Search PubMed⌕ Search

SEARCH · Search PubMed

Results for “ADSORPTION”

Search indexed PubMed citations on genomics, clinical trials, systematic reviews and public health. Explore titles, authors and supplied subject terms, then open the PubMed record.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6Linked to original sources
PubMed1997

Considerations about the Adsorption of Organic Molecules from the Gas Phase to Surfaces: Implications for Inverse Gas Chromatography and the Prediction of Adsorption Coefficients

Whether surfaces are characterized from experimental gas-phase adsorption coefficients of probe molecules with known properties (as is done in inverse gas chromatography (IGC)) or whether adsorption coefficients are to be predicted from known properties of the adsorbate and the adsorbent (as is desirable in environmental chemistry) in both cases a correct quantitative description of the van der Waals and acid-base interactions of organic molecules at surfaces is necessary. The model used to date in IGC for the van der Waals interactions tacitly assumes that the interactions of a dilute gas with a surface can be treated like the interactions between two condensed phases. This only works if the contact area of the adsorbed molecule is treated as an adjusted parameter which makes up for the occurring discrepancies. In this paper an improved equation for the van der Waals interactions will be suggested which works without adjusted parameters. For describing acid-base interactions of dilute gases at surfaces Gutmann's donor and acceptor numbers have found wide use in the IGC literature. However, these parameters are related to the heats of the acid-base interactions rather than the free energies. Thus this approach has the disadvantage of putting the acid-base characterization of surfaces in IGC on a different basis than the van der Waals characterization, and it also does not allow the prediction of gas-phase adsorption coefficients. Here, a different approach will be discussed that was originally introduced by van Oss and coworkers for the acid-base interactions between condensed phases (1). This approach uses acceptor and donor parameters that are free energy related. Validation with experimental data from the literature shows a good performance of the equations introduced in this paper for IGC purposes as well as for the prediction of gas-phase adsorption coefficients.

Journal Article↗
PubMed1997

Enthalpy of Adsorption and Isotherms for Adsorption of Naphthenic Acid onto Clays

The enthalpies of adsorption and the isotherms for adsorption of naphthenic acid onto Na-montmorillonite, Na-kaolinite, and Na-illite were studied by means of calorimetry and the static method at 298.15 K. The results show that the enthalpies of adsorption and saturated adsorption amounts of naphthenic acid on different clays change in the order Na-montmorillonite > Na-illite > Na-kaolinite. The interaction between naphthenic acid and clays is discussed.

Journal Article↗
PubMed1999

Adsorption of a Cationic Surfactant on Na-Montmorillonite: Inspection of Adsorption Layer by X-Ray and Fluorescence Spectroscopies.

The adsorption of the cationic surfactant BDDAC on a hydrophilic smectite (montmorillonite) surface has been investigated, especially in the range of low coverage ratios where surfactant ions are adsorbed through cation-exchange with the counterions of the clay. The surfactant coions (Cl(-)) were found to be adsorbed simultaneously with the cationic part after a complete alkyl ammonium ion-exchange of montmorillonite (CEC). We observe that organoclay particles remain flocculated in aqueous medium in almost all the range of adsorption isotherms up to 1.38 CEC and afterward redisperse incompletely. The intercalation of surfactant in the interlamellar space was followed by X-ray measurements. Fluorescence spectroscopy was used to obtain information about the adsorption layer at the interface. A calculation from geometrical considerations and from adsorption isotherms shows that below 1.38 CEC, there is a flat double layer in the interlamellar space and after this amount of adsorbed surfactant, an interstratified clay-surfactant mixed system is formed. Copyright 1999 Academic Press.

Journal Article↗
PubMed2004

EXAFS studies on adsorption-desorption reversibility at manganese oxide-water interfaces. II. Reversible adsorption of zinc on delta-MnO2.

Microscopic structures of Zn(II) adsorbed at delta-MnO(2)-water interfaces were studied using extended X-ray absorption fine structure (EXAFS) spectroscopy. In a 0.1 M NaNO(3) solution of pH 5.50, hydrous Zn(II) was adsorbed onto the solid surface in the form of octahedral coordination. Adsorbed octahedral Zn(II) was located above and below the vacancy sites of delta-MnO(2). Each Zn was coordinated on one side to H(2)O molecules forming an H(2)O sheet and on the other side to oxygen atoms shared with layer MnO(6) octahedra forming a corner-sharing octahedral interlayer complex. The average Zn-O and Zn-Mn distances were 2.07+/-0.01 and 3.52+/-0.01 A, respectively. Macroscopic adsorption-desorption isotherms showed that, in contrast to that of the Zn-gamma-MnOOH system, adsorption of Zn(II) on delta-MnO(2) was highly reversible. EXAFS results indicated that the highly reversible adsorption was due to the weak adsorption mode of the corner-sharing linkage between the adsorbate and adsorbent polyhedra.

Journal Article↗
PubMed1979

Charge-transfer and water-mediated adsorption. III. Adsorption on tryptophan-substituted Sephadex and Sepharose.

The adsorption of tyrosine, tryptophan and some related compounds on tryptophan and tryptophanyltryptophan gels is similar to but much stronger than that observed with the parent gel Sephadex G-25. The adsorption has been attributed mainly to charge transfer or redistribution of electrons and protons leading to pi-bonding and hydrogen bonding, in addition to hydrophobic adsorption. The participation of organized water surrounding the gel matrix, the ligands and the solute molecules has been considered. The application of this principle of adsorption has been exemplified by chromatographic experiments with a cellulase preparation of tryptophan-Sepharose 4B.

Amino Acids↗
PubMed2003

The adsorption of cationic and amphoteric copolymers on glass surfaces: zeta potential measurements, adsorption isotherm determination, and FT Raman characterization.

The adsorption of cationic and amphoteric copolymers onto controlled pore glass (CPG) powders has been studied by measurement of the powder particle zeta (zeta) potential, by determination of the adsorption isotherm, and by FT Raman measurements of the polymer-coated powder. The cationic polymers consisted chiefly of homopolymers of dimethyldiallylammonium chloride (DMDAAC) or copolymers of DMDAAC and acrylamide. The amphoteric polymers studied included copolymers of DMDAAC and acrylic acid. The comonomer ratio was varied to explore the dependence of cationic charge density on the extent and effect of adsorption. Both types of polymers adsorb onto the anionic glass surface via an ion-exchange mechanism. Consequently, a correspondingly higher mass of a low-charge-density copolymer adsorbs than of a cationic homopolymer. The presence of the anionic portion in the amphoteric polymers does not significantly alter this picture. The zeta potential, however, reflects the overall nature of the polymer. Cationic polymers effectively neutralize the glass surface, while amphoteric polymers leave the zeta potential net negative. Adsorption isotherms, determined via the depletion technique using colloidal titration, were used to "calibrate" a FT Raman method. The latter was used to determined the amount of adsorbed polymer under solution conditions in which colloidal titration could not be performed.

Journal Article↗
PubMed2005

Gas adsorption in active carbons and the slit-pore model 2: Mixture adsorption prediction with DFT and IAST.

We use a fast density functional theory (a "slab-DFT") and the polydisperse independent ideal slit-pore model to predict gas mixture adsorption in active carbons. The DFT is parametrized by fitting to pure gas isotherms generated by Monte Carlo simulation of adsorption in model graphitic slit-pores. Accurate gas molecular models are used in our Monte Carlo simulations with gas-surface interactions calibrated to a high surface area carbon, rather than a low surface area carbon as in all previous work of this type, as described in part 1 of this work. We predict the adsorption of binary mixtures of carbon dioxide, methane, and nitrogen on two active carbons up to about 30 bar at near-ambient temperatures. We compare two sets of results; one set obtained using only the pure carbon dioxide adsorption isotherm as input to our pore characterization process, and the other obtained using both pure gas isotherms as input. We also compare these results with ideal adsorbed solution theory (IAST). We find that our methods are at least as accurate as IAST for these relatively simple gas mixtures and have the advantage of much greater versatility. We expect similar results for other active carbons and further performance gains for less ideal mixtures.

Journal Article↗
PubMed2005

Gas adsorption in active carbons and the slit-pore model 1: Pure gas adsorption.

We describe procedures based on the polydisperse independent ideal slit-pore model, Monte Carlo simulation and density functional theory (a 'slab-DFT') for predicting gas adsorption and adsorption heats in active carbons. A novel feature of this work is the calibration of gas-surface interactions to a high surface area carbon, rather than to a low surface area carbon as in all previous work. Our models are used to predict the adsorption of carbon dioxide, methane, nitrogen, and hydrogen up to 50 bar in several active carbons at a range of near-ambient temperatures based on an analysis of a single 293 K carbon dioxide adsorption isotherm. The results demonstrate that these models are useful for relatively simple gases at near-critical or supercritical temperatures.

Journal Article↗
PubMed2006

Adsorption and electrochemical activity: an in situ electrochemical scanning tunneling microscopy study of electrode reactions and potential-induced adsorption of porphyrins.

The effect of adsorption on molecular properties and reactivity is a central topic in interfacial physical chemistry. At electrochemical interfaces, adsorbed molecules may lose their electrochemical activity. The absence of in situ probes has hindered our understanding of this phenomenon and electrode reactions in general. In this work, classical electrochemistry and electrochemical scanning tunneling microscopy (EC-STM) were combined to provide molecular level insight into electrochemical reactions and the molecular adsorption state at the electrolyte-electrode interface. The metal-free porphyrin 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP) adsorbed on Au(111) in 0.1 M H(2)SO(4) solution was chosen as a model system. TPyP is found to irreversibly adsorb on Au(111) over a wide range of potentials, from -0.25 to 0.6 V(SCE). The adsorption state of TPyP has a dramatic effect on its electrochemistry. Preadsorbed, oxidized TPyP displays no well-defined cathodic peaks in cyclic voltammograms in sharp contrast to solution-phase TPyP. Our present work provides direct, molecular level evidence of the electrochemically "invisible" species. Electrochemical activity of absorbed species is recovered by allowing the oxidized molecule sufficient time (tens of minutes) to reduce. The redox state of adsorbed TPyP also affects the nature of the adsorption. Oxidized species can apparently only form monolayers. However, multilayers, stable enough to be imaged by STM, can form when the adsorbed TPyP is in the reduced state. This suggests that by controlling the electrochemistry one can either promote or suppress the formation of multilayers.

Journal Article↗
PubMed2005

Adsorption of organic matter at mineral/water interfaces. IV. Adsorption of humic substances at boehmite/water interfaces and impact on boehmite dissolution.

The adsorption of Suwannee River fulvic acid (SRFA) and Pahokee peat humic acid (PPHA) at the boehmite (gamma-AlOOH)/water interface and the impact of SRFA on boehmite dissolution have been examined over a wide range of solution pH conditions (pH 2-12), SRFA surface coverages (Gamma(SRFA), total SRFA binding site concentration normalized by the boehmite surface area) of 0.0-5.33 micromol m(-2), and PPHA surface coverages (Gamma(PPHA), PPHA binding site concentration normalized by boehmite surface area) of 0.0-4.0 micromol m(-2), using macroscopic adsorption and in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. At relatively high SRFA surface coverages (Gamma(SRFA) = 5.33 micromol m(-2)), in situ ATR-FTIR spectral features of adsorbed SRFA are very similar to those measured for SRFA in solution at approximately 1-3 pH units higher. At sub-monolayer surface coverages (Gamma(SRFA) = 1.20 and 2.20 micromol m(-2)), several new peaks and enhancements of the intensities of a number of existing peaks are observed. The latter spectral changes arise from several nonorganic extrinsic species (i.e., adsorbed carbonate and water, for alkaline solution conditions), partially protonated SRFA carboxyl functional groups (near-neutral pH conditions), and small quantities of inner-spherically adsorbed SRFA carboxyl groups and/or Al(III)-SRFA complexes (for acidic conditions). The spectra of PPHA adsorbed at boehmite/water interfaces also showed changes generally consistent with our observations for SRFA sorbed on boehmite. These observations confirm that SRFA and PPHA are predominantly adsorbed at the boehmite/water interface in an outer-sphere fashion, with minor inner-sphere adsorption complexes being formed only under quite acidic conditions. They also suggest that the positively charged boehmite/water interface stabilizes SRFA and PPHA carboxyl functional groups against protonation at lower pH. Measurements of the concentration of dissolved Al(III) ions in the absence and presence of SRFA showed that the boehmite dissolution process is clearly inhibited by the adsorption of SRFA, which is consistent with previous observations that outer-spherically adsorbed organic anions inhibit Al-(oxyhydr)oxide dissolution.

Journal Article↗
PubMed2004

Adsorption of organic matter at mineral/water interfaces: 3. Implications of surface dissolution for adsorption of oxalate.

The adsorption of oxalate on a model aluminum oxide, corundum (alpha-Al2O3), has been examined over a broad range of oxalate concentrations (0.125-25.0 mM) and pH conditions (2-10). In situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) measurements indicate that at low to intermediate concentrations ([oxalate] < or = 2.50 mM), oxalate adsorbs to corundum predominantly as a bidentate, mononuclear, inner-sphere complex involving both carboxyl groups. Significant contributions from outer-spherically bound oxalate and aqueous Ox(2-) are additionally observed at higher oxalate concentrations. Consistent with the ATR-FTIR findings, macroscopic adsorption data measured for oxalate concentrations of 0.125-2.50 mM can be generally well modeled with a single bidentate, inner-sphere oxalate complex using the charge distribution multisite complexation (CD-MUSIC) model. However, at intermediate oxalate concentrations (0.50 and 1.25 mM) and pH <5, the extent of oxalate adsorption measured experimentally is found to fall significantly below that predicted by CD-MUSIC simulations. The latter finding is interpreted in terms of competition for oxalate from dissolved Al(III), the formation of which is promoted by the dissolution-enhancing properties of the adsorbed oxalate anion. In accordance with this expectation, increasing concentrations of dissolved Al(III) in solution are found to significantly decrease the extent of oxalate adsorption on corundum under acidic pH conditions, presumably through promoting the formation of Al(III)-oxalate complexes with reduced affinities for the corundum surface compared with the uncomplexed oxalate anion.

Journal Article↗
PubMed2005

Modeling of binary adsorption on heterogeneous surfaces characterized by a quasi-gaussian adsorption energy distribution.

The integral equation (IE) approach coupled with a quasi-Gaussian adsorption energy distribution is used to model the adsorption of single gases and their binary mixture on a heterogeneous solid surface. The adsorbing surface is assumed to be characterized by two, generally different in width, quasi-Gaussian distribution functions, each of them related to a single component of the mixture. The influence of correlations between the distribution functions associated with different components on the corresponding adsorption isotherms and phase diagrams is discussed. In particular, it is demonstrated that a lack of microscopic correlations between the adsorption energies of the components may lead to the formation of an azeotropic mixture. The predictions of the theory are also compared with the results of the grand canonical Monte Carlo (GCMC) simulations carried out for the system studied.

Journal Article↗
PubMed2006

New method to determine PSD using supercritical adsorption: Applied to methane adsorption in activated carbon.

Adsorption of supercritical fluids is increasingly carried out to determine the micropore size distribution. This is largely motivated by the advances in the use of supercritical adsorption in high energy applications, such as hydrogen and methane storage in porous media. Experimental data are reported as mass excess versus pressure, and when these data are matched against the theoretical mass excess, significant errors could occur if the void volume used in the calculation of the experimental mass excess is incorrectly determined [Malbrunot, P.; Vidal, D.; Vermesse, J.; Chahine, R.; Bose, T. K. Langmuir 1997, 13, 539]. The incorrect value for the void volume leads to a wrong description of the maximum in the plot of mass excess versus pressure as well as the part of the isotherm over the pressure region where the isotherm is decreasing. Because of this uncertainty in the maximum and the decreasing part of the isotherm, we propose a new method in which the problems associated with this are completely avoided. Our method involves only the relationship between the amount that is introduced into the adsorption cell and the equilibrium pressure. This information of "direct" experimental data has two distinct advantages. The first is that the data is the "raw" data without any manipulation (i.e., involving further calculations), and the second one is that this relationship always monotonically increases with pressure. We will illustrate this new method with the adsorption data of methane in a commercial sample of activated carbon.

Journal Article↗
PubMed2004

First-principles study of C adsorption, O adsorption, and CO dissociation on flat and stepped Ni surfaces.

The adsorption of atomic oxygen and carbon was studied with plane wave density functional theory on four Ni surfaces, Ni(110), Ni(111), Ni(210), and Ni(531). Various adsorption sites on these surfaces are examined in order to identify the most favorable adsorption site for each atomic species. The dependence of surface bonding on adsorbate coverage is also investigated. Adsorption energies and structural information are obtained and compared with existing experimental results for Ni(110) and Ni(111). In addition, activation barriers to CO dissociation have been determined on Ni(111) and Ni(531) by locating the transition states for these processes. Our results indicate that the binding energies of C are comparatively stronger on stepped surfaces than on flat surfaces, and the energy barriers associated with CO dissociation strongly favor reactions occurring near surface steps.

Journal Article↗
PubMed2000

Water vapor adsorption properties of amorphous cefditoren pivoxil evaluated by adsorption isotherms and microcalorimetry.

Water vapor adsorption of ground cefditoren pivoxil was studied. The amount of water adsorbed increased with a decrease in the crystallinity of cefditoren pivoxil. It was found from the microcalorimetric measurements that the differential heat of water vapor adsorption at 1.5% adsorbed water increased with decreasing crystallinity of cefditoren pivoxil, suggesting that hygroscopicity of cefditoren pivoxil was enhanced by grinding. These results indicated that hydrophilic adsorption sites in cefditoren pivoxil increased through the grinding process. The results of infrared (IR) spectra examination suggested that the increment of hydrophilic adsorption sites through the grinding process resulted from the change of the environment of the carbonyl groups in two esters and amide.

Anti-Bacterial Agents↗
PubMed2005

Adsorption of ruthenium ions on activated charcoal: influence of temperature on the kinetics of the adsorption process.

Influence of temperature on ruthenium adsorption on activated charcoal from 3 mol/L HNO(3) solutions was investigated in the temperature range of 288 K to 308 K. It was observed that the rise in temperature increases the adsorption of ruthenium ions on activated charcoal and follows the kinetics of first order rate law with rate constant values 0.0564-0.0640 min(-1) in the temperature range of 288 K to 308 K respectively. The activation energy for the adsorption process was found to be 1.3806 kJ/mol. Various thermodynamics quantities namely H, S and G were computed from the equilibrium constant K(C) values. The results indicated a positive heat of adsorption, a positive S and a negative G.

Journal Article↗
PubMed1985

pH profile of the adsorption of nucleotides onto montmorillonite. II. Adsorption and desorption of 5'-AMP in iron-calcium montmorillonite systems.

The interaction of 5'-AMP with montmorillonite saturated with various ratios of two metals found ubiquitously on the surface of Earth, that is, iron and calcium, is investigated. Adsorption and desorption of the nucleotide were studied in the pH range of 2-12 at three levels of addition: 0.080, 0.268 and 0.803 mmole 5'-AMP per gram of clay. Two desorption stages were employed--H2O wash and NaOH extraction (pH = 12.0). 5'-AMP was preferentially adsorbed on the Fe-containing clays relative to the Ca clay. The nucleotide was fully recovered by the two desorption stages, mostly by the NaOH extraction. The evidence at hand indicates that 5'-AMP reaction with clay is affected by electrostatic interactions involving both attraction and repulsion forces. Some specific adsorption, possibly the result of covalent bonding and complex formation with the adsorbed ion, cannot be ruled out for iron but does not appear to operate for calcium. Changes in pH cause varying degrees of attraction and repulsion of 5'-AMP and may have been operating on the primitive Earth, leading to sequences of adsorption and release of this biomolecule.

Adenosine Monophosphate↗
PubMed1977

The adsorption of volatile aroma constituents by foods. VIII. Adsorption of volatile carbonyl compounds by amino acids.

The adsorption of some volatile aldehydes and ketones by 22 dry amino-acids was studied. The adsorbed amounts decreased approximately in the order: propanal, biacetyl, hexenal, hexanal, acetone, pentan-3-one, nonan-3-one, undecanal and nonan-5-one, but there were great differences in the adsorption capacity of the amino acids. Lys adsorbed best and often irreversible, arg, his, phe, trp, pro, and val (leu, ile) very good. With cys, thiazolidinecarboxylic acids were formed. In most cases of adsorption exceeding 100 mmol/mol, except for the monoketones, strong discoloration, probably of the maillard type, was observed. Propanal and hexanal were to a great extend converted to aldol addition and condensation products. Tyr and hyp adsorbed less than the corresponding amino-acids without hydroxyl groups. This is attributed to stronger crystal-lattice forces.

Adsorption↗