed using a batchwise process and the organofunctionalized surface showed the ability to adsorb the metal ions Cu (II), Co (II), and Ni (II) from water and ethanol. The adsorption isotherms were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) model. The kinetics of adsorption of metals were performed using three models such as pseudo-first order, pseudo-second order and Elovich. The Langmuir and Elovich models were the most appropriate to describe the adsorption and kinetic data, respectively. Furthermore, the T8-Pr-ATD was successfully applied to the analysis of environmental samples (river and sea water). Subsequently, a new nanomaterial was prepared by functionalization of the T8-Pr-ATD with a Mo (II) organometallic complex (T8-Pr-ATD-Mo). Only a few works in the literature have reported this type of substitution, and none dealt with ATD and Mo (II) complexes. The new Mo-silsesquioxane organometallic nanomaterial was tested as precursor in the epoxidation of cyclooctene and styrene. © 2012 Elsevier B.V.

Macauba palm (acrocomia aculeata) cake from biodiesel processing: an efficient and low cost substrate for the adsorption of dyes

The potential of natural and heat-treated Macauba palm cake as adsorbent for the removal of Methylene Blue (MB) and Congo Red (CR) from solution has been investigated. Equilibrium adsorption was attained in <7 h and the process was favored at pH 5.0 for MB and pH 6.5 for CR with an adsorbent (g):adsorbate (mL) ratio of 1:200 and an initial concentration of adsorbate of 25 mg L−1. The maximum adsorption capacities of the natural and heat-treated materials were, respectively, 25.80 and 32.30 mg g−1 for MB, and 32.00 and 20.30 mg g−1 for CR. The isotherm model proposed by Sips represented most adequately the adsorption of MB and CR. The adsorptions of the dyes were best described in terms of a pseudo second-order reaction. Thermodynamic parameters such as ΔHo, ΔSo and ΔGo were calculated. The adsorption process was found to be endothermic and spontaneous. Macauba palm cake is adequate for the removal of waste dye from industrial effluents by virtue of its abundance, low cost and efficiency of adsorption.