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Sample records for adsorption sites adsorption

  1. Methane Adsorption on Aggregates of Fullerenes: Site-Selective Storage Capacities and Adsorption Energies

    PubMed Central

    Kaiser, Alexander; Zöttl, Samuel; Bartl, Peter; Leidlmair, Christian; Mauracher, Andreas; Probst, Michael; Denifl, Stephan; Echt, Olof; Scheier, Paul

    2013-01-01

    Methane adsorption on positively charged aggregates of C60 is investigated by both mass spectrometry and computer simulations. Calculated adsorption energies of 118–281 meV are in the optimal range for high-density storage of natural gas. Groove sites, dimple sites, and the first complete adsorption shells are identified experimentally and confirmed by molecular dynamics simulations, using a newly developed force field for methane–methane and fullerene–methane interaction. The effects of corrugation and curvature are discussed and compared with data for adsorption on graphite, graphene, and carbon nanotubes. PMID:23744834

  2. Methane adsorption on aggregates of fullerenes: site-selective storage capacities and adsorption energies.

    PubMed

    Kaiser, Alexander; Zöttl, Samuel; Bartl, Peter; Leidlmair, Christian; Mauracher, Andreas; Probst, Michael; Denifl, Stephan; Echt, Olof; Scheier, Paul

    2013-07-01

    Methane adsorption on positively charged aggregates of C60 is investigated by both mass spectrometry and computer simulations. Calculated adsorption energies of 118-281 meV are in the optimal range for high-density storage of natural gas. Groove sites, dimple sites, and the first complete adsorption shells are identified experimentally and confirmed by molecular dynamics simulations, using a newly developed force field for methane-methane and fullerene-methane interaction. The effects of corrugation and curvature are discussed and compared with data for adsorption on graphite, graphene, and carbon nanotubes.

  3. Modeling two-rate adsorption kinetics: Two-site, two-species, bilayer and rearrangement adsorption processes.

    PubMed

    Tripathi, Sumit; Tabor, Rico F

    2016-08-15

    The adsorption kinetics of many systems show apparent two-rate processes, where there appears to be resolved fast and slow adsorption steps. Such non-standard adsorption processes cannot be accounted for by conventional modeling methods, motivating new approaches. In this work, we present four different models that can account for two-rate adsorption and are based upon physically realistic processes - two adsorbing species, two surface sites having different energies, bilayer formation and molecular rearrangement modes. Each model is tested using a range of conditions, and the characteristic behavior is explored and compared. In these models, the effects of mass transport and bulk concentration are also accounted for, making them applicable in systems which are transport-limited or attachment-limited, or intermediate between the two. The applicability of these models is demonstrated by fitting exemplar experimental data for each of the four models, selecting the model on the basis of the known physical behavior of the adsorption kinetics. These models can be applied in a wide range of systems, from stagnant adsorption in large volume water treatment to highly dynamic flow conditions relevant to printing, coating and processing applications.

  4. Adsorption sites, adsorption enthalpies and potential removal of terpenoids by atmospheric ice

    NASA Astrophysics Data System (ADS)

    Czech, Christian; Hammer, Sonja M.; Bonn, Boris; Schmidt, Martin U.

    2011-01-01

    Ice crystal formation and its effect on atmospheric trace gases are currently an important area of research because of its radiation and climate effects. However, the processes of adsorption of trace gases on ice surfaces and absorption into ice crystals are poorly understood. Both processes are investigated by lattice-energy minimisation for a selected number of atmospherically relevant volatile organic compounds, i.e. isoprene, methacrolein, acetone, methylbutenol, perillyl alcohol and 2,10-pinanediol, which can be considered as exemplary substances for similar structured compounds. Adsorption and absorption geometries and enthalpies are computed and the potential uptake strength is approximated. According to our calculations non-polar terpenes like isoprene are not significantly adsorbed by ice crystals. Oxidized terpenoids have stronger interactions with the ice surface (at least two hydrogen bonds) leading to larger adsorption enthalpies. Absorption into the ice crystal plays only a minor role. Correspondingly, in the atmosphere terpenoid compounds are increasingly adsorbed to ice surfaces with increasing oxygen numbers. Subsequently this process can contribute to the wet removal of terpenoids by ice, which is so far ignored in global transport models.

  5. Optimal smoothing of site-energy distributions from adsorption isotherms

    SciTech Connect

    Brown, L.F.; Travis, B.J.

    1983-01-01

    The equation for the adsorption isotherm on a heterogeneous surface is a Fredholm integral equation. In solving it for the site-energy distribution (SED), some sort of smoothing must be carried out. The optimal amount of smoothing will give the most information that is possible without introducing nonexistent structure into the SED. Recently, Butler, Reeds, and Dawson proposed a criterion (the BRD criterion) for choosing the optimal smoothing parameter when using regularization to solve Fredholm equations. The BRD criterion is tested for its suitability in obtaining optimal SED's. This criterion is found to be too conservative. While using it never introduces nonexistent structure into the SED, significant information is often lost. At present, no simple criterion for choosing the optimal smoothing parameter exists, and a modeling approach is recommended.

  6. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    SciTech Connect

    Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption.

  7. Promoting the Adsorption of Metal Ions on Kaolinite by Defect Sites: A Molecular Dynamics Study

    PubMed Central

    Li, Xiong; Li, Hang; Yang, Gang

    2015-01-01

    Defect sites exist abundantly in minerals and play a crucial role for a variety of important processes. Here molecular dynamics simulations are used to comprehensively investigate the adsorption behaviors, stabilities and mechanisms of metal ions on defective minerals, considering different ionic concentrations, defect sizes and contents. Outer-sphere adsorbed Pb2+ ions predominate for all models (regular and defective), while inner-sphere Na+ ions, which exist sporadically only at concentrated solutions for regular models, govern the adsorption for all defective models. Adsorption quantities and stabilities of metal ions on kaolinite are fundamentally promoted by defect sites, thus explaining the experimental observations. Defect sites improve the stabilities of both inner- and outer-sphere adsorption, and (quasi) inner-sphere Pb2+ ions emerge only at defect sites that reinforce the interactions. Adsorption configurations are greatly altered by defect sites but respond weakly by changing defect sizes or contents. Both adsorption quantities and stabilities are enhanced by increasing defect sizes or contents, while ionic concentrations mainly affect adsorption quantities. We also find that adsorption of metal ions and anions can be promoted by each other and proceeds in a collaborative mechanism. Results thus obtained are beneficial to comprehend related processes for all types of minerals. PMID:26403873

  8. Effects of postdosed species on preadsorbed CO on Fe(100): Adsorption site conversion caused by site competition

    SciTech Connect

    Lu, Jiongping; Albert, M.R.; Bernasek, S.L. )

    1990-07-26

    Carbon monoxide (CO) adsorption on the clean Fe(100) surface and the c(2{times}2)CO-Fe(100) surface has been studied. The effects of postdosed oxygen(O{sub 2}) and methanethiol (CH{sub 3}SH) on preadsorbed CO were examined. These studies were performed under ultrahigh-vacuum(UHV) conditions, using high-resolution electron energy loss spectroscopy (HREELS), temperature-programmed desorption spectroscopy (TPD), Auger electron spectroscopy (AES), and low-energy electron diffraction (LEED). For CO, four associative adsorption states and one dissociative adsorption state were identified. Postdosed species were found to cause 4-fold hollow site CO molecules to migrate into lower coordination sites. This type of adsorption site conversion is discussed in terms of adsorption site competition between preadsorbed species and postdosed species.

  9. No Chemisorption on Ni(111): Coverage Effects, Site Preferences and Adsorption Geometry.

    DTIC Science & Technology

    1985-09-03

    U 01TECHNICAL REPORT No. 14 In NO CHEMISORPTION ON Ni(111): COVERAGE EFFECTS, SITE PREFERENCES AND ADSORPTION GEOMETRY by Shen-Shu Sung, Roald ...Adsorption Geometry 6. pER Op ,,GoRG. R --OAT NUmSER 7. ;.-.; T) hOR ( 2) .\\B. CONTRACT OR GRANT N’,UMaEA.I) Shen-Shu Sung, Roald Hoffman and Patricia...PREFERENCES AND ADSORPTION GEOMETRY Shen-Shu Sung , Roald Hoffmann and Patricia A. ThielT t Departent of Chemistry, Cornell University, Ithaca, NY 14853

  10. Primary Adsorption Site of Phage PBS1: the Flagellum of Bacillus subtilis

    PubMed Central

    Raimondo, Linda M.; Lundh, Nancy P.; Martinez, Rafael J.

    1968-01-01

    The adsorption of Bacillus subtilis phage PBS1 was studied, and it was demonstrated that the primary adsorption site for this phage is the flagellum of B. subtilis. The capacity of flagella to function for motility may be lost without the loss of their capacity to adsorb the phage and permit infection. Deoxyribonucleic acid injection by the phage is inhibited by cyanide, suggesting the requirement for cellular energy in the infection process. Images PMID:4986906

  11. Adsorption site analysis of impurity embedded single-walled carbon nanotube bundles

    USGS Publications Warehouse

    Agnihotri, S.; Mota, J.P.B.; Rostam-Abadi, M.; Rood, M.J.

    2006-01-01

    Bundle morphology and adsorptive contributions from nanotubes and impurities are studied both experimentally and by simulation using a computer-aided methodology, which employs a small physisorbed probe molecule to explore the porosity of nanotube samples. Grand canonical Monte Carlo simulation of nitrogen adsorption on localized sites of a bundle is carried out to predict adsorption in its accessible internal pore volume and on its external surface as a function of tube diameter. External adsorption is split into the contributions from the clean surface of the outermost nanotubes of the bundle and from the surface of the impurities. The site-specific isotherms are then combined into a global isotherm for a given sample using knowledge of its tube-diameter distribution obtained by Raman spectroscopy. The structural parameters of the sample, such as the fraction of open-ended nanotubes and the contributions from impurities and nanotube bundles to total external surface area, are determined by fitting the experimental nitrogen adsorption data to the simulated isotherm. The degree of closure between experimental and calculated adsorption isotherms for samples manufactured by two different methods, to provide different nanotube morphology and contamination level, further strengthens the validity and resulting interpretations based on the proposed approach. The average number of nanotubes per bundle and average bundle size, within a sample, are also quantified. The proposed method allows for extrapolation of adsorption properties to conditions where the purification process is 100% effective at removing all impurities and opening access to all intrabundle adsorption sites. ?? 2006 Elsevier Ltd. All rights reserved.

  12. Infrared Spectroscopic Study of the Adsorption of HCN by gamma-Al2O3: Competition with Triethylenediamine for Adsorption Sites

    SciTech Connect

    Kim, S.; Sorescu, D.C.; Yates, J.T., Jr.

    2007-04-12

    The adsorption and vibrational properties of chemisorbed HCN on Lewis acid sites, Lewis base sites, and Brønsted Al-OH acid sites on a partially hydroxylated [gamma]-Al2O3 surface have been obtained by a combination of FTIR and density functional theory studies. The vibrational modes from the molecular and dissociative adsorption of HCN were assigned by using deuterium and 13C-labeled D13CN molecules at 170 K. In addition, [eta]2(C, N)-HCN bonding is also found from the [nu](CdN) vibrational spectra. Good correlation of the calculated vibrational frequencies for the adsorbed species with experimental data is found. The effect of triethylenediamine (TEDA) (also called 1, 4-diazabicyclo [2.2.2]octane, DABCO) on the adsorption of hydrogen cyanide (HCN) on the high area [gamma]-Al2O3 surface has been investigated using transmission FTIR spectroscopy. During HCN adsorption on TEDA-functionalized surfaces, there is no spectral change or emerging feature in either the TEDA or HCN spectral regions, indicating that no direct interaction occurs between these two molecules. Instead, we found that TEDA competes with HCN for the active sites on [gamma]-Al2O3. The observed [nu](C [identical with] N) mode on a TEDA-precovered surface is due to the HCN adsorption on Lewis base sites (Al-O-Al) which are less affected by TEDA preadsorption.

  13. Copper adsorption with Pb and Cd in sand-bentonite liners under various pHs. Part II. Effect on adsorption sites.

    PubMed

    Kaoser, Saleh; Barrington, Suzelle; Elektorowicz, Maria; Wang, Li

    2004-01-01

    The project examined the effect of Pb and Cd on Cu adsorption using sand liners containing 0, 5, and 10% sodium bentonite and exposed to metal solutions at three pH levels (3.7, 5.5, and 7.5). Aliquots of 2 g of liner material were exposed in duplicate, for 14 days, to solutions containing Cu alone or Cu with either Pb or Cd. Selective sequential extraction (SSE) was used to quantity the Cu adsorbed by each liner particle adsorption site (exchangeable, carbonate and hydroxide, oxides and residual). The results indicated that two main factors affected liner material behavior in adsorbing Cu, besides Cd and Pb competition: pH either above or below 6.5; liner cation exchange capacity (CEC) greater or equal and greater than the solution cation equivalence. In general, the liner carbonate and hydroxide fractions precipitated the greatest amount of Cu, under all environmental conditions while the exchangeable, oxide and residual adsorbed more or less the same amount. Lead, and to a lesser extent Cd, significantly increase the mobility of Cu, by competing especially for the exchangeable sites. While Cd also competed against Cu for oxide adsorption, Pb competes for calcium and hydroxide precipitation. Lead, and to a lesser extent Cd, competed especially for the exchangeable site where the adsorption is more dynamic, and less for the more permanent adsorption sites, involving precipitation, and electrostatic bonding.

  14. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series.

    PubMed

    Rodríguez-Albelo, L Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A Rabdel; Calero, Sofia; Navarro, Jorge A R

    2017-02-15

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects.

  15. Adsorption and characterization of MCPA on DDTMA- and raw-montmorillonite: Surface sites involved.

    PubMed

    Santiago, Cintia C; Fernández, Mariela A; Torres Sánchez, Rosa M

    2016-01-01

    The 4-chloro-2-methylphenoxy acid (MCPA) is an herbicide widely used in agriculture, which generates a great concern about contamination of surface water and serious consequences for human health and the environment. In this work, the adsorption of MCPA on an Argentine montmorillonite (MMT) and its organo-montmorillonite product (OMMT) with different dodecyl trimethyl ammonium loading was investigated. MCPA adsorption on OMMT increases at least 3 times, with respect to the amount determined for MMT. X-ray diffraction and zeta potential analyses indicated the inner (interlayer) and outer surface participate as adsorption sites. Changes in surface electric charge and also interlayer expansion suggest that dimethyl amine (MCPA counterion) was also surface-adsorbed. The larger aggregates of OMMT, without and with MCPA, obtained compared to those of MMT samples, generate an improvement in the coagulation efficiency. This property, particularly after MCPA retention, allows an easier separation of the solids from the solution and enables a simple technological process application.

  16. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series

    NASA Astrophysics Data System (ADS)

    Rodríguez-Albelo, L. Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A. Rabdel; Calero, Sofia; Navarro, Jorge A. R.

    2017-02-01

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects.

  17. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series

    PubMed Central

    Rodríguez-Albelo, L. Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A. Rabdel; Calero, Sofia; Navarro, Jorge A.R.

    2017-01-01

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects. PMID:28198376

  18. Monte Carlo simulations of adsorption on heterogeneous surfaces with a random topography of surfaces sites

    NASA Astrophysics Data System (ADS)

    Cortes, Joaquin; Araya, Paulo

    1991-11-01

    Making use of Monte Carlo experiments, a simulation has been carried out of the adsorption of a gas on heterogeneous solids characterized by energy distribution and a random topography of the superficial sites. A good interpretation of the results is achieved by means of the theoretical models introduced by Hill, and later by Rudzinsky, for these types of systems.

  19. Adsorption Refrigeration System

    SciTech Connect

    Wang, Kai; Vineyard, Edward Allan

    2011-01-01

    Adsorption refrigeration is an environmentally friendly cooling technology which could be driven by recovered waste heat or low-grade heat such as solar energy. In comparison with absorption system, an adsorption system has no problems such as corrosion at high temperature and salt crystallization. In comparison with vapor compression refrigeration system, it has the advantages of simple control, no moving parts and less noise. This paper introduces the basic theory of adsorption cycle as well as the advanced adsorption cycles such as heat and mass recovery cycle, thermal wave cycle and convection thermal wave cycle. The types, characteristics, advantages and drawbacks of different adsorbents used in adsorption refrigeration systems are also summarized. This article will increase the awareness of this emerging cooling technology among the HVAC engineers and help them select appropriate adsorption systems in energy-efficient building design.

  20. Multilayer Dye Adsorption in Activated Carbons-Facile Approach to Exploit Vacant Sites and Interlayer Charge Interaction.

    PubMed

    Hadi, Pejman; Guo, Jiaxin; Barford, John; McKay, Gordon

    2016-05-17

    Altering the textural properties of activated carbons (ACs) via physicochemical techniques to increase their specific surface area and/or to manipulate their pore size is a common practice to enhance their adsorption capacity. Instead, this study proposes the utilization of the vacant sites remaining unoccupied after dye uptake saturation by removing the steric hindrance and same-charge repulsion phenomena via multilayer adsorption. Herein, it has been shown that the adsorption capacity of the fresh AC is a direct function of the dye molecular size. As the cross-sectional area of the dye molecule increases, the steric hindrance effect exerted on the neighboring adsorbed molecules increases, and the geometrical packing efficiency is constrained. Thus, ACs saturated with larger dye molecules render higher concentrations of vacant adsorption sites which can accommodate an additional layer of dye molecules on the exhausted adsorbent through interlayer attractive forces. The second layer adsorption capacity (60-200 mg·g(-1)) has been demonstrated to have a linear relationship with the uncovered surface area of the exhausted AC, which is, in turn, inversely proportional to the adsorbate molecular size. Unlike the second layer adsorption, the third layer adsorption is a direct function of the charge density of the second layer.

  1. Galactose adsorption on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Alatalo, Matti; Puisto, Mikko

    2014-03-01

    In order to understand the valorisation of biomass, it is essential to study the behavior of sugar molecules on catalytic surfaces. We have studied the adsorption of galactose molecules on the Ru(0001) surface using first principles calculations. We present results for the fully relaxed configurations of the molecule at different adsorption sites. We also compare the effect of the inclusion of the van der Waals interactions on both the energetics of the free galactose molecule and the adsorption energy of galactose on Ru(0001). We compare our results, obtained using periodically repeated supercells, to those obtained with cluster calculations.

  2. Fabrication of novel magnetic nanocomposite with a number of adsorption sites for the removal of dye.

    PubMed

    Li, Leilei; Duan, Huimin; Wang, Xiaojiao; Luo, Chuannan

    2015-01-01

    In this current work, a novel functional ionic liquid-coated Fe3O4@chitosan@graphene oxide was synthesized and tested as adsorbents for methylene blue through batch adsorption tests. The physicochemical properties of the adsorbent were investigated using scanning electron microscopy, x-ray diffraction, and fourier transform infrared spectroscopy. The adsorption capacity of the adsorbent was evaluated as a function of initial dye concentration, pH, contact time and temperature. The adsorption results indicated that the adsorption followed a pseudo-second-order kinetics. The equilibrium adsorption was well-described by the Langmuir isotherm model and the maximum adsorption capacity was to be 262 mg/g. The negative value of ΔH° shows exothermic nature of adsorption process and the negative value of ΔG° indicated that the adsorption reaction is spontaneous. Moreover, the ionic liquid-coated Fe3O4@chitosan@graphene oxide could be repeatedly used by simple treatment without obvious structure and performance degradation. The obtained results suggested that the potential applications of ionic liquid-coated Fe3O4@chitosan@graphene oxide in deep-purification of polluted water.

  3. Highly Selective Adsorption of Ethylene over Ethane in a MOF Featuring the Combination of Open Metal Site and -Complexation

    DOE PAGES

    Zhang, Yiming; Li, Baiyan; Wu, Zili; ...

    2015-01-01

    The introduction of the combination of open metal site (OMS) and -complexation into MOF has led to very high ethylene/ethane adsorption selectivity at 318K, as illustrated in the context of MIL-101-Cr-SO3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

  4. A Simple Adsorption Experiment

    ERIC Educational Resources Information Center

    Guirado, Gonzalo; Ayllon, Jose A.

    2011-01-01

    The study of adsorption phenomenon is one of the most relevant and traditional physical chemistry experiments performed by chemistry undergraduate students in laboratory courses. In this article, we describe an easy, inexpensive, and straightforward way to experimentally determine adsorption isotherms using pieces of filter paper as the adsorbent…

  5. Phenylamine-Functionalized rGO/TiO2 Photocatalysts: Spatially Separated Adsorption Sites and Tunable Photocatalytic Selectivity.

    PubMed

    Yu, Huogen; Xiao, Pian; Tian, Jing; Wang, Fazhou; Yu, Jiaguo

    2016-11-02

    The preferential adsorption of targeted contaminants on a photocatalyst surface is highly required to realize its photocatalytic selective decomposition in a complex system. To realize the tunable preferential adsorption, altering the surface charge or polarity property of photocatalysts has widely been reported. However, it is quite difficult for a modified photocatalyst to realize the simultaneously preferential adsorption for both cationic and anionic dyes. In this study, to realize the selective adsorption for both cationic and anionic dyes on a photocatalyst surface, the negative reduced graphene oxide (rGO) nanosheets and positive phenylamine (PhNH2) molecules are successfully loaded on the TiO2 surface (PhNH2/rGO-TiO2) with spatially separated adsorption sites, where the negative rGO and positive PhNH2 molecules work as the preferential adsorption sites for cationic and anionic dyes, respectively. It was interesting to find that although all the TiO2 samples (including the naked TiO2, PhNH2/TiO2, rGO-TiO2, and PhNH2/rGO-TiO2) clearly showed a better adsorption performance for cationic dyes than anionic dyes, only the PhNH2/rGO-TiO2 with spatially separated adsorption-active sites exhibited an opposite photocatalytic selectivity, namely, the naked TiO2, PhNH2/TiO2, and rGO-TiO2 showed a preferential decomposition for cationic dyes, while the resultant PhNH2/rGO-TiO2 exhibited an excellently selective decomposition for anionic dyes. In addition, the resultant PhNH2/rGO-TiO2 photocatalyst not only realizes the tunable photocatalytic selectivity but also can completely and sequentially decompose the opposite cationic and anionic dyes.

  6. Adsorption sites on icosahedral quasicrystal surfaces: Dark stars and white flowers

    SciTech Connect

    Unal, B.; Jenks, C.J.; Thiel, P.A.

    2009-01-12

    From other work, two preferred sites have been suggested for metals and semimetals adsorbed on the fivefold surfaces of icosahedral, Al-based quasicrystals. Because of their appearance in scanning tunneling microscopy (STM) images, these sites are known as dark stars and white flowers. In this paper, we analyze four bulk structural models in physical space to determine the types, chemical decorations, and densities of the dark star - and, to a lesser extent, the white flower - adsorption sites for the fivefold planes of icosahedral Al-Pd-Mn. We find that the chemical decorations of these sites are heterogeneous, even within a single model. Both features are also structurally heterogeneous, according to STM measurements, and the structural variation is consistent with the bulk structure models. Finally, from the models, the density of dark stars in the planes correlates with the step height. This may explain previous experimental observations of different properties for different terraces.

  7. CO/Pt(111) : GGA density functional study of site preference for adsorption

    NASA Astrophysics Data System (ADS)

    Alaei, M.; Akbarzadeh, H.; Gholizadeh, H.; de Gironcoli, S.

    2008-02-01

    Based on density functional formalism, we investigate the site preference for the adsorption of CO on Cu, Rh, Ag, Pt, and Au(111) surfaces. The exchange-correlation term was approximated by BLYP, a functional within the generalized gradient approximation (GGA) family that combines Becke’s exchange functional with the Lee-Yang-Parr correlation functional. Our study shows that BLYP, although not a hybrid functional, can correctly predict the adsorption site for CO. This invalidate the general belief that only hybrid functionals are able to predict the correct site preference. We analyze our results by repeating all calculations using another well-known GGA functional, Perdew-Burke-Ernzerhof, which could trace back the origin of the success of BLYP to the different behavior of the two GGA functionals at large values of the reduced density gradients, s∝(∣∇n∣)/(n3/4) . This is a region where different functionals in the GGA family may legitimately behave very differently as it is poorly constrained on physical ground. Our present observation points to the possibility of further improving the accuracy of exchange-correlation functionals in the GGA family by properly constraining the remaining flexibility in the exchange-correlation kernel in this underdetermined region so as to reproduce known results in simple but critically important systems like the one studied here.

  8. Adsorption of cadmium ions on oxygen surface sites in activated carbon

    SciTech Connect

    Jia, Y.F.; Thomas, K.M.

    2000-02-08

    Various types of oxygen functional groups were introduced onto the surface of coconut shell derived activated carbon by oxidation using nitric acid. Fourier-transform infrared spectroscopy (FTIR), temperature-programmed desorption (TPD), and selective neutralization were used to characterize the surface oxygen functional groups. The oxidized carbons were also heat treated to provide a suite of carbons where the oxygen functional groups of various thermal stabilities were varied progressively. The adsorption of cadmium ions was enhanced dramatically by oxidation of the carbon. The ratio of released protons to adsorbed cadmium ions on oxidized carbon was approximately 2, indicating cation exchange was involved in the process of adsorption. Na{sup +} exchange studies with the oxidized carbon gave a similar ratio. After heat treatment of the oxidized carbons to remove oxygen functional groups, the ratio of H{sup +} released to Cd{sup 2+} adsorbed and the adsorption capacity decreased significantly. Both reversible and irreversible processes were involved in cadmium ion adsorption with reversible adsorption having higher enthalpy. The irreversible adsorption resulted from cation exchange with carboxylic acid groups, whereas the reversible adsorption probably involved physisorption of the partially hydrated cadmium ion.

  9. The local adsorption site of methylthiolate on Au(1 1 1): Bridge or atop?

    NASA Astrophysics Data System (ADS)

    Jackson, D. C.; Chaudhuri, A.; Lerotholi, T. J.; Woodruff, D. P.; Jones, Robert G.; Dhanak, V. R.

    2009-03-01

    Measurements of the local adsorption geometry of the S head-group atom in the Au(1 1 1)(√3 × √3) R30°-CH 3S surface have been made using normal incidence X-ray standing waves (NIXSW) and S 1s scanned-energy mode photoelectron diffraction on the same surface preparations. The results confirm that the local adsorption site is atop an Au atom in a bulk-continuation site with a S-Au bondlength of 2.42 ± 0.02 Å, and that there can be no significant fraction of coadsorbed bridging species as recently proposed in a combined molecular dynamics/experimental study by Mazzarello et al. [R. Mazzarello, A. Cossaro, A. Verdini, R. Rousseau, L. Casalis, M.F. Danisman, L. Floreano, S. Scandolo, A. Morgante, G. Scoles, Phys. Rev. Lett. 98 (2007) 016102]. The results do not, however, clearly distinguish the different local reconstruction (adatom) models proposed for this surface.

  10. Uranium(VI) adsorption and surface complexation modeling onto background sediments from the F-Area Savannah River Site.

    PubMed

    Dong, Wenming; Tokunaga, Tetsu K; Davis, James A; Wan, Jiamin

    2012-02-07

    The mobility of an acidic uranium waste plume in the F-Area of Savannah River Site is of great concern. In order to understand and predict uranium mobility, U(VI) adsorption experiments were performed as a function of pH using background F-Area aquifer sediments and reference goethite and kaolinite (major reactive phases of F-Area sediments), and a component-additivity (CA) based surface complexation model (SCM) was developed. Our experimental results indicate that the fine fractions (≤45 μm) in sediments control U(VI) adsorption due to their large surface area, although the quartz sands show a stronger adsorption ability per unit surface area than the fine fractions at pH < 5.0. Kaolinite is a more important sorbent for U(VI) at pH < 4.0, while goethite plays a major role at pH > 4.0. Our CA model combines an existing U(VI) SCM for goethite and a modified U(VI) SCM for kaolinite along with estimated relative surface area abundances of these component minerals. The modeling approach successfully predicts U(VI) adsorption behavior by the background F-Area sediments. The model suggests that exchange sites on kaolinite dominate U(VI) adsorption at pH < 4.0, goethite and kaolinite edge sites cocontribute to U(VI) adsorption at pH 4.0-6.0, and goethite dominates U(VI) adsorption at pH > 6.0.

  11. On sulfur core level binding energies in thiol self-assembly and alternative adsorption sites: An experimental and theoretical study

    SciTech Connect

    Jia, Juanjuan; Kara, Abdelkader E-mail: vladimir.esaulov@u-psud.fr; Pasquali, Luca; Bendounan, Azzedine; Sirotti, Fausto; Esaulov, Vladimir A. E-mail: vladimir.esaulov@u-psud.fr

    2015-09-14

    Characteristic core level binding energies (CLBEs) are regularly used to infer the modes of molecular adsorption: orientation, organization, and dissociation processes. Here, we focus on a largely debated situation regarding CLBEs in the case of chalcogen atom bearing molecules. For a thiol, this concerns the case when the CLBE of a thiolate sulfur at an adsorption site can be interpreted alternatively as due to atomic adsorption of a S atom, resulting from dissociation. Results of an investigation of the characteristics of thiol self-assembled monolayers (SAMs) obtained by vacuum evaporative adsorption are presented along with core level binding energy calculations. Thiol ended SAMs of 1,4-benzenedimethanethiol (BDMT) obtained by evaporation on Au display an unconventional CLBE structure at about 161.25 eV, which is close to a known CLBE of a S atom on Au. Adsorption and CLBE calculations for sulfur atoms and BDMT molecules are reported and allow delineating trends as a function of chemisorption on hollow, bridge, and atop sites and including the presence of adatoms. These calculations suggest that the 161.25 eV peak is due to an alternative adsorption site, which could be associated to an atop configuration. Therefore, this may be an alternative interpretation, different from the one involving the adsorption of atomic sulfur resulting from the dissociation process of the S–C bond. Calculated differences in S(2p) CLBEs for free BDMT molecules, SH group sulfur on top of the SAM, and disulfide are also reported to clarify possible errors in assignments.

  12. Low temperature adsorption and site-conversion process of CO on the Ni(111) surface

    NASA Astrophysics Data System (ADS)

    Beniya, Atsushi; Isomura, Noritake; Hirata, Hirohito; Watanabe, Yoshihide

    2012-12-01

    Low-temperature (25 K) adsorption states and the site conversion of adsorbed CO between the ontop and the hollow sites on Ni(111) were studied by means of temperature programmed desorption and infrared reflection absorption spectroscopy. The activation energy and pre-exponential factor of desorption were estimated to be 1.2 eV and 2.6 × 1013 s- 1, respectively, in the limit of zero coverage. At low coverage, CO molecules preferentially adsorbed at the hollow sites below 100 K. With increasing temperature, the ontop sites were also occupied. Using a van't Hoff plot, the enthalpy and the entropy differences between the hollow and ontop CO were estimated to be 36 meV and 0.043 meV K- 1, respectively, and the vibrational entropy difference was estimated to be 0.085 meV K- 1. The positive entropy difference was the result of the low-energy frustrated translational mode of the ontop CO, which was estimated to be 4.6 ± 0.3 meV. With the harmonic approximation, the upper limit of the activation energy of site hopping from ontop sites to hollow sites was estimated to be 61 meV. In addition, it was suggested that the activation energy of hollow-to-hollow site hopping via a bridge site was less than 37 meV.

  13. Hybrid adsorptive membrane reactor

    NASA Technical Reports Server (NTRS)

    Tsotsis, Theodore T. (Inventor); Sahimi, Muhammad (Inventor); Fayyaz-Najafi, Babak (Inventor); Harale, Aadesh (Inventor); Park, Byoung-Gi (Inventor); Liu, Paul K. T. (Inventor)

    2011-01-01

    A hybrid adsorbent-membrane reactor in which the chemical reaction, membrane separation, and product adsorption are coupled. Also disclosed are a dual-reactor apparatus and a process using the reactor or the apparatus.

  14. Generalized random sequential adsorption

    NASA Astrophysics Data System (ADS)

    Tarjus, G.; Schaaf, P.; Talbot, J.

    1990-12-01

    Adsorption of hard spherical particles onto a flat uniform surface is analyzed by using generalized random sequential adsorption (RSA) models. These models are defined by releasing the condition of immobility present in the usual RSA rules to allow for desorption or surface diffusion. Contrary to the simple RSA case, generalized RSA processes are no longer irreversible and the system formed by the adsorbed particles on the surface may reach an equilibrium state. We show by using a distribution function approach that the kinetics of such processes can be described by means of an exact infinite hierarchy of equations reminiscent of the Kirkwood-Salsburg hierarchy for systems at equilibrium. We illustrate the way in which the systems produced by adsorption/desorption and by adsorption/diffusion evolve between the two limits represented by ``simple RSA'' and ``equilibrium'' by considering approximate solutions in terms of truncated density expansions.

  15. Hybrid adsorptive membrane reactor

    SciTech Connect

    Tsotsis, Theodore T.; Sahimi, Muhammad; Fayyaz-Najafi, Babak; Harale, Aadesh; Park, Byoung-Gi; Liu, Paul K. T.

    2011-03-01

    A hybrid adsorbent-membrane reactor in which the chemical reaction, membrane separation, and product adsorption are coupled. Also disclosed are a dual-reactor apparatus and a process using the reactor or the apparatus.

  16. A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry.

    PubMed

    Goverapet Srinivasan, Sriram; Shivaramaiah, Radha; Kent, Paul R C; Stack, Andrew G; Riman, Richard; Anderko, Andre; Navrotsky, Alexandra; Bryantsev, Vyacheslav S

    2017-03-06

    Bastnäsite, a fluoro-carbonate mineral, is the single largest mineral source of light rare earth elements (REE), La, Ce and Nd. Enhancing the efficiency of separation of the mineral from gangue through froth flotation is the first step towards meeting an ever increasing demand for REE. To design and evaluate collector molecules that selectively bind to bastnäsite, a fundamental understanding of the structure and surface properties of bastnäsite is essential. In our earlier work (J. Phys. Chem. C, 2016, 120, 16767), we carried out an extensive study of the structure, surface stability and water adsorption energies of La-bastnäsite. In this work, we make a comparative study of the surface properties of Ce-bastnäsite, La-bastnäsite, and calcite using a combination of density functional theory (DFT) and water adsorption calorimetry. Spin polarized DFT+U calculations show that the exchange interaction between the electrons in Ce 4f orbitals is negligible and that these orbitals do not participate in bonding with the oxygen atom of the adsorbed water molecule. In agreement with calorimetry, DFT calculations predict larger surface energies and stronger water adsorption energies on Ce-bastnäsite than on La-bastnäsite. The order of stabilities for stoichiometric surfaces is as follows: [101[combining macron]0] > [101[combining macron]1] > [101[combining macron]2] > [0001] > [112[combining macron]2] > [101[combining macron]4] and the most favorable adsorption sites for water molecules are the same as for La-bastnäsite. In agreement with water adsorption calorimetry, at low coverage water molecules are strongly stabilized via coordination to the surface Ce(3+) ions, whereas at higher coverage they are adsorbed less strongly via hydrogen bonding interaction with the surface anions. Due to similar water adsorption energies on bastnäsite [101[combining macron]1] and calcite [101[combining macron]4] surfaces, the design of collector molecules that selectively bind to

  17. High gas storage capacities and stepwise adsorption in a UiO type metal-organic framework incorporating Lewis basic bipyridyl sites.

    PubMed

    Li, Liangjun; Tang, Sifu; Wang, Chao; Lv, Xiaoxia; Jiang, Min; Wu, Huaizhi; Zhao, Xuebo

    2014-03-04

    A UiO type MOF with Lewis basic bipyridyl sites was synthesized and structurally characterized. After being activated by Soxhlet-extraction, this MOF exhibits high storage capacities for H2, CH4 and CO2, and shows unusual stepwise adsorption for liquid CO2 and solvents, indicating a sequential filling mechanism on different adsorption sites.

  18. Highly Selective Adsorption of Ethylene over Ethane in a MOF Featuring the Combination of Open Metal Site and -Complexation

    SciTech Connect

    Zhang, Yiming; Li, Baiyan; Wu, Zili; Ma, Shengqian

    2015-01-01

    The introduction of the combination of open metal site (OMS) and -complexation into MOF has led to very high ethylene/ethane adsorption selectivity at 318K, as illustrated in the context of MIL-101-Cr-SO3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

  19. Study of protein adsorption on indigo particles confirms the existence of enzyme--indigo interaction sites in cellulase molecules.

    PubMed

    Gusakov, A V; Sinitsyn, A P; Markov, A V; Sinitsyna, O A; Ankudimova, N V; Berlin, A G

    2001-04-27

    Adsorption of several crude and purified cellulases (from Trichoderma reesei, Penicillium verruculosum and Chrysosporium lucknowense) on indigo particles and Avicel cellulose was studied. Much higher amounts of protein were bound to indigo than to cellulose under similar conditions. For different purified enzymes, the quantity of bound protein per mg of adsorbent (indigo or cellulose) varied in the range of 57-111 and 0-62 microg x mg(-1), respectively. However, in general, the enzyme adsorption on indigo was less specific than the adsorption on cellulose. Three endoglucanases, having the highest indigo-binding ability, demonstrated the best washing performance in the process of enzymatic denim treatment. These data confirmed our previous findings that certain cellulases, which have indigo-binding sites (clusters of closely located aromatic and other non-polar residues) on the surface of their molecules, may remove indigo from the denim fabric better than cellulases with lower content of hydrophobic residues exposed to solvent.

  20. Adsorption of star polymers

    NASA Astrophysics Data System (ADS)

    Halperin, A.; Joanny, J. F.

    1991-06-01

    The adsorption of star polymers on a flat solid surface is analyzed by means of scalling arguments based on the Daoud-Cotton blob model. For the adsorption of a single star, consisting of f arms comprising each N monomers, we distinguish three regimes determined by the adsorption energy of a monomer at the surface, δ kT. 1) Strong adsorption characterized by the full adsorption of all arms occurs for δ > (f/N)^{3/5}. 2) A “Sombrero” like structure comprising f_ads fully adsorbed arms and f{-}f_ads free arms is obtained for (f/N)^{3/5}> δ > f^{9/20}/N^{3/5}. 3) Weakly adsorbed stars retain, essentially, the structure of a free star. This regime occurs for δ < f^{9/20}/N^{3/5}. The weakly adsorbed structure may also exist as a metastable state if δ > f^{9/5}/N^{3/5}. Nous étudions l'adsorption de polymères en étoile sur une surface solide en utilisant une approche de lois d'échelles basée sur le modèle de blobs de Daoud et Cotton. Pour une étoile formée de f bras contenant chacun N monomères, nous distinguons trois régimes suivant la valeur de l'énergie d'adsorption d'un monomère sur la surface δ kT. 1) L'adsorption forte caractérisée par une adsorption complète de tous les bras se produit lorsque δ > (f/N)^{3/5}. 2) Une structure en “sombrero” avec f_ads bras adsorbés et f{-}f_ads bras libres est obtenue si f^{9/20}/N^{3/5}δ < (f/N)^{3/5}. 3) Les étoiles faiblement adsorbées gardent une structure très similaire à celle des étoiles libres en solution. Ce régime existe si δ < f^{9/20}/N^{3/5}. La structure correspondant aux étoiles faiblement adsorbées peut aussi exister comme un état métastable si δ > f^{9/5}/N^{3/5}.

  1. Metal adsorption on mosses: Toward a universal adsorption model.

    PubMed

    González, A G; Pokrovsky, O S

    2014-02-01

    This study quantifies the adsorption of heavy metals on 4 typical moss species used for environmental monitoring in the moss bag technique. The adsorption of Cu(2+), Cd(2+), Ni(2+), Pb(2+) and Zn(2+) onto Hypnum sp., Sphagnum sp., Pseudoscleropodium purum and Brachytecium rutabulum has been investigated using a batch reactor in a wide range of pH (1.3-11.0) and metal concentrations in solution (1.6μM-3.8mM). A Linear Programming Model (LPM) was applied for the experimental data to derive equilibrium constants and the number of surface binding sites. The surface acid-base titration performed for 4 mosses at a pH range of 3-10 in 0.1M NaNO3 demonstrated that Sphagnum sp. is the most efficient adsorbent as it has the maximal number of proton-binding sites on the surface (0.65mmol g(-1)). The pKa computed for all the moss species suggested the presence of 5 major functional groups: phosphodiester, carboxyl, phosphoryl, amine and polyphenols. The results of pH-edge experiments demonstrated that B. rutabulum exhibits the highest percentage of metal adsorption and has the highest number of available sites for most of the metals studied. However, according to the results of the constant pH "Langmuirian" isotherm, Sphagnum sp. can be considered as the strongest adsorbent, although the relative difference from other mosses is within 20%. The LPM was found to satisfactorily fit the experimental data in the full range of the studied solution parameters. The results of this study demonstrate a rather similar pattern of five metal adsorptions on mosses, both as a function of pH and as a metal concentration, which is further corroborated by similar values of adsorption constants. Therefore, despite the species and geographic differences between the mosses, a universal adsorption edge and constant pH adsorption isotherm can be recommended for 4 studied mosses. The quantitative comparison of metal adsorption with other common natural organic and inorganic materials demonstrates

  2. Fluoride adsorption on goethite in relation to different types of surface sites

    SciTech Connect

    Hiemstra, T.; Van Riemsdijk, W.H.

    2000-05-01

    Metal (hydr)oxides have different types of surface groups. Fluoride ions have been used as a probe to assess the number of surface sites. The authors have studied the F{sup {minus}} adsorption on goethite by measuring the F{sup {minus}} and H{sup +} interaction and F{sup {minus}} adsorption isotherms. Fluoride ions exchange against singly coordinated surface hydroxyls at low F{sup {minus}} concentrations. At higher concentrations also the doubly coordinated OH groups are involved. The replacement of a surface OH{sup {minus}} by F{sup {minus}} suggests that all F charge ({minus}1) is located at the surface in contrast to oxyanions which have a charge distribution in the interface due to the binding structure in which the anion only partially coordinates with the surface. Analysis of their F{sup {minus}} data with the CD-MUSIC approach shows that the formation of the fluoride surface complex is accompanied by a redistribution of charge. This is supposed to be due to a net switch in the H bonding as a result of the change of the type of surface complex from donating (FeOH, FeOH{sub 2}) to proton accepting (FeF). The modeled redistribution of charge is approximately equivalent with the change of a donating H bond into an accepting H bond. At high F{sup {minus}} concentrations precipitation of F{sup {minus}}, as for instance FeF{sub 3}(s), may occur. The rate of formation is catalyzed by the presence of high electrolyte concentrations.

  3. Aspects on the interaction between sodium carboxymethylcellulose and calcium carbonate and the relationship to specific site adsorption.

    PubMed

    Backfolk, Kaj; Lagerge, Serge; Rosenholm, Jarl B; Eklund, Dan

    2002-04-01

    The mechanisms of adsorption and association for sodium carboxymethylcellulose (NaCMC) in calcium carbonate suspensions have been determined from isothermal calorimetry and adsorption measurements. The equilibrium adsorption isotherms were determined by two different methods of separation; a depletion method and a serum exchange method. The enthalpy of dilution for NaCMC was determined on supernatants obtained from the calcium carbonate suspensions in order to investigate the interaction between NaCMC and dissolved species from the mineral. For comparison, NaCMC was injected into CaCl(2) solutions in order to determine the role of calcium ions in the adsorption process. The initial part of the adsorption isotherm showed a quasi-infinite slope indicating a high affinity for the NaCMC to the calcium carbonate surface, which was significantly reduced when anionic sodium polyacrylate was preadsorbed onto the calcium carbonate implying competitive adsorption. An endothermic enthalpy change was observed between the NaCMC and the calcium carbonate surface, suggesting attachment of the carboxylic acid groups onto the hydrated calcium sites. A similar endothermic enthalpy was observed when NaCMC was injected into CaCl(2) solutions or supernatants obtained from the calcium carbonate suspensions, indicating a complexation of carboxylic acid groups and hydrated calcium ions. It was concluded that the mechanisms of interaction of NaCMC in calcium carbonate suspensions are primarily an association between NaCMC and Lewis acid sites on the calcium carbonate surface and the formation of NaCMC-Ca(2+) complexes in the bulk solution, both of which will be affected by the amount of anionic sodium polyacrylate present.

  4. Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado.

    PubMed

    Hyun, Sung Pil; Fox, Patricia M; Davis, James A; Campbell, Kate M; Hayes, Kim F; Long, Philip E

    2009-12-15

    A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2 mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 x 10(-8) to 10(-5) M in [U(VI)](tot), 7.2 to 8.0 in pH, 3.0 x 10(-3) to 6.0 x 10(-3) M in [Ca(2+)], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption K(d) values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters.

  5. Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

    USGS Publications Warehouse

    Hyun, S.P.; Fox, P.M.; Davis, J.A.; Campbell, K.M.; Hayes, K.F.; Long, P.E.

    2009-01-01

    A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10-8 to 10-5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10-3 to 6.0 ?? 10 -3 M in [Ca2+], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

  6. High ionic strength narrows the population of sites participating in protein ion-exchange adsorption: a single-molecule study.

    PubMed

    Kisley, Lydia; Chen, Jixin; Mansur, Andrea P; Dominguez-Medina, Sergio; Kulla, Eliona; Kang, Marci K; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Dhamane, Sagar; Willson, Richard C; Landes, Christy F

    2014-05-23

    The retention and elution of proteins in ion-exchange chromatography is routinely controlled by adjusting the mobile phase salt concentration. It has repeatedly been observed, as judged from adsorption isotherms, that the apparent heterogeneity of adsorption is lower at more-eluting, higher ionic strength. Here, we present an investigation into the mechanism of this phenomenon using a single-molecule, super-resolution imaging technique called motion-blur Points Accumulation for Imaging in Nanoscale Topography (mbPAINT). We observed that the number of functional adsorption sites was smaller at high ionic strength and that these sites had reduced desorption kinetic heterogeneity, and thus narrower predicted elution profiles, for the anion-exchange adsorption of α-lactalbumin on an agarose-supported, clustered-charge ligand stationary phase. Explanations for the narrowing of the functional population such as inter-protein interactions and protein or support structural changes were investigated through kinetic analysis, circular dichroism spectroscopy, and microscopy of agarose microbeads, respectively. The results suggest the reduction of heterogeneity is due to both electrostatic screening between the protein and ligand and tuning the steric availability within the agarose support. Overall, we have shown that single molecule spectroscopy can aid in understanding the influence of ionic strength on the population of functional adsorbent sites participating in the ion-exchange chromatographic separation of proteins.

  7. High ionic strength narrows the population of sites participating in protein ion-exchange adsorption: A single-molecule study

    PubMed Central

    Kisley, Lydia; Chen, Jixin; Mansur, Andrea P.; Dominguez-Medina, Sergio; Kulla, Eliona; Kang, Marci; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Dhamane, Sagar; Willson, Richard C.; Landes, Christy F.

    2014-01-01

    The retention and elution of proteins in ion-exchange chromatography is routinely controlled by adjusting the mobile phase salt concentration. It has repeatedly been observed, as judged from adsorption isotherms, that the apparent heterogeneity of adsorption is lower at more-eluting, higher ionic strength. Here, we present an investigation into the mechanism of this phenomenon using a single-molecule, super-resolution imaging technique called motion-blur Points Accumulation for Imaging in Nanoscale Topography (mbPAINT). We observed that the number of functional adsorption sites was smaller at high ionic strength and that these sites had reduced desorption kinetic heterogeneity, and thus narrower predicted elution profiles, for the anion-exchange adsorption of α-lactalbumin on an agarose-supported, clustered-charge ligand stationary phase. Explanations for the narrowing of the functional population such as inter-protein interactions and protein or support structural changes were investigated through kinetic analysis, circular dichroism spectroscopy, and microscopy of agarose microbeads, respectively. The results suggest the reduction of heterogeneity is due to both electrostatic screening between the protein and ligand and tuning the steric availability within the agarose support. Overall, we have shown that single molecule spectroscopy can aid in understanding the influence of ionic strength on the population of functional adsorbent sites participating in the ion-exchange chromatographic separation of proteins. PMID:24751557

  8. How Surface Heterogeneity Affects Protein Adsorption: Annealing of OTS Patterns and Albumin Adsorption Kinetics*

    PubMed Central

    Hodgkinson, Gerald N.; Hlady, Vladimir

    2009-01-01

    Fluorescence microscopy and intensity histogram analysis techniques were used to monitor spatially-resolved albumin adsorption kinetics to model heterogeneous surfaces on sub-μm scales. Several distinct protein subpopulations were resolved, each represented by a normal distribution of adsorption densities on the adsorbent surface. Histogram analyses provided dynamic information of mean adsorption density, spread in adsorption density, and surface area coverage for each distinct protein subpopulation. A simple adsorption model is proposed in which individual protein binding events are predicted by the summation of multiple protein's surface sub-site interactions with different binding energy sub-sites on adsorbent surfaces. This model is predictive of the albumin adsorption on the patterns produced by one step μ-contact printing (μCP) of octadecyltrichlorosilane (OTS) on glass but fails to describe adsorption once the same patterns are altered by a thermal annealing step. PMID:19746205

  9. Direct inference of site strength in basic solids upon CO2 adsorption: enthalpy-entropy compensation effects.

    PubMed

    Pera-Titus, M

    2016-08-10

    The adsorption of CO2 coupled to calorimetry is a state-of-the-art technique for characterizing the basic properties of solids. In this paper, we show that the differential heat and entropy curves measured upon CO2 adsorption on a basic solid can be reasonably estimated from a single CO2 isotherm with no need for any independent heat (calorimetric) measurement. Our method relies on two important observations: (1) formulation of generalized F-H-TS thermodynamic isotherms, the former (F) being directly generated from the raw CO2 isotherms, and (2) the presence of unexpected enthalpy-entropy compensation effects upon CO2 adsorption linking the integral enthalpy and entropy of adsorption until saturation for different solids. Our thermodynamic method has been validated using a broad library of basic solids with variable site strength and heterogeneity. Finally, a new scale of basicity is proposed using the parameters fitted from the thermodynamic isotherm (free energy basis) as descriptors of basic strength. This method opens an avenue to the inference of site strength of basic solids without the need for expensive calorimeters.

  10. New Adsorption Methods.

    ERIC Educational Resources Information Center

    Wankat, Phillip C.

    1984-01-01

    Discusses a simple method for following the movement of a solute in an adsorption or ion exchange system. This movement is used to study a variety of operational methods, including continuous flow and pulsed flow counter-current operations and simulated counter-current systems. Effect of changing thermodynamic variables is also considered. (JM)

  11. SEPARATION BY ADSORPTION

    DOEpatents

    Lowe, C.S.

    1959-06-16

    Separation of Pu from fission products by adsorption on hydrous aluminum silicate is described. The Pu in a HNO/sub 3/ solution is oxidized to the hexavalent state and contacted with the silicate which adsorbs fission products. (T.R.H.)

  12. Water adsorption onto Y and V sites at the surface of the YVO4 photocatalyst and related electronic properties

    NASA Astrophysics Data System (ADS)

    Oshikiri, Mitsutake; Boero, Mauro; Matsushita, Akiyuki; Ye, Jinhua

    2009-07-01

    The dynamics of water molecules and the adsorption properties at the V and Y sites on the surface of the photocatalyst YVO4 have been investigated by first principles molecular dynamics. This system has shown an excellent performance in the production of both hydrogen and oxygen in the ultraviolet region. Yet, its catalytic properties, related to the electronic structure, are poorly understood. Here we show that imperfectly oxygen coordinated V sites (i.e., not fourfold oxygen coordinated vanadium but threefold oxygen coordinated vanadium) exposed on the catalyst surface play a central role in the dissociation of water molecules. By simulating the H2O adsorption process and by performing an analysis of the electronic structure of the unoccupied orbitals corresponding to the lowest unoccupied energy level of the system, we can infer that the dissociation of water at these imperfectly oxygen coordinated V sites can promote the proton reduction and is expected to trigger the H2 generation.

  13. Adsorption of Carbon Dioxide on Unsaturated Metal Sites in M2 (dobpdc) Frameworks with Exceptional Structural Stability and Relation between Lewis Acidity and Adsorption Enthalpy.

    PubMed

    Yoo, Ga Young; Lee, Woo Ram; Jo, Hyuna; Park, Joonho; Song, Jeong Hwa; Lim, Kwang Soo; Moon, Dohyun; Jung, Hyun; Lim, Juhyung; Han, Sang Soo; Jung, Yousung; Hong, Chang Seop

    2016-05-23

    A series of metal-organic frameworks (MOFs) M2 (dobpdc) (M=Mn, Co, Ni, Zn; H4 dobpdc=4,4'-dihydroxy-1,1'-biphenyl-3,3'-dicarboxylic acid), with a highly dense arrangement of open metal sites along hexagonal channels were prepared by microwave-assisted or simple solvothermal reactions. The activated materials were structurally expanded when guest molecules including CO2 were introduced into the pores. The Lewis acidity of the open metal sites varied in the order MnZn, as confirmed by C=O stretching bands in the IR spectra, which are related to the CO2 adsorption enthalpy. DFT calculations revealed that the high CO2 binding affinity of transition-metal-based M2 (dobpdc) is primarily attributable to the favorable charge transfer from CO2 (oxygen lone pair acting as a Lewis base) to the open metal sites (Lewis acid), while electrostatic effects, the underlying factor responsible for the particular order of binding strength observed across different transition metals, also play a role. The framework stability against water coincides with the order of Lewis acidity. In this series of MOFs, the structural stability of Ni2 (dobpdc) is exceptional; it endured in water vapor, liquid water, and in refluxing water for one month, and the solid remained intact on exposure to solutions of pH 2-13. The DFT calculations also support the experimental finding that Ni2 (dobpdc) has higher chemical stability than the other frameworks.

  14. Modifying the adsorption characteristic of inert silica films by inserting anchoring sites.

    PubMed

    Ulrich, Stefan; Nilius, Niklas; Freund, Hans-Joachim; Martinez, Umberto; Giordano, Livia; Pacchioni, Gianfranco

    2009-01-09

    The adsorption properties of thin silica films on Mo(112) have been tailored by embedding single Pd atoms into the nanopores of the oxide material. The embedded Pd is able to anchor metal adatoms that would not bind to the inert silica surface otherwise. Several adsorption structures, e.g., Pd-Pd, Ag-Pd, and Au-Pd complexes, have been prepared in this way and analyzed with the STM and density functional theory. The binding strength of the different adatoms to the surface is determined by the number of electrons in their frontier orbitals, which introduce a repulsive interaction with the oxide electronic states and weaken the covalent bond to the Pd anchor.

  15. The S(2p) Core Level Binding Energies for Alternative Adsorption Sites and the Example of Thiol Self Assembly

    NASA Astrophysics Data System (ADS)

    Jia, Juanjuan; Esaulov, Vladimir; Kara, Abdelkader

    2015-03-01

    Results of an investigation of the characteristics of thiol SAMs obtained by vacuum evaporative adsorption, useful for reactive substrates, are presented along with core level binding energy (BE) calculations. Thiol ended SAMs of 1,4-benzenedimethanethiol (BDMT) are obtained by evaporation on Au. They display an unconventional BE structure at about 161 eV, which is close to a known BE of an S atom on Au. S(2p) core level BE calculations for molecules chemisorbed on hollow, bridge and atop sites are reported and suggest that the 161 eV peak is indeed due to an alternative adsorption site, which can be associated to an atop configuration. This must therefore not be confused with atomic sulfur and dissociation processes with S-C bond scission. Work partially supported by the U.S. Department of Energy Basic Energy Science under Contract No DE-FG02-11ER16243.

  16. Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

    SciTech Connect

    Hyun, S. P.; Fox, Patricia M.; Davis, James A.; Campbell, Kate M.; Hayes, Kim F.; Long, Philip E.

    2009-12-15

    U(VI) adsorption by two aquifer sediment samples was studied under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Background-A (BKG-A) sediment was collected upstream of a former uranium mill-tailings site at Rifle, Colorado, and Little Rusty Composite (LRC) was collected on site but with low U contamination. Batch adsorption experiments were performed using artificial groundwater solutions prepared to simulate the field groundwater composition in equilibrium with specific partial pressures of carbon dioxide. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8×10-8 to 10-5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0×10-3 to 6.0×10-3 M in [Ca2+], and 0.05 to 2.6% in partial pressure of carbon dioxide. The sediment was extracted with a dilute bicarbonate/carbonate solution to determine the background labile U(VI) already present in the sediment. A semi-empirical surface complexation model was developed to describe U(VI) adsorption using FITEQL4. The non-electrostatic, generalized composite surface complexation model successfully simulated U(VI) adsorption over the range of groundwater conditions at the Old Rifle site, using a two-site, two-reaction fitting scheme. The sensitivity of model parameters to background U(VI) concentration on the two samples was evaluated. U(VI) adsorption experiments were also performed using a sand fraction of BKG-A separated through repeated sonication and wet-sieving. Surface area normalized Kd for the bulk and sand fraction indicated similar reactivity for both. The surface complexation model developed in this work is expected to contribute to the prediction of fate and transport of U(VI) in the alluvial aquifer at the Old Rifle site, and to assist in the simulation of biostimulation field experiments performed at the site.

  17. Regenerable adsorption system

    NASA Technical Reports Server (NTRS)

    Roychoudhury, Subir (Inventor); Perry, Jay (Inventor); Walsh, Dennis (Inventor)

    2006-01-01

    A method for regenerable adsorption includes providing a substrate that defines at least one layer of ultra short channel length mesh capable of conducting an electrical current therethrough, coating at least a portion of the substrate with a desired sorbent for trace contaminant control or CO.sub.2 sorption, resistively heating the substrate, and passing a flowstream through the substrate and in contact with the sorbent.

  18. Predicting Multicomponent Adsorption Isotherms in Open-Metal Site Materials Using Force Field Calculations Based on Energy Decomposed Density Functional Theory.

    PubMed

    Heinen, Jurn; Burtch, Nicholas C; Walton, Krista S; Fonseca Guerra, Célia; Dubbeldam, David

    2016-12-12

    For the design of adsorptive-separation units, knowledge is required of the multicomponent adsorption behavior. Ideal adsorbed solution theory (IAST) breaks down for olefin adsorption in open-metal site (OMS) materials due to non-ideal donor-acceptor interactions. Using a density-function-theory-based energy decomposition scheme, we develop a physically justifiable classical force field that incorporates the missing orbital interactions using an appropriate functional form. Our first-principles derived force field shows greatly improved quantitative agreement with the inflection points, initial uptake, saturation capacity, and enthalpies of adsorption obtained from our in-house adsorption experiments. While IAST fails to make accurate predictions, our improved force field model is able to correctly predict the multicomponent behavior. Our approach is also transferable to other OMS structures, allowing the accurate study of their separation performances for olefins/paraffins and further mixtures involving complex donor-acceptor interactions.

  19. Albumin (BSA) Adsorption over Graphene in Aqueous Environment: Influence of Orientation, Adsorption Protocol, and Solvent Treatment.

    PubMed

    Vilhena, J G; Rubio-Pereda, Pamela; Vellosillo, Perceval; Serena, P A; Pérez, Rubén

    2016-02-23

    We report 150 ns explicit solvent MD simulations of the adsorption on graphene of albumin (BSA) in two orientations and using two different adsorption protocols, i.e., free and forced adsorption. Our results show that free adsorption occurs with little structural rearrangements. Even taking adsorption to an extreme, by forcing it with a 5 nN downward force applied during the initial 20 ns, we show that along a particular orientation BSA is able to preserve the structural properties of the majority of its binding sites. Furthermore, in all the cases considered in this work, the ibuprofen binding site has shown a strong resilience to structural changes. Finally, we compare these results with implicit solvent simulations and find that the latter predicts an extreme protein unfolding upon adsorption. The origin of this discrepancy is attributed to a poor description of the water entropic forces at interfaces in the implicit solvent methods.

  20. Diffusion Influenced Adsorption Kinetics.

    PubMed

    Miura, Toshiaki; Seki, Kazuhiko

    2015-08-27

    When the kinetics of adsorption is influenced by the diffusive flow of solutes, the solute concentration at the surface is influenced by the surface coverage of solutes, which is given by the Langmuir-Hinshelwood adsorption equation. The diffusion equation with the boundary condition given by the Langmuir-Hinshelwood adsorption equation leads to the nonlinear integro-differential equation for the surface coverage. In this paper, we solved the nonlinear integro-differential equation using the Grünwald-Letnikov formula developed to solve fractional kinetics. Guided by the numerical results, analytical expressions for the upper and lower bounds of the exact numerical results were obtained. The upper and lower bounds were close to the exact numerical results in the diffusion- and reaction-controlled limits, respectively. We examined the validity of the two simple analytical expressions obtained in the diffusion-controlled limit. The results were generalized to include the effect of dispersive diffusion. We also investigated the effect of molecular rearrangement of anisotropic molecules on surface coverage.

  1. Arsenic Adsorption Equilibrium Concentration and Adsorption Rate of Activated Carbon Coated with Ferric-Aluminum Hydroxides

    NASA Astrophysics Data System (ADS)

    Zhang, M.; Sugita, H.; Oguma, T.; Hara, J.; Takahashi, S.

    2015-12-01

    In some areas of developing countries, ground or well water contaminated with arsenic has been reluctantly used as drinking water. It is highly desirable that effective and inexpensive arsenic removal agents should be developed and provided to reduce the potential health risk. Previous studies demonstrated that activated carbon coated with ferric-aluminum hydroxides (Fe-Al-C) has high adsorptive potential for removal of arsenic. In this study, a series of experiments using Fe-Al-C were carried to discuss adsorption equilibrium time, adsorption equilibrium concentration and adsorption rate of arsenic for Fe-Al-C. Fe-Al-C used in this study was provided by Astec Co., Ltd. Powder reagent of disodium hydrogen arsenate heptahydrate was dissolved into ion-exchanged water. The solution was then further diluted with ion-exchanged water to be 1 and 10 mg/L as arsenic concentration. The pH of the solution was adjusted to be around 7 by adding HCl and/or NaOH. The solution was used as artificial arsenic contaminated water in two types of experiments (arsenic adsorption equilibrium and arsenic adsorption rate tests). The results of the arsenic equilibrium tests were showed that a time period of about 3 days to reach apparent adsorption equilibrium for arsenic. The apparent adsorption equilibrium concentration and adsorbed amount of arsenic on Fe-Al-C adsorbent could be estimated by application of various adsorption isotherms, but the distribution coefficient of arsenic between solid and liquid varies with experimental conditions such as initial concentration of arsenic and addition concentration of adsorbent. An adsorption rate equation that takes into account the reduction in the number of effective adsorption sites on the adsorbent caused by the arsenic adsorption reaction was derived based on the data obtained from the arsenic adsorption rate tests.

  2. Infrared spectroscopic and thermodynamic assessment of extraframework cationic adsorption sites in the zeolite K-L by using CO as probe molecule

    NASA Astrophysics Data System (ADS)

    Delgado, Montserrat R.; de Yuso, Alicia Martínez; Bulánek, Roman; Arean, Carlos O.

    2015-10-01

    Zeolites are often used as the host material for holding and organizing adsorbed molecules and supramolecular species inside their void channels and cages, in order to exploit space confinement and host-guest interaction for engineering composite materials having novel electronic and optical properties. That endeavour would benefit from improved knowledge about the type and strength of the zeolite adsorption sites. To this end, variable temperature infrared spectroscopy (a technique capable of giving simultaneous information on the type and strength of gas-adsorption complexes) was used herein to characterize the zeolite K-L by means of adsorbed CO. Two types of cationic adsorption sites (termed D‧ and D″) were found on the wall of the zeolite main channel; formation of the corresponding CO adsorption complexes was found to involve a standard enthalpy change of -23.4 and -26.7 kJ mol-1, respectively.

  3. NH3 adsorption on the Lewis and Bronsted acid sites of MoO3 (0 1 0) surface: A cluster DFT study

    NASA Astrophysics Data System (ADS)

    Yan, Zhifeng; Fan, Junyan; Zuo, Zhijun; Li, Zhe; Zhang, Jinshan

    2014-01-01

    The adsorption of NH3 on the Lewis and Bronsted acid sites of MoO3 (0 1 0) surface has been investigated based on the density functional theory (DFT) method using the clusters models. The calculated results indicate that NH3 could strongly adsorb on both the Lewis and Bronsted acid sites in the form of NH3 species and NH4+ respectively, whereas the adsorption on the Lewis acid site is found to be more favorable energetically than that on the Bronsted acid site. For the Lewis acid site Mulliken population analysis shows a donation of lone pairs from NH3 to the surface and activation of N-H bond. The overlaps of N-s, N-p and Mo-d orbitals suggest the strong interaction between N and Mo atoms. For the Bronsted acid site N-H bond is also activated by the formation of NH4+ species. The hybridizations between H and O atoms as well as N and H atoms are the major reasons for strong chemical adsorption of NH3 and the existence of NH4+ species, which partly attributed to the presence of N-H… O hydrogen bonds. Furthermore, the formation of a second Lewis acid site at adjacent or diagonal site results in slight changes of adsorption stability, structural changes and charge redistributions, suggesting its small influence on NH3 adsorption.

  4. Liquid-Phase Adsorption Fundamentals.

    ERIC Educational Resources Information Center

    Cooney, David O.

    1987-01-01

    Describes an experiment developed and used in the unit operations laboratory course at the University of Wyoming. Involves the liquid-phase adsorption of an organic compound from aqueous solution on activated carbon, and is relevant to adsorption processes in general. (TW)

  5. Chromium adsorption by lignin

    SciTech Connect

    Lalvani, S.B.; Huebner, A.; Wiltowski, T.S.

    2000-01-01

    Hexavalent chromium is a known carcinogen, and its maximum contamination level in drinking water is determined by the US Environmental Protection Agency (EPA). Chromium in the wastewaters from plating and metal finishing, tanning, and photographic industries poses environmental problems. A commercially available lignin was used for the removal of hexavalent as well as trivalent chromium from aqueous solution. It is known that hexavalent chromium is present as an anionic species in the solution. It was found that lignin can remove up to 63% hexavalent and 100% trivalent chromium from aqueous solutions. The removal of chromium ions was also investigated using a commercially available activated carbon. This absorbent facilitated very little hexavalent and almost complete trivalent chromium removal. Adsorption isotherms and kinetics data on the metal removal by lignin and activated carbon are presented and discussed.

  6. High temperature adsorption measurements

    SciTech Connect

    Bertani, R.; Parisi, L.; Perini, R.; Tarquini, B.

    1996-12-31

    Adsorption phenomena are a rich and rather new field of study in geothermal research, in particular at very high temperature. ENEL is interested in the exploitation of geothermal regions with super-heated steam, and it is important to understand the behavior of water-rock interaction. We have analyzed in the 170-200{degrees}C temperature range four samples of Monteverdi cuttings; the next experimental effort will be at 220{degrees}C and over in 1996. The first results of the 1995 runs are collected in this paper. We can highlight four main items: (1) At relative pressures over 0.6 the capillarity forces are very important. (2) There is no significant temperature effect. (3) Adsorbed water can be present, and it is able to multiply by a factor of 15 the estimated reserve of super-heated steam only. (4) Pores smaller than 15 {Angstrom} do not contribute to the adsorbed mass.

  7. High temperature adsorption measurements

    SciTech Connect

    Bertani, R.; Parisi, L.; Perini, R.; Tarquini, B.

    1996-01-24

    Adsorption phenomena are a rich and rather new field of study in geothermal research, in particular at very high temperature. ENEL is interested in the exploitation of geothermal regions with superheated steam, and it is important to understand the behavior of water-rock interaction. We have analyzed in the 170-200 °C temperature range four samples of Monteverdi cuttings; the next experimental effort will be at 220 °C and over in 1996. The first results of the 1995 runs are collected in this paper. We can highlight four main items: 1. At relative pressures over 0.6 the capillarity forces are very important. 2. There is no significant temperature effect. 3. Adsorbed water can be present, and it is able to multiply by a factor of 15 the estimated reserve of super-heated steam only. 4. Pores smaller than 15 Å do not contribute to the adsorbed mass.

  8. Adsorption kinetics of laterally and polarly flagellated Vibrio.

    PubMed Central

    Belas, M R; Colwell, R R

    1982-01-01

    The adsorption of laterally and polarly flagellated bacteria to chitin was measured, and from the data obtained, a modified Langmuir adsorption isotherm was derived. Results indicated that the adsorption of laterally flagellated Vibrio parahaemolyticus follows the Langmuir adsorption isotherm, a type of adsorption referred to as surface saturation kinetics, when conditions are favorable for the production of lateral flagella. When conditions were not favorable for the production of lateral flagella, bacterial adsorption did not follow the Langmuir adsorption isotherm; instead, proportional adsorption kinetics were observed. The adsorption of some polarly flagellated bacteria exhibited surface saturation kinetics. However, the binding index (the product of the number of binding sites and bacterial affinity to the surface) of polarly flagellated bacteria differed significantly from that of laterally flagellated bacteria, suggesting that polarly flagellated bacteria adsorb to chitin by a different mechanism from that used by the laterally flagellated bacteria. From the results of dual-label adsorption competition experiments, in which polarly flagellated V. cholerae competed with increasing concentrations of laterally flagellated V. parahaemolyticus, it was observed that laterally flagellated bacteria inhibited the adsorption of polarly flagellated bacteria. In contrast, polarly flagellated bacteria enhanced the adsorption of V. cholerae. In competition experiments, where V. parahaemolyticus competed against increasing concentrations of other bacteria, polarly flagellated bacteria enhanced V. parahaemolyticus adsorption significantly, whereas laterally flagellated bacteria only slightly enhanced the process. The direct correlation observed between surface saturation kinetics, the production of lateral flagella, and the ability of laterally flagellated bacteria to inhibit the adsorption of polarly flagellated bacteria suggests that lateral flagella represent a

  9. Random sequential adsorption on fractals.

    PubMed

    Ciesla, Michal; Barbasz, Jakub

    2012-07-28

    Irreversible adsorption of spheres on flat collectors having dimension d < 2 is studied. Molecules are adsorbed on Sierpinski's triangle and carpet-like fractals (1 < d < 2), and on general Cantor set (d < 1). Adsorption process is modeled numerically using random sequential adsorption (RSA) algorithm. The paper concentrates on measurement of fundamental properties of coverages, i.e., maximal random coverage ratio and density autocorrelation function, as well as RSA kinetics. Obtained results allow to improve phenomenological relation between maximal random coverage ratio and collector dimension. Moreover, simulations show that, in general, most of known dimensional properties of adsorbed monolayers are valid for non-integer dimensions.

  10. Protein Adsorption in Three Dimensions

    PubMed Central

    Vogler, Erwin A.

    2011-01-01

    Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and

  11. Methanethiolate Adsorption Site on Au(111): A Combined STM/DFT Study at the Single-Molecule Level

    SciTech Connect

    Maksymovych, P.; Sorescu, D.C.; Yates, J.T.

    2006-10-26

    The chemisorptive bonding of methanethiolate (CH3S) on the Au(111) surface has been investigated at a single-molecule level using low-temperature scanning tunneling microscopy (LT-STM) and density functional theory (DFT). The CH3S species were produced by STM-tip-induced dissociation of methanethiol (CH3SH) or dimethyl disulfide (CH3SSCH3) at 5 K. The adsorption site of an isolated CH3S species was assigned by comparing the experimental and calculated STM images. We conclude that the S-headgroup of chemisorbed CH3S adsorbs on the 2-fold coordinated bridge site between two Au atoms, consistent with theoretical predictions for CH3S on the nondefective Au(111) surface. Our assignment is also supported by the freezing of the tip-induced rotational dynamics of a single CH3SH molecule upon conversion to CH3S via deprotonation.

  12. Bromide Adsorption by Reference Minerals and Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bromide, Br-, adsorption behavior was investigated on amorphous Al and Fe oxide, montmorillonite, kaolinite, and temperate and tropical soils. Bromide adsorption decreased with increasing solution pH with minimal adsorption occurring above pH 7. Bromide adsorption was higher for amorphous oxides t...

  13. Centrifugal Adsorption Cartridge System

    NASA Technical Reports Server (NTRS)

    Gonda, Steve R.; Tsao, Yow-Min D.; Lee, Wenshan

    2004-01-01

    The centrifugal adsorption cartridge system (CACS) is an apparatus that recovers one or more bioproduct(s) from a dilute aqueous solution or suspension flowing from a bioreactor. The CACS can be used both on Earth in unit gravity and in space in low gravity. The CACS can be connected downstream from the bioreactor; alternatively, it can be connected into a flow loop that includes the bioreactor so that the liquid can be recycled. A centrifugal adsorption cartridge in the CACS (see figure) includes two concentric cylinders with a spiral ramp between them. The volume between the inner and outer cylinders, and between the turns of the spiral ramp is packed with an adsorbent material. The inner cylinder is a sieve tube covered with a gas-permeable, hydrophobic membrane. During operation, the liquid effluent from the bioreactor is introduced at one end of the spiral ramp, which then constrains the liquid to flow along the spiral path through the adsorbent material. The spiral ramp also makes the flow more nearly uniform than it would otherwise be, and it minimizes any channeling other than that of the spiral flow itself. The adsorbent material is formulated to selectively capture the bioproduct(s) of interest. The bioproduct(s) can then be stored in bound form in the cartridge or else eluted from the cartridge. The centrifugal effect of the spiral flow is utilized to remove gas bubbles from the liquid. The centrifugal effect forces the bubbles radially inward, toward and through the membrane of the inner cylinder. The gas-permeable, hydrophobic membrane allows the bubbles to enter the inner cylinder while keeping the liquid out. The bubbles that thus enter the cylinder are vented to the atmosphere. The spacing between the ramps determines rate of flow along the spiral, and thereby affects the air-bubble-removal efficiency. The spacing between the ramps also determines the length of the fluid path through the cartridge adsorbent, and thus affects the bioproduct

  14. A quantum chemical study for exploring the inhibitory effect of nitrogen containing species on the adsorption of polynuclear aromatic hydrocarbons over a Bronsted acid site

    NASA Astrophysics Data System (ADS)

    Celis-Cornejo, C. M.; Garnica Mantilla, M. M.; Baldovino-Medrano, V. G.; Ramírez-Caballero, G. E.

    2016-08-01

    The analysis of the inhibitory effect of nitrogenated compounds on the hydroprocessing and hydropurification of oil derived fuels is important to produce cleaner fuels. In this work, density functional theory calculations were performed to investigate the effect of the nitrogen containing molecules on the adsorption of Polynuclear Aromatic Hydrocarbons (PAHs). Mordenite was chosen as a zeolitic structure for simulating a Bronsted acid site. The character of the acid site was confirmed by both a vibrational frequency calculation and a Bader charge analysis. From the adsorption calculations, it was found that the adsorption energy of PAHs increases with the number of aromatic rings in the structure. Also, the nitrogen containing species possibly inhibit more extensively two and three rings PAHs because of their lower adsorption energies. Finally, it was observed that the nitrogen species tend to drag the proton from the mordenite acid site. This explains the inhibitory effect in the adsorption of PAHs and contributes to understanding the dynamics of hydrocarbon hydroprocessing in refineries.

  15. Multilayer adsorption on fractal surfaces.

    PubMed

    Vajda, Péter; Felinger, Attila

    2014-01-10

    Multilayer adsorption is often observed in liquid chromatography. The most frequently employed model for multilayer adsorption is the BET isotherm equation. In this study we introduce an interpretation of multilayer adsorption measured on liquid chromatographic stationary phases based on the fractal theory. The fractal BET isotherm model was successfully used to determine the apparent fractal dimension of the adsorbent surface. The nonlinear fitting of the fractal BET equation gives us the estimation of the adsorption equilibrium constants and the monolayer saturation capacity of the adsorbent as well. In our experiments, aniline and proline were used as test molecules on reversed phase and normal phase columns, respectively. Our results suggest an apparent fractal dimension 2.88-2.99 in the case of reversed phase adsorbents, in the contrast with a bare silica column with a fractal dimension of 2.54.

  16. Short-Cycle Adsorption Refrigerator

    NASA Technical Reports Server (NTRS)

    Chan, C. K.

    1988-01-01

    Modular adsorption/Joule-Thomson-effect refrigerator offers fast regeneration; adsorption/desorption cycle time expected to be 1 minute. Pressurized hydrogen generated by bank of compressor modules during heating phase passes through system of check valves and expands in Joule-Thomson junction as it enters refrigeration chamber. Hydrogen absorbs heat from load before it is sucked out by another bank of compressor modules in cooling phase.

  17. Adsorption hysteresis in nanopores

    PubMed

    Neimark; Ravikovitch; Vishnyakov

    2000-08-01

    Capillary condensation hysteresis in nanopores is studied by Monte Carlo simulations and the nonlocal density functional theory. Comparing the theoretical results with the experimental data on low temperature sorption of nitrogen and argon in cylindrical channels of mesoporous siliceous molecular sieves of MCM-41 type, we have revealed four qualitatively different sorption regimes depending on the temperature and pore size. As the pore size increases at a given temperature, or as the temperature decreases at a given pore size, the following regimes are consequently observed: volume filling without phase separation, reversible stepwise capillary condensation, irreversible capillary condensation with developing hysteresis, and capillary condensation with developed hysteresis. We show that, in the regime of developed hysteresis (pores wider than 5 nm in the case of nitrogen sorption at 77 K), condensation occurs spontaneously at the vaporlike spinodal while desorption takes place at the equilibrium. A quantitative agreement is found between the modeling results and the experimental hysteresis loops formed by the adsorption-desorption isotherms. The results obtained provide a better understanding of the general behavior of confined fluids and the specifics of sorption and phase transitions in nanomaterials.

  18. Surfactant adsorption kinetics in microfluidics

    PubMed Central

    Riechers, Birte; Maes, Florine; Akoury, Elias; Semin, Benoît; Gruner, Philipp; Baret, Jean-Christophe

    2016-01-01

    Emulsions are metastable dispersions. Their lifetimes are directly related to the dynamics of surfactants. We design a microfluidic method to measure the kinetics of adsorption of surfactants to the droplet interface, a key process involved in foaming, emulsification, and droplet coarsening. The method is based on the pH decay in the droplet as a direct measurement of the adsorption of a carboxylic acid surfactant to the interface. From the kinetic measurement of the bulk equilibration of the pH, we fully determine the adsorption process of the surfactant. The small droplet size and the convection during the droplet flow ensure that the transport of surfactant through the bulk is not limiting the kinetics of adsorption. To validate our measurements, we show that the adsorption process determines the timescale required to stabilize droplets against coalescence, and we show that the interface should be covered at more than 90% to prevent coalescence. We therefore quantitatively link the process of adsorption/desorption, the stabilization of emulsions, and the kinetics of solute partitioning—here through ion exchange—unraveling the timescales governing these processes. Our method can be further generalized to other surfactants, including nonionic surfactants, by making use of fluorophore–surfactant interactions. PMID:27688765

  19. Surfactant adsorption kinetics in microfluidics

    NASA Astrophysics Data System (ADS)

    Riechers, Birte; Maes, Florine; Akoury, Elias; Semin, Benoît; Gruner, Philipp; Baret, Jean-Christophe

    2016-10-01

    Emulsions are metastable dispersions. Their lifetimes are directly related to the dynamics of surfactants. We design a microfluidic method to measure the kinetics of adsorption of surfactants to the droplet interface, a key process involved in foaming, emulsification, and droplet coarsening. The method is based on the pH decay in the droplet as a direct measurement of the adsorption of a carboxylic acid surfactant to the interface. From the kinetic measurement of the bulk equilibration of the pH, we fully determine the adsorption process of the surfactant. The small droplet size and the convection during the droplet flow ensure that the transport of surfactant through the bulk is not limiting the kinetics of adsorption. To validate our measurements, we show that the adsorption process determines the timescale required to stabilize droplets against coalescence, and we show that the interface should be covered at more than 90% to prevent coalescence. We therefore quantitatively link the process of adsorption/desorption, the stabilization of emulsions, and the kinetics of solute partitioning—here through ion exchange—unraveling the timescales governing these processes. Our method can be further generalized to other surfactants, including nonionic surfactants, by making use of fluorophore-surfactant interactions.

  20. Adsorption of aqueous copper on peanut hulls

    NASA Astrophysics Data System (ADS)

    Davis, Kanika Octavia

    A method was established for measuring the adsorption of Cu(II) from aqueous solution to unmodified and modified peanut hulls at constant temperature and pH. Modification of the hulls was performed by oxidation with alkaline hydrogen peroxide. During the modification process, the hydrogen peroxide solubilizes the lignin component, making the surface more porous which increases the availability of binding sites, while simultaneously oxidizing the cellulose. The oxidation of alcohol groups creates more binding sites by creating functional groups such as COO-, which increases chelation to metal ions. Fourier transform infrared spectroscopy confirms delignification of the peanut hulls by the disappearance of carboxyl peaks of the modified hulls, which were originally produced from the lignin content. Although, oxidation is not fully confirmed, it is not ruled out because the expected carboxylate peak (1680 cm-1) maybe overshadowed by a broad peak due to OH bending of water adsorbed to the hulls. Hulls adsorbed copper from solutions in the concentration range of 50-1000 ppm of CuCl2. Concentrations of pre- and post-adsorption solutions were determined using inductively coupled plasma optical emission spectroscopy. The adsorption isotherms were fit to known two and three-parameter models, evaluated and the binding mechanism was inferred. Maximum surface coverage was 3.5 +/- 0.6 mg Cu2+ /g hull for unmodified hulls and 11 +/- 1 mg Cu2+/g hull for modified hulls. The adsorption for the hulls is best described by the Langmuir model, suggesting monolayer, homogeneous adsorption. With a free energy of adsorption of 10.5 +/- 0.9 kJ/mol for unmodified hulls and 14.5 +/-0.4 kJ/mol for modified hulls, the process is categorized as chemisorption for both types of hulls. The adsorption for both hulls is also described by the Redlich-Peterson model, giving beta nearer to 1 than 0, which further suggests homogeneous adsorption described by the Langmuir model. After rinsing the hulls

  1. Methane Adsorption on Graphitic Nanostructures: Every Molecule Counts

    PubMed Central

    2012-01-01

    Bundles of single-walled nanotubes are promising candidates for storage of hydrogen, methane, and other hydrogen-rich molecules, but experiments are hindered by nonuniformity of the tubes. We overcome the problem by investigating methane adsorption on aggregates of fullerenes containing up to six C60; the systems feature adsorption sites similar to those of nanotube bundles. Four different types of adsorption sites are distinguished, namely, registered sites above the carbon hexagons and pentagons, groove sites between adjacent fullerenes, dimple sites between three adjacent fullerenes, and exterior sites. The nature and adsorption energies of the sites in C60 aggregates are determined by density functional theory and molecular dynamics (MD) simulations. Excellent agreement between experiment and theory is obtained for the adsorption capacity in these sites. PMID:23378887

  2. Adsorption kinetics of silicic acid on akaganeite.

    PubMed

    Naren, Gaowa; Ohashi, Hironori; Okaue, Yoshihiro; Yokoyama, Takushi

    2013-06-01

    As part of a series of studies on the interaction between ferric ions and silicic acid in the hydrosphere, the adsorption of silicic acid on akaganeite was investigated kinetically at various pH values. The adsorption of silicic acid increased with increasing pH over an initial pH range of 4-11.5. In the kinetic experiment, the Cl(-) was released from akaganeite much faster than silicic acid was adsorbed. From this result, we concluded that chloride ions bound on the surface of akaganeite are released and Fe-OH or Fe-O(-) sites are formed, which then acts as an adsorption site for silicic acid. The uptake mechanism of silicic acid by akaganeite is significantly different from that by schwertmannite, despite the presence of the same tunnel structure.

  3. Assessing the Adsorption Properties of Shales

    NASA Astrophysics Data System (ADS)

    Pini, R.

    2014-12-01

    Fine-grained rocks, such as shales, contain a significant amount of nanopores that can significantly contribute to their storage capacity through the mechanism of adsorption. The current ability to extract natural gas that is adsorbed in the rock's matrix is limited and current technology focuses primarily on the free gas in the fractures, thus leading to very low recovery efficiencies. Shales constitute also a great portion of so-called caprocks above potential CO2 sequestration sites; hereby, the adsorption process may limit the CO2 mobility within the cap-rock, thus minimizing leakage phenomena. Whether it is a reservoir or a caprock, understanding and quantifying the mechanisms of adsorption in these natural materials is key to improve the engineering design of subsurface operations. Results will be presented from a laboratory study that combines conventional techniques for the measurement of adsorption isotherms with novel methods that allows for the imaging of adsorption using x-rays. Various nanoporous materials are considered, thus including rocks, such as shales and coals, pure clay minerals and engineered adsorbents with well-defined nanopore structures, such as zeolites. Supercritical CO2 adsorption isotherms have been measured with a Rubotherm Magnetic Suspension balance by covering the pressure range 0.1-20~MPa. A medical x-ray CT scanner has been used to identify three-dimensional patterns of the adsorption properties of a packed-bed of adsorbent, thus enabling to assess the spatial variability of the adsorption isotherm. The data are analyzed by using thermodynamically rigorous measures of adsorption and a graphical method is applied for their interpretation. The density of the adsorbed phase is estimated and compared to data reported in the literature; the latter is key to disclose gas-reserves and/or potential storage capacity estimates. When evaluated against classic adsorbent materials, the adsorption mechanism in shales is further complicated by

  4. C2H2 adsorption in three isostructural metal-organic frameworks: boosting C2H2 uptake by rational arrangement of nitrogen sites.

    PubMed

    Song, Chengling; Jiao, Jingjing; Lin, Qiyi; Liu, Huimin; He, Yabing

    2016-03-21

    Replacing the benzene spacer in the organic linker 5,5'-(benzene-1,4-diyl)diisophthalate with the nitrogen containing heterocyclic rings, namely, pyrazine, pyridazine, and pyrimidine results in three organic linkers, which were reacted with copper ions under solvothermal conditions to form three isostructural metal-organic frameworks (ZJNU-46, ZJNU-47 and ZJNU-48) exhibiting exceptionally high sorption capacities with regard to acetylene due to the simultaneous immobilization of open metal sites and Lewis basic nitrogen sites in the frameworks. At 1 atm and 295 K, the gravimetric C2H2 adsorption uptakes reach 187, 213 and 193 cm(3) (STP) g(-1) for these three compounds. The gravimetric C2H2 adsorption amount of ZJNU-47a is the second highest reported for MOF materials. Notably, despite their same porosities, and densities of open metal sites and uncoordinated nitrogen sites, distinctly different C2H2 adsorption capacities were observed for these three compounds, which we think are mainly associated with the difference in the relative position of nitrogen atoms leading to different binding affinities of the frameworks towards C2H2 guest molecules, and thus different C2H2 adsorptions. This work demonstrates that the rational arrangement of open nitrogen sites will favorably improve the C2H2 uptake and thus provides useful information for future design of porous MOFs with high acetylene storage capacities.

  5. Electrokinetic investigation of surfactant adsorption.

    PubMed

    Bellmann, C; Synytska, A; Caspari, A; Drechsler, A; Grundke, K

    2007-05-15

    Fuerstenau [D.W. Fuerstenau, in: M.L. Hair (Ed.), Dekker, New York, 1971, p. 143] has already discussed the role of hydrocarbon chain of surfactants, the effect of alkyl chain length, chain structure and the pH of the solution on the adsorption process of surfactants. Later Kosmulski [M. Kosmulski, Chemical Properties of Material Surfaces, Surfactant Science Series, vol. 102, Dekker, New York, Basel, 2001] included the effect of surfactant concentration, equilibration time, temperature and electrolyte in his approaches. Certainly, the character of the head groups of the surfactant and the properties of the adsorbent surface are the basis for the adsorption process. Different surfactants and adsorbents cause different adsorption mechanisms described firstly by Rosen [M.J. Rosen, Surfactants and Interfacial Phenomena, second ed., Wiley, New York, 1989]. These adsorption mechanisms and their influencing factors were studied by electrokinetic investigations. Here only changes of the charges at the surfaces could be detected. To control the results of electrokinetic investigations they were compared with results from ellipsometric measurements. In the case of surfactant adsorption the chain length was vitally important. It could be shown by the adsorption of alkyl trimethyl ammonium bromides onto polymer films spin coated at wafer surfaces. The influence of the chain length depending on surface properties of the polymer film was studied. Streaming potential measurements were applied for these investigations. The obtained results enabled us to calculate the molar cohesive free energy per mol of CH2-group in the alkaline chain of the surfactant if all other specific adsorption effects were neglected.

  6. Adsorption of oxygen on W/100/ - Adsorption kinetics and structure

    NASA Technical Reports Server (NTRS)

    Bauer, E.; Poppa, H.; Viswanath, Y.

    1976-01-01

    The adsorption of oxygen on W(100) single-crystal surfaces is studied by Auger electron spectroscopy (AES), flash desorption, low-energy electron diffraction (LEED), and retarding-field work-function measurements. The AES results reveal stepwise changes in the sticking coefficients in the coverage range 0 to 1 and activated adsorption at higher coverages. Upon room-temperature adsorption, a series of complex LEED patterns is observed. In layers adsorbed at 1050 K and cooled to room temperature, the p(2 x 1) structure is the first ordered structure observed. This structure shows a reversible order-disorder transition between 700 and 1000 K and is characterized by a work function which is lower than that of the clean surface. Heating room-temperature adsorbates changes their structure irreversibly. At temperatures below 750 K, some new structures are observed.

  7. Ab initio molecular dynamics determination of competitive O2 vs. N2 adsorption at open metal sites of M2 (dobdc)

    DOE PAGES

    Parkes, Marie V.; Greathouse, Jeffery A.; Hart, David B.; ...

    2016-04-04

    The separation of oxygen from nitrogen using metal–organic frameworks (MOFs) is of great interest for potential pressure-swing adsorption processes for the generation of purified O2 on industrial scales. This study uses ab initio molecular dynamics (AIMD) simulations to examine for the first time the pure-gas and competitive gas adsorption of O2 and N2 in the M2(dobdc) (M = Cr, Mn, Fe) MOF series with coordinatively unsaturated metal centers. Effects of metal, temperature, and gas composition are explored. Lastly, this unique application of AIMD allows us to study in detail the adsorption/desorption processes and to visualize the process of multiple guestsmore » competitively binding to coordinatively unsaturated metal sites of a MOF.« less

  8. Adsorptive desulfurization by activated alumina.

    PubMed

    Srivastav, Ankur; Srivastava, Vimal Chandra

    2009-10-30

    This study reports usage of commercial grade activated alumina (aluminum oxide) as adsorbent for the removal of sulfur from model oil (dibenthiophene (DBT) dissolved in n-hexane). Bulk density of alumina was found to be 1177.77 kg/m(3). The BET surface area of alumina was found to decrease from 143.6 to 66.4 m(2)/g after the loading of DBT at optimum conditions. The carbon-oxygen functional groups present on the surface of alumina were found to be effective in the adsorption of DBT onto alumina. Optimum adsorbent dose was found to be 20 g/l. The adsorption of DBT on alumina was found to be gradual process, and quasi-equilibrium reached in 24 h. Langmuir isotherm best represented the equilibrium adsorption data. The heat of adsorption and change in entropy for DBT adsorption onto alumina was found to be 19.5 kJ/mol and 139.2 kJ/mol K, respectively.

  9. Reduced protein adsorption by osmolytes.

    PubMed

    Evers, Florian; Steitz, Roland; Tolan, Metin; Czeslik, Claus

    2011-06-07

    Osmolytes are substances that affect osmosis and are used by cells to adapt to environmental stress. Here, we report a neutron reflectivity study on the influence of some osmolytes on protein adsorption at solid-liquid interfaces. Bovine ribonuclease A (RNase) and bovine insulin were used as model proteins adsorbing at a hydrophilic silica and at a hydrophobic polystyrene surface. From the neutron reflectivity data, the adsorbed protein layers were characterized in terms of layer thickness, protein packing density, and adsorbed protein mass in the absence and presence of urea, trehalose, sucrose, and glycerol. All data point to the clear effect of these nonionic cosolvents on the degree of protein adsorption. For example, 1 M sucrose leads to a reduction of the adsorbed amount of RNase by 39% on a silica surface and by 71% on a polystyrene surface. Trehalose was found to exhibit activity similar to that of sucrose. The changes in adsorbed protein mass can be attributed to a decreased packing density of the proteins in the adsorbed layers. Moreover, we investigated insulin adsorption at a hydrophobic surface in the absence and presence of glycerol. The degree of insulin adsorption is decreased by even 80% in the presence of 4 M of glycerol. The results of this study demonstrate that nonionic cosolvents can be used to tune and control nonspecific protein adsorption at aqueous-solid interfaces, which might be relevant for biomedical applications.

  10. A biological oil adsorption filter.

    PubMed

    Pasila, Antti

    2004-12-01

    A new oil adsorption method called adsorption filtration (AF) has been developed. It is a technology where by oil residues can be cleaned from water by running it through a simple filter made from freeze treated, dried, milled and then fragmented plant material. By choosing suitable plants and fragmentation sizes it is possible to produce filters, which pass water but adsorb oil. The aim of this study was to investigate the possibilities of manufacturing oil adsorbing filter materials from reed canary grass (Phalaris arundinacea), flax (Linum usitatissimum L.) or hemp fibre (Cannabis sativa L.). The oil (80 ml) was mixed with de-ionised water (200 ml) and this mixture was filtered through 10 or 20 g adsorption filters. Fine spring harvested hemp fibre (diameter less than 1 mm) and reed canary grass fragments adsorb 2-4 g of oil per gram of adsorption material compared to 1-3 g of water. Adsorption filtration is thus a novel way of gathering spilled oil in shallow coastal waters before the oil reaches the shore.

  11. Adsorption of gases on carbon molecular sieves

    SciTech Connect

    Vyas, S.N.; Patwardhan, S.R.; Vijayalakshmi, S. . Dept. of Chemical Engineering); Ganesh, K.S. )

    1994-12-01

    Adsorption on carbon molecular sieves (CMS) prepared by coke deposition has become an interesting area of adsorption due to its microporous nature and favorable separation factor on size and shape selectivity basis for many gaseous systems. In the present work CMS was synthesized from coconut shell through three major steps, namely, carbonization, activation, and coke deposition by hydrocarbon cracking. The crushed, washed, and sieved granules of coconut shell (particle size 2--3 mm) were pretreated with sodium silicate solution and oven-dried at 150 C to create the inorganic sites necessary for coke deposition. Carbonization and activation of the dried granules were carried out at 800 C, for 30 min each. The activated char thus produced was subjected to hydrocarbon cracking at 600 C for periods varying from 30 to 180 min. The product samples were characterized in terms of adsorption isotherm, kinetic adsorption curve, surface area, pore volume, pore size distribution, and characteristic energy for adsorption by using O[sub 2], N[sub 2], C[sub 2]H[sub 2], CO[sub 2], C[sub 3]H[sub 6], and CH[sub 4].

  12. Comparative isosteric ion adsorption for minerals

    NASA Technical Reports Server (NTRS)

    Omenyi, Samuel N.; Herren, Blair J.; Snyder, Robert S.; Seaman, Geoffrey V. F.

    1986-01-01

    A comparative isosteric ion adsorption study for minerals (kaolinite, rutile, and quartz) was performed in aqueous solutions of CaCl2, LaCl3, and Th(NO3)4 in the presence of the neutral salt NaCl. It was observed that the concentration of Ca(2+) ions required to produce a standard reduction in the electrophoretic mobility of mineral particles was always appreciably greater than the concentration required for the Th(4+) ions. The effectiveness of adsorption of the cations differed from particle to particle and showed that ion adsorption on a mineral surface depends, among other things, on the nature of the mineral surface and on the particular adsorbed cation. The number of cation binding sites on mineral surfaces and the electrochemical free energies of cation adsorption were calculated. It was found that the adsorption energy of La(3+) and Th(4+) ions on rutile, kaolinite, and quartz was greater than that of Ca(2+) on these minerals.

  13. Effect of cropping systems on adsorption of metals by soils: I. Single-metal adsorption

    SciTech Connect

    Basta, N.T.; Tabatabai, M.A. )

    1992-02-01

    The effect of long-term cropping systems on adsorption of metals was studied for soils obtained from two sites, Clarion-Webster Research Center (CWRC site) at Kanawha and Galva-Primghar Research Center (GPRC site) at Sutherland, under long-term rotation experiments in Iowa. Each experiment consisted of three cropping systems: continuous corn (CCCC), corn-soybean-corn-soybean (CSCS), and corn-oats-meadow-meadow (COMM), and treated with (+N) and without (0 N) ammoniacal fertilizer. In general, CSCS and COMM cropping systems did not significantly affect the metal adsorption maxima of soils obtained from both sites. Cadmium, Cu, and Pb adsorption were significantly correlated with pH and percentage base saturation for soils from both sites.

  14. Periodic DFT study of acidic trace atmospheric gas molecule adsorption on Ca- and Fe-doped MgO(001) surface basic sites.

    PubMed

    Baltrusaitis, Jonas; Hatch, Courtney; Orlando, Roberto

    2012-08-02

    The electronic properties of undoped and Ca- or Fe-doped MgO(001) surfaces, as well as their propensity toward atmospheric acidic gas (CO2, SO2, and NO2) uptake was investigated with an emphasis on gas adsorption on the basic MgO oxygen surface sites, O(surf), using periodic density functional theory (DFT) calculations. Adsorption energy calculations show that MgO doping will provide stronger interactions of the adsorbate with the O(surf) sites than the undoped MgO for a given adsorbate molecule. Charge transfer from the iron atom in Fe-doped MgO(001) to NO2 was shown to increase the binding interaction between adsorbate by an order of magnitude, when compared to that of undoped and Ca-doped MgO(001) surfaces. Secondary binding interactions of adsorbate oxygen atoms were observed with surface magnesium sites at distances close to those of the Mg-O bond within the crystal. These interactions may serve as a preliminary step for adsorption and facilitate further adsorbate transformations into other binding configurations. Impacts on global atmospheric chemistry are discussed as these adsorption phenomena can affect atmospheric gas budgets via altered partitioning and retention on mineral aerosol surfaces.

  15. Adsorption isotherms of charged nanoparticles.

    PubMed

    Dos Santos, Alexandre P; Bakhshandeh, Amin; Diehl, Alexandre; Levin, Yan

    2016-10-19

    We present theory and simulations which allow us to quantitatively calculate the amount of surface adsorption excess of charged nanoparticles onto a charged surface. The theory is very accurate for weakly charged nanoparticles and can be used at physiological concentrations of salt. We have also developed an efficient simulation algorithm which can be used for dilute suspensions of nanoparticles of any charge, even at very large salt concentrations. With the help of the new simulation method, we are able to efficiently calculate the adsorption isotherms of highly charged nanoparticles in suspensions containing multivalent ions, for which there are no accurate theoretical methods available.

  16. Thermodynamic features of dioxins' adsorption.

    PubMed

    Prisciandaro, Marina; Piemonte, Vincenzo; di Celso, Giuseppe Mazziotti; Ronconi, Silvia; Capocelli, Mauro

    2017-02-15

    In this paper, the six more poisonous species among all congeners of dioxin group are taken into account, and the P-T diagram for each of them is developed. Starting from the knowledge of vapour tensions and thermodynamic parameters, the theoretical adsorption isotherms are calculated according to the Langmuir's model. In particular, the Langmuir isotherm parameters (K and wmax) have been validated through the estimation of the adsorption heat (ΔHads), which varies in the range 20-24kJ/mol, in agreement with literature values. This result will allow to put the thermodynamical basis for a rational design of different process units devoted to dioxins removal.

  17. Counterion release and electrostatic adsorption

    PubMed

    Sens; Joanny

    2000-05-22

    The effective charge of a rigid polyelectrolyte (PE) approaching an oppositely charged surface is studied. The cases of a weak (annealed) and strongly charged PE with condensed counterions (such as DNA) are discussed. In the most interesting case of the adsorption onto a substrate of low dielectric constant (such as a lipid membrane or a mica sheet) the condensed counterions are not always released as the PE approaches the substrate, because of the major importance of the image-charge effect. For the adsorption onto a surface with freely moving charges, the image-charge effect becomes less important and full release is often expected.

  18. A cluster DFT study of NH3 and NO adsorption on the (MoO2)2+/HZSM-5 surface: Lewis versus Brønsted acid sites

    NASA Astrophysics Data System (ADS)

    Yan, Zhifeng; Zuo, Zhijun; Li, Zhe; Zhang, Jinshan

    2014-12-01

    A systematic DFT study was carried out to investigate NH3 and NO adsorption on both Lewis and Brønsted acid sites of (MoO2)2+/HZSM-5 catalyst by using cluster models. The adsorption energy results indicate that NH3 could strongly adsorb on both Lewis and Brønsted acid sites in the form of coordinated NH3 and NH4+, respectively, whereas NO represents poorer adsorption ability. It is also found that Lewis and Brønsted acid sites are competitive energetically for NH3 adsorption. According to the difference in the proposed mechanisms for NH3 adsorption on different acid sites, particular attention has been focused on the first dissociation of coordinated NH3 for Lewis acid site and the effect of Mo site on the introduction of NO for Brønsted acid site. For the coordinated NH3 on Lewis acid site, the more electron donation from NH3 is, the greater its adsorption stability is and the higher active its H atoms are. In addition, DOS results show that stability of the H atoms is enhanced by interacting with framework oxygen and especially the H atoms chemical-bonded with framework oxygen. For the NH4+ on Brønsted acid site, reduced-state Mo5+ holds stronger reducibility and oxidizability than terminal oxygen, which is suggested to play a key role in adsorption and activation of NOx together with the adsorbed NH4+.

  19. Adsorption of Organics from Domestic Water Supplies.

    ERIC Educational Resources Information Center

    McGuire, Michael J.; Suffet, Irwin H.

    1978-01-01

    This article discusses the current state of the art of organics removal by adsorption. Various theoretical explanations of the adsorption process are given, along with practical results from laboratory, pilot-scale, and full-scale applications. (CS)

  20. CONTAMINANT ADSORPTION AND OXIDATION VIA FENTON REACTION

    EPA Science Inventory

    A ground water treatment process is proposed involving two cgemical processes: adsorption and oxidation. Adsorption of an organic compound onto granulated activated carbon (GAC) containing iron conveniently results in immobilizing and concentrating contaminants from the ground w...

  1. Adsorption of Gases on Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Mbaye, Mamadou Thiao

    2014-01-01

    This research focus in studying the interaction between various classical and quantum gases with novel carbon nanostructures, mainly carbon nanotubes (CNTs). Since their discovery by the Japanese physicist Sumio Iijima [1] carbon nanotubes have, experimentally and theoretically, been subjected to many scientific investigation. Studies of adsorption on CNTs are particularly directed toward their better usage in gas storage, gas separation, catalyst, drug delivery, and water purification. We explore the adsorption of different gases entrapped in a single, double, or multi-bundles of CNTs using computer simulations. The first system we investigate consists of Ar and Kr films adsorbed on zigzag or armchair nanotubes. Our simulations revealed that Kr atoms on intermediate size zigzag NTs undergo two phase transitions: A liquid-vapor (L→V), and liquid-commensurate (L→CS) with a fractional coverage of one Kr atoms adsorbed for every four carbon atoms. For Ar on zigzag and armchair NTs, the only transition observed is a L→V. In the second problem, we explore the adsorption of CO2 molecules in a nanotube bundle and calculate the isosteric heat of adsorption of the entrapped molecules within the groove. We observed that the lower the temperature, the higher the isosteric of adsorption. Last, we investigate the adsorption of hydrogen, Helium, and Neon gases on the groove site of two parallel nanotubes. At low temperature, the transverse motion on the plane perpendicular to the tubes' axis is frozen out and as a consequence, the heat capacity is reduced to 1/2. At high temperature, the atoms gain more degree of freedom and as a consequence the heat capacity is 5/2.

  2. ADSORPTION OF SURFACTANT ON CLAYS

    EPA Science Inventory

    Surfactants used to enhance remediation of soils by soil washing are often lost in the process. Neither the amount nor the cause of this loss is known. It is assumed that clays present in the soil are responsible for the loss of the surfactant. In this papere, adsorption prope...

  3. Adsorption of pesticides on resins.

    PubMed

    Kyriakopoulos, Grigorios; Hourdakis, Adamadia; Doulia, Danae

    2003-03-01

    The objective of this work was to assess the capability of organic hydrophobic polymeric resins Amberlite XAD-4 and XAD-7 to remove the pesticides alachlor and amitrole from water. The pesticides adsorption on the two different adsorbents was measured by batch equilibrium technique and isotherm types and parameters were estimated. Two theoretical models were applied based on a Freundlich and a Langmuir isotherms. The effect of pesticides chemical composition and structure as well as the nature of solid surface on the efficiency of adsorption was evaluated. The influence of pH also was studied. In low pH solutions adsorption of amitrole was higher upon the nonionic aliphatic acrylic ester copolymer XAD-7 in comparison to the nonionic, crosslinked macroreticular copolymer of styrene divinylbenzene XAD-4. In neutral and intermediate pH solutions the polar acrylic ester copolymer XAD-7 was more effective to the retention of alachlor. The acrylic ester copolymer showed at pH 3 the lower effectiveness in alachlor removal from water. The data of the adsorption isotherms of pesticides upon the examined polymeric resins seemed to conform to both the Freundlich and the Langmuir isotherm models.

  4. Engineering and Design: Adsorption Design Guide

    DTIC Science & Technology

    2001-03-01

    adsorptive media addressed in- clude granular activated carbon (GAC) and other alternative adsorption carbon media, such as powdered activated carbon (PAC... Adsorption Media. a. Activated Carbon . Activated carbon can be manufactured from carbonaceous material, in- cluding coal (bituminous, subbituminous...information contained in Corps of Engineers Guide Specification 11225: Downflow Liquid Granular Activated Carbon

  5. Effect of grain size on uranium(VI) surface complexation kinetics and adsorption additivity.

    PubMed

    Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John M

    2011-07-15

    The contribution of variable grain sizes to uranium adsorption/desorption was studied using a sediment from the US DOE Hanford site. The sediment was wet sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.053-0.2 mm), and clay/silt fraction (<0.053 mm). For each size fraction and their composite (sediment), batch and flow-cell experiments were performed to determine uranium adsorption isotherms and kinetic uranium adsorption and subsequent desorption. The results showed that uranium adsorption isotherms and adsorption/desorption kinetics were size specific, reflecting the effects of size-specific adsorption site concentration and kinetic rate constants. The larger-size fraction had a larger mass percentage in the sediment but with a smaller adsorption site concentration and generally a slower uranium adsorption/desorption rate. The same equilibrium surface complexation reaction and reaction constant could describe uranium adsorption isotherms for all size fractions and the composite after accounting for the effect of adsorption site concentration. Mass-weighted, linear additivity was observed for both uranium adsorption isotherms and adsorption/desorption kinetics in the composite. One important implication of this study is that grain-size distribution may be used to estimate uranium adsorption site and adsorption/desorption kinetic rates in heterogeneous sediments from a common location.

  6. Role of [FeOx(OH)y] surface sites on the adsorption of β-lactamic antibiotics on Al2O3 supported Fe oxide.

    PubMed

    Pinto, Paula S; Medeiros, Tayline P V; Ardisson, José D; Lago, Rochel M

    2016-11-05

    In this work, [FeOx(OH)y]/Al2O3 composites with different Fe oxyhydroxy contents, i.e. 10, 20 and 50wt% treated at 150, 200, 300 and 450°C were investigated as adsorbents of β-lactamic antibiotics, i.e. cephalexin, ceftriaxone and especially amoxicillin, from aqueous solutions. The obtained results showed that the nature of the surface Fe(3+) species play a fundamental role on the adsorption process. The most efficient adsorption was obtained for the sample 150Fe50A (50% [FeOx(OH)y] supported in Al2O3 treated at 150°C) whereas the thermal treatment at higher temperatures caused a strong decrease on the adsorption capacity. Mössbauer, XRD, FTIR, Raman, TG-MS, SEM, CHN and BET of the composite 150Fe50A suggested an approximate composition of FeO0.65(OH)1.7 whereas at 450°C strong dehydroxylation process takes place to form FeO1.4(OH)0.21. These results combined with competitive adsorption using amoxicillin mixed with phosphate or H2O2 suggest that the antibiotic molecules adsorb by complexation on surface sites likely based on FeOx(OH)y by the replacement of the labile OH ligands.

  7. [Adsorption kinetics and mechanism of lead (II) on polyamine-functionalized mesoporous activated carbon].

    PubMed

    Li, Kun-Quan; Wang, Yan-Jin; Yang, Mei-Rong; Zhu, Zhi-Qiang; Zheng, Zheng

    2014-08-01

    Bagasse mesoporous carbon was prepared by microwave assisted H3 PO4 activation. Amido and imido groups were modified with ethanediamine on the channels' surface of mesoporous carbon through nitric oxidation and amide reaction. The influence of Pb(II) concentration, adsorption time on Pb(II) adsorption on the ethanediamine-modified mesoporous carbon (AC-EDA) was investigated. The adsorption kinetics and mechanism were also discussed. The results showed that AC-EDA had a great performance for Pb(II) adsorption, and more than 70% of Pb(II) was adsorbed in 5 minutes. The adsorption amount of Pb(II) on the carbon increased with the increase of solution pH in acidic conditions. It was found that AC-EDA had different binding energies on different adsorption sites for Pb(II) separation. The Pb(II) adsorption process on AC-EDA was controlled by intra-particle diffusion in the first 3 min, and then film diffusion played the important pole on the adsorption. The adsorption amount increased with the increase of temperature, indicating the adsorption was an endothermic reaction. The high adsorption energy (> 11 kJ x mol(-1)) implied that the) adsorption was a chemical adsorption. The XPS of AC-EDA before and after Pb(II) adsorption showed that the polyamine group was involved in the adsorption, and should be a main factor of the high efficient adsorption.

  8. pH dependence of tailing in reversed-phase chromatography of a cationic dye: measurement of the strong adsorption site surface density.

    PubMed

    Smith, Emily A; Wirth, Mary J

    2004-12-10

    A question that has interested Dr. J.J. Kirkland is addressed: what is the nature of the silanols that cause tailing to persist at low pH in reversed-phase chromatography? Chromatograms for a cationic dye, 1,1'-didodecyl-3,3,3'3'-tetramethylindocarbocyanine perchlorate (DiI), were studied at varying pH using an Agilent SB-C8 column and 80% ACN/water for six DiI concentrations ranging from 0.9 to 316 microM. The chromatograms showed increased retention and tailing from pH 1 to 5, as expected. Simulations of the chromatograms agreed well with experiment for a bi-Langmuir isotherm with weak (C8) and strong (silica) adsorption sites. The simulation parameters revealed that the number of strong adsorption sites decreases by 40% from pH 1 to 5, which indicates that the silanols causing tailing are in the SiOH, not the SiO-, form. This seems paradoxical because tailing increases with increasing pH. The simulation parameters reveal that this increased tailing from pH 1 to 5 owes to doubling of the partition coefficient for DiI to the strong adsorption site, which more than compensates for the decreasing number of sites. We attribute this increased partition coefficient to increased long-range coulombic interactions with the increasingly abundant SiO- groups at higher pH, which boosts DiI's partition coefficient for both the C8 and SiOH sites. The picture thus emerges that for DiI, higher pH causes increased tailing because the SiO- groups exacerbate tailing that actually originates from adsorption to SiOH groups.

  9. Phosphate adsorption on lanthanum loaded biochar.

    PubMed

    Wang, Zhanghong; Shen, Dekui; Shen, Fei; Li, Tianyu

    2016-05-01

    To attain a low-cost and high-efficient phosphate adsorbent, lanthanum (La) loaded biochar (La-BC) prepared by a chemical precipitation method was developed. La-BC and its pristine biochar (CK-BC) were comparatively characterized using zeta potential, BET surface area, scanning electron microscopy/energy dispersive spectrometer (SEM-EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). The adsorption ability and the mechanisms during adsorption process for the La-BC samples were also investigated. La loaded on the surface of biochar can be termed as La-composites (such as LaOOH, LaONO3 and La(OH)3), leading to the decrease of negative charge and surface area of biochar. La-BC exhibited the high adsorption capacity to phosphate compared to CK-BC. Adsorption isotherm and adsorption kinetic studies showed that the Langmuir isotherm and second order model could well describe the adsorption process of La-BC, indicating that the adsorption was dominated by a homogeneous and chemical process. The calculated maximum adsorption capacity was as high as 46.37 mg g(-1) (computed in P). Thermodynamic analysis revealed that the adsorption was spontaneous and endothermic. SEM, XRD, XPS and FT-IR analysis suggested that the multi-adsorption mechanisms including precipitation, ligand exchange and complexation interactions can be evidenced during the phosphate adsorption process by La-composites in La-BC.

  10. Adsorption of organic chemicals in soils.

    PubMed Central

    Calvet, R

    1989-01-01

    This paper presents a review on adsorption of organic chemicals on soils sediments and their constituents. The first part of this review deals with adsorption from gas and liquid phases and gives a discussion on the physical meaning of the shape of adsorption isotherms. Results show that no general rules can be proposed to describe univocally the relation between the shape of isotherms and the nature of adsorbate-adsorbent system. Kinetics of adsorption is discussed through the description of various models. Theoretical developments exist both for the thermodynamics and the kinetics of adsorption, but there is a strong need for experimental results. Possible adsorption mechanisms are ion exchange, interaction with metallic cations, hydrogen bonds, charge transfers, and London-van der Waals dispersion forces/hydrophobic effect. However, direct proofs of a given mechanism are rare. Several factors influence adsorption behavior. Electronic structure of adsorbed molecules, properties of adsorbents, and characteristics of the liquid phase are discussed in relation to adsorption. Such properties as water solubility, organic carbon content of adsorbing materials, and the composition of the liquid phase are particularly important. Evaluation of adsorption can be obtained through either laboratory measurements or use of several correlations. Adsorption measurements must be interpreted, taking into account treatment of adsorbent materials, experimental conditions, and secondary phenomena such as degradations. Correlations between adsorption coefficients and water-octanol partition coefficient or water solubility are numerous. They may be useful tools for prediction purposes. Relations with transport, bioavailability, and degradation are described. PMID:2695323

  11. Assessing the adsorption properties of shales

    NASA Astrophysics Data System (ADS)

    Pini, Ronny

    2015-04-01

    Physical adsorption refers to the trapping of fluid molecules at near liquid-like densities in the pores of a given adsorbent material. Fine-grained rocks, such as shales, contain a significant amount of nanopores that can significantly contribute to their storage capacity. As a matter of fact, the current ability to extract natural gas that is adsorbed in the rock's matrix is limited, and current technology focuses primarily on the free gas in the fractures (either natural or stimulated), thus leading to recovery efficiencies that are very low. Shales constitute also a great portion of so-called cap-rocks above potential CO2 sequestration sites; hereby, the adsorption process may limit the CO2 mobility within the cap-rock, thus minimizing the impact of leakage on the whole operation. Whether it is an unconventional reservoir or a cap-rock, understanding and quantifying the mechanisms of adsorption in these natural materials is key to improve the engineering design of subsurface operations. Results will be presented from a laboratory study that combines conventional techniques for the measurement of adsorption isotherms with novel methods that allows for the imaging of adsorption using x-rays. Various nanoporous materials are considered, thus including rocks, such as shales and coals, pure clay minerals (a major component in mudrocks) and engineered adsorbents with well-defined nanopore structures, such as zeolites. Supercritical CO2 adsorption isotherms have been measured with a Rubotherm Magnetic Suspension balance by covering the pressure range 0.1-20~MPa. A medical x-ray CT scanner has been used to identify three-dimensional patterns of the adsorption properties of a packed-bed of adsorbent, thus enabling to assess the spatial variability of the adsorption isotherm in heterogeneous materials. The data are analyzed by using thermodynamically rigorous measures of adsorption, such as the net- and excess adsorbed amounts and a recently developed methodology is

  12. The adsorption of HCl on volcanic ash

    NASA Astrophysics Data System (ADS)

    Gutiérrez, Xochilt; Schiavi, Federica; Keppler, Hans

    2016-03-01

    Understanding the interaction between volcanic gases and ash is important to derive gas compositions from ash leachates and to constrain the environmental impact of eruptions. Volcanic HCl could potentially damage the ozone layer, but it is unclear what fraction of HCl actually reaches the stratosphere. The adsorption of HCl on volcanic ash was therefore studied from -76 to +150 °C to simulate the behavior of HCl in the dilute parts of a volcanic plume. Finely ground synthetic glasses of andesitic, dacitic, and rhyolitic composition as well as a natural obsidian from Vulcano (Italy) served as proxies for fresh natural ash. HCl adsorption is an irreversible process and appears to increase with the total alkali content of the glass. Adsorption kinetics follow a first order law with rate constants of 2.13 ṡ10-6 s-1 to 1.80 ṡ10-4 s-1 in the temperature range investigated. For dacitic composition, the temperature and pressure dependence of adsorption can be described by the equation ln ⁡ c = 1.26 + 0.27 ln ⁡ p - 715.3 / T, where c is the surface concentration of adsorbed HCl in mg/m2, T is temperature in Kelvin, and p is the partial pressure of HCl in mbar. A comparison of this model with a large data set for the composition of volcanic ash suggests that adsorption of HCl from the gas phase at relatively low temperatures can quantitatively account for the majority of the observed Cl concentrations. The model implies that adsorption of HCl on ash increases with temperature, probably because of the increasing number of accessible adsorption sites. This temperature dependence is opposite to that observed for SO2, so that HCl and SO2 are fractionated by the adsorption process and the fractionation factor changes by four orders of magnitude over a temperature range of 250 K. The assumption of equal adsorption of different species is therefore not appropriate for deriving volcanic gas compositions from analyses of adsorbates on ash. However, with the experimental

  13. A large gap opening of graphene induced by the adsorption of CO on the Al-doped site.

    PubMed

    Peyghan, Ali Ahmadi; Noei, Maziar; Tabar, Mohammad Bigdeli

    2013-08-01

    We investigated CO adsorption on the pristine, Stone-Wales (SW) defected, Al- and Si- doped graphenes by using density functional calculations in terms of geometric, energetic and electronic properties. It was found that CO molecule is weakly adsorbed on the pristine and SW defected graphenes and their electronic properties were slightly changed. The Al- and Si- doped graphenes show high reactivity toward CO, so calculated adoption energies are about -11.40 and -13.75 kcal mol(-1) in the most favorable states. It was found that, among all the structures, the electronic properties of Al-doped graphene are strongly sensitive to the presence of CO molecule. We demonstrate the existence of a large Eg opening of 0.87 eV in graphene which is induced by Al-doping and CO adsorption.

  14. Adsorption modeling for macroscopic contaminant dispersal analysis

    SciTech Connect

    Axley, J.W.

    1990-05-01

    Two families of macroscopic adsorption models are formulated, based on fundamental principles of adsorption science and technology, that may be used for macroscopic (such as whole-building) contaminant dispersal analysis. The first family of adsorption models - the Equilibrium Adsorption (EA) Models - are based upon the simple requirement of equilibrium between adsorbent and room air. The second family - the Boundary Layer Diffusion Controlled Adsorption (BLDC) Models - add to the equilibrium requirement a boundary layer model for diffusion of the adsorbate from the room air to the adsorbent surface. Two members of each of these families are explicitly discussed, one based on the linear adsorption isotherm model and the other on the Langmuir model. The linear variants of each family are applied to model the adsorption dynamics of formaldehyde in gypsum wall board and compared to measured data.

  15. Adsorption Behavior of Nonplanar Phthalocyanines: Competition of Different Adsorption Conformations

    PubMed Central

    2016-01-01

    Using density functional theory augmented with state-of-the-art van der Waals corrections, we studied the geometric and electronic properties of nonplanar chlorogallium-phthalocyanine GaClPc molecules adsorbed on Cu(111). Comparing these results with published experimental data for adsorption heights, we found indications for breaking of the metal–halogen bond when the molecule is heated during or after the deposition process. Interestingly, the work-function change induced by this dissociated geometry is the same as that computed for an intact adsorbate layer in the “Cl-down” configuration, with both agreeing well with the experimental photoemission data. This is unexpected, as the chemical natures of the adsorbates and the adsorption distances are markedly different in the two cases. The observation is explained as a consequence of Fermi-level pinning due to fractional charge transfer at the interface. Our results show that rationalizing the adsorption configurations on the basis of electronic interface properties alone can be ambiguous and that additional insight from dispersion-corrected DFT simulations is desirable. PMID:27066160

  16. Adsorption sites of single noble metal atoms on the rutile TiO2 (1 1 0) surface influenced by different surface oxygen vacancies.

    PubMed

    Matsunaga, Katsuyuki; Chang, Teng-Yuan; Ishikawa, Ryo; Dong, Qian; Toyoura, Kazuaki; Nakamura, Atsutomo; Ikuhara, Yuichi; Shibata, Naoya

    2016-05-05

    Atomic adsorption of Au and Pt on the rutile (1 1 0) surface was investigated by atomic-resolution aberration-corrected scanning transmission electron microscopy (STEM) measurements combined with density functional theory calculations. Au single atoms were deposited on the surface in a vacuum condition, and the observed results were compared with Pt single atoms on the same surface prepared by the same experimental manner. It was found that Au single atoms are stably adsorbed only at the bridging oxygen vacancy sites, which is quite different from Pt single atoms exhibiting the most frequently observed adsorption at the basal oxygen vacancy sites. Such a difference in oxygen-vacancy effect between Au and Pt can be explained by electronic structures of the surface vacancies as well as characters of outermost atomic orbitals of Au and Pt.

  17. The role of outer surface/inner bulk Brønsted acidic sites in the adsorption of a large basic molecule (simazine) on H-Y zeolite.

    PubMed

    Sannino, Filomena; Pansini, Michele; Marocco, Antonello; Bonelli, Barbara; Garrone, Edoardo; Esposito, Serena

    2015-11-21

    The simple means adopted for investigating H-Y zeolite acidity in water is the pH-dependence of the amount of a basic molecule adsorbed under isochoric conditions, a technique capable of yielding, under equilibrium conditions, an estimate of the pKa value of the involved acidic centres: the behaviour with temperature of adsorbed amounts yields instead some information on thermodynamics. Simazine (Sim, 2-chloro-4,6-bis(ethylamino)-s-triazine) was chosen as an adsorbate because its transverse dimension (7.5 Å) is close to the opening of the supercage in the faujasite structure of H-Y (7.4 Å). In short term measurements, Sim adsorption at 25 °C occurs only at the outer surface of H-Y particles. Two types of mildly acidic centres are present (with pKaca. 7 and ca. 8, respectively) and no strong one is observed. Previous adsorption of ammonia from the gas phase discriminates between the two. The former survives, and shows features common with the silanols of amorphous silica. The latter is suppressed: because of this and other features distinguishing this site from silanol species (e.g. the formation of dimeric Sim2H(+) species, favoured by coverage and unfavoured by temperatures of adsorption higher than ambient temperature) a candidate is an Al based site. We propose a Lewis centre coordinating a water molecule, exhibiting acidic properties. This acidic water molecule can be replaced by the stronger base ammonia, also depleting inner strong Brønsted sites. A mechanism for the generation of the two sites from surface Brønsted species is proposed. Long term adsorption measurements at 25 °C already show the onset of the interaction with inner strongly acidic Brønsted sites: because of its size, activation is required for Sim to pass the supercage openings and reach inner acidic sites. When adsorption is run at 40-50 °C, uptake is much larger and increases with temperature. Isochoric measurements suggest a pKa value of ca. 3 compatible with its marked acidic

  18. Adsorption of two gas molecules at a single metal site in a metal–organic framework

    SciTech Connect

    Runčevski, Tomče; Kapelewski, Matthew T.; Torres-Gavosto, Rodolfo M.; Tarver, Jacob D.; Brown, Craig M.; Long, Jeffrey R.

    2016-01-01

    One strategy to markedly increase the gas storage capacity of metal-organic frameworks is to introduce coordinatively-unsaturated metal centers capable of binding multiple gas molecules. Herein, we provide an initial demonstration that a single metal site within a framework can support the terminal coordination of two gas molecules--specifically hydrogen, methane, or carbon dioxide.

  19. Adsorption of two gas molecules at a single metal site in a metal–organic framework

    SciTech Connect

    Runčevski, Tomče; Kapelewski, Matthew T.; Torres-Gavosto, Rodolfo M.; Tarver, Jacob D.; Brown, Craig M.; Long, Jeffrey R.

    2016-11-21

    One strategy to markedly increase the gas storage capacity of metal–organic frameworks is to introduce coordinatively-unsaturated metal centers capable of binding multiple gas molecules. Herein, we provide an initial demonstration that a single metal site within a framework can support the terminal coordination of two gas molecules—specifically hydrogen, methane, or carbon dioxide.

  20. A periodic DFT study of ammonia adsorption on the V2O5 (001), V2O5 (010) and V2O5 (100) surfaces: Lewis versus Brönsted acid sites

    NASA Astrophysics Data System (ADS)

    Yao, Huichao; Chen, Yu; Wei, Yuechang; Zhao, Zhen; Liu, Zhichang; Xu, Chunming

    2012-11-01

    The adsorption of ammonia at Brönsted and Lewis acid sites on three low-index (001), (010) and (100) surfaces of V2O5 catalyst was investigated using density functional theory (DFT) method. Three levels of surface relaxation periodic models including top single layer relaxation (S-model), moderately deeper relaxation (M-model) and full relaxation model (F-model) were applied to examine the effect of the surface relaxation on the binding structures and adsorption energies. The results of calculations showed that on the saturated basal plane V2O5 (001), ammonia adsorption at the Brönsted acid sites (VOH) is energetically more favorable. On unsaturated (010) and (100) surfaces, ammonia is adsorbed strongly on both Brönsted (VOH) and Lewis acid sites (V). Surface relaxations have no influence on ammonia adsorption on saturated (001) surface, while a strong dependence on the relaxation models is observed for NH3-adsorption energies on (010) and (100) surfaces, especially at the Lewis acid sites of both side planes. When complete relaxation considered (F-model), ammonia adsorption on the Lewis acid sites (V) dominates for side planes (010) and (100). In the presence of VOH as neighbor, the ammonia adsorption at V sites is however weakened significantly due to steric hindrance. Hydrogen bonds may play a role, although not determining one, in the respect of the adsorption of ammonia on (010) and (100) surfaces. Moderate relaxation and full relaxation are absolutely necessary for the description of both H and NH3 adsorption on unsaturated (100) and (010) surfaces, respectively.

  1. Probing Defect Sites on CeO2 Nanocrystals with Well-Defined Surface Planes by Raman Spectroscopy and O2 Adsorption

    SciTech Connect

    Wu, Zili; Li, Meijun; Howe, Jane Y; Meyer III, Harry M; Overbury, Steven {Steve} H

    2010-01-01

    Defect sites play an essential role in ceria catalysis. In this study, ceria nanocrystals with well defined surface planes have been synthesized and utilized for studying defect sites with both Raman spectroscopy and O2 adsorption. Ceria nanorods ({110} + {100}), nanocubes ({100}), and nano-octahedrons ({111}) are employed to analyze the quantity and quality of defect sites on different ceria surfaces. On oxidized surface, nanorods have the most abundant intrinsic defect sites, followed by nanocubes and nano-octahedrons. When reduced, the induced defect sites are more clustered on nanorods than on nanocubes although similar amount (based on surface area) of such defect sites are produced on the two surfaces. Very few defect sites can be generated on the nano-octahedrons due to the least reducibility. These differences can be rationalized by the crystallographic surface terminations of the ceria nanocrystals. The different defect sites on these nanocrystals lead to the adsorption of different surface dioxygen species. Superoxide on one-electron defect sites and peroxide on two-electron defect sites with different clustering degree are identified on the ceria nanocrystals depending on their morphology. Furthermore, the stability and reactivity of these oxygen species are also found to be surface-dependent, which is of significance for ceria-catalyzed oxidation reactions.

  2. Studies on Vapor Adsorption Systems

    NASA Technical Reports Server (NTRS)

    Shamsundar, N.; Ramotowski, M.

    1998-01-01

    The project consisted of performing experiments on single and dual bed vapor adsorption systems, thermodynamic cycle optimization, and thermal modeling. The work was described in a technical paper that appeared in conference proceedings and a Master's thesis, which were previously submitted to NASA. The present report describes some additional thermal modeling work done subsequently, and includes listings of computer codes developed during the project. Recommendations for future work are provided.

  3. Hydrogen Adsorption in Carbon nanoparticles

    NASA Astrophysics Data System (ADS)

    Cabrera, A. L.; Rojas, S.; Dias-Droguett, D. E.; Bhuyan, H.; Aomoa, N.; Kakati, M.

    2013-03-01

    We have studied hydrogen adsorption in carbon nanoparticles using a quartz crystal microbalance. The carbon nanoparticles were synthesized from a thermal plasma jet at different pressure (15 - 263 torr) of the reactants and different current (50 - 250 A) to generate the plasma. The as-prepared carbon nanoparticles were directly deposited on top of the gold electrode of a quartz crystal and we monitored in-situ the changes in resonance frequency while the chamber was pressurized at different hydrogen pressures. These changes enabled determination of absorbed hydrogen mass in order to get H/C mass ratio curves as a function of H2 pressure. Adsorption curves obtained in some carbon nanoparticles indicated the formation of hydrogen monolayer inside the pores of the carbon nanoparticles. Using the value of the jump due to the formation of a H2\\ monolayer, a surface area was estimated between 40-60 m2/g for hydrogen adsorption. In other carbon samples, hydrogen uptake curves indicated that H2 was filling the sample's pores when pore volume was large. These observations will be discussed in detail for several carbon nanoparticles samples. Funds provided by VRI Puente 9/2012 and 10/2012

  4. Water-quality characteristics, including sodium-adsorption ratios, for four sites in the Powder River drainage basin, Wyoming and Montana, water years 2001-2004

    USGS Publications Warehouse

    Clark, Melanie L.; Mason, Jon P.

    2006-01-01

    The U.S. Geological Survey, in cooperation with the Wyoming Department of Environmental Quality, monitors streams throughout the Powder River structural basin in Wyoming and parts of Montana for potential effects of coalbed natural gas development. Specific conductance and sodium-adsorption ratios may be larger in coalbed waters than in stream waters that may receive the discharge waters. Therefore, continuous water-quality instruments for specific conductance were installed and discrete water-quality samples were collected to characterize water quality during water years 2001-2004 at four sites in the Powder River drainage basin: Powder River at Sussex, Wyoming; Crazy Woman Creek near Arvada, Wyoming; Clear Creek near Arvada, Wyoming; and Powder River at Moorhead, Montana. During water years 2001-2004, the median specific conductance of 2,270 microsiemens per centimeter at 25 degrees Celsius (?S/cm) in discrete samples from the Powder River at Sussex, Wyoming, was larger than the median specific conductance of 1,930 ?S/cm in discrete samples collected downstream from the Powder River at Moorhead, Montana. The median specific conductance was smallest in discrete samples from Clear Creek (1,180 ?S/cm), which has a dilution effect on the specific conductance for the Powder River at Moorhead, Montana. The daily mean specific conductance from continuous water-quality instruments during the irrigation season showed the same spatial pattern as specific conductance values for the discrete samples. Dissolved sodium, sodium-adsorption ratios, and dissolved solids generally showed the same spatial pattern as specific conductance. The largest median sodium concentration (274 milligrams per liter) and the largest range of sodium-adsorption ratios (3.7 to 21) were measured in discrete samples from the Powder River at Sussex, Wyoming. Median concentrations of sodium and sodium-adsorption ratios were substantially smaller in Crazy Woman Creek and Clear Creek, which tend to

  5. Adsorption of Gemini surfactants onto clathrate hydrates.

    PubMed

    Salako, O; Lo, C; Couzis, A; Somasundaran, P; Lee, J W

    2013-12-15

    This work addresses the adsorption of two Gemini surfactants at the cyclopentane (CP) hydrate-water interface. The Gemini surfactants investigated here are Dowfax C6L and Dowfax 2A1 that have two anionic head groups and one hydrophobic tail group. The adsorption of these surfactants was quantified using adsorption isotherms and the adsorption isotherms were determined using liquid-liquid titrations. Even if the Gemini surfactant adsorption isotherms show multi-layer adsorption, they possess the first Langmuir layer with the second adsorption layer only evident in the 2A1 adsorption isotherm. Zeta potentials of CP hydrate particles in the surfactant solution of various concentrations of Dowfax C6L and Dowfax 2A1 were measured to further explain their adsorption behavior at the CP hydrate-water interface. Zeta potentials of alumina particles as a model particle system in different concentrations of sodium dodecyl sulfate (SDS), Dowfax C6L and Dowfax 2A1 were also measured to confirm the configuration of all the surfactants at the interface. The determination of the isotherms and zeta-potentials provides an understanding framework for the adsorption behavior of the two Gemini surfactants at the hydrate-water interface.

  6. Effect of Grain Size on Uranium(VI) Surface Complexation Kinetics and Adsorption Additivity

    SciTech Connect

    Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John M.

    2011-07-27

    Laboratory experiments were performed to investigate the contribution of variable grain sizes to uranium adsorption/desorption in a sediment collected from the US DOE Hanford site. The sediment was wet-sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.05-0.2 mm), and clay/silt fraction (< 0.05mm). For each size fraction and their composite (sediment), batch experiments were performed to determine uranium adsorption isotherms, and stirred flow-cell experiments were conducted to derive kinetic data of uranium adsorption and subsequent desorption. The results showed that uranium adsorption isotherms and adsorption/desorption kinetics were size-specific, reflecting the effects of size-specific adsorption site concentration and kinetic rate constants. The larger-size fraction had a larger mass percentage in the sediment, but with a smaller adsorption site concentration and generally a slower uranium adsorption/desorption rate. The same equilibrium surface complexation reaction and reaction constant could describe uranium adsorption isotherms for all size fractions and the composite after accounting for the effect of adsorption site concentration. Mass-weighted, linear additivity was observed for both uranium adsorption isotherms and adsorption/desorption kinetics in the composite. Our analysis also showed that uranium adsorption site concentration estimated from the adsorption isotherms was 3 orders of magnitude less than a site concentration estimated from sediment surface area and generic site density. One important implication of this study is that grain size distribution may be used to estimate uranium adsorption site, and adsorption/desorption kinetic rates in heterogeneous sediments from a common location.

  7. Adsorption edge study about cadmium, copper, nickel and zinc adsorption by variable charge soils

    NASA Astrophysics Data System (ADS)

    Casagrande, J. C.; Mouta, E. R.; Soares, M. R.

    2009-04-01

    The improper discharge of industrial and urban residues and the inadvertent use of fertilizers and pesticides can result in soil and water pollution and improve the potential of trace metals to enter in the human food chain. Adsorption reactions occur at the solid/liquid interface and are the most important mechanisms for controlling the activity of metal ions in soil solution. In a complex system with amphoteric behavior, the comprehension of the mobility, availability and fate of pollutants in the soil system is crucial for the prediction of the environmental consequences and for development of prevention/remediation strategies. A comparative study of cadmium (Cd), copper (Cu), nickel (Ni) and zinc (Zn) adsorption by highly weathered soils was carried out. Surface (0-0.2m) and subsoil (B horizon) samples were taken from a Rhodic Kandiudalf (RH), an Anionic "Xanthic" Acrudox (XA) and an Anionic "Rhodic" Acrudox (RA), located in brazilian humid tropical area. As the pH and the ionic strength are important environmental factors influencing the solution chemistry of heavy metals in variable charge systems, adsorption envelopes, in a batch adsorption experiment, were elaborated by reacting, for 24 h, soil samples with individual 0.01, 0.1 and 1.0 mol L-1 Ca(NO3)2 aqueous solutions containing nitrate salts of the adsorptive heavy metal (Cd, Cu, Ni and Zn) at the initial concentration of 5 mg L-1, with an increasing pH value from 3.0 to 8.0. pH50-100%, the difference between the pH of 100 and 50 percent metal adsorption was determined. A sharp increase of adsorption density (adsorption edge) was observed within a very narrow pH range, usually less than two pH units. Commonly, the relative affinity of a soil for a metal cation increases with the tendency of the cation to form inner-sphere surface complexes. This may be caused by differences in extent of hydrolysis of Cu ions and in affinity of adsorption sites for Cu. In general, subsurface samples showed low pH50

  8. Thiol adsorption at gold surfaces: self-assembly, chiral recognition, and enantioselective adsorption at chiral surfaces.

    NASA Astrophysics Data System (ADS)

    Hammer, Bjork

    2003-03-01

    Density functional theory calculations are presented for the adsorption of thiol containing molecules on to Au(111), Au(110), and Au(17 11 9). The thiol group becomes dehydrogenated during the adsorption process and the resulting thiolate group shows a strong preference for the Au-Au bridging adsorption site.[1] For methylthiolate adsorption, a restructuring of the Au(111) surface in to a honeycomb pattern with every 3rd Au atom missing is found to lead an overall strengthening of the thiolate-gold bonding.[2] Since the surface restructuring must happen through-out the system, it represents a net attractive interaction between the adsorbates and it is speculated to have implications for the self-assembly of alkanethiols found at close packed gold surfaces. Adsorption studies of the naturally occuring amino acid, cysteine, at Au(110) also reveal enhanced thiolate-gold bonding at restructured Au sites.[3] The cysteine molecules are found to interact pairwise forming dimers that are hydrogen bonded through the cysteine carboxyl groups. The gold surface restructuring required to hold this complex involves the creation of a four Au atom wide vacancy in the outermost close packed row of the Au(110) surface. The binding of the the cysteine dimer to this vacancy site causes chiral recognition -- only cysteine dimers formed between like cysteine enantiomers are able to bind to the surface. For cysteine adsorption over the chiral (kinked) Au(17 11 9) surface no enantiospecific adsorption is found since the molecule only binds through the thiolate and amino groups.[4] Modifying the adsorbate by substituting the noninteracting carboxyl group with a dimethylphosphino group provides a third strong adsorbate-surface bond thereby enabling the discrimination during adsorption of two molecular enantiomers by one particular chiral Au surface. [1] J. Gottschalck and B. Hammer, J. Chem. Phys. 116, 784 (2002). [2] L.M. Molina and B. Hammer, Chem. Phys. Lett. 360, 264 (2002). [3] A

  9. Adsorption of mercury from water by modified multi-walled carbon nanotubes: adsorption behaviour and interference resistance by coexisting anions.

    PubMed

    Chen, Paris Honglay; Hsu, Cheng-Feng; Tsai, David Dah-wei; Lu, Yen-Ming; Huang, Winn-Jung

    2014-08-01

    This investigation reports the use of modified multi-walled carbon nanotubes (MWCNTs) with various functional groups for adsorbing inorganic divalent mercury (Hg(II)) from water samples. To elucidate the behaviours and mechanisms of Hg(II) adsorption by modified MWCNTs, their adsorption capacity was studied by considering adsorption isotherms and kinetics. Particular attention was paid to interference of coexisting inorganic ions with Hg(II) adsorption. The results reveal that functionalization with oxygen-containing groups improved the Hg(II) adsorption capacity of the MWCNTs. Kinetic analysis demonstrated that the adsorption of Hg(II) by MWCNTs was closely described by the pseudo-second-order and Elovich models, suggesting that the adsorption of Hg(II) by MWCNTs was significantly affected by chemical adsorption. The kinetic results were also analysed using the intraparticle diffusion model, which revealed that intraparticle diffusion was not the only rate-controlling mechanism. The adsorption of Hg(II) on MWCNTs fell drastically as the ionic strength increased from 0 to 1.0mol/L chloride ions, and declined significantly as the pH increased from 2.2 to 10.5. The elemental maps obtained by energy-dispersive spectrometer (EDS) revealed the formation of surface complexes of chloride ions with functional groups on MWCNTs, which reduced the number of available sites for the adsorption of Hg(II) and strengthened the repulsive forces between Hg(II) and MWCNTs. The EDS results suggest that chloride ions are important in controlling Hg(II) speciation and adsorption on the surfaces of MWCNTs.

  10. Adsorption isotherm special study. Final report

    SciTech Connect

    1993-05-01

    The study was designed to identify methods to determine adsorption applicable to Uranium Mill Tailings Remedial Action (UMTRA) Project sites, and to determine how changes in aquifer conditions affect metal adsorption, resulting retardation factors, and estimated contaminant migration rates. EPA and ASTM procedures were used to estimate sediment sorption of U, As, and Mo under varying groundwater geochemical conditions. Aquifer matrix materials from three distinct locations at the DOE UMTRA Project site in Rifle, CO, were used as the adsorbents under different pH conditions; these conditions stimulated geochemical environments under the tailings, near the tailings, and downgradient from the tailings. Grain size, total surface area, bulk and clay mineralogy, and petrography of the sediments were characterized. U and Mo yielded linear isotherms, while As had nonlinear ones. U and Mo were adsorbed strongly on sediments acidified to levels similar to tailings leachate. Changes in pH had much less effect on As adsorption. Mo was adsorbed very little at pH 7-7.3, U was weakly sorbed, and As was moderately sorbed. Velocities were estimated for metal transport at different pHs. Results show that the aquifer materials must be characterized to estimate metal transport velocities in aquifers and to develop groundwater restoration strategies for the UMTRA project.

  11. Carbon adsorption onsite for remedial actions

    SciTech Connect

    Githens, G.D.

    1984-01-01

    Environmental remediation options range from various offsite disposal methods to onsite concentration, treatment or storage. Onsite treatment using mobile carbon adsorption treatment systems has long been a favored option for remedial actions because of its proven performance in the clean-up of transportation spills, waste sites, runoff from chemical warehouse fires and many types of groundwater pollution. Carbon adsorption is fundamentally a concentration technology. It will, for example, preferentially concentrate organics. Following its use, the carbon is usually transported offsite for thermal regeneration (mobile regeneration is not generally available) or landfilled if certain contaminants such as PCBs are on the carbon. Most remediation projects are temporary in nature and involve removing contamination from finite areas to attain specific pollutant limits. The best way to approach these circumstances is to utilize mobile, rapidly deployed, modular units. With mobile pretreatment equipment, the field engineer can solve problems with control over cost and system performance.

  12. DNA stickers promote polymer adsorption onto cellulose.

    PubMed

    Sato, Teruaki; Ali, Md Monsur; Pelton, Robert; Cranston, Emily D

    2012-10-08

    Adsorption of oligonucleotides onto model cellulose surfaces was investigated by comparing the Boese and Breaker's cellulose binding oligonucleotide (CBO) with a nonspecific oligonucleotide control (NSO). Measurements using the quartz crystal microbalance with dissipation technique confirmed that CBO adsorbed onto cellulose more than NSO, particularly at high ionic strengths (100 mM CaCl(2)). CBO showed a higher maximum adsorption on nanofibrillated and nanocrystalline cellulose than on regenerated cellulose, indicating a preference for the native cellulose I crystal structure under conditions that favored specific adsorption over calcium-mediated electrostatically driven adsorption. In addition, an anionic polyacrylamide (A-PAM) with grafted CBO also adsorbed onto the surface of cellulose in CaCl(2), whereas the unmodified A-PAM did not. This work shows that CBO performs as a "sticker", facilitating the adsorption of polyacrylamide onto cellulose, even under high ionic strength conditions where the adsorption of conventional polyelectrolytes is inhibited.

  13. Adsorption of goethite onto quartz and kaolinite

    USGS Publications Warehouse

    Goldberg, M.C.; Weiner, Eugene R.; Boymel, P.M.

    1984-01-01

    The adsorption of colloidal goethite onto quartz and kaolinite substrates has been studied as a function of pH and NaCl concentration. Goethite adsorption was measured quantitatively by Fourier-transform infrared spectroscopy. The results indicate that adsorption onto both substrates is due primarily to coulombic forces; however, the pH dependence of adsorption is very different for the two substrates. This is explained by the fact that the surface charge on quartz is entirely pH-dependent, while kaolinite has surface faces which carry a permanent negative charge. Adsorption of goethite on to kaolinite increases markedly with increasing NaCl concentration, while adsorption onto quartz is relatively independent of NaCl concentration. This can be explained by the influence of NaCl concentration upon the development of surface charge on the substrates. A method is described for separating surface-bound goethite from free goethite.

  14. Adsorption and isotopic fractionation of Xe

    NASA Technical Reports Server (NTRS)

    Bernatowicz, T. J.; Podosek, F. A.

    1986-01-01

    A theoretical description of the mechanisms of isotopic fractionation arising during adsorption of noble gases in a Henry's Law pressure regime is given. Experimental data on the isotopic composition of Xe adsorbed on activated charcoal in the temperature range 220 K to 350 K are presented. Both theoretical considerations and the experimental data indicate that equilibrium adsorption does not significantly alter the isotopic structure of adsorbed structure of adsorbed noble gases. Therefore, if adsorption is responsible for the elemental noble gas pattern in meteorites and the earth, the heavy noble gas isotopic fractionation between them must have been produced prior to and by a different process than equilibrium adsorption.

  15. Adsorption of water vapor on reservoir rocks

    SciTech Connect

    Not Available

    1993-07-01

    Progress is reported on: adsorption of water vapor on reservoir rocks; theoretical investigation of adsorption; estimation of adsorption parameters from transient experiments; transient adsorption experiment -- salinity and noncondensible gas effects; the physics of injection of water into, transport and storage of fluids within, and production of vapor from geothermal reservoirs; injection optimization at the Geysers Geothermal Field; a model to test multiwell data interpretation for heterogeneous reservoirs; earth tide effects on downhole pressure measurements; and a finite-difference model for free surface gravity drainage well test analysis.

  16. Adsorption of acid dye onto organobentonite.

    PubMed

    Baskaralingam, P; Pulikesi, M; Elango, D; Ramamurthi, V; Sivanesan, S

    2006-02-06

    Removal of Acid Red 151 from aqueous solution at different dye concentrations, adsorbent doses and pH has been studied. The bentonite clay has been modified using cationic surfactants, which has been confirmed using XRD and FT-IR analyses. Experimental result has shown that the acidic pH favours the adsorption. The adsorption isotherms are described by means of Langmuir and Freundlich isotherms. The adsorption capacity has been found to be 357.14 and 416.66 mg g(-1) for the cetyldimethylbenzylammonium chloride-bentonite (CDBA-bent) and cetylpyridinium chloride-bentonite (CP-bent), respectively. Kinetic studies show that the adsorption followed second-order kinetics.

  17. Ozone adsorption on carbon nanoparticles

    NASA Astrophysics Data System (ADS)

    Chassard, Guillaume; Gosselin, Sylvie; Visez, Nicolas; Petitprez, Denis

    2014-05-01

    Carbonaceous particles produced by incomplete combustion or thermal decomposition of hydrocarbons are ubiquitous in the atmosphere. On these particles are adsorbed hundreds of chemical species. Those of great concern to health are polycyclic aromatic hydrocarbons (PAHs). During atmospheric transport, particulate PAHs react with gaseous oxidants. The induced chemical transformations may change toxicity and hygroscopicity of these potentially inhalable particles. The interaction between ozone and carbon particles has been extensively investigated in literature. However ozone adsorption and surface reaction mechanisms are still ambiguous. Some studies described a fast catalytic decomposition of ozone initiated by an atomic oxygen chemisorption followed by a molecular oxygen release [1-3]. Others suggested a reversible ozone adsorption according to Langmuir-type behaviour [4,5]. The aim of this present study is a better understanding of ozone interaction with carbon surfaces. An aerosol of carbon nanoparticles was generated by flowing synthetic air in a glass tube containing pure carbon (primary particles < 50 nm), under magnetic stirring. The aerosol was then mixed with ozone in an aerosol flow tube. Ozone uptake experiments were performed with different particles concentrations with a fixed ozone concentration. The influence of several factors on kinetics was examined: initial ozone concentration, particle size (50 nm ≤ Dp ≤ 200 nm) and competitive adsorption (with probe molecule and water). The effect of initial ozone concentration was first studied. Accordingly to literature, it has been observed that the number of gas-phase ozone molecules lost per unit particle surface area tends towards a plateau for high ozone concentration suggesting a reversible ozone adsorption according to a Langmuir mechanism. We calculated the initial reaction probability between O3 and carbon particles.An initial uptake coefficient of 1.10-4 was obtained. Similar experiments were

  18. Influence of Adsorption Site and Wavelength on the Photodesorption of NO from the (Fe,Cr) 3 O 4 (111) Mixed Oxide Surface

    SciTech Connect

    Henderson, M. A.

    2014-09-11

    The photochemical properties of nitric oxide on a mixed oxide single crystal surface was examined in ultrahigh vacuum (UHV) using temperature programmed desorption (TPD), photon stimulated desorption (PSD) and low energy electron diffraction (LEED). The mixed oxide was a 75% Fe and 25% Cr corundum (0001) oxide film prepared on an α-Al2O3(0001) crystal, however its surface became terminated with a magnetite-like (111) structure after sputter/anneal cleaning, leading to a surface designated of (Fe,Cr)3O4(111). TPD of NO from the (Fe,Cr)3O4(111) surface revealed three chemisorbed states at 220, ~315 and 370 K assigned to NO binding at Fe3+, Cr3+ and Fe2+ sites, respectively. No significant thermal chemistry of NO was detected. NO photodesorption, the primary photochemical pathway in UHV, was sensitive to the adsorption site, with rates at the three adsorption sites following the trend: Fe3+ > Fe2+ > Cr3+. Multiexponential rate behavior seen in the overall NO PSD spectra was linked directly to site heterogeneity being manifested as a convolution of the individual NO photodesorption rates at the three types of surface sites. The photodesorption rate with UV light (365 nm) was ~10 times greater than that in the visible, but the per-photon rates across the visible spectrum (from 460 to 630 nm) were independent of the wavelength, which is suggestive of localized photon absorption at the adsorption site. Results in this study demonstrate that the adsorption site plays a critical role in determining photochemical rates on complex oxide surfaces. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multi-program national laboratory operated for DOE by Battelle. The research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located

  19. Anion adsorption induced surface reconstructions

    NASA Astrophysics Data System (ADS)

    Tang, Lei

    2005-11-01

    Surface stress plays an important role in the behavior of solid surfaces. Potential-controlled anion adsorption in electrolytes alters the surface stress of the electrode and results in morphology changes to the surfaces. With a combination of potential-induced surface stress measurement and in situ electrochemical scanning tunneling microscopy (STM), it is demonstrated that anion adsorption induces changes in structure of thin films and modifies the growth morphology and stress evolution in epitaxially grown films. Surface structural transitions in the heteroepitaxial system consisting of one to two gold monolayers on platinum substrates were observed. By increasing the potential, structural transitions, from (1 x 1), to a striped phase, to a hexagonal structure, occurred in the gold bilayer. This hexagonal structure was related to the formation of an ordered sulfate adlayer with a ( 3x7 ) structure. Such transitions were repeatable by cycling the potential. Furthermore, the transitions between various dislocation structures were affected by anion adsorption. The surface composition of the gold bilayer on Pt was measured by underpotential deposition of copper. By subtracting the contribution of a pure Pt surface from the gold bi-layer on Pt, a stress change of -2.4 N/m was observed, which agrees with the stress change of -2.46 N/m predicted to accompany formation of 1.5 MLs of coherent Au on Pt(111) from epitaxy theory. The Cu monolayer deposited on Au(111) from an acid sulfate electrolyte was found to be pseudomorphic while the Cu monolayer formed on Au(111) in vacuum was incoherent. The stress-thickness change associated with the coherent monolayer of copper on Au(111) in electrolyte was -0.6 N/m, while conventional epitaxy theories predict a value of +7.76 N/m. STM results elucidated the sulfate adsorption on the copper monolayer caused an expansion of the layer as evidenced by a Moire Structure. For the Cu monolayer on Au(111), the sulfate-induced expansion

  20. Charcoal/Nitrogen Adsorption Cryocooler

    NASA Technical Reports Server (NTRS)

    Bard, Steven

    1987-01-01

    Refrigerator with no wear-related moving parts produces 0.5 W of cooling at 118 K. When fully developed, refrigerator needs no electrical power, and life expectancy of more than 10 yr, operates unattended to cool sensitive infrared detectors for long periods. Only moving parts in adsorption cryocooler are check valves. As charcoal is cooled in canister, gas pressure drops, allowing inlet check valve to open and admit more nitrogen. When canister is heated, pressure rises, closing inlet valve and eventually opening outlet valve.

  1. Moisture adsorption in optical coatings

    NASA Technical Reports Server (NTRS)

    Macleod, H. Angus

    1988-01-01

    The thin film filter is a very large aperture component which is exceedingly useful because of its small size, flexibility and ease of mounting. Thin film components, however, do have defects of performance and especially of stability which can cause problems in systems, particularly where long-term measurements are being made. Of all of the problems, those associated with moisture absorption are the most serious. Moisture absorption occurs in the pore-shaped voids inherent in the columnar structure of the layers. Ion-assisted deposition is a promising technique for substantially reducing moisture adsorption effects in thin film structures.

  2. Hydrogen adsorption on sulphur-doped SiC nanotubes

    NASA Astrophysics Data System (ADS)

    Sevak Singh, Ram

    2016-07-01

    Hydrogen (H2) is an energy carrier and clean fuel that can be used for a broad range of applications that include fuel cell vehicles. Therefore, development of materials for hydrogen storage is demanded. Nanotubes, in this context, are appropriate materials. Recently, silicon carbide nanotube (SiCNTs) have been predicted as potential nanomaterials for hydrogen storage, and atomic doping into the nanotubes improves the H2 adsorption. Here, we report H2 adsorption properties of sulphur-doped (S-doped) SiCNTs using first-principles calculations based on density functional theory. The H2 adsorption properties are investigated by calculations of energy band structures, density of states (DOS), adsorption energy and Mulliken charge population analysis. Our findings show that, compared to the intrinsic SiCNT, S-doped SiCNT is more sensitive to H2 adsorption. H2 gas adsorption on S-doped C-sites of SiCNT brings about significant modulation of the electronic structure of the nanotube, which results in charge transfer from the nanotube to the gas, and dipole-dipole interactions cause chemisorptions of hydrogen. However, in the case of H2 gas adsorption on S-doped Si-sites of the nanotube, lesser charge transfer from the nanotube to the gas results in physisorptions of the gas. The efficient hydrogen sensing properties of S-doped SiCNTs, studied here, may have potential for its practical realization for hydrogen storage application.

  3. Adsorption of imidazole on Au(111) surface: Dispersion corrected density functional study

    NASA Astrophysics Data System (ADS)

    Izzaouihda, Safia; Mahjoubi, Khaled; Abou El Makarim, Hassna; Komiha, Najia; Benoit, David M.

    2016-10-01

    We use density functional theory in the generalized gradient approximation to study the adsorption of imidazole on the Au(111) surface and account for dispersion effect using Grimme's empirical dispersion correction technique. Our results show that the adsorption energy of imidazole depends on the slab size and on the adsorption site. In agreement with other studies, we find the largest adsorption energy for imidazole on a top site of Au(111). However, we also note that the adsorption energy at other sites is substantial.

  4. Dissociative adsorption of H2 on Cu(100): Fixed-site calculations for impact at hollow and top sites

    NASA Astrophysics Data System (ADS)

    Mowrey, R. C.; Kroes, G. J.; Baerends, E. J.

    1998-04-01

    The reaction of H2 on Cu(100) is studied using a wave-packet method to solve a four-dimensional quantum mechanical model for impact on the high-symmetry hollow and top sites. The potential energy surface (PES) is a fit to the results of density functional calculations treating a periodic overlayer of H2 on a Cu slab. The dynamics calculations include motion in the azimuthal coordinate although the PES does not depend on φ for impact on the top and hollow sites. Large dissociation probabilities (˜0.9) are found for impact at the hollow site but those for impact at the top site are lower (˜0.3). Dissociation probabilities for molecules incident with "helicoptering" motion (mj=j) are larger than those for molecules with "cartwheeling" motion (mj=0). This differs from the results of previous calculations for impact at the azimuthally corrugated bridge site which predicted comparable probabilities for the two orientations of incident molecules. The dissociation probabilities from fixed-site calculations at the different impact sites are combined to yield an averaged probability which is compared with experiment and the results of six-dimensional quantum calculations. Vibrationally inelastic scattering is predicted to occur primarily for impact at the top site.

  5. Nitrogen Adsorption on Graphite: Defying Physisorption

    NASA Astrophysics Data System (ADS)

    Tkatchenko, Alexandre; Scheffler, Matthias

    2010-03-01

    The adsorption of a nitrogen molecule at the graphite surface can be considered a paradigm of molecular physisorption [1]. The binding of N2 can be phenomenologically described in terms of a competition between quadrupole--quadrupole and van der Waals dispersion energies. Of particular interest is the relative stability of the so-called ``in-plane'', ``out-of-plane'' and ``pin-wheel'' monolayer structures, in which the nitrogen molecules alternate between parallel and perpendicular configurations on the surface. By combining state-of-the-art electronic structure methods, such as dispersion-corrected density-functional theory and Møller-Plesset second-order perturbation theory along with high-level coupled cluster [CCSD(T)] calculations, we are able to gain quantitative insight into the adsorption mechanism of N2@graphite and achieve very good agreement with experimental desorption enthalpy. We challenge the commonly held view of a closed-shell adsorbed N2 molecule, finding a noticeable charge-density polarization for nitrogen in a perpendicular configuration on the surface. We map out the N2@graphite potential energy surface as a function of sliding and orientation and discuss the influence of quantum zero-point energy for different adsorption sites. [1] D. Marx and H. Wiechert, Adv. Chem. Phys. 95, 213 (1996).

  6. Multisite adsorption of cadmium on goethite

    SciTech Connect

    Venema, P.; Hiemstra, T.; Riemsdijk, W.H. van

    1996-11-10

    Recently a new general ion adsorption model has been developed for ion binding to mineral surfaces (Hiemstra and van Riemsdijk, 1996). The model uses the Pauling concept of charge distribution (CD) and is an extension of the multi-site complexation (MUSIC) approach. In the CD-MUSIC model the charge of an adsorbing ion that forms an inner sphere complex is distributed over its ligands, which are present in two different electrostatic planes. In this paper the authors have applied the CD-MUSIC model to the adsorption of metal cations, using an extended data set for cadmium adsorbing on goethite. The adsorption of cadmium and the cadmium-proton exchange ratio were measured as function of metal ion concentration, pH, and ionic strength. The data could be described well, taking into account the surface heterogeneity resulting from the presence of two different crystal planes (the dominant 110 face and the minor 021 face). The surface species used in the model are consistent with recent EXAFS data. In accordance with the EXAFS results, high-affinity complexes at the 021 face were used in the model.

  7. Effects of oxygen adsorption on carbon nanotube field emitters

    NASA Astrophysics Data System (ADS)

    Park, Noejung; Han, Seungwu; Ihm, Jisoon

    2001-09-01

    Effects of oxygen adsorption on the field emission of carbon nanotubes are studied through first-principles calculations. Calculated emission currents are significantly enhanced when oxygen is adsorbed at the tip and the underlying physics is explained in terms of the change in the electronic structure by oxidation and the local field increase at the adsorption site. The issue of the current degradation accompanied by the oxidative etching is also addressed. The field-emission-microscopy images on the phosphor screen are simulated, displaying various patterns characteristic of each adsorption configuration.

  8. Adsorption and Gas Separation of Molecules by Carbon Nanohorns.

    PubMed

    Gatica, Silvina M; Nekhai, Anton; Scrivener, Adam

    2016-05-19

    In this paper, we report the results of Monte Carlo simulations of the adsorption of neon, argon, methane and carbon dioxide in carbon nanohorns. We model the nanohorns as an array of carbon cones and obtained adsorption isotherms and isosteric heats. The main sites of adsorption are inside the cones and in the interstices between three cones. We also calculated the selectivity of carbon dioxide/methane, finding that nanohorns are a suitable substrate for gas separation. Our simulations are compared to available experimental data.

  9. Alkali cation specific adsorption onto fcc(111) transition metal electrodes.

    PubMed

    Mills, J N; McCrum, I T; Janik, M J

    2014-07-21

    The presence of alkali cations in electrolyte solutions is known to impact the rate of electrocatalytic reactions, though the mechanism of such impact is not conclusively determined. We use density functional theory (DFT) to examine the specific adsorption of alkali cations to fcc(111) electrode surfaces, as specific adsorption may block catalyst sites or otherwise impact surface catalytic chemistry. Solvation of the cation-metal surface structure was investigated using explicit water models. Computed equilibrium potentials for alkali cation adsorption suggest that alkali and alkaline earth cations will specifically adsorb onto Pt(111) and Pd(111) surfaces in the potential range of hydrogen oxidation and hydrogen evolution catalysis in alkaline solutions.

  10. Hydrogen adsorption on functionalized nanoporous activated carbons.

    PubMed

    Zhao, X B; Xiao, B; Fletcher, A J; Thomas, K M

    2005-05-12

    There is considerable interest in hydrogen adsorption on carbon nanotubes and porous carbons as a method of storage for transport and related energy applications. This investigation has involved a systematic investigation of the role of functional groups and porous structure characteristics in determining the hydrogen adsorption characteristics of porous carbons. Suites of carbons were prepared with a wide range of nitrogen and oxygen contents and types of functional groups to investigate their effect on hydrogen adsorption. The porous structures of the carbons were characterized by nitrogen (77 K) and carbon dioxide (273 K) adsorption methods. Hydrogen adsorption isotherms were studied at 77 K and pressure up to 100 kPa. All the isotherms were Type I in the IUPAC classification scheme. Hydrogen isobars indicated that the adsorption of hydrogen is very temperature dependent with little or no hydrogen adsorption above 195 K. The isosteric enthalpies of adsorption at zero surface coverage were obtained using a virial equation, while the values at various surface coverages were obtained from the van't Hoff isochore. The values were in the range 3.9-5.2 kJ mol(-1) for the carbons studied. The thermodynamics of the adsorption process are discussed in relation to temperature limitations for hydrogen storage applications. The maximum amounts of hydrogen adsorbed correlated with the micropore volume obtained from extrapolation of the Dubinin-Radushkevich equation for carbon dioxide adsorption. Functional groups have a small detrimental effect on hydrogen adsorption, and this is related to decreased adsorbate-adsorbent and increased adsorbate-adsorbate interactions.

  11. Number and strength of surface acidic sites on porous aluminosilicates of the MCM-41 type inferred from a combined microcalorimetric and adsorption study

    SciTech Connect

    Meziani, M.J.; Zajac, J.; Jones, D.J.; Partyka, S.; Roziere, J.

    2000-03-07

    A combined microcalorimetry and adsorption study has been used to characterize the surface acidity of two series of MCM-41 aluminosilicates (referred to as SiAlxCn, where x is the mole Si:Al ration and n the chain length of the surfactant template). {sup 29}Si magic angle spinning NMR spectra of a selected sample (SiAl32C16) indicates the presence of siloxane groups, Si(OSi){sub 4}, and three types of silanol groups, that is, single (SiO){sub 3}-Si-OH, hydrogen-bonded (SiO){sub 3}-SiOH{hor{underscore}ellipsis}HO-Si-(SiO){sub 3}, and germinal (SiO){sub 2}-Si(OH){sub 2}. It is also possible to detect the contributions from Si(3Si, 1Al) and Si(2Si,2Al) sites. The volumetric and calorimetric measurements of gas ammonia adsorption at 353 K were used to determine the number and strength of surface acidic sites. With the exception of H{sup +}-SiAl32C14 and SiAl8C14, all samples have low surface acidity. Following the pyridine-TPD study on SiAl9C14 sample, Lewis acid sites producing surface pyridine complexes constitute the strongest acidic site.

  12. Neon and CO2 adsorption on open carbon nanohorns.

    PubMed

    Krungleviciute, Vaiva; Ziegler, Carl A; Banjara, Shree R; Yudasaka, Masako; Iijima, S; Migone, Aldo D

    2013-07-30

    We present the results of a thermodynamics and kinetics study of the adsorption of neon and carbon dioxide on aggregates of chemically opened carbon nanohorns. Both the equilibrium adsorption characteristics, as well as the dependence of the kinetic behavior on sorbent loading, are different for these two adsorbates. For neon the adsorption isotherms display two steps before reaching the saturated vapor pressure, corresponding to adsorption on strong and on weak binding sites; the isosteric heat of adsorption is a decreasing function of sorbent loading (this quantity varies by about a factor of 2 on the range of loadings studied), and the speed of the adsorption kinetics increases with increasing loading. By contrast, for carbon dioxide there are no substeps in the adsorption isotherms; the isosteric heat is a nonmonotonic function of loading, the value of the isosteric heat never differs from the bulk heat of sublimation by more than 15%, and the kinetic behavior is opposite to that of neon, with equilibration times increasing for higher sorbent loadings. We explain the difference in the equilibrium properties observed for neon and carbon dioxide in terms of differences in the relative strengths of adsorbate-adsorbate to adsorbate-sorbent interaction for these species.

  13. Temperature-dependent adsorption of nitrogen on porous vycor glass

    NASA Astrophysics Data System (ADS)

    Huber, Tito E.; Tsou, Hsi Lung

    1998-03-01

    Adsorption isotherms of N2 have been measured in the temperature range from 77 to 120 K in samples of porous vycor glass. From the Brunauer-Emmett-Teller theory the surface layer coverages are determined. These are found to be temperature dependent. When adsorption-isotherm coverage data are expressed as a function of the adsorption potential δμ, the result is roughly temperature independent for coverages ranging from submonolayer to thin film, below capillary condensation. This characteristic curve, which represents the distribution of adsorption sites vs the adsorption potential, is compared with results from two models for the adsorbate: Dubinin's isotherm for microporous solids and its extension to rough surfaces, which places importance on the porosity of the surface, and Halsey's extension of the Frankel-Halsey-Hill isotherm, which takes into account the long-range variations of the substrate adsorption potential. The impact of this work on the interpretation of N2 adsorption data in terms of a surface area is discussed.

  14. Adsorption of beta blockers to environmental surfaces.

    PubMed

    Kibbey, Tohren C G; Paruchuri, Rajiv; Sabatini, David A; Chen, Lixia

    2007-08-01

    Beta-adrenergic blocking agents (beta blockers) are widely used pharmaceuticals which have been detected in the environment. Predicting the transport and ultimate fate of beta blockers in the environment requires understanding their adsorption to soils and sediments, something for which little information is currently available. The objective of this work was to examine the adsorption of three beta blockers, propranolol, metoprolol and nadolol, to a natural alluvial material, as well as to six minerals present as components of the alluvial material. Batch adsorption experiments indicate that, for most of the minerals studied, compound hydrophobicity is an important predictor of adsorption, with propranolol,the most hydrophobic compound studied, adsorbing to the greatest extent. Results further suggest that, for the minerals studied, electrostatic effects are not a good predictor of adsorption; adsorption extent was not well-predicted by either surface zeta potential or by the difference between experiment pH and point of zero charge, despite the cationic nature af the three beta blockers at experiment pH values. Experiments were conducted to examine the effect of an anionic surfactant, sodium dodecyl benzene sulfonate (SDBS), on adsorption. Results indicate that SDBS significantly increases the adsorption of propranolol to two different sorbents. This result is potentially important because surfactants such as SDBS are likely to be present in wastewater effluents with beta blockers and could influence their mobility in the environment.

  15. Polychelated cryogels: hemoglobin adsorption from human blood.

    PubMed

    Erol, Kadir

    2017-02-01

    The separation and purification methods are extremely important for the hemoglobin (Hb) which is a crucial biomolecule. The adsorption technique is popular among these methods and the cryogels have been used quite much due to their macropores and interconnected flow channels. In this study, the Hb adsorption onto the Cu(II) immobilized poly(2-hydroxyethyl methacrylate-glycidyl methacrylate), poly(HEMA-GMA)-Cu(II), cryogels was investigated under different conditions (pH, interaction time, initial Hb concentration, temperature and ionic strength) to optimize adsorption conditions. The swelling test, Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), surface area (BET), elemental and ICP-OES analysis were performed for the characterization of cryogels. Polyethyleneimine (PEI) molecule was used as a Cu(II)-chelating ligand. The Hb adsorption capacity of cryogels was determined as 193.8 mg Hb/g cryogel. The isolation of Hb from human blood was also studied under optimum adsorption conditions determined and the Hb (124.5 mg/g cryogel) was isolated. The adsorption model was investigated in the light of Langmuir and Freundlich adsorption isotherm models and it was determined to be more appropriate to the Langmuir adsorption isotherm model.

  16. Arsenate adsorption by unsaturated alluvial sediments

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Arsenate adsorption as a function of solution arsenic concentration and solution pH was investigated on five alluvial sediments from the Antelope Valley, Western Mojave Desert, California. Arsenate adsorption increased with increasing solution pH, exhibited a maximum around pH 4 to 5, and then decr...

  17. BSA adsorption on bimodal PEO brushes.

    PubMed

    Bosker, W T E; Iakovlev, P A; Norde, W; Cohen Stuart, M A

    2005-06-15

    BSA adsorption onto bimodal PEO brushes at a solid surface was measured using optical reflectometry. Bimodal brushes consist of long (N=770) and short (N=48) PEO chains and were prepared on PS surfaces, applying mixtures of PS(29)-PEO(48) and PS(37)-PEO(770) block copolymers and using the Langmuir-Blodgett technique. Pi-A isotherms of (mixtures of) the block copolymers were measured to establish the brush regime. The isotherms of PS(29)-PEO(48) show hysteresis between compression and expansion cycles, indicating aggregation of the PS(29)-PEO(48) upon compression. Mixtures of PS(29)-PEO(48) and PS(37)-PEO(770) demonstrate a similar hysteresis effect, which eventually vanishes when the ratio of PS(37)-PEO(770) to PS(29)-PEO(48) is increased. The adsorption of BSA was determined at brushes for which the grafting density of the long PEO chains was varied, while the total grafting density was kept constant. BSA adsorption onto monomodal PEO(48) and PEO(770) brushes was determined for comparison. The BSA adsorption behavior of the bimodal brushes is similar to the adsorption of BSA at PEO(770) monomodal brushes. The maximum of BSA adsorption at low grafting density of PEO(770) can be explained by ternary adsorption, implying an attraction between BSA and PEO. The contribution of primary adsorption to the total adsorbed amount is negligible.

  18. Ion Exchange and Adsorption of Inorganic Contaminants

    EPA Science Inventory

    In the first part of the chapter, the fundamentals of ion exchange and adsorption processes are explained, with the goal of demonstrating how these principles influence process design for inorganic contaminant removal. In the second part, ion exchange and adsorption processes th...

  19. Phosphoryl functionalized mesoporous silica for uranium adsorption

    NASA Astrophysics Data System (ADS)

    Xue, Guo; Yurun, Feng; Li, Ma; Dezhi, Gao; Jie, Jing; Jincheng, Yu; Haibin, Sun; Hongyu, Gong; Yujun, Zhang

    2017-04-01

    Phosphoryl functionalized mesoporous silica (TBP-SBA-15) was synthesized by modified mesoporous silica with γ-amino propyl triethoxy silane and tributyl phosphate. The obtained samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD), thermo-gravimetric/differential thermalanalyzer (TG/DTA), N2 adsorption-desorption (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. Results showed that TBP-SBA-15 had large surface areas with ordered channel structure. Moreover, the effects of adsorption time, sorbent dose, solution pH, initial uranium concentration and temperature on the uranium adsorption behaviors were investigated. TBP-SBA-15 showed a high uranium adsorption capacity in a broad range of pH values. The U(VI) adsorption rate of TBP-SBA-15 was fast and nearly achieved completion in 10 min with the sorbent dose of 1 g/L. The U(VI) adsorption of TBP-SBA-15 followed the pseudo-second-order kinetic model and Freundlich isotherm model, indicating that the process was belonged to chemical adsorption. Furthermore, the thermodynamic parameters (ΔG0, ΔH0 and ΔS0) confirmed that the adsorption process was endothermic and spontaneous.

  20. Coulometric Study of Ethanol Adsorption at a Polycrystalline Platinum Electrode

    DTIC Science & Technology

    2011-07-01

    value of the ratio Ian/Icalc: 1. The minimal ratio would be 1, corresponding to a one- electron oxidation of one-site attached CH3CH2O surface...Coulometric Study of Ethanol Adsorption at a Polycrystalline Platinum Electrode Sol Gilman Sensors and Electron Devices Directorate, ARL...noble metals and noble metal alloys that can provide what amounts to an adsorbed oxygen “valve” for initiating adsorption/reaction on a clean and

  1. Factors affecting drug adsorption on beta zeolites.

    PubMed

    Pasti, Luisa; Sarti, Elena; Cavazzini, Alberto; Marchetti, Nicola; Dondi, Francesco; Martucci, Annalisa

    2013-05-01

    The adsorption behaviour of three commonly used drugs, namely ketoprofen, hydrochlorothiazide and atenolol, from diluted aqueous solutions on beta zeolites with different SiO2/Al2O3 ratio (i.e. 25, 38 and 360) was investigated by changing the ionic strength and the pH, before and after thermal treatment of the adsorbents. The selective adsorption of drugs was confirmed by thermogravimetry and X-ray diffraction. The adsorption capacity of beta zeolites was strongly dependent on both the solution pH and the alumina content of the adsorbent. Such a remarkable difference was interpreted as a function of the interactions between drug molecules and zeolite surface functional groups. Atenolol was readily adsorbed on the less hydrophobic zeolite, under pH conditions in which electrostatic interactions were predominant. On the other hand, ketoprofen adsorption was mainly driven by hydrophobic interactions. For undissociated molecules the adsorption capability increased with the increase of hydrophobicity.

  2. Adsorption and desorption of reversible supramolecular polymers

    NASA Astrophysics Data System (ADS)

    Zweistra, Henk J. A.; Besseling, N. A. M.

    2006-08-01

    We report numerical mean-field results on the quasichemical level of approximation that describe adsorption of reversible supramolecular polymers at a flat interface. Emphasis is laid on the regime of strong adsorption from a dilute solution. There are two differences with respect to macromolecular polymer adsorption: (i) adsorption sets in at relatively high monomer concentrations of the surrounding solution, and (ii) the surface is filled within a much narrower concentration range. Contrary to macromolecular polymers, supramolecular polymers can therefore be desorbed by dilution of the equilibrium solution by solvent within an experimentally accessible concentration window. Based on simple thermodynamic arguments, we provide a quantitative explanation why supramolecular polymers adsorb at relatively high concentrations. Moreover, we discuss the (by comparison) narrow concentration window wherein filling of the surface occurs. This is attributed to the cooperative nature of supramolecular polymer adsorption. The degree of cooperativity is quantified by means of the Hill parameter n .

  3. Adsorption of xenon and krypton on shales

    NASA Technical Reports Server (NTRS)

    Podosek, F. A.; Bernatowicz, T. J.; Kramer, F. E.

    1981-01-01

    A method that uses a mass spectrometer as a manometer is employed in the measurement of Xe and Kr adsorption parameters on shales and related samples, where gas partial pressures were lower than 10 to the -11th atm, corresponding adsorption coverages are only small fractions of a monolayer, and Henry's Law behavior is expected and observed. Results show heats of adsorption in the 2-7 kcal/mol range, and Henry constants at 0-25 C of 1 cu cm STP/g per atmosphere are extrapolated. Although the adsorption properties obtained are variable by sample, the range obtained suggests that shales may be capable of an equilibrium adsorption with modern air high enough to account for a significant fraction of the atmospheric inventory of Xe, and perhaps even of Kr. This effect will nevertheless not account for the factor-of-25 defficiency of atmospheric Xe, in comparison with the planetary gas patterns observed in meteorites.

  4. Influence of cationic surfactant on adsorption of Cr(VI) onto activated carbon.

    PubMed

    Choi, Hyun-Doc; Cho, Jung-Min; Baek, Kitae; Yang, Jung-Seok; Lee, Jae-Young

    2009-01-30

    The effect of a cationic surfactant on the adsorption of Cr(VI) on activated carbon was investigated using cetylpyridinium chloride (CPC). At a concentration below the critical micelle concentration (CMC) of CPC, the adsorption of CPC and Cr(VI) reached equilibrium within 60 min, while it took 180 min at the concentration above CMC. CPC decreased the adsorption rate of Cr(VI) and increased the adsorption amount of Cr(VI) onto activated carbon. To analyze adsorption phenomena of Cr(VI), adsorption kinetic and isotherm were used and fitted well with the pseudo-second order kinetic model and Langmuir adsorption model, respectively. CPC introduced a cationic functional group on the surface of activated carbon and provided an adsorption site for Cr(VI).

  5. Adsorption site of c(2×2) O on Ni(0001): An off-normal-direction energy-dependent photoelectron-diffraction study

    NASA Astrophysics Data System (ADS)

    Mei, W. N.; Tong, S. Y.

    1986-01-01

    We have used the technique of energy-dependent photoelectron diffraction (EDPD) to study the pseudo-bridge-site model proposed by Demuth et al. for the adsorption of c(2×2) O on Ni(001). Calculated EDPD curves at the normal exit direction for the pseudo-bridge site, averaged over four domains, were compared with those for the fourfold hollow site. We found no significant differences in the EDPD curves for the two different structural models. However, the calculated EDPD curves at off-normal directions, such as those along the [011] direction, or along the O-Ni bond directions, were qualitatively different for the two sites. We therefore conclude that off-normal-direction EDPD curves, when compared with measured data, can effectively determine the lateral coordinates of the oxygen overlayer on Ni(001).

  6. How strong is the edge effect in the adsorption of anticancer drugs on a graphene cluster?

    PubMed

    Rungnim, Chompoonut; Chanajaree, Rungroj; Rungrotmongkol, Thanyada; Hannongbua, Supot; Kungwan, Nawee; Wolschann, Peter; Karpfen, Alfred; Parasuk, Vudhichai

    2016-04-01

    The adsorption of nucleobase-analog anticancer drugs (fluorouracil, thioguanine, and mercaptopurine) on a graphene flake (C54H18) was investigated by shifting the site at which adsorption occurs from one end of the sheet to the other end. The counterpoise-corrected M06-2X/cc-pVDZ binding energies revealed that the binding stability decreases in the sequence thioguanine > mercaptopurine > fluorouracil. We found that adsorption near the middle of the sheet is more favorable than adsorption near the edge due to the edge effect. This edge effect is stronger for the adsorption of thioguanine or mercaptopurine than for fluorouracil adsorption. However, the edge effect reduces the binding energy of the drug to the flake by only a small amount, <5 kcal/mol, depending on the adsorption site and the alignment of the drug at this site.

  7. Isotherms for Water Adsorption on Molecular Sieve 3A: Influence of Cation Composition

    SciTech Connect

    Lin, Ronghong; Ladshaw, Austin; Nan, Yue; Liu, Jiuxu; Yiacoumi, Sotira; Tsouris, Costas; DePaoli, David W.; Tavlarides, Lawrence L.

    2015-06-16

    This study is part of our continuing efforts to address engineering issues related to the removal of tritiated water from off-gases produced in used nuclear fuel reprocessing facilities. In the current study, adsorption equilibrium of water on molecular sieve 3A beads was investigated. Adsorption isotherms for water on the UOP molecular sieve 3A were measured by a continuous-flow adsorption system at 298, 313, 333, and 353 K. Experimental data collected were analyzed by the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm model. The K+/Na+ molar ratio of this particular type of molecular sieve 3A was ~4:6. Our results showed that the GSTA isotherm model worked very well to describe the equilibrium behavior of water adsorption on molecular sieve 3A. The optimum number of parameters for the current experimental data was determined to be a set of four equilibrium parameters. This result suggests that the adsorbent crystals contain four energetically distinct adsorption sites. In addition, it was found that water adsorption on molecular sieve 3A follows a three-stage adsorption process. This three-stage adsorption process confirmed different water adsorption sites in molecular sieve crystals. In addition, the second adsorption stage is significantly affected by the K+/Na+ molar ratio. In this stage, the equilibrium adsorption capacity at a given water vapor pressure increases as the K+/Na+ molar ratio increases.

  8. Isotherms for Water Adsorption on Molecular Sieve 3A: Influence of Cation Composition

    DOE PAGES

    Lin, Ronghong; Ladshaw, Austin; Nan, Yue; ...

    2015-06-16

    This study is part of our continuing efforts to address engineering issues related to the removal of tritiated water from off-gases produced in used nuclear fuel reprocessing facilities. In the current study, adsorption equilibrium of water on molecular sieve 3A beads was investigated. Adsorption isotherms for water on the UOP molecular sieve 3A were measured by a continuous-flow adsorption system at 298, 313, 333, and 353 K. Experimental data collected were analyzed by the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm model. The K+/Na+ molar ratio of this particular type of molecular sieve 3A was ~4:6. Our results showed that themore » GSTA isotherm model worked very well to describe the equilibrium behavior of water adsorption on molecular sieve 3A. The optimum number of parameters for the current experimental data was determined to be a set of four equilibrium parameters. This result suggests that the adsorbent crystals contain four energetically distinct adsorption sites. In addition, it was found that water adsorption on molecular sieve 3A follows a three-stage adsorption process. This three-stage adsorption process confirmed different water adsorption sites in molecular sieve crystals. In addition, the second adsorption stage is significantly affected by the K+/Na+ molar ratio. In this stage, the equilibrium adsorption capacity at a given water vapor pressure increases as the K+/Na+ molar ratio increases.« less

  9. Temperature Swing Adsorption Compressor Development

    NASA Technical Reports Server (NTRS)

    Finn, John E.; Mulloth, Lila M.; Affleck, Dave L.

    2001-01-01

    Closing the oxygen loop in an air revitalization system based on four-bed molecular sieve and Sabatier reactor technology requires a vacuum pump-compressor that can take the low-pressure CO, from the 4BMS and compress and store for use by a Sabatier reactor. NASA Ames Research Center proposed a solid-state temperature-swing adsorption (TSA) compressor that appears to meet performance requirements, be quiet and reliable, and consume less power than a comparable mechanical compressor/accumulator combination. Under this task, TSA compressor technology is being advanced through development of a complete prototype system. A liquid-cooled TSA compressor has been partially tested, and the rest of the system is being fabricated. An air-cooled TSA compressor is also being designed.

  10. Dynamics and thermodynamics of toxic metals adsorption onto soil-extracted humic acid.

    PubMed

    Shaker, Medhat A; albishri, Hassan M

    2014-09-01

    Humic acids, HA represent a large portion of natural organic matter in soils, sediments and waters. They are environmentally important materials due to their extensive ubiquity and strong complexation ability, which can influence heavy metal removal and transportation in waters. The thermodynamics and kinetics of the adsorption of Cd(II) and Cr(VI) onto solid soil-derived HA have been investigated at optimum conditions of pH (5.5±0.1), metal concentration (10-100mmolL(-1)) and different temperatures (293-323K). The suitability of adsorption models such as Freundlich and Langmuir to equilibrium data was investigated. The adsorption was well described by Langmuir isotherm model in multi-detectable steps. Adsorption sites, i (i=A, B, C) with different capacities, νi are characterized. The stoichiometric site capacity is independent of temperature and equilibrium constant, Ki. Adsorption sites A and B are selectively occupied by Cr(VI) cations while sites A and C are selectively occupied by Cd(II) cations. The thermodynamic parameters of adsorption systems are correlated for each adsorption step. The adsorption is endothermic, spontaneous and favorable. Different kinetic models are applied and the adsorption of these heavy metals onto HA follows pseudo-second-order kinetics and equilibrium is achieved within 24h. The adsorption reaction is controlled by diffusion processes and the type of the adsorption is physical.

  11. Adsorption behaviour of dibutyl phthalate on marine sediments.

    PubMed

    Xu, Xiang-Rong; Li, Xiao-Yan

    2008-01-01

    Laboratory experiments were carried out to investigate the adsorption behaviour of dibutyl phthalate (DBP) on marine sediments collected from five different sites in Victoria Harbour, Hong Kong. DBP adsorption can be well described by the Langmuir isotherm. The maximum DBP adsorption capacity (Q(max)) of the marine sediments ranges from 53 to 79 mg g(-1), which has a positive correlation with their organic content. Around 90% of the organic can be removed from the sediments with treatment by H(2)O(2) oxidation, and the Q(max) then decreases to a range between 13 and 22 mg g(-1). The black carbon content of the sediments has a much greater DBP adsorption capacity than does the natural organic matter of the sediments. The amount of DBP adsorbed on the sediments increases as the salinity of the marine water increases.

  12. Adsorption of carbon monoxide on activated carbon tin ligand

    NASA Astrophysics Data System (ADS)

    Mohamad, A. B.; Iyuke, S. E.; Daud, W. R. W.; Kadhum, A. A. H.; Fisal, Z.; Al-Khatib, M. F.; Shariff, A. M.

    2000-09-01

    Activated carbon was impregnated with 34.57% SnCl 2·2H 2O salt and then dried at 180°C to produce AC-SnO 2 to improve its adsorptive interaction with CO. Besides the fact that activated carbon has its original different pore sizes for normal gas phase CO adsorption (as in the case of pure carbon), the impregnated carbon has additional CO adsorption ability due to the presence of O -(ads) on the active sites. AC-SnO 2 proved to be a superior adsorber of CO than pure carbon when used for H 2 purification in a PSA system. Discernibly, the high adsorptive selectivity of AC-SnO 2 towards gas phase CO portrays a good future for the applicability of this noble adsorbent, since CO has become a notorious threat to the global ecosystem due to the current level of air pollution.

  13. Enthalpy and entropy effects in hydrogen adsorption on carbon nanotubes.

    PubMed

    Efremenko, Irena; Sheintuch, Moshe

    2005-07-05

    Interaction energies and entropies associated with hydrogen adsorption on the inner and outer surfaces of zigzag single-wall carbon nanotubes (SWCNT) of various diameters are analyzed by means of molecular mechanics, density functional theory, and ab initio calculations. For a single molecule the strongest interaction, which is 3.5 greater than that with the planar graphite sheet, is found inside a (8,0) nanotube. Adsorption on the outer surfaces is weaker than that on graphite. Due to the steric considerations, both processes are accompanied by an extremely strong decline in entropy. Absence of specific adsorption sites and weak attractive interaction between hydrogen molecules within carbon nanotubes results in their close packing at low temperatures. Using the calculated geometric and thermodynamic parameters in Langmuir isotherms we predict the adsorption capacity of SWCNTs at room temperature to be smaller than 1 wt % even at 100 bar.

  14. Atomic and Molecular Adsorption on Re(0001)

    SciTech Connect

    Hahn, Konstanze; Mavrikakis, Manos

    2014-02-01

    Using periodic, self-consistent density functional theory calculations, the adsorption of several atomic (H, S, N, O and C) and molecular (CO2, N2, NH3, HCN, CO and NO) species and molecular fragments (NH2, NH, CN, CNH2, HNO, NOH, CH3, CH2, CH and OH) on the (0001) facet of rhenium at a coverage of 0.25 ML has been studied. Preferred binding sites with their corresponding binding energy and deformation energy of the surface, as well as an estimated diffusion barrier of each species have been determined. Atomic species and molecular fragments tend to bind to threefold sites, whereas molecular species tend to bind to top sites. The binding strength, with respect to the corresponding gas phase species and in increasing order for all species studied, is: CO2 < N2 < NH3 < CO < CH3 < HCN < NO < H < NH2 < OH < CH2 < CNH2 < CN < HNO < NH < NOH < S < N < O < CH < C. The vibrational frequencies of all species in their most energetically favorable adsorbed configuration have been calculated. Finally, the thermochemistry of adsorption and decomposition of NO, NO + H, NH3, N2, CO2, CO and CH4 on Re(0001) has been analyzed.

  15. Adsorption of Cadmium, Nickel and Zinc in a Brazilian Oxisoil

    NASA Astrophysics Data System (ADS)

    Casagrande, José Carlos; Martins, Susian Christian; Soares, Marcio Roberto

    2010-05-01

    The adsorption reactions mechanisms provide the understanding of the pollutant fate metals and often control the bioavailability and transport of heavy metals ions in soil, indicating the preventive environmental control. The cadmium, nickel and zinc behavior in the soils are explained by the reactions of adsorption, influenced by pH and ionic strength. The objective of this work was to study the influence of those factors on cadmium, nickel and zinc adsorption in an oxisol. It was studied the Cd, Ni and Zn adsorption in soil samples of the State of São Paulo (Anionic "Xanthic" Acrudox), collected in surface and in depth and submitted to solutions of Ca(NO3)2 1,0; 0,1 and 0,01 mol L-1. The pH of the samples from 3,0 to 10,0 was varied adding NaOH or HCl 4 mol L-1 not surpassing 2% of the electrolyte volume. The soil samples received 5,0 mg dm-3 of cadmium, nickel and zinc, ratio 1:10 (2,0 g of soil: 20 solution ml) and were shacked for 24 hours. The cadmium, nickel and zinc adsorption increased with pH, reaching it picks at pH 7,0 for cadmium and approximately at pH 6,0 for nickel and zinc. This indicates that zinc and nickel have higher affinity than cadmium with the soil colloids, because it reached the maximum adsorption in a small pH value. In other words, the amount of negative charges necessary to promote the maximum adsorption was small for zinc. The influence of ionic strengths was small for cadmium, nickel and zinc adsorption, being similar from pH 3,0 to 10,0, in surface soil layer and in depth, demonstrating that competition with Ca2+ for the retention colloid sites of the soils didn't interfere in the adsorption. In that way, it is supposed that cadmium, nickel and zinc binding energy is high in a soil rich in Fe and Al oxides. Adsorption of cadmium, nickel and zinc was similar for the ionic strengths, not depending on PZSE. The cadmium, nickel and zinc adsorption increased with pH elevation, with small ionic strength influence. Nickel and zinc have

  16. Mercury adsorption properties of sulfur-impregnated adsorbents

    USGS Publications Warehouse

    Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

    2002-01-01

    Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

  17. Adsorption of water vapor by poly(styrenesulfonic acid), sodium salt: isothermal and isobaric adsorption equilibria.

    PubMed

    Toribio, F; Bellat, J P; Nguyen, P H; Dupont, M

    2004-12-15

    Air conditioning and dehumidifying systems based on sorption on solids are of great interest, especially in humid climates, because they allow reduction of thermal loads and use of chlorofluorocarbons. Previous studies have shown that hydrophilic polymers such as sulfonic polymers can have very high performance in water adsorption from air. The aim of this study was to characterize the water vapor adsorption properties of fully sulfonated and monosulfonated poly(styrenesulfonic acid), sodium salt, and to elucidate the mechanism of adsorption on these materials. Adsorption isotherms have been determined by TGA between 298 and 317 K for pressures ranging from 0.1 to 45 hPa. They have type II of the IUPAC classification and a small hysteresis loop between adsorption and desorption processes was observed only for the monosulfonated sample. Water content is up to 80% weight at 80% relative humidity. Adsorption isotherms have been well fitted with the FHH model. Adsorption-desorption isobars have been determined by TGA under 37 hPa in the temperature range 298-373 K. They show that these polymers can be completely regenerated by heating at 313 K under humidified air. No degradation of the adsorption properties has been observed after several regenerations. Adsorption enthalpies and entropies have been deduced from the Clapeyron equation and from DSC measurements. A good agreement was found. A mechanism of adsorption is proposed considering two kinds of adsorbate: bounded water in electrostatic interaction with functional groups and free water resulting from condensation.

  18. Modeling the adsorption of mixed gases based on pure gas adsorption properties

    NASA Astrophysics Data System (ADS)

    Tzabar, N.; Holland, H. J.; Vermeer, C. H.; ter Brake, H. J. M.

    2015-12-01

    Sorption-based Joule-Thomson (JT) cryocoolers usually operate with pure gases. A sorption-based compressor has many benefits; however, it is limited by the pressure ratios it can provide. Using a mixed-refrigerant (MR) instead of a pure refrigerant in JT cryocoolers allows working at much lower pressure ratios. Therefore, it is attractive using MRs in sorption- based cryocoolers in order to reduce one of its main limitations. The adsorption of mixed gases is usually investigated under steady-state conditions, mainly for storage and separation processes. However, the process in a sorption compressor goes through various temperatures, pressures and adsorption concentrations; therefore, it differs from the common mixed gases adsorption applications. In order to simulate the sorption process in a compressor a numerical analysis for mixed gases is developed, based on pure gas adsorption characteristics. The pure gas adsorption properties have been measured for four gases (nitrogen, methane, ethane, and propane) with Norit-RB2 activated carbon. A single adsorption model is desired to describe the adsorption of all four gases. This model is further developed to a mixed-gas adsorption model. In future work more adsorbents will be tested using these four gases and the adsorption model will be verified against experimental results of mixed-gas adsorption measurements.

  19. Understanding the site selectivity in small-sized neutral and charged Al(n) (4 ≤ N ≤ 7) clusters using density functional theory based reactivity descriptors: a validation study on water molecule adsorption.

    PubMed

    Das, Susanta; Pal, Sourav; Krishnamurty, Sailaja

    2013-09-12

    Aluminum clusters are now technologically important due to their high catalytic activity. Our present study on the small-sized aluminum clusters applies density functional theory (DFT)-based reactivity descriptors to identify potential sites for adsorption and eventual chemical reaction. Depending on symmetry, susceptibility of various type of reactive sites within a cluster toward an impending electrophilic and/or nucleophilic attack is predicted using the reactivity descriptors. In addition, the study devises general rules as to how the size, shape, and charge of the cluster influences the number of available sites for an electrophilic and/or nucleophilic attack. The predictions by reactivity descriptors are validated by performing an explicit adsorption of water molecule on Al clusters with four atoms. The adsorption studies demonstrate that the most stable water-cluster complex is obtained when the molecule is adsorbed through an oxygen atom on the site with the highest relative electrophilicity.

  20. A structural study of the K adsorption site on a Si(001)2 × 1 surface: Dimer, caves or both

    NASA Astrophysics Data System (ADS)

    Asensio, M. C.; Michel, E. G.; Alvarez, J.; Ocal, C.; Miranda, R.; Ferrer, S.

    1989-04-01

    The atomic structure of the clean Si(100) and K covered surfaces has been investigated by Auger electron diffraction (AED) monitoring the intensities along polar scans. This technique is sensitive to the asymmetric-dimer nature of the 2 × 1 reconstruction of the Si(001) surface. Data taken at room temperature for submonolayer coverages are consistent with adsorption of K on the troughs (cave position) existing between two consecutive dimer chains along the [110] direction. At 110 K both dimer and cave sites are occupied. A mild annealing to 300 K produces an overlayer redistribution in favor of the "cave" site further indicating that this site is energetically favoured as found in some recent calculations.

  1. Monte Carlo simulations of Protein Adsorption

    NASA Astrophysics Data System (ADS)

    Sharma, Sumit; Kumar, Sanat K.; Belfort, Georges

    2008-03-01

    Amyloidogenic diseases, such as, Alzheimer's are caused by adsorption and aggregation of partially unfolded proteins. Adsorption of proteins is a concern in design of biomedical devices, such as dialysis membranes. Protein adsorption is often accompanied by conformational rearrangements in protein molecules. Such conformational rearrangements are thought to affect many properties of adsorbed protein molecules such as their adhesion strength to the surface, biological activity, and aggregation tendency. It has been experimentally shown that many naturally occurring proteins, upon adsorption to hydrophobic surfaces, undergo a helix to sheet or random coil secondary structural rearrangement. However, to better understand the equilibrium structural complexities of this phenomenon, we have performed Monte Carlo (MC) simulations of adsorption of a four helix bundle, modeled as a lattice protein, and studied the adsorption behavior and equilibrium protein conformations at different temperatures and degrees of surface hydrophobicity. To study the free energy and entropic effects on adsorption, Canonical ensemble MC simulations have been combined with Weighted Histogram Analysis Method(WHAM). Conformational transitions of proteins on surfaces will be discussed as a function of surface hydrophobicity and compared to analogous bulk transitions.

  2. Functionalized SBA-15 materials for bilirubin adsorption

    NASA Astrophysics Data System (ADS)

    Tang, Tao; Zhao, Yanling; Xu, Yao; Wu, Dong; Xu, Jun; Deng, Feng

    2011-05-01

    To investigate the driving force for bilirubin adsorption on mesoporous materials, a comparative study was carried out between pure siliceous SBA-15 and three functionalized SBA-15 mesoporous materials: CH 3-SBA-15 (MS), NH 2-SBA-15 (AS), and CH 3/NH 2-SBA-15 (AMS) that were synthesized by one-pot method. The obtained materials exhibited large surface areas (553-810 m 2/g) and pore size (6.6-7.1 nm) demonstrated by XRD and N 2-ad/desorption analysis. The SEM images showed that the materials had similar fiberlike morphology. The functionalization extent was calculated according to 29Si MAS NMR spectra and it was close to the designed value (10%). The synthesized mesoporous materials were used as bilirubin adsorbents and showed higher bilirubin adsorption capacities than the commercial active carbon. The adsorption capacities of amine functionalized samples AMS and AS were larger than those of pure siliceous SBA-15 and MS, indicating that electrostatic interaction was the dominant driving force for bilirubin adsorption on mesoporous materials. Increasing the ionic strength of bilirubin solution by adding NaCl would decrease the bilirubin adsorption capacity of mesoporous material, which further demonstrated that the electrostatic interaction was the dominant driving force for bilirubin adsorption. In addition, the hydrophobic interaction provided by methyl groups could promote the bilirubin adsorption.

  3. Sub-ambient carbon dioxide adsorption properties of nitrogen doped graphene

    SciTech Connect

    Tamilarasan, P.; Ramaprabhu, Sundara

    2015-04-14

    Carbon dioxide adsorption on carbon surface can be enhanced by doping the surface with heterogeneous atoms, which can increase local surface affinity. This study presents the carbon dioxide adsorption properties of nitrogen doped graphene at low pressures (<100 kPa). Graphene was exposed to nitrogen plasma, which dopes nitrogen atoms into carbon hexagonal lattice, mainly in pyridinic and pyrrolic forms. It is found that nitrogen doping significantly improves the CO{sub 2} adsorption capacity at all temperatures, due to the enrichment of local Lewis basic sites. In general, isotherm and thermodynamic parameters suggest that doped nitrogen sites have nearly same adsorption energy of surface defects and residual functional groups. The isosteric heat of adsorption remains in physisorption range, which falls with surface coverage, suggesting the distribution of magnitude of adsorption energy. The absolute values of isosteric heat and entropy of adsorption are slightly increased upon nitrogen doping.

  4. Adsorption of amylase enzyme on ultrafiltration membranes.

    PubMed

    Beier, Søren Prip; Enevoldsen, Ann Dorrit; Kontogeorgis, Georgios M; Hansen, Ernst B; Jonsson, Gunnar

    2007-08-28

    A method to measure the static adsorption on membrane surfaces has been developed and described. The static adsorption of amylase-F has been measured on two different ultrafiltration membranes, both with a cutoff value of 10 kDa (a PES membrane and the ETNA10PP membrane, which is a surface-modified PVDF membrane). The adsorption follows the Langmuir adsorption theory. Thus, the static adsorption consists of monolayer coverage and is expressed both as a permeability drop and an adsorption resistance. From the adsorption isotherms, the maximum static permeability drops and the maximum static adsorption resistances are determined. The maximum static permeability drop for the hydrophobic PES membrane is 75%, and the maximum static adsorption resistance is 0.014 m2.h.bar/L. The maximum static permeability drop for the hydrophilic surface-modified PVDF membrane (ETNA10PP) is 23%, and the maximum static adsorption resistance is 0.0046 m2.h.bar/L. The difference in maximum static adsorption, by a factor of around 3, affects the performance during the filtration of a 5 g/L amylase-F solution at 2 bar. The two membranes behave very similarly during filtration with almost equal fluxes and retentions even though the initial water permeability of the PES membrane is around 3 times larger than the initial water permeability of the ETNA10PP membrane. This is mainly attributed to the larger maximum static adsorption of the PES membrane. The permeability drop during filtration exceeds the maximum static permeability drop, indicating that the buildup layer on the membranes during filtration exceeds monolayer coverage, which is also seen by the increase in fouling resistance during filtration. The accumulated layer on the membrane surface can be described as a continually increasing cake-layer thickness, which is independent of the membrane type. At higher concentrations of enzyme, concentration polarization effects cannot be neglected. Therefore, stagnant film theory and the osmotic

  5. Apparatus for the study of macromolecular adsorption

    NASA Astrophysics Data System (ADS)

    Mayo, C. S.; Hallock, R. B.

    1989-04-01

    A surface plasmon adsorbate monitor (SPAM) is described which allows the adsorption of macromolecules or other adsorbates to a metal surface to be monitored. Surface plasmons are employed and the apparatus has no moving parts. The kinetics of adsorption may be studied on a time scale of seconds rather than the more common time scale of minutes; a simple improvement in computer memory access should allow temporal studies in the millisecond range. As an illustration, the adsorption of carboxyl-terminated polystyrene from a solution with acetone onto a silver surface is measured.

  6. Adsorption of lead over graphite oxide.

    PubMed

    Olanipekun, Opeyemi; Oyefusi, Adebola; Neelgund, Gururaj M; Oki, Aderemi

    2014-01-24

    The adsorption efficiency and kinetics of removal of lead in presence of graphite oxide (GO) was determined using the Atomic Absorption Spectrophotometer (AAS). The GO was prepared by the chemical oxidation of graphite and characterized using FTIR, SEM, TGA and XRD. The adsorption efficiency of GO for the solution containing 50, 100 and 150 ppm of Pb(2+) was found to be 98%, 91% and 71% respectively. The adsorption ability of GO was found to be higher than graphite. Therefore, the oxidation of activated carbon in removal of heavy metals may be a viable option to reduce pollution in portable water.

  7. Random sequential adsorption on imprecise lattice

    NASA Astrophysics Data System (ADS)

    Privman, Vladimir; Yan, Han

    2016-06-01

    We report a surprising result, established by numerical simulations and analytical arguments for a one-dimensional lattice model of random sequential adsorption, that even an arbitrarily small imprecision in the lattice-site localization changes the convergence to jamming from fast, exponential, to slow, power-law, with, for some parameter values, a discontinuous jump in the jamming coverage value. This finding has implications for irreversible deposition on patterned substrates with pre-made landing sites for particle attachment. We also consider a general problem of the particle (depositing object) size not an exact multiple of the lattice spacing, and the lattice sites themselves imprecise, broadened into allowed-deposition intervals. Regions of exponential vs. power-law convergence to jamming are identified, and certain conclusions regarding the jamming coverage are argued for analytically and confirmed numerically.

  8. Beyond carbon nanotubes: adsorptions on and electronic structures of silicon nanotubes.

    PubMed

    Chen, Haoliang; Ray, Asok K

    2014-02-01

    In this paper, we have reviewed some of the recent theoretical studies on the electronic and structural properties of silicon nanotubes from single-walled to double-walled nanostructures, primarily focusing on the studies performed by the present authors. The studies so far have not indicated any metallic behavior in both single-walled and double-walled silicon nanotubes. Atomic and molecular adsorptions of elements including hydrogen, oxygen and alkali metals on single-walled silicon nanotubes are also reviewed and new results presented in detail. A systematic study of molecular adsorption and co-adsorptions of hydrogen and oxygen molecules in zigzag silicon nanotube (SiNT) has been performed using hybrid density functional theory. For adsorption of two hydrogen molecules in SiNT (10, 0), the original diatomic molecular structure was maintained after adsorption. The most preferred final site for hydrogen molecules is the on-top site. For adsorption of two oxygen molecules, the most preferred sites are bridge sites, which are the parallel or zigzag bridge sites. Complete dissociation, partial dissociation and non-dissociation were observed for adsorption of two oxygen molecules. Peroxide structure and Si-O-O structures have also been observed in adsorption of two oxygen molecules with smaller adsorption energies rather than complete dissociation. For the co-adsorption of one hydrogen molecule and one oxygen molecule, the hydrogen molecule is slightly polarized, and a suppression effect on HOMO-LUMO gap was observed.

  9. Adsorption of Benzoic Compounds onto Stainless Steel Particles

    PubMed

    Suzuki; Shibata; Inoue

    1997-09-15

    Equilibrium experiment was conducted to investigate the factors determining the adsorption of benzoic acid (BA) and its derivatives, m- and p-hydroxy BA, onto SUS316L stainless steel particles of 8-10 &mgr;m diameter and under 100 mesh. Adsorption isotherms of these benzoic compounds were determined in the presence of 0.05 M NaCl at pH 4 and 30°C. The adsorptions of the these compounds were described well by a Langmuirian model for both adsorbents. When the maximum number of the benzoic compound adsorption sites was expressed on the basis of unit surface area (N, mol/m2), the N values were relatively constant, while the greatest value of the affinity (K, ml/&mgr;mol) was obtained for p-hydroxy BA, although its value was in the same range as that of the other two adsorbates. Diffuse-reflectance Fourier transform infrared spectra of the fine adsorbent (8-10 &mgr;m diameter) after equilibration suggest that the adsorption mainly takes place through the carboxyl group of the adsorbate-stainless steel surface interaction for all adsorbates, whereas concomitant interaction occurs in part with participation of the phenolic hydroxyl group for p-OH BA adsorbate, accounting for the difference in adsorption properties. Copyright 1997 Academic Press. Copyright 1997Academic Press

  10. Adsorption onto fluidized powdered activated carbon flocs-pACF.

    PubMed

    Serpa, Ana Lídia; Schneider, Ivo André H; Rubio, Jorge

    2005-02-01

    This work presents a new adsorption technique where the adsorbent (powdered activated carbon-PAC) is in the form of suspended flocs formed with water-soluble polymer flocculants. Thus, the adsorption of a typical dye, methylene blue (MB), was studied onto polyacrylamide flocs of PAC (PACF) in a fluidized bed reactor. The technique is based on the fact that the adsorption capacity of PAC does not decrease after flocculation because the adsorbed polymer occupies only a few surface sites, in the form of trains, loops, and tails. Moreover, the adsorption was found to proceed through a rapid mass transfer of MB to the adsorbing PAC flocs, in the same extent as onto PAC. Because of the rapid settling characteristics of the aggregates formed, the two phase separations, loaded PAC and solution, become easier. Thus, the technique offers the advantages of conducting simultaneously both adsorption and solid/liquid separation all in one single stage. Results obtained showed that high MB removal values can be attained in a fluidized bed reactor (>90%) and that PACF presents a much higher adsorption capacity (breakthrough points) than granulated activated carbon (GAC) in the same adsorbing bed. It is believed that this technique highly broadens the potential of the use of powdered activated carbon or other similar ultrafine adsorbents.

  11. CO2 adsorption on chemically modified activated carbon.

    PubMed

    Caglayan, Burcu Selen; Aksoylu, A Erhan

    2013-05-15

    CO2 adsorption capacity of a commercial activated carbon was improved by using HNO3 oxidation, air oxidation, alkali impregnation and heat treatment under helium gas atmosphere. The surface functional groups produced were investigated by diffuse reflectance infrared Fourier transform spectrometer (DRIFTS). CO2 adsorption capacities of the samples were determined by gravimetric analyses for 25-200°C temperature range. DRIFTS studies revealed the formation of carboxylic acid groups on the HNO3 oxidized adsorbents. Increased aromatization and uniform distribution of the Na particles were observed on the samples prepared by Na2CO3 impregnation onto HNO3 oxidized AC support. The adsorption capacities of the nonimpregnated samples were increased by high temperature helium treatments or by increasing the adsorption temperature; both leading to decomposition of surface oxygen groups, forming sites that can easily adsorb CO2. The adsorption capacity loss due to cyclic adsorption/desorption procedures was overcome with further surface stabilization of Na2CO3 modified samples with high temperature He treatments. With Na2CO3 impregnation the mass uptakes of the adsorbents at 20 bars and 25 °C were improved by 8 and 7 folds and at 1 bar were increased 15 and 16 folds, on the average, compared to their air oxidized and nitric acid oxidized supports, respectively.

  12. Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test

    SciTech Connect

    Nam, Sangchul; Namkoong, Wan; Kang, Jeong-Hee; Park, Jin-Kyu; Lee, Namhoon

    2013-10-15

    Highlights: • Equilibrium test was attempted to evaluate adsorption characteristics of siloxane. • L2 had higher removal efficiency in carbon compared to noncarbon adsorbents. • Total adsorption capacity of siloxane was 300 mg/g by coal activated carbon. • Adsorption characteristics rely on size of siloxane molecule and adsorbent pore. • Conversion of siloxane was caused by adsorption of noncarbon adsorbents. - Abstract: Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane.

  13. Macromolecule simulation and CH4 adsorption mechanism of coal vitrinite

    NASA Astrophysics Data System (ADS)

    Yu, Song; Yan-ming, Zhu; Wu, Li

    2017-02-01

    The microscopic mechanism of interactions between CH4 and coal macromolecules is of significant practical and theoretical importance in CBM development and methane storage. Under periodic boundary conditions, the optimal energy configuration of coal vitrinite, which has a higher torsion degree and tighter arrangement, can be determined by the calculation of molecular mechanics (MM) and molecular dynamics (MD), and annealing kinetics simulation based on ultimate analysis, 13C NMR, FT IR and HRTEM. Macromolecular stabilization is primarily due to the van der Waals energy and covalent bond energy, mainly consisting of bond torsion energy and bond angle energy. Using the optimal configuration as the adsorbent, GCMC simulation of vitrinite adsorption of CH4 is conducted. A saturated state is reached after absorbing 17 CH4s per coal vitrinite molecule. CH4 is preferentially adsorbed on the edge, and inclined to gathering around the branched chains of the inner vitrinite sites. Finally, the adsorption parameters are calculated through first principle DFT. The adsorbability order is as follows: aromatic structure> heteroatom rings > oxygen functional groups. The adsorption energy order is as follows: Top < Bond < Center, Up < Down. The order of average RDF better reflects the adsorption ability and that of [-COOH] is lower than those of [sbnd Cdbnd O] and [Csbnd Osbnd C]. CH4 distributed in the distance of 0.99-16 Å to functional groups in the type of monolayer adsorption and the average distance order manifest as [sbnd Cdbnd O] (1.64 Å) < [Csbnd Osbnd C] (1.89 Å) < [sbnd COOH] (3.78 Å) < [-CH3] (4.11 Å) according to the average RDF curves. CH4 enriches around [sbnd Cdbnd O] and [Csbnd O-C] whereas is rather dispersed about [-COOH] and [CH3]. Simulation and experiment data are both in strong agreement with the Langmuir and D-A isothermal adsorption model and the D-A model fit better than Langmuir model. Preferential adsorption sites and orientations in vitrinite are

  14. Adsorptive denitrogenation of model fuels with porous metal-organic framework (MOF) MIL-101 impregnated with phosphotungstic acid: effect of acid site inclusion.

    PubMed

    Ahmed, Imteaz; Khan, Nazmul Abedin; Hasan, Zubair; Jhung, Sung Hwa

    2013-04-15

    A metal-organic framework (MOF) MIL-101 was impregnated with phosphotungstic acid (PWA) and used as an adsorbent in liquid phase adsorption of nitrogen-containing compounds (NCCs) from a model fuel. The model fuel contained one sulfur-containing compound (SCC), benzothiophene (BT); one basic NCC, quinoline (QUI); and one neutral NCC, indole (IND). In both MIL-101 and PWA-impregnated MIL-101s, NCC adsorption selectivity was very high compared to the SCC selectivity. Additionally, the adsorption capacity of basic QUI increased by 20% with only 1% PWA impregnation in MIL-101. The adsorption of a neutral compound, IND, was slightly reduced with PWA impregnation in the MOF. The adsorption capacity/selectivity can be remarkably improved by a slight modification of MOFs, for example, to impart acidity. The MOF impregnated with PWA may be very interesting in commercial denitrogenation, especially for coal-derived fuels which contain mainly basic NCCs, by adsorption since the selectivity for NCCs (compared to SCCs) over the adsorbent is very high and the adsorbent can be reused many times.

  15. Study of the adsorption of aromatic hydrocarbons by marine sediments. Final report

    SciTech Connect

    Henrichs, S.M.; Luoma, M.; Smith, S.

    1997-08-01

    Three aromatic hydrocarbons--benzene, naphthalene, and phenanthrene--were rapidly and strongly adsorbed by intertidal sediments from Jakolof Bay, lower Cook Inlet. Adsorption of phenanthrene was more than twice that of naphthalene and benzene. Adsorption was not completely, rapidly reversible by suspension of the sediment in clean seawater. Longer adsorption reaction times led to decreased desorption, except for benzene. All sites for adsorption on the sediment surface appeared to be equivalent, and availability of adsorption sites did not limit adsorption over the concentration range studied. Adsorption coefficients for phenanthrene varied among sediment samples by as much as a factor of 3. This variability was not correlated with sediment organic carbon content, indicating that organic matter was not solely responsible for the adsorption properties of these sediments. The bioavailability of phenanthrene was decreased by adsorption to sediment. Combined with the finding that adsorption is not completely reversible, these results indicate that adsorption could contribute to the persistence of aromatic hydrocarbons in lower Cook Inlet sediments.

  16. Adsorption Isotherms and Surface Reaction Kinetics

    ERIC Educational Resources Information Center

    Lobo, L. S.; Bernardo, C. A.

    1974-01-01

    Explains an error that occurs in calculating the conditions for a maximum value of a rate expression for a bimolecular reaction. The rate expression is derived using the Langmuir adsorption isotherm to relate gas pressures and corresponding surface coverages. (GS)

  17. Capillary condensation and adsorption of binary mixtures.

    PubMed

    Weinberger, B; Darkrim-Lamari, F; Levesque, D

    2006-06-21

    The adsorption of equimolar binary mixtures of hydrogen-carbon dioxide, hydrogen-methane, and methane-carbon dioxide in porous material models is determined by grand canonical Monte Carlo simulations. The material models have an adsorbent surface similar to that of nanofibers with a herringbone structure. Our main result, which is relevant for hydrogen purification and carbon dioxide capture, is that the adsorption selectivities calculated for the mixtures can differ significantly from those deduced from simulations of the adsorption of pure gases, in particular, when one of the adsorbed gases presents a capillary condensation induced by confinement within the pore network. A comparison of our data is also made with theoretical models used in the literature for predicting the properties of the mixture adsorption.

  18. Fluorocarbon Adsorption in Hierarchical Porous Frameworks

    SciTech Connect

    Motkuri, Radha K.; Annapureddy, Harsha V.; Vijayakumar, M.; Schaef, Herbert T.; Martin, P F.; McGrail, B. Peter; Dang, Liem X.; Krishna, Rajamani; Thallapally, Praveen K.

    2014-07-09

    The adsorption behavior of a series of fluorocarbon derivatives was examined on a set of microporous metal organic framework (MOF) sorbents and another set of hierarchical mesoporous MOFs. The microporous M-DOBDC (M = Ni, Co) showed a saturation uptake capacity for R12 of over 4 mmol/g at a very low relative saturation pressure (P/Po) of 0.02. In contrast, the mesoporous MOF MIL-101 showed an exceptionally high uptake capacity reaching over 14 mmol/g at P/Po of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption were found to generally correlate with the polarizability of the refrigerant with R12 > R22 > R13 > R14 > methane. These results suggest the possibility of exploiting MOFs for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling and refrigeration applications.

  19. Adsorption of nisin and pediocin on nanoclays.

    PubMed

    Meira, Stela Maris Meister; Jardim, Arthur Izé; Brandelli, Adriano

    2015-12-01

    Three different nanoclays (bentonite, octadecylamine-modified montmorillonite and halloysite) were studied as potential carriers for the antimicrobial peptides nisin and pediocin. Adsorption occurred from peptide solutions in contact with nanoclays at room temperature. Higher adsorption of nisin and pediocin was obtained on bentonite. The antimicrobial activity of the resultant bacteriocin-nanoclay systems was analyzed using skimmed milk agar as food simulant and the largest inhibition zones were observed against Gram-positive bacteria for halloysite samples. Bacteriocins were intercalated into the interlayer space of montmorillonites as deduced from the increase of the basal spacing measured by X-ray diffraction (XRD) assay. Infrared spectroscopy suggested non-electrostatic interactions, such as hydrogen bonding between siloxane groups from clays and peptide molecules. Transmission electron microscopy did not show any alteration in morphologies after adsorption of antimicrobial peptides on bentonite and halloysite. These results indicate that nanoclays, especially halloysite, are suitable nanocarriers for nisin and pediocin adsorption.

  20. Ionic Adsorption and Desorption of CNT Nanoropes

    PubMed Central

    Shang, Jun-Jun; Yang, Qing-Sheng; Yan, Xiao-Hui; He, Xiao-Qiao; Liew, Kim-Meow

    2016-01-01

    A nanorope is comprised of several carbon nanotubes (CNTs) with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment. PMID:28335306

  1. H2O Adsorption Kinetics on Smectites

    NASA Technical Reports Server (NTRS)

    Zent, Aaron P.; Howard, J.; Quinn, R. C.

    2000-01-01

    The adsorptive equilibration of H2O with montomorillonite has been measured. At low temperatures and pressures equilibration can require many hours, effectively preventing smectites at the martian surface from responding to diurnal pressure and temperature variations.

  2. Argon adsorption and the lunar atmosphere

    NASA Technical Reports Server (NTRS)

    Bernatowicz, T. J.; Podosek, F. A.

    1991-01-01

    The results of Ar adsorption experiments on a terrestrial labradorite and lunar rock 15415 crushed in vacuo are reported. The experiments were designed to test lunar atmosphere simulation models for the behavior of Ar on the lunar surface, as determined from the Apollo 17 mass spectrometer results. These models (Hodges, 1980, 1982) used a single adsorption potential to characterize the surfaces of lunar soil grains, with the result that high (6-7 kcal/mol) heats of adsorption were inferred. The present experimental results show that very high adsorption potentials are indeed associated with fresh mineral surfaces, but that these energetic surfaces occupy only small fractions of the total surface area. Nonetheless, these small fractions of surface, if they can be maintained in the lunar regolith in steady-state condition, could be sufficient to account for the Apollo 17 mass spectrometer observations.

  3. Krypton based adsorption type cryogenic refrigerator

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor); Schember, Helene R. (Inventor)

    1989-01-01

    Krypton and a monolithic porous carbon such as Saran carbon are used respectively as the sorbate and sorbent of an adsorption type refrigerator to improve refrigeration efficiency and operational longevity.

  4. Model carcinogen adsorption dynamics of DNA gel.

    PubMed

    Tomita, Naoko; Naito, Daisuke; Rokugawa, Isamu; Yamamoto, Takao; Dobashi, Toshiaki

    2014-09-01

    We have derived theoretical equations describing the adsorption of carcinogen to gels in an immersion medium containing carcinogens. The theory was developed for a cylindrical boundary condition under the assumption of a carcinogen diffusion-limited process combined with the "moving boundary picture (Furusawa et al., 2007)". The time course of the adsorbed carcinogen layer thickness and that of the carcinogen concentration in an immersion medium were expressed by a set of scaled variables, and the asymptotic behavior in the initial stage was derived. Experiments based on the theory were performed using a DNA gel sandwiched between a set of coverglasses in a medium containing acridine orange (AO). The boundary between the AO-adsorbed gel layer and AO-nonadsorbed gel layer was traced during the immersion. The time courses of the AO-adsorbed gel layer thickness and the AO concentration in the immersion medium were well explained by the theory, and the number ratio of the total AO molecules to the adsorption sites in the DNA gel was determined.

  5. Defluoridation of drinking water using adsorption processes.

    PubMed

    Loganathan, Paripurnanda; Vigneswaran, Saravanamuthu; Kandasamy, Jaya; Naidu, Ravi

    2013-03-15

    Excessive intake of fluoride (F), mainly through drinking water, is a serious health hazard affecting humans worldwide. There are several methods used for the defluoridation of drinking water, of which adsorption processes are generally considered attractive because of their effectiveness, convenience, ease of operation, simplicity of design, and for economic and environmental reasons. In this paper, we present a comprehensive and a critical literature review on various adsorbents used for defluoridation, their relative effectiveness, mechanisms and thermodynamics of adsorption, and suggestions are made on choice of adsorbents for various circumstances. Effects of pH, temperature, kinetics and co-existing anions on F adsorption are also reviewed. Because the adsorption is very weak in extremely low or high pHs, depending on the adsorbent, acids or alkalis are used to desorb F and regenerate the adsorbents. However, adsorption capacity generally decreases with repeated use of the regenerated adsorbent. Future research needs to explore highly efficient, low cost adsorbents that can be easily regenerated for reuse over several cycles of operations without significant loss of adsorptive capacity and which have good hydraulic conductivity to prevent filter clogging during the fixed-bed treatment process.

  6. Gibbs adsorption and the compressibility equation

    SciTech Connect

    Aranovich, G.L.; Donohue, M.D.

    1995-08-08

    A new approach for deriving the equation of state is developed. It is shown that the integral in the compressibility equation is identical to the isotherm for Gibbs adsorption in radial coordinates. The Henry, Langmuir, and Frumkin adsorption isotherms are converted into equations of state. It is shown that using Henry`s law gives an expression for the second virial coefficient that is identical to the result from statistical mechanics. Using the Langmuir isotherm leads to a new analytic expression for the hard-sphere equation of state which can be explicit in either pressure or density. The Frumkin isotherm results in a new equation of state for the square-well potential fluid. Conversely, new adsorption isotherms can be derived from equations of state using the compressibility equation. It is shown that the van der Waals equation gives an adsorption isotherm equation that describes both polymolecular adsorption and the unusual adsorption behavior observed for supercritical fluids. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  7. Differential Heat of Adsorption and Isosteres.

    PubMed

    Tian, Yun; Wu, Jianzhong

    2017-01-31

    Heat of adsorption is a basic thermodynamic property extensively used not only for understanding thermal effects and heat management in industrial gas storage and separation processes but also for development and validation of adsorption models and materials force fields. Despite a long history of theoretical studies and a vast experimental literature, controversies often arise in the thermodynamic analysis of heat effects due to various assumptions used to describe gas adsorption and inconsistencies between direct calorimetric measurements and isosteric heat obtained from various adsorption isotherms. Here we present a rigorous theoretical procedure for predicting isosteric heat without any assumption about the geometry of porous adsorbents or operating conditions. Quantitative relations between the differential heat and various isosteres have been established with the grand-canonical Monte Carlo simulation for gas adsorption in amorphous as well as crystalline porous materials. The inconsistencies and practical issues with conventional methods for the analysis of the heat effect have been clarified in the context of the exact results for model systems. Via the resolution of a number of controversies about heat analysis, we hope that the new theoretical procedure will be adopted for both fundamental research and industrial applications of gas adsorption processes.

  8. Gas adsorption capacity of wood pellets

    DOE PAGES

    Yazdanpanah, F.; Sokhansanj, Shahabaddine; Lim, C. Jim; ...

    2016-02-03

    In this paper, temperature-programmed desorption (TPD) analysis was used to measure and analyze the adsorption of off-gases and oxygen by wood pellets during storage. Such information on how these gases interact with the material helps in the understanding of the purging/stripping behavior of off-gases to develop effective ventilation strategies for wood pellets. Steam-exploded pellets showed the lowest carbon dioxide (CO2) uptake compared to the regular and torrefied pellets. The high CO2 adsorption capacity of the torrefied pellets could be attributed to their porous structure and therefore greater available surface area. Quantifying the uptake of carbon monoxide by pellets was challengingmore » due to chemical adsorption, which formed a strong bond between the material and carbon monoxide. The estimated energy of desorption for CO (97.8 kJ/mol) was very high relative to that for CO2 (7.24 kJ/mol), demonstrating the mechanism of chemical adsorption and physical adsorption for CO and CO2, respectively. As for oxygen, the strong bonds that formed between the material and oxygen verified the existence of chemical adsorption and formation of an intermediate material.« less

  9. Gas adsorption capacity of wood pellets

    SciTech Connect

    Yazdanpanah, F.; Sokhansanj, Shahabaddine; Lim, C. Jim; Lau, A.; Bi, X. T.

    2016-02-03

    In this paper, temperature-programmed desorption (TPD) analysis was used to measure and analyze the adsorption of off-gases and oxygen by wood pellets during storage. Such information on how these gases interact with the material helps in the understanding of the purging/stripping behavior of off-gases to develop effective ventilation strategies for wood pellets. Steam-exploded pellets showed the lowest carbon dioxide (CO2) uptake compared to the regular and torrefied pellets. The high CO2 adsorption capacity of the torrefied pellets could be attributed to their porous structure and therefore greater available surface area. Quantifying the uptake of carbon monoxide by pellets was challenging due to chemical adsorption, which formed a strong bond between the material and carbon monoxide. The estimated energy of desorption for CO (97.8 kJ/mol) was very high relative to that for CO2 (7.24 kJ/mol), demonstrating the mechanism of chemical adsorption and physical adsorption for CO and CO2, respectively. As for oxygen, the strong bonds that formed between the material and oxygen verified the existence of chemical adsorption and formation of an intermediate material.

  10. Carbon dioxide adsorption in graphene sheets

    NASA Astrophysics Data System (ADS)

    Mishra, Ashish Kumar; Ramaprabhu, Sundara

    2011-09-01

    Control over the CO2 emission via automobiles and industrial exhaust in atmosphere, is one of the major concerns to render environmental friendly milieu. Adsorption can be considered to be one of the more promising methods, offering potential energy savings compared to absorbent systems. Different carbon nanostructures (activated carbon and carbon nanotubes) have attracted attention as CO2 adsorbents due to their unique surface morphology. In the present work, we have demonstrated the CO2 adsorption capacity of graphene, prepared via hydrogen induced exfoliation of graphitic oxide at moderate temperatures. The CO2 adsorption study was performed using high pressure Sieverts apparatus and capacity was calculated by gas equation using van der Waals corrections. Physical adsorption of CO2 molecules in graphene was confirmed by FTIR study. Synthesis of graphene sheets via hydrogen exfoliation is possible at large scale and lower cost and higher adsorption capacity of as prepared graphene compared to other carbon nanostructures suggests its possible use as CO2 adsorbent for industrial application. Maximum adsorption capacity of 21.6 mmole/g was observed at 11 bar pressure and room temperature (25 °C).

  11. Adsorption of lanthanum to goethite in the presence of gluconate

    SciTech Connect

    Hull, Laurence C.; Sarah Pepper; Sue Clark

    2005-05-01

    Adsorption of Lanthanum to Goethite in the Presence of Gluconic Acid L. C. HULL,1 S. E. PEPPER2 AND S. B. CLARK2 1Idaho National Engineering and Environmental Laboratory, Idaho Falls, ID (hulllc@inel.gov) 2Washington State University, Pullman, WA (spepper@wsu.edu), (s_clark@wsu.edu) Lanthanide and trivalent-actinide elements in radioactive waste can pose risks to humans and ecological systems for many years. Organic complexing agents, from natural organic matter or the degradation of waste package components, can alter the mobility of these elements. We studied the effect of gluconic acid, as an analogue for cellulose degradation products, on the adsorption of lanthanum, representing lanthanide and trivalent-actinide elments, to goethite, representing natural iron minearals and degradation products of waste packages. Batch pH adsorption edge experiments were conducted with lanthanum alone, and with lanthanum and gluconate at a 1:1 mole ratio. Lanthanum concentrations studied were 0.1, 1, and 10 mM, covering a range from 10% to 1000% of the calculated available adsorption sites on goethite. In the absence of gluconate, lanthanum was primarily present in solution as free lanthanum ion. With gluconate present, free lanthanum concentration in solution decreased with increasing pH as step-wise deprotonation of the gluconate molecule increased the fraction lanthanum complexed with gluconate. Adsorption to the goethite surface was represented with the diffuse double-layer model. The number of adsorption sites and the intrinsic binding constants for the surface complexes were estimated from the pH adsorption edge data using the computer code FITEQL 4.0. Two surface reactions were used to fit the adsorption data in the absence of gluconate. A strong binding site with no proton release and a much higher concentration of weak binding sites with release of two protons per lanthanum adsorbed. The adsorption of lanthanum was not measurably affected by the presence of gluconate

  12. Bidentate surface structures of glycylglycine on Si(111)7×7 by high-resolution scanning tunneling microscopy: site-specific adsorption via N-H and O-H or double N-H dissociation.

    PubMed

    Chatterjee, A; Zhang, L; Leung, K T

    2012-08-28

    The early adsorption stage of glycylglycine on Si(111)7×7 surface has been studied by scanning tunneling microscopy (STM). Filled-state imaging shows that glycylglycine adsorbs dissociatively in a bidentate fashion on two adjacent Si adatoms across a dimer wall or an adatom-restatom pair, with the dissociated H atoms on neighboring restatoms. The present STM result validates our hypothesis that both bidentate configurations involving N-H and O-H dissociation and double N-H dissociation are equally probable. Our STM results further show that the relative surface concentrations of the five bidentate configurations follow a specific ordering. This suggests that N-H dissociation at a center adatom site would likely be followed by N-H dissociation at an adjacent restatom, while N-H dissociation at a corner adatom site would be succeeded by O-H dissociation at an adatom across the dimer wall. Evidently, the strong bidentate interactions also inhibit surface diffusion of the adsorbed glycylglycine fragment, and the adsorption apparently follows random sequential adsorption statistics. The random nature of adsorption is also supported by the similar relative occupancies of the center adatom and corner adatom sites, indicating that the relative reactivities of these adatom sites do not play a significant role. Our DFT computational study shows that all three bidentate (Si-)NHCH(2)CONHCH(2)COO(-Si) adatom-adatom configurations (center-center, corner-corner, center-corner) have similar adsorption energies for a double adatom-adatom pair across the dimer wall, while the (Si-)NHCH(2)CON(-Si)CH(2)COOH bidentate adatom-restatom configuration is energetically favorable. The free -CONH- and -COOH groups remaining on the respective bidentate adstructures could facilitate adsorption of the second adlayer through the formation of hydrogen bonding.

  13. Contrasting nitrate adsorption in Andisols of two coffee plantations in Costa Rica.

    PubMed

    Ryan, M C; Graham, G R; Rudolph, D L

    2001-01-01

    Fertilizer use in coffee plantations is a suspected cause of rising ground water nitrate concentrations in the ground water-dependent Central Valley of Costa Rica. Nitrate adsorption was evaluated beneath two coffee (Coffea arabica L.) plantations in the Central Valley. Previous work at one site had identified unsaturated zone nitrate retardation relative to a tritium tracer. Differences in nitrate adsorption were assessed in cores to 4 m depth in Andisols at this and one other plantation using differences in KCl- and water-extractable nitrate as an index. Significant adsorption was confirmed at the site of the previous tracer test, but not at the second site. Anion exchange capacity, X-ray diffraction data, extractable Al and Si, and soil pH in NaF corroborated that differences in adsorption characteristics were related to subtle differences in clay mineralogy. Soils at the site with significant nitrate adsorption showed an Al-rich allophane clay content compared with a more weathered, Si-rich allophane and halloysite clay mineral content at the site with negligible adsorption. At the site with significant nitrate adsorption, nitrate occupied less than 10% of the total anion adsorption capacity, suggesting that adsorption may provide long-term potential for mitigation or delay of nitrate leaching. Evaluation of nitrate sorption potential of soil at local and landscape scales would be useful in development of nitrogen management practices to reduce nitrate leaching to ground water.

  14. Atomic and molecular adsorption on Au(111)

    SciTech Connect

    Santiago-Rodríguez, Yohaselly; Herron, Jeffrey A.; Curet-Arana, María C.; Mavrikakis, Manos

    2014-09-01

    Periodic self-consistent density functional theory (DFT-GGA) calculations were used to study the adsorption of several atomic species, molecular species and molecular fragments on the Au(111) surface with a coverage of 1/4 monolayer (ML). Binding geometries, binding energies, and diffusion barriers were calculated for 27 species. Furthermore, we calculated the surface deformation energy associated with the binding events. The binding strength for all the analyzed species can be ordered as follows: NH3 < NO < CO < CH3 < HCO < NH2 < COOH < OH < HCOO < CNH2 < H < N < NH < NOH < COH < Cl,< HCO3 < CH2 < CN b HNO < O < F < S < C < CH. Although the atomic species preferred to bind at the three-fold fcc site, no tendency was observed in site preference for the molecular species and fragments. The intramolecular and adsorbate-surface vibrational frequencies were calculated for all the adsorbates on their most energetically stable adsorption site. Most of the theoretical binding energies and frequencies agreed with experimental values reported in the literature. In general, the values obtained with the PW91 functional are more accurate than RPBE in reproducing these experimental binding energies. The energies of the adsorbed species were used to calculate the thermochemical potential energy surfaces for decomposition of CO, NO, N2, NH3 and CH4, oxidation of CO, and hydrogenation of CO, CO2 and NO, giving insight into the thermochemistry of these reactions on gold nanoparticles. These potential energy surfaces demonstrated that: the decomposition of species is not energetically favorable on Au(111); the desorption of NH3, NO and CO are more favorable than their decomposition; the oxidation of CO and hydrogenation of CO and NO on Au(111) to form HCO and HNO, respectively, are also thermodynamically favorable.

  15. Heavy metal adsorption changes of EAF steel slag after phosphorus adsorption.

    PubMed

    Song, Guanling; Cao, Lijing; Chen, Xiao; Hou, Wenhua; Wang, Qunhui

    2012-01-01

    A kind of electric arc furnace (EAF) steel slag was phosphated, and its isothermal and dynamic adsorptions of copper, cadmium, and lead ions were measured to determine if heavy metal adsorption changes after phosphorus adsorption. The surface area increased greatly after the slag was phosphated. Isothermal adsorption experiments showed that the theoretical Q(max) of the EAF steel slag on Cu(2+), Cd(2+), and Pb(2+) improved 59, 50, and 89% respectively after it was phosphated. Dynamic adsorption results showed that the greatest adsorption capacities of unit volume of Cu(2+), Cd(2+), and Pb(2+) were 2.2, 1.8, and 1.8 times that of the column packed with original EAF steel slag when the column was packed with phosphate EAF steel slag at the same heavy metal ion concentration. The breakthrough time, the exhaustion time and elution efficiency of the column also increased when the column was packed with phosphated EAF steel slag compared with that packed with original EAF steel slag. Phosphorus adsorption could further improve the heavy metal ion adsorption of the EAF steel slag.

  16. Modeling adsorption: Investigating adsorbate and adsorbent properties

    NASA Astrophysics Data System (ADS)

    Webster, Charles Edwin

    1999-12-01

    Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas

  17. Poliovirus Adsorption by 34 Minerals and Soils

    PubMed Central

    Moore, Rebecca S.; Taylor, Dene H.; Sturman, Lawrence S.; Reddy, Michael M.; Fuhs, G. Wolfgang

    1981-01-01

    The adsorption of radiolabeled infectious poliovirus type 2 by 34 well-defined soils and mineral substrates was analyzed in a synthetic freshwater medium containing 1 mM CaCl2 and 1.25 mM NaHCO3 at pH 7. In a model system, adsorption of poliovirus by Ottawa sand was rapid and reached equilibrium within 1 h at 4°C. Near saturation, the adsorption could be described by the Langmuir equation; the apparent surface saturation was 2.5 × 106 plaque-forming units of poliovirus per mg of Ottawa sand. At low surface coverage, adsorption was described by the Freundlich equation. The soils and minerals used ranged from acidic to basic and from high in organic content to organic free. The available negative surface charge on each substrate was measured by the adsorption of a cationic polyelectrolyte, polydiallyldimethylammonium chloride. Most of the substrates adsorbed more than 95% of the virus. In general, soils, in comparison with minerals, were weak adsorbents. Among the soils, muck and Genesee silt loam were the poorest adsorbents; among the minerals, montmorillonite, glauconite, and bituminous shale were the least effective. The most effective adsorbents were magnetite sand and hematite, which are predominantly oxides of iron. Correlation coefficients for substrate properties and virus adsorption revealed that the elemental composition of the adsorbents had little effect on poliovirus uptake. Substrate surface area and pH, by themselves, were not significantly correlated with poliovirus uptake. A strong negative correlation was found between poliovirus adsorption and both the contents of organic matter and the available negative surface charge on the substrates as determined by their capacities for adsorbing the cationic polyelectrolyte, polydiallyldimethylammonium chloride. PMID:6274259

  18. Toward Accurate Adsorption Energetics on Clay Surfaces

    PubMed Central

    2016-01-01

    Clay minerals are ubiquitous in nature, and the manner in which they interact with their surroundings has important industrial and environmental implications. Consequently, a molecular-level understanding of the adsorption of molecules on clay surfaces is crucial. In this regard computer simulations play an important role, yet the accuracy of widely used empirical force fields (FF) and density functional theory (DFT) exchange-correlation functionals is often unclear in adsorption systems dominated by weak interactions. Herein we present results from quantum Monte Carlo (QMC) for water and methanol adsorption on the prototypical clay kaolinite. To the best of our knowledge, this is the first time QMC has been used to investigate adsorption at a complex, natural surface such as a clay. As well as being valuable in their own right, the QMC benchmarks obtained provide reference data against which the performance of cheaper DFT methods can be tested. Indeed using various DFT exchange-correlation functionals yields a very broad range of adsorption energies, and it is unclear a priori which evaluation is better. QMC reveals that in the systems considered here it is essential to account for van der Waals (vdW) dispersion forces since this alters both the absolute and relative adsorption energies of water and methanol. We show, via FF simulations, that incorrect relative energies can lead to significant changes in the interfacial densities of water and methanol solutions at the kaolinite interface. Despite the clear improvements offered by the vdW-corrected and the vdW-inclusive functionals, absolute adsorption energies are often overestimated, suggesting that the treatment of vdW forces in DFT is not yet a solved problem. PMID:27917256

  19. A Study of Adsorptive Characteristics of Australian Coals

    NASA Astrophysics Data System (ADS)

    Lan, Y. P.; Tsai, L. L.

    2012-04-01

    Ever since the Kyoto Protocol, controlling carbon dioxide emission and reducing its content in atmosphere are very important environmental issues up to today. One of the effective methods for permanent sequestration of anthropogenic CO2 is to inject CO2 into deep, unminable coal seams and recover coal bed methane at the same time. CO2-ECBM technology had been proved to be very promising to meet the needs of both environment and energy. Beside other external environment factors, capacity of CO2 adsorption and CH4 desorption are the most influencing factors in selection of sites for the geological storage of CO2. Therefore, the objective of this study is to understand the relationship between gas adsorption and CO2 sequestration, by various experiments for the characterization of Australian of coals. Generally speaking, coal seam gas comprises mostly of CH4, CO2, C2H6, and N2. However, some of the Australian coals were reported with significant amount of CO2 up to 90%, which might strongly affect their capacity of CO2 capture and storage (CCS). High to medium volatile bituminous coals from Sydney Basin and Bowen Basin, southeast Australia were selected in this study. Experiments include maceral composition and vitrinite reflectance measurements, petrographic analysis, Proximate analysis, Ultimate analysis, specific surface area analysis as well as CO2 and CH4 adsorption experiments were performed. Parameters for difference adsorption functions (Langmuir, BET, D-R and D-A) were then calculated to fit their adsorption isotherms the best fitting curve can then be found. Among these adsorption functions, Langmuir is the most basic and commonly used function theory. The results of all experiments were synthesized to discuss the relations among each other, so as to establish the relationship between gas adsorption and coal characteristics.

  20. Computation of Adsorption Energies of Some Interstellar Species

    NASA Astrophysics Data System (ADS)

    Sil, Milan; Chakrabarti, Sandip Kumar; Das, Ankan; Majumdar, Liton; Gorai, Prasanta; Etim, Emmanuel; Arunan, Elangannan

    2016-07-01

    Adsorption energies of surface species are most crucial for chemical complexity of interstellar grain mantle. Aim of this work is to study the variation of the adsorption energies depending upon the nature of adsorbent. We use silicate and carbonaceous grains for the absorbents. For silicate grains, we use very simple crystalline ones, namely, Enstatite (MgSiO_3)_n, Ferrosilite (FeSiO_3)_n, Forsterite (Mg_2SiO_4)_n and Fayalite (Fe_2SiO_4)_n. We use n=1, 2, 4, 8 to study the variation of adsorption energies with the increase in cluster size. For carbonaceous grain, we use Coronene (polyaromatic hydrocarbon surface). Adsorption energy of all these species are calculated by means of quantum chemical calculation using self consistent density functional theory (DFT). MPWB1K hybrid meta-functional is employed since it has been proven useful to study the systems with weak interactions such as van der Waals interactions. Optimization are also carried out with MPWB1K/6-311g(d) and MPWB1K/6311g(d,p) and a comparison of adsorption energies are discussed for these two different basis sets. We use crystalline structure of the adsorbent. The adsorbate is placed in the different site of the grain with a suitable distance. The energy of adsorption for a species on the grain surface is defined as follows: E_a_d_s = E_s_s - (E_s_u_r_f_a_c_e + E_s_p_e_c_i_e_s), where E_a_d_s is the adsorption energy, E_s_s is the optimized energy for species placed in a suitable distance from the grain surface, E_s_u_r_f_a_c_e and E_s_p_e_c_i_e_s respectively are the optimized energies of the surface and species separately.

  1. Apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption

    DOEpatents

    Wegeng, Robert S.; Rassat, Scot D.; Stenkamp, Victoria S.; TeGrotenhuis, Ward E.; Matson, Dean W.; Drost, M. Kevin; Viswanathan, Vilayanur V.

    2005-12-13

    The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

  2. Method for thermal swing adsorption and thermally-enhanced pressure swing adsorption

    DOEpatents

    Wegeng, Robert S.; Rassat, Scot D.; Stenkamp, Victoria S.; TeGrotenhuis, Ward E.; Matson, Dean W.; Drost, M. Kevin; Viswanathan, Vilayanur V.

    2003-10-07

    The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

  3. Method and apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption

    DOEpatents

    Wegeng, Robert S.; Rassat, Scot D.; TeGrotenhuis, Ward E.; Drost, Kevin; Vishwanathan, Vilayanur V.

    2004-06-08

    The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. In another aspect, the apparatus or methods utilize heat exchange channels of varying lengths that have volumes controlled to provide equal heat fluxes. Methods of fuel cell startup are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

  4. H Adsorption on RH (110) Surface

    NASA Astrophysics Data System (ADS)

    Chen, Shao-Ping

    2006-03-01

    We have used the density functional theory to study the H adsorption phenomena on Rh (110) surface with H coverage from 0.33 to 2.00 mono-layers. We found H atom favors the three- fold coordinated site as observed experimentally. We confirmed the existence of 1x3-H, 1x2-H, 1x3-2H, 1x1-2H ordered structures. We also found that the proposed 1x2-2H structure for coverage of 1.0 is not the lowest energy configuration. We have proposed a new 1x2-2H structure which needs to be tested by future experiments.

  5. Conceptual adsorption models and open issues pertaining to performance assessment

    SciTech Connect

    Serne, R.J.

    1991-10-01

    Recently several articles have been published that question the appropriateness of the distribution coefficient, Rd, concept to quantify radionuclide migration. Several distinct issues are raised by various critics. In this paper I provide some perspective on issues surrounding the modeling of nuclide retardation. The first section defines adsorption terminology and discusses various adsorption processes. The next section describes five commonly used adsorption conceptual models, specifically emphasizing what attributes that affect adsorption are explicitly accommodated in each model. I also review efforts to incorporate each adsorption model into performance assessment transport computer codes. The five adsorption conceptual models are (1) the constant Rd model, (2) the parametric Rd model, (3) isotherm adsorption models, (4) mass-action adsorption models, and (5) surface-complexation with electrostatics models. The final section discusses the adequacy of the distribution ratio concept, the adequacy of transport calculations that rely on constant retardation factors and the status of incorporating sophisticated adsorption models into transport codes.

  6. Adsorption of phenolic compound by aged-refuse.

    PubMed

    Xiaoli, Chai; Youcai, Zhao

    2006-09-01

    The adsorption of phenol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol by aged-refuse has been studied. Adsorption isotherms have been determined for phenol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol and the data fits well to the Freundlich equation. The chlorinated phenols are absorbed more strongly than the phenol and the adsorption capacity has an oblivious relationship with the numbers and the position of chlorine subsistent. The experiment data suggests that both the partition function and the chemical adsorption involve in the adsorption process. Pseudo-first-order and pseudo-second-order model were applied to investigate the kinetics of the adsorption and the results show that it fit the pseudo-second-order model. More than one step involves in the adsorption process and the overall rate of the adsorption process appears to be controlled by the chemical reaction. The thermodynamic analysis indicates that the adsorption is spontaneous and endothermic.

  7. Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies

    SciTech Connect

    Srinivasan, Sriram Goverapet; Shivaramaiah, Radha; Kent, Paul R. C.; Stack, Andrew G.; Navrotsky, Alexandra; Riman, Richard; Anderko, Andre; Bryantsev, Vyacheslav S.

    2016-07-11

    Bastnasite is a fluoro-carbonate mineral that is the largest source of rare earth elements such as Y, La and Ce. With increasing demand for REE in many emerging technologies, there is an urgent need for improving the efficiency of ore beneficiation by froth flotation. In order to design improved flotation agents that can selectively bind to the mineral surface, a fundamental understanding of the bulk and surface properties of bastnasite is essential. Density functional theory calculations using the PBEsol exchange correlation functional and the DFT-D3 dispersion correction reveal that the most stable form of La bastnsite is isomorphic to the structure of Ce bastnasite belonging to the P2c space group, while the Inorganic Crystal Structure Database structure in the P2m space group is ca. 11.3 kJ/mol higher in energy per LaFCO3 formula unit. We report powder X-ray diffraction measurements on synthetic of La bastnasite to support these theoretical findings. Six different surfaces are studied by DFT, namely [100], [0001], [101], [102], [104] and [112]. Among these, the [100] surface is the most stable with a surface energy of 0.73 J/m2 in vacuum and 0.45 J/m2 in aqueous solution. We predicted the shape of a La bastnasite nanoparticle via thermodynamic Wulff construction to be a hexagonal prism with [100] and [0001] facets, chiseled at its ends by the [101] and [102] facets. The average surface energy of the nanoparticle in the gas phase is estimated to be 0.86 J/m2, in good agreement with a value of 1.11 J/m2 measured by calorimetry. The calculated adsorption energy of a water molecule varies widely with the surface plane and specific adsorption sites on a given surface. Moreover, the first layer of water molecules is predicted to adsorb strongly on the La-bastnasite surface, in agreement with water adsorption calorimetry experiments. Our work provides an important step towards a detailed atomistic understanding of

  8. Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies

    DOE PAGES

    Srinivasan, Sriram Goverapet; Shivaramaiah, Radha; Kent, Paul R. C.; ...

    2016-07-11

    Bastnasite is a fluoro-carbonate mineral that is the largest source of rare earth elements such as Y, La and Ce. With increasing demand for REE in many emerging technologies, there is an urgent need for improving the efficiency of ore beneficiation by froth flotation. In order to design improved flotation agents that can selectively bind to the mineral surface, a fundamental understanding of the bulk and surface properties of bastnasite is essential. Density functional theory calculations using the PBEsol exchange correlation functional and the DFT-D3 dispersion correction reveal that the most stable form of La bastnsite is isomorphic to themore » structure of Ce bastnasite belonging to the P2c space group, while the Inorganic Crystal Structure Database structure in the P2m space group is ca. 11.3 kJ/mol higher in energy per LaFCO3 formula unit. We report powder X-ray diffraction measurements on synthetic of La bastnasite to support these theoretical findings. Six different surfaces are studied by DFT, namely [100], [0001], [101], [102], [104] and [112]. Among these, the [100] surface is the most stable with a surface energy of 0.73 J/m2 in vacuum and 0.45 J/m2 in aqueous solution. We predicted the shape of a La bastnasite nanoparticle via thermodynamic Wulff construction to be a hexagonal prism with [100] and [0001] facets, chiseled at its ends by the [101] and [102] facets. The average surface energy of the nanoparticle in the gas phase is estimated to be 0.86 J/m2, in good agreement with a value of 1.11 J/m2 measured by calorimetry. The calculated adsorption energy of a water molecule varies widely with the surface plane and specific adsorption sites on a given surface. Moreover, the first layer of water molecules is predicted to adsorb strongly on the La-bastnasite surface, in agreement with water adsorption calorimetry experiments. Our work provides an important step towards a detailed atomistic understanding of the bastnasite water interface and designing

  9. Neptunium(V) adsorption to calcite.

    PubMed

    Heberling, Frank; Brendebach, Boris; Bosbach, Dirk

    2008-12-12

    The migration behavior of the actinyl ions U(VI)O2(2+), Np(V)O2+ and Pu(V,VI)O2(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO2+ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0-9.4) and concentration (0.4 microM-40 microM) conditions. pH is adjusted by variation of CO2 partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85+/-0.01 angstroms for the adsorbed and 1.82+/-0.01 angstroms for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45+/-0.02 angstroms. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46+/-0.01 angstroms. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05+/-0.03 angstroms and 3 to 6 oxygen backscatterers (O-eq2) at 3.31+/-0.02 angstroms. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased KD values after desorption compared to adsorption.

  10. Ab initio molecular dynamics determination of competitive O2 vs. N2 adsorption at open metal sites of M2 (dobdc)

    SciTech Connect

    Parkes, Marie V.; Greathouse, Jeffery A.; Hart, David B.; Sava Gallis, Dorina F.; Nenoff, Tina M.

    2016-04-04

    The separation of oxygen from nitrogen using metal–organic frameworks (MOFs) is of great interest for potential pressure-swing adsorption processes for the generation of purified O2 on industrial scales. This study uses ab initio molecular dynamics (AIMD) simulations to examine for the first time the pure-gas and competitive gas adsorption of O2 and N2 in the M2(dobdc) (M = Cr, Mn, Fe) MOF series with coordinatively unsaturated metal centers. Effects of metal, temperature, and gas composition are explored. Lastly, this unique application of AIMD allows us to study in detail the adsorption/desorption processes and to visualize the process of multiple guests competitively binding to coordinatively unsaturated metal sites of a MOF.

  11. The influence of CO adsorption on the surface composition of cobalt/palladium alloys

    NASA Astrophysics Data System (ADS)

    Murdoch, A.; Trant, A. G.; Gustafson, J.; Jones, T. E.; Noakes, T. C. Q.; Bailey, P.; Baddeley, C. J.

    2016-04-01

    Segregation induced by the adsorption of gas phase species can strongly influence the composition of bimetallic surfaces and can therefore play an important role in influencing heterogeneous catalytic reactions. The addition of palladium to cobalt catalysts has been shown to promote Fischer Tropsch catalysis. We investigate the adsorption of CO onto bimetallic CoPd surfaces on Pd{111} using a combination of reflection absorption infrared spectroscopy and medium energy ion scattering. The vibrational frequency of adsorbed CO provides crucial information on the adsorption sites adopted by CO and medium energy ion scattering probes the surface composition before and after CO exposure. We show that cobalt segregation is induced by CO adsorption and rationalise these observations in terms of the strength of adsorption of CO in various surface adsorption sites.

  12. Phosphorus recovery using pelletized adsorptive materials ...

    EPA Pesticide Factsheets

    Phosphorous (P) is one of the essential nutrients for growth and is generally the most limiting nutrient since, it cannot be fixed from the atmosphere. Methods for recovering phosphorous from water systems already exist, but advances are being made to find a more economic, efficient, effective and easy to use method that can allow for reuse of the recovered P. One area of study is in adsorption, which involves finding the best material for adsorption of phosphorous from water and for releasing it back into the environment through desorption or leaching. The goal of this research was to first optimize the capacity for a pelletized adsorptive material that was synthesized with varying amounts of a binder material from 0-20 % and then to study recovering the phosphate for reuse. The pelletized materials were studied through kinetics experiments as well as isotherm experiments to gain insight into the adsorption capacity and mechanism. Following successful adsorption, a simple leaching study was conducted to see how much phosphate would be released back into water without any added desorption aid. Desorption was then studied by changing the pH of solution. Presenting my thesis work with a poster at ACS.

  13. Adsorption behavior of heavy metals on biomaterials.

    PubMed

    Minamisawa, Mayumi; Minamisawa, Hiroaki; Yoshida, Shoichiro; Takai, Nobuharu

    2004-09-08

    We have investigated adsorption of Cd(II) and Pb(II) at pH 2-6.7 onto the biomaterials chitosan, coffee, green tea, tea, yuzu, aloe, and Japanese coarse tea, and onto the inorganic adsorbents, activated carbon and zeolite. High adsorptive capabilities were observed for all of the biomaterials at pH 4 and 6.7. In the adsorption of Cd(II), blend coffee, tea, green tea, and coarse tea have comparable loading capacities to activated carbon and zeolite. Although activated carbon, zeolite, and chitosan are utilized in a variety of fields such as wastewater treatment, chemical and metallurgical engineering, and analytical chemistry, these adsorbents are costly. On the other hand, processing of the test biomaterials was inexpensive, and all the biomaterials except for chitosan were able to adsorb large amounts of Pb(II) and Cd(II) ions after a convenient pretreatment of washing with water followed by drying. The high adsorption capability of the biomaterials prepared from plant materials is promising in the development of a novel, low-cost adsorbent. From these results, it is concluded that heavy metal removal using biomaterials would be an effective method for the economic treatment of wastewater. The proposed adsorption method was applied to the determination of amounts of Cd(II) and Pb(II) in water samples.

  14. Sulfate adsorption in Michigan forest soils

    SciTech Connect

    MacDonald, N.W.

    1987-01-01

    The occurrence of acidic atmospheric deposition raised concerns over adverse cation leaching effects on Michigan forest soils with low cation exchange capacities. Leaching effects of acid deposition depend on mobility of sulfate in the soil. Little was known, however, concerning the ability of these soils to adsorb sulfate. The objectives of this study were to determine the ability of representative Michigan forest soils to adsorb sulfate, to relate sulfate adsorption to soil properties, and to develop equations to predict sulfate adsorption in similar forest soils. Frigid zone soil series studied were Grayling (Typic Udipsamments), Rubicon (Entic Haplorthods), Kalkaska (Typic Haplorthods), and Montcalm (Eutric Glossoboralfs). Mesic zone series studied were Spinks (Psammentic Hapludals) and Oshtemo (Typic Hapludalfs). Six randomly located pedons of each series were sampled. Sulfate adsorption was determined by shaking 10 gram soil samples for 24 hours in 50 mL 0.01 M CaCl/sub 2/ solution containing 10 mg SO/sub 4/-S L/sup -1/. Solution filtrates were turbidimetrically analyzed for SO/sub 4/-S and adsorption was calculated from reduction in SO/sub 4/-S concentration. Bw, Bs, and Bh horizons of frigid zone soils and E and Bt horizons of mesic zone soils had the highest sulfate adsorbing abilities. No significant differences were found between series in total sulfate adsorptive capacity.

  15. DNA adsorption by indium tin oxide nanoparticles.

    PubMed

    Liu, Biwu; Liu, Juewen

    2015-01-01

    The high conductivity and optical transparency of indium tin oxide (ITO) has made it a popular material in the electronic industry. Recently, its application in biosensors is also explored. To understand its biointerface chemistry, we herein investigate its interaction with fluorescently labeled single-stranded oligonucleotides using ITO nanoparticles (NPs). The fluorescence of DNA is efficiently quenched after adsorption, and the interaction between DNA and ITO NPs is strongly dependent on the surface charge of ITO. At low pH, the ITO surface is positively charged to afford a high DNA adsorption capacity. Adsorption is also influenced by the sequence and length of DNA. For its components, In2O3 adsorbs DNA more strongly while SnO2 repels DNA at neutral pH. The DNA adsorption property of ITO is an averaging result from both components. DNA adsorption is confirmed to be mainly by the phosphate backbone via displacement experiments using free phosphate or DNA bases. Last, DNA-induced DNA desorption by forming duplex DNA is demonstrated on ITO, while the same reaction is more difficult to achieve on other metal oxides including CeO2, TiO2, and Fe3O4 because these particles adsorb DNA more tightly.

  16. Adsorption of Wine Constituents on Functionalized Surfaces.

    PubMed

    Mierczynska-Vasilev, Agnieszka; Smith, Paul A

    2016-10-18

    The adsorption of macromolecules on solid surfaces is of great importance in the field of nanotechnology, biomaterials, biotechnological, and food processes. In the field of oenology adsorption of wine macromolecules such as polyphenols, polysaccharides, and proteins is much less desirable on membrane materials because of fouling and reduced filtering performance. On the other hand, adsorption of these molecules on processing aids is very beneficial for achieving wine clarity and stability. In this article, the effect of surface chemical functionalities on the adsorption of white, rosé, and red wine constituents was evaluated. Allylamine, acrylic acid, and ethanol were selected as precursors for plasma polymerization in order to generate coatings rich in amine, carboxyl, and hydroxyl chemical groups, respectively. The surface chemical functionalities were characterized by X-ray photoelectron spectroscopy (XPS) and the ability of different surface chemical functionalities to adsorb wine constituents were characterized by quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM). The results demonstrated that the amine and carboxyl modified surfaces encourage adsorption of constituents from white wine. The hydroxyl modified surfaces have the ability to preferentially adsorb rosé wine constituents, whereas red wine adsorbed to the highest extent on acrylic acid surface.

  17. Adsorption of phenanthrene on natural snow.

    PubMed

    Domine, Florent; Cincinelli, Alessandra; Bonnaud, Elodie; Martellini, Tania; Picaud, Sylvain

    2007-09-01

    The snowpack is a reservoir for semivolatile organic compounds (SVOCs) and, in particular, for persistent organic pollutants (POPs), which are sequestered in winter and released to the atmosphere or hydrosphere in the spring. Modeling these processes usually assumes that SVOCs are incorporated into the snowpack by adsorption to snow surfaces, but this has never been proven because the specific surface area (SSA) of snow has never been measured together with snow composition. Here we expose natural snow to phenanthrene vapors (one of the more volatile POPs) and measure for the first time both the SSA and the chemical composition of the snow. The results are consistent with an adsorption equilibrium. The measured Henry's law constant is H(Phen)(T) = 2.88 x 10(22) exp(-10660/7) Pa m2 mol(-1), with Tin Kelvin. The adsorption enthalpy is delta H(ads) = -89 +/- 18 kJ mol(-1). We also perform molecular dynamics calculations of phenanthrene adsorption to ice and obtain AHads = -85 +/- 8 kJ mol(-1), close to the experimental value. Results are applied to the adsorption of phenanthrene to the Arctic and subarctic snowpacks. The subarctic snowpack, with a low snow area index (SAI = 1000), is a negligible reservoir of phenanthrene, butthe colder Arctic snowpack, with SAI = 2500, sequesters most of the phenanthrene present in the (snow + boundary layer) system.

  18. Ethanol, acetic acid, and water adsorption from binary and ternary liquid mixtures on high-silica zeolites.

    PubMed

    Bowen, Travis C; Vane, Leland M

    2006-04-11

    Adsorption isotherms were measured for ethanol, acetic acid, and water adsorbed on high-silica ZSM-5 zeolite powder from binary and ternary liquid mixtures at room temperature. Ethanol and water adsorption on two high-silica ZSM-5 zeolites with different aluminum contents and a high-silica beta zeolite were also compared. The amounts adsorbed were measured using a recently developed technique that accurately measures the changes in adsorbent/liquid mixture density and liquid concentration. This technique allows the adsorption of each compound in a liquid mixture to be measured. Adsorption data for binary mixtures were fit with the dual-site extended Langmuir model, and the parameters were used to predict ternary adsorption isotherms for each compound with reasonable accuracy. In ternary mixtures, acetic acid competed with ethanol and water for adsorption sites and reduced ethanol adsorption more than it reduced water adsorption.

  19. Adsorption of plutonium oxide nanoparticles.

    PubMed

    Schmidt, Moritz; Wilson, Richard E; Lee, Sang Soo; Soderholm, L; Fenter, P

    2012-02-07

    Adsorption of monodisperse cubic plutonium oxide nanoparticles ("Pu-NP", [Pu(38)O(56)Cl(x)(H(2)O)(y)]((40-x)+), with a fluorite-related lattice, approximately 1 nm in edge size) to the muscovite (001) basal plane from aqueous solutions was observed in situ (in 100 mM NaCl background electrolyte at pH 2.6). Uptake capacity of the surface quantified by α-spectrometry was 0.92 μg Pu/cm(2), corresponding to 10.8 Pu per unit cell area (A(UC)). This amount is significantly larger than that of Pu(4+) needed for satisfying the negative surface charge (0.25 Pu(4+) for 1 e(-)/A(UC)). The adsorbed Pu-NPs cover 17% of the surface area, determined by X-ray reflectivity (XR). This correlates to one Pu-NP for every 14 unit cells of muscovite, suggesting that each particle compensates the charge of the unit cells onto which it adsorbs as well as those in its direct proximity. Structural investigation by resonant anomalous X-ray reflectivity distinguished two different sorption states of Pu-NPs on the surface at two different regimes of distance from the surface. A fraction of Pu is distributed within 11 Å from the surface. The distribution width matches the Pu-NP size, indicating that this species represents Pu-NPs adsorbed directly on the surface. Beyond the first layer, an additional fraction of sorbed Pu was observed to extend more broadly up to more than 100 Å from the surface. This distribution is interpreted as resulting from "stacking" or aggregation of the nanoparticles driven by sorption and accumulation of Pu-NPs at the interface although these Pu-NPs do not aggregate in the solution. These results are the first in situ observation of the interaction of nanoparticles with a charged mineral-water interface yielding information important to understanding the environmental transport of Pu and other nanophase inorganic species.

  20. Enhancement of elemental mercury adsorption by silver supported material.

    PubMed

    Khunphonoi, Rattabal; Khamdahsag, Pummarin; Chiarakorn, Siriluk; Grisdanurak, Nurak; Paerungruang, Adjana; Predapitakkun, Somrudee

    2015-06-01

    Mercury, generally found in natural gas, is extremely hazardous. Although average mercury levels are relatively low, they are further reduced to comply with future mercury regulations, which are stringent in order to avoid releasing to the environment. Herein, vapor mercury adsorption was therefore investigated using two kinds of supports, granular activated carbon (GAC) and titanium dioxide (TiO2). Both supports were impregnated by silver (5 and 15 wt.%), before testing against a commercial adsorbent (sulfur-impregnated activated carbon, SAC). The adsorption isotherm, kinetics, and its thermodynamics of mercury adsorption were reported. The results revealed that Langmuir isotherm provided a better fit to the experimental data. Pseudo second-order was applicable to describe adsorption kinetics. The higher uniform Ag dispersion was a key factor for the higher mercury uptake. TiO2 supported silver adsorbent showed higher mercury adsorption than the commercial one by approximately 2 times. Chemisorption of mercury onto silver active sites was confirmed by an amalgam formation found in the spent adsorbents.

  1. Mercury adsorption-desorption and transport in soils.

    PubMed

    Liao, Lixia; Selim, H M; Delaune, R D

    2009-01-01

    Kinetic sorption and column miscible displacement transport experiments were performed to quantify the extent of retention/release and the mobility of mercury in different soils. Results indicated that adsorption of mercury was rapid and highly nonlinear with sorption capacities having the following sequence: Sharkey clay > Olivier loam > Windsor sand. Mercury adsorption by all soils was strongly irreversible where the amounts released or desorbed were often less than 1% of that applied. Moreover, the removal of soil organic matter resulted in a decrease of mercury adsorption in all soils. Adsorption was described with limited success using a nonlinear (Freundlich) model. Results from the transport experiments indicated that the mobility of mercury was highly retarded, with extremely low concentrations of mercury in column effluents. Furthermore, mercury breakthrough curves exhibited erratic patterns with ill-distinguished peaks. Therefore, mercury is best regarded as strongly retained and highly "immobile" in the soils investigated. This is most likely due to highly stable complex formation (irreversible forms) and strong binding to high-affinity sites. In a column packed with reference sand material, a symmetric breakthrough curve was obtained where the recovery of mercury in the leachate was only 17.3% of that applied. Mercury retention by the reference sand was likely due to adsorption by quartz and metal-oxides.

  2. A solvable model for localized adsorption in a Coulomb system

    SciTech Connect

    Rosinberg, M.L.; Blum, L.; Lebowitz, J.L.

    1986-07-01

    A model for an interface with localized adsorption is presented, in which the surface has a distribution of sticky adhesive sites in contact with a Coulomb fluid. Contrary to the current literature on the electrical double layer the surface charge is in dynamic equilibrium with the bulk fluid. The sum rules obeyed by the one- and two-body correlation functions are investigated. Explicit results are obtained for a solvable model, the two-dimensional one-component plasma at reduced temperature 2. The effect of the granularity of the adsorbed charge on the adsorption isotherm is discussed.

  3. Effect of low molecular weight organic acids on phosphorus adsorption by ferric-alum water treatment residuals.

    PubMed

    Wang, Changhui; Wang, Ziyuan; Lin, Lu; Tian, Binghui; Pei, Yuansheng

    2012-02-15

    Effects of low molecular weight organic acids (LMWOAs; citric acid, oxalic acid and tartaric acid) on phosphorus (P) adsorption by ferric-alum water treatment residuals (FARs) were studied. Both batch and column experiments indicated that the effects of LMWOAs on P adsorption were closely related to adsorption time. Initially, all acids presented inhibitory function on P adsorption. The inhibition became weaker with time, eventually promoting P adsorption for citric acid and tartaric acid. In the column experiment with a 61-day duration, high P adsorption rates (>55%) were observed for the test groups containing citric acid and tartaric acid. Interestingly, higher pH likely enhanced P adsorption with the effects of LMWOAs and a distinct relationship between LMWOAs' effects on P adsorption and their concentrations was not observed. Moreover, fractionation of the adsorbed P from the FARs demonstrated that oxalic acid reduced P adsorption capacity, while citric acid and tartaric acid increased. Based on the forms of Fe and Al existing in the FARs and Fourier transform infrared spectroscopy analyses, LMWOAs can promote P adsorption through activating crystalline Fe/Al and preventing crystallization of amorphous Fe/Al to increase P adsorption sites, and can also inhibit P adsorption by competition with adsorption sites.

  4. Competitive adsorption of metal cations onto two gram positive bacteria: testing the chemical equilibrium model

    NASA Astrophysics Data System (ADS)

    Fowle, David A.; Fein, Jeremy B.

    1999-10-01

    In order to test the ability of a surface complexation approach to account for metal-bacteria interactions in near surface fluid-rock systems, we have conducted experiments that measure the extent of adsorption in mixed metal, mixed bacteria systems. This study tests the surface complexation approach by comparing estimated extents of adsorption based on surface complexation modeling to those we observed in the experimental systems. The batch adsorption experiments involved Ca, Cd, Cu, and Pb adsorption onto the surfaces of 2 g positive bacteria: Bacillus subtilis and Bacillus licheniformis. Three types of experiments were performed: 1. Single metal (Ca, Cu, Pb) adsorption onto a mixture of B. licheniformis and B. subtilis; 2. mixed metal (Cd, Cu, and Pb; Ca and Cd) adsorption onto either B. subtilis or B. licheniformis; and 3. mixed or single metal adsorption onto B. subtilis and B. licheniformis. %Independent of the experimental results, and based on the site specific stability constants for Ca, Cd, Cu, and Pb interactions with the carboxyl and phosphate sites on B. licheniformis and B. subtilis determined by Fein et al. (1997), by Daughney et al. (1998) and in this study, we estimate the extent of adsorption that is expected in the above experimental systems. Competitive cation adsorption experiments in both single and double bacteria systems exhibit little adsorption at pH values less than 4. With increasing pH above 4.0, the extent of Ca, Cu, Pb and Cd adsorption also increases due to the increased deprotonation of bacterial surface functional groups. In all cases studied, the estimated adsorption behavior is in excellent agreement with the observations, with only slight differences that were within the uncertainties of the estimation and experimental procedures. Therefore, the results indicate that the use of chemical equilibrium modeling of aqueous metal adsorption onto bacterial surfaces yields accurate predictions of the distribution of metals in complex

  5. Water adsorption constrained Frenkel-Halsey-Hill adsorption activation theory: Montmorillonite and illite

    NASA Astrophysics Data System (ADS)

    Hatch, Courtney D.; Greenaway, Ann L.; Christie, Matthew J.; Baltrusaitis, Jonas

    2014-04-01

    Fresh mineral aerosol has recently been found to be effective cloud condensation nuclei (CCN) and contribute to the number of cloud droplets in the atmosphere due to the effect of water adsorption on CCN activation. The work described here uses experimental water adsorption measurements on Na-montmorillonite and illite clay to determine empirical adsorption parameters that can be used in a recently derived theoretical framework (Frenkel-Halsey-Hill Activation Theory, FHH-AT) that accounts for the effect of water adsorption on CCN activation. Upon fitting the Frenkel-Halsey-Hill (FHH) adsorption model to water adsorption measurements, we find FHH adsorption parameters, AFHH and BFHH, to be 98 ± 22 and 1.79 ± 0.11 for montmorillonite and 75 ± 17 and 1.77 ± 0.11 for illite, respectively. The AFHH and BFHH values obtained from water adsorption measurements differ from values reported previously determined by applying FHH-AT to CCN activation measurements. Differences in FHH adsorption parameters were attributed to different methods used to obtain them and the hydratable nature of the clays. FHH adsorption parameters determined from water adsorption measurements were then used to calculate the critical super-saturation (sc) for CCN activation using FHH-AT. The relationship between sc and the dry particle diameter (Ddry) gave CCN activation curve exponents (xFHH) of -0.61 and -0.64 for montmorillonite and illite, respectively. The xFHH values were slightly lower than reported previously for mineral aerosol. The lower exponent suggests that the CCN activity of hydratable clays is less sensitive to changes in Ddry and the hygroscopicity parameter exhibits a broader variability with Ddry compared to more soluble aerosols. Despite the differences in AFHH, BFHH and xFHH, the FHH-AT derived CCN activities of montmorillonite and illite are quite similar to each other and in excellent agreement with experimental CCN measurements resulting from wet-generated clay aerosol

  6. Orbitalwise Coordination Number for Predicting Adsorption Properties of Metal Nanocatalysts

    NASA Astrophysics Data System (ADS)

    Ma, Xianfeng; Xin, Hongliang

    2017-01-01

    We present the orbitalwise coordination number CNα (α =s or d ) as a reactivity descriptor for metal nanocatalysts. With the noble metal Au (5 d106 s1 ) as a specific case, the CNs computed using the two-center s -electron hopping integrals to neighboring atoms provides an accurate and robust description of the trends in CO and O adsorption energies on extended surfaces terminated with different facets and nanoparticles of varying size and shape, outperforming existing bond-counting methods. Importantly, the CNs has a solid physiochemical basis via a direct connection to the moment characteristics of the projected density of states onto the s orbital of a Au adsorption site. Furthermore, the CNs shows promise as a viable descriptor for predicting adsorption properties of Au alloy nanoparticles with size-dependent lattice strains and coinage metal ligands.

  7. Orbitalwise Coordination Number for Predicting Adsorption Properties of Metal Nanocatalysts.

    PubMed

    Ma, Xianfeng; Xin, Hongliang

    2017-01-20

    We present the orbitalwise coordination number CN^{α} (α=s or d) as a reactivity descriptor for metal nanocatalysts. With the noble metal Au (5d^{10}6s^{1}) as a specific case, the CN^{s} computed using the two-center s-electron hopping integrals to neighboring atoms provides an accurate and robust description of the trends in CO and O adsorption energies on extended surfaces terminated with different facets and nanoparticles of varying size and shape, outperforming existing bond-counting methods. Importantly, the CN^{s} has a solid physiochemical basis via a direct connection to the moment characteristics of the projected density of states onto the s orbital of a Au adsorption site. Furthermore, the CN^{s} shows promise as a viable descriptor for predicting adsorption properties of Au alloy nanoparticles with size-dependent lattice strains and coinage metal ligands.

  8. Effects of Zeolite Structure and Si/Al Ratio on Adsorption Thermodynamics and Intrinsic Kinetics of Monomolecular Cracking and Dehydrogenation of Alkanes over Bronsted Acid Sites

    NASA Astrophysics Data System (ADS)

    Janda, Amber Leigh

    It is well known that the efficacy of acidic zeolite catalysts for the cracking of hydrocarbons originates from the shape and size of the zeolite pores. However, the mechanisms by which changes in pore structure influence cracking kinetics are not well understood or exploited. The aim of this dissertation is to use experiments and simulations to shed light on the ways by which zeolite structure and acid site location affect the apparent and intrinsic kinetics of n-alkane monomolecular cracking and dehydrogenation. In the rate-determining step of these processes, C-C or C-H bonds are cleaved catalytically by Bronsted protons. Thus, the kinetics of monomolecular activation reactions are useful for characterizing the influence of active site structural environment on catalysis. In Chapter 2, the effects of active site distribution on n-butane monomolecular activation kinetics are investigated for commercial samples of MFI having a range of the Si/Al ratio. Based on UV-visible spectroscopic analyses of (Co,Na)-MFI, it is inferred that, with increasing Al concentration, the fraction of Co---and, by extension, Bronsted protons in H-MFI---located at channel intersections increases relative to the fraction located at channels. Concurrently, the first-order rate coefficients (kapp) for cracking and dehydrogenation, the selectivity to terminal cracking versus central cracking, and the selectivity to dehydrogenation versus cracking increase. The stronger dependence of the selectivity to dehydrogenation on Al content is attributed to a product-like transition state, the stability of which is more sensitive to confinement than the stabilities of cracking transition states, which occur earlier along the reaction coordinate. For terminal cracking and dehydrogenation, the intrinsic activation entropy (DeltaS‡int ) increases with Al content, consistent with the larger dimensions of intersections relative to channels. Surprisingly, the rate of dehydrogenation is inhibited by

  9. ADSORPTION AND DISSOCIATION OF O2 ON Ti3Al (0001) STUDIED BY FIRST-PRINCIPLES

    NASA Astrophysics Data System (ADS)

    Wei, Li-Jing; Guo, Jian-Xin; Dai, Xiu-Hong; Wang, Ying-Long; Liu, Bao-Ting

    2015-05-01

    The adsorption and dissociation of oxygen molecule on Ti3Al (0001) surface have been investigated by density functional theory (DFT) with the generalized gradient approximation (GGA). All possible adsorption sites including nine vertical and fifteen parallel sites of O2 are considered on Ti3Al (0001) surface. It is found that all oxygen molecules dissociate except for three vertical adsorption sites after structure optimization. This indicates that oxygen molecules prefer to dissociate on the junction site between Ti and Al atoms. Oxygen atoms coming from dissociation of oxygen molecule tend to occupy the most stable adsorption sites of the Ti3Al (0001) surface. The distance of O-O is related to the surface dissociation distance of Ti3Al (0001) surface. The valence electron localization function (ELF) and projected density of states (DOS) show that the bonds of O-O are breakaway at parallel adsorption end structures.

  10. Adsorption on Highly Ordered Porous Alumina

    NASA Astrophysics Data System (ADS)

    Mistura, Giampaolo; Bruschi, Lorenzo; Lee, Woo

    2016-10-01

    Porous anodic aluminum oxide (AAO) is characterized by a regular arrangement of the pores with a narrow pore size distribution over extended areas, uniform pore depth, and solid pore walls without micropores. Thanks to significant improvements in anodization techniques, structural engineering of AAO allows to accurately tailor the pore morphology. These features make porous AAO an excellent substrate to study adsorption phenomena. In this paper, we review recent experiments involving the adsorption in porous AAO. Particular attention will be devoted to adsorption in straight and structured pores with a closed end which shed new light on fundamental issues like the origin of hysteresis in closed end pores and the nature of evaporation from ink-bottle pores. The results will be compared to those obtained in other synthetic materials like porous silicon and silica.

  11. Porous silicon functionalization for possible arsenic adsorption

    PubMed Central

    2014-01-01

    Thiol-functionalized porous silicon (PS) monolayer was evaluated for its possible application in As (III) adsorption. Dimercaptosuccinic acid (DMSA) attached to mesoporous silicon via amide bond linkages was used as a chelate for As (III). Two different aminosilanes namely 3-(aminopropyl) triethoxysilane (APTES) and 3-aminopropyl (diethoxy)-methylsilane (APDEMS) were tested as linkers to evaluate the relative response for DMSA attachment. The aminosilane-modified PS samples were attached to DMSA by wet impregnation followed by the adsorption of As (III). Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) have been used to identify the functional groups and to estimate the As (III) content, respectively. FTIR spectroscopy confirmed the covalent bonding of DMSA with amide and R-COOH groups on the nanostructured porous surface. XPS confirms the preferred arsenic adsorption on the surface of PS/DMSA samples as compared to the aminosilane-modified and bare PS substrates. PMID:25249826

  12. Bromate adsorption using Fe-pillared bentonite.

    PubMed

    He, Shilong; Zhang, Dandan; Gu, Li; Zhang, Shenghua; Yu, Xin

    2012-01-01

    Bromate is an emerging hazardous substance in drinking water. In this study, the removal ofbromate by Fe-pillared bentonite was investigated using various experimental parameters: contact time, initial concentration (Co), temperature, initial pH and competing anions. The adsorption ofbromate followed the pseudo-second-order kinetic better than it followed other kinetic models, and the pseudo-second-order kinetic study showed that equilibrium could be achieved within 60 min. Equilibrium isotherms were analyzed by Freundlich, Langmuir, Redlich-Peterson and Toth isotherm models. The Toth and Redlich-Peterson models better represented the bromate adsorption. Results also indicated that, other than the competing anions and solution pH, temperature was a key parameter affecting adsorption. It was ultimately concluded that Fe-pillared bentonite was effective at removing bromate from water.

  13. Cotton cellulose: enzyme adsorption and enzymic hydrolysis

    SciTech Connect

    Beltrame, P.L.; Carniti, P.; Focher, B.; Marzetti, A.; Cattaneo, M.

    1982-01-01

    The adsorption of a crude cellulase complex from Trichoderma viride on variously pretreated cotton cellulose samples was studied in the framework of the Langmuir approach at 2-8 degrees. The saturation amount of adsorbed enzyme was related to the susceptibility of the substrates to hydrolysis. In every case the adsorption process was faster by 2-3 orders of magnitude than the hydrolysis step to give end products. For ZnCl/sub 2/-treated cotton cellulose the Langmuir parameters correlated fairly well with the value of the Michaelis constant, measured for its enzymic hydrolysis, and the adsorptive complex was indistinguishable from the complex of the Michaelis-Menten model for the hydrolysis.

  14. Adsorption of monoclonal antibodies to glass microparticles.

    PubMed

    Hoehne, Matthew; Samuel, Fauna; Dong, Aichun; Wurth, Christine; Mahler, Hanns-Christian; Carpenter, John F; Randolph, Theodore W

    2011-01-01

    Microparticulate glass represents a potential contamination to protein formulations that may occur as a result of processing conditions or glass types. The effect of added microparticulate glass to formulations of three humanized antibodies was tested. Under the three formulation conditions tested, all three antibodies adsorbed irreversibly at near monolayer surface coverages to the glass microparticles. Analysis of the secondary structure of the adsorbed antibodies by infrared spectroscopy reveal only minor perturbations as a result of adsorption. Likewise, front-face fluorescence quenching measurements reflected minimal tertiary structural changes upon adsorption. In contrast to the minimal effects on protein structure, adsorption of protein to suspensions of glass microparticles induced significant colloidal destabilization and flocculation of the suspension.

  15. Novel nano bearings constructed by physical adsorption

    NASA Astrophysics Data System (ADS)

    Zhang, Yongbin

    2015-09-01

    The paper proposes a novel nano bearing formed by the physical adsorption of the confined fluid to the solid wall. The bearing is formed between two parallel smooth solid plane walls sliding against one another, where conventional hydrodynamic lubrication theory predicted no lubricating effect. In this bearing, the stationary solid wall is divided into two subzones which respectively have different interaction strengths with the lubricating fluid. It leads to different physical adsorption and slip properties of the lubricating fluid at the stationary solid wall respectively in these two subzones. It was found that a significant load-carrying capacity of the bearing can be generated for low lubricating film thicknesses, because of the strong physical adsorption and non-continuum effects of the lubricating film.

  16. Utilisation of chitinous materials in pigment adsorption.

    PubMed

    Wang, San-Lang; Chen, Yan-Cheng; Yen, Yue-Horng; Liang, Tzu-Wen

    2012-12-01

    The effect of adding the cells of four lactobacilli to a squid pen powder (SPP)-containing medium on prodigiosin (PG) production by Serratia marcescens TKU011 is examined. The best increase in PG productivity was shown by strain TKU012. Among the samples of strain TKU012 and the chitinous materials of cicada casting powder (CCP), shrimp shell powder (SSP), squid pen powder (SPP), α-chitin, and β-chitin, TKU012 cells displayed the best adsorption rate (84%) for PG, followed by CCP, SSP, SPP, α-chitin, and β-chitin. As for the water-soluble food colourants, Allura Red AC (R40) and Tartrazne (Y4), SPP and SSP had better adsorptive powers than pure chitin preparations, strain TKU012, and CCP. Treatment with organic solvents, hot alkali, or proteases (papain, bromelain) diminished the adsorption rates of the biosorbents.

  17. Effect of polymer adsorption on mobility ratio

    SciTech Connect

    Omar, A.E.

    1983-03-01

    Several properties of two of the viscous polymer fluids used in rheological control were investigated. Polymer adsorption on the rock surfaces of porous sandstones and its effect on permeability of producing formation was studied. A naturally occurring polymer, a Guar gum, was found greatly to reduce the permeability of the producing formation, although the use of a breaker solution was found to restore the permeability lost through polymer plugging. Use of appropriate breaker solution was found to reduce the permeability loss to only one or two per cent of the original value. Adsorption of the synthetic polymer, acrylamide, was found to be directly related to the shaliness of the porous sand. Deactivation of polymer due to adsorption was found to be significant in formations having large surface areas. The results indicate that polymer loss eventually results in a water bank ahead of the polymer solution and thus greatly reduces the polymer's effectiveness in water-flooding.

  18. Novel nano bearings constructed by physical adsorption

    PubMed Central

    Zhang, Yongbin

    2015-01-01

    The paper proposes a novel nano bearing formed by the physical adsorption of the confined fluid to the solid wall. The bearing is formed between two parallel smooth solid plane walls sliding against one another, where conventional hydrodynamic lubrication theory predicted no lubricating effect. In this bearing, the stationary solid wall is divided into two subzones which respectively have different interaction strengths with the lubricating fluid. It leads to different physical adsorption and slip properties of the lubricating fluid at the stationary solid wall respectively in these two subzones. It was found that a significant load-carrying capacity of the bearing can be generated for low lubricating film thicknesses, because of the strong physical adsorption and non-continuum effects of the lubricating film. PMID:26412488

  19. Porous silicon functionalization for possible arsenic adsorption

    NASA Astrophysics Data System (ADS)

    Balderas-Valadez, Ruth Fabiola; Agarwal, Vivechana

    2014-09-01

    Thiol-functionalized porous silicon (PS) monolayer was evaluated for its possible application in As (III) adsorption. Dimercaptosuccinic acid (DMSA) attached to mesoporous silicon via amide bond linkages was used as a chelate for As (III). Two different aminosilanes namely 3-(aminopropyl) triethoxysilane (APTES) and 3-aminopropyl (diethoxy)-methylsilane (APDEMS) were tested as linkers to evaluate the relative response for DMSA attachment. The aminosilane-modified PS samples were attached to DMSA by wet impregnation followed by the adsorption of As (III). Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) have been used to identify the functional groups and to estimate the As (III) content, respectively. FTIR spectroscopy confirmed the covalent bonding of DMSA with amide and R-COOH groups on the nanostructured porous surface. XPS confirms the preferred arsenic adsorption on the surface of PS/DMSA samples as compared to the aminosilane-modified and bare PS substrates.

  20. The effect of species diversity on metal adsorption onto bacteria

    NASA Astrophysics Data System (ADS)

    Ginn, Brian R.; Fein, Jeremy B.

    2008-08-01

    In this study, we measure proton, Pb, and Cd adsorption onto the bacteria Deinococcus radiodurans, Thermus thermophilus, Acidiphlium angustum, Flavobacterium aquatile, and Flavobacterium hibernum, and we calculate the thermodynamic stability constants for the important surface complexes. These bacterial species represent a wide genetic diversity of bacteria, and they occupy a wide range of habitats. All of the species, except for A. angustum, exhibit similar proton and metal uptake. The only species tested that exhibits significantly different protonation behavior is A. angustum, an acidophile that grows at significantly lower pH than the other species of this study. We demonstrate that a single, metal-specific, surface complexation model can be used to reasonably account for the acid/base and metal adsorption behaviors of each species. We use a four discrete site non-electrostatic model to describe the protonation of the bacterial functional groups, with averaged p Ka values of 3.1 ± 0.3, 4.8 ± 0.2, 6.7 ± 0.1, and 9.2 ± 0.3, and site concentrations of (1.0 ± 0.17) × 10 -4, (9.0 ± 3.0) × 10 -5, (4.6 ± 1.8) × 10 -5, and (6.1 ± 2.3) × 10 -5 mol of sites per gram wet mass of bacteria, respectively. Adsorption of Cd and Pb onto the bacteria can be accounted for by the formation of complexes with each of the bacterial surface sites. The average log stability constants for Cd complexes with Sites 1-4 are 2.4 ± 0.4, 3.2 ± 0.1, 4.4 ± 0.1, and 5.3 ± 0.1, respectively. The average log stability constants for Pb complexes with Sites 1-4 are 3.3 ± 0.2, 4.5 ± 0.3, 6.5 ± 0.1, and 7.9 ± 0.5, respectively. This study demonstrates that a wide range of bacteria exhibit similar proton and metal adsorption behaviors, and that a single set of averaged acidity constants, site concentrations, and stability constants for metal-bacterial surface complexes yields a reasonable model for the adsorption behavior of many of these species. The differences in adsorption

  1. Adsorption of arsenate on untreated dolomite powder.

    PubMed

    Ayoub, G M; Mehawej, M

    2007-09-05

    Raw dolomite powder was evaluated for its efficiency in adsorbing As(V) from water. An experimental setup comprised of a fluidized dolomite powder bed was used to assess the impact of various test variables on the efficiency of removal of As(V). Test influents including distilled water (DW), synthetic groundwater (SGW) and filtered sewage effluent (FSE) were employed to assess the effect of influent parameters on the adsorption process and the quality of the effluent generated. Dolomite exhibited good As(V) removal levels for distilled water (>92%) and synthetic ground water (>84%) influents at all initial As(V) concentrations tested (0.055-0.600 ppm). Breakthrough of dolomite bed occurred after 45 bed volumes for DW and 20 bed volumes for SGW influents with complete breakthrough taking place at more than 300 bed volumes. As(V) removal from FSE influents was relatively unsuccessful as compared to the DW and SGW influents. Partial removal in the order of 32% from filtered sewage effluent at initial concentration of 0.6 mg/L started at 75 bed volumes and gradually stopped at 165 bed volumes. Varying degrees of As(V) adsorption capacities were observed by the different test influents employed, which indicate that the adsorption of As(V) is adversely affected by competing species, mainly sulfates and phosphates present in the influent. The adsorptive behavior of dolomite was described by fitting data generated from the study into the Langmuir and Freundlich isotherm models. Both models described well the adsorption of dolomite. The average isotherm adsorptive capacity was determined at 5.02 mug/g. Regeneration of the dolomite bed can be achieved with the use of caustic soda solution at a pH of 10.5.

  2. Applications and limits of theoretical adsorption models for predicting the adsorption properties of adsorbents.

    PubMed

    Park, Hyun Ju; Nguyen, Duc Canh; Na, Choon-Ki; Kim, Chung-il

    2015-01-01

    The objective of this study is to evaluate the applicability of adsorption models for predicting the properties of adsorbents. The kinetics of the adsorption of NO3- ions on a PP-g-AA-Am non-woven fabric have been investigated under equilibrium conditions in both batch and fixed bed column processes. The adsorption equilibrium experiments in the batch process were carried out under different adsorbate concentration and adsorbent dosage conditions and the results were analyzed using adsorption isotherm models, energy models, and kinetic models. The results of the analysis indicate that the adsorption occurring at a fixed adsorbate concentration with a varying adsorbent dosage occur more easily compared to those under a fixed adsorbent dosage with a varying adsorbate concentration. In the second part of the study, the experimental data obtained using fixed bed columns were fit to Bed Depth Service Time, Bohart-Adams, Clark, and Wolborska models, to predict the breakthrough curves and determine the column kinetic parameters. The adsorption properties of the NO3- ions on the PP-g-AA-Am non-woven fabric were differently described by different models for both the batch and fixed bed column process. Therefore, it appears reasonable to assume that the adsorption properties were dominated by multiple mechanisms, depending on the experimental conditions.

  3. Adsorptive Removal and Adsorption Kinetics of Fluoroquinolone by Nano-Hydroxyapatite.

    PubMed

    Chen, Yajun; Lan, Tao; Duan, Lunchao; Wang, Fenghe; Zhao, Bin; Zhang, Shengtian; Wei, Wei

    2015-01-01

    Various kinds of antibiotics, especially fluoroquinolone antibiotics (FQs) have been widely used for the therapy of infectious diseases in human and livestock. For their poorly absorbed by living organisms, large-scale misuse or abuse of FQs will foster drug resistance among pathogenic bacteria, as well as a variety of environmental problems when they were released in the environment. In this work, the adsorption properties of two FQs, namely norfloxacin (NOR) and ciprofloxacin (CIP), by nano-hydroxyapatite (n-HAP) were studied by batch adsorption experiments. The adsorption curves of FQs by n-HAP were simulated by Langmuir and Freundlich isotherms. The results shown that NOR and CIP can be adsorbed effectively by the adsorbent of n-HAP, and the adsorption capacity of FQs increase with increasing dosage of n-HAP. The optimum dosage of n-HAP for FQs removal was 20 g · L(-1), in which the removal efficiencies is 51.6% and 47.3%, and an adsorption equilibrium time is 20 min. The maximum removal efficiency occurred when pH is 6 for both FQs. The adsorption isotherm of FQs fits well for both Langmuir and Freundlich equations. The adsorption of both FQs by n-HAP follows second-order kinetics.

  4. Study on the adsorption feature of rutin aqueous solution on macroporous adsorption resins.

    PubMed

    Chen, Zhenbin; Zhang, Anjie; Li, Jie; Dong, Fang; Di, Duolong; Wu, Youzhi

    2010-04-15

    The adsorption feature of different kinds of polystyrene-based macroporous adsorption resins (MARs) was investigated systemically at constant temperature employing Rutin as the adsorbate. Different from traditional adsorption patterns, Langmuir and Freundlich adsorption, and the results showed interesting aspects: (1) With the increase of the volume of the initial solution, the adsorption capacity increased to the maximum, and then decreased gradually. (2) Experimental results clearly verified the opinion that the adsorption process of MARs could be divided into three stages-macropores, mesopores, and micropores-by the capillary effects occurring at the two intersections, and the adsorption feature for every stage could be described well by the fourth type of Brunauer model. (3) The model that the inductive effect transmitted to the first layer could not interpret our experimental results reasonably. Thus, the model that the inductive effect passed on to a higher layer was proposed by investigating regression of the experimental results and the conclusion that the inductive effect transmitted to the third layer was drawn.

  5. Adsorptive Removal and Adsorption Kinetics of Fluoroquinolone by Nano-Hydroxyapatite

    PubMed Central

    Chen, Yajun; Lan, Tao; Duan, Lunchao; Wang, Fenghe; Zhao, Bin; Zhang, Shengtian; Wei, Wei

    2015-01-01

    Various kinds of antibiotics, especially fluoroquinolone antibiotics (FQs) have been widely used for the therapy of infectious diseases in human and livestock. For their poorly absorbed by living organisms, large-scale misuse or abuse of FQs will foster drug resistance among pathogenic bacteria, as well as a variety of environmental problems when they were released in the environment. In this work, the adsorption properties of two FQs, namely norfloxacin (NOR) and ciprofloxacin (CIP), by nano-hydroxyapatite (n-HAP) were studied by batch adsorption experiments. The adsorption curves of FQs by n-HAP were simulated by Langmuir and Freundlich isotherms. The results shown that NOR and CIP can be adsorbed effectively by the adsorbent of n-HAP, and the adsorption capacity of FQs increase with increasing dosage of n-HAP. The optimum dosage of n-HAP for FQs removal was 20 g·L-1, in which the removal efficiencies is 51.6% and 47.3%, and an adsorption equilibrium time is 20 min. The maximum removal efficiency occurred when pH is 6 for both FQs. The adsorption isotherm of FQs fits well for both Langmuir and Freundlich equations. The adsorption of both FQs by n-HAP follows second-order kinetics. PMID:26698573

  6. Electrochemical study on the adsorption of carbon oxides and oxidation of their adsorption products on platinum group metals and alloys.

    PubMed

    Siwek, Hanna; Lukaszewski, Mariusz; Czerwiński, Andrzej

    2008-07-07

    CO(2) reduction and CO adsorption on noble metals (Pt, Rh, Pd) and their alloys (Pt-Rh, Pd-Pt, Pd-Rh, Pd-Pt-Rh) prepared as thin rough deposits have been studied by chronoamperometry (CA), cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM). The influence of alloy surface composition on the values of surface coverage, eps (electron per site) and potential of the oxidation of CO(2) reduction and CO adsorption products is shown. The oxidation of the adsorbate on Pt-Rh alloys proceeds more easily (at lower potentials) than on pure metals. On the other hand, in the case of Pd-Pt and Pd-Rh alloys the adsorbate oxidation is more difficult and requires higher potentials than on Pt or Rh. The analysis of the EQCM signal is presented for the case of adsorption and oxidation of carbon oxide adsorption products on the electrodes studied. The comparison of adsorption parameters and the EQCM response obtained for platinum group metals and alloys leads to the conclusion that reduced CO(2) cannot be totally identified with adsorbed CO.

  7. Investigating the thermodynamic stability of Bacillus subtilis spore-uranium(VI) adsorption though surface complexation modeling

    NASA Astrophysics Data System (ADS)

    Harrold, Z.; Hertel, M.; Gorman-Lewis, D.

    2012-12-01

    Dissolved uranium speciation, mobility, and remediation are increasingly important topics given continued and potential uranium (U) release from mining operations and nuclear waste. Vegetative bacterial cell surfaces are known to adsorb uranium and may influence uranium speciation in the environment. Previous investigations regarding U(VI) adsorption to bacterial spores, a differentiated and dormant cell type with a tough proteinaceous coat, include U adsorption affinity and XAFS data. We investigated the thermodynamic stability of aerobic, pH dependent uranium adsorption to bacterial spore surfaces using purified Bacillus subtilis spores in solution with 5ppm uranium. Adsorption reversibility and kinetic experiments indicate that uranium does not precipitate over the duration of the experiments and equilibrium is reached within 20 minutes. Uranium-spore adsorption edges exhibited adsorption at all pH measured between 2 and 10. Maximum adsorption was achieved around pH 7 and decreased as pH increased above 7. We used surface complexation modeling (SCM) to quantify uranium adsorption based on balanced chemical equations and derive thermodynamic stability constants for discrete uranium-spore adsorption reactions. Site specific thermodynamic stability constants provide insight on interactions occurring between aqueous uranium species and spore surface ligands. The uranium adsorption data and SCM parameters described herein, also provide a basis for predicting the influence of bacterial spores on uranium speciation in natural systems and investigating their potential as biosorption agents in engineered systems.

  8. Adsorption of deamidated antibody variants on macroporous and dextran-grafted cation exchangers: II. Adsorption kinetics.

    PubMed

    Tao, Yinying; Carta, Giorgio; Ferreira, Gisela; Robbins, David

    2011-03-18

    Single and multicomponent batch adsorption kinetics were obtained for deamidated mAb variants on two commercial cation exchangers, one with an open macroporous structure--UNOsphere S--and the other with charged dextran grafts--Capto S. The adsorption kinetics for the macroporous matrix was found to be controlled largely by pore diffusion. The effective diffusivity estimated from single component data was a fraction of the mAb free solution diffusivity, and its value could be used to accurately predict the adsorption kinetics for two- and three-component systems. In this case, when two or more variants were adsorbed simultaneously, both experimental and predicted results showed a temporary overshoot of the amount adsorbed above the equilibrium value for the more deamidated variant followed by a gradual approach to equilibrium. Adsorption rates on the dextran grafted material were much faster than those observed for the macroporous matrix for both single component and simultaneous adsorption cases. In this case, no significant overshoot was observed for the more deamidated forms. The Capto S adsorption kinetics could be described well by a diffusion model with an adsorbed phase driving force for single component adsorption and for the simultaneous adsorption of multiple variants. However, this model failed to predict the adsorption kinetics when more deamidated forms pre-adsorbed on the resin were displaced by less deamidated ones. In this case, the kinetics of the displacement process was much slower indicating that the pre-adsorbed components severely hindered transport of the more strongly bound variants. Overall, the results indicate that despite the lower capacity, the macroporous resin may be more efficient in process applications where displacement of one variant by another takes place as a result of the faster and more predictable kinetics.

  9. Water adsorption constrained Frenkel-Halsey-Hill adsorption activation theory: Montmorillonite and illite clays

    NASA Astrophysics Data System (ADS)

    Hatch, C. D.; Greenaway, A.; Christie, M. J.; Baltrusaitis, J.

    2013-12-01

    Recently, fresh, unprocessed mineral aerosol has been found to contribute to the number of available cloud condensation nuclei (CCN) and cloud droplets in the atmosphere due to the effect of water adsorption on CCN activation. The work described here uses experimental water adsorption measurements on montmorillonite and illite clay to determine empirical adsorption parameters for a recently derived theoretical framework (Frenkel-Halsey-Hill Activation Theory, FHH-AT) used to calculate CCN activities of clay minerals. Upon fitting the Frenkel-Halsey-Hill (FHH) adsorption model to experimental water adsorption measurements, we find FHH adsorption parameters, AFHH and BFHH, to be 98×22 and 1.79×0.11 for Na-montmorillonite and 75×17 and 1.77×0.11 for illite, respectively. The AFHH and BFHH values obtained for these clays are significantly different from FHH adsorption parameters derived from CCN activation measurements reported previously for similar clay minerals. Differences in FHH adsorption parameters were attributed to the different approaches used, the hydratable nature of the clays and the relative difficulty in measuring CCN activation of hydratable clays due to relatively long adsorption and desorption equilibration times. However, despite these differences, the calculated CCN activities of montmorillonite and illite are quite similar and are in excellent agreement with experimental CCN activation measurements reported previously for similar clays. The different FHH adsorption parameters, however, translate to lower sc-Ddry CCN activation curve exponents (xFHH = -0.61 and -0.64 for montmorillonite and illite, respectively) than have been reported previously. The lower exponent suggests that the CCN activity of hydratable clay aerosol is less sensitive to changes in dry particle diameter (Ddry) and the hygroscopicity parameter exhibits a broader variability with Ddry compared to more soluble aerosols. This study illustrates that FHH-AT using adsorption

  10. Adsorption and desorption of chlorpyrifos to soils and sediments.

    PubMed

    Gebremariam, Seyoum Yami; Beutel, Marc W; Yonge, David R; Flury, Markus; Harsh, James B

    2012-01-01

    Chlorpyrifos, one of the most widely used insecticides, has been detected in air, rain, marine sediments, surface waters, drinking water wells, and solid and liquid dietary samples collected from urban and rural areas. Its metabolite, TCP, has also been widely detected in urinary samples collected from people of various age groups. With a goal of elucidating the factors that control the environmental contamination, impact, persistence, and ecotoxicity of chlorpyrifos, we examine, in this review, the peer-reviewed literature relating to chlorpyrifos adsorption and desorption behavior in various solid-phase matrices. Adsorption tends to reduce chlorpyrifos mobility, but adsorption to erodible particulates, dissolved organic matter, or mobile inorganic colloids enhances its mobility. Adsorption to suspended sediments and particulates constitutes a major off-site migration route for chlorpyrifos to surface waters, wherein it poses a potential danger to aquatic organisms. Adsorption increases the persistence of chlorpyrifos in the environment by reducing its avail- ability to a wide range of dissipative and degradative forces, whereas the effect of adsorption on its ecotoxicity is dependent upon the route of exposure. Chlorpyrifos adsorbs to soils, aquatic sediments, organic matter, and clay minerals to differing degrees. Its adsorption strongly correlates with organic carbon con- tent of the soils and sediments. A comprehensive review of studies that relied on the batch equilibrium technique yields mean and median Kd values for chlorpyrifos of 271 and 116 L/kg for soils, and 385 and 403 L/kg for aquatic sediments. Chlorpyrifos adsorption coefficients spanned two orders of magnitude in soils. Normalizing the partition coefficient to organic content failed to substantially reduce variability to commonly acceptable level of variation. Mean and median values for chlorpyrifos partition coefficients normalized to organic carbon, K, were 8,163 and 7,227 L/kg for soils and 13

  11. NO2 adsorption behaviour on germanene nanosheet - A first-principles investigation

    NASA Astrophysics Data System (ADS)

    Nagarajan, V.; Chandiramouli, R.

    2017-01-01

    The electronic properties and NO2 adsorption behaviour on pristine, In and P substituted germanene nanosheet are studied using DFT method. The formation energy, dipole moment are reported for pristine and impurity substituted germanene nanosheet. The density of states spectrum gives the insights on the electronic properties of germanene nanosheet. The adsorption behaviour of NO2 on pristine, In and P substituted germanene nanosheet is explored in terms of adsorption energy, energy gap, Mulliken charge transfer and average energy gap variation. The favourable adsorption sites of NO2 on germanene nanosheet are studied in atomistic level. The adsorption of NO2 gas molecule on pristine germanene nanosheet is found to be more favourable than impurity substituted germanene nanosheet. The present work gives a clear insight on adsorption properties of NO2 molecules on germanene nanosheet.

  12. Adsorption of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates

    NASA Astrophysics Data System (ADS)

    Ma, Feng-Ji; Liu, Shu-Xia; Liang, Da-Dong; Ren, Guo-Jian; Wei, Feng; Chen, Ya-Guang; Su, Zhong-Min

    2011-11-01

    The functionalization of porous metal-organic frameworks (Cu 3( BTC) 2) was achieved by incorporating Keggin-type polyoxometalates (POMs), and further optimized via alkali metal ion-exchange. In addition to thermal gravimetric analysis, IR, single-crystal X-ray diffraction, and powder X-ray diffraction, the adsorption properties were characterized by N 2 and volatile organic compounds (VOCs) adsorption measurements, including short-chain alcohols ( C<4), cyclohexane, benzene, and toluene. The adsorption enthalpies estimated by the modified Clausius-Clapeyron equation provided insight into the impact of POMs and alkali metal cations on the adsorption of VOCs. The introduction of POMs not only improved the stability, but also brought the increase of adsorption capacity by strengthening the interaction with gas molecules. Furthermore, the exchanged alkali metal cations acted as active sites to interact with adsorbates and enhanced the adsorption of VOCs.

  13. Kinetic and thermodynamic studies of sulforaphane adsorption on macroporous resin.

    PubMed

    Yuanfeng, Wu; Lei, Zhang; Jianwei, Mao; Shiwang, Liu; Jun, Huang; Yuru, You; Lehe, Mei

    2016-08-15

    The adsorption equilibrium, kinetic and thermodynamic of sulforaphane (SF) adsorption onto macroporous resin in aqueous phase were studied. The SP850 resin was screened as the appropriate resin for SF purification. From the equilibrium studies, the Redlich-Peterson model was found to be the best for description of the adsorption behavior of SF onto SP850 resin, followed by the Freundlich model and the Langmuir model. Batch equilibrium experiments demonstrated that, in the examined temperature range, the equilibrium adsorption capacity of SP850 resin decreased with increasing adsorption temperature. Thermodynamics studies indicated that the adsorption of SF was a physical, exothermic, and spontaneous process. The adsorption kinetics revealed that the pseudo-second-order kinetic model was suitable to characterize the kinetics of adsorption of SF onto SP850. Finally, the intra-particle diffusion model demonstrated that SF diffused quickly into macropores, and that diffusion slowed down in the meso- and micropores.

  14. The Calculation of Adsorption Isotherms from Chromatographic Peak Shapes

    ERIC Educational Resources Information Center

    Neumann, M. G.

    1976-01-01

    Discusses the relationship between adsorption isotherms and elution peak shapes in gas chromatography, and describes a laboratory experiment which involves the adsorption of hexane, cyclohexane, and benzene on alumina at different temperatures. (MLH)

  15. Adsorption ability comparison of plasma proteins on amorphous carbon surface

    NASA Astrophysics Data System (ADS)

    Takeda, Aoi; Akasaka, Hiroki; Ohshio, Shigeo; Toda, Ikumi; Nakano, Masayuki; Saitoh, Hidetoshi

    2012-11-01

    To understand why amorphous carbon (a-C:H) film shows antithrombogenicity, an adsorption ability of plasma proteins on a-C:H surface was investigated. Protein adsorption is the initial process of clot formation. The protein adsorption ability on a-C:H film surface was compared by the detection using the surface plasmon resonance (SPR) phenomenon to estimate the protein adsorption. The protein adsorption abilities of a fibrinogen (Fib) and a human γ-globulin (HGG) were estimated by the SPR method using a multilayer structure of a-C:H/Au/Cr/glass. Although the adsorption of HGG for a-C:H was saturated at 32 μM in HGG concentration, the adsorption of Fib was not saturated under the detection limit of this method. These results indicated that the adsorption ability to the a-C:H film surface of Fib was higher than HGG.

  16. In vitro adsorption of tilidine HCl by activated charcoal.

    PubMed

    Cordonnier, J A; Van den Heede, M A; Heyndrickx, A M

    In vitro studies were carried out in order to determine the adsorption of tilidine HCl, a narcotic analgesic, by activated charcoal (max. adsorption capacity 185.5 mg/g of charcoal). The path of the adsorption isotherms at pH 1.2 and 7.5 suggests that the in vivo adsorption of tilidine HCl may be increased when the drug passes from the stomach to the intestine, unless the intestinal content exerts a displacing effect. Nevertheless, the adsorption was dependent on the quantity of activated charcoal used, becoming more complete when the quantity of activated charcoal was increased. The effects of additives on the adsorption capacity of activated charcoal were also investigated in vitro. Ethanol, sorbitol and sucrose significantly reduced drug adsorption, while cacao powder, milk and starch had no effect on tilidine adsorption. At an acid pH, Federa Activated Charcoal significantly adsorbed more drug than either Norit A or Activated Charcoal Merck.

  17. Competitive adsorption of VOCcs and BOM: Oxic and anoxic environments

    SciTech Connect

    Sorial, G.A.; Papadimas, S.P.; Suidan, M.T.; Speth, T.F.

    1994-01-01

    The effect of the presence of molecular oxygen on the adsorption of volatile organic compounds (VOCs) in distilled Milli-Q water and in water supplemented with background organic matter (BOM) is evaluated. Experiments are conducted under conditions where molecular oxygen is present in the test environment (oxic adsorption), and where oxygen is absent from the test environment (anoxic adsorption). Adsorption isotherms for tetrachloroethylene (PCE) and trichloroethylene (TCE) in Milli-Q water showed no impact of the presence of oxygen on their adsorption behavior, while adsorption isotherms for cis-1,2-dichloroethylene (DCE) showed higher capacities under toxic conditions. The Ideal Adsorbed Solution Theory (IAST) successfully predicted the VOCs anoxic adsorption isotherms in BOM. However, the IAST model did not predict the VOCs oxic adsorption isotherms in BOM.

  18. IMPACT OF OXYGEN MEDIATED OXIDATIVE COUPLING ON ADSORPTION KINETICS

    EPA Science Inventory

    The presence of molecular oxygen in the test environment promotes oxidative coupling (polymer formation) of phenolic compounds on the surface of granular activated carbon (GAC). Both adsorption equilibria and adsorption kinetics are affected by these chemical reactions. Lack of...

  19. Adsorption of thorium from aqueous solutions by perlite.

    PubMed

    Talip, Z; Eral, M; Hiçsönmez, U

    2009-02-01

    The use of expanded perlite for the adsorption of thorium from aqueous solution by batch technique is presented. The effects of particle size, pH of the solution, initial thorium concentration, shaking time, V/m ratio and temperature were determined. It was found that the adsorption capacity increases by the increase in the pH of the suspensions. The rate of thorium adsorption on expanded perlite was observed to be fast in the first hour of the reaction time. Adsorption isotherms were expressed by Langmuir and Freundlich adsorption models and the adsorption experiments conducted at 30 +/- 1 degrees C showed that the adsorption isotherms correlated well with the Langmuir model. From the adsorption data, thermodynamic parameters such as DeltaG(o), DeltaH(o) and DeltaS(o) were calculated as a function of temperature.

  20. Adsorption of alkali metals on Ge(001)(2×1) surface

    SciTech Connect

    Xiao, H Y.; Zu, Xiaotao; Zhang, Yanfeng; Gao, Fei

    2006-01-09

    Ab initio total energy calculations have been performed for Na, K and Rb adsorption on Ge(001)(2?1) surface. It was found that the adsorption site of AM is AM size dependent. Structural analysis showed that the Ge-Ge dimer bond becomes stronger with increasing AM size. As the coverage increases from 0.5 to 1 ML it turns out that no depolarization effect occurs upon Na adsorption, while this effect become more important with increasing AM size. We also found that for all adsorption systems investigated the germanium surface is metallic and semiconducting for the coverage of 0.5 and 1 ML, respectively.

  1. A study of metal ion adsorption at low suspended-solid concentrations

    USGS Publications Warehouse

    Chang, Cecily C.Y.; Davis, J.A.; Kuwabara, J.S.

    1987-01-01

    A procedure for conducting adsorption studies at low suspended solid concentrations in natural waters (<50 mg l-1) is described. Methodological complications previously associated with such experiments have been overcome. Adsorption of zinc ion onto synthetic colloidal titania (TiO2) was studied as a function of pH, supporting electrolyte (NaCl) concentration (0??1-0??002 m) and particle concentration (2-50 mg l-1). The lack of success of the Davis Leckie site bonding model in describing Zn(II) adsorption emphasizes the need for further studies of adsorption at low suspended-solid concentrations. ?? 1987.

  2. Étude par chromatographie gazeuse inverse, à concentration finie, des propriétés de surface d'échantillons obtenus par traitement thermique de la goethite : distribution des sites d'adsorption des alcanes

    NASA Astrophysics Data System (ADS)

    Brendlé, E.; Balard, H.; Papirer, E.

    1998-07-01

    Inverse Gas Chromatography (IGC), at finite concentration conditions, was applied for the evaluation of the surface properties of hematite samples obtained by heat treatment of goethite. From the alkane adsorption isotherms, the distribution of surface sites according to the adsorption energy is determined. It is shown that the surface of hematite undergoes significant changes when heated up to 500 circC. La chromatographie Gazeuse Inverse (CGI), à concentration finie, a été utilisée pour évaluer les propriétés de surface d'échantillons d'hématite obtenus par traitement thermique de la goethite. A partir des isothermes d'adsorption des alcanes, on détermine la courbe de distribution des sites de surface en fonction de l'énergie d'adsorption de molécules sondes. On montre que ces courbes évoluent en fonction du traitement thermique de la goethite et traduisent une importante modification de surface de l'hématite formée après un chauffage à 500 circC.

  3. Oxygen adsorption on the Al₉Co₂(001) surface: first-principles and STM study.

    PubMed

    Villaseca, S Alarcón; Loli, L N Serkovic; Ledieu, J; Fournée, V; Gille, P; Dubois, J-M; Gaudry, E

    2013-09-04

    Atomic oxygen adsorption on a pure aluminum terminated Al9Co2(001) surface is studied by first-principle calculations coupled with STM measurements. Relative adsorption energies of oxygen atoms have been calculated on different surface sites along with the associated STM images. The local electronic structure of the most favourable adsorption site is described. The preferential adsorption site is identified as a 'bridge' type site between the cluster entities exposed at the (001) surface termination. The Al-O bonding between the adsorbate and the substrate presents a covalent character, with s-p hybridization occurring between the states of the adsorbed oxygen atom and the aluminum atoms of the surface. The simulated STM image of the preferential adsorption site is in agreement with experimental observations. This work shows that oxygen adsorption generates important atomic relaxations of the topmost surface layer and that sub-surface cobalt atoms strongly influence the values of the adsorption energies. The calculated Al-O distances are in agreement with those reported in Al2O and Al2O3 oxides and for oxygen adsorption on Al(111).

  4. Electrical swing adsorption gas storage and delivery system

    DOEpatents

    Judkins, Roddie R.; Burchell, Timothy D.

    1999-01-01

    Systems and methods for electrical swing natural gas adsorption are described. An apparatus includes a pressure vessel; an electrically conductive gas adsorptive material located within the pressure vessel; and an electric power supply electrically connected to said adsorptive material. The adsorptive material can be a carbon fiber composite molecular sieve (CFCMS). The systems and methods provide advantages in that both a high energy density and a high ratio of delivered to stored gas are provided.

  5. Carbon dioxide separation using adsorption with steam regeneration

    DOEpatents

    Elliott, Jeannine Elizabeth; Copeland, Robert James; Leta, Daniel P.; McCall, Patrick P.; Bai, Chuansheng; DeRites, Bruce A.

    2016-11-29

    A process for separating a carbon dioxide from a gas stream is disclosed. The process can include passing the gas stream over a sorbent that adsorbs the carbon dioxide by concentration swing adsorption and adsorptive displacement. The sorbent can be regenerated and the carbon dioxide recaptured by desorbing the carbon dioxide from the sorbent using concentration swing adsorption and desorptive displacement. A carbon dioxide separation system is also disclosed. Neither the system nor the process rely on temperature swing or pressure swing adsorption.

  6. Electrical swing adsorption gas storage and delivery system

    DOEpatents

    Judkins, R.R.; Burchell, T.D.

    1999-06-15

    Systems and methods for electrical swing natural gas adsorption are described. An apparatus includes a pressure vessel; an electrically conductive gas adsorptive material located within the pressure vessel; and an electric power supply electrically connected to said adsorptive material. The adsorptive material can be a carbon fiber composite molecular sieve (CFCMS). The systems and methods provide advantages in that both a high energy density and a high ratio of delivered to stored gas are provided. 5 figs.

  7. Factors affecting the adsorption of xenon on activated carbon

    SciTech Connect

    Underhill, D.W.; DiCello, D.C.; Scaglia, L.A.; Watson, J.A.

    1986-08-01

    The presence of water vapor was found to interfere strongly with the dynamic adsorption of /sup 133/Xe on coconut-base activated charcoal. The percent loss in the xenon adsorption coefficient was similar to values reported earlier for the adsorption of krypton on humidified charcoal. Attempts to increase the adsorption of xenon by (a) using a petroleum-based adsorbent with an extremely high surface area and (b) by impregnation of the adsorbent with iodine were not successful.

  8. Lanthanide Metal-Organic Frameworks with Six-Coordinated Ln(III) Ions and Free Functional Organic Sites for Adsorptions and Extensive Catalytic Activities

    PubMed Central

    Zhu, Yu; Zhu, Min; Xia, Li; Wu, Yunlong; Hua, Hui; Xie, Jimin

    2016-01-01

    Three chelating-amino-functionalized lanthanide metal-organic frameworks, Y-DDQ, Dy-DDQ and Eu-DDQ, were synthesized with a flexible dicarboxylate ligand based on quinoxaline (H2DDQ = N, N′-dibenzoic acid-2,3-diaminoquinoxaline). The three-dimensional framework is constructed by the H2DDQ linkers connecting the zigzag ladders, showing a net of sra topology. In the structures, one kind of Ln(III) ions metal centers are six-coordinated and thus can potentially behave as open metal sites (OMSs), while the free chelating amino groups can act as free functional organic sites (FOSs). The N2 and Ar adsorption behaviors indicate that these Ln-DDQ exhibits stable microporous frameworks with high surface area after remove of the solvents. Owing to presence of OMSs and FOSs, these MOFs show good ability of CO2, dyes captures and Lewis acid catalyst for cyanosilylation reaction. In view of the existing FOSs in the framework, Pd NPs were immobilized onto the MOFs through graft interactions between free chelating amino groups and metal ions precursor using postsynthetic modification. The well dispersed Pd@Ln-DDQs exhibit efficient and recyclable catalytic reduction of 4-nitrophenol to 4-aminophenol, and they can also act as an excellent catalyst for Suzuki-Miyaura cross-coupling reactions with the exposed Pd NPs. PMID:27431731

  9. Adsorption site and structure determination of c(2x2) N{sub 2}/Ni(100) using angle-resolved photoemission extended fine structure

    SciTech Connect

    Moler, E.J.; Kellar, S.A.; Huff, W.R.A.

    1997-04-01

    The authors have determined the atomic spatial structure of c(2x2) N2Ni(100) with Angle-Resolved Photoemission Extended Fine Structure (ARPEFS) from the nitrogen 1s core level using monochromatized x-rays from beamline 6.1 at SSRL and beamline 9.3.2 at the ALS. The chemically shifted N 1s peak intensities were summed together to obtain ARPEFS curves for both nitrogen atoms in the molecule. They used a new, highly-optimized program based on the Rehr-Albers scattering matrix formalism to find the adsorption site and to quantitatively determine the bond-lengths. The nitrogen molecule stands upright at an atop site, with a N-Ni bond length of 2.25(1) {angstrom}, a N-N bond length of 1.10(7) {angstrom}, and a first layer Ni-Ni spacing of 1.76(4) {angstrom}. The shake-up peak shows an identical ARPEFS diffraction pattern, confirming its intrinsic nature and supporting a previous use of this feature to decompose the peak into contributions from the chemically inequivalent nitrogen atoms. Comparison to a previously published theoretical treatment of N-N-Ni and experimental structures of analogous adsorbate systems demonstrates the importance of adsorbate-adsorbate interactions in weakly chemisorbed systems.

  10. Lanthanide Metal-Organic Frameworks with Six-Coordinated Ln(III) Ions and Free Functional Organic Sites for Adsorptions and Extensive Catalytic Activities

    NASA Astrophysics Data System (ADS)

    Zhu, Yu; Zhu, Min; Xia, Li; Wu, Yunlong; Hua, Hui; Xie, Jimin

    2016-07-01

    Three chelating-amino-functionalized lanthanide metal-organic frameworks, Y-DDQ, Dy-DDQ and Eu-DDQ, were synthesized with a flexible dicarboxylate ligand based on quinoxaline (H2DDQ = N, N‧-dibenzoic acid-2,3-diaminoquinoxaline). The three-dimensional framework is constructed by the H2DDQ linkers connecting the zigzag ladders, showing a net of sra topology. In the structures, one kind of Ln(III) ions metal centers are six-coordinated and thus can potentially behave as open metal sites (OMSs), while the free chelating amino groups can act as free functional organic sites (FOSs). The N2 and Ar adsorption behaviors indicate that these Ln-DDQ exhibits stable microporous frameworks with high surface area after remove of the solvents. Owing to presence of OMSs and FOSs, these MOFs show good ability of CO2, dyes captures and Lewis acid catalyst for cyanosilylation reaction. In view of the existing FOSs in the framework, Pd NPs were immobilized onto the MOFs through graft interactions between free chelating amino groups and metal ions precursor using postsynthetic modification. The well dispersed Pd@Ln-DDQs exhibit efficient and recyclable catalytic reduction of 4-nitrophenol to 4-aminophenol, and they can also act as an excellent catalyst for Suzuki-Miyaura cross-coupling reactions with the exposed Pd NPs.

  11. Adsorption site and structure determination of c(2 × 2) N2/Ni(100) using angle-resolved photoemission extended fine structure

    NASA Astrophysics Data System (ADS)

    Moler, Edward J.; Kellar, Scot A.; Huff, W. R. A.; Hussain, Zahid; Zheng, Yu; Hudson, Eric A.; Chen, Yufeng; Shirley, David A.

    1997-01-01

    We have determined the atomic spatial structure of c(2 × 2) N2/Ni(100) with angle-resolved photoemission extended fine structure using the nitrogen 1s core level. The chemically shifted N 1s peak intensities were summed to obtain ARPEFS curves for both nitrogen atoms in the molecule. We used a new, highly optimized program based on the Rehr-Albers scattering matrix formalism to find the adsorption site and to determine the bond lengths quantitatively. The nitrogen molecule stands upright at an atop site, with a NNi bond length of 2.25(1) Å, a NN bond length of 1.10(7) Å, and a first layer NiNi spacing of 1.76(4) Å. The shake-up peak shows an identical ARPEFS diffraction pattern, confirming its intrinsic nature and supporting a previous use of this feature to decompose the peak into contributions from the chemically inequivalent nitrogen atoms. Comparison to a previously published theoretical treatment of NNNi and experimental structures of analogous adsorbate systems demonstrates the importance of adsorbate-adsorbate interactions in weakly chemisorbed systems.

  12. Synergistic adsorption of mixtures of cationic gemini and nonionic sugar-based surfactant on silica.

    PubMed

    Zhou, Qiong; Somasundaran, P

    2009-03-15

    Adsorption behavior of cationic C(12)-C(4)-C(12) gemini surfactant on silica has been investigated, along with that of nonionic surfactant n-dodecyl-beta-D-maltoside (DM). While DM alone shows meager adsorption on silica, because of the lack of any electrostatic adsorption, cationic gemini adsorbs significantly on the oppositely charged silica surface. Due to the electrostatic nature of cationic gemini adsorption on silica, solution pH affects adsorption of C(12)-C(4)-C(12) gemini dramatically. Meanwhile, C(12)-C(4)-C(12) gemini hemimicelle size at silica/water interface does not seem to change with solution pH. For the mixtures of DM and cationic C(12)-C(4)-C(12) gemini, there is a sharp increase of DM adsorption at silica/water interface, up to 100 times more than DM alone. After mixing with DM, saturation adsorption of cationic C(12)-C(4)-C(12) gemini decreases, due to competition for adsorption sites from DM. At the same time, in its mixture with DM, there is an increased adsorption of C(12)-C(4)-C(12) gemini in the rising part of the adsorption isotherm. Hydrophobic chain-chain interactions, especially with two hydrophobic chains in one C(12)-C(4)-C(12) gemini molecule, and adsorbed C(12)-C(4)-C(12) gemini molecule acting as an anchor or nucleation sites for forming mixed aggregates with DM on silica surface, are attributed to the marked adsorption synergy between DM and cationic C(12)-C(4)-C(12) gemini. The adsorption of surfactants and their mixtures has a marked effect on silica surface charge and silica's wettability.

  13. Insights into tetracycline adsorption onto kaolinite and montmorillonite: experiments and modeling.

    PubMed

    Zhao, Yanping; Gu, Xueyuan; Li, Shiyin; Han, Ruiming; Wang, Guoxiang

    2015-11-01

    Adsorption of tetracycline (TC) on kaolinite and montmorillonite was investigated using batch adsorption experiments with different pH, ionic strength, and surface coverage. As a result, pH and ionic strength-dependent adsorption of TC was observed for the two clay minerals. The adsorption of TC decreased with the increase of pH and ionic strength, and high initial TC concentration had high adsorption. In addition, a triple-layer model was used to predict the adsorption and surface speciation of TC on the two minerals. As a result, four complex species on kaolinite (≡X(-)∙H3TC(+), ≡X(-)∙H2TC(±), ≡SOH(0)∙H2TC(±), and ≡SOH(0)∙HTC(-)) and three species on montmorillonite (≡X(-)∙H3TC(+), ≡X(-)∙H2TC(±), and ≡SOH(0)∙HTC(-)) were structurally constrained by spectroscopy, and these species were also successfully fitted to the adsorption edges of TC. Three functional groups of TC were involved in these adsorption reactions, including the positively charged dimethylamino group, the C=O amide I group, and the C=O group at the C ring. Combining adsorption experiments and model in this study, the adsorption of TC on kaolinite and montmorillonite was mainly attributed to cation exchange on the surface sites (≡X(-)) compared to surface complexation on the edge sites (≡SOH) at natural soil pH condition. Moreover, the surface adsorption species, the corresponding adsorption modes, and the binding constants for the surface reactions were also estimated.

  14. Zinc modulates thrombin adsorption to fibrin

    SciTech Connect

    Hopmeier, P.; Halbmayer, M.; Fischer, M.; Marx, G. )

    1990-05-01

    Human thrombin with high affinity to Sepharose insolubilized fibrin monomers (high-affinity thrombin) was used to investigate the effect of Zn(II) on the thrombin adsorption to fibrin. Results showed that at Zn(II) concentrations exceeding 100 mumols/l, thrombin binding to fibrin was decreased concomitant with the Zn(II) concentration and time; at lower Zn(II) concentrations, thrombin adsorption was enhanced. Experimental results were identical by using 125I-labelled high-affinity alpha-thrombin or by measuring the thrombin activity either by chromogenic substrate or by a clotting time method. In contrast, Ca(II) alone (final conc. 3 mmol/l) or in combination with Zn(II) was not effective. However, at higher Ca(II) concentrations (7.5-15 mmol/l), thrombin adsorption was apparently decreased. Control experiments revealed that Zn(II) had no impact on the clottability of fibrinogen, and that the results of the experiments with Ca(II) were not altered by possible cross-linking of fibrin. We conclude that unlike Ca(II), Zn(II) is highly effective in modulating thrombin adsorption to fibrin.

  15. Asphaltene adsorption and desorption from mineral surfaces

    SciTech Connect

    Dubey, S.T. ); Waxman, M.H.

    1991-02-01

    This paper reports results of asphaltene adsorption/desorption on clay minerals, silica, and carbonates. It also describes the effect of adsorbed asphaltenes on rock wettability and a screening pyrolysis-flame-ionization-detection (P-FID) test to evaluate the ability of solvents to remove asphaltene from kaolin and formation core material.

  16. Adsorption modeling for off-gas treatment

    SciTech Connect

    Ladshaw, A.; Sharma, K.; Yiacoumi, S.; Tsouris, C.; De Paoli, D.W.

    2013-07-01

    Off-gas generated from the reprocessing of used nuclear fuel contains a mixture of several radioactive gases including {sup 129}I{sub 2}, {sup 85}Kr, HTO, and {sup 14}CO{sub 2}. Over the past few decades, various separation and recovery processes have been studied for capturing these gases. Adsorption data for gaseous mixtures of species can be difficult to determine experimentally. Therefore, procedures capable of predicting the adsorption behavior of mixtures need to be developed from the individual isotherms of each of the pure species. A particular isotherm model of interest for the pure species is the Generalized Statistical Thermodynamic Adsorption isotherm. This model contains an adjustable number of parameters and will therefore describe a wide range of adsorption isotherms for a variety of components. A code has been developed in C++ to perform the non-linear regression analysis necessary for the determination of the isotherm parameters, as well as the least number of parameters needed to describe an entire set of data. (authors)

  17. Modeling adsorption with lattice Boltzmann equation

    PubMed Central

    Guo, Long; Xiao, Lizhi; Shan, Xiaowen; Zhang, Xiaoling

    2016-01-01

    The research of adsorption theory has recently gained renewed attention due to its critical relevance to a number of trending industrial applications, hydrogen storage and shale gas exploration for instance. The existing theoretical foundation, laid mostly in the early twentieth century, was largely based on simple heuristic molecular interaction models and static interaction potential which, although being insightful in illuminating the fundamental mechanisms, are insufficient for computations with realistic adsorbent structure and adsorbate hydrodynamics, both critical for real-life applications. Here we present and validate a novel lattice Boltzmann model incorporating both adsorbate-adsorbate and adsorbate-adsorbent interactions with hydrodynamics which, for the first time, allows adsorption to be computed with real-life details. Connection with the classic Ono-Kondo lattice theory is established and various adsorption isotherms, both within and beyond the IUPAC classification are observed as a pseudo-potential is varied. This new approach not only enables an important physical to be simulated for real-life applications, but also provides an enabling theoretical framework within which the fundamentals of adsorption can be studied. PMID:27256325

  18. Adsorption of carboxymethyl cellulose on alumina particles.

    PubMed

    Zhivkov, Alexandar M; Hristov, Rosen P

    2015-06-01

    The polyelectrolyte adsorption on colloid particles is often used for stabilization or flocculation of water suspensions. The aim of this work is to study the adsorption of carboxymethyl cellulose (CMC) on alumina (γ-Al2O3) colloid particles. The particles and polymer are chosen because of the capability of the metal-oxide ampholyte surface and the weak polyelectrolytes to alter their charge by pH. The measurements are done at pH 6.0 where the CMC carboxylic gropes are almost fully dissociated and the alumina surface is positively charged. The high linear charge density of the polyelectrolyte chain provides Na(+) counterions condensation on the COO(-) groups. The main employed method is the electric light scattering based on particle orientation in sinusoidal electric field. The electric polarizability and the relaxation time after field switching off (both depending on the particle charge and size) are used as criteria for polymer adsorption and particle aggregation. Micro-electrophoresis is applied as additional techniques indicating the sign and density of the surface charge. The results obtained give the conditions (time dependence, particle and polymer concentrations) where the CMC adsorption is complete and the suspension is stable.

  19. Adsorption of diblock polypeptides on polystyrene latex.

    PubMed

    Jain, Ritesh; Forciniti, Daniel

    2012-10-30

    The adsorption of peptides at solid/liquid interfaces is affected by peptide/surface and peptide/peptide hydrophobic and electrostatic forces. Three diblock copolypeptides and two homopeptides were adsorbed on poly(styrene) nanospheres from water, water/methanol, and water/glycerol mixtures at different pH's to study both of these effects. Peptides with one hydrophilic (glutamic acid or lysine) and one nonpolar block (alanine) or with both hydrophilic blocks with opposite charges (glutamic acid and lysine) were chemically synthesized and used as adsorbates in this study. The amount adsorbed was determined, and dynamic light scattering (DLS) was used to measure the adsorbed layer thickness. It was found that peptide/surface and peptide/peptide electrostatic interactions dominate the adsorption process. Hydrophobic forces also play a role, but secondary to electrostatic forces. Positively charged blocks show high affinity for the surface, whereas negatively charged blocks were excluded from it. Poly(Lys) has the highest affinity by the surface, while (Glu)(14)-b-(Ala)(5) has the lowest. Adsorption of all peptides was inhibited by methanol and promoted by glycerol. The adsorption for (Lys)(5)-b-(Glu)(6) was extremely sensitive to pH, irrespective of cosolvent, whereas the thickness for (Lys)(30)-b-(Ala)(41) was sensitive to pH as well as cosolvent. Aggregation was observed in the presence of the nanosurfaces but not in the bulk peptides under some pH and solvent conditions.

  20. Adsorption of Ions at Uncharged Insoluble Monolayers.

    PubMed

    Peshkova, Tatyana V; Minkov, Ivan L; Tsekov, Roumen; Slavchov, Radomir I

    2016-09-06

    A method is proposed for the experimental determination of the adsorption of inorganic electrolytes at a surface covered with insoluble surfactant monolayer. This task is complicated by the fact that the change of the salt concentration alters both chemical potentials of the electrolyte and the surfactant. Our method resolves the question by combining data for the surface pressure versus area of the monolayer at several salt concentrations with data for the equilibrium spreading pressure of crystals of the surfactant (used to fix a standard state). We applied the method to alcohols spread at the surface of concentrated halide solutions. The measured salt adsorption is positive and has nonmonotonic dependence on the area per surfactant molecule. For the liquid expanded film, depending on the concentration, there is one couple of ions adsorbed per each 3-30 surfactant molecules. We analyzed which ion, the positive or the negative, stands closer to the surface, by measuring the effect of NaCl on the Volta potential of the monolayer. The potentiometric data suggest that Na(+) is specifically adsorbed, while Cl(-) remains in the diffuse layer, i.e., the surface is positively charged. The observed reverse Hofmeister series of the adsorptions of NaF, NaCl, and NaBr suggests the same conclusion holds for all these salts. The force that causes the adsorption of Na(+) seems to be the interaction of the ion with the dipole moment of the monolayer.

  1. Fluorocarbon adsorption in hierarchical porous frameworks

    SciTech Connect

    Motkuri, RK; Annapureddy, HVR; Vijaykumar, M; Schaef, HT; Martin, PF; McGrail, BP; Dang, LX; Krishna, R; Thallapally, PK

    2014-07-09

    Metal-organic frameworks comprise an important class of solid-state materials and have potential for many emerging applications such as energy storage, separation, catalysis and bio-medical. Here we report the adsorption behaviour of a series of fluorocarbon derivatives on a set of microporous and hierarchical mesoporous frameworks. The microporous frameworks show a saturation uptake capacity for dichlorodifluoromethane of >4 mmol g(-1) at a very low relative saturation pressure (P/P-o) of 0.02. In contrast, the mesoporous framework shows an exceptionally high uptake capacity reaching >14 mmol g(-1) at P/P-o of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption is found to generally correlate with the polarizability and boiling point of the refrigerant, with dichlorodifluoromethane >chlorodifluoromethane >chlorotrifluoromethane >tetrafluoromethane >methane. These results suggest the possibility of exploiting these sorbents for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling.

  2. Modeling adsorption with lattice Boltzmann equation.

    PubMed

    Guo, Long; Xiao, Lizhi; Shan, Xiaowen; Zhang, Xiaoling

    2016-06-03

    The research of adsorption theory has recently gained renewed attention due to its critical relevance to a number of trending industrial applications, hydrogen storage and shale gas exploration for instance. The existing theoretical foundation, laid mostly in the early twentieth century, was largely based on simple heuristic molecular interaction models and static interaction potential which, although being insightful in illuminating the fundamental mechanisms, are insufficient for computations with realistic adsorbent structure and adsorbate hydrodynamics, both critical for real-life applications. Here we present and validate a novel lattice Boltzmann model incorporating both adsorbate-adsorbate and adsorbate-adsorbent interactions with hydrodynamics which, for the first time, allows adsorption to be computed with real-life details. Connection with the classic Ono-Kondo lattice theory is established and various adsorption isotherms, both within and beyond the IUPAC classification are observed as a pseudo-potential is varied. This new approach not only enables an important physical to be simulated for real-life applications, but also provides an enabling theoretical framework within which the fundamentals of adsorption can be studied.

  3. Adsorption of dyes on Sahara desert sand.

    PubMed

    Varlikli, Canan; Bekiari, Vlasoula; Kus, Mahmut; Boduroglu, Numan; Oner, Ilker; Lianos, Panagiotis; Lyberatos, Gerasimos; Icli, Siddik

    2009-10-15

    Sahara desert sand (SaDeS) was employed as a mineral sorbent for retaining organic dyes from aqueous solutions. Natural sand has demonstrated a strong affinity for organic dyes but significantly lost its adsorption capacity when it was washed with water. Therefore, characterization of both natural and water washed sand was performed by XRD, BET, SEM and FTIR techniques. It was found that water-soluble kyanite, which is detected in natural sand, is the dominant factor affecting adsorbance of cationic dyes. The sand adsorbs over 75% of cationic dyes but less than 21% for anionic ones. Among the dyes studied, Methylene Blue (MB) demonstrated the strongest affinity for Sahara desert sand (Q(e)=11.98 mg/g, for initial dye solution concentration 3.5 x 10(-5)mol/L). The effects of initial dye concentration, the amount of the adsorbent, the temperature and the pH of the solution on adsorption capacity were tested by using Methylene Blue as model dye. Pseudo-first-order, pseudo-second-order and intraparticle diffusion models were applied. It was concluded that adsorption of Methylene Blue on Sahara desert sand followed pseudo-second order kinetics. Gibbs free energy, enthalpy change and entropy change were calculated and found -6411 J/mol, -30360 J/mol and -76.58 J/mol K, respectively. These values indicate that the adsorption is an exothermic process and has a spontaneous nature at low temperatures.

  4. Critical analysis of adsorption data statistically

    NASA Astrophysics Data System (ADS)

    Kaushal, Achla; Singh, S. K.

    2016-09-01

    Experimental data can be presented, computed, and critically analysed in a different way using statistics. A variety of statistical tests are used to make decisions about the significance and validity of the experimental data. In the present study, adsorption was carried out to remove zinc ions from contaminated aqueous solution using mango leaf powder. The experimental data was analysed statistically by hypothesis testing applying t test, paired t test and Chi-square test to (a) test the optimum value of the process pH, (b) verify the success of experiment and (c) study the effect of adsorbent dose in zinc ion removal from aqueous solutions. Comparison of calculated and tabulated values of t and χ 2 showed the results in favour of the data collected from the experiment and this has been shown on probability charts. K value for Langmuir isotherm was 0.8582 and m value for Freundlich adsorption isotherm obtained was 0.725, both are <1, indicating favourable isotherms. Karl Pearson's correlation coefficient values for Langmuir and Freundlich adsorption isotherms were obtained as 0.99 and 0.95 respectively, which show higher degree of correlation between the variables. This validates the data obtained for adsorption of zinc ions from the contaminated aqueous solution with the help of mango leaf powder.

  5. Adsorption of Ions at Uncharged Insoluble Monolayers

    NASA Astrophysics Data System (ADS)

    Peshkova, T. V.; Minkov, I. L.; Tsekov, R.; Slavchov, R. I.

    2016-08-01

    A method is proposed for the experimental determination of the adsorption of inorganic electrolytes at a surface covered with insoluble surfactant monolayer. This task is complicated by the fact that the change of the salt concentration alters both chemical potentials of the electrolyte and the surfactant. Our method resolves the question by combining data for the surface pressure versus area of the monolayer at several salt concentrations with data for the equilibrium spreading pressure of crystals of the surfactant (used to fix a standard state). We applied the method to alcohols spread at the surface of concentrated halide solutions. The measured salt adsorption is positive and has nonmonotonic dependence on the area per surfactant molecule. For the liquid expanded film, depending on the concentration, there is one couple of ions adsorbed per each 3–30 surfactant molecules. We analyzed which ion, the positive or the negative, stands closer to the surface, by measuring the effect of NaCl on the Volta potential of the monolayer. The potentiometric data suggest that Na+ is specifically adsorbed, while Cl– remains in the diffuse layer, i.e., the surface is positively charged. The observed reverse Hofmeister series of the adsorptions of NaF, NaCl, and NaBr suggests the same conclusion holds for all these salts. The force that causes the adsorption of Na+ seems to be the interaction of the ion with the dipole moment of the monolayer.

  6. CARBON ADSORPTION FOR INDOOR AIR CLEANING

    EPA Science Inventory

    The paper discusses the use of carbon adsorption for indoor air cleaning, focusing on the removal of volatile organic compounds (VOCs) using granular activated carbon (GAC). It addresses GAC performance in two directions. Initially, it presents performance measurements for GAC at...

  7. H2O Adsorption Kinetics on Smectites

    NASA Technical Reports Server (NTRS)

    Zent, Aaron P.; Quinn, Richard C.; Howard, Jeanie; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    The adsorptive equilibration of H2O a with montomorillonite, a smectite clay has been measured. At low temperatures and pressures, equilibration can require many hours, effectively preventing smectites at the martian surface from responding rapidly to diurnal pressure and temperature variations.

  8. ADSORPTION OF ORGANIC CATIONS TO NATURAL MATERIALS

    EPA Science Inventory

    The factors that control the extent of adsorption of amphiphilic organic cations on environmental and pristine surfaces have been studied. The sorbents were kaolinite, montmorillonite, two aquifer materials, and a soil; solutions contained various concentrations of NaCl and CaCl,...

  9. Adsorption Kinetics in Nanoscale Porous Coordination Polymers

    SciTech Connect

    Nune, Satish K.; Thallapally, Praveen K.; McGrail, Benard Peter; Annapureddy, Harsha V. R.; Dang, Liem X.; Mei, Donghai; Karri, Naveen; Alvine, Kyle J.; Olszta, Matthew J.; Arey, Bruce W.; Dohnalkova, Alice

    2015-10-07

    Nanoscale porous coordination polymers were synthesized using simple wet chemical method. The effect of various polymer surfactants on colloidal stability and shape selectivity was investigated. Our results suggest that the nanoparticles exhibited significantly improved adsorption kinetics compared to bulk crystals due to decreased diffusion path lengths and preferred crystal plane interaction.

  10. Fluorocarbon adsorption in hierarchical porous frameworks

    NASA Astrophysics Data System (ADS)

    Motkuri, Radha Kishan; Annapureddy, Harsha V. R.; Vijaykumar, M.; Schaef, H. Todd; Martin, Paul F.; McGrail, B. Peter; Dang, Liem X.; Krishna, Rajamani; Thallapally, Praveen K.

    2014-07-01

    Metal-organic frameworks comprise an important class of solid-state materials and have potential for many emerging applications such as energy storage, separation, catalysis and bio-medical. Here we report the adsorption behaviour of a series of fluorocarbon derivatives on a set of microporous and hierarchical mesoporous frameworks. The microporous frameworks show a saturation uptake capacity for dichlorodifluoromethane of >4 mmol g-1 at a very low relative saturation pressure (P/Po) of 0.02. In contrast, the mesoporous framework shows an exceptionally high uptake capacity reaching >14 mmol g-1 at P/Po of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption is found to generally correlate with the polarizability and boiling point of the refrigerant, with dichlorodifluoromethane >chlorodifluoromethane >chlorotrifluoromethane >tetrafluoromethane >methane. These results suggest the possibility of exploiting these sorbents for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling.

  11. Adsorption mechanism of BMP-7 on hydroxyapatite (001) surfaces

    SciTech Connect

    Zhou, Hailong; Wu, Tao; Dong, Xiuli; Wang, Qi . E-mail: qiwang@zju.edu.cn; Shen, Jiawei

    2007-09-14

    Many properties and functions of bone-related proteins perform through the interface with the hydroxyapatite. However, the mechanism of difference of proteins adsorbing behaviors caused by the variation of calcium and phosphate ions on hydroxyapatite is still unclear at atomic level. In this work, we investigated the site-selective adhesion and the adsorption mechanism of protein BMP-7 to the hydroxyapatite surfaces in aqueous media during adsorption and desorption processes. Molecular dynamics (MD) and steered molecular dynamics (SMD) simulations combined with trajectory analysis were employed to give insight into the underlying behaviors of BMP-7 binding. The results suggest that the adsorption sites could be divided into two categories: COO{sup -} and NH{sub 2}/NH3+. For COO{sup -}, the adsorption phenomenon is driven by the electrostatic interaction formed between the negative charged carboxylate groups and the Ca1 cations on the hydroxyapatite surface. While for NH{sub 2}/NH3+, the interaction is through the intermolecular H-bonds between the N-containing groups and the phosphate on the hydroxyapatite surface.

  12. Visualizing Gas Adsorption on Porous Solids: Four Simple, Effective Demonstrations

    ERIC Educational Resources Information Center

    Cheung, Ocean

    2014-01-01

    Gas adsorption on porous solids is a topic that is often discussed in an undergraduate chemistry or chemical engineering course. The idea of porosity and gas adsorption on a porous solid is usually discussed with adsorption isotherms recorded using commercially available equipment. This discussion can be rather abstract and can be difficult for…

  13. Adsorption of halogenated aliphatic contaminants by graphene nanomaterials.

    PubMed

    Zhou, Yang; Apul, Onur Guven; Karanfil, Tanju

    2015-08-01

    In this study, adsorption of ten environmentally halogenated aliphatic synthetic organic compounds (SOCs) by a pristine graphene nanosheet (GNS) and a reduced graphene oxide (rGO) was examined, and their adsorption behaviors were compared with those of a single-walled carbon nanotube (SWCNT) and a granular activated carbon (GAC). In addition, the impacts of background water components (i.e., natural organic matter (NOM), ionic strength (IS) and pH) on the SOC adsorption behavior were investigated. The results indicated HD3000 and SWCNT with higher microporous volumes exhibited higher adsorption capacities for the selected aliphatic SOCs than graphenes, demonstrating microporosity of carbonaceous adsorbents played an important role in the adsorption. Analysis of adsorption isotherms demonstrated that hydrophobic interactions were the dominant contributor to the adsorption of aliphatic SOCs by graphenes. However, π-π electron donor-acceptor and van der Waals interactions are likely the additional mechanisms contributing to the adsorption of aliphatic SOCs on graphenes. Among the three background solution components examined, NOM showed the most influential effect on adsorption of the selected aliphatic SOCs, while pH and ionic strength had a negligible effects. The NOM competition on aliphatic adsorption was less pronounced on graphenes than SWCNT. Overall, in terms of adsorption capacities, graphenes tested in this study did not exhibit a major advantage over SWCNT and GAC for the adsorption of aliphatic SOCs.

  14. Influence of Soil Solution Salinity on Molybdenum Adsorption by Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Molybdenum (Mo) adsorption on five arid-zone soils from California was investigated as a function of equilibrium solution Mo concentration (0-30 mg L-1), solution pH (4-8), and electrical conductivity (EC = 0.3 or 8 dS m-1). Molybdenum adsorption decreased with increasing pH. An adsorption maximum...

  15. Adsorption isotherm of non-azeotropic solution onto porous adsorbents

    NASA Astrophysics Data System (ADS)

    Bono, A.; Ramlan, N. A.; Anisuzzaman, S. M.; Chu, C. M.; Farm, Y. Y.

    2016-06-01

    Adsorption isotherm is essential component in the understanding of the adsorption process. Several methods of the measurements, analysis and interpretation of adsorption from solution have been reported in the literature. Most of the measurements of adsorption isotherm from solution were involved the measurement of excess isotherm conducted at low region of sorbates concentration. Direct interpretation of excess adsorption isotherm as adsorption isotherm is always been practice. Therefore, in this work a study on the measurement of the adsorption isotherm from solution of non-azeotropic organic solvent mixture onto porous adsorbents for whole range of liquid concentration was conducted. The study included the measurement of excess adsorption isotherm using conventional technique. Theoretical analysis and interpretation of adsorption isotherm from the excess isotherm were conducted using Pseudo Ideal Adsorption, Gibbs Dividing Plane Model and Langmuir-Fruendlich binary isotherm model. For organic solvents, acetone and propanol were chosen as the adsorbates due to the non-azeotropic properties in the mixture. Activated carbon and silicalite were chosen as adsorbents due to the different in their porosity such as macro porous and micro porous structure. The result of the study has revealed that the adsorption isotherm of non-azeotropic mixture onto activated carbon and silicalite can be interpreted as monolayer type of adsorption.

  16. Initial stages of CO2 adsorption on CaO: a combined experimental and computational study.

    PubMed

    Solis, Brian H; Cui, Yi; Weng, Xuefei; Seifert, Jan; Schauermann, Swetlana; Sauer, Joachim; Shaikhutdinov, Shamil; Freund, Hans-Joachim

    2017-02-08

    Room temperature adsorption of carbon dioxide (CO2) on monocrystalline CaO(001) thin films grown on a Mo(001) substrate was studied by infrared reflection-absorption spectroscopy (IRAS) and quantum chemical calculations. For comparison, CO2 adsorption was examined on poorly ordered, nanoparticulate CaO films prepared on Ru(0001). For both systems, CO2 readily adsorbs on the clean CaO surface. However, additional bands were observable on the CaO/Ru(0001) films compared with CaO/Mo(001), because the stricter IRAS surface selection rules do not apply to adsorption on the disordered thin films grown on Ru(0001). Spectral evolution with increasing exposure of the IRA bands suggested the presence of several adsorption sites which are consecutively populated by CO2. Density functional calculations showed that CO2 adsorption occurs as monodentate surface carbonate (CO3(2-)) species at monatomic step sites and other low-coordinated sites, followed by formation of carbonates on terraces, which dominate at increasing CO2 exposure. To explain the coverage-dependent IRAS results, we propose CO2 surface islanding from the onset, most likely in the form of pairs and other chain-like species, which were calculated as thermodynamically favorable. The calculated adsorption energy for isolated CO2 on the terrace sites (184 ± 10 kJ mol(-1)) is larger than the adsorption energy obtained by temperature programmed desorption (∼120-140 kJ mol(-1)) and heat of adsorption taken from microcalorimetry measurements at low coverage (∼125 kJ mol(-1)). However, the calculated adsorption energies become less favorable when carbonate chains intersect on CaO terraces, forming kinks. Furthermore, our assignments of the initial stages of CO2 adsorption are consistent with the observed coverage effect on the CO2 adsorption energy measured by microcalorimetry and the IRAS results.

  17. Simulations of glass surfaces structure, water adsorption, and bond rupture

    NASA Astrophysics Data System (ADS)

    Garofalini, Stephen H.

    1990-12-01

    Molecular dynamics simulations of the structure of silica glass surfaces formed in a perfect vacuum as well as in the presence of a water vapor show the type, location, and concentration of specific features formed in the surface. A bond rupture mechanism which causes silanol formation far removed from the original reaction site is observed. The 3-membered ring is proposed as a site for H adsorption in the glass.

  18. UPS STUDY OF THE ADSORPTION OF OXYGEN ON REDUCED SrTiO{sub 3} SURFACES

    SciTech Connect

    Ferrer, S.; Somorjai, G. A.

    1980-10-01

    The adsorption of oxygen on a reduced SrTiO{sub 3} (111) surface occurs in two distinct phases. At low exposures (less than 1 L), the adsorption leads to the incorporation of O{sup =} ions into the vacant lattice oxygen sites. At higher exposures a second different oxygen species adsorbs.

  19. How specific halide adsorption varies hydrophobic interactions.

    PubMed

    Stock, Philipp; Müller, Melanie; Utzig, Thomas; Valtiner, Markus

    2016-03-11

    Hydrophobic interactions (HI) are driven by the water structure around hydrophobes in aqueous electrolytes. How water structures at hydrophobic interfaces and how this influences the HI was subject to numerous studies. However, the effect of specific ion adsorption on HI and hydrophobic interfaces remains largely unexplored or controversial. Here, the authors utilized atomic force microscopy force spectroscopy at well-defined nanoscopic hydrophobic interfaces to experimentally address how specific ion adsorption of halide ions as well as NH4 (+), Cs(+), and Na(+) cations alters interaction forces across hydrophobic interfaces. Our data demonstrate that iodide adsorption at hydrophobic interfaces profoundly varies the hydrophobic interaction potential. A long-range and strong hydration repulsion at distances D > 3 nm, is followed by an instability which could be explained by a subsequent rapid ejection of adsorbed iodides from approaching hydrophobic interfaces. In addition, the authors find only a weakly pronounced influence of bromide, and as expected no influence of chloride. Also, all tested cations do not have any significant influence on HI. Complementary, x-ray photoelectron spectroscopy and quartz-crystal-microbalance with dissipation monitoring showed a clear adsorption of large halide ions (Br(-)/I(-)) onto hydrophobic self-assembled monolayers (SAMs). Interestingly, iodide can even lead to a full disintegration of SAMs due to specific and strong interactions of iodide with gold. Our data suggest that hydrophobic surfaces are not intrinsically charged negatively by hydroxide adsorption, as it was generally believed. Hydrophobic surfaces rather interact strongly with negatively charged large halide ions, leading to a surface charging and significant variation of interaction forces.

  20. Adsorption Model for Off-Gas Separation

    SciTech Connect

    Veronica J. Rutledge

    2011-03-01

    The absence of industrial scale nuclear fuel reprocessing in the U.S. has precluded the necessary driver for developing the advanced simulation capability now prevalent in so many other countries. Thus, it is essential to model complex series of unit operations to simulate, understand, and predict inherent transient behavior and feedback loops. A capability of accurately simulating the dynamic behavior of advanced fuel cycle separation processes will provide substantial cost savings and many technical benefits. The specific fuel cycle separation process discussed in this report is the off-gas treatment system. The off-gas separation consists of a series of scrubbers and adsorption beds to capture constituents of interest. Dynamic models are being developed to simulate each unit operation involved so each unit operation can be used as a stand-alone model and in series with multiple others. Currently, an adsorption model has been developed in gPROMS software. Inputs include gas stream constituents, sorbent, and column properties, equilibrium and kinetic data, and inlet conditions. It models dispersed plug flow in a packed bed under non-isothermal and non-isobaric conditions for a multiple component gas stream. The simulation outputs component concentrations along the column length as a function of time from which the breakthrough data is obtained. It also outputs temperature along the column length as a function of time and pressure drop along the column length. Experimental data will be input into the adsorption model to develop a model specific for iodine adsorption on silver mordenite as well as model(s) specific for krypton and xenon adsorption. The model will be validated with experimental breakthrough curves. Another future off-gas modeling goal is to develop a model for the unit operation absorption. The off-gas models will be made available via the server or web for evaluation by customers.

  1. Kinetics of phosphate adsorption on goethite: comparing batch adsorption and ATR-IR measurements.

    PubMed

    Luengo, Carina; Brigante, Maximiliano; Antelo, Juan; Avena, Marcelo

    2006-08-15

    The adsorption kinetics of phosphate on goethite has been studied by batch adsorption experiments and by in situ ATR-IR spectroscopy at different pH, initial phosphate concentrations and stirring rates. Batch adsorption results are very similar to those reported by several authors, and show a rather fast initial adsorption taking place in a few minutes followed by a slower process taking place in days or weeks. The adsorption kinetics could be also monitored by integrating the phosphate signals obtained in ATR-IR experiments, and a very good agreement between both techniques was found. At pH 4.5 two surface complexes, the bidentate nonprotonated (FeO)(2)PO(2) and the bidentate protonated (FeO)(2)(OH)PO complexes, are formed at the surface. There are small changes in the relative concentrations of these species as the reaction proceeds, and they seem to evolve in time rather independently. At pH 7.5 and 9 the dominating surface species is (FeO)(2)PO(2), which is accompanied by an extra unidentified species at low concentration. They also seem to evolve independently as the reaction proceeds. The results are consistent with a mechanism that involve a fast adsorption followed by a slow diffusion into pores, and are not consistent with surface precipitation of iron phosphate.

  2. Adsorption of alkyltrimethylammonium bromides at water/alkane interfaces: competitive adsorption of alkanes and surfactants.

    PubMed

    Fainerman, V B; Mucic, N; Pradines, V; Aksenenko, E V; Miller, R

    2013-11-12

    The adsorption of members of the homologous series of alkyl trimethylammonium bromides (C(n)TAB) is studied at water/alkane interfaces by drop profile analysis tensiometry. The results are discussed in terms of a competitive adsorption process of alkane and surfactant molecules. A thermodynamic model, derived originally for the adsorption of surfactant mixtures, is adapted such that it describes a competitive adsorption of the surfactant molecules from the aqueous phase and alkane molecules from the oil phase. This new model involves the interspecies attraction coefficient, which mutually increases the adsorption activities of the alkane and C(n)TAB. The effects of the alkyl chain length n of C(n)TABs and the influence of the number of C atoms in the alkane chain are discussed, and the physical quantities are compared to those determined at the aqueous solution/air interface. The new theoretical model for aqueous solution/oil interfaces is also compared to a theory that does not consider the adsorption of alkane. The proposed new model demonstrates good agreement with the experimental data.

  3. Adsorption of ammonium dinitramide (ADN) from aqueous solutions. 1. Adsorption on powdered activated charcoal.

    PubMed

    Santhosh, G; Venkatachalam, S; Ninan, K N; Sadhana, R; Alwan, S; Abarna, V; Joseph, M A

    2003-03-17

    Investigations on the adsorption of ammonium dinitramide (NH(4)N(NO(2))(2)) (ADN) from aqueous solutions on powdered activated charcoal (PAC) were carried out in order to find out an effective and easier method of separating ADN from aqueous solutions. The effectiveness of PAC in the selective adsorption of ADN from aqueous solutions of ADN (ADN-F) and ADN in presence of sulfate (SO(4)(2-)) and nitrate (NO(3)(-)) ions (ADN-PS) was examined and compared using batch and column methods. The adsorption process follows both Langmuir and Freundlich adsorption isotherms and the isotherm parameters for the models were determined. The observed data favor the formation of monolayer adsorption. The adsorption capacities were found to be 63.3, 119, 105.3 and 82 mg of ADN per g of PAC for ADN-F (batch), ADN-PS (batch), ADN-F (column) and ADN-PS (column), respectively. Break-through curves for ADN-F and ADN-PS were obtained for the optimization of separation of ADN from aqueous solutions. Elution curves were generated for the desorption of ADN from PAC using hot water as eluent.

  4. Ammonium sulfide-assisted hydrothermal activation of palygorskite for enhanced adsorption of methyl violet.

    PubMed

    Tian, Guangyan; Wang, Wenbo; Kang, Yuru; Wang, Aiqin

    2016-03-01

    Herein, palygorskite (PAL) was activated via a simple hydrothermal process in the presence of ammonium sulfide, and the effects of activation on the microstructure, physico-chemical feature and adsorption behaviors of PAL were intensively investigated. The hydrothermal process evidently improved the dispersion of PAL crystal bundles, increased surface negative charges and built more active -Si-O(-) groups served as the new "adsorption sites". The adsorption property of the activated PAL for Methyl Violet (MV) was systematically investigated by optimizing the adsorption variables, including pH, ionic strength, contact time and initial MV concentration. The activated PAL exhibited a superior adsorption capability to the raw PAL for the removal of MV (from 156.05 to 218.11mg/g). The kinetics for MV adsorption followed pseudo second-order kinetic models, while the isotherm and thermodynamics results showed that the adsorption pattern well followed the Langmuir model. The structure analysis of PAL before and after adsorption demonstrated that electrostatic interaction and chemical association of -X-O(-) are the prominent driving forces for the adsorption process.

  5. New BET-like models for heterogeneous adsorption in microporous adsorbents

    NASA Astrophysics Data System (ADS)

    Milewska-Duda, Janina; Duda, Jan T.

    2002-08-01

    The paper presents a package of isotherm equations for heterogeneous adsorption aimed at the analysis of pore structure of sub- and microporous materials. One considers adsorption of small nearly spherical molecules in irregular pores of molecular size. The generalized BET theory is exploited respecting restrictions for multilayer adsorption (LBET approach). The model is based on thermodynamic relationships expressing changes of internal energy and configurational entropy due to the process. The adsorption energy is evaluated by using the Berthelot rule, and corrected with a factor Z a representing a fraction of effective contacts enabling full adsorbent-adsorbate interaction. Side adsorbate-adsorbate interactions are neglected and constrained multilayer adsorption is considered. One assumes the values for Z a to be uniformly distributed over the first layer adsorption sites within a range depending on the pore size. New models make it possible to obtain information on structure of pores and adsorption mechanisms on the basis of adsorption isotherms of small molecule adsorbates. Exemplary results of new models application for adsorption of CO 2 and CH 4 in an activated carbon are discussed.

  6. Adsorption of V on a Hematite (0001) Surface and its Oxidation: Submonolayer Coverage

    SciTech Connect

    Jin, J.; Ma, X.; Kim, C.-Y.; Ellis, D.E.; Bedzyk, M.J.

    2008-10-06

    The adsorption of submonolayer V on an idealized model hematite (0 0 0 1) surface and subsequent oxidation under atomic O adsorption are studied by density functional theory. The preferred adsorption sites, adsorption energy and configuration changes due to V and O adsorption are investigated. It is found that in most cases V forms threefold bonds with surface O atoms, inducing a large geometry change at the hematite surface and near surface region and a bond stretch between surface Fe and O. The adsorption energy is mainly decided by interplay between adsorbed metal-surface oxygen bonding and adsorbed metal - subsurface metal interaction. The relative energy of subsequent O adsorption and geometry depends on the reformed V/hematite structure. Electronic properties such as projected densities of states and chemical state change upon V adsorption are studied through both periodic slab and embedded cluster localized orbital calculations; both strong vanadium-oxygen and vanadium-iron interactions are found. While V generally donates electrons to a hematite surface, causing nearby Fe to be partially reduced, the Fe and V oxidization state depends very much on the coverage and detailed adsorption configuration. When the V/hematite system is exposed to atomic O, V is further oxidized and surface/near surface Fe is re-oxidized. Our theoretical results are compared with X-ray surface standing wave and X-ray photoelectron spectroscopic measurements. The influence of d-electron correlation on the predicted structures is briefly discussed, making use of the DFT + U scheme.

  7. Adsorptive removal of α-endosulfan from water by hydrophobic zeolites. An isothermal study.

    PubMed

    Yonli, Arsène H; Batonneau-Gener, Isabelle; Koulidiati, Jean

    2012-02-15

    This paper deals with the removal of α-endosulfan from water over HY and steamed HBEA zeolites. Experiments were performed to understand the adsorption mechanisms of α-endosulfan on zeolites and to determine the most efficient adsorbent for the purification of water contaminated by this pesticide. The experiments exhibit that α-endosulfan was adsorbed in the micropores. In the case of HY zeolites an adsorption of α-endosulfan molecules on BrØnsted sites was pointed out, due to a preferential water adsorption in mesopores. Moreover a physisorption of α-endosulfan occurred in micropores. For steamed HBEA zeolites physisorption in micropores was pointed out as the adsorption mode. For both types of zeolites a decrease of the adsorption capacities was noticed when the acidity of zeolites increased. There was also a linear relation between the adsorption capacities of α-endosulfan and the hydrophobicity (HI) of the samples and by determining the values of HI for a type of zeolite it was possible to deduce the uptake of α-endosulfan. The HY(40) sample was the most efficient for the removal of α-endosulfan from water because of preferential adsorption of water molecules in mesopores and lower acidity. For this sample the adsorption capacity for α-endosulfan was about 833.33 mg/g where for the most effective HBEA sample (St700(3)) the adsorption capacity was about 793.65 mg/g.

  8. Adsorption of a cationic surfactant by a magsorbent based on magnetic alginate beads.

    PubMed

    Obeid, Layaly; El Kolli, Nadia; Dali, Noëlle; Talbot, Delphine; Abramson, Sébastien; Welschbillig, Mathias; Cabuil, Valérie; Bée, Agnès

    2014-10-15

    Adsorption of cetylpyridinium chloride (CPC), a cationic surfactant, by magnetic alginate beads (MagAlgbeads) was investigated. The magnetic adsorbent (called magsorbent) was prepared by encapsulation of magnetic functionalized nanoparticles in an alginate gel. The influence on CPC adsorption of several parameters such as contact time, pH and initial surfactant concentration was studied. The equilibrium isotherm shows that adsorption occurs through both electrostatic interactions with charge neutralization of the carboxylate groups of the beads and hydrophobic interactions inducing the formation of surfactant aggregates in the beads. The dosage of calcium ions released in the solution turns out to be a useful tool for understanding the adsorption mechanisms. Adsorption is accompanied by a shrinking of the beads that corresponds to a 45% reduction of the volume. Adsorption kinetic experiments show that equilibrium time is strongly dependent on the surfactant concentration, which monitors the nature of the interactions. On the other hand, since the pH affects the ionization state of adsorption sites, adsorption depends on the pH solution, maximum adsorption being obtained in a large pH range (3.2-12) in agreement with the pKa value of alginate (pKa=3.4-4.2). Finally, due to the formation of micelle-like surfactants aggregates in the magnetic alginate beads, they could be used as a new efficient magsorbent for hydrophobic pollutants.

  9. Effect of organic waste amendments on zinc adsorption by two soils

    SciTech Connect

    Shuman, L.M. . Georgia Experiment station)

    1999-03-01

    Two soils (fine and coarse textured) were amended with five organic wastes or humic acid. One adsorption experiment was carried out at 1 mmol L[sup [minus]1] Zn and at pH levels from 4 to 8. A second experiment was at pH 6 and 0 to 4 mmol/L[sup [minus]1] Zn. The greatest variation in Zn adsorption among organic treatments came at pH 6, with a lesser range for the fine textured soil (pH 5--6) and a wider range for the sandy soil (pH 5--7). Adsorption followed a two-site Langmuir model, and maxima were higher for the finer textured soil compared with the sandy soil. Adsorption maxima were not changed by the organic wastes for the fine textured soil, but all were increased over the controls for the sandy soil. Zinc adsorption for poultry litter was lower than the control for the sandy soil. Industrial sewage sludge and humic acid increased Zn adsorption more than did commercial compost, spent mushroom compost, and cotton litter. It was concluded that organic materials have more influence on Zn adsorption for sandy soils than for fine textured soils and that most materials will increase Zn adsorption, whereas those with high soluble C can decrease Zn adsorption.

  10. Adsorption energy distribution of carbon tetrachloride on carbon nanofiber arrays prepared by template synthesis

    NASA Astrophysics Data System (ADS)

    Wu, Chi-Hsin; Shr, Jin-Fang; Wu, Chu-Fu; Hsieh, Chien-Te

    2008-02-01

    The influence of pore size distribution on adsorption energy distributions (AEDs) of aligned carbon nanofiber (CNF) arrays in vapor phase was conducted in the present study. A template-assisted synthesis was employed to fabricate aligned CNF arrays with different pore size distributions (PSDs). Adsorption isotherms of CCl 4 onto the CNF arrays were investigated within an entire pressure of 0.05-0.18 atm at 30 °C. The adsorptive surface coverage was found to decrease with the average pore size, indicating the presence of heterogeneity for gas adsorption. An AED model was postulated to describe the heterogeneous surface consisting of numerous surface pitchwises that obey a localized Langmuir model. It was found that all CNF arrays exhibit a similar Gaussian-type AED, in where the peak adsorption energy shifts to a higher energy with decreasing the pore size of CNFs. This finding can be ascribed to a fact that micropores are major providers of adsorption sites, whereas in mesopores only weaker adsorption is observed, thus resulting in the shift of energy distribution. An excellent prediction to the adsorption isotherms of CCl 4 by the AED model indicates that the PSD of CNFs acts a crucial factor in affecting the adsorptive coverage.

  11. IgG adsorption on a new protein A adsorbent based on macroporous hydrophilic polymers. I. Adsorption equilibrium and kinetics.

    PubMed

    Perez-Almodovar, Ernie X; Carta, Giorgio

    2009-11-20

    Experimental determination and modeling of IgG binding on a new protein A adsorbent based on a macroporous resin were performed. The new adsorbent consists of polymeric beads based on hydrophilic acrylamido and vinyl monomers with a pore structure optimized to allow favorable interactions of IgG with recombinant protein A coupled to the resin. The particles have average diameter of 57 microm and a narrow particle size distribution. The IgG adsorption equilibrium capacity is 46 mg/cm(3) and the effective pore diffusivity determined from pulse response experiments for non-binding conditions is 8.0 x 10(-8) cm(2)/s. The IgG adsorption kinetics can be described with the same effective diffusivity by taking into account a heterogeneous binding mechanism with fast binding sites, for which adsorption is completely diffusion controlled, and slow binding sites for which adsorption is controlled by the binding kinetics. As a result of this mechanism, the breakthrough curve exhibits a tailing behavior, which appears to be associated with the slow binding sites. A detailed rate model taking into account intraparticle diffusion and binding kinetics is developed and is found capable of predicting both batch adsorption and breakthrough behavior over an ample range of experimental conditions. The corresponding effective diffusivity is independent of protein concentration in solution over the range 0.2-2 mg/cm(3) and of protein binding as a result of the large pore size of the support matrix. Overall, the small particle size and low diffusional hindrance allow capture of IgG with short residence times while attaining substantial dynamic binding capacities.

  12. Adsorption of basic dyes from aqueous solution onto pumice powder.

    PubMed

    Akbal, Feryal

    2005-06-15

    The adsorption of methylene blue and crystal violet on pumice powder samples of varying compositions was investigated using a batch adsorption technique. The effects of various experimental parameters, such as adsorbent dosage, initial dye concentration, and contact time, were also investigated. The extent of dye removal increased with decreased initial concentration of the dye and also increased with increased contact time and amount of adsorbent used. Adsorption data were modeled using the Freundlich adsorption isotherm. The adsorption kinetic of methylene blue and crystal violet could be described by the pseudo-second-order reaction model.

  13. Adsorption and transformation of tetracycline antibiotics with aluminum oxide.

    PubMed

    Chen, Wan-Ru; Huang, Ching-Hua

    2010-05-01

    Tetracycline antibiotics (TCs) including tetracycline (TTC), chlorotetracycline (CTC) and oxytetracycline (OTC) adsorb strongly to aluminum oxide (Al(2)O(3)), and the surface interaction promotes structural transformation of TCs. The latter phenomenon was not widely recognized previously. Typically, rapid adsorption of TCs to Al(2)O(3) occurs in the first 3h ([TC]=40microM, [Al(2)O(3)]=1.78gL(-1), pH=5, and T=22 degrees C), followed by continuous first-order decay of the parent compound (k(obs)=15+/-1.0, 18+/-1.0 and 6.2+/-0.9x10(-3)h(-1) for TTC, CTC and OTC, respectively) and product formation. The transformation reaction rate of TCs strongly correlates with adsorption to Al(2)O(3) surfaces. Both adsorption and transformation occur at the highest rate at around neutral pH conditions. Product evaluation indicates that Al(2)O(3) promotes dehydration of TTC to yield anhydrotetracycline (AHTTC), epimerization of TTC, and formation of Al-TTC complexes. Al(2)O(3) promotes predominantly the transformation of CTC to iso-CTC. The surface-bound Al(+III) acts as a Lewis acid site to promote the above transformation of TCs. Formation of AHTTC is of special concern because of its higher cytotoxicity. Results of this study indicate that aluminum oxide will likely affect the fate of TC antibiotics in the aquatic environment via both adsorption and transformation.

  14. Visualization of Adsorption: Luminescent Mesoporous Silica-Carbon Dots Composite for Rapid and Selective Removal of U(VI) and in Situ Monitoring the Adsorption Behavior.

    PubMed

    Wang, Zhe; Xu, Chao; Lu, Yuexiang; Wu, Fengcheng; Ye, Gang; Wei, Guoyu; Sun, Taoxiang; Chen, Jing

    2017-03-01

    The removal and separation of uranium from aqueous solutions are quite important for resource reclamation and environmental protection. Being one of the most effective techniques for metal separation, adsorption of uranium by a variety of adsorbent materials has been a subject of study with high interest in recent years. However, current methods for monitoring the adsorption process require complicated procedures and tedious measurements, which hinders the development of processes for efficient separation of uranium. In this work, we prepared a type of luminescent mesoporous silica-carbon dots composite material that has high efficiency for the adsorption of uranium and allows simultaneous in situ monitoring of the adsorption process. Carbon dots (CDs) were prepared in situ and introduced onto amino-functionalized ordered mesoporous silica (SBA-NH2) by a facile microplasma-assisted method. The prepared CDs/SBA-NH2 nanocomposites preserved the high specific surface area of the mesoporous silica, as well as the fluorescent properties of the CDs. Compared with bare SBA-NH2, the CDs/SBA-NH2 nanocomposites showed much improved adsorption ability and excellent selectivity for uranyl ions. Moreover, the fluorescence intensity of the composites decreased along with the increase of uranium uptake, indicating that the CDs/SBA-NH2 nanocomposites could be used for on-site monitoring of the adsorption behavior. More interestingly, the adsorption selectivity of the composites for metal ions was in good agreement with the selective fluorescence response of the original CDs, which means that the adsorption selectivity of CDs-based composite materials can be predicted by evaluating the fluorescence selectivity of the CDs for metal ions. As the first study of CDs-based nanocomposites for the adsorption of actinide elements, this work opens a new avenue for the in situ monitoring of adsorption behavior of CDs-based nanocomposites while extending their application areas.

  15. Adsorption orientations and immunological recognition of antibodies on graphene

    NASA Astrophysics Data System (ADS)

    Vilhena, J. G.; Dumitru, A. C.; Herruzo, Elena T.; Mendieta-Moreno, Jesús I.; Garcia, Ricardo; Serena, P. A.; Pérez, Rubén

    2016-07-01

    Large-scale molecular dynamics (MD) simulations and atomic force microscopy (AFM) in liquid are combined to characterize the adsorption of Immunoglobulin G (IgG) antibodies over a hydrophobic surface modeled with a three-layer graphene slab. We consider explicitly the water solvent, simulating systems with massive sizes (up to 770 000 atoms), for four different adsorption orientations. Protocols based on steered MD to speed up the protein diffusion stage and to enhance the dehydration process are combined with long simulation times (>150 ns) in order to make sure that the final adsorption states correspond to actual stable configurations. Our MD results and the AFM images demonstrate that the IgG antibodies are strongly adsorbed, do not unfold, and retain their secondary and tertiary structures upon deposition. Statistical analysis of the AFM images shows that many of the antibodies adopt vertical orientations, even at very small coverages, which expose at least one Fab binding site for recognition events. Single molecule force spectroscopy experiments demonstrate the immunological response of the deposited antibodies by recognizing its specific antigens. The above properties together with the strong anchoring and preservation of the secondary structure, make graphene an excellent candidate for the development of immunosensors.Large-scale molecular dynamics (MD) simulations and atomic force microscopy (AFM) in liquid are combined to characterize the adsorption of Immunoglobulin G (IgG) antibodies over a hydrophobic surface modeled with a three-layer graphene slab. We consider explicitly the water solvent, simulating systems with massive sizes (up to 770 000 atoms), for four different adsorption orientations. Protocols based on steered MD to speed up the protein diffusion stage and to enhance the dehydration process are combined with long simulation times (>150 ns) in order to make sure that the final adsorption states correspond to actual stable configurations. Our

  16. A comparative adsorption study: 17β-estradiol onto aerobic granular sludge and activated sludge.

    PubMed

    Zheng, Xiao-ying; He, Yu-jie; Chen, Wei; Wang, Ming-yang; Cao, Su-lan; Ni, Ming; Chen, Yu

    2016-01-01

    Adsorption plays a significant role in removing hydrophobic 17β-estradiol (E2) from wastewater. Batch experiments were conducted to compare the adsorption of E2 onto activated aerobic granular sludge (AGS) and activated sludge (AS), and features evaluated included the adsorption kinetics, thermodynamics, and influence of other environmental factors. By using a non-chemical wet-heat technique, both AGS and AS were treated to inactivated status. Then, after loading E2, the adsorption equilibrium capacity of the AGS was found to be greater than that of the AS at the same initial concentration of E2. Moreover, both the adsorption processes corresponded to a pseudo-second-order kinetic model; the adsorption rate constant of AGS was found to be higher and the half-adsorption time was shorter than that of AS. Next, evaluations of adsorption isotherms and thermodynamics indicated that the adsorption process was mainly a physical process. Lower temperatures facilitated a higher equilibrium adsorption capacity. However, the adsorption binding sites of AGS were distributed more uniformly at higher temperature, in contrast to the distribution found for AS. Finally, acidic conditions and an appropriate ionic strength (0.4 mol/L) were found to be particularly conducive to the adsorption process. Overall, the results showed that AGS has the potential to adsorb E2 with significant efficiency, thereby offering a new and more efficient means of treating E2 and trace oestrogens in wastewater.

  17. [Adsorption dynamics and breakthrough characteristics based on the fluidization condition].

    PubMed

    Wang, Jun; Wang, Yao; Huang, Xing; Yuan, Yi-Long; Chen, Rui-Hui; Zhou, Hang; Zhou, Dan-Dan

    2014-02-01

    Few studies on the adsorption dynamics and breakthrough characteristics based on the fluidization condition have been reported. In a fluidized bed adsorption reactor with phenol as the adsorbate and granular activated carbon as the adsorbent, the adsorption efficiency, adsorption dynamic characteristics, adsorption breakthrough curves and adsorption capacities were studied and compared with those of a fixed bed operated under the same conditions. The results showed that the adsorption efficiencies exceeded 93% in 5 min in both the fluidized conditions and fixed conditions at the superficial velocities of 8 mm x s(-1) and 13 mm x s(-1). Meanwhile, the above adsorption reactions fitted to Pseudo-second-order with linear correlation coefficients greater than 0.999. The adsorption capacity of fluidized conditions was 8.77 mg x g(-1) and 24.70 mg x g(-1) at the superficial velocities of 6 mm x s(-1) and 8 mm x s(-1). Generally, the fluidized bed reactor showed a higher adsorption efficiency and greater adsorption capacity than the fixed bed reactor.

  18. Adsorption of selected volatile organic vapors on multiwall carbon nanotubes.

    PubMed

    Shih, Yang-hsin; Li, Mei-syue

    2008-06-15

    Carbon nanotubes are expected to play an important role in sensing, pollution treatment and separation techniques. This study examines the adsorption behaviors of volatile organic compounds (VOCs), n-hexane, benzene, trichloroethylene and acetone on two multiwall carbon nanotubes (MWCNTs), CNT1 and CNT2. Among these VOCs, acetone exhibits the highest adsorption capacity. The highest adsorption enthalpies and desorption energies of acetone were also observed. The strong chemical interactions between acetone and both MWCNTs may be the result from chemisorption on the topological defects. The adsorption heats of trichloroethylene, benzene, and n-hexane are indicative of physisorption on the surfaces of both MWCNTs. CNT2 presents a higher adsorption capacity than CNT1 due to the existence of an exterior amorphous carbon layer on CNT2. The amorphous carbon enhances the adsorption capacity of organic chemicals on carbon nanotubes. The morphological and structure order of carbon nanotubes are the primary affects on the adsorption process of organic chemicals.

  19. Adsorption of EDTA on activated carbon from aqueous solutions.

    PubMed

    Zhu, Hai-song; Yang, Xiao-juan; Mao, Yan-peng; Chen, Yu; Long, Xiang-li; Yuan, Wei-kang

    2011-01-30

    In this study, the adsorption of EDTA on activated carbon from aqueous solutions has been investigated in a batch stirred cell. Experiments have been carried out to investigate the effects of temperature, EDTA concentration, pH, activated carbon mass and particle size on EDTA adsorption. The experimental results manifest that the EDTA adsorption rate increases with its concentration in the aqueous solutions. EDTA adsorption also increases with temperature. The EDTA removal from the solution increases as activated carbon mass increases. The Langmuir and Freundlich equilibrium isotherm models are found to provide a good fitting of the adsorption data, with R(2) = 0.9920 and 0.9982, respectively. The kinetic study shows that EDTA adsorption on the activated carbon is in good compliance with the pseudo-second-order kinetic model. The thermodynamic parameters (E(a), ΔG(0), ΔH(0), ΔS(0)) obtained indicate the endothermic nature of EDTA adsorption on activated carbon.

  20. Adsorption of crude oil on anhydrous and hydrophobized vermiculite.

    PubMed

    da Silva, Umberto G; de F Melo, Marcus A; da Silva, Adaílton F; de Farias, Robson F

    2003-04-15

    This publication reports the adsorption of crude oil on vermiculite samples, expanded and hydrophobized with carnauba (Copernícia Cerífera) wax. The adsorption studies were performed by using columns filled with the vermiculite matrices and by dispersion of the vermiculite samples in an oil-water (50 ppm of oil) emulsion. The hydrate vermiculite exhibits a very low adsorption capacity against crude oil. On the other hand, anhydrous (expanded) and hydrophobized matrices show a high adsorption capacity. The 10% hydrophobized matrix show a 50% increased adsorption capacity, in comparison with the expanded one. For adsorption performed in the water-oil emulsion, saturation of the solid hydrophobized matrix is achieved after 60 min. The hydrophobized samples exhibit adsorption factors in the 0.7-1.0 range.

  1. Screening of active metals for reactive adsorption desulfurization adsorbent using density functional theory

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Zhao, Liang; Xu, Chunming; Wang, Yuxian; Gao, Jinsen

    2017-03-01

    To explore characteristics of active metals for reactive adsorption desulfurization (RADS) technology, the adsorption of thiophene on M (100) (M = Cr, Mo, Co, Ni, Cu, Au, and Ag) surfaces was systematically studied by density functional theory with vdW correction (DFT + D3). We found that, in all case, the most stable molecular adsorption site was the hollow site and adsorptive capabilities of thiophene followed the order: Cr > Mo > Co ≈ Ni > Cu > Au ≈ Ag. By analyzing the nature of binding between thiophene and corresponding metals and the electronic structure of metals, the excessive activities of Cr and Mo were found to have a negative regeneration, the passive activities of Au and Ag were found to have an inactive adsorption for RADS adsorbent alone, while Ni and Co have appropriate characteristics as the active metals for RADS, followed by Cu.

  2. Thermodynamic formalism of water uptakes on solid porous adsorbents for adsorption cooling applications

    NASA Astrophysics Data System (ADS)

    Sun, Baichuan; Chakraborty, Anutosh

    2014-05-01

    This Letter presents a thermodynamic formulation to calculate the amount of water vapor uptakes on various adsorbents such as zeolites, metal organic frameworks, and silica gel for the development of an advanced adsorption chiller. This formalism is developed from the rigor of the partition distribution function of each water vapor adsorptive site on adsorbents and the condensation approximation of adsorptive water molecules and is validated with experimental data. An interesting and useful finding has been established that the proposed model is thermodynamically connected with the pore structures of adsorbent materials, and the water vapor uptake highly depends on the isosteric heat of adsorption at zero surface coverage and the adsorptive sites of the adsorbent materials. Employing the proposed model, the thermodynamic trends of water vapor uptakes on various adsorbents can be estimated.

  3. Molecular basis for the high CO2 adsorption capacity of chabazite zeolites.

    PubMed

    Pham, Trong D; Hudson, Matthew R; Brown, Craig M; Lobo, Raul F

    2014-11-01

    CO2 adsorption in Li-, Na-, K-CHA (Si/Al=6,=12), and silica chabazite zeolites was investigated by powder diffraction. Two CO2 adsorption sites were found in all chabazites with CO2 locating in the 8-membered ring (8MR) pore opening being the dominant site. Electric quadrupole-electric field gradient and dispersion interactions drive CO2 adsorption at the middle of the 8 MRs, while CO2 polarization due to interaction with cation sites controls the secondary CO2 site. In Si-CHA, adsorption is dominated by dispersion interactions with CO2 observed on the pore walls and in 8 MRs. CO2 adsorption complexes on dual cation sites were observed on K-CHA, important for K-CHA-6 samples due to a higher probability of two K(+) cations bridging CO2. Trends in isosteric heats of CO2 adsorption based on cation type and concentration can be correlated with adsorption sites and CO2 quantity. A decrease in the hardness of metal cations results in a decrease in the direct interaction of these cations with CO2.

  4. Goethite surface reactivity: a macroscopic investigation unifying proton, chromate, carbonate, and lead(II) adsorption.

    PubMed

    Villalobos, Mario; Pérez-Gallegos, Ayax

    2008-10-15

    The goethite surface structure has been extensively studied, but no convincing quantitative description of its highly variable surface reactivity as inversely related to its specific surface area (SSA) has been found. The present study adds experimental evidence and provides a unified macroscopic explanation to this anomalous behavior from differences in average adsorption capacities, and not in average adsorption affinities. We investigated the chromate anion and lead(II) cation adsorption behavior onto three different goethites with SSA varying from 50 to 94 m(2)/g, and analyzed an extensive set of published anion adsorption and proton charging data for variable SSA goethites. Maximum chromate adsorption was found to occupy on average from 3.1 to 9.7 sites/nm(2), inversely related to SSA. Congruency of oxyanion and Pb(II) adsorption behavior based on fractional site occupancy using these values, and a site density analysis suggest that: (i) ion binding occurs to singly and doubly coordinated sites, (ii) proton binding occurs to singly and triply coordinated sites (ranging from 6.2 to 8 total sites/nm(2), in most cases), and (iii) a predominance of (210) and/or (010) faces explains the high reactivity of low SSA goethites. The results imply that the macroscopic goethite adsorption behavior may be predicted without a need to investigate extensive structural details of each specific goethite of interest.

  5. Ibuprofen adsorption in four agricultural volcanic soils.

    PubMed

    Estevez, Esmeralda; Hernandez-Moreno, Jose Manuel; Fernandez-Vera, Juan Ramon; Palacios-Diaz, Maria Pino

    2014-01-15

    Ibuprofen (IB) is a high environmental risk drug and one of the most frequently prescribed in human medicine. Recently, IB has been detected in Gran Canaria in reclaimed water for irrigation and in groundwater. Adsorption was studied in four volcanic soils from three islands of the Canarian Archipelago. Once the biodegradation process has been excluded from the experimental conditions, a batch method was applied using initial concentrations of 1-5-10-20-50-100-200 mg L(-1) and two soil/water ratios (w/V): 1:5 (OECD, 2000) and 1:1. Non-linear and linearized Langmuir and Freundlich equations were well fitted. The wide IB range tested in our batch studies allowed us to measure experimental adsorption values close to the maximum adsorption capacity (S(max)) as estimated by Langmuir, making it possible thereby to validate the use of the Langmuir equation when there is a burst of contamination at high concentration. The distribution coefficient (Kd), S(max) and Retardation Factor (RF) varied from 0.04 to 0.5 kg L(-1), 4-200 mgk g(-1) and 1.2-1.9, respectively. The lowest S(max) and Kd values were found for the 1:1S/W ratio whereas most batch studies employ 1:5S/W ratios, thus obtaining higher adsorption parameters than when considering field conditions (1:1). Despite the high anion retention of andic soils, similar Kd and RF to those reported for other soils were obtained in 1:5, while high S(max) was found. Our results demonstrate that IB adsorption in volcanic areas responds not only to the soil properties commonly cited in adsorption studies, but also depends on andic properties, sorbent concentration and Dissolved Organic Carbon, the higher values of which are related to the lower Kd and S(max). The low RF and low detection frequency of the IB in groundwater suggests that a) reclaimed water irrigation is not the main source of IB, and b) the existence of some uncontrolled water disposal points in the zone.

  6. SO2 adsorption on silica supported iridium

    NASA Astrophysics Data System (ADS)

    Bounechada, Djamela; Anderson, David P.; Skoglundh, Magnus; Carlsson, Per-Anders

    2017-02-01

    The interaction of SO2 with Ir/SiO2 was studied by simultaneous in situ diffuse reflectance infrared Fourier transform spectroscopy and mass spectrometry, exposing the sample to different SO2 concentrations ranging from 10 to 50 ppm in the temperature interval 200-400 °C. Evidences of adsorption of sulfur species in both absence and presence of oxygen are found. For a pre-reduced sample in the absence of oxygen, SO2 disproportionates such that the iridium surface is rapidly saturated with adsorbed S while minor amounts of formed SO3 may adsorb on SiO2. Adding oxygen to the feed leads to the oxidation of sulfide species that either (i) desorb as SO2 and/or SO3, (ii) remain at metal sites in the form of adsorbed SO2, or (iii) spillover to the oxide support and form sulfates (SO42-). Notably, significant formation of sulfates on silica is possible only in the presence of both SO2 and O2, suggesting that SO2 oxidation to SO3 is a necessary first step in the mechanism of formation of sulfates on silica. During the formation of sulfates, a concomitant removal/rearrangement of surface silanol groups is observed. Finally, the interaction of SO2 with Ir/SiO2 depends primarily on the temperature and type of gas components but only to a minor extent on the inlet SO2 concentration.

  7. Adsorption of bacteriophages on clay minerals

    USGS Publications Warehouse

    Chattopadhyay, Sandip; Puls, Robert W.

    1999-01-01

    The ability to predict the fate of microorganisms in soil is dependent on an understanding of the process of their sorption on soil and subsurface materials. Presently, we have focused on studying the thermodynamics of sorption of bacteriophages (T-2, MS-2, and φX-174) on clays (hectorite, saponite, kaolinite, and clay fraction of samples collected from a landfill site). The thermodynamic study not only determines the feasibility of the process but also provides information on the relative magnitudes of the different forces under a particular set of conditions. The total free energy of interaction during sorption of bacteriophages on clays (ΔG) has been assumed to be the summation of ΔGH (ΔG due to hydrophobic interactions) and ΔGEL (ΔG due to electrostatic interactions). The magnitude of ΔGH was determined from the different interfacial tensions (γ) present in the system, while ΔGEL was calculated from ζ-potentials of the colloidal particles. Calculated results show that surface hydrophobicities of the selected sorbents and sorbates dictate sorption. Among the selected bacteriophages, maximum sorption was observed with T-2, while hectorite has the maximum sorption capacity. Experimental results obtained from the batch adsorption studies also corroborated those obtained from the theoretical study.

  8. Evaluation of the adsorption capacity of alkali-treated waste materials for the adsorption of sulphamethoxazole.

    PubMed

    Kurup, Lisha

    2012-01-01

    The present work is to develop potential adsorbents from waste material and employ them for the removal of a hazardous antibacterial, sulphamethoxazole, from the wastewater by the Adsorption technique. The Adsorption technique was used to impound the dangerous antibiotics from wastewater using Deoiled Soya (DOS), an agricultural waste, and Water Hyacinth (WH), a prolific colonizer. The adsorption capacity of these adsorbents was further enhanced by treating them with sodium hydroxide solution and it was seen that the adsorption capacity increases by 10 to 25%. Hence a comparative account of the adsorption studies of all the four adsorbents, i.e. DOS, Alkali-treated DOS, WH and Alkali-treated Water Hyacinth has been discussed in this paper. Different isotherms like Freundlich, Langmuir and Dubinin-Radushkevich were also deduced from the adsorption data. Isotherm studies were in turn used in estimating the thermodynamic parameters. DOS showed sorption capacity of 0.0007 mol g(-1) while Alkali-treated Deoiled Soya exhibited 0.0011 mol g(-1) of sorption capacity, which reveals that the adsorption is higher in case of alkali-treated adsorbent. The mean sorption energy (E) was obtained between 9 and 12 kJ mol, which shows that the reaction proceeds by ion exchange reaction. Kinetic study reveals that the reaction follows pseudo-second-order rate equation. Moreover, mass transfer studies performed for the ongoing processes show that the mass transfer coefficient obtained for alkali-treated moieties was higher than the parent moieties. The breakthrough curves plotted from the column studies show percentage saturation of 90-98%. About 87-97% of sulphamethoxazole was recovered from column by desorption.

  9. [Characteristic of ammonia nitrogen adsorption on karst underground river sediments].

    PubMed

    Guo, Fang; Chen, Kun-Kun; Jiang, Guang-Hui

    2011-02-01

    Karst aquifers are one of the most important aquifers in Southwestern China. One of the characteristics of karst aquifers is the enhanced permeability permits high flow velocities are capable of transporting suspended and bedload sediments. Mobile sediment in karst may act as a vector for the transport of contaminates. 14 sediment samples were collected from two underground rivers in two typical karst areas in Liuzhou city, Guangxi Autonomous Region, China. According to simulated experiment methods, characteristic of adsorption of ammonia nitrogen on sediment was studied. The results of ammonia nitrogen adsorption dynamics on sediments showed that the maximum adsorption velocity was less than 2 h. The adsorption balance quantity in 5 h accounted for 71% - 98% of the maximum adsorption quantity. The maximum adsorption quantity of ammonia nitrogen was 385.5 mg/kg, which was sediment from a cave in the middle areas of Guancun underground river system. The study of isotherm adsorption indicated adsorption quantity of NH4+ increase followed by incremental balance concentration of NH4+ in the aquatic phase. Adsorption quantity of ammonia nitrogen in sediments has a relative linear relationship with adsorption balance concentrations. Adsorption-desorption balance concentrations were all low, indicating sediments from underground rivers have great adsorption potential. Under the condition of low and high concentrations of ammonia nitrogen in overlying water, Langmuir and Tempkin couldn't simulate or simulate results couldn't reach remarkable level, whilst Linear and Freundlich models could simulate well. Research on different type sediments, sampling times and depths from two underground rivers shows characteristic of ammonia nitrogen adsorption on karst underground river sediments doesn't have good correspondence with the type of sediments. One of the reasons is there is no big difference between sediments in the development of climate, geology, hydrological conditions

  10. Phosphate adsorption performance of a novel filter substrate made from drinking water treatment residuals.

    PubMed

    Wang, Wendong; Ma, Cui; Zhang, Yinting; Yang, Shengjiong; Shao, Yue; Wang, Xiaochang

    2016-07-01

    Phosphate is one of the most predominant pollutants in natural waters. Laboratory experiments were conducted to investigate the phosphate adsorption performance of a (NFS) made from drinking water treatment residuals. The adsorption of phosphate on the NFS fitted well with the Freundlich isotherm and pseudo second-order kinetic models. At pH7.0, the maximum adsorption capacity of 1.03mg/g was achieved at 15°C corresponding to the wastewater temperature in cold months, and increased notably to 1.31mg/g at 35°C. Under both acidic conditions (part of the adsorption sites was consumed) and basic conditions (negative charges formed on the surface of NFS, which led to a static repulsion of PO4(3-) and HPO4(2-)), the adsorption of phosphate was slightly inhibited. Further study showed that part of the adsorption sites could be recovered by 0.25mol/L NaOH. The activation energy was calculated to be above 8.0kJ/mol, indicating that the adsorption of phosphate on NFS was probably a chemical process. Considering the strong phosphate adsorption capacity and recoverability, NFS showed great promise on enhancing phosphate removal from the secondary treated wastewater in the filtration process.

  11. Adsorption of SO2 on bituminous coal char and activated carbon fiber

    USGS Publications Warehouse

    DeBarr, Joseph A.; Lizzio, Anthony A.; Daley, Michael A.

    1997-01-01

    The SO2 adsorption behaviors of activated carbons produced from Illinois coal and of commercially prepared activated carbon fibers (ACFs) were compared. There was no relation between surface area of coal-based carbons and SO2 adsorption, whereas adsorption of SO2 on the series of ACFs was inversely proportional to N2 BET surface area. Higher surface area ACFs had wider pores and adsorbed less SO2; thus, pore size distribution is thought to play a significant role in SO2 adsorption for these materials. Oxidation with HNO3 and/or H2SO4, followed by heat treatment at 700−925°C to remove carbon−oxygen complexes, resulted in increased SO2 adsorption for both coal chars and ACFs. This behavior was explained by an increase in the available number of free sites, previously occupied by oxygen and now available for SO2 adsorption. The use of nitrogen-containing functional groups on ACFs of proper pore size shows promise for further increasing SO2 adsorption capacities. Knowledge of the relationship among the number of free sites, pore size, and surface chemistry on corresponding SO2 adsorption should lead to the development of more efficient adsorbents prepared from either coal or ACFs.

  12. Surface chemistry of ferrihydrite: Part 2. Kinetics of arsenate adsorption and coprecipitation

    USGS Publications Warehouse

    Fuller, C.C.; Dadis, J.A.; Waychunas, G.A.

    1993-01-01

    The kinetics of As(V) adsorption by ferrihydrite was investigated in coprecipitation and postsynthesis adsorption experiments conducted in the pH range 7.5-9.0. In coprecipitation experiments, As(V) was present in solution during the hydrolysis and precipitation of iron. In adsorption experiments, a period of rapid (<5 min) As(V) uptake from solution was followed by continued uptake for at least eight days, as As(V) diffused to adsorption sites on ferrihydrite surfaces within aggregates of colloidal particles. The time dependence of As(V) adsorption is well described by a general model for diffusion into a sphere if a subset of surface sites located near the exterior of aggregates is assumed to attain adsorptive equilibrium rapidly. The kinetics of As(V) desorption after an increase in pH were also consistent with diffusion as a rate-limiting process. Aging of pure ferrihydrite prior to As(V) adsorption caused a decrease in adsorption sites on the precipitate owing to crystallite growth. In coprecipitation experiments, the initial As(V) uptake was significantly greater than in post-synthesis adsorption experiments, and the rate of uptake was not diffusion limited because As(V) was coordinated by surface sites before crystallite growth and coagulation processes could proceed. After the initial adsorption, As(V) was slowly released from coprecipitates for at least one month, as crystallite growth caused desorption of As(V). Adsorption densities as high as 0.7 mole As(V) per mole of Fe were measured in coprecipitates, in comparison to 0.25 mole As(V) per mole of Fe in post-synthesis adsorption experiments. Despite the high Concentration of As(V) in the precipitates, EXAFS spectroscopy (Waychunas et al., 1993) showed that neither ferric arsenate nor any other As-bearing surface precipitate or solid solution was formed. The high adsorption densities are possible because the ferrihydrite particles are extremely small, approaching the size of small dioctahedral chains at

  13. Adsorption of Atmospheric Gases on Pu Surfaces

    SciTech Connect

    Nelson, A J; Holliday, K S; Stanford, J A; Grant, W K; Erler, R G; Allen, P G; McLean, W; Roussel, P

    2012-03-29

    Surface adsorption represents a competition between collision and scattering processes that depend on surface energy, surface structure and temperature. The surface reactivity of the actinides can add additional complexity due to radiological dissociation of the gas and electronic structure. Here we elucidate the chemical bonding of gas molecules adsorbed on Pu metal and oxide surfaces. Atmospheric gas reactions were studied at 190 and 300 K using x-ray photoelectron spectroscopy. Evolution of the Pu 4f and O 1s core-level states were studied as a function of gas dose rates to generate a set of Langmuir isotherms. Results show that the initial gas dose forms Pu{sub 2}O{sub 3} on the Pu metal surface followed by the formation of PuO{sub 2} resulting in a layered oxide structure. This work represents the first steps in determining the activation energy for adsorption of various atmospheric gases on Pu.

  14. Removal of mercury by adsorption: a review.

    PubMed

    Yu, Jin-Gang; Yue, Bao-Yu; Wu, Xiong-Wei; Liu, Qi; Jiao, Fei-Peng; Jiang, Xin-Yu; Chen, Xiao-Qing

    2016-03-01

    Due to natural and production activities, mercury contamination has become one of the major environmental problems over the world. Mercury contamination is a serious threat to human health. Among the existing technologies available for mercury pollution control, the adsorption process can get excellent separation effects and has been further studied. This review is attempted to cover a wide range of adsorbents that were developed for the removal of mercury from the year 2011. Various adsorbents, including the latest adsorbents, are presented along with highlighting and discussing the key advancements on their preparation, modification technologies, and strategies. By comparing their adsorption capacities, it is evident from the literature survey that some adsorbents have shown excellent potential for the removal of mercury. However, there is still a need to develop novel, efficient adsorbents with low cost, high stability, and easy production and manufacture for practical utility.

  15. Carbon adsorption system protects LPG storage sphere

    SciTech Connect

    Gothenquist, C.A.; Rooker, K.M.

    1996-07-01

    Chevron U.S.A. Products Co. installed a carbon adsorption system to protect an LPG storage sphere at its refinery in Richmond, Calif. Vessel damage can result when amine contamination leads to emulsion formation and consequent amine carry-over, thus promoting wet-H{sub 2}S cracking. In Chevron`s No. 5 H{sub 2}S recovery plant, a mixture of butane and propane containing H{sub 2}S is contacted with diethanolamine (DEA) in a liquid-liquid absorber. The absorber is a countercurrent contactor with three packed beds. Because the sweetening system did not include a carbon adsorption unit for amine purification, contaminants were building up in the DEA. The contaminants comprised: treatment chemicals, hydrocarbons, foam inhibitors, and amine degradation products. The paper describes the solution to this problem.

  16. Alkoxysilane adsorption on metal oxide substrates

    NASA Technical Reports Server (NTRS)

    Ramsier, R. D.; Zhuang, G. R.; Henriksen, P. N.

    1989-01-01

    Reflection-absorption infrared and inelastic electron tunneling spectroscopies have been used to study adsorption of liquid phase mono-, di-, and trialkoxysilanes on evaporated Al and Cu substrates. Spectral evidence shows that substrate properties influence the chemical and physical nature of trialkoxysilane films and that silane functionality plays a role in molecular orientation. Results show that dialkoxysilane films contain structural gradients, with adsorption at the monomolecular level influenced by surface morphology, and with organofunctionality and dosing procedure affecting the formation of thicker films. Evidence is presented that monoalkoxysilanes react with alumina surfaces, and a broad, multipeaked band from 1600 to 1900/cm has been interpreted as characteristic of the silylated AlO(x)Pb interface.

  17. Adsorption of cellulase on cellulose: effect of physicochemical properties of cellulose on adsorption and rate of hydrolysis

    SciTech Connect

    Lee, S.B.; Shin, H.S.; Ryu, D.D.Y.

    1982-11-01

    In the cellulase-cellulose reaction system, the adsorption of cellulase on the solid cellulose substrate was found to be one of the important parameters that govern the enzymatic hydrolysis rate of cellulose. The adsorption of cellulase usually parallels the rate of hydrolysis of cellulose. The affinity for cellulase varies depending on the structural properties of cellulose. Adsorption parameters such as the half-saturation constant, the maximum adsorption constant, and the distribution coefficient for both the cellulase and cellulose have been experimentally determined for several substrates. These adsorption parameters vary with the source of cellulose and the pretreatment methods and are correlated with the crystallinity and the specific surface area of cellulose substrates. The changing pattern of adsorption profile of cellulase during the hydrolysis reaction has also been elucidated. For practical utilization of cellulosic materials, the cellulose structural properties and their effects on cellulase adsorption, and the rate of hydrolysis must be taken into consideration. (Refs. 24).

  18. Coverage dependent adsorption and co-adsorption of CO and H₂ on the CdI₂-antitype metallic Mo₂C(001) surface.

    PubMed

    Wang, Tao; Tian, Xinxin; Yang, Yong; Li, Yong-Wang; Wang, Jianguo; Beller, Matthias; Jiao, Haijun

    2015-01-21

    The adsorption and co-adsorption of CO and H2 at different coverage on the CdI2-antitype metallic Mo2C(001) surface termination have been systematically computed at the level of periodic density functional theory. Only molecular CO adsorption is possible and the monolayer coverage (1 ML) can have 16CO adsorbed at the top sites. Dissociative H2 adsorption is favored thermodynamically and the monolayer coverage (1 ML) can have 16H adsorbed at the hollow sites. Since CO has much stronger adsorption energy than H2, pre-adsorption of CO is possible. CO pre-adsorption strongly affects atomic hydrogen co-adsorption at a high CO/H2 ratio, while hardly affects that at a low CO/H2 ratio. Under ultra-high vacuum conditions (200 K, 10(-12) atm and CO/H2 = 1/1), the most stable adsorbed surface state has CO/H2 = 15/1. Comparison among the metallic terminations of the CdI2-antitype Mo2C(001), eclipsed Mo2C(001) and orthorhombic Mo2C(100) surfaces shows their different CO and hydrogen adsorption as well as activation properties, which reveals that the CdI2-antitype Mo2C(001) surface is least active. These differences come from their surface bonding properties; the CdI2-antitype Mo2C(001) surface is saturated and less metallic, while the eclipsed Mo2C(001) and orthorhombic Mo2C(100) surfaces are unsaturated and more metallic.

  19. Investigation of Hydrogen Adsorption on Single Wall Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Nam, Sang-Hun; Jeong, Seong Hun; Lee, Soon-Bo; Boo, Jin-Hyo

    We have investigated adsorption and desorption condition of atomic hydrogen on single-walled nanotubes (SWCNTs) using ultraviolet photoelectron spectroscopy (UPS) and thermal desorption spectroscopy (TDS). The SWCNTs were made by the high pressure carbon monoxide (HiPCO) method. In our results, we observe from UPS data absorptive states reduce with increasing hydrogen doses and a new peak is developed near 8.6 eV and other points. But this peak is gradually diminished with pumping time. The TDS data show two characteristic peaks at 640 and 790K. By comparing with density functional calculations, we propose these peaks to be related to the presence of atomic hydrogen. Therefore, we can know that there are two adsorption sites on SWCNTs. Also we observed physisorption and chemisorption site by pumping time. We note that the UPS data are fully recoverable after hydrogen desorption at 1200K.

  20. Adsorption of phosphate on hydroxyaluminum- and hydroxyiron-montmorillonite complexes.

    PubMed

    Zhu, Mao-Xu; Ding, Kui-Ying; Xu, Shao-Hui; Jiang, Xin

    2009-06-15

    One hydroxyaluminum-montmorillonite complex (HyAl-Mt), two hydroxyiron-montmorillonite complexes (HyFe-Mts) with different iron contents, and three hydroxyiron/aluminum-montmorillonite complexes (HyFeAl-Mts) with various Fe:Al molar ratios were synthesized. Behavior and kinetics of phosphate (P) sorption on selected Mt-complexes mentioned above were investigated under acidic conditions. The results indicated that the intercalations of polymeric HyFe and/or HyAl ions in interlayers of Na-saturated montmorillonite (Na-Mt) caused significant changes in surface properties of the Na-Mt, such as cation exchange capacity, specific surface area, pH at zero point of charge. In pH range tested (3.0-6.5), P adsorption on the Mt-complexes decreased with increasing pH, whereas the effect became weaker with increasing Fe contents in the Mt-complexes. The adsorption capacities of the HyFeAl-Mts were greater than those of the HyAl-Mt and HyFe-Mt, which could be attributed to decreasing crystallinity of Fe and Al oxides in the HyFeAl-Mts. The equilibrium adsorption of P on the Mt-complexes could be well described using the Langmuir isotherm, and the kinetics of P adsorption could be well described by both the pseudo-second-order and Elovich models. An increase in Fe contents in the Mt-complexes could enhance the initial kinetic rate of P adsorption, as suggested by the Elovich models. It is inferred that a great number of Fe-related active sorption sites have been located on the outer surfaces of the HyFe-Mt, as indicated by extremely high alpha value in the Elovich model. Previous studies focusing mainly on P sorption on HyAl-Mt complexes might have underestimated the contributions of Mt-complexes to P retention in acidic soils high in Fe contents.

  1. Mesoscopic coarse-grained simulations of lysozyme adsorption.

    PubMed

    Yu, Gaobo; Liu, Jie; Zhou, Jian

    2014-05-01

    Coarse-grained simulations are adopted to study the adsorption behavior of lysozyme on different (hydrophobic, neutral hydrophilic, zwitterionic, negatively charged, and positively charged) surfaces at the mesoscopic microsecond time scale (1.2 μs). Simulation results indicate the following: (i) the conformation change of lysozyme on the hydrophobic surface is bigger than any other studied surfaces; (ii) the active sites of lysozyme are faced to the hydrophobic surface with a "top end-on" orientation, while they are exposed to the liquid phase on the hydrophilic surface with a "back-on" orientation; (iii) the neutral hydrophilic surface can induce the adsorption of lysozyme, while the nonspecific protein adsorption can be resisted by the zwitterionic surface; (iv) when the solution ionic strength is low, lysozyme can anchor on the negatively charged surface easily but cannot adsorb on the positively charged surface; (v) when the solution ionic strength is high, the positively charged lysozyme can also adsorb on the like-charged surface; (vi) the major positive potential center of lysozyme, especially the residue ARG128, plays a vital role in leading the adsorption of lysozyme on charged surfaces; (vii) when the ionic strength is high, a counterion layer is formed above the positively charged surface, which is the key factor why lysozyme can adsorb on a like-charged surface. The coarse-grained method based on the MARTINI force field for proteins and the BMW water model could provide an efficient way to understand protein interfacial adsorption behavior at a greater length scale and time scale.

  2. SEPARATION PROCESS USING COMPLEXING AND ADSORPTION

    DOEpatents

    Spedding, J.H.; Ayers, J.A.

    1958-06-01

    An adsorption process is described for separating plutonium from a solution of neutron-irradiated uranium containing ions of a compound of plutonium and other cations. The method consists of forming a chelate complex compound with plutoniunn ions in the solution by adding a derivative of 8- hydroxyquinoline, which derivative contains a sulfonic acid group, and adsorbing the remaining cations from the solution on a cation exchange resin, while the complexed plutonium remains in the solution.

  3. Thin layer joining by gas adsorption

    NASA Astrophysics Data System (ADS)

    Taga, Yasunori; Fukumura, Toshio

    2014-10-01

    Attempt has been made to join borosilicate glass and cycloolefin (COP) polymer film by using gas adsorption method. After corona plasma treat, COP was exposed to (3-glycidoxypropyl) trimethoxysilane (GPS) and glass to (3-aminopropyl) triethoxysilane (APS) both in air atmosphere, resulting in co-adsorption of water vapor in the atmosphere and organosilane gases. Surface characterization of plasma treated and gas adsorbed surfaces was carried out by X-ray photoelectron spectroscopy (XPS) using Mg Kα X-ray source. Joining was carried out by a roll laminator after contact of both surfaces at room temperature, followed by annealing at 130 °C for 10 min. Adhesion strength was evaluated by 180 degree peel test based on ASTM D-903 and durability was examined under the conditions of 60 °C and 95% RH. It was found that after plasma treatment, complex functional groups such as Csbnd H, Csbnd O, Cdbnd O, Osbnd Cdbnd O and CO3 were found on COP and Osbnd H on glass. Thickness of GPS gas adsorption layer on COP was evaluated by the XPS to be at least 1.1 nm by taking inelastic mean free path of Si2p photoelectron into consideration. Joining force was found to be more than 5 N/25 mm corresponding to almost equal to COP bulk tensile strength. In addition, durability of this adhesion strength remained unchanged over 2000 h even after exposure to the durability test conditions of 60 °C and 95% RH. The results can be explained in terms of formation of Hsbnd H hydrogen bonding and Sisbnd O covalent bonding via silanols will be made at the interface as a result of lamination and annealing processes. In conclusion, ultrathin joining method by gas adsorption was established by the formation of hydrogen and covalent bonds at the interface by low temperature reaction process.

  4. Water Adsorption Equilibria on Microporous Carbons

    DTIC Science & Technology

    1988-11-01

    of water adsorption on activated carbon is the presence of a large hysteresis loop indicating that the amount adsorbed depends on the past exposure...conditions of the carbon. The theories to describe hysteresis in microporous adsorbents and the experimental evidence to support each theory have been...observed behaviors on activated carbon. Neither the Dubinin- Serpinsky, nor the Sircar equations provide any explanation for hysteresis . It appears that

  5. Interlamellar adsorption of carbon dioxide by smectites

    USGS Publications Warehouse

    Fripiat, J.J.; Cruz, M.I.; Bohor, B.F.; Thomas, J.

    1974-01-01

    The adsorption of CO2 at low temperature (~ -70 ??C) on thin films of homoionic smectites was studied by X-ray diffraction and by i.r. absorption. An increase in the d001 spacings of these clay films upon adsorption of CO2 was observed. In addition, a dichroic effect was readily discernible by comparing the i.r. spectra at two different orientations of the smectite films; i.e. with the film normal and tilted 35 with respect to the i.r. beam. The CO2 stretching vibration at 2350 cm-1 was used for the i.r. study. These observations conclusively show that CO2 intercalates the smectite structure rather than being adsorbed only in pores between clay tactoids- the limiting process proposed by other investigators. Adsorption isotherm data from earlier surface area studies are re-examined here through application of the Dubinin equation. Again, intercalation is demonstrated by convergence of the plotted experimental data for smectites containing large monovalent interlayer cations toward a pore volume that is near the calculated theoretical value for a monolayer of intercalated CO2. Scanning electron photomicrographs of Li-and Cs- smectites provide additional evidence that aggregation differences are not responsible for the large observed difference in BET surface areas obtained for these smectites with CO2 as the adsorbate. At low magnification, visual differences in macro-aggregates are apparent, but at high magnification no significant differences are observed in the micro-structure of individual aggregates where the major amount of gas adsorption really occurs. ?? 1974.

  6. The adsorption of sympathomimetic agents by activated carbon hemoperfusion.

    PubMed

    Horres, C R; Hill, J B; Ellis, F W

    1976-01-01

    Sympathomimetic agents with mixed and pure alpha and beta adrenergic activity are adsorbed by coconut shell activated carbon from blood, sufficiently rapidly to markedly reduce the activity of these agents. The results of this study suggest that the site of injection of sympathomimetic agents being considered for correcting hypotension during activated carbon hemoperfusion be selected to permit systemic mixing before circulation into the adsorption device.

  7. Adsorption mechanism-based screening of cyclodextrin polymers for adsorption and separation of pesticides from water.

    PubMed

    Liu, Huihui; Cai, Xiyun; Wang, Yu; Chen, Jingwen

    2011-05-01

    A rational screening of cyclodextrin-based polymer (CDP), in terms of the relationship between adsorption potential and adsorbent-adsorbate, was investigated to adsorb and separate pesticides from water. Seven spherical porous CDPs were prepared with onefold or composite cyclodextrin(s) as complex and epichlorohydrin as cross-linking reagent. The adsorption kinetics and isotherms of the polymers toward a mixture of ten distinct pesticides clearly demonstrate that the adsorbents with a homogeneous open network structure can absorb pesticides via multiple adsorption interactions such as CD inclusion, loading into swelling water and physical adsorption on network. The multivariate regression analysis distinguishes the quantitative contributions of polymer properties to its adsorption potential, among which CD content, swelling capacity and pore size appear to be major influencing factors. Consequently, a facile mixture of three CDPs (i.e., β-CDP, RM-CDP and HP-CDP) was screened to obtain above prerequisite properties. The multiplex polymer could superiorly separate the pesticides at environmentally relevant levels from water.

  8. Adsorption energies and prefactor determination for CH3OH adsorption on graphite.

    PubMed

    Doronin, M; Bertin, M; Michaut, X; Philippe, L; Fillion, J-H

    2015-08-28

    In this paper, we have studied adsorption and thermal desorption of methanol CH3OH on graphite surface, with the specific aim to derive from experimental data quantitative parameters that govern the desorption, namely, adsorption energy Eads and prefactor ν of the Polanyi-Wigner law. In low coverage regime, these two values are interconnected and usually the experiments can be reproduced with any couple (Eads, ν), which makes intercomparison between studies difficult since the results depend on the extraction method. Here, we use a method for determining independently the average adsorption energy and a prefactor value that works over a large range of incident methanol coverage, from a limited set of desorption curves performed at different heating rates. In the low coverage regime the procedure is based on a first order kinetic law, and considers an adsorption energy distribution which is not expected to vary with the applied heating rate. In the case of CH3OH multilayers, Eads is determined as 430 meV with a prefactor of 5 × 10(14) s(-1). For CH3OH submonolayers on graphite, adsorption energy of 470 ± 30 meV and a prefactor of (8 ± 3) × 10(16) s(-1) have been found. These last values, which do not change between 0.09 ML and 1 ML initial coverage, suggest that the methanol molecules form island-like structure on the graphite even at low coverage.

  9. Aqueous mercury adsorption by activated carbons.

    PubMed

    Hadi, Pejman; To, Ming-Ho; Hui, Chi-Wai; Lin, Carol Sze Ki; McKay, Gordon

    2015-04-15

    Due to serious public health threats resulting from mercury pollution and its rapid distribution in our food chain through the contamination of water bodies, stringent regulations have been enacted on mercury-laden wastewater discharge. Activated carbons have been widely used in the removal of mercuric ions from aqueous effluents. The surface and textural characteristics of activated carbons are the two decisive factors in their efficiency in mercury removal from wastewater. Herein, the structural properties and binding affinity of mercuric ions from effluents have been presented. Also, specific attention has been directed to the effect of sulfur-containing functional moieties on enhancing the mercury adsorption. It has been demonstrated that surface area, pore size, pore size distribution and surface functional groups should collectively be taken into consideration in designing the optimal mercury removal process. Moreover, the mercury adsorption mechanism has been addressed using equilibrium adsorption isotherm, thermodynamic and kinetic studies. Further recommendations have been proposed with the aim of increasing the mercury removal efficiency using carbon activation processes with lower energy input, while achieving similar or even higher efficiencies.

  10. Interfacial adsorption and aggregation of amphiphilic proteins

    NASA Astrophysics Data System (ADS)

    Cheung, David

    2012-02-01

    The adsorption and aggregation on liquid interfaces of proteins is important in many biological contexts, such as the formation of aerial structures, immune response, and catalysis. Likewise the adsorption of proteins onto interfaces has applications in food technology, drug delivery, and in personal care products. As such there has been much interest in the study of a wide range of biomolecules at liquid interfaces. One class of proteins that has attracted particular attention are hydrophobins, small, fungal proteins with a distinct, amphiphilic surface structure. This makes these proteins highly surface active and they recently attracted much interest. In order to understand their potential applications a microscopic description of their interfacial and self-assembly is necessary and molecular simulation provides a powerful tool for providing this. In this presentation I will describe some recent work using coarse-grained molecular dynamics simulations to study the interfacial and aggregation behaviour of hydrophobins. Specifically this will present the calculation of their adsorption strength at oil-water and air-water interfaces, investigate the stability of hydrophobin aggregates in solution and their interaction with surfactants.

  11. Modelling the arsenic (V) and (III) adsorption

    NASA Astrophysics Data System (ADS)

    Rau, I.; Meghea, A.; Peleanu, I.; Gonzalo, A.; Valiente, M.; Zaharescu, M.

    2003-01-01

    Arsenic has gained great notoriety historically for its toxic properties. In aquatic environment, arsenic can exist in several oxidation states, as both inorganic and organometallic species. As (V) is less toxic than As (III). Most research has been directed to the control of arsenic pollution of potable water. Various techniques such as precipitation with iron and aluminium hydroxides, ion exchange, reverse osmosis, and adsorption are used for As (V) removal from surface and waste waters. Because of the easy handling of sludge, its free operation and regeneration capability, the adsorption technique has secured a place as one of the advanced methods of arsenic removal. A study of As (III) and As (V) sorption onto some different adsorbents (Fe (III) — iminodiacetate resin, nanocomposite materials, Fe(III) — forager sponge) referring to kinetic considerations and modelling of the process will be presented. All the systems studied are better described by Freundlich-Langmuir isotherm and the rate constant evaluation shows a sub-unitary order for the adsorption process.

  12. Adsorptive separation of propylene-propane mixtures

    SciTech Connect

    Jaervelin, H.; Fair, J.R. )

    1993-10-01

    The separation of propylene-propane mixtures is of great commercial importance and is carried out by fractional distillation. It is claimed to be the most energy-intensive distillation practiced in the United States. The purpose of this paper is to describe experimental work that suggests a practical alternative to distillation for separating the C[sub 3] hydrocarbons: adsorption. As studied, the process involves three adsorptive steps: initial separation with molecular sieves with heavy dilution with an inert gas; separation of propylene and propane separately from the inert gas, using activated carbon; and drying of the product streams with any of several available desiccants. The research information presented here deals with the initial step and includes both equilibrium and kinetic data. Isotherms are provided for propylene and propane adsorbed on three zeolites, activated alumina, silica gel, and coconut-based activated carbon. Breakthrough data are provided for both adsorption and regeneration steps for the zeolites, which were found to be superior to the other adsorbents for breakthrough separations. A flow diagram for the complete proposed process is included.

  13. Adsorption of Nanoplastics on Algal Photosynthesis

    NASA Astrophysics Data System (ADS)

    Turner, James; Bhattacharya, Priyanka; Lin, Sijie; Ke, Pu Chun

    2010-03-01

    The rapid accumulation of disposed plastics in the environment, especially in the Pacific Ocean, has become a global concern in recent years. Photo, chemical and physical degradations constantly fragment these plastics into a wide array of macroscopic to microscopic particles. As a result, marine organisms such as algae may be exposed to plastic particles through ingestion, adsorption and other forms of uptake. Such interactions, currently little understood, could potentially impact on the health state of the entire food chain. Here we report on polystyrene-algae interaction and its impact on algal photosynthesis. We first investigated the adsorption of polystyrene beads (20 nm) on a cellulose film coated on a 96-well plate. We derived a supralinear increase of the adsorption with the beads concentration for both positively and negatively charged polystyrene beads, with a saturation observed for the negatively charged polystyrene beads of concentration above 1.6 mg/mL. Using a bicarbonate indicator we discovered decreased carbon dioxide depletion due to polystyrene-algae binding. Since polystyrene beads also mediated algae aggregation, nanoplastics may alternatively be harnessed for waste water treatment.

  14. The role of the cationic Pt sites in the adsorption properties of water and ethanol on the Pt4/Pt(111) and Pt4/CeO2(111) substrates: A density functional theory investigation

    NASA Astrophysics Data System (ADS)

    Seminovski, Yohanna; Tereshchuk, Polina; Kiejna, Adam; Da Silva, Juarez L. F.

    2016-09-01

    Finite site platinum particles, Ptn, supported on reduced or unreduced cerium oxide surfaces, i.e., CeO2-x(111) ( 0 < x < /1 2 ), have been employed and studied as catalysts for a wide range of applications, which includes hydrogen production using the ethanol steam reforming processes. Our atomic-level understanding of the interaction of Pt with CeO2-x has been improved in the last years; however, the identification of the active sites on the Ptn/CeO2-x(111) substrates is still far from complete. In this work, we applied density functional theory based calculations with the addition of the on-site Coulomb interactions (DFT+U) for the investigation of the active sites and the role of the Pt oxidation state on the adsorption properties of water and ethanol (probe molecules) on four selected substrates, namely, Pt(111), Pt4/Pt(111), CeO2(111), and Pt4/CeO2(111). Our results show that water and ethanol preferentially bind in the cationic sites of the base of the tetrahedron Pt4 cluster instead of the anionic lower-coordinated Pt atoms located on the cluster-top or in the surface Ce (cationic) and O (anionic) sites. The presence of the Pt4 cluster contributes to increase the adsorption energy of both molecules on Pt(111) and CeO2(111) surfaces; however, its magnitude increases less for the case of Pt4/CeO2(111). Thus, the cationic Pt sites play a crucial role in the adsorption properties of water and ethanol. Both water and ethanol bind to on-top sites via the O atom and adopt parallel and perpendicular configurations on the Pt(111) and CeO2(111) substrates, respectively, while their orientation is changed once the Pt4 cluster is involved, favoring H binding with the surface sites.

  15. The role of the cationic Pt sites in the adsorption properties of water and ethanol on the Pt4/Pt(111) and Pt4/CeO2(111) substrates: A density functional theory investigation.

    PubMed

    Seminovski, Yohanna; Tereshchuk, Polina; Kiejna, Adam; Da Silva, Juarez L F

    2016-09-28

    Finite site platinum particles, Ptn, supported on reduced or unreduced cerium oxide surfaces, i.e., CeO2-x(111) (0sites on the Ptn/CeO2-x(111) substrates is still far from complete. In this work, we applied density functional theory based calculations with the addition of the on-site Coulomb interactions (DFT+U) for the investigation of the active sites and the role of the Pt oxidation state on the adsorption properties of water and ethanol (probe molecules) on four selected substrates, namely, Pt(111), Pt4/Pt(111), CeO2(111), and Pt4/CeO2(111). Our results show that water and ethanol preferentially bind in the cationic sites of the base of the tetrahedron Pt4 cluster instead of the anionic lower-coordinated Pt atoms located on the cluster-top or in the surface Ce (cationic) and O (anionic) sites. The presence of the Pt4 cluster contributes to increase the adsorption energy of both molecules on Pt(111) and CeO2(111) surfaces; however, its magnitude increases less for the case of Pt4/CeO2(111). Thus, the cationic Pt sites play a crucial role in the adsorption properties of water and ethanol. Both water and ethanol bind to on-top sites via the O atom and adopt parallel and perpendicular configurations on the Pt(111) and CeO2(111) substrates, respectively, while their orientation is changed once the Pt4 cluster is involved, favoring H binding with the surface sites.

  16. Novel biosorbent with high adsorption capacity prepared by chemical modification of white pine (Pinus durangensis) sawdust. Adsorption of Pb(II) from aqueous solutions.

    PubMed

    Salazar-Rabago, J J; Leyva-Ramos, R

    2016-03-15

    The natural sawdust (NS) from white pine (Pinus durangensis) was chemically modified by a hydrothermal procedure using citric, malonic and tartaric acids. The adsorption capacity of modified sawdust (MS) towards Pb(II) was considerably enhanced due to the introduction of carboxylic groups on the surface of MS during the modification, and the adsorption capacity was almost linearly dependent on the concentration of carboxylic sites. The NS surface was acidic, and the MS surface became more acidic after the modification. At T = 25 °C and pH = 5, the maximum adsorption capacity of the optimal MS towards Pb(II) was 304 mg/g, which is exceptionally high compared to NS and other MS reported previously. The adsorption capacity of MS was considerably reduced from 304 to 154 mg/g by decreasing the solution pH from 5 to 3 due to electrostatic interactions. The adsorption of Pb(II) on MS was reversible at pH = 2, but not at pH = 5. The contribution percentage of ion exchange to the overall adsorption capacity ranged from 70 to 99% and 10-66% at the initial pH of 3 and 5, respectively. Hence, the adsorption of Pb(II) on MS was mainly due to ion exchange at pH = 3 and to both ion exchange and electrostatic attraction at pH = 5.

  17. Adsorption of ammonium on biochar prepared from giant reed.

    PubMed

    Hou, Jie; Huang, Lei; Yang, Zhimin; Zhao, Yaqi; Deng, Chaoren; Chen, Yucheng; Li, Xin

    2016-10-01

    Giant reed was used as precursor for making biochar in order for the adsorption of NH4 (+)-N from aqueous solution. And the adsorption of the product to NH4 (+)-N was examined. The surface features of biochar were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy/energy dispersive spectrometer (SEM-EDS), and X-ray diffraction (XRD). XRD patterns showed several peaks and correspond to the high amount of crystalline material. The crystals contain KCl, K2O, CaO, MgO, and SiO and possess high surface area which enhances adsorption. The influence of different parameters such as initial concentration, adsorption time, pH, and ionic strength has been carried out. The adsorption could reach equilibrium through 24 h reaction and had the best adsorption amount at the solution pH values from 7 to 9. The cation has great influence on the adsorption of NH4 (+)-N, whereas the anion exerted a weaker effect. The adsorption followed pseudo-first-order and pseudo-second-order models. And the intraparticle diffusion and desorption studies further elucidated that the mechanism of adsorption on the product was ion exchange. The product equilibrium data was well described by the Langmuir and Freundlich model. The maximum adsorption capacities were 1.490 mg/g. Biochar derived from giant reed at 500 °C was suggested as a promising adsorbent for the removal of NH4 (+)-N from slightly polluted wastewater.

  18. Adsorption Behavior of Pb(II) Onto Potassium Polytitanate Nanofibres.

    PubMed

    Shahid, Mohammad; Tiling, Leonard D; El Saliby, Ibrahim; McDonagh, Andrew; Kim, Jong-Beom; Kim, Jong-Ho; Shon, Ho Kyong

    2016-02-01

    Potassium polytitanate nanofibres prepared by a hydrothermal method were investigated for their possible application in removing toxic metals from aqueous solution. Particular attention was paid to employing the titanate as a novel effective adsorbent for the removal of Pb(II). Batch adsorption experiments demonstrated that the adsorption was influenced by various conditions such as solution pH, adsorbent dosage and initial Pb(II) concentration. The results showed that the adsorption rate was faster in the first 5 min and equilibrium was achieved after 180 min. The maximum amount of adsorption was detected at pH 5. Potassium titanate showed much higher adsorption capacity compared to P25. The kinetic studies indicated that the adsorption of Pb(II) onto titanate best fit the pseudo-second-order kinetic model. FTIR spectra revealed that the hydroxyl groups in titanate were responsible for Pb(II) adsorption. The principal mechanism of the adsorption of Pb(II) in the present study is attributed to both ion exchange and oxygen bonding. The adsorption-desorption results demonstrated that the titanate could be readily regenerated after adsorption. Therefore, the present titanate exhibits great potential for the removal of Pb(II) from wastewater.

  19. Adsorption mechanism of chloroacetanilide herbicides to modified montmorillonite.

    PubMed

    El-Nahhal, Yasser

    2003-09-01

    This study was undertaken to characterize the adsorption mechanism of alachlor and metolachlor on montmorillonite modified with cationic surfactants. Adsorbed amounts of cationic surfactant on montmorillonite surfaces were determined by CNHSO analyzer. Equilibrium concentrations of alachlor and metolachlor were determined by GC and adsorption results were fit to a linear regression equation. The slope of the isotherms (Kd) was normalized to the fraction of organic carbon on montmorillonite complexes to produce corresponding Koc. Adsorption of surfactants fit very well to Langmuir equation. Increased basal spacing indicates that surfactant molecules could penetrate through the interlayer spacing and arrange themselves in different ways. Equilibrium data of alachlor and metolachlor suggest that adsorption may occur via physical or chemical bonds. Koc values of alachlor or metolachlor decreased as the fraction of the organic carbon increased in montmorillonite complexes indicating independent adsorption process. Changes of the molar free energy of the adsorption reactions were in the range of physical adsorption, indicating that adsorption reactions are spontaneous and the molecules either adsorb on the surface or penetrate into the inter-layers of montmorillonite-surfactant complex. Careful investigation of the adsorption data suggests that interaction may occur via the active groups such as carbonyl group (-C=O), anilidic (C-N) group and/or phenyl rings. This information may provide better understanding on adsorption mechanism and be useful in designing ecologically acceptable herbicide formulations.

  20. Effects of chemical functional groups on elemental mercury adsorption on carbonaceous surfaces.

    PubMed

    Liu, Jing; Cheney, Marcos A; Wu, Fan; Li, Meng

    2011-02-15

    A systematic theoretical study using density functional theory is performed to provide molecular-level understanding of the effects of chemical functional groups on mercury adsorption on carbonaceous surfaces. The zigzag and armchair edges were used in modeling the carbonaceous surfaces to simulate different adsorption sites. The edge atoms on the upper side of the models are unsaturated to simulate active sites. All calculations (optimizations, energies, and frequencies) were made at B3PW91 density functional theory level, using RCEP60VDZ basis set for mercury and 6-31G(d) pople basis set for other atoms. The results indicate that the embedding of halogen atom can increase the activity of its neighboring site which in turn increases the adsorption capacity of the carbonaceous surface for Hg(0). The adsorption belongs to chemisorptions, which is in good agreement with the experimental results. For the effects of oxygen functional groups, lactone, carbonyl and semiquinone favor Hg(0) adsorption because they increase the neighboring site's activity for mercury adsorption. On the contrary, phenol and carboxyl functional groups show a physisorption of Hg(0), and reduce Hg capture. This result can explain the seemingly conflicting experimental results reported in the literature concerning the influence of oxygen functional groups on mercury adsorption on carbonaceous surface.

  1. First Principles and STM Studies of Cl Adsorption on TiO2 (110) Surfaces

    NASA Astrophysics Data System (ADS)

    Vogtenhuber, D.; Podloucky, R.; Redinger, J.; Hebenstreit, E. L. D.; Hebenstreit, W.; Diebold, U.

    2000-03-01

    Atomic Cl adsorption on reduced and stoichiometric TiO2 (110) surfaces was calculated by applying a Full Potential Linearized Augmented Plane Wave method (FLEUR), and the Tersoff-Hamann model for simulating STM images. The electronic structure results are compared to experimental ISS, STM and XPS data for dissociative adsorption of Cl_2. Adsorption on O-defect sites, which is favored from our results of the adsorption energies, is found experimentally at elevated T (> 200^circ C) only. According to measurements at low T, adsorption in registry with the bridging O seems to be kinetically hindered. Distinct differences between high- and low T adsoption types are found for ISS, STM, \\varphi and Cl-2p bonding energies, in excellent agreement between calculations and experiment.

  2. Two fold modified chitosan for enhanced adsorption of hexavalent chromium from simulated wastewater and industrial effluents.

    PubMed

    Kahu, S S; Shekhawat, A; Saravanan, D; Jugade, R M

    2016-08-01

    Ionic solid (Ethylhexadecyldimethylammoniumbromide) impregnated phosphated chitosan (ISPC) was synthesized and applied for enhanced adsorption of hexavalent chromium from industrial effluent. The compound obtained was extensively characterized using instrumental techniques like FT-IR, TGA-DTA, XRD, SEM, BET and EDX. ISPC showed high adsorption capacity of 266.67mg/g in accordance with Langmuir isotherm model at pH 3.0 due to the presence of multiple sites which contribute for ion pair and electrostatic interactions with Cr(VI) species. The sorption kinetics and thermodynamic studies revealed that adsorption of Cr(VI) followed pseudo-second-order kinetics with exothermic and spontaneous behaviour. Applicability of ISPC for higher sample volumes was discerned through column studies. The real chrome plating industry effluent was effectively treated with total chromium recovery of 94%. The used ISPC was regenerated simply by dilute ammonium hydroxide treatment and tested for ten adsorption-desorption cycles with marginal decrease in adsorption efficiency.

  3. Surface sites on Pt-CeO2 mixed oxide catalysts probed by CO adsorption: a synchrotron radiation photoelectron spectroscopy study.

    PubMed

    Neitzel, Armin; Lykhach, Yaroslava; Skála, Tomáš; Tsud, Nataliya; Vorokhta, Mykhailo; Mazur, Daniel; Prince, Kevin C; Matolín, Vladimír; Libuda, Jörg

    2014-12-07

    By means of synchrotron radiation photoemission spectroscopy, we have investigated Pt-CeO2 mixed oxide films prepared on CeO2(111)/Cu(111). Using CO molecules as a probe, we associate the corresponding surface species with specific surface sites. This allows us to identify the changes in the composition and morphology of Pt-CeO2 mixed oxide films caused by annealing in an ultrahigh vacuum. Specifically, two peaks in C 1s spectra at 289.4 and 291.2 eV, associated with tridentate and bidentate carbonate species, are formed on the nanostructured stoichiometric CeO2 film. The peak at 290.5-291.0 eV in the C 1s spectra indicates the onset of restructuring, i.e. coarsening, of the Pt-CeO2 film. This peak is associated with a carbonate species formed near an oxygen vacancy. The onset of cerium oxide reduction is indicated by the peak at 287.8-288.0 eV associated with carbonite species formed near Ce(3+) cations. The development of surface species on the Pt-CeO2 mixed oxides suggests that restructuring of the films occurs above 300 K irrespective of Pt loadings. We do not find any adsorbed CO species associated with Pt(4+) or Pt(2+). The onset of Pt(2+) reduction is indicated by the peak at 286.9 eV in the C 1s spectra due to CO adsorption on metallic Pt particles. The thermal stability of Pt(2+) in Pt-CeO2 mixed oxide depends on Pt loading. We find excellent stability of Pt(2+) for 12% Pt content in the CeO2 film, whereas at a Pt concentration of 25% in the CeO2 film, a large fraction of the Pt(2+) is converted into metallic Pt particles above 300 K.

  4. Site preference of NH3-adsorption on Co, Pt and CoPt surfaces: the role of charge transfer, magnetism and strain.

    PubMed

    Bhattacharjee, S; Gupta, K; Jung, N; Yoo, S J; Waghmare, U V; Lee, S C

    2015-04-14

    Oxidation of Co at the surface poses a major problem in the cyclable use of CoPt, a cost-effective catalyst for proton exchange membrane fuel cells. This can be alleviated by attaching a ligand selectively to Co-sites to stop its oxidation without compromising the catalytic activity. Here, we present a comparative analysis of adsorption of NH3 on the (0001) surface of Co in the HCP structure and (111) surfaces of Pt and CoPt alloy in the FCC structure, using first-principles density functional theoretical calculations. While NH3 binds more strongly with the Pt surface than with the Co surface, we find that its binding with the Co atom is stronger than that with the Pt atom on the surface of the CoPt alloy. Our analysis of the charge density and electronic structure shows how this originates from (a) the electron transfer from the minority spin d-band of Co to Pt, and (b) shift in the energy of d-bands and the magnetic moments of Co atoms on the surface of the CoPt alloy relative to those on the (0001) surface of Co. Hybridization of the d-states of Co in CoPt with pz states of N in NH3 used to stop Co oxidation also results in improving the charge transfer from Co to Pt that is relevant to the catalytic activity of CoPt. We finally present the analysis of how the interaction of NH3 with the CoPt surface can be tuned with strain.

  5. Effect of pore blockage on adsorption isotherms and dynamics: Anomalous adsorption of iodine on activated carbon

    SciTech Connect

    Bhatia, S.K.; Liu, F.; Arvind, G.

    2000-04-18

    Isotherm hysteresis and pore-clocking effects of trapped molecules on adsorption dynamics is studied here, using the iodine-carbon system in the 300--343 K temperature range. It is found that a portion of the iodine is strongly adsorbed, and does not desorb, even over very long time scales, while the remainder adsorbs reversibly as a homogeneous monolayer with a Langmuirian isotherm in mesopores. The strongly adsorbed iodine appears to adsorb in micropores and at the mesopore mouths, hindering uptake of the reversible iodine. The uptake data for the adsorption and desorption dynamics of the reversible part is found to be best explained by means of a pore mouth resistance control mechanism. it is concluded that the dynamics of the adsorption and desorption at the pore mouth is important at early stages of the process.

  6. High Efficiency Adsorption Chillers: High Efficiency Adsorption Cooling Using Metal Organic Heat Carriers

    SciTech Connect

    2010-10-01

    BEETIT Project: PNNL is incorporating significant improvements in materials that adsorb liquids or gases to design more efficient adsorption chillers. An adsorption chiller is a type of air conditioner that is powered by heat, solar or waste heat, or combustion of natural gas. Unlike typical chillers, this type has few moving parts and uses almost no electricity to operate. PNNL is designing adsorbent materials at the molecular level with at least 3 times higher refrigerant capacity and up to 20 times faster kinetics than adsorbents used in current chillers. By using the new adsorbent, PNNL is able to create a chiller that is significantly smaller, has twice the energy efficiency, and lower costs for materials and assembly time compared to conventional adsorption chillers.

  7. Siloxane treatment by adsorption into porous materials.

    PubMed

    Ricaurte Ortega, D; Subrenat, A

    2009-09-01

    Siloxanes are widely used in different applications: health care, dry cleaning, household products, paints and coatings, paper, personal care, for example. This explains their prevalence in the environment. Because of their volatile nature, most of the time they are dispersed in the atmosphere, but they can also be present in the slurry from landfills. During anaerobic digestion, when the temperature goes up to 60 degrees C, siloxanes are volatilized, forming part of the biogas. Operational problems using biogas to produce energy, heat and hydrogen have been identified. At high temperatures the siloxanes are transformed into silicate dioxide (commonly called sand transmission). These white deposits may adhere to metal or catalytic substrate surfaces, seriously reducing equipment efficiency, and this can be a reason for changing equipment warranties. Consequently, elimination of siloxanes has become very important. Unfortunately, relatively little information can be found on this subject. Nevertheless some authors have described different analytical methods for siloxane quantification, and recent studies have looked at the presence of siloxanes in landfills and the restriction on the energy recovery equipment using the biogas produced. The growing consumption of siloxanes and silicones in industrial processes consequently increase their prevalence in the environment, hampering the use of biogas as a source of 'green energy'. Therefore, the principal focus of this study is the treatment of siloxanes. Their elimination was carried out using an adsorption process with four different porous materials: activated carbon cloths (ACC), granular activated carbon (GAC), zeolite and silica gel. Two representative siloxane compounds were used in this study, hexamethyldisiloxane (L2) and octamethylcyclotetrasiloxane (D4). Adsorption kinetics and isotherms in batch reactors were performed. It was observed that the mass transfer into the porous material was more rapid for the

  8. Dipalladium(I) Terphenyl Diphosphine Complexes as Models for Two-Site Adsorption and Activation of Organic Molecules

    PubMed Central

    Lin, Sibo; Herbert, David E.; Velian, Alexandra; Day, Michael W.; Agapie, Theodor

    2013-01-01

    Well-defined models for binding of organic molecules across two metal centers are relatively rare. A paraterphenyl diphosphine was employed to support a dipalladium(I) moiety. Unlike previously reported dipalladium(I) species, the present system provides a single molecular hemisphere for binding of ligands across two metal centers, enabling the characterization and comparison of the binding of a wide variety of saturated and unsaturated organic molecules. The dipalladium(I) terphenyl diphosphine toluene-capped complex was synthesized from a dipalladium(I) hexaacetonitrile precursor in the presence of toluene. The palladium centers display interactions with the π-systems of the central ring of the terphenyl unit and that of the toluene. Exchange of toluene for anisole, 1,3-butadiene, 1,3-cyclohexadiene, thiophenes, pyrroles, or furans resulted in well-defined π-bound complexes which were studied by crystallography, nuclear magnetic resonance (NMR) spectroscopy, and density functional theory. Structural characterization shows that the interactions of the dipalladium unit with the central arene of the diphosphine does not vary significantly in this series allowing for a systematic comparison of the binding of the incoming ligands to the dipalladium moiety. Several of the complexes exhibit rare μ2-η2:η2 or μ2-η2:η1 (O or S) bridging motifs. Hydrogenation of the thiophene and benzothiophene adducts was demonstrated to proceed at room temperature. The relative binding strength of the neutral ligands was determined by competition experiments monitored by NMR spectroscopy. The relative equilibrium constants for ligand substitution span over 13 orders of magnitude. This represents the most comprehensive analysis to date of the relative binding of heterocycles and unsaturated ligands to bimetallic sites. Binding interactions were computationally studied with electrostatic potentials and molecular orbital analysis. Anionic ligands were also demonstrated to form

  9. Effects of the oxidation degree of graphene oxide on the adsorption of methylene blue.

    PubMed

    Yan, Han; Tao, Xue; Yang, Zhen; Li, Kun; Yang, Hu; Li, Aimin; Cheng, Rongshi

    2014-03-15

    In this current work, a series of graphene oxides (GO) with different oxidation degrees (OD) was prepared using Hummer method. Fundamental adsorption behavior of the GO series for removal of methylene blue (MB) from aqueous solutions has been studied. The GO series shows an overall fast and pH-independent MB adsorption, which is even capable of removing trace levels of dye completely from very dilute solutions. Furthermore, the effects of the oxidation degree (OD) on MB adsorption behavior have been investigated systematically, indicating that the dye uptakes of GO exponentially increase with the increase of OD. Further study on the adsorption mechanism shows that adsorption behavior of GO would change from a Freundlich-type to a Langmuir-type adsorption as the OD increases. It may be due to both the enhanced exfoliation degree of the carbon planes in graphite caused by oxidation and the production of more active adsorption sites. The binding features of the MB loaded GO gradually change from MB molecule parallel stacking on graphite plane through hydrophobic π-π interaction to vertical standing via electrostatic interaction with increasing OD, resulting in a significant improvement of MB uptakes. In addition, the adsorption capacity of the regenerated GO has little loss until four cycles.

  10. High-capacity hydrogen and nitric oxide adsorption and storage in a metal-organic framework.

    PubMed

    Xiao, Bo; Wheatley, Paul S; Zhao, Xuebo; Fletcher, Ashleigh J; Fox, Sarah; Rossi, Adriano G; Megson, Ian L; Bordiga, S; Regli, L; Thomas, K Mark; Morris, Russell E

    2007-02-07

    Gas adsorption experiments have been carried out on a copper benzene tricarboxylate metal-organic framework material, HKUST-1. Hydrogen adsorption at 1 and 10 bar (both 77 K) gives an adsorption capacity of 11.16 mmol H2 per g of HKUST-1 (22.7 mg g(-)1, 2.27 wt %) at 1 bar and 18 mmol per g (36.28 mg g(-)1, 3.6 wt %) at 10 bar. Adsorption of D2 at 1 bar (77 K) is between 1.09 (at 1 bar) and 1.20(at <100 mbar) times the H2 values depending on the pressure, agreeing with the theoretical expectations. Gravimetric adsorption measurements of NO on HKUST-1 at 196 K (1 bar) gives a large adsorption capacity of approximately 9 mmol g(-1), which is significantly greater than any other adsorption capacity reported on a porous solid. At 298 K the adsorption capacity at 1 bar is just over 3 mmol g(-1). Infra red experiments show that the NO binds to the empty copper metal sites in HKUST-1. Chemiluminescence and platelet aggregometry experiments indicate that the amount of NO recovered on exposure of the resulting complex to water is enough to be biologically active, completely inhibiting platelet aggregation in platelet rich plasma.

  11. Individual and competitive adsorption of phenol and nickel onto multiwalled carbon nanotubes

    PubMed Central

    Abdel-Ghani, Nour T.; El-Chaghaby, Ghadir A.; Helal, Farag S.

    2014-01-01

    Individual and competitive adsorption studies were carried out to investigate the removal of phenol and nickel ions by adsorption onto multiwalled carbon nanotubes (MWCNTs). The carbon nanotubes were characterized by different techniques such as X-ray diffraction, scanning electron microscopy, thermal analysis and Fourier transformation infrared spectroscopy. The different experimental conditions affecting the adsorption process were investigated. Kinetics and equilibrium models were tested for fitting the adsorption experimental data. The characterization experimental results proved that the studied adsorbent possess different surface functional groups as well as typical morphological features. The batch experiments revealed that 300 min of contact time was enough to achieve equilibrium for the adsorption of both phenol and nickel at an initial adsorbate concentration of 25 mg/l, an adsorbent dosage of 5 g/l, and a solution pH of 7. The adsorption of phenol and nickel by MWCNTs followed the pseudo-second order kinetic model and the intraparticle diffusion model was quite good in describing the adsorption mechanism. The Langmuir equilibrium model fitted well the experimental data indicating the homogeneity of the adsorbent surface sites. The maximum Langmuir adsorption capacities were found to be 32.23 and 6.09 mg/g, for phenol and Ni ions, respectively. The removal efficiency of MWCNTs for nickel ions or phenol in real wastewater samples at the optimum conditions reached up to 60% and 70%, respectively. PMID:26257938

  12. Entropically favored adsorption of cellulosic molecules onto carbon materials through hydrophobic functionalities.

    PubMed

    Yabushita, Mizuho; Kobayashi, Hirokazu; Hasegawa, Jun-Ya; Hara, Kenji; Fukuoka, Atsushi

    2014-05-01

    Carbon-based materials have attracted interest as high-performance catalysts for the aqueous-phase conversion of cellulose. The adsorption of β-glucans plays a crucial role in the catalytic performance of carbons, although the primary driving force and details of the adsorption process remain unclear. This study demonstrates that adsorption occurs at hydrophobic sites on the carbon surface and that hydrophilic groups are not involved. Analysis of adsorption temperature dependence also reveals that the entropy change associated with adsorption is positive. Our results indicate that adsorption occurs by entropically driven hydrophobic interactions in addition to CH-π hydrogen bonding. These same CH-π hydrogen bonds are also confirmed by DFT calculations. The adsorption of β-glucans on carbons is significantly stronger than the affinity between β-glucans. The adsorption equilibrium constants of β-glucans on carbons increase exponentially with increasing degrees of polymerization, which supports the theory of strong interactions between the carbon and the long β-glucans found in cellulose.

  13. Adsorption characteristics of N-nitrosodimethylamine from aqueous solution on surface-modified activated carbons.

    PubMed

    Dai, Xiaodong; Zou, Linda; Yan, Zifeng; Millikan, Mary

    2009-08-30

    This study investigated the removal of N-nitrosodimethylamine (NDMA) by an adsorption mechanism using commercially available activated carbons and surface-modified activated carbons. The effects of the modification on the properties of the activated carbon were studied by N(2) adsorption/desorption, Diffuse Reflectance Infrared Fourier Transmission (DRIFT) analysis and X-Ray Photoelectron Spectroscopy (XPS). Adsorption experiments revealed that the activated carbons demonstrated a greater capacity for NDMA adsorption capacity than can be achieved using zeolite. The equilibrium data was fitted to the Freundlich equation and it was found that the adsorption capacity was significantly influenced by the micropore size, relative pore volume and surface characteristics. Adsorption experiments were conducted using unmodified and modified activated carbons. The results indicated that the adsorption capacity of NDMA can be significantly improved by heat treatment and doping of TiO(2) particles. This was because the surface treatments yielded more hydrophobic sites and fewer oxygen-containing surface functional groups, and consequently an increased capacity for NDMA adsorption.

  14. Removal of the antibiotic metronidazole by adsorption on various carbon materials from aqueous phase.

    PubMed

    Carrales-Alvarado, D H; Ocampo-Pérez, R; Leyva-Ramos, R; Rivera-Utrilla, J

    2014-12-15

    The adsorption of the antibiotic metronidazole (MNZ) on activated carbon (F400), activated carbon cloth (ACF), mesoporous activated carbon (CMK-3), and carbon nanotubes (MWCNT) was investigated in this work. The effect of the adsorbent-adsorbate interactions as well as the operating conditions (ionic strength, solution pH, temperature, chemical modification of the adsorbents by HNO3 treatment, and water matrix) on the adsorption capacity were analyzed to substantiate the adsorption mechanism. The adsorption capacity markedly varied as function of the carbon material, decreasing in the following order: F400>ACF>F400-HNO3>CMK-3>MWCNT>MWCNT-HNO3, and depended not only on their surface area and pore size distribution, but also on their chemical nature. The adsorption of MNZ was influenced by the solution pH, but was not significantly affected by the ionic strength and temperature. The adsorption of MNZ was enhanced when the MNZ solutions were prepared using wastewater. Therefore, the electrolytes present in the wastewater cooperated rather than competed with the MNZ molecules for the adsorption sites. Desorption equilibrium data of MNZ on all carbon materials demonstrated that the adsorption was reversible corroborating the weakness of the adsorbent-adsorbate interactions.

  15. First Principles Study of HCN Adsorption on Graphene Doped with 5d Transition Metal

    NASA Astrophysics Data System (ADS)

    Dong, Hai-Kuan; Wang, Yong-Ping; Shi, Li Bin

    2016-11-01

    Hydrogen cyanide (HCN) adsorption on graphene doped with 5d transition metal (TM) is investigated by the first principles based on density functional theory. It is observed that Hg atom cannot be doped into graphene due to saturated valence electron configurations of 5d106s2. Three kinds of HCN adsorption configurations are investigated, in which H, C and N in HCN are close to the adsorption site, respectively. The most stable adsorption configuration is obtained by total energy optimization. HCN adsorption can be studied by adsorption energy and electron density difference. HCN can only be physisorbed on Ir, Pt and Au-doped graphenes, while chemisorption is observed for Lu, Hf, Ta, W, Re and Os-doped graphenes. The band structure is calculated by B3LYP and Generalized gradient approximation (GGA) functionals. It is observed from B3LYP method that the conductivity of Lu, Hf, Re and Os-doped graphenes does not obviously change before and after HCN adsorption. Ta and W-doped graphenes change from semiconductor to metal after adsorption of HCN molecule. The results indicate that Ta and W-doped graphenes may be a promising sensor for detecting HCN. This study provides a useful basis for understanding of a wide variety of physical properties on graphene.

  16. Role of the oxidation state of cerium on the ceria surfaces for silicate adsorption

    NASA Astrophysics Data System (ADS)

    Seo, Jihoon; Moon, Jinok; Kim, Joo Hyun; Lee, Kangchun; Hwang, Junha; Yoon, Heesung; Yi, Dong Kee; Paik, Ungyu

    2016-12-01

    In this study, we have investigated the role of the Ce oxidation state (Ce3+/Ce4+) on the CeO2 surfaces for silicate adsorption. In aqueous medium, the Ce3+ sites lead to the formation of -OH groups at the CeO2 surface through H2O dissociation. Silicate ions can adsorb onto the CeO2 surface through interaction with the -OH groups (-Ce-OH- + -Si-O- ↔ -Ce-O-Si- + OH-). As the Ce3+ concentration increased from 19.3 to 27.6%, the surface density of -OH group increased from 0.34 to 0.72 OH/nm2. To evaluate the adsorption behaviors of silicate ions onto CeO2 NPs, we carried out an adsorption isothermal analysis, and the adsorption isotherm data followed the Freundlich model. The Freundlich constant for the relative adsorption capacity (KF) and adsorption intensity (1/n) indicated that CeO2 NPs with high Ce3+ concentration show higher adsorption affinity with silicate ions. As a result, we have demonstrated that the Ce oxidation state (Ce3+/Ce4+) on the CeO2 surface can have a significant influence on the silicate adsorption.

  17. Size, adsorption site, and spin effects in the reaction of Al clusters with water molecules: Al17 and Al28 as examples.

    PubMed

    Álvarez-Barcia, Sonia; Flores, Jesús R

    2012-08-02

    The first step of the reaction of two relatively large Alm clusters (m = 17, 28) with a few water molecules has been studied by electronic structure methods. The complexes Alm·(H2O)n (n = 1-2) have been characterized, and the saddle points corresponding to the first step in the reaction, namely, formation of HAlmOH·(H2O)n-1 systems, have been located. The Al28 cluster is special in the sense it has two electronic states, singlet and triplet, which are very close in energy and also have quite similar equilibrium structures. The preferred adsorption and reaction sites have been determined. We find quite clear preferences toward some sites, the effect of cluster distortion being moderately significant in the stability of the complexes. The interaction with water does not appear, in general, to bring the triplet state of the Al28·(H2O)2 adducts below the singlet; not even the corresponding saddle points appear to be lower in energy. The rate coefficients, tunneling transmission factors, and activation free energies have been computed and compared with those of the Al13 and Al3 clusters, even with those of the Al atom. It turns out the rates are quite close to those of Al3 and much larger than those of Al and Al13. There is no dramatic difference between the reactivity of the singlet and triplet state of Al28; however, there are very significant differences between different sites. Finally, we studied the interaction between the lowest-lying singlet and triplet states of Al28 through multireference configuration interaction (MRCI) spin-orbit computations. The vertical excitation energies corresponding to a number of low-lying singlet and triplet states are also determined by MRCI computations. It turns out that the spin-orbit interaction is very weak, which suggests that both states, the lowest-lying singlet and triplet, could evolve somehow independently, at least when interacting with closed-shell molecules. It is suggested that the situation could be quite

  18. Effect of surface property of activated carbon on adsorption of nitrate ion.

    PubMed

    Iida, Tatsuya; Amano, Yoshimasa; Machida, Motoi; Imazeki, Fumio

    2013-01-01

    In this study, the removal of acidic functional groups and introduction of basic groups/sites on activated carbons (ACs) by outgassing and ammonia gas treatment were respectively carried out to enhance the nitrate ion adsorption in aqueous solution. Then, the relationships between nitrate ion adsorption and solution pH as well as surface charge of AC were investigated to understand the basic mechanisms of nitrate ion adsorption by AC. The result showed that the nitrate ion adsorption depended on the equilibrium solution pH (pHe) and the adsorption amount was promoted with decreasing pHe. The ACs treated by outgassing and ammonia gas treatment showed larger amount of nitrate ion adsorption than that by untreated AC. These results indicated that, since basic groups/sites could adsorb protons in the solution, the AC surface would be charged positively, and that the nitrate ion would be electrically interacted with positively charged carbon surface. Accordingly, it was concluded that basic groups/sites on the surface of AC could promote nitrate ion adsorption.

  19. Adsorption and flocculation by polymers and polymer mixtures.

    PubMed

    Gregory, John; Barany, Sandor

    2011-11-14

    Polymers of various types are in widespread use as flocculants in several industries. In most cases, polymer adsorption is an essential prerequisite for flocculation and kinetic aspects are very important. The rates of polymer adsorption and of re-conformation (relaxation) of adsorbed chains are key factors that influence the performance of flocculants and their mode of action. Polyelectrolytes often tend to adopt a rather flat adsorbed configuration and in this state their action is mainly through charge effects, including 'electrostatic patch' attraction. When the relaxation rate is quite low, particle collisions may occur while the adsorbed chains are still in an extended state and flocculation by polymer bridging may occur. These effects are now well understood and supported by much experimental evidence. In recent years there has been considerable interest in the use of multi-component flocculants, especially dual-polymer systems. In the latter case, there can be significant advantages over the use of single polymers. Despite some complications, there is a broad understanding of the action of dual polymer systems. In many cases the sequence of addition of the polymers is important and the pre-adsorbed polymer can have two important effects: providing adsorption sites for the second polymer or causing a more extended adsorbed conformation as a result of 'site blocking'.

  20. Molecular dynamics simulations of cesium adsorption on illite nanoparticles.

    PubMed

    Lammers, Laura N; Bourg, Ian C; Okumura, Masahiko; Kolluri, Kedarnath; Sposito, Garrison; Machida, Masahiko

    2017-03-15

    The charged surfaces of micaceous minerals, especially illite, regulate the mobility of the major radioisotopes of Cs ((134)Cs, (135)Cs, (137)Cs) in the geosphere. Despite the long history of Cs adsorption studies, the nature of the illite surface sites remains incompletely understood. To address this problem, we present atomistic simulations of Cs competition with Na for three candidate illite adsorption sites - edge, basal plane, and interlayer. Our simulation results are broadly consistent with affinities and selectivities that have been inferred from surface complexation models. Cation exchange on the basal planes is thermodynamically ideal, but exchange on edge surfaces and within interlayers shows complex, thermodynamically non-ideal behavior. The basal planes are weakly Cs-selective, while edges and interlayers have much higher affinity for Cs. The dynamics of NaCs exchange are rapid for both cations on the basal planes, but considerably slower for Cs localized on edge surfaces. In addition to new insights into Cs adsorption and exchange with Na on illite, we report the development of a methodology capable of simulating fully-flexible clay mineral nanoparticles with stable edge surfaces using a well-tested interatomic potential model.

  1. Adsorption of light hydrocarbons and carbon dioxide on silica gel

    SciTech Connect

    Olivier, M.G.; Jadot, R.

    1997-03-01

    The main component of natural gas is methane, but small quantities of other gases are also present. These compounds are in negligible quantities in natural gas but can become a problem for the storage of methane by adsorption, being less volatile than methane and so preferentially occupying the active sites of adsorbents. Adsorption isotherms of methane, ethane, ethylene, propane, propane, propadiene, butane, 2-methylpropane, and carbon dioxide on silica gel are given at three temperatures (278 K, 293 K, and 303 K). The results at pressures up to 0.8 P/P{sub s} for the subcritical compounds and up to 3,500 kPa for the supercritical compounds are measured using an automated apparatus.

  2. Adsorption of basic dyes onto activated carbon using microcolumns

    SciTech Connect

    El Qada, E.N.; Allen, S.J.; Walker, G.M.

    2006-08-16

    Column studies for the adsorption of basic dyes (methylene blue, basic red, and basic yellow) onto PAC2 (activated carbon produced from bituminous coal using steam activation) and F400 were undertaken in fixed-bed microcolumns. Experimental data were correlated using the bed depth service time (BDST) model. The effect of bisolute interactions on the performance of microcolumn fixed beds was studied. The BDST model was successful in describing the breakthrough curves for the adsorption of MB onto PAC2 and predicts the experimental data with a good degree of accuracy. The results emphasized that the interactions and competition for the available binding sites have considerable influence on the efficiency of adsorbents to remove dyes from the solution.

  3. Adsorption of HP Lattice Proteins on Patterned Surfaces

    NASA Astrophysics Data System (ADS)

    Wilson, Matthew; Shi, Guangjie; Landau, David P.; Li, Ying Wai; Wuest, Thomas

    2014-03-01

    The HP lattice model[2] is a course-grained, yet useful tool for modeling protein sequences where amino acids are treated as either hydrophobic (H) or polar (P) monomers. With the use of Wang-Landau sampling and an efficient set of Monte-Carlo moves[3], HP lattice proteins adsorbed on patterned surfaces are studied. Each substrate is modeled as a periodically bounded pattern of lattice sites that interact with either H or P monomers in the lattice protein, where the energy contributions of the surface are determined by assigned coupling strengths. By analyzing energy degeneracies, along with the thermodynamic and structural quantities of the protein, both the protein folding and surface adsorption can be observed. The adsorption behavior of the lattice proteins on patterned surfaces will be compared to those interacting with uniform surfaces. Research supported by NSF.

  4. Adsorption studies of methylene blue dye on tunisian activated lignin

    NASA Astrophysics Data System (ADS)

    Kriaa, A.; Hamdi, N.; Srasra, E.

    2011-02-01

    Activated carbon prepared from natural lignin, providing from a geological deposit, was used as the adsorbent for the removal of methylene blue (MB) dye from aqueous solutions. Batch adsorption studies were conducted to evaluate various experimental parameters like pH and contact time for the removal of this dye. Effective pH for MB removal was 11. Kinetic study showed that the adsorption of dye was gradual process. Quasi equilibrium reached in 4 h. Pseudo-first-order, pseudo-second-order were used to fit the experimental data. Pseudo-second-order rate equation was able to provide realistic description of adsorption kinetics. The experimental isotherms data were also modelled by the Langmuir and Freundlich equation of adsorption. Equilibrium data fitted well with the Langmuir model with maximum monolayer adsorption capacity of 147 mg/g. Activated lignin was shown to be a promising material for adsorption of MB from aqueous solutions.

  5. Communication: Thermodynamic analysis of critical conditions of polymer adsorption

    NASA Astrophysics Data System (ADS)

    Cimino, R.; Rasmussen, C. J.; Neimark, A. V.

    2013-11-01

    Polymer adsorption to solid surfaces is a ubiquitous phenomenon, which has attracted long-lasting attention. Dependent on the competition between the polymer-solid adsorption and polymer-solvent solvation interactions, a chain may assume either 3d solvated conformation when adsorption is weak or 2d adsorbed conformation when adsorption is strong. The transition between these conformations occurring upon variation of adsorption strength is quite sharp, and in the limit of "infinite" chain length, can be treated as a critical phenomenon. We suggest a novel thermodynamic definition of the critical conditions of polymer adsorption from the equality of incremental chemical potentials of adsorbed and free chains. We show with the example of freely jointed Lennard-Jones chains tethered to an adsorbing surface that this new definition provides a link between thermodynamic and geometrical features of adsorbed chains and is in line with classical scaling relationships for the fraction of adsorbed monomers, chain radii of gyration, and free energy.

  6. Adsorption of carbon black using carboxymethyl chitosan in deinking process

    NASA Astrophysics Data System (ADS)

    Muryeti, Budimulyani, Estuti; Sinurat, Ellya

    2017-03-01

    The study about synthesis, characterization, and application carboxymethyl chitosan as adsorbent in deinking process was conducted. Adsorption of carbon black onto carboxymethyl chitosan has been investigated in a batch system. This research was conducted to obtain the adsorption capacity of carboxymethyl chitosan. The experiments were carried out to study the effect of carbon black concentration, contact time and dosage of carboxymethyl chitosan to the adsorption capacity of carboxymethyl chitosan. The optimum condition of carbon black adsorption was achieved at contact time of 60 min and weight doses of 1.0 g. The adsorption capacity of carboxymethyl chitosan was 14.34 mg/g and the adsorption effectivity was 70.54%. The result indicates that carboxymethyl chitosan could be used as adsorbent of carbon black in deinking process.

  7. Computational Investigation of Conformational Changes in Proteins upon Adsorption

    NASA Astrophysics Data System (ADS)

    Sharma, Sumit; Anand, Gaurav; Belfort, Georges; Kumar, Sanat K.

    2009-03-01

    Amyloidogenic diseases, such as, Alzheimer's, are caused by adsorption and aggregation of partially unfolded proteins. Protein adsorption is often accompanied by conformational rearrangements, which are thought to affect many properties such as their adhesion strength to the surface, biological activity, and aggregation tendency. Experiments have shown that many proteins, upon adsorption to hydrophobic surfaces, undergo a helix to sheet or random coil secondary structural rearrangement. To better understand the equilibrium structural complexities of this phenomenon, we have performed Monte Carlo (MC) simulations and Single Chain Mean Field calculations of adsorption of different proteins, modeled as lattice chains, to study the adsorption behavior and equilibrium protein conformations at different temperatures, protein concentration and surface hydrophobicity. Free energy and entropic effects on adsorption have been studied by determining density of states using Weighted Histogram Analysis Method. Conformational transitions of proteins on surfaces will be discussed as a function of surface hydrophobicity.

  8. Factors affecting the adsorption of chromium (VI) on activated carbon

    SciTech Connect

    Yavuz, R.; Orbak, I.; Karatepe, N.

    2006-09-15

    The aim of this investigation was to determine the adsorption behavior of chromium (VI) on two different activated carbon samples produced from Tuncbilek lignite. The effects of the initial chromium (VI) concentration (250-1000 mg/L), temperature (297-323 K) and pH (2.0-9.5) on adsorption were investigated systematically. The effectiveness of the parameters on chromium adsorption was found to be in the order of pH, the initial Cr(VI) concentration and the temperature. Increasing the pH from 2.0 to 9.5 caused a decrease in adsorption. However, the adsorption was increased by increasing the initial Cr(VI) concentration and temperature. The multilinear mathematical model was also developed to predict the Cr(VI) adsorption on activated carbon samples within the experimental conditions.

  9. CRYOGENIC ADSORPTION OF HYDROGEN ISOTOPES OVER NANO-STRUCTURED MATERIALS

    SciTech Connect

    Xiao, S.; Heung, L.

    2010-10-07

    Porous materials such as zeolites, activated carbon, silica gels, alumina and a number of industrial catalysts are compared and ranked for hydrogen and deuterium adsorption at liquid nitrogen temperature. All samples show higher D{sub 2} adsorption than that of H{sub 2}, in which a HY sample has the greatest isotopic effect while 13X has the highest hydrogen uptake capacity. Material's moisture content has significant impact to its hydrogen uptake. A material without adequate drying could result in complete loss of its adsorption capacity. Even though some materials present higher H{sub 2} adsorption capacity at full pressure, their adsorption at low vapor pressure may not be as good as others. Adsorption capacity in a dynamic system is much less than in a static system. A sharp desorption is also expected in case of temperature upset.

  10. Communication: Thermodynamic analysis of critical conditions of polymer adsorption

    SciTech Connect

    Cimino, R.; Neimark, A. V.; Rasmussen, C. J.

    2013-11-28

    Polymer adsorption to solid surfaces is a ubiquitous phenomenon, which has attracted long-lasting attention. Dependent on the competition between the polymer-solid adsorption and polymer-solvent solvation interactions, a chain may assume either 3d solvated conformation when adsorption is weak or 2d adsorbed conformation when adsorption is strong. The transition between these conformations occurring upon variation of adsorption strength is quite sharp, and in the limit of “infinite” chain length, can be treated as a critical phenomenon. We suggest a novel thermodynamic definition of the critical conditions of polymer adsorption from the equality of incremental chemical potentials of adsorbed and free chains. We show with the example of freely jointed Lennard-Jones chains tethered to an adsorbing surface that this new definition provides a link between thermodynamic and geometrical features of adsorbed chains and is in line with classical scaling relationships for the fraction of adsorbed monomers, chain radii of gyration, and free energy.

  11. Studies on adsorption of formaldehyde in zirconium phosphate-glyphosates

    NASA Astrophysics Data System (ADS)

    Zhang, Yuejuan; Yi, Jianjun; Xu, Qinghong

    2011-01-01

    In our previous work [22], a kind of layered compound of zirconium phosphate-glyphosate (ZrGP) was synthesized. Its large surface area (445 m 2/g) indicates this compound has possible application in adsorptions. In this paper, adsorption to formaldehyde in ZrGP and mechanisms of the adsorption were studied carefully. Balance time of adsorption (about 6 h) and largest adsorbed amount (7.8%) were found when adsorption temperature was at 40 °C and pH value of adsorption environment was about 3.0. H-bonds were found existing between molecules of formaldehyde and ZrGP, and formaldehyde molecules could exist in ZrGP stably.

  12. Adsorption characteristics of brilliant green dye on kaolin.

    PubMed

    Nandi, B K; Goswami, A; Purkait, M K

    2009-01-15

    Experimental investigations were carried out to adsorb toxic brilliant green dye from aqueous medium using kaolin as an adsorbent. Characterization of kaolin is done by measuring: (i) particle size distribution using particle size analyzer, (ii) BET surface area using BET surface analyzer, and (iii) structural analysis using X-ray diffractometer. The effects of initial dye concentration, contact time, kaolin dose, stirring speed, pH and temperature were studied for the adsorption of brilliant green in batch mode. Adsorption experiments indicate that the extent of adsorption is strongly dependent on pH of solution. Free energy of adsorption (DeltaG0), enthalpy (DeltaH0) and entropy (DeltaS0) changes are calculated to know the nature of adsorption. The calculated values of DeltaG0 at 299K and 323K indicate that the adsorption process is spontaneous. The estimated values of DeltaH0 and DeltaS0 both show the negative sign, which indicate that the adsorption process is exothermic and the dye molecules are organized on the kaolin surface in less randomly fashion than in solution. The adsorption kinetic has been described by first-order, pseudo-second-order and intra-particle-diffusion models. It was observed that the rate of dye adsorption follows pseudo-second-order model for the dye concentration range studied in the present case. Standard adsorption isotherms were used to fit the experimental equilibrium data. It was found that the adsorption of brilliant green on kaolin follows the Langmuir adsorption isotherm.

  13. Adsorption to fish sperm of vertically transmitted fish viruses

    USGS Publications Warehouse

    Mulcahy, D.; Pascho, R.J.

    1984-01-01

    More than 99 percent of a vertically transmitted fish rhabdovirus, infectious hematopoietic necrosis virus, was removed from suspension in less than 1 minute by adsorption to the surface membrane of sperm from two genera of salmonid fishes. The vertically transmitted, infectious pancreatic necrosis virus adsorbed to a lesser degree, but no adsorption occurred with a second fish rhabdovirus that is not vertically transmitted. Such adsorption may be involved in vertical transmission of these viruses.

  14. Adsorption of thiophene on silica-supported Mo clusters

    NASA Astrophysics Data System (ADS)

    Komarneni, M.; Kadossov, E.; Justin, J.; Lu, M.; Burghaus, U.

    2010-07-01

    The adsorption/decomposition kinetics/dynamics of thiophene has been studied on silica-supported Mo and MoS x clusters. Two-dimensional cluster formation at small Mo exposures and three-dimensional cluster growth at larger exposures would be consistent with the Auger electron spectroscopy (AES) data. Thermal desorption spectroscopy (TDS) indicates two reaction pathways. H 4C 4S desorbs molecularly at 190-400 K. Two TDS features were evident and could be assigned to molecularly on Mo sites, and S sites adsorbed thiophene. Assuming a standard preexponential factor (ν = 1 × 10 13/s) for first-order kinetics, the binding energies for adsorption on Mo (sulfur) sites amount to 90 (65) kJ/mol for 0.4 ML Mo exposure and 76 (63) kJ/mol for 2 ML Mo. Thus, smaller clusters are more reactive than larger clusters for molecular adsorption of H 4C 4S. The second reaction pathway, the decomposition of thiophene, starts at 250 K. Utilizing multimass TDS, H 2, H 2S, and mostly alkynes are detected in the gas phase as decomposition products. H 4C 4S bond activation results in partially sulfided Mo clusters as well as S and C residuals on the surface. S and C poison the catalyst. As a result, with an increasing number of H 4C 4S adsorption/desorption cycles, the uptake of molecular thiophene decreases as well as the H 2 and H 2S production ceases. Thus, silica-supported sulfided Mo clusters are less reactive than metallic clusters. The poisoned catalyst can be partially reactivated by annealing in O 2. However, Mo oxides also appear to form, which passivate the catalyst further. On the other hand, while annealing a used catalyst in H/H 2, it is poisoned even more (i.e., the S AES signal increases). By means of adsorption transients, the initial adsorption probability, S0, of C 4H 4S has been determined. At thermal impact energies ( Ei = 0.04 eV), S0 for molecular adsorption amounts to 0.43 ± 0.03 for a surface temperature of 200 K. S0 increases with Mo cluster size, obeying the

  15. Effective surface areas of coals measured by dye adsorption

    SciTech Connect

    Spitzer, D.P.

    1988-01-01

    The primary interest has been to examine adsorption behavior especially at short contact times, ten minutes to an hour, to determine whether such measurements might give useful data on effective surface areas - i.e., the surface that would be accessible to reagents within times comparable to those typical of most coal processing. Accordingly, most of the emphasis is on the effect of time on adsorption, rather than on traditional adsorption isotherms. Although most literature on cationic dye adsorption (mostly on carbons) uses methylene blue, it happened that the authors originally used safranin O instead because this dye was reported to be useful in distinguishing oxidized coals from fresh coals. Many of their experiments were repeated using methylene blue (in water), with very similar results. It was noted early that swelling of coals in water was common, especially for more oxidized or lower rank coals, and adsorption experiments were also done in another solvent, namely methanol. This produced quite striking differences for some coals. Coal surfaces that are readily accessible to adsorption by safranin are found to correlate well with N/sub 2/ surface areas, with adsorption of 1.0 mg safranin per gram of coal corresponding to essentially a surface area of 1.0 m/sup 2//g. Highly oxidized coals were found to swell considerably in water, with correspondingly increased adsorption. Areas of such coals can be estimated by adsorption of safranin from methanol solutions.

  16. Adsorption of Ar on individual carbon nanotubes, graphene, and graphite

    NASA Astrophysics Data System (ADS)

    Dzyubenko, Boris; Kahn, Joshua; Vilches, Oscar; Cobden, David

    2015-03-01

    We compare and contrast results of adsorption measurements of Ar on single-walled carbon nanotubes, graphene, and graphite. Adsorption isotherms on individual suspended nanotubes were obtained using both the mechanical resonance frequency shift (sensitive to mass adsorption) and the electrical conductance. Isotherms on graphene mounted on hexagonal boron nitride were obtained using only the conductance. New volumetric adsorption isotherms on bulk exfoliated graphite were also obtained, paying special attention to the very low coverage region (less than 2% of a monolayer). This allowed us to compare the degree of heterogeneity on the three substrate types, the binding energies, and the van der Waals 2D parameters. Research supported by NSF DMR 1206208.

  17. Adsorption coefficients for TNT on soil and clay minerals

    NASA Astrophysics Data System (ADS)

    Rivera, Rosángela; Pabón, Julissa; Pérez, Omarie; Muñoz, Miguel A.; Mina, Nairmen

    2007-04-01

    To understand the fate and transport mechanisms of TNT from buried landmines is it essential to determine the adsorption process of TNT on soil and clay minerals. In this research, soil samples from horizons Ap and A from Jobos Series at Isabela, Puerto Rico were studied. The clay fractions were separated from the other soil components by centrifugation. Using the hydrometer method the particle size distribution for the soil horizons was obtained. Physical and chemical characterization studies such as cation exchange capacity (CEC), surface area, percent of organic matter and pH were performed for the soil and clay samples. A complete mineralogical characterization of clay fractions using X-ray diffraction analysis reveals the presence of kaolinite, goethite, hematite, gibbsite and quartz. In order to obtain adsorption coefficients (K d values) for the TNT-soil and TNT-clay interactions high performance liquid chromatography (HPLC) was used. The adsorption process for TNT-soil was described by the Langmuir model. A higher adsorption was observed in the Ap horizon. The Freundlich model described the adsorption process for TNT-clay interactions. The affinity and relative adsorption capacity of the clay for TNT were higher in the A horizon. These results suggest that adsorption by soil organic matter predominates over adsorption on clay minerals when significant soil organic matter content is present. It was found that, properties like cation exchange capacity and surface area are important factors in the adsorption of clayey soils.

  18. [Adsorption of Cd2+ on biochar from aqueous solution].

    PubMed

    Guo, Wen-juan; Liang, Xue-feng; Lin, Da-song; Xu, Ying-ming; Wang, Lin; Sun, Yue-bing; Qin, Xu

    2013-09-01

    Biomass-based materials such as biochar have a good performance in heavy metal adsorption. The adsorption of Cd2+ on biochar converted from cotton straw was studied. Adsorption isotherm, kinetics and effect factors such as temperature, pH and ionic strength were investigated. The adsorption of Cd2+ on biochar can be fitted by the Freundlich isotherm better than the Langmuir isotherm. The maximum adsorption amounts of Cd2+ at different temperatures were 9.738 mg x g(-1) (288.15 K), 10.14 mg x g(-1) (298.15 K), 10.40 mg x g(-1) (308.15 K) and 10.71 mg x g(-1) (318.15 K), respectively. The free energies AG(theta) were from -8.346 kJ x mol(-1) to -10.276 kJ x mol(-1) at different temperatures, indicating that the adsorption of Cd2+ onto biochar is spontaneous and is an endothermic process. The adsorption process can reach equilibrium within 40 minutes and can be fitted by the pseudo second order kinetic model. pH showed a significant effect on the adsorption of Cd2+ on biochar in the range of 2-8. The adsorption amount of Cd2+ on biochar shows a reducing trend with the increasing ionic strength.

  19. Adsorption of glucose, cellobiose, and cellotetraose onto cellulose model surfaces.

    PubMed

    Hoja, Johannes; Maurer, Reinhard J; Sax, Alexander F

    2014-07-31

    Reliable simulation of molecular adsorption onto cellulose surfaces is essential for the design of new cellulose nanocomposite materials. However, the applicability of classical force field methods to such systems remains relatively unexplored. In this study, we present the adsorption of glucose, cellobiose, and cellotetraose on model surfaces of crystalline cellulose Iα and Iβ. The adsorption of the two large carbohydrates was simulated with the GLYCAM06 force field. To validate this approach, quantum theoretical calculations for the adsorption of glucose were performed: Equilibrium geometries were studied with density functional theory (DFT) and dispersion-corrected DFT, whereas the adsorption energies were calculated with two standard density functional approximations and five dispersion-containing DFT approaches. We find that GLYCAM06 gives a good account of geometries and, in most cases, accurate adsorption energies when compared to dispersion-corrected DFT energies. Adsorption onto the (100) surface of cellulose Iα is, in general, stronger than onto the (100) surface of cellulose Iβ. Contrary to intuition, the adsorption energy is not directly correlated with the number of hydrogen bonds; rather, it is dominated by dispersion interactions. Especially for bigger adsorbates, a neglect of these interactions leads to a dramatic underestimation of adsorption energies.

  20. Adsorption of cellulase from Trichoderma viride on cellulose

    SciTech Connect

    Ooshima, H.; Sakata, M.; Harano, Y.

    1983-12-01

    The adsorption of cellulase from Trichoderma viride (Meicelase CEP) on the surface of pure cellulose was studied. The adsorption was found to obey apparently the Langmuir isotherm. From the data concerning the effects of temperature and the crystallinity of cellulose on the Langmuir adsorption parameters, the characteristics of the adsorption of the individual cellulase components, namely CMCase (endoglucanase) and Avicelase (exoglucanase), were discussed. While beta-glucosidase also adsorbed on the surface of cellulose at 5 degrees C, it did not at 50 degrees C. (Refs. 27).

  1. Adsorption properties and gaseous mercury transformation rate of natural biofilm.

    PubMed

    Cheng, Jinping; Zhao, Wenchang; Liu, Yuanyuan; Wu, Cheng; Liu, Caie; Wang, Wenhua

    2008-11-01

    Biofilms were developed on glass microscope slides in a natural aquatic environment and their mercury adsorption properties were evaluated. Results demonstrated that the biofilms contained a large number of bacterial cells and associated extracellular polymers. Mercury forms detected in the biofilms were mainly bound to residual matter and organic acids. The adsorption processes could be described by a Langmuir isotherm. The optimum conditions for adsorption of mercury to natural biofilm were an ionic strength of 0.1 mol/L, pH 6 and an optimum adsorption time of 40 min. The transformation rate was 0.79 microg gaseous mercury per gram of biofilm.

  2. Adsorption of malathion on thermally treated egg shell material.

    PubMed

    Elwakeel, Khalid Z; Yousif, Ahmed M

    2010-01-01

    Thermally treated egg shell materials were prepared at different temperatures. The samples were investigated by means of FT-IR and thermogravimetric analysis (TGA). The adsorption behaviour of malathion on egg shell and its thermally treated samples was studied using batch method and gave uptake capacities up to 0.964 mmol/g. Adsorption kinetics as well as the adsorption isotherms were discussed. Regeneration of the loaded adsorbent beads towards the successive cycles was also clarified. The adsorption of malathion is maintained until the third cycle without a significant activity loss.

  3. A continuum hard-sphere model of protein adsorption

    NASA Astrophysics Data System (ADS)

    Finch, Craig; Clarke, Thomas; Hickman, James J.

    2013-07-01

    Protein adsorption plays a significant role in biological phenomena such as cell-surface interactions and the coagulation of blood. Two-dimensional random sequential adsorption (RSA) models are widely used to model the adsorption of proteins on solid surfaces. Continuum equations have been developed so that the results of RSA simulations can be used to predict the kinetics of adsorption. Recently, Brownian dynamics simulations have become popular for modeling protein adsorption. In this work a continuum model was developed to allow the results from a Brownian dynamics simulation to be used as the boundary condition in a computational fluid dynamics (CFD) simulation. Brownian dynamics simulations were used to model the diffusive transport of hard-sphere particles in a liquid and the adsorption of the particles onto a solid surface. The configuration of the adsorbed particles was analyzed to quantify the chemical potential near the surface, which was found to be a function of the distance from the surface and the fractional surface coverage. The near-surface chemical potential was used to derive a continuum model of adsorption that incorporates the results from the Brownian dynamics simulations. The equations of the continuum model were discretized and coupled to a CFD simulation of diffusive transport to the surface. The kinetics of adsorption predicted by the continuum model closely matched the results from the Brownian dynamics simulation. This new model allows the results from mesoscale simulations to be incorporated into micro- or macro-scale CFD transport simulations of protein adsorption in practical devices.

  4. [Effects of dissolved organic matter on phenanthrene adsorption by soil].

    PubMed

    Xiong, Wei; Ling, Wan-ting; Gao, Yan-zheng; Li, Qiu-ling; Dai, Jing-yu

    2007-02-01

    This paper studied the effects of exotic and native dissolved organic matter (DOM) on the phenanthrene adsorption by three soils differed in soil organic carbon content (foc). The exotic DOM came from decayed rice straw, while the native DOM was extracted from the test soils. In all cases, the adsorption of phenanthrene by treated soils could be well described with linear-type model, and there was a positive correlation between adsorption coefficient (Kd) and foc Compared with the control, the Kd value of test soils after native DOM removed was increased by 7. 08% -21. 4% , and the increment (deltaKd) was positively correlated with fo,, indicating that the presence of soil native DOM impeded the phenanthrene adsorption by soil. The effects of exotic DOM on phenanthrene adsorption had a close relation with its added concentration in soil-water system. Within the range of 0-106 mg DOC x L(-1) , the K, value increased first, and then decreased with the increase of added exotic DOM concentration. Lower concentrations of added exotic DOM promoted the phenanthrene adsorption by soil, while higher concentrations ( I> or =52 mg DOC x L(-1)) of it obviously impeded this adsorption. These effects of exotic and native DOM on soil phenanthrene adsorption were considered to be related to the association of phenanthrene with DOM in solution, and the ' cumulative adsorption effect' between soil solid and aqueous phases.

  5. Computational investigation of the adsorption of carbon dioxide onto zirconium oxide clusters.

    PubMed

    Boulet, Pascal; Knöfel, Christina; Kuchta, Bogdan; Hornebecq, Virginie; Llewellyn, Philip L

    2012-11-01

    A theoretical investigation of the adsorption of CO₂ onto ZrO₂ is presented. Various cluster models were used to mimic different basic and acidic sites on the surface. The method used was the density functional theory with the generalized gradient approximation and including Grimme's empirical model in order to properly describe the weak interactions that may occur between the adsorbate and the surface. We found that the adsorption at sites exhibiting two adjacent unsaturated zirconium atoms led to either the exothermic dissociation of CO₂ or to a strongly physisorbed state. By contrast, on a single unsaturated zirconium, CO₂ was adsorbed in an apical manner. In this case, the molecule is highly polarized and the adsorption energy amounts to -64.6 kJ mol⁻¹. Finally, the weakest adsorption of CO₂ occurred on the basic OH sites on the surface.

  6. The effect of high ionic strength on neptunium (V) adsorption to a halophilic bacterium

    NASA Astrophysics Data System (ADS)

    Ams, David A.; Swanson, Juliet S.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Richmann, Michael; Reed, Donald T.

    2013-06-01

    The mobility of neptunium (V) in subsurface high ionic strength aqueous systems may be strongly influenced by adsorption to the cell wall of the halophilic bacteria Chromohalobacter sp. This study is the first to evaluate the adsorption of neptunium (V) to the surface of a halophilic bacterium as a function of pH from approximately 2 to 10 and at ionic strengths of 2 and 4 M. This is also the first study to evaluate the effects of carbonate complexation with neptunium (V) on adsorption to whole bacterial cells under high pH conditions. A thermodynamically-based surface complexation model was adapted to describe experimental adsorption data under high ionic strength conditions where traditional corrections for aqueous ion activity are invalid. Adsorption of neptunium (V) was rapid and reversible under the conditions of the study. Adsorption was significant over the entire pH range evaluated for both ionic strength conditions and was shown to be dependent on the speciation of the sites on the bacterial surface and neptunium (V) in solution. Adsorption behavior was controlled by the relatively strong electrostatic attraction of the positively charged neptunyl ion to the negatively charged bacterial surface at pH below circum-neutral. At pH above circum-neutral, the adsorption behavior was controlled by the presence of negatively charged neptunium (V) carbonate complexes resulting in decreased adsorption, although adsorption was still significant due to the adsorption of negatively charged neptunyl-carbonate species. Adsorption in 4 M NaClO4 was enhanced relative to adsorption in 2 M NaClO4 over the majority of the pH range evaluated, likely due to the effect of increasing aqueous ion activity at high ionic strength. The protonation/deprotonation characteristics of the cell wall of Chromohalobacter sp. were evaluated by potentiometric titrations in 2 and 4 M NaClO4. Bacterial titration results indicated that Chromohalobacter sp. exhibits similar proton buffering

  7. Synthesis and adsorption of functionalized polystyrenes

    SciTech Connect

    Iyengar, D.R.

    1992-12-31

    The effect of specifically interacting functional groups located at the chain ends of polystyrene on the absorption rate, adsorbance, graft density and surface excess are discussed from cyclohexane, a theta solvent and toluene. Polystyrenes with hydroxyl and carboxylic acid-end-groups in narrow molecular weight distribution are synthesized by anionic polymerization of styrene followed by suitable termination reactions. Thin layer chromatography (TLC) is developed as an analytical technique to predict trends in the adsorption of the polymers in a range of solvents. In particular the information about the localization of the end-group and therefore different chain architectures at the interface are inferred from this simple technique. Adsorption isotherms are obtained for each of the functionalized polymers of four different molecular weights, the selection of which was based on the TLC results. Kinetics of adsorption and the adsorbance data are determined by liquid counting of tritium labelled polymers. Graft density and surface excess data are calculated from the adsorbance data and other known parameters. It is shown, from these data, that polystyrenes with a carboxylic acid end-group form weakly stretched brushes at the glass-cyclohexane interface and mushrooms at the glass-toluene interface a result consistent with the higher osmotic repulsions towards packing in good solvents. Polystyrenes with function groups at both the chain ends are hypothesized to form a range of structures from those dominated by tails at higher concentrations to those dominated by loops and trains at lower solution concentrations. At higher molecular weights it is shown that functionalized a result consistent with the TLC predictions. Hydroxyl end-group is shown to be an ineffective sticky foot from its adsorbance vis-a-vis polystyrene.

  8. Adsorption of aniline and toluidines on montmorillonite: Implications for the disposal of shale oil production wastes

    SciTech Connect

    Essington, M.E.; Bowen, J.M.; Wills, R.A.; Hart, B.K.

    1992-01-01

    Bentonite clay liners are commonly employed to mitigate the movement of contaminants from waste disposal sites. Solid and liquid waste materials that arise from the production of shale oil contain a vast array of organic compounds. Common among these compounds are the aromatic amines. in order to assess the ability of clay liner material to restrict organic compound mobility, the adsorption of aniline and o-, m-, and p-toluidine on Ca{sup 2+} - and K{sup +}-saturated Wyoming bentonite was investigated. Adsorption experiments were performed under conditions of varied pH, ionic strength, and dominate electrolyte cation and anion. organic adsorption on Ca{sup 2+} - and K{sup +}-saturated montmorillonite is pH dependent. For any given organic compound, maximum adsorption increases with decreasing ionic strength. organic compound adsorption is inhibited in the presence of sulfate and is greater in the Ca{sup 2+} systems than in the K{sup +} systems at any given ionic strength. High salt content and K{sup +} collapse the bentonite layers and limit access to and compete for adsorption sites. The K{sup +} ion is also more difficult to displace than Ca{sup 2+} from interlayer positions. Fourier transform infrared spectroscopic data show that the aniline compounds are adsorbed on bentonite through the hydrogen bonding of an amine hydrogen to a surface silica oxygen. Sulfate reduces amine adsorption by removing positively charged anilinium species from solution to form negatively charge sulfate complexes. Although adsorption of the substituted amines on bentonite is observed, aniline and toluidine adsorption is minimal in saline systems and not detected in alkaline systems. Thus, in shale oil process waste disposal sites, the mobility of the anilines through bentonite liners will not be mitigated by sorption processes, as spent oil shale leachates are both highly alkaline and saline.

  9. Adsorption of aniline and toluidines on montmorillonite: Implications for the disposal of shale oil production wastes

    SciTech Connect

    Essington, M.E.; Bowen, J.M.; Wills, R.A.; Hart, B.K.

    1992-01-01

    Bentonite clay liners are commonly employed to mitigate the movement of contaminants from waste disposal sites. Solid and liquid waste materials that arise from the production of shale oil contain a vast array of organic compounds. Common among these compounds are the aromatic amines. in order to assess the ability of clay liner material to restrict organic compound mobility, the adsorption of aniline and o-, m-, and p-toluidine on Ca[sup 2+] - and K[sup +]-saturated Wyoming bentonite was investigated. Adsorption experiments were performed under conditions of varied pH, ionic strength, and dominate electrolyte cation and anion. organic adsorption on Ca[sup 2+] - and K[sup +]-saturated montmorillonite is pH dependent. For any given organic compound, maximum adsorption increases with decreasing ionic strength. organic compound adsorption is inhibited in the presence of sulfate and is greater in the Ca[sup 2+] systems than in the K[sup +] systems at any given ionic strength. High salt content and K[sup +] collapse the bentonite layers and limit access to and compete for adsorption sites. The K[sup +] ion is also more difficult to displace than Ca[sup 2+] from interlayer positions. Fourier transform infrared spectroscopic data show that the aniline compounds are adsorbed on bentonite through the hydrogen bonding of an amine hydrogen to a surface silica oxygen. Sulfate reduces amine adsorption by removing positively charged anilinium species from solution to form negatively charge sulfate complexes. Although adsorption of the substituted amines on bentonite is observed, aniline and toluidine adsorption is minimal in saline systems and not detected in alkaline systems. Thus, in shale oil process waste disposal sites, the mobility of the anilines through bentonite liners will not be mitigated by sorption processes, as spent oil shale leachates are both highly alkaline and saline.

  10. ION EXCHANGE ADSORPTION PROCESS FOR PLUTONIUM SEPARATION

    DOEpatents

    Boyd, G.E.; Russell, E.R.; Taylor, M.D.

    1961-07-11

    Ion exchange processes for the separation of plutonium from fission products are described. In accordance with these processes an aqueous solution containing plutonium and fission products is contacted with a cation exchange resin under conditions favoring adsorption of plutonium and fission products on the resin. A portion of the fission product is then eluted with a solution containing 0.05 to 1% by weight of a carboxylic acid. Plutonium is next eluted with a solution containing 2 to 8 per cent by weight of the same carboxylic acid, and the remaining fission products on the resin are eluted with an aqueous solution containing over 10 per cent by weight of sodium bisulfate.

  11. Fractional statistical theory of finite multilayer adsorption

    NASA Astrophysics Data System (ADS)

    Takara, E. A.; Quiroga, E.; Matoz-Fernandez, D. A.; Ochoa, N. A.; Ramirez-Pastor, A. J.

    2016-01-01

    In the present paper, finite multilayer adsorption is described as a fractional statistics problem, based on Haldane's statistics. In this scheme, the Helmholtz free energy and its derivatives are written in terms of a parameter g, which relates to the configuration of the molecules in the adsorbed state. For values of g ranging between 0 and 1 the formalism is used to model experimental data of bovine serum albumin (BSA) adsorbed onto an ion exchange resin for different values of pH and temperature. Excellent agreement between theory and experiments was found.

  12. Competitive adsorption of Pb and Cd on bacteria-montmorillonite composite.

    PubMed

    Du, Huihui; Chen, Wenli; Cai, Peng; Rong, Xingmin; Feng, Xionghan; Huang, Qiaoyun

    2016-11-01

    The characteristics and mechanisms of competitive adsorption of trace metals on bacteria-associated clay mineral composites have never been studied, despite their being among the most common organic-mineral complexes in geological systems. Herein, competitive adsorption of Pb and Cd on Pseudomonas putida-montmorillonite composite was investigated through adsorption-desorption experiment, isothermal titration calorimetry (ITC), and synchrotron micro X-ray fluorescence (μ-XRF). From the experiment, stronger competition was observed on clay mineral than on bacteria-clay composite because more non-specific sites accounted for heavy metal adsorption on clay mineral surface at the studied pH 5. Both competing heavy metals tended to react with bacterial fractions in the composite, which was verified by the higher correlation of Cd (and Pb) with Zn (R(2) = 0.41) elemental distribution than with Si (R(2) = 0.10). ITC results showed that competitive adsorption exhibited a lower entropy change (ΔS) at the metal-sorbent interfaces compared with single-metal adsorption, revealing that Cd and Pb are bound to the same types of adsorption sites on the sorbent. The competitive effect on bacteria-clay composite was found to be helpful for a better understanding on the fixation, remobilization and subsequent migration of heavy metals in multi-metal contaminated environments.

  13. Laser temperature jump relaxation measurements of adsorption/desorption kinetics at liquid/solid interfaces

    SciTech Connect

    Waite, S.W.; Harris, J.M.; Holzwarth, J.F.

    1995-04-15

    The iodine laser temperature jump method is used to study adsorption/desorption kinetics at a methylated silica/solution interface. A suspension of C1-derivatized fumed silica is used for the kinetic measurements. The colloidal silica does not significantly change the attenuation of near-IR radiation from the iodine laser and allows the surface site concentration to be varied so that adsorption and desorption rates can be determined. The temperature jump relaxation method was used to investigate the effect of electrolyte on adsorption of a charged solute (ANS) on a C1 silica surface. Adsorption equilibrium conditions were optimized to observe a maximum relaxation signal. Without electrolyte, the relaxation signal is biexponential, which is also reflected in a broad chromatographic peak shape and a two-site sorption isotherm. When electrolyte is added, the relaxation signal is primarily single exponential, which agrees with the linear adsorption isotherm. The adsorption rate and equilibrium constant were found to increase significantly with added electrolyte, which showed that adsorption kinetics can influence both band broadening and retention. 28 refs., 7 figs., 4 tab.

  14. Cadmium-109 Radioisotope Adsorption onto Polypyrrole Coated Sawdust of Dryobalanops aromatic: Kinetics and Adsorption Isotherms Modelling

    PubMed Central

    Olatunji, Michael Adekunle; Khandaker, Mayeen Uddin; Amin, Yusoff Mohd; Mahmud, Habibun Nabi Muhammad Ekramul

    2016-01-01

    A radiotracer study was conducted to investigate the removal characteristics of cadmium (109Cd) from aqueous solution by polypyrrole/ sawdust composite. Several factors such as solution pH, sorbent dosage, initial concentration, contact time, temperature and interfering metal ions were found to have influence on the adsorption process. The kinetics of adsorption was relatively fast, reaching equilibrium within 3 hours. A lowering of the solution pH reduced the removal efficiency from 99.3 to ~ 46.7% and an ambient temperature of 25°C was found to be optimum for maximum adsorption. The presence of sodium and potassium ions inhibited 109Cd removal from its aqueous solution. The experimental data for 109Cd adsorption showed a very good agreement with the Langmuir isotherm and a pseudo-first order kinetic model. The surface condition of the adsorbent before and after cadmium loading was investigated using BET, FESEM and FTIR. Considering the low cost of the precursor’s materials and the toxicity of 109Cd radioactive metal, polypyrrole synthesized on the sawdust of Dryobalanops aromatic could be used as an efficient adsorbent for the removal of 109Cd radioisotope from radionuclide-containing effluents. PMID:27706232

  15. Cadmium-109 Radioisotope Adsorption onto Polypyrrole Coated Sawdust of Dryobalanops aromatic: Kinetics and Adsorption Isotherms Modelling.

    PubMed

    Olatunji, Michael Adekunle; Khandaker, Mayeen Uddin; Amin, Yusoff Mohd; Mahmud, Habibun Nabi Muhammad Ekramul

    2016-01-01

    A radiotracer study was conducted to investigate the removal characteristics of cadmium (109Cd) from aqueous solution by polypyrrole/ sawdust composite. Several factors such as solution pH, sorbent dosage, initial concentration, contact time, temperature and interfering metal ions were found to have influence on the adsorption process. The kinetics of adsorption was relatively fast, reaching equilibrium within 3 hours. A lowering of the solution pH reduced the removal efficiency from 99.3 to ~ 46.7% and an ambient temperature of 25°C was found to be optimum for maximum adsorption. The presence of sodium and potassium ions inhibited 109Cd removal from its aqueous solution. The experimental data for 109Cd adsorption showed a very good agreement with the Langmuir isotherm and a pseudo-first order kinetic model. The surface condition of the adsorbent before and after cadmium loading was investigated using BET, FESEM and FTIR. Considering the low cost of the precursor's materials and the toxicity of 109Cd radioactive metal, polypyrrole synthesized on the sawdust of Dryobalanops aromatic could be used as an efficient adsorbent for the removal of 109Cd radioisotope from radionuclide-containing effluents.

  16. Modeling oxyanion adsorption on ferralic soil, part 2: chromate, selenate, molybdate, and arsenate adsorption.

    PubMed

    Pérez, Claudio; Antelo, Juan; Fiol, Sarah; Arce, Florencio

    2014-10-01

    High levels of oxyanions are found in the soil environment, often as a result of human activity. At high concentrations, oxyanions can be harmful to both humans and wildlife. Information about the interactions between oxyanions and natural samples is essential for understanding the bioavailability, toxicity, and transport of these compounds in the environment. In the present study, the authors investigated the reactivity of different oxyanions (AsO4 , MoO4 , SeO4 , and CrO4 ) at different pH values in 2 horizons of a ferralic soil. By combining available microscopic data on iron oxides with the macroscopic data obtained, the authors were able to use the charge distribution model to accurately describe the adsorption of these 4 oxyanions and thus to determine the surface speciation. The charge distribution model was previously calibrated and evaluated using phosphate adsorption/desorption data. The adsorption behavior on ferralic soil is controlled mainly by the natural iron oxides present, and it is qualitatively analogous to that exhibited by synthetic iron oxides. The highest adsorption was found for arsenate ions, whereas the lowest was found for selenate, with chromate and molybdate ions showing an intermediate behavior.

  17. Adsorption and co-adsorption of diclofenac and Cu(II) on calcareous soils.

    PubMed

    Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

    2016-02-01

    Pharmaceuticals are emerging contaminants and their presence in different compartments of the environment has been detected in many countries. In this study, laboratory batch experiments were conducted to characterize the adsorption of diclofenac, a widely used non-steroidal anti-inflammatory drug, on six calcareous soils. The adsorption of diclofenac was relatively low, which may lead to a risk of groundwater contamination and plant uptake. A correlation between the soil-water distribution coefficient Kd and soil characteristics has been highlighted. Indeed, diclofenac adsorption as a function of soil organic matter content (% OM) and Rt=% CaCO3/% OM was successfully described through a simple empirical model, indicating the importance of considering the inhibiting effect of CaCO3 on OM retention properties for a better assessment of diclofenac fate in the specific case of calcareous soils. The simultaneous co-adsorption of diclofenac and copper - a ubiquitous pollutant in the environment - at the water/soil interface, was also investigated. It appeared quite unexpectedly that copper did not have a significant influence on diclofenac retention.

  18. Adsorption of SOx and NOx in activated viscose fibers.

    PubMed

    Plens, Ana Carolina O; Monaro, Daniel L G; Coutinho, Aparecido R

    2015-01-01

    SOx and NOx are emissions resulting from combustion processes and are the main agents that contribute to the formation of acid rain, which causes harm to humans and the environment. Several techniques for removing these pollutants are applied in i.e. oil refineries, thermoelectric that use petroleum oils and vehicular pollution. Among these, highlight the adsorption of contaminants by the usage of activated carbon fibers and activated carbon, which are characterized by high surface area and uniform distribution of pores, providing appropriate conditions for application in processes of removing environmental contaminants. In the present work, activated viscose fibers (AVF) were prepared and applied in adsorption experiments of NO and SO2. The materials produced showed high values of surface area, with a predominance of micro pores with diameters in the range of 1.0 nm. The AVF had satisfactory performance in the removal of contaminants and are compatible with other synthetic fibers. Thus, the formation of active sites of carbon provides contaminants adsorption, demonstrating that carbon fibers cloth can be applied for the removal of pollutants.

  19. Adsorption orientations and immunological recognition of antibodies on graphene.

    PubMed

    Vilhena, J G; Dumitru, A C; Herruzo, Elena T; Mendieta-Moreno, Jesús I; Garcia, Ricardo; Serena, P A; Pérez, Rubén

    2016-07-07

    Large-scale molecular dynamics (MD) simulations and atomic force microscopy (AFM) in liquid are combined to characterize the adsorption of Immunoglobulin G (IgG) antibodies over a hydrophobic surface modeled with a three-layer graphene slab. We consider explicitly the water solvent, simulating systems with massive sizes (up to 770 000 atoms), for four different adsorption orientations. Protocols based on steered MD to speed up the protein diffusion stage and to enhance the dehydration process are combined with long simulation times (>150 ns) in order to make sure that the final adsorption states correspond to actual stable configurations. Our MD results and the AFM images demonstrate that the IgG antibodies are strongly adsorbed, do not unfold, and retain their secondary and tertiary structures upon deposition. Statistical analysis of the AFM images shows that many of the antibodies adopt vertical orientations, even at very small coverages, which expose at least one Fab binding site for recognition events. Single molecule force spectroscopy experiments demonstrate the immunological response of the deposited antibodies by recognizing its specific antigens. The above properties together with the strong anchoring and preservation of the secondary structure, make graphene an excellent candidate for the development of immunosensors.

  20. Equilibrium and kinetic adsorption study of the adsorptive removal of Cr(VI) using modified wheat residue.

    PubMed

    Chen, Suhong; Yue, Qinyan; Gao, Baoyu; Xu, Xing

    2010-09-01

    A new adsorbent modified from wheat residue was synthesized after reaction with epichlorohydrin and triethylamine by using the modifying agents of diethylenetriamine in the presence of organic medium of N,N-dimethylformamide. The performance of the modified wheat straw (MWS) was characterized by Fourier transform infrared spectroscopy and point of zero charge analysis. The adsorption was investigated in a batch adsorption system, including both equilibrium adsorption isotherms and kinetics. Results showed that MWR had great anion-adsorbing capacity, due to the existence of a large number of introduced amino groups, and the value of pH(PZC) was around 5.0. Equilibrium data were analyzed using the Langmuir, Freundlich, and Temkin isotherm models and were found to be best represented by the Freundlich isotherm model. Evaluation of the adsorption process identified its endothermic nature. The maximum adsorption capacity of MWS for the removal of Cr(VI) was 322.58mg/g at 328K, indicating that MWS has high chromium removal efficiency, compared to other adsorbents reported. The kinetics of adsorption followed the pseudo-second-order kinetic equation. The mechanism of adsorption was investigated using the intraparticle diffusion model. Thermodynamic parameters (free energy change, enthalpy change, and entropy change) revealed that the adsorption of Cr(VI) onto MWS was endothermic and spontaneous; additionally, the adsorption can be characterized as an ion-exchange process. The results suggest that MWS is an inexpensive and efficient adsorbent for removing Cr(VI) ions from aqueous solution.

  1. Effect of complexing ligands on the adsorption of Cu(II) onto the silica gel surface. 1: Adsorption of ligands

    SciTech Connect

    Park, Y.J.; Jung, K.H.; Park, K.K.; Park, K.K.

    1995-04-01

    The adsorption of several ligands on silica gel was investigated in aqueous solutions. The ligands used were 2,2{prime},6{prime},2{double_prime}-terpyridine, pyridine, 3,4-lutidine, 2-aminomethyl pyridine, 2-pyridine methanol, picolinic acid, salicylic acid, and 5-sulfosalicylic acid. The adsorption behaviors of these ligands were interpreted by means of three adsorption modes: ion exchange, hydrogen bonding, and hydrophobic interaction. For 2,2{prime},6{prime},2{double_prime}-terpyridine, pyridine, and 3,4-lutidine, the adsorption maxima appeared near their respective pK{sub a} values and were found to be due mainly to ion exchange, whereas the adsorption of these ligands at low pH was strongly attributed to hydrophobic interaction. The adsorption of 2-aminomethyl pyridine increased with increasing pH over the entire pH range investigated and was due mainly to ion exchange. Picolinic acid was adsorbed mainly by hydrogen bonding either via pyridine N atoms at low pH or via carboxylic O atoms at high pH. 2-Pyridine methanol was adsorbed by hydrophobic interaction at low pH and by hydrogen bonding at high pH. The adsorptions of salicylic and 5-sulfosalicylic acid were very small over the entire pH ranges investigated. For the adsorption mechanism, the Stern model was used to fit adsorption data.

  2. A compact low-temperature single crystal adsorption calorimetry setup for measuring coverage dependent heats of adsorption at cryogenic temperatures.

    PubMed

    Hörtz, Peter; Schäfer, Rolf

    2014-07-01

    Here we present the modification of an already existing Single Crystal Adsorption Calorimetry (SCAC) apparatus which has been extended by a compact cooling system to measure the coverage dependent heats of adsorption of gaseous compounds on thin metal substrates in a temperature range from 80 K to 430 K. The setup is characterized and its performance is tested by studying the adsorption of CO on Pt(111) at 150 K and 300 K. Coverage dependent sticking probabilities and heat of adsorption measurements are compared to previous experimental and theoretical studies proving the reliability of our compact low-temperature-SCAC setup.

  3. Studies on adsorption characteristics and mechanism of adsorption of chlorhexidine mainly by carbon black.

    PubMed

    Akaho, E; Fukumori, Y

    2001-09-01

    The extent of adsorption of chlorhexidine to carbon black and sanitary cotton was determined by measuring the amounts of chlorhexidine adsorbed to carbon black or sanitary cotton from the chlorhexidine solution containing specific amount of carbon black or sanitary cotton. As another comparative antiseptic example of adsorption phenomena, adsorption of acrinol to sanitary cotton was also studied. The specific surface area of carbon black was measured by the BET method of adsorption isotherm. The pattern of adsorption of chlorhexidine to carbon black was temperature-dependent Langmuir isotherms, and the amounts adsorbed increased as the temperature was raised. Since chlorhexidine, whose pKa's are 2.2 and 10.3, is considered to exist in aqueous solution as the di-cation, an ion-ion interaction should be formed between protonated biguanide and anionic portions of carbon black or sanitary cotton. The chlorophenyl and hexane moieties interact with hydrophobic portions of carbon black or sanitary cotton. The perturbation experiment conducted on this interaction system showed that the nature of interaction was irreversible. The enthalpy change calculated from Langmuir constants was small, indicating the existence of ion-ion interaction. The entropy values, 27.4 to 28.2 e.u. obtained in this system, suggested that the hydration shells of the ions were rather tightly bound. The area occupied by a chlorhexidine molecule, 548 (A)(2), was twice greater than the projection area, 276 (A)(2), suggesting that chlorhexidine was adsorbed in such a way that each molecule is sufficiently well spaced.

  4. Mechanism of Cr(VI) adsorption by coir pith studied by ESR and adsorption kinetic.

    PubMed

    Suksabye, Parinda; Nakajima, Akira; Thiravetyan, Paitip; Baba, Yoshinari; Nakbanpote, Woranan

    2009-01-30

    The oxidation state of chromium in coir pith after Cr(VI) adsorption from aqueous solution was investigated using electron spin resonance (ESR). To elucidate the mechanism of chromium adsorption on coir pith, the adsorption studies of Cr(VI) onto lignin, alpha-cellulose and holocellulose extracted from coir pith were also studied. ESR signals of Cr(V) and Cr(III) were observed in coir pith adsorbed Cr(VI) at solution pH 2, while ESR spectra of lignin extracted from coir pith revealed only the Cr(III) signal. In addition, ESR signal of Cr(V) was observed in alpha-cellulose and holocellulose extracted from coir pith adsorbed Cr(VI). These results confirmed that lignin in coir pith reduced Cr(VI) to Cr(III) while alpha-cellulose and holocellulose extracted from coir pith reduced Cr(VI) to Cr(V). The Cr(V) signal exhibited in ESR of alpha-cellulose and holocellulose might be bound with glucose in cellulose part of coir pith. In addition, xylose which is main in pentosan part of coir pith, indicated that it is involved in form complex with Cr(V) on coir pith. The adsorption kinetic of Cr(VI) from aqueous solution on coir pith was also investigated and described well with pseudo second order model. ESR and desorption experiments confirmed that Cr(VI), Cr(V) and Cr(III), exist in coir pith after Cr(VI) adsorption. The desorption data indicated that the percentage of Cr(VI), Cr(V) and Cr(III) in coir pith were 15.63%, 12.89% and 71.48%, respectively.

  5. Assessment of multi-mycotoxin adsorption efficacy of grape pomace.

    PubMed

    Avantaggiato, Giuseppina; Greco, Donato; Damascelli, Anna; Solfrizzo, Michele; Visconti, Angelo

    2014-01-15

    Grape pomace (pulp and skins) was investigated as a new biosorbent for removing mycotoxins from liquid media. In vitro adsorption experiments showed that the pomace obtained from Primitivo grapes is able to sequester rapidly and simultaneously different mycotoxins. Aflatoxin B1 (AFB1) was the most adsorbed mycotoxin followed by zearalenone (ZEA), ochratoxin A (OTA), and fumonisin B1 (FB1), whereas the adsorption of deoxynivalenol (DON) was negligible. AFB1 and ZEA adsorptions were not affected by changing pH values in the pH 3-8 range, whereas OTA and FB1 adsorptions were significantly affected by pH. Equilibrium adsorption isotherms obtained at different temperatures (5-70 °C) and pH values (3 and 7) were modeled and evaluated using the Freundlich, Langmuir, Sips, and Hill models. The goodness of the fits and the parameters involved in the adsorption mechanism were calculated by the nonlinear regression analysis method. The best-fitting models to describe AFB1, ZEA, and OTA adsorption by grape pomace were the Sips, Langmuir, and Freundlich models, respectively. The Langmuir and Sips models were the best models for FB1 adsorption at pH 7 and 3, respectively. The theoretical maximum adsorption capacities (mmol/kg dried pomace) calculated at pH 7 and 3 decreased in the following order: AFB1 (15.0 and 15.1) > ZEA (8.6 and 8.3) > OTA (6.3-6.9) > FB1 (2.2 and 0.4). Single- and multi-mycotoxin adsorption isotherms showed that toxin adsorption is not affected by the simultaneous presence of different mycotoxins in the liquid medium. The profiles of adsorption isotherms obtained at different temperatures and pH and the thermodynamic parameters (ΔG°, ΔH°, ΔS°) suggest that mycotoxin adsorption is an exothermic and spontaneous process, which involves physisorption weak associations. Hydrophobic interactions may be associated with AFB1 and ZEA adsorption, whereas polar noncovalent interactions may be associated with OTA and FB1 adsorption. In conclusion, this study

  6. Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

    SciTech Connect

    Alyoshina, Nonna A.; Parfenyuk, Elena V.

    2013-09-15

    A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N{sub 2} adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption process of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica.

  7. Adsorption of dimeric surfactants in lamellar silicates

    NASA Astrophysics Data System (ADS)

    Balcerzak, Mateusz; Pietralik, Zuzanna; Domka, Ludwik; Skrzypczak, Andrzej; Kozak, Maciej

    2015-12-01

    The adsorption of different types of cationic surfactants in lamellar silicates changes their surface character from hydrophilic to hydrophobic. This study was undertaken to obtain lamellar silicates modified by a series of novel dimeric (gemini) surfactants of different length alkyl chains and to characterise these organophilised materials. Synthetic sodium montmorillonite SOMASIF® ME 100 (M) and enriched bentonite of natural origin (Nanoclay - hydrophilic bentonite®) were organophilised with dimeric (gemini) surfactants (1,1‧-(1,4-butanediyl)bis(alkoxymethyl)imidazolium dichlorides). As a result of surfactant molecule adsorption in interlamellar space, the d-spacing (d001) increased from 0.97 nm (for the anhydrous structure) to 2.04 nm. A Fourier transform infrared spectroscopy (FTIR) analysis of the modified systems reveals bands assigned to the stretching vibrations of the CH2 and CH3 groups and the scissoring vibrations of the NH group from the structure of the dimeric surfactants. Thermogravimetric (TG) and derivative thermogravimetric (DTG) studies imply a four-stage process of surfactant decomposition. Scanning electron microscopy (SEM) images provide information on the influence of dimeric surfactant intercalation into the silicate structures. Particles of the modified systems show a tendency toward the formation of irregularly shaped agglomerates.

  8. REVIEW ARTICLE: The transmission interferometric adsorption sensor

    NASA Astrophysics Data System (ADS)

    Heuberger, M.; Balmer, T. E.

    2007-12-01

    This paper describes a high-speed adsorption sensor based on thin-film interference at the interfaces. The sensor can be used as a stand-alone instrument or in combination with a direct surface force measurement, which yields a wide range of additional information on molecular interactions on adsorbed films. The achieved mass resolution of the presented method (1-10 ng cm-2 Hz-1/2) is comparable to or better than other modern bio-sensors. The dependence of mass resolution on various factors is presented and demonstrated in a number of relevant examples. The described method is suitable for the implementation of a low-cost bio-sensor with a minimal number of optical elements. The measurement spot size is one micrometre or more and sampling rates >10 Hz are readily possible. In contrast to other bio-sensors, the signal baseline has a remarkable long-term stability since the measured signal is virtually independent of refractive index changes in the fluid medium above the sensor surface. In combination with an optical spectral correlation method, the classical computer calculations are substituted by an optical calculator and a label-free real-time imaging adsorption sensor is realized. We demonstrate sensor operation both inside the extended surface forces apparatus as well as in a stand-alone bio-sensor configuration. As a final point, we illustrate the imaging capability of this new sensor technology on a patterned bio-functionalized surface.

  9. Trichloroethylene (TCE) adsorption using sustainable organic mulch.

    PubMed

    Wei, Zongsu; Seo, Youngwoo

    2010-09-15

    Soluble substrates (electron donors) have been commonly injected into chlorinated solvent contaminated plume to stimulate reductive dechlorination. Recently, different types of organic mulches with economic advantages and sustainable benefits have received much attention as new supporting materials that can provide long term sources of electron donors for chlorinated solvent bioremediation in engineered biowall systems. However, sorption capacities of organic mulches for chlorinated solvents have not been studied yet. In this study, the physiochemical properties of organic mulches (pine, hardwood and cypress mulches) were measured and their adsorption capacity as a potential media was elucidated. Single, binary and quaternary isotherm tests were conducted with trichloroethylene (TCE), tetrachloroethylene (PCE), trans-dichloroethylene (trans-DCE) and cis-dichloroethylene (cis-DCE). Among the three tested mulches, pine mulch showed the highest sorption capacity for the majority of the tested chemicals in single isotherm test. In binary or quaternary isotherm tests, competition among chemicals appears to diminish the differences in Q(e) for tested mulches. However, pine mulch also showed higher adsorption capacity for most chemicals when compared to hardwood and cypress mulches in the two isotherm tests. Based upon physicochemical properties of the three mulches, higher sorption capacity of pine mulch over hardwood and cypress mulches appears to be attributed to a higher organic carbon content and the lower polarity.

  10. Particle morphology effects in random sequential adsorption

    NASA Astrophysics Data System (ADS)

    Budinski-Petković, Lj.; Lončarević, I.; Dujak, D.; Karač, A.; Šćepanović, J. R.; Jakšić, Z. M.; Vrhovac, S. B.

    2017-02-01

    The properties of the random sequential adsorption of objects of various shapes on a two-dimensional triangular lattice are studied numerically by means of Monte Carlo simulations. The depositing objects are formed by self-avoiding lattice steps, whereby the size of the objects is gradually increased by wrapping the walks in several different ways. The aim of this work is to investigate the impact of the geometrical properties of the shapes on the jamming density θJ and on the temporal evolution of the coverage fraction θ (t ) . Our results suggest that the order of symmetry axis of a shape exerts a decisive influence on adsorption kinetics near the jamming limit θJ. The decay of probability for the insertion of a new particle onto a lattice is described in a broad range of the coverage θ by the product between the linear and the stretched exponential function for all examined objects. The corresponding fitting parameters are discussed within the context of the shape descriptors, such as rotational symmetry and the shape factor (parameter of nonsphericity) of the objects. Predictions following from our calculations suggest that the proposed fitting function for the insertion probability is consistent with the exponential approach of the coverage fraction θ (t ) to the jamming limit θJ.

  11. Macroscopic and spectroscopic investigations of the adsorption of nitroaromatic compounds on graphene oxide, reduced graphene oxide, and graphene nanosheets.

    PubMed

    Chen, Xiaoxiao; Chen, Baoliang

    2015-05-19

    The surface properties and adsorption mechanisms of graphene materials are important for potential environmental applications. The adsorption of m-dinitrobenzene, nitrobenzene, and p-nitrotoluene onto graphene oxide (GO), reduced graphene oxide (RGO), and graphene (G) nanosheets was investigated using IR spectroscopy to probe the molecular interactions of graphene materials with nitroaromatic compounds (NACs). The hydrophilic GO displayed the weakest adsorption capability. The adsorption of RGO and G was significantly increased due to the recovery of hydrophobic π-conjugation carbon atoms as active sites. RGO nanosheets, which had more defect sites than did GO or G nanosheets, resulted in the highest adsorption of NACs which was 10-50 times greater than the reported adsorption of carbon nanotubes. Superior adsorption was dominated by various interaction modes including π-π electron donor-acceptor interactions between the π-electron-deficient phenyls of the NACs and the π-electron-rich matrix of the graphene nanosheets, and the charge electrostatic and polar interactions between the defect sites of graphene nanosheets and the -NO2 of the NAC. The charge transfer was initially proved by FTIR that a blue shift of asymmetric -NO2 stretching was observed with a concomitant red shift of symmetric -NO2 stretching after m-dinitrobenzene was adsorbed. The multiple interaction mechanisms of the adsorption of NAC molecule onto flat graphene nanosheets favor the adsorption, detection, and transformation of explosives.

  12. Adsorption of ethanol on V2O5 (010) surface for gas-sensing applications: Ab initio investigation

    NASA Astrophysics Data System (ADS)

    Qin, Yuxiang; Cui, Mengyang; Ye, Zhenhua

    2016-08-01

    The adsorption of ethanol on V2O5 (010) surface was investigated by means of density functional theory (DFT) with a combined generalized gradient approximation (GGA) plus Hubbard U approach to exploit the potential sensing applications. The adsorption configurations were first constructed by considering different orientations of ethanol molecule to V and O sites on the "Hill"- and "Valley"-like regions of corrugated (010) surface. It is found that ethanol molecule can adsorb on whole surface in multiple stable configurations. Nevertheless the molecular adsorption on the "Hill"-like surface is calculated to occur preferentially, and the single coordinated oxygen on "Hill"-like surface (O1(H)) acting as the most energetically favorable adsorption site shows the strongest adsorption ability to ethanol molecule. Surface adsorption of ethanol tunes the electronic structure of V2O5 and cause an n-doping effect. As a consequence, the Fermi levels shift toward the conductive bond increasing the charge carrier concentration of electrons in adsorbed V2O5. The sensitive electronic structure and the multiple stable configurations to ethanol adsorption highlight the high adsorption activity and then the potential of V2O5 (010) surface applied to high sensitive sensor for ethanol vapor detection. Further Mulliken population and Natural bond orbital (NBO) calculations quantify the electron transfer from the adsorbed ethanol to the surface, and correlates the adsorption ability of surface sites with the charge donation and dispersion.

  13. Combined DFT and XPS investigation of iodine anions adsorption on the sulfur terminated (001) chalcopyrite surface

    NASA Astrophysics Data System (ADS)

    Li, Kui; Zhao, Yaolin; Zhang, Peng; He, Chaohui; Deng, Jia; Ding, Shujiang; Shi, Weiqun

    2016-12-01

    The adsorption of iodine anions (iodide and iodate) on the sulfur terminated (001) chalcopyrite surface has been systematically investigated combining first-principles calculations based on density functional theory (DFT) with X-ray photoelectron spectroscopy (XPS) measurements. Based on the total energy calculations and geometric optimization, the thermodynamically preferred site was copper atom for iodide adsorption and iron atom for iodate adsorption, respectively. In the case of Cu site mode, the iodate underwent a dissociative adsorption, where one Isbnd O bond of iodate ion was broken and the dissociative oxygen atom adsorbed on the adjacent sulphur site. Projected density of states (PDOS) analysis further clarified the interaction mechanism between active sites of chalcopyrite surface and adsorbates. In addition, full-range XPS spectra qualitatively revealed the presence of iodine on chalcopyrite surface. High resolution XPS spectra of the I 3d peaks after adsorption verified the chemical environment of iodine. The binding energies of 618.8 eV and 623.5 eV for I 3d5/2 peaks unveiled that the adsorption of iodide and iodate ions on copper-iron sulfide minerals was the result of formation of low solubility metal iodides precipitate. Also two I 3d peaks with low intensity around 618 eV and 630 eV might be related to the inorganic reduction of iodate to iodide by reducing S2- ion of chalcopyrite.

  14. Correlations and adsorption mechanisms of aromatic compounds on a high heat temperature treated bamboo biochar.

    PubMed

    Yang, Kun; Yang, Jingjing; Jiang, Yuan; Wu, Wenhao; Lin, Daohui

    2016-03-01

    Adsorption of aromatic compounds, including polycyclic aromatic hydrocarbons, nitrobenzenes, phenols, and anilines, on a bamboo biochar produced at 700 °C (Ba700) was investigated with the mechanism discussion by isotherm fitting using the Polanyi-theory based Dubinin-Ashtakhov (DA) model. Correlations of adsorption capacity (Q(0)) of organic compounds with their molecular sizes and melting points, as well as correlations of adsorption affinity (E) with their solvatochromic parameters (i.e., π* and αm), on the biochar, were developed and indicating that adsorption is captured by the pore filling mechanism and derived from the hydrophobic effects of organic compounds and the forming of π-π electron donor-acceptor (EDA) interactions and hydrogen bonding interactions of organic molecules with surface sites of the biochar. The effects of organic molecular sizes and melting points on adsorption capacity are ascribed to the molecular sieving effect and the packing efficiency of the organic molecules in the biochar pores, respectively. These correlations can be used to quantitatively estimate the adsorption of organic compounds on biochars from their commonly physicochemical properties including solvatochromic parameters, melting points and molecular cross-sectional area. The prediction using these correlations is important for assessing the unknown adsorption behaviors of new organic compounds and also helpful to guide the surface modification of biochars and make targeted selection in the environmental applications of biochars as adsorbents.

  15. Effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils.

    PubMed

    Wang, Yu-Jun; Zhou, Dong-mei; Sun, Rui-juan

    2005-01-01

    Glyphosate (GPS) is a non-selective, post-mergence herbicide that is widely used throughout the world. Due to the similar molecular structures of glyphosate and phosphate, adsorption of glyphosate on soil is easily affected by coexisting phosphate, especially when phosphate is applied at a significant rate in farmland. This paper studied the effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils including two variable charge soils and one permanent charge soil. The results indicated that Freundlich equations used to simulate glyphosate adsorption isotherms gave high correlation coefficients (0.990-0.998) with K values of 2751, 2451 and 166 for the zhuanhong soil(ZH soil, Laterite), red soil(RS, Udic Ferrisol) and Wushan paddy soil (WS soil, Anthrosol), respectively. The more the soil iron and aluminum oxides and clay contained, the more glyphosate adsorbed. The presence of phosphate significantly decreased the adsorption of glyphosate to the soils by competing with glyphosate for adsorption sites of soils. Meanwhile, the effects of phosphate on adsorption of glyphosate on the two variable charge soils were more significant than that on the permanent charge soil. When phosphate and glyphosate were added in the soils in different orders, the adsorption quantities of glyphosate on the soils were different, which followed GPS-soil > GPS-P-soil = GPS-soil-P > P-soil-GPS, meaning a complex interaction occurred among glyphosate, phosphate and the soils.

  16. First principles derived, transferable force fields for CO2 adsorption in Na-exchanged cationic zeolites.

    PubMed

    Fang, Hanjun; Kamakoti, Preeti; Ravikovitch, Peter I; Aronson, Matthew; Paur, Charanjit; Sholl, David S

    2013-08-21

    The development of accurate force fields is vital for predicting adsorption in porous materials. Previously, we introduced a first principles-based transferable force field for CO2 adsorption in siliceous zeolites (Fang et al., J. Phys. Chem. C, 2012, 116, 10692). In this study, we extend our approach to CO2 adsorption in cationic zeolites which possess more complex structures. Na-exchanged zeolites are chosen for demonstrating the approach. These methods account for several structural complexities including Al distribution, cation positions and cation mobility, all of which are important for predicting adsorption. The simulation results are validated with high-resolution experimental measurements of isotherms and microcalorimetric heats of adsorption on well-characterized materials. The choice of first-principles method has a significant influence on the ability of force fields to accurately describe CO2-zeolite interactions. The PBE-D2 derived force field, which performed well for CO2 adsorption in siliceous zeolites, does not do so for Na-exchanged zeolites; the PBE-D2 method overestimates CO2 adsorption energies on multi-cation sites that are common in cationic zeolites with low Si/Al ratios. In contrast, a force field derived from the DFT/CC method performed well. Agreement was obtained between simulation and experiment not only for LTA-4A on which the force field fitting is based, but for other two common adsorbents, NaX and NaY.

  17. Fabrication of polyaniline hydrogel: Synthesis, characterization and adsorption of methylene blue

    NASA Astrophysics Data System (ADS)

    Yan, Bo; Chen, Zhonghui; Cai, Lu; Chen, Zhimin; Fu, Jianwei; Xu, Qun

    2015-11-01

    Polyaniline (PAni) hydrogel was synthesized in a facial method by using phytic acid as both dopant and cross-linking agent. Then the fabricated hydrogel was employed as an efficient adsorbent to remove the methylene blue (MB) in an aqueous solution. The as-synthesized PAni hydrogel was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images. The characterization results indicate that the obtained PAni hydrogel has a 3D structure, which is available for the contact between the adsorbent and dye molecules. During the adsorption, the phytic acid provides a large number of anionic phosphate groups as adsorption sites for MB molecules, which induces the high adsorption capacity up to 71.2 mg/g. The effects of pH, the PAni hydrogel mass and temperatures on adsorption efficiency were studied in details. Further experimental results indicate the adsorption kinetic fits well with the pseudo-second-order kinetic model. Compared with Freundlich model, Langmuir isotherm model was more acceptable to fit the equilibrium adsorption data. Moreover, the conceivable mechanism of the adsorption was also proposed in this work.

  18. Competitive adsorption of metals onto magnetic graphene oxide: comparison with other carbonaceous adsorbents.

    PubMed

    Hur, Jin; Shin, Jaewon; Yoo, Jeseung; Seo, Young-Soo

    2015-01-01

    Competitive adsorption isotherms of Cu(II), Pb(II), and Cd(II) were examined on a magnetic graphene oxide (GO), multiwalled carbon nanotubes (MWCNTs), and powered activated carbon (PAC). A series of analyses confirmed the successful synthesis of the magnetic GO based on a simple ultrasonification method. Irrespective of the adsorbents, the adsorption was highly dependent on pH, and the adsorption was well described by the Langmuir isotherm model. The maximum adsorption capacities of the adsorbents were generally higher in the order of Pb(II)>Cu(II)>Cd(II), which is the same as the degree of the electronegativity and the hydrated radius of the metals, suggesting that the metal adsorption may be governed by an ion exchange between positively charged metals and negatively charged surfaces, as well as diffusion of metals into the surface layer. The adsorption of each metal was mostly lower for multi- versus single-metal systems. The antagonistic effects were influenced by solution pH as well as the type of metals, and they were higher in the order of the magnetic GO>MWCNT>PAC. Dissolved HS played a greater role than HS adsorbed onto the adsorbents, competing with the adsorption sites for metal complexation.

  19. Adsorption decontamination of radioactive waste solvent by activated alumina and bauxites

    SciTech Connect

    Hassan, N.M.; Marra, J.C.; Kyser, E.A.

    1994-10-01

    An adsorption process utilizing activated alumina and activated bauxite adsorbents was evaluated as a function of operating parameters for the removal of low level radioactive contaminants from organic waste solvent generated in the fuel reprocessing facilities and support operations at Savannah River Site. The waste solvent, 30% volume tributyl phosphate in n-paraffin diluent, was degraded due to hydrolysis and radiolysis reactions of tributyl phosphate and n-paraffin diluent, producing fission product binding degradation impurities. The process, which has the potential for removing these activity-binding degradation impurities from the solvent, was operated downflow through glass columns packed with activated alumina and activated bauxite adsorbents. Experimental breakthrough curves were obtained under various operating temperatures and flow rates. The results show that the adsorption capacity of the activated alumina was in the order 10{sup 4} dpm/g and the capacity of the activated bauxite was 10{sup 5} dpm/g. The performance of the adsorption process was evaluated in terms of dynamic parameters (i.e. adsorption capacity, the height and the efficiency of adsorption zone) in such a way as to maximize the adsorption capacity and to minimize the height of the mass transfer or adsorption zone.

  20. Adsorption decontamination of radioactive waste solvent by activated alumina and bauxites

    SciTech Connect

    Hassan, N.M.; Matthews, R.S.; Marra, J.C.; Kyser, E.A.

    1995-06-01

    An adsorption process utilizing activated alumina and activated bauxite adsorbents was evaluated as a function of operating parameters for the removal of low level radioactive contaminants from organic waste solvent generated in the fuel reprocessing facilities and support operations at Savannah River Site. The waste solvent, 30 vol% tributyl phosphate in n-paraffin diluent, was degraded due to hydrolysis and radiolysis reaction of tributyl phosphate and n-paraffin diluent, producing fission product binding degradation impurities. The process, which has the potential for removing these activity-binding degradation impurities from the solvent, was operated downflow through glass columns packed with activated alumina and activated bauxite adsorbents. Experimental breakthrough curves were obtained under various operating temperatures and flow rates. The results show that the adsorption capacities of activated alumina and activated bauxite were in the order of 10{sup 4} and 10{sup 5} dpm/g of adsorbent, respectively. The performance of the adsorption process was evaluated in terms of dynamic parameters (i.e., adsorption capacity, the height and the efficiency of adsorption zone) in such a way as to maximize the adsorption capacity and to minimize the height of the mass transfer or adsorption zone.

  1. Adsorption of oxazole and isoxazole on BNNT surface: A DFT study

    NASA Astrophysics Data System (ADS)

    Kaur, Jasleen; Singla, Preeti; Goel, Neetu

    2015-02-01

    The adsorption behavior of oxazole and isoxazole heterocycles over the (6,0) zigzag and (5,5) armchair boron nitride nanotube (BNNT) has been studied within the formalism of density functional theory (DFT). The adsorption energies, the frontier molecular orbital (FMO) analysis and the structural changes at the adsorption site are indicative of covalent adsorption on the zigzag BNNT surface, while the adsorption is physical in nature on the armchair BNNT surface. The role of solvent in improving the adsorption properties over the BNNT surface is elucidated by reoptimizing the structures in aqueous phase. The solvation energy is indicative of remarkable increase in the solubility of BNNTs after adsorption of heterocyclic rings. The Density of states (DOS) Plots, natural bond orbital (NBO) analysis and the quantum molecular descriptors (QMD) are witness to the substantial changes in the electronic properties of the BNNT systems following the attachment of these heterocycles with the tube surface. The study envisages the functionalization of the BNNT as well as its applicability as carrier of the drugs containing heterocyclic rings oxazole and isoxazole with marked sensitivity to the type of adsorbate and the adsorbent.

  2. Competitive Adsorption of Metals onto Magnetic Graphene Oxide: Comparison with Other Carbonaceous Adsorbents

    PubMed Central

    Hur, Jin; Shin, Jaewon; Yoo, Jeseung; Seo, Young-Soo

    2015-01-01

    Competitive adsorption isotherms of Cu(II), Pb(II), and Cd(II) were examined on a magnetic graphene oxide (GO), multiwalled carbon nanotubes (MWCNTs), and powered activated carbon (PAC). A series of analyses confirmed the successful synthesis of the magnetic GO based on a simple ultrasonification method. Irrespective of the adsorbents, the adsorption was highly dependent on pH, and the adsorption was well described by the Langmuir isotherm model. The maximum adsorption capacities of the adsorbents were generally higher in the order of Pb(II) > Cu(II) > Cd(II), which is the same as the degree of the electronegativity and the hydrated radius of the metals, suggesting that the metal adsorption may be governed by an ion exchange between positively charged metals and negatively charged surfaces, as well as diffusion of metals into the surface layer. The adsorption of each metal was mostly lower for multi- versus single-metal systems. The antagonistic effects were influenced by solution pH as well as the type of metals, and they were higher in the order of the magnetic GO > MWCNT > PAC. Dissolved HS played a greater role than HS adsorbed onto the adsorbents, competing with the adsorption sites for metal complexation. PMID:25861683

  3. Temperature-dependent adsorption of hydrogen, deuterium, and neon on porous Vycor glass

    NASA Astrophysics Data System (ADS)

    Huber, T. E.; Scardino, D.; Tsou, H. L.

    1995-10-01

    Adsorption isotherms of H2, D2, and Ne have been measured in the temperature range from 15 K to the corresponding critical points in samples of porous Vycor glass. From the Brunauer-Emmett-Teller theory the surface layer coverages are determined. These are found to be temperature dependent. A model-independent approach allows us to fit the data for coverages ranging from submonolayer to thin film, below capillary condensation, for each adsorbate at all temperatures with a temperature-independent curve. This characteristic curve represents the distribution of adsorption sites versus the adsorption potential. In the intermediate coverage range, the isotherms exhibit the modified Frenkel-Halsey-Hill (FHH) behavior. The adsorption saturates for low-adsorption potentials. The characteristic curve is a useful universal curve since it is roughly the same for the three species investigated. We examine the relative strengths of the surface potentials and densities of the two isotopic modifications of hydrogen and of the more classical Ne adsorbed on porous Vycor glass. The characteristic adsorption curve is compared with results from two models for the adsorbate: Dubinin's isotherm for microporous solids and its extension to rough surfaces which places importance on the porosity of the surface, and Halsey's model, which is an extension of the FHH isotherm that takes into account the long-range variations of substrate adsorption potential.

  4. Perchlorate adsorption and desorption on activated carbon and anion exchange resin.

    PubMed

    Yoon, In-Ho; Meng, Xiaoguang; Wang, Chao; Kim, Kyoung-Woong; Bang, Sunbaek; Choe, Eunyoung; Lippincott, Lee

    2009-05-15

    The mechanisms of perchlorate adsorption on activated carbon (AC) and anion exchange resin (SR-7 resin) were investigated using Raman, FTIR, and zeta potential analyses. Batch adsorption and desorption results demonstrated that the adsorption of perchlorate by AC and SR-7 resin was reversible. The reversibility of perchlorate adsorption by the resin was also proved by column regeneration test. Solution pH significantly affected perchlorate adsorption and the zeta potential of AC, while it did not influence perchlorate adsorption and the zeta potential of resin. Zeta potential measurements showed that perchlorate was adsorbed on the negatively charged AC surface. Raman spectra indicated the adsorption resulted in an obvious position shift of the perchlorate peak, suggesting that perchlorate was associated with functional groups on AC at neutral pH through interactions stronger than electrostatic interaction. The adsorbed perchlorate on the resin exhibited a Raman peak at similar position as the aqueous perchlorate, indicating that perchlorate was adsorbed on the resin through electrostatic attraction between the anion and positively charged surface sites.

  5. [Adsorption of perfluorooctanesulfonate (PFOS) onto modified activated carbons].

    PubMed

    Tong, Xi-Zhen; Shi, Bao-You; Xie, Yue; Wang, Dong-Sheng

    2012-09-01

    Modified coal and coconut shell based powdered activated carbons (PACs) were prepared by FeCl3 and medium power microwave treatment, respectively. Batch experiments were carried out to evaluate the characteristics of adsorption equilibrium and kinetics of perfluorooctanesulfonate (PFOS) onto original and modified PACs. Based on pore structure and surface functional groups characterization, the adsorption behaviors of modified and original PACs were compared. The competitive adsorption of humic acid (HA) and PFOS on original and modified coconut shell PACs were also investigated. Results showed that both Fe3+ and medium power microwave treatments changed the pore structure and surface functional groups of coal and coconut shell PACs, but the changing effects were different. The adsorption of PFOS on two modified coconut shell-based PACs was significantly improved. While the adsorption of modified coal-based activated carbons declined. The adsorption kinetics of PFOS onto original and modified coconut shell-based activated carbons were the same, and the time of reaching adsorption equilibrium was about 6 hours. In the presence of HA, the adsorption of PFOS by modified PAC was reduced but still higher than that of the original.

  6. Adsorption of mercury on laterite from Guizhou Province, China.

    PubMed

    Yu, Xiaohong; Zhu, Lijun; Guo, Baiwei; He, Shouyang

    2008-01-01

    The adsorption behaviors of Hg(II) on laterite from Guizhou Province, China, were studied and the adsorption mechanism was discussed. The results showed that different mineral compositons in the laterite will cause differences in the adsorption capacity of laterite to Hg(II). Illite and non-crystalloids are the main contributors to enhancing the adsorption capacity of laterite to Hg(II). The pH of the solution is an important factor affecting the adsorption of Hg(II) on laterite. The alkalescent environment (pH 7-9) is favorable to the adsorption of Hg(II). The amount of adsorbed Hg(II) increases with increasing pH. When the pH reaches a certain value, the amount of the adsorbed Hg(II) will reach the maximum level. The amount of adsorbed Hg(II) decreases with increasing pH. The optimal pHs of laterite and kaolinite are 9 and 8, respectively. The optimal initial concentrations of Hg(II) on laterite and kaolinite are 250 and 200 microg/ml, respectively. The adsorption isotherms were described by the Langmuir model. The adsorption of Hg(II) on laterite is a quick process while that of Hg(II) on kaolinite is a slow reaction. Laterite from Guizhou Province is a promising environmental material which can be used in the removal of Hg(II) from wastewater.

  7. Adsorption dynamics of molecular nitrogen at an Fe(111) surface.

    PubMed

    Nosir, M A; Martin-Gondre, L; Bocan, G A; Díez Muiño, R

    2017-03-08

    We present an extensive theoretical study of N2 adsorption mechanisms on an Fe(111) surface. We combine the static analysis of a six-dimensional potential energy surface (6D-PES), based on ab initio density functional theory (DFT) calculations for the system, with quasi-classical trajectory (QCT) calculations to simulate the adsorption dynamics. There are four molecular adsorption states, usually called γ, δ, α, and ε, arising from our DFT calculations. We find that N2 adsorption in the γ-state is non-activated, while the threshold energy is associated with the entrance channel for the other three adsorption states. Our QCT calculations confirm that there are activated and nonactivated paths for the adsorption of N2 on the Fe(111) surface, which is in agreement with previous experimental investigations. Molecular dynamics at a surface temperature Ts = 300 K and impact energies Ei in the 0-5 eV range show the relative occupancy of the γ, δ, α, and ε states. The δ-state, however, is only marginally populated despite its adsorption energy being very similar to that of the γ-state. Our QCT calculations trace the dependence of molecular trapping on the surface temperature Ts and initial impact energy Ei and quantify the rates of the different competitive channels that eventually lead to molecular adsorption.

  8. [Adsorption of Congo red from aqueous solution on hydroxyapatite].

    PubMed

    Zhan, Yan-Hui; Lin, Jian-Wei

    2013-08-01

    The adsorption of Congo red (CR) from aqueous solution on hydroxyapatite was investigated using batch experiments. The hydroxyapatite was effective for CR removal from aqueous solution. The adsorption kinetics of CR on hydroxyapatite well followed a pseudo-second-order model. The equilibrium adsorption data of CR on hydroxyapatite could be described by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and showed that the adsorption of CR on hydroxyapatite was spontaneous and exothermic in nature. The CR adsorption capacity for hydroxyapatite decreased significantly with increasing pH from 8 to 10. Thermal regeneration showed that hydroxyapatite could be used for six desorption-adsorption cycles with high removal efficiency for CR in each cycle. The mechanisms for CR adsorption on hydroxyapatite with pH value below the pH at point of zero charge (pH(PZC)) include electrostatic attraction, hydrogen bonding and Lewis acid-base interaction. The mechanisms for CR adsorption on hydroxyapatite with pH value above its pH(PZC) include hydrogen bonding and Lewis acid-base interaction. Results of this work indicate that hydroxyapatite is a promising adsorbent for CR removal from aqueous solution.

  9. Derivation of the Freundlich Adsorption Isotherm from Kinetics

    ERIC Educational Resources Information Center

    Skopp, Joseph

    2009-01-01

    The Freundlich adsorption isotherm is a useful description of adsorption phenomena. It is frequently presented as an empirical equation with little theoretical basis. In fact, a variety of derivations exist. Here a new derivation is presented using the concepts of fractal reaction kinetics. This derivation provides an alternative basis for…

  10. Adsorption of Pyrene onto the Agricultural By-Product: Corncob.

    PubMed

    Li, Xiaojun; Tong, Dongli; Allinson, Graeme; Jia, Chunyun; Gong, Zongqing; Liu, Wan

    2016-01-01

    The adsorption behavior of pyrene on corncob was studied to provide a theoretical basis for the possible use of this material as an immobilized carrier for improving the bioremediation of PAH-contaminated soil. The results were as follows. Kinetic experiments showed that the adsorption processes obeyed a pseudo-second-order model. The intraparticle diffusion of Weber-Morris model fitting showed that the film and intraparticle diffusions were the key rate-limiting processes, and the adsorption process mainly consisted of three steps: boundary layer diffusion and two intra-particle diffusions. Experimental adsorption data for pyrene were successfully described by the adsorption-partition equilibrium model. The maximum adsorption capacity at 25°C was 214.8 μg g(-1). The adsorption contribution decreased significantly when the Ce/Sw (the equilibrium concentration/solubility in water) was higher than 1. Adsorption decreased with increased temperature. Based on the above results, the corncob particles could be helpful in the bioremediation of pyrene-contaminated soil.

  11. Predicting Boron, Molybdenum, Selenium, and Arsenic Adsorption in Soil Systems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A chemical surface complexation model was applied to boron, molybdenum, selenium, and arsenic adsorption on up to 49 soils selected for variation in soil properties. The surface complexation model was able to fit boron, molybdenum, selenite, and arsenate adsorption on the soils. General regression...

  12. Mechanism of amitriptyline adsorption on Ca-montmorillonite (SAz-2).

    PubMed

    Chang, Po-Hsiang; Jiang, Wei-Teh; Li, Zhaohui; Kuo, Chung-Yih; Jean, Jiin-Shuh; Chen, Wan-Ru; Lv, Guocheng

    2014-07-30

    The uptake of amitriptyline (AMI) from aqueous environment by Ca-montmorillonite (SAz-2) was studied in a batch system under different physicochemical conditions. The adsorbent was characterized by X-ray diffraction and Fourier transform infrared (FTIR) analyses. The AMI adsorption on SAz-2 obeyed the Langmuir isotherm with a capacity of 330mg/g (1.05mmol/g) at pH 6-7. The adsorption kinetics was fast, almost reaching equilibrium in 2h, and followed a pseudo-second-order kinetic model. Desorption of exchangeable cations correlated with the AMI adsorption well, indicating that cation exchange was the major mechanism. X-ray diffraction patterns showing significant expansions of the d001 spacing and characteristic FTIR band shifts toward higher frequencies after AMI adsorption onto SAz-2 indicated that the adsorbed AMI molecules were intercalated into the interlayers of the mineral. Thermodynamic parameters based on partitioning coefficients suggested that the AMI adsorption was an endothermic physisorption at high adsorption levels. At low and higher AMI adsorption levels, the intercalated AMI molecules take a horizontal monolayer and bilayer conformation, respectively. The higher adsorption capacity suggested that SAz-2 could be a good candidate to remove AMI from wastewater and would be an important environmental sink for the fate and transport of AMI in soils and groundwater.

  13. Adsorptive removal of PPCPs by biomorphic HAP templated from cotton.

    PubMed

    Huang, Bin; Xiong, Dan; Zhao, Tingting; He, Huan; Pan, Xuejun

    2016-01-01

    Biomorphic nano-hydroxyapatite (HAP) was fabricated by a co-precipitation method using cotton as bio-templates and employed in adsorptive removal of ofloxacin (OFL) and triclosan (TCS) that are two representative pharmaceuticals and personal care products (PPCPs). The surface area and porosity, crystal phase, functional group, morphology and micro-structure of the synthesized HAP were characterized by Brunauer-Emmett-Teller isotherm, X-ray powder diffraction, Fourier transform infrared spectroscopy, scanning electron macroscopic and transmission electron microscopy. The effects of initial pH, ionic strength, initial concentration, contact time and temperature on the removal of PPCPs were studied in a batch experiment. The adsorption of OFL and TCS was rapid and almost accomplished within 50 min. Kinetic studies indicated that the adsorption process of OFL and TCS followed the pseudo-first-order and pseudo-second-order models, respectively. The Freundlich isotherm described the OFL adsorption process well but the adsorption of TCS fitted the Langmuir isotherm better. Thermodynamics and isotherm parameters suggested that both OFL and TCS adsorption were feasible and spontaneous. Hydrogen bond and Lewis acid-base reaction may be the dominating adsorption mechanism of OFL and TCS, respectively. Compared to other adsorbents, biomorphic HAP is environmentally friendly and has the advantages of high adsorption capacity, exhibiting potential application for PPCPs removal.

  14. Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

    EPA Science Inventory

    Arsenate adsorption on amorphous (RuO2•1.1H2O) and crystalline (RuO2) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

  15. EFFECT OF GAC CHARACTERISTICS ON ADSORPTION OF ORGANIC POLLUTANTS

    EPA Science Inventory

    The impact of the characteristics of granular activated carbon (GAC) on adsorption capacity and on the potential for polymerization of phenolic compounds on the surface of GAC in the presence of molecular oxygen is evaluated in this study. Adsorption isotherm data were collected...

  16. Antimony(V) Adsorption by Variable-Charge Minerals

    DTIC Science & Technology

    2013-10-01

    Sb(OH)6, SO4, and PO4 adsorption by gibbsite , kaolinite , goethite, and birnessite...pKa triple layer surface complexation modeling of Sb(OH)6, SO4, and PO4 adsorption by gibbsite , kaolinite , goethite, and birnessite...Competition Surface Complexation Triple Layer Model Gibbsite Kaolinite Goethite Birnessite xviii Abstract Background. Antimony (Sb) is a

  17. Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

    NASA Astrophysics Data System (ADS)

    Feng, Qinzhong; Zhang, Zhiyong; Ma, Yuhui; He, Xiao; Zhao, Yuliang; Chai, Zhifang

    2012-01-01

    The rapid increase in the use of engineered nanoparticles [ENPs] has resulted in an increasing concern over the potential impacts of ENPs on the environmental and human health. ENPs tend to adsorb a large variety of toxic chemicals when they are emitted into the environment, which may enhance the toxicity of ENPs and/or adsorbed chemicals. The study was aimed to investigate the adsorption and desorption behaviors of arsenic on ceria NPs in aqueous solution using batch technique. Results show that the adsorption behavior of arsenic on ceria NPs was strongly dependent on pH and independent of ionic strength, indicating that the electrostatic effect on the adsorption of these elements was relatively not important compared to surface chemical reactions. The adsorption isotherms fitted very well to both the Langmuir and Freundlich models. The thermodynamic parameters (Δ H 0 , Δ S 0 , and Δ G 0 ) for the adsorption of arsenic were determined at three different temperatures of 283, 303, and 323 K. The adsorption reaction was endothermic, and the process of adsorption was favored at high temperature. The desorption data showed that desorption hysteresis occurred at the initial concentration studied. High adsorption capacity of arsenic on ceria NPs suggests that the synergistic effects of ceria NPs and arsenic on the environmental systems may exist when they are released into the environment.

  18. Adsorption behavior of some radionuclides on the Chinese weathered coal.

    PubMed

    Wu, Jianfeng; Xu, Qichu; Bai, Tao

    2007-08-01

    The equilibrium and kinetic properties of Am(III), Eu(III) and Cs(I) ions adsorption by three weathered coals (WCs) from China, have been investigated in batch stirred-tank experiments. The effects of contact time, solution acidity and initial sorbate concentration on the adsorption of Am(III), Eu(III) and Cs(I) by Yuxian(YX) Tongchuan (TC) and Pingxiang (PX) WC were evaluated. The radionuclide ions are able to form complex compounds with carboxylic and phenolic groups of WCs and they are also bounded with phenolic groups even at high acidity reaction solution (>0.1 mol/L). Mechanisms including ion exchange, complexation and adsorption to the coal surface are possible in the sorption process. The acidity of the solution played an important role in the adsorption. Even acidity as high as 0.1 mol/L, 60% of Am(III) or Eu(III), 40% of Cs(I) were found to be sorbed on the YX WC, which had the best adsorption capacity for Am(III) and Eu(III). Our batch adsorption studies showed the equilibrium adsorption data fit the linear Langmuir and Freundlich adsorption isotherm. The maximum equilibrium uptake of Eu(III) were 0.412, 3.701, 5.446 mmol/g for JXWC, TCWC and YXWC, respectively.

  19. Adsorption of soluble oil from water to graphene.

    PubMed

    Wang, Na; Zhang, Yuchang; Zhu, Fuzhen; Li, Jingyi; Liu, Shuaishuai; Na, Ping

    2014-05-01

    The toxicity of soluble oil to the aquatic environment has started to attract wide attention in recent years. In the present work, we prepare graphene according to oxidation and thermal reduction methods for the removal of soluble oil from the solution. Characterization of the as-prepared graphene are performed by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectra, Brunauer-Emmett-Teller, X-ray photoelectron spectroscopy, and contact angle analysis. The adsorption behavior of soluble oil on graphene is examined, and the obtained adsorption data are modeled using conventional theoretical models. Adsorption experiments reveal that the adsorption rate of soluble oil on graphene is notably fast, especially for the soluble diesel oil, which could reach equilibrium within 30 min, and the kinetics of adsorption is perfectly consistent with a pseudo-second-order model. Furthermore, it is determined that the adsorption isotherm of soluble diesel oil with graphene fit the Freundlich model best, and graphene has a very strong adsorption capacity for soluble diesel oil in the solution. These results demonstrate that graphene is the material that provided both good adsorptive capacity and good kinetics, implying that it could be used as a promising sorbent for soluble oil removal from wastewater.

  20. First-principles study of adsorption of methanethiol on Co(0001)

    NASA Astrophysics Data System (ADS)

    Wang, L. G.; Tsymbal, E. Y.; Jaswal, S. S.

    2004-08-01

    Investigation of the resident site and the adsorption phase structure of thiolates is of fundamental importance for understanding the formation of self-assembled organic monolayers on metal substrate surfaces. In the present study, we have investigated adsorption of methanethiol, CH3SH , on the ferromagnetic Co(0001) surface using density functional theory calculations. We find that the dissociative adsorption of CH3SH forming an adsorbed methylthiolate (CH3S) and an adsorbed H atom is energetically favorable, and that the CH3S molecule adsorbed at the threefold fcc and hcp hollow sites is most stable. The adsorption energy at the bridge site is only ˜0.2eV smaller than that at the threefold hollow site, and the adsorption of CH3S at the atop site is unstable. For the (3×3)R30° , (2×2) and (2×3) adsorptions, we find that the S-C bond tends to be normal to the surface, whereas for the (2×1) adsorption it tilts away from the surface normal direction by ˜40° . The (2×1) adsorption phase is much less stable. The reduction of the adsorption energy with the increasing coverage is attributed to the repulsive interaction between the adsorbates. Our calculations show that the (3×3)R30° structure may form in the process of methylthiolate adsorption on Co(0001) due to its adsorption energy being only 0.1eV lower than that for the (2×2) and (2×3) structures. We find that there is a charge transfer from the substrate surface atoms to the S atoms, and that the S-Co bond is strongly polar. The surface Co atoms bound to S have a magnetic moment of ˜1.66μB , while the surface Co atoms unbound to S have a larger magnetic moment of ˜1.85μB . The S atom in the adsorbed CH3S acquires a magnetic moment of ˜0.08μB .

  1. Simultaneous adsorption of methyl red and methylene blue onto biochar and an equilibrium modeling at high concentration.

    PubMed

    Ding, Guanyu; Wang, Buyun; Chen, Lingyu; Zhao, Shuangjiao

    2016-11-01

    Methyl red, methylene blue and biochar were used to investigate simultaneous adsorption of dyes onto low-cost adsorbent at different concentrations combinations. Langmuir mixed model could describe the adsorption well at low concentrations. However, it could not describe the adsorption anymore when concentrations of methyl red and methylene blue were higher than 255 and 300 mg L(-1) respectively with 0.5 g L(-1) biochar loading. A new model on the interaction among adsorbed adsorbates at equilibrium was developed. It could describe the adsorption at high concentrations well. According to the experimental results, interaction among dyes molecules would replace the competition onto adsorbent to be the main factor influencing adsorption when amount of adsorbed adsorbates were higher than those required to form a monolayer on all the adsorbing sites of adsorbent. The model was further verified by adsorption with other solute such as glucose or NaCl in solution.

  2. The adsorption mechanism of nortryptiline on C18-bonded discovery

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2005-08-01

    The adsorption isotherms of an ionizable compound, nortriptyline, were accurately measured by frontal analysis (FA) on a C{sub 18}-Discovery column, first without buffer (in an aqueous solution of acetonitrile at 15%, v/v of ACN), then with a buffer (in 28%, v/v ACN solution). The buffers were aqueous solutions containing 20 mM of formic acid or a phosphate buffer at pH 2.70. The linear range of the isotherm could not be reached with the non-buffered mobile phase using a dynamic range larger than 40,000 (from 1.2 x 10{sup -3} g/L to 50 g/L). With a 20 mM buffer in the liquid phase, the isotherm is linear for concentrations of nortriptyline inferior to 10{sup -3} g/L (or 3 {micro} mol/L). The adsorption energy distribution (AED) was calculated to determine the heterogeneity of the adsorption process. AED and FA were consistent and lead to a trimodal distribution. A tri-Moreau and a tri-Langmuir isotherm models accounted the best for the adsorption of nortriptyline without and with buffer, respectively. The nature of the buffer affects significantly the middle-energy sites while the properties of the lowest and highest of the three types of energy sites are almost unchanged. The desorption profiles of nortriptyline show some anomalies in relation with the formation of a complex multilayer adsorbed phase of acetonitrile whose excess isotherm was measured by the minor disturbance method. The C{sub 18}-Discovery column has about the same total saturation capacity, around 200 g of nortriptyline per liter of adsorbent (or 116 mg/g), with or without buffer. About 98-99% of the available surface consists in low energy sites. The coexistence of these different types of sites on the surface solves the McCalley's enigma, that the column efficiency begins to drop rapidly when the analyte concentration reaches values that are almost one hundred times lower than those that could be predicted from the isotherm data acquired under the same experimental conditions. Due to the

  3. Porous cellulose spheres: Preparation, modification and adsorption properties.

    PubMed

    Ma, Xiaofei; Liu, Congzhi; Anderson, Debbie P; Chang, Peter R

    2016-12-01

    Porous cellulose spheres (PCS) were fabricated by precipitating the spheres from a cellulose ionic liquid solution, followed by freezing, solvent exchange, and drying. PCS had low crystallinity and a large surface area that facilitated modification with trisodium trimetaphosphate (STMP) to introduce phosphate ester groups into the porous structure of the heterogeneous system. The STMP-modified PCS (SPCS) were used to remove heavy metal ions from aqueous solution. With increasing STMP dosage, the adsorption capacity of SPCS obviously improved due to chelation between Pb(2+) and phosphate ester groups. The kinetic adsorption and isotherm data matched the pseudo-second order model and the Langmuir model well. The maximum adsorption capacity reached 150.6 mg g(-1) for SPCS. SPCS were competitive with other absorbents because the phosphate ester groups and porous structure contributed to Pb(2+) adsorption. Moreover, SPCS can be regenerated with ethylenediamine tetraacetic acid disodium salt (EDTA) solution for repetitious adsorption of Pb(2+).

  4. Adsorption of methylene blue from aqueous solution by graphene.

    PubMed

    Liu, Tonghao; Li, Yanhui; Du, Qiuju; Sun, Jiankun; Jiao, Yuqin; Yang, Guangming; Wang, Zonghua; Xia, Yanzhi; Zhang, Wei; Wang, Kunlin; Zhu, Hongwei; Wu, Dehai

    2012-02-01

    Graphene was prepared using a modified Hummers' method. The physico-chemical properties of graphene were characterized by TEM, BET specific surface area, FTIR, Raman and XRD measurements. The effect factors including pH, contact time, temperature and dosage on the adsorption properties of methylene blue onto graphene were investigated. The experimental data of isotherm followed the Langmuir isotherm model better than the Freundlich model. The maximum adsorption capacity obtained from Langmuir isotherm equation at 293 K was 153.85 mg/g, indicating graphene is a good adsorbent for the adsorption of MB. The kinetic study illustrated that the adsorption of methylene blue onto graphene fit the pseudo second-order model. The thermodynamic parameters indicated that the adsorption of methylene blue onto graphene was an endothermic and spontaneous process.

  5. Study of Methylene Blue adsorption on keratin nanofibrous membranes.

    PubMed

    Aluigi, A; Rombaldoni, F; Tonetti, C; Jannoke, L

    2014-03-15

    In this work, keratin nanofibrous membranes (mean diameter of about 220nm) were prepared by electrospinning and tested as adsorbents for Methylene Blue through batch adsorption tests. The adsorption capacity of the membranes was evaluated as a function of initial dye concentration, pH, adsorbent dosage, time and temperature. The adsorption capacity increased with increasing the initial dye concentration and pH, while it decreased with increasing the adsorbent dosage and temperature, indicating an exothermic process. The adsorption results indicated that the Langmuir isotherm fitted the experimental data better than the Freundlich and Temkin isotherm models. A mean free energy evaluated through the Dubinin-Radushkevich model of about 16kJmol(-1), indicated a chemisorption process which occurred by ion exchange. The kinetic data were found to fit the pseudo-second-order model better than the pseudo-first-order model. The obtained results suggest that keratin nanofibrous membranes could be promising candidates as dye adsorption filters.

  6. Adsorption of trihalomethanes from water with carbon nanotubes.

    PubMed

    Lu, Chungsying; Chung, Yao-Lei; Chang, Kuan-Foo

    2005-03-01

    Commercial carbon nanotubes (CNTs) were purified by acid solution and were employed as adsorbents to study adsorption of trihalomethanes (THMs) from water. The properties of CNTs such as purity, structure and nature of the surface were greatly improved after acid treatment which made CNTs become more hydrophilic and suitable for adsorption of low molecular weight and relatively polar THM molecules. The adsorption of THMs onto CNTs fluctuates very little in the pH range 3-7, but decreases with pH value as pH exceeds 7. A comparative study between CNTs and powdered activated carbon (PAC) for adsorption of THMs from water was also conducted. The short time needed to reach equilibrium as well as the high adsorption capacity of CHCl3, which accounts for a significant portion of THMs in the chlorinated drinking water, suggests that CNTs possess highly potential applications for THMs removal from water.

  7. Adsorption of humic acids and trace metals in natural waters

    NASA Technical Reports Server (NTRS)

    Leung, W. H.

    1982-01-01

    Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.

  8. High capacity adsorption media and method of producing

    DOEpatents

    Tranter, Troy J.; Herbst, R. Scott; Mann, Nicholas R.; Todd, Terry A.

    2008-05-06

    A method of producing an adsorption medium to remove at least one constituent from a feed stream. The method comprises dissolving at least one metal compound in a solvent to form a metal solution, dissolving polyacrylonitrile into the metal solution to form a PAN-metal solution, and depositing the PAN-metal solution into a quenching bath to produce the adsorption medium. The at least one constituent, such as arsenic, selenium, or antimony, is removed from the feed stream by passing the feed stream through the adsorption medium. An adsorption medium having an increased metal loading and increased capacity for arresting the at least one constituent to be removed is also disclosed. The adsorption medium includes a polyacrylonitrile matrix and at least one metal hydroxide incorporated into the polyacrylonitrile matrix.

  9. High capacity adsorption media and method of producing

    DOEpatents

    Tranter, Troy J.; Mann, Nicholas R.; Todd, Terry A.; Herbst, Ronald S.

    2010-10-05

    A method of producing an adsorption medium to remove at least one constituent from a feed stream. The method comprises dissolving and/or suspending at least one metal compound in a solvent to form a metal solution, dissolving polyacrylonitrile into the metal solution to form a PAN-metal solution, and depositing the PAN-metal solution into a quenching bath to produce the adsorption medium. The at least one constituent, such as arsenic, selenium, or antimony, is removed from the feed stream by passing the feed stream through the adsorption medium. An adsorption medium having an increased metal loading and increased capacity for arresting the at least one constituent to be removed is also disclosed. The adsorption medium includes a polyacrylonitrile matrix and at least one metal hydroxide incorporated into the polyacrylonitrile matrix.

  10. Competitive Protein Adsorption on Polysaccharide and Hyaluronate Modified Surfaces

    PubMed Central

    Ombelli, Michela; Costello, Lauren; Postle, Corinne; Anantharaman, Vinod; Meng, Qing Cheng; Composto, Russell J.; Eckmann, David M.

    2011-01-01

    We measured adsorption of bovine serum albumin (BSA) and fibrinogen (Fg) onto six distinct bare and dextran- and hyaluronate-modified silicon surfaces created using two dextran grafting densities and three hyaluronic acid (HA) sodium salts derived from human umbilical cord, rooster comb and streptococcus zooepidemicus. Film thickness and surface morphology depended on HA molecular weight and concentration. BSA coverage was enhanced on surfaces upon competitive adsorption of BSA:Fg mixtures. Dextranization differentially reduced protein adsorption onto surfaces based on oxidation state. Hyaluronization was demonstrated to provide the greatest resistance to protein coverage, equivalent to that of the most resistant dextranized surface. Resistance to protein adsorption was independent of the type of hyaluronic acid utilized. With changing bulk protein concentration from 20 to 40 µg ml−1 for each species, Fg coverage on silicon increased by 4×, whereas both BSA and Fg adsorption on dextran and HA were far less dependent of protein bulk concentration. PMID:21623481

  11. Hydrogen-graphite interaction: Experimental evidences of an adsorption barrier

    NASA Astrophysics Data System (ADS)

    Aréou, E.; Cartry, G.; Layet, J.-M.; Angot, T.

    2011-01-01

    The interaction of H atoms having relatively low average kinetic energy (˜0.025 eV) with both perfectly clean and D-covered HOPG surfaces is investigated using high resolution electron energy loss spectroscopy. From this study we confirm, in a controlled fashion, the presence of the theoretically predicted adsorption barrier since no adsorption is detected for such H atoms on HOPG. Moreover, we demonstrate that the exposure of a D saturated HOPG surface to these H atoms results in the complete removal of adatoms, with no further adsorption despite the prediction of the adsorption barrier to vanish for H dimers in para configuration. Therefore, the recombinative abstraction mechanism which competes with the adsorption process is more efficient.

  12. Reuse of Solid Waste in Adsorption of the Textile Dye

    NASA Astrophysics Data System (ADS)

    Meziti, Chafika; Boukerroui, Abdelhamid

    This work presents the study of the reuse of a regenerated spent bleaching earth (RSBE). The RSBE material was tested in the removal of a basic textile dye presents in aqueous solution. The effect of physicochemical parameters such as stirring speed, initial concentration, contact time and temperature have been invested and thermodynamic nature of the adsorption process was determined by calculating the ΔH°, ΔS° and ΔG° values The results obtained show that the adsorption mechanism was described by the Langmuir model and the adsorption capacity, qmax (72.41 to 82.37 mg.g-1), increases with temperature (20-50 °C). The thermodynamic parameters show a presence of a strong affinity between two phases (liquid-solid) and an endothermic equilibrium adsorption process. However, the phenomenon of the adsorption kinetic follows the pseudo second order kinetic model.

  13. Adsorption of organic phenols onto hexadecyltrimethylammonium-treated montmorillonite

    SciTech Connect

    Kim, Young S.; Song, Dong I.; Jeon, Young W.; Choi, Sang J.

    1996-12-01

    Montmorillonite used as an adsorbent was organically modified by using a cationic surfactant, hexadecyltrimethylammonium (HDTMA), to enhance the removal capacity of organic phenol contaminants dissolved in an aqueous solution. This modification produces a change of the surface property of montmorillonite from hydrophilic to organophilic. The single- and multicomponent competitive adsorptions were performed in a batch reactor to investigate the removal of three toxic organic phenols, 2-chlorophenol, 3-cyanophenol, and 4-nitrophenol, on the modified HDTMA-montmorillonite. It was observed from the experimental results that the adsorption affinity for HDTMA-montmorillonite was 2-chlorophenol, 4-nitrophenol, 3-cyanophenol in decreasing order. Langmuir and the Redlich-Peterson models were used to analyze the single-component adsorption results, while the IAST and the LCM models predicted the multicomponent adsorption equilibria. These models yielded favorable representations of both individual and competitive adsorption behaviors.

  14. Adsorption of trichlorophenol on zeolite and adsorbent regeneration with ozone.

    PubMed

    Zhang, Yongjun; Mancke, Raoul Georg; Sabelfeld, Marina; Geißen, Sven-Uwe

    2014-04-30

    A FAU-type zeolite was studied as an adsorbent to remove 2,4,6-trichlorophenol (TCP), a frequently detected recalcitrant pollutant in water bodies. Both adsorption isotherm and kinetics were studied with TCP concentrations from 10 to 100mg/L. It was observed that TCP was effectively adsorbed onto the zeolite with a high adsorption capacity and a high kinetic rate. Freundlich model and pseudo-second-order kinetics were successfully applied to describe the experimental data. The influence of solution pH was also studied. Furthermore, ozone was applied to regenerate the loaded zeolite. It was found that an effective adsorption of TCP was kept for at least 8 cycles of adsorption and regeneration. The ozonation also increased the BET specific surface of zeolite by over 60% and consequently enhanced the adsorption capacity.

  15. Computational Molecular Simulation of the Oxidative Adsorption of Ferrous Iron at the Hematite (001)-Water Interface

    SciTech Connect

    Kerisit, Sebastien N.; Zarzycki, Piotr P.; Rosso, Kevin M.

    2015-04-30

    The interaction of Fe(II) with ferric oxide/oxyhydroxide phases is central to the biogeochemical redox chemistry of iron. Molecular simulation techniques were employed to determine the mechanisms and quantify the rates of Fe(II) oxidative adsorption at the hematite (001)-water interface. Molecular dynamics potential of mean force calculations of Fe(II) adsorbing on the hematite surface revealed the presence of three free energy minima corresponding to Fe(II) adsorbed in an outersphere complex, a monodentate innersphere complex, and a tridentate innersphere complex. The free energy barrier for adsorption from the outersphere position to the monodentate innersphere site was calculated to be similar to the activation enthalpy for water exchange around aqueous Fe(II). Adsorption at both innersphere sites was predicted to be unfavorable unless accompanied by release of protons. Molecular dynamics umbrella sampling simulations and ab initio cluster calculations were performed to determine the rates of electron transfer from Fe(II) adsorbed as an innersphere and outersphere complex. The electron transfer rates were calculated to range from 10^-4 to 10^2 s-1, depending on the adsorption site and the potential parameter set, and were generally slower than those obtained in the bulk hematite lattice. The most reliable estimate of the rate of electron transfer from Fe(II) adsorbed as an outersphere complex to lattice Fe(III) was commensurate with the rate of adsorption as an innersphere complex suggesting that adsorption does not necessarily need to precede oxidation.

  16. A first-principles study of oxygen adsorption on Ir(111) surface

    NASA Astrophysics Data System (ADS)

    Gao, Hengjiao; Xiong, Yuqing; Liu, Xiaoli; Zhao, Dongcai; Feng, Yudong; Wang, Lanxi; Wang, Jinxiao

    2016-12-01

    In order to understand deposition mechanism of iridium thin film by atomic layer deposition, the adsorption of oxygen on Ir(111) surface was studied by use of density functional theory and a periodical slab model. By calculating the adsorption energy and structure of oxygen at four adsorption sites (top, bridge, fcc-hollow and hcp-hollow) on Ir(111) surface, the most stable adsorption site was determined. On this basis, the banding mechanism of O and Ir atoms was studied by density of states of oxygen and iridium atoms. Oxygen adsorbed at hcp(parallel) site on Ir(111) surface was the most stable one according to the adsorption energy calculation results. Orbital charge analysis indicate that charge transferred from 5p and 5d orbit to 2p orbit of adsorbed O atoms, and 6s orbit of iridium atoms. Meanwhile, density of state study indicated that adsorption of oxygen on Ir(111) surface is mainly due to the interaction between 2p orbit of O atoms and 5d orbit of iridium atoms.

  17. Avidity of influenza virus: model-based identification of adsorption kinetics from surface plasmon resonance experiments.

    PubMed

    Wang, Wenjing; Wolff, Michael W; Reichl, Udo; Sundmacher, Kai

    2014-01-24

    Affinity chromatography and membrane adsorption are highly promising methods for the downstream processing of cell culture-derived influenza virus. For the optimization of this separation process, it is desirable to quantify the kinetics of virus adsorption. For this reason, the adsorption kinetics of the influenza A virus (Puerto Rico/8/34 (H1N1)) on a surface with the immobilized ligand Euronymus europaeus lectin (EEL) was investigated. The adsorption kinetics was experimentally monitored in a microfluidic flow cell by surface plasmon resonance (SPR) spectroscopy. The boundary layer theory was applied to analyze the convective and diffusive mass transport of the virus particles in the SPR flow cell. A multi-site kinetic adsorption model was found to describe the experimentally recorded adsorption curves adequately. According to the proposed model, under the applied experimental conditions, the number of sites (galactose residuals) binding one single virus particle to the EEL surface is in the range of 300 to 460, which is in average about 4% of the total number of sites available on the virus surface. The avidity of individual virus particles to the EEL surface was estimated to be in the order of magnitude of 10(6)M(-1)s(-1).

  18. Hydrogen Adsorption by Alkali Metal Graphite Intercalation Compounds

    NASA Astrophysics Data System (ADS)

    Purewal, Justin

    Adsorption occurs whenever a solid surface is exposed to a gas or liquid, and is characterized by an increase in fluid density near the interface. Adsorbents have drawn attention in the current effort to engineer materials that store hydrogen at high densities within moderate temperature and pressure regimes. Carbon adsorbents are a logical choice as a storage material due to their low costs and large surface areas. Unfortunately, carbon adsorbents suffer from a low binding enthalpy for H2 (about 5 kJ mol-1), well below the 15 to 18 kJ mol-1) that is considered optimal for hydrogen storage systems. Binding interactions can be increased by the following methods: (1) adjusting the graphite interplanar separation with a pillared structure, and (2) introducing dopant species that interact with H2 molecules by strong electrostatic forces. Graphite intercalation compounds are a class of materials that contain both pillared structures and chemical dopants, making them an excellent model system for studying the fundamentals of hydrogen adsorption in nanostructured carbons. Pressure-composition-temperature diagrams of the MC24(H 2)x graphite intercalation compounds were measured for M = (K, Rb, Cs). Adsorption enthalpies were measured as a function of H2 concentration. Notably, CsC24 had an average adsorption enthalpy of 14.9 kJ mol-1), nearly three times larger than that of pristine graphite. The adsorption enthalpies were found to be positively correlated with the alkali metal size. Adsorption capacities were negatively correlated with the size of the alkali metal. The rate of adsorption is reduced at large H2 compositions, due to the effects of site-blocking and correlation on the H2 diffusion. The strong binding interaction and pronounced molecular-sieving behavior of KC24 is likely to obstruct the translational diffusion of adsorbed H2 molecules. In this work, the diffusion of H2 adsorbed in KC24 was studied by quasielastic neutron scattering measurements and molecular

  19. Selective adsorption of flavor-active components on hydrophobic resins.

    PubMed

    Saffarionpour, Shima; Sevillano, David Mendez; Van der Wielen, Luuk A M; Noordman, T Reinoud; Brouwer, Eric; Ottens, Marcel

    2016-12-09

    This work aims to propose an optimum resin that can be used in industrial adsorption process for tuning flavor-active components or removal of ethanol for producing an alcohol-free beer. A procedure is reported for selective adsorption of volatile aroma components from water/ethanol mixtures on synthetic hydrophobic resins. High throughput 96-well microtiter-plates batch uptake experimentation is applied for screening resins for adsorption of esters (i.e. isoamyl acetate, and ethyl acetate), higher alcohols (i.e. isoamyl alcohol and isobutyl alcohol), a diketone (diacetyl) and ethanol. The miniaturized batch uptake method is adapted for adsorption of volatile components, and validated with column breakthrough analysis. The results of single-component adsorption tests on Sepabeads SP20-SS are expressed in single-component Langmuir, Freundlich, and Sips isotherm models and multi-component versions of Langmuir and Sips models are applied for expressing multi-component adsorption results obtained on several tested resins. The adsorption parameters are regressed and the selectivity over ethanol is calculated for each tested component and tested resin. Resin scores for four different scenarios of selective adsorption of esters, higher alcohols, diacetyl, and ethanol are obtained. The optimal resin for adsorption of esters is Sepabeads SP20-SS with resin score of 87% and for selective removal of higher alcohols, XAD16N, and XAD4 from Amberlite resin series are proposed with scores of 80 and 74% respectively. For adsorption of diacetyl, XAD16N and XAD4 resins with score of 86% are the optimum choice and Sepabeads SP2MGS and XAD761 resins showed the highest affinity towards ethanol.

  20. Advances in principal factors influencing carbon dioxide adsorption on zeolites

    PubMed Central

    Bonenfant, Danielle; Kharoune, Mourad; Niquette, Patrick; Mimeault, Murielle; Hausler, Robert

    2008-01-01

    We report the advances in the principal structural and experimental factors that might influence the carbon dioxide (CO2) adsorption on natural and synthetic zeolites. The CO2 adsorption is principally govern by the inclusion of exchangeable cations (countercations) within the cavities of zeolites, which induce basicity and an electric field, two key parameters for CO2 adsorption. More specifically, these two parameters vary with diverse factors including the nature, distribution and number of exchangeable cations. The structure of framework also determines CO2 adsorption on zeolites by influencing the basicity and electric field in their cavities. In fact, the basicity and electric field usually vary inversely with the Si/Al ratio. Furthermore, the CO2 adsorption might be limited by the size of pores within zeolites and by the carbonates formation during the CO2 chemisorption. The polarity of molecules adsorbed on zeolites represents a very important factor that influences their interaction with the electric field. The adsorbates that have the most great quadrupole moment such as the CO2, might interact strongly with the electric field of zeolites and this favors their adsorption. The pressure, temperature and presence of water seem to be the most important experimental conditions that influence the adsorption of CO2. The CO2 adsorption<