Science.gov

Sample records for adsorption thermodynamic parameters

  1. Experimental determination of the thermodynamic parameters affecting the adsorption behaviour and dispersion effectiveness of PCE superplasticizers

    SciTech Connect

    Plank, J.; Sachsenhauser, B.; Reese, J. de

    2010-05-15

    For adsorption of three different allylether-based PCE superplasticizers on CaCO{sub 3} surface, the thermodynamic parameters DELTAH, DELTAS and DELTAG were determined experimentally. The GIBBS standard free energy of adsorption DELTAG{sub 0ads}, the standard enthalpy of adsorption DELTAH{sub 0ads} and the standard entropy of adsorption DELTAS{sub 0ads} applying to an unoccupied CaCO{sub 3} surface were obtained via a linear regression of ln K (equilibrium constant) versus 1 / T (VAN'T HOFF plot). Additionally, the thermodynamic parameters characteristic for a CaCO{sub 3} surface loaded already with polymer (isosteric conditions) were determined using a modified CLAUSIUS-CLAPEYRON equation. For all PCE molecules, negative DELTAG values were found, indicating that adsorption of these polymers is energetically favourable and a spontaneous process. Adsorption of PCEs possessing short side chains is mainly instigated by electrostatic attraction and a release of enthalpy. Contrary to this, adsorption of PCEs with long side chains occurs because of a huge gain in entropy. The gain in entropy results from the release of counter ions attached to the carboxylate groups of the polymer backbone and of water molecules and ions adsorbed on the CaCO{sub 3} surface. With increased surface loading, however, DELTAG{sub isosteric} decreases and adsorption ceases when DELTAG becomes 0. The presence of Ca{sup 2+} ions in the pore solution strongly impacts PCE adsorption, due to complexation of carboxylate groups and a reduced anionic charge amount of the molecule. In the presence of Ca{sup 2+}, adsorption of allylether-based PCEs is almost exclusively driven by a gain in entropy. Consequently, PCEs should produce a strong entropic effect upon adsorption to be effective cement dispersants. Molecular architecture, anionic charge density and molecular weight as well as the type of anchor groups present in a superplasticizer determine whether enthalpy or entropy is the dominant force for

  2. Theoretical predictions of thermodynamic parameters of adsorption of nitrogen containing environmental contaminants on kaolinite.

    PubMed

    Scott, Andrea Michalkova; Burns, Elizabeth A; Lafferty, Brandon J; Hill, Frances C

    2015-02-01

    In this study thermodynamic parameters of adsorption of nitrogen containing environmental contaminants (NCCs, 2,4,6, trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dinitroanisole (DNAN), and 3-one-1,2,4-triazol-5-one (NTO)) interacting with the tetrahedral and octahedral surfaces of kaolinite were predicted. Adsorption complexes were investigated using a density functional theory and both periodic and cluster approach. The complexes, modeled using the periodic boundary conditions approach, were fully optimized at the BLYP-D2 level to obtain the structures and adsorption energies. The relaxed kaolinite-NCCs structures were used to prepare cluster models to calculate thermodynamic parameters and partition coefficients at the M06-2X-D3 and BLYP-D2 levels from the gas phase. The entropy effect on the Gibbs free energies of adsorption of NCCS on kaolinite was also studied and compared with available experimental data. The results showed that in all calculated models, the NCCs molecules are physisorbed and they favor a parallel orientation toward both kaolinite surfaces. It was found that all calculated NCCs compounds are more stable on the octahedral than on the tetrahedral surface of kaolinite. The Gibbs free energies and partition coefficients were also predicted for interactions of NCCs with Na-kaolinite from aqueous solution. Calculations revealed adsorption of NCCs is effective from the gas phase on both cation free kaolinite surfaces and on Na-kaolinite from aqueous solution at room temperature. Theoretical data were validated against experimental results, and the reasons for small differences between calculated and measured partition coefficients are discussed.

  3. Thermodynamic parameters for adsorption equilibrium of heavy metals and dyes from wastewaters: Research updated.

    PubMed

    Chang, Yingju; Lai, Juin-Yih; Lee, Duu-Jong

    2016-12-01

    The standard Gibbs free energy, enthalpy and entropy change data for adsorption equilibrium reported in biosorption literature during January 2013-May2016 were listed. Since the studied biosorption systems are all near-equilibrium processes, the enthalpy and entropy change data evaluated by fitting temperature-dependent free energy data using van Hoff's equation reveal a compensation artifact. Additional confusion is introduced with arbitrarily chosen adsorbate concentration unit in bulk solution that added free energy change of mixing into the reported free energy and enthalpy change data. Different standard states may be chosen for properly describing biosorption processes; however, this makes the general comparison between data from different systems inappropriate. No conclusion should be drawn based on unjustified thermodynamic parameters reported in biosorption studies.

  4. 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.

  5. Thermodynamic description of peptide adsorption on mixed-mode resins.

    PubMed

    Chilamkurthi, Sreekanth; Sevillano, David Méndez; Albers, Leonoor H G; Sahoo, Manas Ranjan; Verheijen, Peter J T; van der Wielen, Luuk A M; den Hollander, Jeroen L; Ottens, Marcel

    2014-05-09

    In this work the adsorption of tri-peptides on a mixed-mode resin was studied using isocratic pulse response experiments. Various salt concentration, temperature and pH combinations were used to measure retention times of several tri-peptides. The experiments were evaluated according to an extension of the stoichiometric displacement model and the steric mass action model of protein-ligand binding. The application of this model in the understanding of mixed mode adsorption process is discussed. A unique set of meaningful thermodynamic parameters was obtained for each resin-peptide-temperature and resin-peptide-pH combination. Finally it was shown that these thermodynamic parameters can be used in defining quantitative relationships within the framework of extra thermodynamic relationships.

  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. Improved Estimates of Thermodynamic Parameters

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.

    1982-01-01

    Techniques refined for estimating heat of vaporization and other parameters from molecular structure. Using parabolic equation with three adjustable parameters, heat of vaporization can be used to estimate boiling point, and vice versa. Boiling points and vapor pressures for some nonpolar liquids were estimated by improved method and compared with previously reported values. Technique for estimating thermodynamic parameters should make it easier for engineers to choose among candidate heat-exchange fluids for thermochemical cycles.

  8. Adsorption of chromium onto activated alumina: kinetics and thermodynamics studies.

    PubMed

    Marzouk, Ikhlass; Dammak, Lassaad; Hamrouni, Béchir

    2013-02-01

    In this study, the removal of chromium (VI) by adsorption on activated alumina was investigated and the results were fitted to Langmuir, Freundlich, Dubinin-Redushkevich, and Temkin adsorption models at various temperatures. The constants of each model were evaluated depending on temperature. Thermodynamic parameters for the adsorption system were determined at 10, 25 and 40 degrees C. (deltaH degrees = -21.18 kJ x mol(-1); deltaG degrees = -8.75 to -7.43 kJ x mol(-1) and deltaS degrees = -0.043 kJ x K(-1) x mol(-1)). The obtained values showed that chromium (VI) adsorption is a spontaneous and exothermic process. The kinetic process was evaluated by first-order, second-order and Elovich kinetic models.

  9. Adsorption kinetics, isotherms and thermodynamics of atrazine on surface oxidized multiwalled carbon nanotubes.

    PubMed

    Chen, Guang-Cai; Shan, Xiao-Quan; Zhou, Yi-Quan; Shen, Xiu-e; Huang, Hong-Lin; Khan, Shahamat U

    2009-09-30

    The adsorption kinetics, isotherms and thermodynamic of atrazine on multiwalled carbon nanotubes (MWCNTs) containing 0.85%, 2.16%, and 7.07% oxygen was studied. Kinetic analyses were performed using pseudo-first-order, pseudo-second-order and intraparticle diffusion models. The regression results showed that the pseudo-second-order law fit the adsorption kinetics. The calculated thermodynamic parameters indicated that adsorption of atrazine on MWCNTs was spontaneous and exothermic. Standard free energy (DeltaG(0)) became less negative when the oxygen content of MWCNTs increased from 0.85% to 7.07% which is consistent with the low adsorption affinity of MWCNTs for atrazine.

  10. 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.

  11. Kinetics and Thermodynamics of Reserpine Adsorption onto Strong Acidic Cationic Exchange Fiber.

    PubMed

    Guo, Zhanjing; Liu, Xiongmin; Huang, Hongmiao

    2015-01-01

    The kinetics and thermodynamics of the adsorption process of reserpine adsorbed onto the strong acidic cationic exchange fiber (SACEF) were studied by batch adsorption experiments. The adsorption capacity strongly depended on pH values, and the optimum reserpine adsorption onto the SACEF occurred at pH = 5 of reserpine solution. With the increase of temperature and initial concentration, the adsorption capacity increased. The equilibrium was attained within 20 mins. The adsorption process could be better described by the pseudo-second-order model and the Freundlich isotherm model. The calculated activation energy Ea was 4.35 kJ/mol. And the thermodynamic parameters were: 4.97<ΔH<7.44 kJ/mol, -15.29<ΔG<-11.87 kJ/mol and 41.97<ΔS<47.35 J/mol·K. The thermodynamic parameters demonstrated that the adsorption was an endothermic, spontaneous and feasible process of physisorption within the temperature range between 283 K and 323 K and the initial concentration range between 100 mg/L and 300 mg/L. All the results showed that the SACEF had a good adsorption performance for the adsorption of reserpine from alcoholic solution.

  12. Kinetics and Thermodynamics of Reserpine Adsorption onto Strong Acidic Cationic Exchange Fiber

    PubMed Central

    Guo, Zhanjing; Liu, Xiongmin; Huang, Hongmiao

    2015-01-01

    The kinetics and thermodynamics of the adsorption process of reserpine adsorbed onto the strong acidic cationic exchange fiber (SACEF) were studied by batch adsorption experiments. The adsorption capacity strongly depended on pH values, and the optimum reserpine adsorption onto the SACEF occurred at pH = 5 of reserpine solution. With the increase of temperature and initial concentration, the adsorption capacity increased. The equilibrium was attained within 20 mins. The adsorption process could be better described by the pseudo-second-order model and the Freundlich isotherm model. The calculated activation energy Ea was 4.35 kJ/mol. And the thermodynamic parameters were: 4.97<ΔH<7.44 kJ/mol, -15.29<ΔG<-11.87 kJ/mol and 41.97<ΔS<47.35 J/mol·K. The thermodynamic parameters demonstrated that the adsorption was an endothermic, spontaneous and feasible process of physisorption within the temperature range between 283 K and 323 K and the initial concentration range between 100 mg/L and 300 mg/L. All the results showed that the SACEF had a good adsorption performance for the adsorption of reserpine from alcoholic solution. PMID:26422265

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Equilibrium, kinetic and thermodynamic studies on the adsorption of phenol onto graphene

    SciTech Connect

    Li, Yanhui; Du, Qiuju; Liu, Tonghao; Sun, Jiankun; Jiao, Yuqin; Xia, Yanzhi; Xia, Linhua; Wang, Zonghua; Zhang, Wei; Wang, Kunlin; Zhu, Hongwei; Wu, Dehai

    2012-08-15

    Graphical abstract: The effect of temperature on phenol adsorbed by graphene shows that the equilibrium adsorption capacity of phenol increases with the increase in temperature from 285 to 333 K. Increasing adsorption capacities with temperature indicates that the adsorption of phenol is controlled by an endothermic reaction. Highlights: ► The graphene has high phenol adsorption capacity. ► The graphene has a high specific surface area of 305 m{sup 2}/g. ► The adsorption capacity is high at acidic pH range. ► The graphene has rapid phenol adsorption rate. ► Phenol adsorption is a spontaneous and endothermic process. -- Abstract: Graphene, a new member of carbon family, has been prepared, characterized and used as adsorbent to remove phenol from aqueous solution. The effect parameters including pH, dosage, contact time, and temperature on the adsorption properties of phenol onto graphene were investigated. The results showed that the maximum adsorption capacity can reach 28.26 mg/g at the conditions of initial phenol concentration of 50 mg/L, pH 6.3 and 285 K. Adsorption data were well described by both Freundlich and Langmuir models. The kinetic study illustrated that the adsorption of phenol onto graphene fit the pseudo second-order model. The thermodynamic parameters indicated that the adsorption of phenol onto graphene was endothermic and spontaneous.

  18. A thermodynamic analysis of gas adsorption on microporous materials: evaluation of energy heterogeneity.

    PubMed

    Llorens, Joan; Pera-Titus, Marc

    2009-03-15

    This paper presents a thermodynamic isotherm derived from solution thermodynamics principles to describe gas adsorption on microporous materials. This isotherm relies on a potential relationship between the integral free energy of adsorption relative to saturation, Psi/RT, expressed by the Kiselev equation, and the variable Z = 1/-Ln(Pi), being Pi the relative pressure. A mathematical analysis reveals that the adsorption energy heterogeneity in the micropores is collected in a characteristic parameter of the isotherm, m, that can be related to the alpha parameter of the Dubinin-Astakhov isotherm in a simple way (m = alpha + 1). The isotherm also predicts a plateau in Psi/RT at extremely low pressures (Pi < 10(-7)). Neimark's thermodynamic equation accounting for gas adsorption on mesoporous solids is found to be a particular case of the isotherm presented in this study. The Langmuir isotherm only shows consistency with the thermodynamic isotherm for a reduced combination of values of the relevant parameters, not usually found in common adsorbents. The suitability of the thermodynamic isotherm is experimentally assessed by testing a collection of microporous materials, including activated carbons, carbon nanotubes, and zeolites.

  19. Application of isothermal titration calorimetry for characterizing thermodynamic parameters of biomolecular interactions: peptide self-assembly and protein adsorption case studies.

    PubMed

    Kabiri, Maryam; Unsworth, Larry D

    2014-10-13

    The complex nature of macromolecular interactions usually makes it very hard to identify the molecular-level mechanisms that ultimately dictate the result of these interactions. This is especially evident in the case of biological systems, where the complex interaction of molecules in various situations may be responsible for driving biomolecular interactions themselves but also has a broader effect at the cell and/or tissue level. This review will endeavor to further the understanding of biomolecular interactions utilizing the isothermal titration calorimetry (ITC) technique for thermodynamic characterization of two extremely important biomaterial systems, viz., peptide self-assembly and nonfouling polymer-modified surfaces. The advantages and shortcomings of this technique will be presented along with a thorough review of the recent application of ITC to these two areas. Furthermore, the controversies associated with the enthalpy-entropy compensation effect as well as thermodynamic equilibrium state for such interactions will be discussed.

  20. Interfacial thermodynamics of gallic acid adsorption on a chargeable hydrophobic surface.

    PubMed

    Giannakopoulos, Evangelos; Deligiannakis, Yiannis

    2011-06-15

    The thermodynamics of adsorption of gallic acid (GA, 3,4,5-trihydroxylbenzoic acid) on the hanging mercury drop electrode (HMDE) surface was studied by temperature-dependent stripping voltammetry (TD-SV), at physiological pH 7.4. The thermodynamic parameters, e.g., Gibbs free energy, ΔG(ADS), enthalpy, ΔΗ(ADS) and entropy, ΔS(ADS), of adsorption have been determined at physiological temperatures 2-40 °C. Chemisorption of the radical species ≡[GA(OH)(2)(O(-))]* is the energetically important reaction. The thermodynamic data show a complex mechanism of adsorption of GA on the electrode surface, which is strongly dependent on temperature. At low-temperatures T<12 °C, adsorption is controlled by enthalpy, while at T>22 °C, adsorption is entropy driven. In the temperature range 12 °C and 22 °C, a combined enthalpy-entropy stabilization occurs. A mechanism is proposed which analyses the implication of thermodynamics to the interfacial adsorption of polyphenols with cell membranes under physiological conditions.

  1. Isotherm, thermodynamic, kinetics and adsorption mechanism studies of methyl orange by surfactant modified silkworm exuviae.

    PubMed

    Chen, Hao; Zhao, Jie; Wu, Junyong; Dai, Guoliang

    2011-08-15

    This paper reports on the development of organo-modified silkworm exuviae (MSE) adsorbent prepared by using hexadecyltrimethylammonium bromide (HDTMAB) for removing methyl orange (MO), a model anionic dye, from aqueous solution. The natural and modified samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectroscopy (FT-IR). Batch adsorption experiments were carried out to remove MO from its aqueous solutions using SE and MSE. It was observed that the adsorption capacity of MSE is 5-6 times of SE. The different parameters effecting on the adsorption capacity such as pH of the solution, initial dye concentration, temperature and contact time have been investigated. Analysis of adsorption results obtained at different temperatures showed that the adsorption pattern on the MSE can be described perfectly with Langmuir isotherm model compared with Freundlich and Dubinin-Radushkevich (D-R) isotherm models, and the characteristic parameters for each adsorption isotherm were also determined. The adsorption process has been found exothermic in nature and thermodynamic parameters have been calculated. The adsorption kinetic followed the pseudo-second order kinetic model. The results of FT-IR, EDS and desorption studies all suggest that methyl orange adsorption onto the MSE should be mainly controlled by the hydrophobic interaction mechanism, along with a considerable contribution of the anionic exchange mechanism. The results indicate that HDTMAB-modified silkworm exuviae could be employed as low-cost material for the removal of methyl orange anionic dye from wastewater.

  2. Equilibrium, kinetic and thermodynamic study of cesium adsorption onto nanocrystalline mordenite from high-salt solution.

    PubMed

    Lee, Keun-Young; Park, Minsung; Kim, Jimin; Oh, Maengkyo; Lee, Eil-Hee; Kim, Kwang-Wook; Chung, Dong-Yong; Moon, Jei-Kwon

    2016-05-01

    In this study, the equilibrium, kinetics and thermodynamics of cesium adsorption by nanocrystalline mordenite were investigated under cesium contamination with high-salt solution, simulating the case of an operation and decommissioning of nuclear facilities or an accident during the processes. The adsorption rate constants were determined using a pseudo second-order kinetic model. The kinetic results strongly demonstrated that the cesium adsorption rate of nano mordenite is extremely fast, even in a high-salt solution, and much faster than that of micro mordenite. In the equilibrium study, the Langmuir isotherm model fit the cesium adsorption data of nano mordenite better than the Freundlich model, which suggests that cesium adsorption onto nano mordenite is a monolayer homogeneous adsorption process. The obtained thermodynamic parameters indicated that the adsorption involved a very stable chemical reaction. In particular, the combination of rapid particle dispersion and rapid cesium adsorption of the nano mordenite in the solution resulted in a rapid and effective process for cesium removal without stirring, which may offer great advantages for low energy consumption and simple operation.

  3. Adsorption laboratory experiment for undergraduate chemical engineering: Introducing kinetic, equilibrium and thermodynamic concepts

    NASA Astrophysics Data System (ADS)

    Muryanto, S.; Djatmiko Hadi, S.

    2016-11-01

    Adsorption laboratory experiment for undergraduate chemical engineering program is discussed. The experiment demonstrated adsorption of copper ions commonly found in wastewater using bio-sorbent, i.e. agricultural wastes. The adsorption was performed in a batch mode under various parameters: adsorption time (up to 120 min), initial pH (2 to 6), adsorbent dose (2.0 to 12.0 g L-1), adsorbent size (50 to 170 mesh), initial Cu2+ concentration (25 to 100 ppm) and temperatures (room temp to 40°C). The equilibrium and kinetic data of the experiments were calculated using the two commonly used isotherms: Langmuir and Lagergren pseudo-first-order kinetics. The maximum adsorption capacity for Cu2+ was found as 94.34 mg g-1. Thermodynamically, the adsorption process was spontaneous and endothermic. The calculated activation energy for the adsorption was observed as high as 127.94 kJ mol-1. Pedagogically, the experiment was assumed to be important in increasing student understanding of kinetic, equilibrium and thermodynamic concepts.

  4. Kinetic and thermodynamic studies on the adsorption of anionic surfactant on quaternary ammonium cationic cellulose.

    PubMed

    Zhang, Yuanzhang; Shi, Wenjian; Zhou, Hualan; Fu, Xing; Chen, Xuan

    2010-06-01

    Removal of anionic surfactants from aqueous solutions by adsorption onto quaternary ammonium cationic cellulose (QACC) was investigated. The effects of solution acidity, initial concentration, adsorption time, and temperature on the adsorption of sodium dodecyl-benzene sulfonate (SDBS), sodium lauryl sulfate (SLS), and sodium dodecyl sulfonate (SDS) were studied. The kinetic experimental data fit well with the pseudo-second-order model; the rate constant of the adsorption increased with temperature. The values of apparent activation energy for the adsorption were calculated as ranging from 10.2 to 17.4 kJ/ mol. The adsorption isotherm can be described by the Langmuir isotherm. The values of thermodynamic parameters (deltaH0, deltaS0, and deltaG0) for the adsorption indicated that this process was spontaneous and endothermic. At 318 K, the saturated adsorption capacities of QACC for SDBS, SLS, and SDS were 1.75, 1.53, and 1.39 mmol/g, respectively. The adsorption process was mainly chemisorption and partially physisorption. The results show that QACC is effective for the removal of anionic surfactants.

  5. [Thermodynamics adsorption and its influencing factors of chlorpyrifos and triazophos on the bentonite and humus].

    PubMed

    Zhu, Li-Jun; Zhang, Wei; Zhang, Jin-Chi; Zai, De-Xin; Zhao, Rong

    2010-11-01

    The adsorption of chlorpyrifos and triazophos on bentonite and humus was investigated by using the equilibrium oscillometry. The adsorption capacity of chlorpyrifos and triazophos on humus was great higher than bentonite at the same concentration. Equilibrium data of Langmuir, Freundlich isotherms showed significant relationship to the adsorption of chlorpyrifos and triazophos on humus (chlorpyrifos: R2 0.996 4, 0.996 3; triazophos: R2 0.998 9, 0.992 4). Langmuir isotherm was the best for chlorpyrifos and triazophos on bentonite (chlorpyrifos: R2 = 0.995 7, triazophos: R2 = 0.998 9). The pH value, adsorption equilibrium time and temperature were the main factors affecting adsorption of chlorpyrifos and triazophos on bentonite and humus. The adsorption equilibrium time on mixed adsorbent was 12h for chlorpyrifos and 6h for triazophos respectively. The mass ratio of humus and bentonite was 12% and 14% respectively, the adsorption of chlorpyrifos and triazophos was the stronglest and tended to saturation. At different temperatures by calculating the thermodynamic parameters deltaG, deltaH and deltaS, confirmed that the adsorption reaction was a spontaneous exothermic process theoretically. The adsorption was the best when the pH value was 6.0 and the temperature was 15 degrees C.

  6. Eriobotrya japonica seed biocomposite efficiency for copper adsorption: Isotherms, kinetics, thermodynamic and desorption studies.

    PubMed

    Mushtaq, Mehwish; Bhatti, Haq Nawaz; Iqbal, Munawar; Noreen, Saima

    2016-07-01

    Adsorption techniques are widely used to remove pollutants from wastewater; however, composites are gaining more importance due to their excellent adsorption properties. Bentonite composite with Eriobotrya japonica seed was prepared and used for the adsorption of copper (Cu) metal from aqueous media. The process variables such as pH, Cu(II) ions initial concentration, adsorbent dose, contact time and temperature were optimized for maximum Cu(II) adsorption. At pH 5, adsorbent dose 0.1 g, contact time 45 min, Cu(II) ions initial concentration 75 mg/L and temperature 45 °C, maximum Cu(II) adsorption was achieved. Desorption studies revealed that biocomposite is recyclable. Langmuir, Freundlich and Harkins-Jura isotherms as well as pseudo-first and pseudo-second-order kinetics models were applied to understand the adsorption mechanism. Thermodynamic parameters (ΔG(0), ΔH(0) and ΔS(0)) suggest that the adsorption process was spontaneous and endothermic in nature. The pseudo-second-order kinetic model and Langmuir isotherm fitted well to the adsorption data. Results showed that biocomposite was more efficient for Cu(II) adsorption in comparison to individuals native Eriobotrya japonica seed biomass and Na-bentonite.

  7. Kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain from aqueous solutions

    NASA Astrophysics Data System (ADS)

    Li, Qingzhu; Chai, Liyuan; Yang, Zhihui; Wang, Qingwei

    2009-01-01

    Spent grain, a main by-product of the brewing industry, is available in large quantities, but its main application has been limited to animal feeding. Nevertheless, in this study, spent grain modified with 1 M NaCl solution as a novel adsorbent has been used for the adsorption of Pb(II) in aqueous solutions. Isotherms, kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain were studied. The equilibrium data were well fitted with Langmuir, Freundlich and Dubinin-Radushkevick (D-R) isotherm models. The kinetics of Pb(II) adsorption followed pseudo-second-order model, using the rate constants of pseudo-second-order model, the activation energy ( Ea) of Pb(II) adsorption was determined as 12.33 kJ mol -1 according to the Arrhenius equation. Various thermodynamic parameters such as Δ Gads, Δ Hads and Δ Sads were also calculated. Thermodynamic results indicate that Pb(II) adsorption onto modified spent grain is a spontaneous and endothermic process. Therefore, it can be concluded that modified spent grain as a new effective adsorbent has potential for Pb(II) removal from aqueous solutions.

  8. Adsorption of chromium (VI) by ethylenediamine-modified cross-linked magnetic chitosan resin: isotherms, kinetics and thermodynamics.

    PubMed

    Hu, Xin-jiang; Wang, Jing-song; Liu, Yun-guo; Li, Xin; Zeng, Guang-ming; Bao, Zheng-lei; Zeng, Xiao-xia; Chen, An-wei; Long, Fei

    2011-01-15

    The adsorption of chromium (VI) ions from aqueous solution by ethylenediamine-modified cross-linked magnetic chitosan resin (EMCMCR) was studied in a batch adsorption system. Chromium (VI) removal is pH dependent and the optimum adsorption was observed at pH 2.0. The adsorption rate was extremely fast and the equilibrium was established within 6-10min. The adsorption data could be well interpreted by the Langmuir and Temkin model. The maximum adsorption capacities obtained from the Langmuir model are 51.813mgg(-1), 48.780mgg(-1) and 45.872mgg(-1) at 293, 303 and 313K, respectively. The adsorption process could be described by pseudo-second-order kinetic model. The intraparticle diffusion study revealed that film diffusion might be involved in the present case. Thermodynamic parameters revealed the feasibility, spontaneity and exothermic nature of adsorption. The sorbents were successfully regenerated using 0.1N NaOH solutions.

  9. Phosphate adsorption from wastewater using zirconium (IV) hydroxide: Kinetics, thermodynamics and membrane filtration adsorption hybrid system studies.

    PubMed

    Johir, M A H; Pradhan, M; Loganathan, P; Kandasamy, J; Vigneswaran, S

    2016-02-01

    Excessive phosphate in wastewater should be removed to control eutrophication of water bodies. The potential of employing amorphous zirconium (Zr) hydroxide to remove phosphate from synthetic wastewater was studied in batch adsorption experiments and in a submerged membrane filtration adsorption hybrid (MFAH) reactor. The adsorption data satisfactorily fitted to Langmuir, pseudo-first order and pseudo-second order models. Langmuir adsorption maxima at 22 °C and pHs of 4.0, 7.1, and 10.0 were 30.40, 18.50, and 19.60 mg P/g, respectively. At pH 7.1 and temperatures of 40 °C and 60 °C, they were 43.80 and 54.60 mg P/g, respectively. The thermodynamic parameters, ΔG° and ΔS° were negative and ΔH° was positive. FTIR, zeta potential and competitive phosphate, sulphate and nitrate adsorption data showed that the mechanism of phosphate adsorption was inner-sphere complexation. In the submerged MFAH reactor experiment, when Zr hydroxide was added at doses of 1-5 g/L once only at the start of the experiment, the removal of phosphate from 3 L of wastewater containing 10 mg P/L declined after 5 h of operation. However, when Zr hydroxide was repeatedly added at 5 g/L dose every 24 h, satisfactory removal of phosphate was maintained for 3 days.

  10. Kinetics and thermodynamics studies of silver ions adsorption onto coconut shell activated carbon.

    PubMed

    Silva-Medeiros, Flávia V; Consolin-Filho, Nelson; Xavier de Lima, Mateus; Bazzo, Fernando Previato; Barros, Maria Angélica S D; Bergamasco, Rosângela; Tavares, Célia R G

    2016-12-01

    The presence of silver in the natural water environment has been of great concern because of its toxicity, especially when it is in the free ion form (Ag(+)). This paper aims to study the adsorption kinetics of silver ions from an aqueous solution onto coconut shell activated carbon using batch methods. Batch kinetic data were fitted to the first-order model and the pseudo-second-order model, and this last equation fits correctly the experimental data. Equilibrium experiments were carried out at 30°C, 40°C, and 50°C. The adsorption isotherms were reasonably fit using Langmuir model, and the adsorption process was slightly influenced by changes in temperature. Thermodynamic parameters (ΔH°, ΔG°, and ΔS°) were determined. The adsorption process seems to be non-favorable, exothermic, and have an increase in the orderness.

  11. Thermodynamic and kinetic investigations of PO3-4 adsorption on blast furnace slag.

    PubMed

    Oguz, Ensar

    2005-01-01

    The kinetics of adsorption of PO(3-)(4) by blast furnace slag were found to be fast, reaching equilibrium in 20 min and following a pseudo-second-order rate equation. The adsorption behavior of PO(3-)(4) on blast furnace slag has been studied as a function of the solution agitation speed, pH, and temperature. Results have been analyzed by Freundlich, Langmuir, BET, and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption, 10.31 kJ mol(-1), was calculated from the D-R adsorption isotherm. The rate constants were calculated for 293, 298, 303, and 308 K using a pseudo-second-order rate equation and the activation energy (E(a)) was derived using the Arrhenius equation. Thermodynamic parameters such as DeltaH(0), DeltaS(0), and DeltaG(0) were calculated from the slope and intercept of linear plot of lnK(D) against 1/T. The DeltaH(0) and DeltaG(0) values of PO(3-)(4) adsorption on the blast furnace slag show endothermic heat of adsorption. But there is a negative free energy value, indicating that the process of PO(3-)(4) adsorption is favored at high temperatures.

  12. Adsorption of cadmium from aqueous solution onto untreated coffee grounds: equilibrium, kinetics and thermodynamics.

    PubMed

    Azouaou, N; Sadaoui, Z; Djaafri, A; Mokaddem, H

    2010-12-15

    Adsorption can be used as a cost effective and efficient technique for the removal of toxic heavy metals from wastewater. Waste materials with no further treatment such as coffee grounds from cafeterias may act as adsorbents for the removal of cadmium. Batch kinetic and equilibrium experiments were conducted to study the effects of contact time, adsorbent dose, initial pH, particle size, initial concentration of cadmium and temperature. Three adsorption isotherm models namely, Langmuir, Freundlich and Dubinin-Radushkevich were used to analyse the equilibrium data. The Langmuir isotherm which provided the best correlation for Cd(2+) adsorption onto coffee grounds, shows that the adsorption was favourable and the adsorption capacity found was equal to 15.65 mg g(-1). Thermodynamic parameters were evaluated and the adsorption was exothermic. The equilibrium was achieved less than 120 min. The adsorption kinetic data was fitted with first and second order kinetic models. Finally it was concluded that the cadmium adsorption kinetic onto coffee grounds was well fitted by second order kinetic model rather than first order model. The results suggest that coffee grounds have high possibility to be used as effective and economical adsorbent for Cd(2+) removal.

  13. Kinetics and thermodynamic study of aniline adsorption by multi-walled carbon nanotubes from aqueous solution.

    PubMed

    Al-Johani, Hind; Abdel Salam, Mohamed

    2011-08-15

    Multi-walled carbon nanotubes (MWCNTs) were used in the adsorptive removal of aniline, an organic pollutant, from an aqueous solution. It was found that carbon nanotubes with a higher specific surface area adsorbed and removed more aniline from an aqueous solution. The adsorption was dependent on factors, such as MWCNTs dosage, contact time, aniline concentration, solution pH and temperature. The adsorption study was analyzed kinetically, and the results revealed that the adsorption followed pseudo-second order kinetics with good correlation coefficients. In addition, it was found that the adsorption of aniline occurred in two consecutive steps, including the slow intra-particle diffusion of aniline molecules through the nanotubes. Various thermodynamic parameters, including the Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°), were calculated. The results indicated that the spontaneity of the adsorption, exothermic nature of the adsorption and the decrease in the randomness reported as ΔG°, ΔH° and ΔS°, respectively, were all negative.

  14. Adsorption studies of Dichloromethane on some commercially available GACs: Effect of kinetics, thermodynamics and competitive ions.

    PubMed

    Khan, Moonis Ali; Kim, Seong-wook; Rao, Rifaqat Ali Khan; Abou-Shanab, R A I; Bhatnagar, Amit; Song, Hocheol; Jeon, Byong-Hun

    2010-06-15

    The objective of this work was to compare the effectiveness of four commercially available granular activated carbons (GACs); coconut (CGAC), wood (WGAC), lignite (LGAC) and bituminous (BGAC) for the removal of dichloromethane (DCM) from aqueous solution by batch process. Various parameters such as thermodynamics, kinetics, pH, concentration of adsorbate, dosages of adsorbent and competitive ions effect on DCM adsorption were investigated. Maximum adsorption capacity (45.5mg/g for CGAC) was observed at pH 6.0-8.0. The kinetics data indicate better applicability of pseudo-second-order kinetics model at 25 and 35 degrees C. Freundlich model was better obeyed on CGAC, WGAC, and BGAC, while LGAC followed Langmuir model. The adsorption process for 100mg/L initial DCM concentration on CGAC was exothermic in nature. The adsorption of DCM on various adsorbents involves physical adsorption process. The adsorption of DCM over a large range of initial concentration on CGAC and LGAC is effective even in presence of ionic salts.

  15. On an isotherm thermodynamically consistent in Henry's region for describing gas adsorption in microporous materials.

    PubMed

    Pera-Titus, Marc

    2010-05-15

    The Dubinin-Astakhov and Dubinin-Radushkevich isotherms, originally formulated from the classical volume filling theory of micropores, constitute the most accepted models for describing gas adsorption in microporous materials. The most important weakness of these equations relies on the fact that they do not reduce to Henry's law at low pressures, not providing therefore a proper characterization of adsorbents in the early stage of adsorption. In this paper, we propose a way out of this inherent problem using the thermodynamic isotherm developed in a previous study [J. Llorens, M. Pera-Titus, J. Colloid Interface Sci. 331 (2009) 302]. This isotherm allows the generation of a series of equations that make available a comprehensive description of gas adsorption for the whole set of relative pressures (including Henry's region), also providing explicit information about energy heterogeneity of the adsorbent through the two characteristic m parameters of the thermodynamic isotherm (i.e., m(1) and m(2)). The obtained isotherm converges into the Dubinin-Astakhov isotherm for relative pressures higher than 0.1, the characteristic α parameter of this isotherm being expressed as α=m(2)-1 and the affinity coefficient (β) as a sole function of m(2). An expression differing from the Dubinin-Astakhov isotherm has been obtained for describing Henry's region, providing relevant information about confinement effects when applied to zeolites.

  16. Equilibrium, kinetic and thermodynamic studies of mercury adsorption on almond shell.

    PubMed

    Khaloo, Shokooh Sadat; Matin, Amir Hossein; Sharifi, Sahar; Fadaeinia, Masoumeh; Kazempour, Narges; Mirzadeh, Shaghayegh

    2012-01-01

    The application of almond shell as a low cost natural adsorbent to remove Hg(2+) from aqueous solution was investigated. Batch experiments were carried out to evaluate the adsorption capacity of the material. The chemical and physical parameters such as pH, sorbent amount, initial ion concentration, and contact time were optimized for the maximum uptake of mercury onto the solid surface. Adsorption isotherms were expressed by Langmuir and Freundlich adsorption models, and the experimental data were found to fit the Langmuir model rather than the Freundlich. The maximum adsorption capacity obtained from the Langmuir isotherm was 135.13 mg/g. A kinetic study was carried out with pseudo-first-order and pseudo-second-order reaction equations and it was found that the Hg(2+) uptake process followed the pseudo-second-order rate expression. The thermodynamic values, ΔG(0), ΔH(0) and ΔS(0), indicated that adsorption was an endothermic and spontaneous process. The potential of this material for mercury elimination was demonstrated by efficient Hg(2+) removal from a synthetic effluent.

  17. Equilibrium isotherms, kinetics and thermodynamics studies of phenolic compounds adsorption on palm-tree fruit stones.

    PubMed

    Ahmed, Muthanna J; Theydan, Samar K

    2012-10-01

    Adsorption capacity of an agricultural waste, palm-tree fruit stones (date stones), for phenolic compounds such as phenol (Ph) and p-nitro phenol (PNPh) at different temperatures was investigated. The characteristics of such waste biomass were determined and found to have a surface area and iodine number of 495.71 m2/g and 475.88 mg/g, respectively. The effects of pH (2-12), adsorbent dose (0.6-0.8 g/L) and contact time (0-150 min) on the adsorptive removal process were studied. Maximum removal percentages of 89.95% and 92.11% were achieved for Ph and PNPh, respectively. Experimental equilibrium data for adsorption of both components were analyzed by the Langmuir, Freundlich and Tempkin isotherm models. The results show that the best fit was achieved with the Langmuir isotherm equation with maximum adsorption capacities of 132.37 and 161.44 mg/g for Ph and PNPh, respectively. The kinetic data were fitted to pseudo-first order, pseudo-second order and intraparticle diffusion models, and was found to follow closely the pseudo-second order model for both components. The calculated thermodynamic parameters, namely ΔG, ΔH, and ΔS showed that adsorption of Ph and PNPh was spontaneous and endothermic under examined conditions.

  18. Adsorption equilibrium, kinetics and thermodynamics of dichloroacetic acid from aqueous solution using mesoporous carbon.

    PubMed

    Ding, Ying; Zhu, Jianzhong; Cao, Yang; Chen, Shenglu

    2014-08-01

    The presence of disinfection by-products, such as trihalomethanes and haloacetic acids in water, is believed to be harmful to human health. In this work, mesoporous carbon was synthesized with the evaporation-induced self-assembly method and employed to evaluate the effects of initial concentration, contact time, pH and temperature on the removal of dichloroacetic acid in batch experiments. Adsorption equilibrium was established in 480 min and the maximum adsorption (350mg/g) of dichloroacetic acid on the mesoporous carbon was observed to occur at 308 K and pH 3.0. Freundlich and Langmuir isotherms were used to analyse the equilibrium data at different temperatures; kinetic data were fitted to the pseudo-first-order and pseudo-second-order models and found that the adsorption capacity, mass transfer coefficient and diffusivity of dichloroacetic acid were directly affected by the physical and chemical parameters. In addition, the various thermodynamic parameters, such as Gibbs free energy (Delta G), enthalpy (Delta H = 54.35 kJmol-1) and entropy (Delta S = 258.36 Jmol-1 K-1) were calculated to analyse the adsorption process. The experimental results indicated that the mesoporous carbon was an excellent adsorbent for dichloroacetic acid removal from aqueous solutions.

  19. Adsorption Properties of Tetracycline onto Graphene Oxide: Equilibrium, Kinetic and Thermodynamic Studies

    PubMed Central

    Ghadim, Ehsan Ezzatpour; Manouchehri, Firouzeh; Soleimani, Gholamreza; Hosseini, Hadi; Kimiagar, Salimeh; Nafisi, Shohreh

    2013-01-01

    Graphene oxide (GO) nanoparticle is a high potential effective absorbent. Tetracycline (TC) is a broad-spectrum antibiotic produced, indicated for use against many bacterial infections. In the present research, a systematic study of the adsorption and release process of tetracycline on GO was performed by varying pH, sorption time and temperature. The results of our studies showed that tetracycline strongly loads on the GO surface via π–π interaction and cation–π bonding. Investigation of TC adsorption kinetics showed that the equilibrium was reached within 15 min following the pseudo-second-order model with observed rate constants of k2 = 0.2742–0.5362 g/mg min (at different temperatures). The sorption data has interpreted by the Langmuir model with the maximum adsorption of 323 mg/g (298 K). The mean energy of adsorption was determined 1.83 kJ/mol (298 K) based on the Dubinin–Radushkevich (D–R) adsorption isotherm. Moreover, the thermodynamic parameters such as ΔH°, ΔS° and ΔG° values for the adsorption were estimated which indicated the endothermic and spontaneous nature of the sorption process. The electrochemistry approved an ideal reaction for the adsorption under electrodic process. Simulation of GO and TC was done by LAMMPS. Force studies in z direction showed that tetracycline comes close to GO sheet by C8 direction. Then it goes far and turns and again comes close from amine group to the GO sheet. PMID:24302989

  20. Statistical thermodynamics of adsorption of dye DR75 onto natural materials and its modifications: double-layer model with two adsorption energies.

    PubMed

    Khalfaoui, M; Nakhli, A; Aguir, Ch; Omri, A; M'henni, M F; Ben Lamine, A

    2014-02-01

    In this article, adsorption modelling was presented to describe the sorption of textile dye, Direct Red 75 (DR75), from coloured wastewater onto the natural and modified adsorbent, Posidonia oceanica. The formulation of the double-layer model with two energy levels was based on statistical physics and theoretical considerations. Thanks to the grand canonical ensemble in statistical physics some physico-chemical parameters related to the adsorption process were introduced in the analytical model expression. Fitting results show that the dye molecules are adsorbed in parallel position to the adsorbent surface. The magnitudes of the calculated adsorption energies show that the DR75 dye is physisorbed onto Posidonia. Both Van der Waals and hydrogen interactions are implicated in the adsorption process. Despite its simplicity, the model fits a wide range of experimental data, thereby supporting the underlying data that the grafted groups facilitate the parallel anchorage of the anionic dye molecule. Thermodynamic parameters, such as adsorption energy, entropy, Gibbs free adsorption energy and internal energy were calculated according to the double-layer model. Results suggested that the DR75 adsorption onto Posidonia was a spontaneous and exothermic process.

  1. Equilibrium, kinetic and thermodynamic studies on the adsorption of the toxins of Bacillus thuringiensis subsp. kurstaki by clay minerals

    NASA Astrophysics Data System (ADS)

    Fu, Qingling; Deng, Yali; Li, Huishu; Liu, Jie; Hu, Hongqing; Chen, Shouwen; Sa, Tongmin

    2009-02-01

    The persistence of Bacillus thuringiensis ( Bt) toxins in soil is further enhanced through association with soil particles. Such persistence may improve the effectiveness of controlling target pests, but impose a hazard to non-target organisms in soil ecosystems. In this study, the equilibrium adsorption of the Bt toxin by four clay minerals (montmorillonite, kaolinite, goethite, and silicon dioxide) was investigated, and the kinetic and thermodynamic parameters were calculated. The results showed that Bt toxin could be adsorbed easily by minerals, and the adsorption was much easier at low temperature than at high temperature at the initial concentration varying from 0 to 1000 mg L -1. The adsorption fitted well to both Langmuir and Freundlich isotherm models, but the Freundlich equation was more suitable. The pseudo-second-order (PSO) was the best application model to describe the adsorption kinetic. The adsorption process appeared to be controlled by chemical process, and the intra-particle diffusion was not the only rate-controlling step. The negative standard free energy ( ΔGmθr) values of the adsorption indicated that the adsorption of the Bt toxin by the minerals was spontaneous, and the changes of the standard enthalpy ( ΔHmθr) showed that the adsorption of the Bt toxin by montmorillonite was endothermic while the adsorption by the other three minerals was exothermic.

  2. Adsorption of ammonium ion by coconut shell-activated carbon from aqueous solution: kinetic, isotherm, and thermodynamic studies.

    PubMed

    Boopathy, Ramasamy; Karthikeyan, Sekar; Mandal, Asit Baran; Sekaran, Ganesan

    2013-01-01

    Ammonium ions are one of the most encountered nitrogen species in polluted water bodies. High level of ammonium ion in aqueous solution imparts unpleasant taste and odor problems, which can interfere with the life of aquatics and human population when discharged. Many chemical methods are developed and being used for removal of ammonium ion from aqueous solution. Among various techniques, adsorption was found to be the most feasible and environmentally friendly with the use of natural-activated adsorbents. Hence, in this study, coconut shell-activated carbon (CSAC) was prepared and used for the removal of ammonium ion by adsorption techniques. Ammonium chloride (analytical grade) was purchased from Merck Chemicals for adsorption studies. The CSAC was used to adsorb ammonium ions under stirring at 100 rpm, using orbital shaker in batch experiments. The concentration of ammonium ion was estimated by ammonia distillate, using a Buchi distillation unit. The influence of process parameters such as pH, temperature, and contact time was studied for adsorption of ammonium ion, and kinetic, isotherm models were validated to understand the mechanism of adsorption of ammonium ion by CSAC. Thermodynamic properties such as ∆G, ∆H, and ∆S were determined for the ammonium adsorption, using van't Hoff equation. Further, the adsorption of ammonium ion was confirmed through instrumental analyses such as SEM, XRD, and FTIR. The optimum conditions for the effective adsorption of ammonium ion onto CSAC were found to be pH 9.0, temperature 283 K, and contact time 120 min. The experimental data was best followed by pseudosecond order equation, and the adsorption isotherm model obeyed the Freundlich isotherm. This explains the ammonium ion adsorption onto CSAC which was a multilayer adsorption with intraparticle diffusion. Negative enthalpy confirmed that this adsorption process was exothermic. The instrumental analyses confirmed the adsorption of ammonium ion onto CSAC.

  3. Adsorption of Phenol from Aqueous Solution Using Lantana camara, Forest Waste: Kinetics, Isotherm, and Thermodynamic Studies

    PubMed Central

    Girish, C. R.; Ramachandra Murty, V.

    2014-01-01

    The present work investigates the potential of Lantana camara, a forest waste, as an adsorbent for the phenol reduction in wastewater. Batch studies were conducted with adsorbent treated with HCl and KOH to determine the influence of various experimental parameters such as pH, contact time, adsorbent dosage, and phenol concentration. The experimental conditions were optimized for the removal of phenol from wastewater. Equilibrium isotherms for the adsorption of phenol were analyzed by Freundlich, Langmuir, Temkin, and Dubinin-Radushkevich isotherm models. Thermodynamic parameters like the Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were also determined and they showed that the adsorption process was feasible, spontaneous, and exothermic in the temperature range of 298–328 K. The kinetic data were fitted with pseudo-second-order model. The equilibrium data that followed Langmuir model with the monolayer adsorption capacity was found to be 112.5 mg/g and 91.07 mg/g for adsorbent treated with HCl and KOH, respectively, for the concentration of phenol ranging from 25 to 250 mg/L. This indicates that the Lantana camara was a promising adsorbent for the removal of phenol from aqueous solutions. PMID:27350997

  4. Adsorption of Phenol from Aqueous Solution Using Lantana camara, Forest Waste: Kinetics, Isotherm, and Thermodynamic Studies.

    PubMed

    Girish, C R; Ramachandra Murty, V

    2014-01-01

    The present work investigates the potential of Lantana camara, a forest waste, as an adsorbent for the phenol reduction in wastewater. Batch studies were conducted with adsorbent treated with HCl and KOH to determine the influence of various experimental parameters such as pH, contact time, adsorbent dosage, and phenol concentration. The experimental conditions were optimized for the removal of phenol from wastewater. Equilibrium isotherms for the adsorption of phenol were analyzed by Freundlich, Langmuir, Temkin, and Dubinin-Radushkevich isotherm models. Thermodynamic parameters like the Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were also determined and they showed that the adsorption process was feasible, spontaneous, and exothermic in the temperature range of 298-328 K. The kinetic data were fitted with pseudo-second-order model. The equilibrium data that followed Langmuir model with the monolayer adsorption capacity was found to be 112.5 mg/g and 91.07 mg/g for adsorbent treated with HCl and KOH, respectively, for the concentration of phenol ranging from 25 to 250 mg/L. This indicates that the Lantana camara was a promising adsorbent for the removal of phenol from aqueous solutions.

  5. 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.

  6. Simultaneous and sequential adsorption of crystal violet and 2-naphthol onto montmorillonite: a microstructural and thermodynamic study.

    PubMed

    Zhu, Jianxi; Wei, Jingming; Zhu, Runliang; Qing, Yanhong; Ge, Fei; Yuan, Peng; He, Hongping

    2010-01-01

    Thermodynamic analysis of simultaneous and sequential adsorption of crystal violet (CV) and 2-naphthol adsorption on montmorillonite has been conducted, and the changes of microstructure of the clay after adsorption were investigated using X-ray diffraction (XRD). The basal spacing and structural order of CV and 2-naphthol adsorbed montmorillonites varied with different CV loadings. In principle, larger basal spacing was resulted from a higher loading of CV in montmorillonites. The excellent structural order of the resultant hybrids is achieved in samples with 0.50-0.75 CEC (cation exchange capacity) loadings of CV. The effects of temperature and ionic strength on the adsorption of CV and 2-naphthol on montmorillonite were also investigated. The Freundlich isotherm model was applied for curve-fitting of the equilibrium isotherm data. The resulting thermodynamics parameters suggested that the sorption process was a spontaneous exothermic process in the case of low CV concentrations. The negative values of Gibbs free energy in all of the adsorption processes indicated that these processes are spontaneous processes. With the increase of CV concentration, the sequential adsorption of 2-naphthol onto montmorillonite proved to be an endothermic process.

  7. Adsorption and correlation with their thermodynamic properties of triazine herbicides on soils.

    PubMed

    Yang, Wei-chun; Liu, Wei-ping; Liu, Hui-jun; Liu, Guang-shen

    2003-07-01

    Adsorption of atrazine, prometryne and prometon was determined on six soils with different physical and chemical properties. The adsorption isotherms of three herbicides could well fit Freundlich equation. On all of six soils, adsorption of herbicides increased in the order: atrazine approximately = prometon < prometryne. This order is quite the same to the calculation result of by means of excess thermodynamic properties of triazine. The Freundlich adsorption constants, Kf, showed to have good correlation with organic matter (OM%) of soils for each of these herbicides, suggesting that OM is the main factor, which dominates in the adsorption process of these triazine herbicides.

  8. Maghemite nanosorbcats for methylene blue adsorption and subsequent catalytic thermo-oxidative decomposition: Computational modeling and thermodynamics studies.

    PubMed

    El-Qanni, Amjad; Nassar, Nashaat N; Vitale, Gerardo; Hassan, Azfar

    2016-01-01

    In this study methylene blue (MB) has been investigated for its adsorption and subsequent catalytic thermo-oxidative decomposition on surface of maghemite (γ-Fe2O3) nanoparticles. The experimental adsorption isotherm fit well to the Freundlich model, indicating multi-sites adsorption. Computational modeling of the interaction between the MB molecule and γ-Fe2O3 nanoparticle surface was carried out to get more insights into its adsorption behavior. Adsorption energies of MB molecules on the surface indicated that there are different adsorption sites on the surface of γ-Fe2O3 confirming the findings regarding the adsorption isotherm. The catalytic activity of the γ-Fe2O3 nanoparticles toward MB thermo-oxidative decomposition has been confirmed by subjecting the adsorbed MB to a thermo oxidation process up to 600 °C in a thermogravimetric analyzer. The experimental results showed a catalytic activity for post adsorption oxidation. The oxidation kinetics were studied using the Ozawa-Flyn-Wall (OFW) corrected method. The most probable mechanism functions were fifth and third orders for virgin MB and MB adsorbed onto γ-Fe2O3 nanoparticles, respectively. Moreover, the results of thermodynamic transition state parameters, namely changes in Gibbs free energy of activation (ΔG(‡)), enthalpy of activation (ΔH(‡)), and entropy of activation (ΔS(‡)), emphasized the catalytic activity of γ-Fe2O3 nanoparticles toward MB oxidation.

  9. Moisture Adsorption Isotherms and Thermodynamic Characteristics of Tannic Acid

    NASA Astrophysics Data System (ADS)

    Červenka, L.; Cacková, L.

    2016-09-01

    Moisture adsorption isotherms of tannic acid were determined at 5, 15, and 35°C with the use of the static gravimetric method in the range 0.113-0.980 aw (aw is the water activity). It was shown that tannic acid adsorbed more water at 5°C. The experimental data fitted well to the Guggenheim-Anderson-de Boer and Yanniotis-Blahovec equations, giving the corresponding parameters by nonlinear regression. The monolayer moisture content, number of monolayers, and the surface area of sorption were demonstrated to decrease with increasing temperature. Mesopores dominated below the monolayer moisture content followed by the formation of macropores. The variation of the differential enthalpy and entropy with the moisture content showed that water was strongly bound to the surface of tannic acid below the moisture content 5.0 g water/100 g dry basis. The adsorption process was found to be enthalpy-driven; however, it was not spontaneous at a low moisture content, as follows from the enthalpy-entropy compensation theory. The variation of the net integral enthalpy and entropy (at a constant spreading pressure) with the moisture content exhibited maximum and minimum values, respectively. This behavior indicated that water molecules were strongly bound to the tannic acid surface at the moisture content up to its monolayer values.

  10. Thermodynamics of the adsorption of flexible polymers on nanowires

    SciTech Connect

    Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

    2015-03-09

    Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached to or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. In conclusion, the classification of the transitions is performed by microcanonical inflection-point analysis.

  11. Thermodynamics of the adsorption of flexible polymers on nanowires

    DOE PAGES

    Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

    2015-03-09

    Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached tomore » or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. In conclusion, the classification of the transitions is performed by microcanonical inflection-point analysis.« less

  12. Thermodynamics of the adsorption of flexible polymers on nanowires

    SciTech Connect

    Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

    2015-03-14

    Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached to or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. The classification of the transitions is performed by microcanonical inflection-point analysis.

  13. Thermodynamics of the adsorption of flexible polymers on nanowires

    NASA Astrophysics Data System (ADS)

    Vogel, Thomas; Gross, Jonathan; Bachmann, Michael

    2015-03-01

    Generalized-ensemble simulations enable the study of complex adsorption scenarios of a coarse-grained model polymer near an attractive nanostring, representing an ultrathin nanowire. We perform canonical and microcanonical statistical analyses to investigate structural transitions of the polymer and discuss their dependence on the temperature and on model parameters such as effective wire thickness and attraction strength. The result is a complete hyperphase diagram of the polymer phases, whose locations and stability are influenced by the effective material properties of the nanowire and the strength of the thermal fluctuations. Major structural polymer phases in the adsorbed state include compact droplets attached to or wrapping around the wire, and tubelike conformations with triangular pattern that resemble ideal boron nanotubes. The classification of the transitions is performed by microcanonical inflection-point analysis.

  14. Removal of phenol from aqueous solutions by adsorption onto organomodified Tirebolu bentonite: equilibrium, kinetic and thermodynamic study.

    PubMed

    Senturk, Hasan Basri; Ozdes, Duygu; Gundogdu, Ali; Duran, Celal; Soylak, Mustafa

    2009-12-15

    A natural bentonite modified with a cationic surfactant, cetyl trimethylammonium bromide (CTAB), was used as an adsorbent for removal of phenol from aqueous solutions. The natural and modified bentonites (organobentonite) were characterized with some instrumental techniques (FTIR, XRD and SEM). Adsorption studies were performed in a batch system, and the effects of various experimental parameters such as solution pH, contact time, initial phenol concentration, organobentonite concentration, and temperature, etc. were evaluated upon the phenol adsorption onto organobentonite. Maximum phenol removal was observed at pH 9.0. Equilibrium was attained after contact of 1h only. The adsorption isotherms were described by Langmuir and Freundlich isotherm models, and both model fitted well. The monolayer adsorption capacity of organobentonite was found to be 333 mg g(-1). Desorption of phenol from the loaded adsorbent was achieved by using 20% acetone solution. The kinetic studies indicated that the adsorption process was best described by the pseudo-second-order kinetics (R(2) > 0.99). Thermodynamic parameters including the Gibbs free energy (DeltaG degrees), enthalpy (DeltaH degrees), and entropy (DeltaS degrees) were also calculated. These parameters indicated that adsorption of phenol onto organobentonite was feasible, spontaneous and exothermic in the temperature range of 0-40 degrees C.

  15. Adsorption kinetics, thermodynamics and desorption of natural dissolved organic matter by multiwalled carbon nanotubes.

    PubMed

    Su, Fengsheng; Lu, Chungsying

    2007-09-01

    Multiwalled carbon nanotubes (CNTs) were thermally treated and were employed as adsorbents to study their adsorption kinetics and thermodynamics of natural dissolved organic matter (NDOM) from aqueous solutions. The adsorption kinetics follows the first-order rate law while the adsorption thermodynamics indicates the exothermic and spontaneous nature. A comparative study on the adsorption/desorption properties of NDOM between CNTs and granular activated carbon (GAC) was also conducted and revealed that the CNTs possess more NDOM adsorption capacities and show less weight loss through 10 cycles of water treatment and reactivation than the GAC. This suggests that the CNTs are promising NDOM adsorbents for preventing the microbiological degradation of drinking water quality as well as the formation of disinfection by products in water treatment.

  16. Adsorption kinetics, thermodynamics and isotherm of Hg(II) from aqueous solutions using buckwheat hulls from Jiaodong of China.

    PubMed

    Wang, Zengdi; Yin, Ping; Qu, Rongjun; Chen, Hou; Wang, Chunhua; Ren, Shuhua

    2013-02-15

    The adsorption kinetics and adsorption isotherms of buckwheat hulls in the region of Jiaodong, China (BHJC) for Hg(II) were investigated. Results revealed that the adsorption kinetics of BHJC for Hg(II) were well described by a pseudo second-order reaction model, and the adsorption thermodynamic parameters ΔG, ΔH and ΔS were -5.83 kJ mol(-1)(35°C), 73.1, and 256 JK(-1) mol(-1), respectively. Moreover, Langmuir, Freundlich and Redlich-Peterson isotherm models were applied to analyse the experimental data and to predict the relevant isotherm parameters. The best interpretation for the experimental data was given by the Langmuir isotherm equation, and the maximum adsorption capacity for Hg(II) is 243.90 mg/g at 35°C. Furthermore, investigation of the adsorption selectivity showed that BHJC displayed strong affinity for mercury in the aqueous solutions and exhibited 100% selectivity for mercury in the presence of Zn(II) and Cd(II).

  17. Adsorption of Zn2+ ions onto NaA and NaX zeolites: kinetic, equilibrium and thermodynamic studies.

    PubMed

    Nibou, D; Mekatel, H; Amokrane, S; Barkat, M; Trari, M

    2010-01-15

    The adsorption of Zn(2+) onto NaA and NaX zeolites was investigated. The samples were synthesized according to a hydrothermal crystallization using aluminium isopropoxide (Al[OCH(CH(3))(2)](3)) as a new alumina source. The effects of pH, initial concentration, solid/liquid ratio and temperature were studied in batch experiments. The Freundlich and the Langmuir models were applied and the adsorption equilibrium followed Langmuir adsorption isotherm. The uptake distribution coefficient (K(d)) indicated that the Zn(2+) removal was the highest at minimum concentration. Thermodynamic parameters were calculated. The negative values of standard enthalpy of adsorption revealed the exothermic nature of the adsorption process whereas the negative activation entropies reflected that no significant change occurs in the internal structure of the zeolites solid matrix during the sorption of Zn(2+). The negative values of Gibbs free energy were indicative of the spontaneity of the adsorption process. Analysis of the kinetic and rate data revealed that the pseudo second-order sorption mechanism is predominant and the intra particle diffusion was the determining step for the sorption of zinc ions. The obtained optimal parameters have been applied to wastewater from the industrial zone (Algeria) in order to remove the contained zinc effluents.

  18. Adsorption of cesium from aqueous solution using agricultural residue--walnut shell: equilibrium, kinetic and thermodynamic modeling studies.

    PubMed

    Ding, Dahu; Zhao, Yingxin; Yang, Shengjiong; Shi, Wansheng; Zhang, Zhenya; Lei, Zhongfang; Yang, Yingnan

    2013-05-01

    A novel biosorbent derived from agricultural residue - walnut shell (WS) is reported to remove cesium from aqueous solution. Nickel hexacyanoferrate (NiHCF) was incorporated into this biosorbent, serving as a high selectivity trap agent for cesium. Field emission scanning electron microscope (FE-SEM) and thermogravimetric and differential thermal analysis (TG-DTA) were utilized for the evaluation of the developed biosorbent. Determination of kinetic parameters for adsorption was carried out using pseudo first-order, pseudo second-order kinetic models and intra-particle diffusion models. Adsorption equilibrium was examined using Langmuir, Freundlich and Dubinin-Radushkevich adsorption isotherms. A satisfactory correlation coefficient and relatively low chi-square analysis parameter χ(2) between the experimental and predicted values of the Freundlich isotherm demonstrate that cesium adsorption by NiHCF-WS is a multilayer chemical adsorption. Thermodynamic studies were conducted under different reaction temperatures and results indicate that cesium adsorption by NiHCF-WS is an endothermic (ΔH° > 0) and spontaneous (ΔG° < 0) process.

  19. Comparing the removal of perchlorate when using single-walled carbon nanotubes (SWCNTs) or granular activated carbon: adsorption kinetics and thermodynamics.

    PubMed

    Lou, Jie C; Hsu, Yung S; Hsu, Kai L; Chou, Ming S; Han, Jia Y

    2014-01-01

    This study aims to remove perchlorate using single-walled carbon nanotubes (SWCNTs) or granular activated carbon (GAC). Dynamic and equilibrium adsorption experiments were performed to evaluate the thermodynamic behavior of perchlorate on SWCNTs and GAC. Key parameters affecting the adsorption, such as pH, ionic strength, and temperature were studied. The experimental results showed that the dynamic adsorption experiment achieved equilibrium in approximately eight hours. The adsorption capacity increased as the concentration of perchlorate increased or as the ionic strength decreased. The selected adsorption models were the modified Freundlich, the pseudo-1st-order, and the pseudo-2nd-order equations. The results showed that the modified Freundlich equation best described the kinetic adsorption processes. The maximal adsorption capacities of GAC and SWCNTs were 33.87-28.21 mg/g and 13.64 - 10.03 mg/g, respectively, at a constant temperature between 5°C and 45°C. The thermodynamic parameters, such as the equilibrium constant (K0 ), the standard free energy changes (ΔG°), the standard enthalpy change (ΔH°) and the standard entropy change (ΔS°), were obtained. The results of the isothermal equilibrium adsorption experiment showed that low pH levels, low ionic strength, and low-temperature conditions facilitated the perchlorate adsorption, indicating that GAC and SWCNTs are potential absorbents for water treatment.

  20. Thermodynamic consistency of the interaction parameter formalism

    NASA Astrophysics Data System (ADS)

    Srikanth, S.; Jacob, K. T.

    1988-04-01

    The apparent contradiction between the exact nature of the interaction parameter formalism as presented by Lupis and Elliott and the inconsistencies discussed recently by Pelton and Bale arise from the truncation of the Maclaurin series in the latter treatment. The truncation removes the exactness of the expression for the logarithm of the activity coefficient of a solute in a multi-component system. The integrals are therefore path dependent. Formulae for integration along paths of constant Xi, or X i/Xj are presented. The expression for In γsolvent given by Pelton and Bale is valid only in the limit that the mole fraction of solvent tends to one. The truncation also destroys the general relations between interaction parameters derived by Lupis and Elliott. For each specific choice of parameters special relationships are obtained between interaction parameters.

  1. Equilibrium isotherms, kinetics, and thermodynamics studies for congo red adsorption using calcium alginate beads impregnated with nano-goethite.

    PubMed

    Munagapati, Venkata Subbaiah; Kim, Dong-Su

    2017-03-24

    The present study is concerned with the batch adsorption of congo red (CR) from an aqueous solution using calcium alginate beads impregnated with nano-goethite (CABI nano-goethite) as an adsorbent. The optimum conditions for CR removal were determined by studying operational variables viz. pH, adsorbent dose, contact time, initial dye ion concentration and temperature. The CABI nano-goethite was characterized by Fourier transform infrared spectroscopy (FTIR), X- ray diffraction (XRD) and Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) analysis. The CR sorption data onto CABI nano-goethite were described using Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models. The results show that the best fit was achieved with the Langmuir isotherm model. The maximum adsorption capacity (181.1mg/g) of CR was occurred at pH 3.0. Kinetic studies showed that the adsorption followed a pseudo-second-order model. Desorption experiments were carried out to explore the feasibility of regenerating the adsorbent and the adsorbed CR from CABI nano-goethite. The best desorbing agent was 0.1M NaOH with an efficiency of 94% recovery. The thermodynamic parameters ΔG°, ΔH°, and ΔS° for the CR adsorption were determined by using adsorption capacities at five different temperatures (293, 303, 313, 323 and 303K). Results show that the adsorption process was endothermic and favoured at high temperature.

  2. Isotherm and thermodynamic studies of Zn (II) adsorption on lignite and coconut shell-based activated carbon fiber.

    PubMed

    Shrestha, Sohan; Son, Guntae; Lee, Seung Hwan; Lee, Tae Gwan

    2013-08-01

    The Zn (II) adsorption capacity of lignite and coconut shell-based activated carbon fiber (ACF) was evaluated as a function of initial Zn (II) concentration, temperature and contact time in batch adsorption process in this study. Adsorption uptake increased with initial Zn (II) concentration and temperature. Optimal contact time for the adsorption of Zn (II) ions onto lignite and coconut shell-based ACF was found to be 50 min. Removal percentage decreased from 88.0% to 78.54% with the increment in initial Zn (II) concentration from 5 to 50 mg L(-1). Equilibrium data fit well with Langmuir-I isotherm indicating homogeneous monolayer coverage of Zn (II) ions on the adsorbent surface. Maximum monolayer adsorption capacity of Zn (II) ions on ACF was found to be 9.43 mg g(-1). Surface morphology and functionality of ACF prior to and after adsorption were characterized by electron microscopy and infrared spectroscopy. Various thermodynamic parameters such as standard Gibbs free energy (ΔG°), standard enthalpy (ΔH°), and standard entropy (ΔS°) were evaluated.

  3. Adsorption thermodynamic and kinetic studies of trihalomethanes on multiwalled carbon nanotubes.

    PubMed

    Lu, Chungsying; Chung, Yao-Lei; Chang, Kuan-Foo

    2006-11-16

    Multiwalled carbon nanotubes (MWCNTs) were purified by mixed HNO3/H2SO4 solution and were employed as adsorbents to study adsorption kinetics and thermodynamics of trihalomethanes (THMs) from chlorinated drinking water. The amount of THMs adsorbed onto CNTs decreased with a rise in temperature and high adsorption capacities were found at 5 and 15 degrees C. Under the same conditions, the purified CNTs possess two to three times more adsorption capacities of CHCl3, which accounts for a major portion of THMs in the chlorinated drinking water, than the commercially available PAC suggesting that CNTs are efficient adsorbents. The thermodynamic analysis revealed that the adsorption of THMs onto CNTs is exothermic and spontaneous.

  4. Krypton Adsorption on Zeolite-Templated Carbon and Anomalous Surface Thermodynamics.

    PubMed

    Murialdo, Maxwell; Stadie, Nicholas P; Ahn, Channing C; Fultz, Brent

    2015-07-28

    Krypton adsorption was measured at eight temperatures between 253 and 433 K on a zeolite-templated carbon and two commercial carbons. The data were fitted using a generalized Langmuir isotherm model and thermodynamic properties were extracted. Differing from that on commercial carbons, krypton adsorption on the zeolite-templated carbon is accompanied by an increasing isosteric enthalpy of adsorption, rising by up to 1.4 kJ mol(-1) as a function of coverage. This increase is a result of enhanced adsorbate-adsorbate interactions promoted by the ordered, nanostructured surface of the adsorbent. An assessment of the strength and nature of these adsorbate-adsorbate interactions is made by comparing the measured isosteric enthalpies of adsorption (and other thermodynamic quantities) to fundamental metrics of intermolecular interactions of krypton and other common gases.

  5. Arsenic (III) adsorption on iron acetate coated activated alumina: thermodynamic, kinetics and equilibrium approach

    PubMed Central

    2013-01-01

    The adsorption potential of iron acetate coated activated alumina (IACAA) for removal of arsenic [As (III)] as arsenite by batch sorption technique is described. IACAA was characterized by XRD, FTIR, EDAX and SEM instruments. Percentage adsorption on IACAA was determined as a function of pH, contact time and adsorbent dose. The study revealed that the removal of As (III) was best achieved at pH =7.4. The initial As (III) concentration (0.45 mg/L) came down to less than 0.01 mg/L at contact time 90 min with adsorbent dose of 1 g/100 mL. The sorption was reasonably explained with Langmuir and Freundlich isotherms. The thermodynamic parameters such as ΔG 0 , ΔH 0 , ΔS 0 and E a were calculated in order to understand the nature of sorption process. The sorption process was found to be controlled by pseudo-second order and intraparticle diffusion models. PMID:24359995

  6. Adsorption behavior of activated carbon derived from pyrolusite-modified sewage sludge: equilibrium modeling, kinetic and thermodynamic studies.

    PubMed

    Chen, Yao; Jiang, Wenju; Jiang, Li; Ji, Xiujuan

    2011-01-01

    Activated carbon was developed from sewage sludge using pyrolusite as an additive. It was demonstrated that the removal efficiency of two synthetic dyes (Tracid orange GS and Direct fast turquoise blue GL) by the produced adsorbent was up to 97.6%. The activated carbon with pyrolusite addition had 38.2% higher surface area, 43.8% larger micropore and 54.4% larger mesopore production than ordinary sludge-based activated carbons. Equilibrium adsorption isotherms and kinetics were also investigated based on dyes adsorption tests. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption, and the results fitted well to the Langmuir isotherm. The kinetic data have been analyzed using pseudo-first-order, pseudo-second-order and intraparticle diffusion equation. The experimental data fitted very well with pseudo-second-order kinetic model. Activation energies for the adsorption processes ranged between 8.7 and 19.1 kJ mol 1. Thermodynamic parameters such as standard free energy (deltaG0), standard enthalpy (deltaH0) and standard entropy (deltaS0) were evaluated. The adsorption of these two dyes on the activated carbon was found to be a spontaneous and endothermic process in nature.

  7. Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics Driven by Soft Vibration Modes

    SciTech Connect

    Woo, Sung-Jae; Lee, Eui-Sup; Yoon, Mina; Yong-Hyun, Kim

    2013-01-01

    It is widely accepted that room-temperature hydrogen storage on nanostructured or porous materials requires enhanced dihydrogen adsorption. In this work we reveal that room-temperature hydrogen storage is possible not only by the enhanced adsorption, but also by making use of the vibrational free energy from soft vibration modes. These modes exist for example in the case of metallo-porphyrin-incorporated graphenes (M-PIGs) with out-of-plane ( buckled ) metal centers. There, the in-plane potential surfaces are flat because of multiple-orbital-coupling between hydrogen molecules and the buckled-metal centers. This study investigates the finite-temperature adsorption/desorption thermodynamics of hydrogen molecules adsorbed on M-PIGs by employing first-principles total energy and vibrational spectrum calculations. Our results suggest that the current design strategy for room-temperature hydrogen storage materials should be modified by explicitly taking finite-temperature vibration thermodynamics into account.

  8. [Adsorption kinetic and thermodynamic studies of lead onto activated carbons from cotton stalk].

    PubMed

    Li, Kun-quan; Zheng, Zheng; Jiang, Jian-chun; Zhang, Ji-biao

    2010-05-01

    Low-cost high surface area microporous carbons were prepared from cotton stalk and cotton stalk fiber by H3PO4 activation. The adsorption of lead ions on the carbons was investigated by conducting a series of batch adsorption experiments. The influence of solution pH value, contact time and temperature was investigated. The adsorption kinetics, thermodynamic behavior and mechanism were also discussed. The surface area and pore structure of the activated carbons were analyzed by BET equation, BJH method and H-K method according to the data from nitrogen adsorption at 77K. Boehm titration, Fourier transform infrared spectroscopy (FTIR), the point of zero charge (pH(PZC)) measurement and elemental analysis were used to characterize the surface properties. The results show that the carbons from cotton stalk and cotton stalk fiber have high surface area of 1570 and 1731 m2 x g(-1), and high content of oxygen-containing functional groups of 1.43 and 0.83 mmol x g(-1). The adsorption experiments show that the carbons have high adsorption capacity for lead, and the maximum adsorption equilibrium amount was found to be 120 mg x g(-1). The adsorption amount increased with contact time, and almost 80% of the adsorption occurred in the first 5 min. The pseudo-second-order model describes the adsorption kinetics most effectively. The Freundlich isotherm was found to the best explanation for experimental data. The negative change in free energy (delta G0) and positive change in enthalpy (delta H0) indicate that the adsorption is a spontaneous and endothermic process, and the adsorption of lead ions onto the carbons might be involved in an ion-exchange mechanism.

  9. Solvothermal synthesis of different phase N-TiO2 and their kinetics, isotherm and thermodynamic studies on the adsorption of methyl orange.

    PubMed

    Fan, Jimin; Zhao, Zhihuan; Liu, Wenhui; Xue, Yongqiang; Yin, Shu

    2016-05-15

    The different crystal forms of nitrogen doped-titanium oxide (N-TiO2) with different particle sizes were produced by precipitation-solvothermal method and their adsorption mechanism were also investigated. The adsorption kinetics showed that rutile N-TiO2 displayed higher adsorption capacity than anatase for methyl orange (MO) and its adsorption behavior followed the pseudo-second-order kinetics. The equilibrium adsorption rate of N-TiO2 for MO was well fitted by the Langmuir isotherm model and the adsorption process was monolayer adsorption. The adsorption capacity decreased with increasing temperature. The average correlation coefficient was beyond 97%. The thermodynamic parameters (ΔaGm(ө), ΔaHm(ө), and ΔaSm(ө)) were calculated. It was found that anatase and rutile N-TiO2 had different adsorption enthalpy and entropy. The smaller the particle size, the greater the surface area and surface energy was, then ΔaGm(ө) decreased and the standard equilibrium constant increased at the same time. The adsorption process onto different crystalline phase N-TiO2 was exothermic and non-spontaneous.

  10. Thermodynamic and kinetic behaviors of trinitrotoluene adsorption on powdered activated carbons

    SciTech Connect

    Lee, J.W.; Hwang, K.J.; Shim, W.G.; Moon, I.S.

    2006-07-01

    Regulations on the removal of trinitrotoluene (TNT) from wastewater have become increasingly more stringent, demanding faster, less expensive, and more efficient treatment. This study focuses on the adsorption equilibrium and kinetics of TNT on powered activated carbons (PAC). Three types of PACs (i.e., wood based, coal based, and coconut-shell based) were studied as functions of temperature and pH. Thermodynamic properties including Gibbs free energy, enthalpy, and entropy, were evaluated by applying the Van't Hoff equation. In addition, the adsorption energy distribution functions which describe heterogeneous characteristics of porous solid sorbents were calculated by using the generalized nonlinear regularization method. Adsorption kinetic studies were carried out in batch adsorber under important conditions such as PAC types, temperature, pH, and concentration. We found that fast and efficient removal of TNT dissolved in water can be successfully achieved by PAC adsorption.

  11. Enhanced decolorization of dyes by an iron modified clay and thermodynamic parameters.

    PubMed

    Contreras Olivares, N; Díaz-Nava, M C; Solache-Ríos, M

    2016-01-01

    The sorption processes of red 5 (R5) and yellow 5 (Y5) dyes by iron modified and sodium bentonite in aqueous solutions was evaluated. The modified clay was prepared, conditioned and characterized. The sodium clay did not remove any of either dye. The sorption kinetics and isotherms of R5 and Y5 dyes by iron modified clay were determined. The maximum removal percentages achieved were 97% and 98% for R5 and Y5, respectively, and a contact time of 72 h; the experimental data were best adjusted to Ho model. The isotherms of both dyes were best adjusted to the Langmuir model and the maximum adsorption capacities of the modified clay were 11.26 mg/g and 5.28 mg/g for R5 and Y5, respectively. These results indicate that adsorption processes have a high probability to be described as chemisorption on a homogeneous material. Temperature range between 283 and 213 K does not affect the adsorption of Y5 by the iron modified clay, but the adsorption process of R5 was affected, and the thermodynamic parameters could be calculated, which indicate a chemisorption mechanism.

  12. Thermodynamic criteria for estimating the kinetic parameters of catalytic reactions

    NASA Astrophysics Data System (ADS)

    Mitrichev, I. I.; Zhensa, A. V.; Kol'tsova, E. M.

    2017-01-01

    Kinetic parameters are estimated using two criteria in addition to the traditional criterion that considers the consistency between experimental and modeled conversion data: thermodynamic consistency and the consistency with entropy production (i.e., the absolute rate of the change in entropy due to exchange with the environment is consistent with the rate of entropy production in the steady state). A special procedure is developed and executed on a computer to achieve the thermodynamic consistency of a set of kinetic parameters with respect to both the standard entropy of a reaction and the standard enthalpy of a reaction. A problem of multi-criterion optimization, reduced to a single-criterion problem by summing weighted values of the three criteria listed above, is solved. Using the reaction of NO reduction with CO on a platinum catalyst as an example, it is shown that the set of parameters proposed by D.B. Mantri and P. Aghalayam gives much worse agreement with experimental values than the set obtained on the basis of three criteria: the sum of the squares of deviations for conversion, the thermodynamic consistency, and the consistency with entropy production.

  13. A self-consistent model describing the thermodynamics of Eu(III) adsorption onto hematite

    NASA Astrophysics Data System (ADS)

    Estes, Shanna L.; Arai, Yuji; Becker, Udo; Fernando, Sandra; Yuan, Ke; Ewing, Rodney C.; Zhang, Jiaming; Shibata, Tomohiro; Powell, Brian A.

    2013-12-01

    The environmental fate of actinides is greatly influenced by interfacial reactions, including adsorption onto solid surfaces where the adsorption of trivalent and tetravalent actinides is generally a very strong and potentially irreversible reaction. Changes in the primary hydration sphere of the actinide during inner-sphere adsorption could greatly influence the thermodynamics of these reactions. However, few researchers have studied actinide adsorption thermodynamics. Therefore, using Eu(III) as an analog for trivalent actinides, we examined the thermodynamics of Eu(III) adsorption onto hematite, with particular emphasis on changes in the Eu(III) coordination number and the influence of temperature upon sorption. Our working hypothesis was that a decrease in hydration number upon adsorption, as indicated by a decrease in coordination number and an increase in adsorption with increasing temperature, results in energetically favorable sorption reactions, which are driven by a large, positive entropy term. To perform these studies, we applied the diffuse layer model to describe Eu(III) adsorption onto hematite at pH values ranging from ∼3 to 7 and at 15, 25, 35, and 50 °C. Additionally, we characterized the Eu(III)-hematite surface complex and changes in the Eu(III) primary hydration sphere using extended X-ray absorption fine structure spectroscopy (EXAFS) and computational modeling. High-resolution transmission electron microscopy (HRTEM) was used to identify possible europium surface precipitates or morphological changes in the hematite. The data indicate that the adsorption reaction (1) is endothermic, (2) proceeds with a decrease in the Eu(III) coordination number, and (3) results in the formation of a bidentate mononuclear surface complex, (tbnd FeO)2Eu+. The enthalpy and entropy values for the formation of this surface complex, which were estimated using a van’t Hoff plot, were 131 ± 8 kJ mol-1 and 439 ± 26 J K-1 mol-1, respectively, indicating that

  14. Comparisons of kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide adsorption in aqueous solution with graphene oxide, zeolite and activated carbon

    NASA Astrophysics Data System (ADS)

    Chang, Shenteng; Lu, Chungsying; Lin, Kun-Yi Andrew

    2015-01-01

    Graphene oxide (GO), sodium Y-type zeolite (NaY) and granular activated carbon (GAC) are selected as adsorbents to study their kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide (TMAH) adsorption from water. The adsorption kinetics follows the pseudo-second-order rate law while the adsorption thermodynamics shows an exothermic reaction with GO and GAC but displays an endothermic reaction with NaY. The adsorbed TMAH can be readily desorbed from the surface of GO and NaY by 0.05 M NaCl solution. A comparative study on the cyclic TMAH adsorption with GO, NaY and GAC is also conducted and the results reveal that GO exhibits the greatest TMAH adsorption capacity as well as superior reversibility of TMAH adsorption over 10 cycles of adsorption and desorption process. These features indicate that GO is a promising and efficient adsorbent for TMAH removal in wastewater treatment.

  15. Adsorption behaviour of direct yellow 50 onto cotton fiber: equilibrium, kinetic and thermodynamic profile.

    PubMed

    Ismail, L F M; Sallam, H B; Abo Farha, S A; Gamal, A M; Mahmoud, G E A

    2014-10-15

    This study investigated the adsorption of direct yellow 50 onto cotton fiber from aqueous solution by using parameters, such as pH, temperature, contact time, initial dye concentration and the effect of sodium sulphate, tetrasodium edate and trisodium citrate. The extent of dye adsorption increased with increasing contact time, temperature and solution concentration. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. It was found that the Langmuir equation fit better than the Freundlich equation. The results show that the presence of SE and SC significantly enhance the dye adsorption onto cotton fiber. In addition, the adsorption data obtained at different temperatures of DY50 onto cotton fiber were applied to pseudo first-order, pseudo second-order and intraparticle diffusion models. The rates of adsorption were found to conform to pseudo second-order kinetics with good correlation. Also, free energy of adsorption (ΔG(#)), enthalpy (ΔH(#)), and entropy (ΔS(#)) changes were determined to predict the nature of adsorption. The positive value of the enthalpy change indicated that the adsorption is endothermic process. The activation energy, Ea, is ranged between 1.9 and 3.9kJmol(-1) indicated that the adsorption process is a physisorption. This low value of Ea generally indicates diffusion controlled process.

  16. Adsorption behaviour of direct yellow 50 onto cotton fiber: Equilibrium, kinetic and thermodynamic profile

    NASA Astrophysics Data System (ADS)

    Ismail, L. F. M.; Sallam, H. B.; Abo Farha, S. A.; Gamal, A. M.; Mahmoud, G. E. A.

    2014-10-01

    This study investigated the adsorption of direct yellow 50 onto cotton fiber from aqueous solution by using parameters, such as pH, temperature, contact time, initial dye concentration and the effect of sodium sulphate, tetrasodium edate and trisodium citrate. The extent of dye adsorption increased with increasing contact time, temperature and solution concentration. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. It was found that the Langmuir equation fit better than the Freundlich equation. The results show that the presence of SE and SC significantly enhance the dye adsorption onto cotton fiber. In addition, the adsorption data obtained at different temperatures of DY50 onto cotton fiber were applied to pseudo first-order, pseudo second-order and intraparticle diffusion models. The rates of adsorption were found to conform to pseudo second-order kinetics with good correlation. Also, free energy of adsorption (ΔG#), enthalpy (ΔH#), and entropy (ΔS#) changes were determined to predict the nature of adsorption. The positive value of the enthalpy change indicated that the adsorption is endothermic process. The activation energy, Ea, is ranged between 1.9 and 3.9 kJ mol-1 indicated that the adsorption process is a physisorption. This low value of Ea generally indicates diffusion controlled process.

  17. Cloud and Thermodynamic Parameters Retrieved from Satellite Ultraspectral Infrared Measurements

    NASA Technical Reports Server (NTRS)

    Zhou, Daniel K.; Smith, William L.; Larar, Allen M.; Liu, Xu; Taylor, Jonathan P.; Schluessel, Peter; Strow, L. Larrabee; Mango, Stephen A.

    2008-01-01

    Atmospheric-thermodynamic parameters and surface properties are basic meteorological parameters for weather forecasting. A physical geophysical parameter retrieval scheme dealing with cloudy and cloud-free radiance observed with satellite ultraspectral infrared sounders has been developed and applied to the Infrared Atmospheric Sounding Interferometer (IASI) and the Atmospheric InfraRed Sounder (AIRS). The retrieved parameters presented herein are from radiance data gathered during the Joint Airborne IASI Validation Experiment (JAIVEx). JAIVEx provided intensive aircraft observations obtained from airborne Fourier Transform Spectrometer (FTS) systems, in-situ measurements, and dedicated dropsonde and radiosonde measurements for the validation of the IASI products. Here, IASI atmospheric profile retrievals are compared with those obtained from dedicated dropsondes, radiosondes, and the airborne FTS system. The IASI examples presented here demonstrate the ability to retrieve fine-scale horizontal features with high vertical resolution from satellite ultraspectral sounder radiance spectra.

  18. Synergistic improvement of gas sensing performance by micro-gravimetrically extracted kinetic/thermodynamic parameters.

    PubMed

    Guo, Shuanbao; Xu, Pengcheng; Yu, Haitao; Cheng, Zhenxing; Li, Xinxin

    2015-03-10

    A novel method is explored for comprehensive design/optimization of organophosphorus sensing material, which is loaded on mass-type microcantilever sensor. Conventionally, by directly observing the gas sensing response, it is difficult to build quantitative relationship with the intrinsic structure of the material. To break through this difficulty, resonant cantilever is employed as gravimetric tool to implement molecule adsorption experiment. Based on the sensing data, key kinetic/thermodynamic parameters of the material to the molecule, including adsorption heat -ΔH°, adsorption/desorption rate constants Ka and Kd, active-site number per unit mass N' and surface coverage θ, can be quantitatively extracted according to physical-chemistry theories. With gaseous DMMP (simulant of organophosphorus agents) as sensing target, the optimization route for three sensing materials is successfully demonstrated. Firstly, a hyper-branched polymer is evaluated. Though suffering low sensitivity due to insufficient N', the bis(4-hydroxyphenyl)-hexafluoropropane (BHPF) sensing-group exhibits satisfactory reproducibility due to appropriate -ΔH°. To achieve more sensing-sites, KIT-5 mesoporous-silica with higher surface-area is assessed, resulting in good sensitivity but too high -ΔH° that brings poor repeatability. After comprehensive consideration, the confirmed BHPF sensing-group is grafted on the KIT-5 carrier to form an optimized DMMP sensing nanomaterial. Experimental results indicate that, featuring appropriate kinetic/thermodynamic parameters of -ΔH°, Ka, Kd, N' and θ, the BHPF-functionalized KIT-5 mesoporous silica exhibits synergistic improvement among reproducibility, sensitivity and response/recovery speed. The optimized material shows complete signal recovery, 55% sensitivity improvement than the hyper-branched polymer and 2∼3 folds faster response/recovery speed than the KIT-5 mesoporous silica.

  19. Adsorption thermodynamics of two-domain antifreeze proteins: theory and Monte Carlo simulations.

    PubMed

    Narambuena, Claudio F; Sanchez Varretti, Fabricio O; Ramirez-Pastor, Antonio J

    2016-09-21

    In this paper we develop the statistical thermodynamics of two-domain antifreeze proteins adsorbed on ice. We use a coarse-grained model and a lattice network in order to represent the protein and ice, respectively. The theory is obtained by combining the exact analytical expression for the partition function of non-interacting linear k-mers adsorbed in one dimension, and its extension to higher dimensions. The total and partial adsorption isotherms, and the coverage and temperature dependence of the Helmholtz free energy and configurational entropy are given. The formalism reproduces the classical Langmuir equation, leads to the exact statistical thermodynamics of molecules adsorbed in one dimension, and provides a close approximation for two-dimensional systems. Comparisons with analytical data obtained using the modified Langmuir model (MLM) and Monte Carlo simulations in the grand canonical ensemble were performed in order to test the validity of the theoretical predictions. In the MC calculations, the different mechanisms proposed in the literature to describe the adsorption of two-domain antifreeze proteins on ice were analyzed. Indistinguishable results were obtained in all cases, which verifies the thermodynamic equivalence of these mechanisms and allows the choice of the most suitable mechanism for theoretical studies of equilibrium properties. Even though a good qualitative agreement is obtained between MLM and MC data, it is found that the new theoretical framework offers a more accurate description of the phenomenon of adsorption of two-domain antifreeze proteins.

  20. Thermodynamic modeling of solute adsorption equilibrium from near-critical carbon dioxide.

    PubMed

    Yang, Xiaoning

    2004-05-15

    Modeling of adsorption equilibrium for supercritical fluid mixtures, with as few parameters as possible, is important in applications of the technology of supercritical fluid adsorption. In this paper, a correlative model has been developed to represent the adsorption equilibria of solutes from the near-critical CO(2) fluid. A two-dimensional van der Waals equation of state and the three-dimensional P - R equation of state were used to describe the adsorbed and bulk phases, respectively. This model contains five parameters for adsorption equilibrium isotherms at finite concentrations and two parameters for adsorption equilibrium constants at infinite dilution. All the parameters are independent of temperature and pressure. By applying the model to the experimental data from the literature, it was shown that this model is capable of describing the adsorption behavior of solutes from supercritical carbon dioxide over relatively wide temperature and pressure ranges. In addition, the adsorption behavior of supercritical fluid mixtures was investigated at finite and infinite dilution conditions.

  1. pH effect on protein G orientation on gold surfaces and characterization of adsorption thermodynamics.

    PubMed

    Johnson, Blake N; Mutharasan, Raj

    2012-05-01

    The pH effect on adsorbed antibody-binding protein (protein G) orientation on gold (Au) and its adsorption thermodynamic characteristics were investigated using quartz crystal microbalance (QCM) and X-ray photoelectron spectroscopy (XPS). The adsorbed protein G orientation was measured by binding response of two antibody-antigen systems: the model bovine serum albumin (BSA) and the foodborne pathogen E. coli O157:H7. Surface coverage was not significantly affected by pH, but its orientation was. The most properly oriented protein G for antibody binding was achieved at near-neutral pH. Adsorption was verified by XPS measurements using nitrogen (N) 1s, oxygen (O) 1s, and Au 4p peak heights. Adsorption energetics were determined by van't Hoff and Langmuir kinetic analyses of adsorption data obtained at 296, 303, and 308 K. Large characteristic entropy change of protein adsorption was observed (ΔS° = 0.52 ± 0.01 kcal/mol·K). The adsorption process was not classical physisorption but exhibited chemisorption characteristics based on significant enthalpy change (ΔH° = -25 ± 6 kcal/mol).

  2. Modeling of 1,4-cyclohexadiene adsorption thermodynamics on Si(001)-2 × 1 surface

    NASA Astrophysics Data System (ADS)

    Gorbunov, V. A.; Myshlyavtsev, A. V.; Myshlyavtseva, M. D.; Fefelov, V. F.

    2015-06-01

    The adsorption thermodynamics of 1,4-cyclohexadiene on Si(001)-2 × 1 are studied in the framework of the lattice gas model with the Monte Carlo and transfer-matrix methods. Adsorption isotherms, heat capacity, entropy as function of chemical potential and adlayer density were calculated. It is shown that there are two ordered phases for the model under consideration. The first phase consists of the tetra-σ complexes and there is a low surface concentration of the adsorbed molecules. The second phase consists of the π-complexes and there is a high surface concentration. The ordered phase consisting of the di-σ complexes is absent within the constructed model. The obtained set of ordered phases and the sequence of its arising with growth of chemical potential are in close correspondence with the experimental data. In the framework of the model under consideration the observed behavior of 1,4-cyclohexadiene adsorption layer on Si(001)-2 × 1 is explained by the presence of three adsorption states with different surface area per molecule and repulsive lateral interactions. Thus, the transition between π- and di-σ configurations and the formation of the π-complex phase can be the thermodynamically driven effect.

  3. Corrected thermodynamic description of adsorption via formalism of the theory of volume filling of micropores.

    PubMed

    Terzyk, Artur P; Gauden, Piotr A; Rychlicki, Gerhard

    2006-06-01

    Based on the series of benzene adsorption and related enthalpy of adsorption data measured on porous carbons that possess various porous structures, we show that the creation of a solidlike structure in pores depends on the average pore diameter of an adsorbent. Taking into account the solidlike adsorbed phase in the thermodynamic description of the adsorption process via the formalism of the theory of volume filling of micropores (TVFM) leads to very good agreement between the data measured experimentally and those calculated from TVFM. Finally we show that the boundary between solidlike and liquidlike structures of benzene molecules in carbon pores is located around the average pore diameter, close to ca. 2.1-2.4 nm.

  4. Adsorption of methyl orange from aqueous solution by aminated pumpkin seed powder: Kinetics, isotherms, and thermodynamic studies.

    PubMed

    Subbaiah, Munagapati Venkata; Kim, Dong-Su

    2016-06-01

    Present research discussed the utilization of aminated pumpkin seed powder (APSP) as an adsorbent for methyl orange (MO) removal from aqueous solution. Batch sorption experiments were carried to evaluate the influence of pH, initial dye concentration, contact time, and temperature. The APSP was characterized by using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). The experimental equilibrium adsorption data were fitted using two two-parameter models (Langmuir and Freundlich) and two three-parameter models (Sips and Toth). Langmuir and Sips isotherms provided the best model for MO adsorption data. The maximum monolayer sorption capacity was found to be 200.3mg/g based on the Langmuir isotherm model. The pseudo-first-order and pseudo-second-order model equations were used to analyze the kinetic data of the adsorption process and the data was fitted well with the pseudo-second-order kinetic model (R(2)>0.97). The calculated thermodynamic parameters such as ΔG(0), ΔH(0) and ΔS(0) from experimental data showed that the sorption of MO onto APSP was feasible, spontaneous and endothermic in the temperature range 298-318 K. The FTIR results revealed that amine and carboxyl functional groups present on the surface of APSP. The SEM results show that APSP has an irregular and porous surface which is adequate morphology for dye adsorption. Desorption experiments were carried to explore the feasibility of adsorbent regeneration and the adsorbed MO from APSP was desorbed using 0.1M NaOH with an efficiency of 93.5%. Findings of the present study indicated that APSP can be successfully used for removal of MO from aqueous solution.

  5. Adsorption isotherms, kinetics, thermodynamics and desorption studies of 2,4,6-trichlorophenol on oil palm empty fruit bunch-based activated carbon.

    PubMed

    Tan, I A W; Ahmad, A L; Hameed, B H

    2009-05-30

    The adsorption characteristics of 2,4,6-trichlorophenol (TCP) on activated carbon prepared from oil palm empty fruit bunch (EFB) were evaluated. The effects of TCP initial concentration, agitation time, solution pH and temperature on TCP adsorption were investigated. TCP adsorption uptake was found to increase with increase in initial concentration, agitation time and solution temperature whereas adsorption of TCP was more favourable at acidic pH. The adsorption equilibrium data were best represented by the Freundlich and Redlich-Peterson isotherms. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The mechanism of the adsorption process was determined from the intraparticle diffusion model. Boyd plot revealed that the adsorption of TCP on the activated carbon was mainly governed by particle diffusion. Thermodynamic parameters such as standard enthalpy (DeltaH degrees ), standard entropy (DeltaS degrees ), standard free energy (DeltaG degrees ) and activation energy were determined. The regeneration efficiency of the spent activated carbon was high, with TCP desorption of 99.6%.

  6. Parameter Estimation as a Problem in Statistical Thermodynamics

    NASA Astrophysics Data System (ADS)

    Earle, Keith A.; Schneider, David J.

    2011-03-01

    In this work, we explore the connections between parameter fitting and statistical thermodynamics using the maxent principle of Jaynes as a starting point. In particular, we show how signal averaging may be described by a suitable one particle partition function, modified for the case of a variable number of particles. These modifications lead to an entropy that is extensive in the number of measurements in the average. Systematic error may be interpreted as a departure from ideal gas behavior. In addition, we show how to combine measurements from different experiments in an unbiased way in order to maximize the entropy of simultaneous parameter fitting. We suggest that fit parameters may be interpreted as generalized coordinates and the forces conjugate to them may be derived from the system partition function. From this perspective, the parameter fitting problem may be interpreted as a process where the system (spectrum) does work against internal stresses (non-optimum model parameters) to achieve a state of minimum free energy/maximum entropy. Finally, we show how the distribution function allows us to define a geometry on parameter space, building on previous work[1, 2]. This geometry has implications for error estimation and we outline a program for incorporating these geometrical insights into an automated parameter fitting algorithm.

  7. Flavonoid-DNA binding studies and thermodynamic parameters

    NASA Astrophysics Data System (ADS)

    Janjua, Naveed Kausar; Shaheen, Amber; Yaqub, Azra; Perveen, Fouzia; Sabahat, Sana; Mumtaz, Misbah; Jacob, Claus; Ba, Lalla Aicha; Mohammed, Hamdoon A.

    2011-09-01

    Interactional studies of new flavonoid derivatives (Fl) with chicken blood ds.DNA were investigated spectrophotometrically in DMSO-H 2O (9:1 v/v) at various temperatures. Spectral parameters suggest considerable binding between the flavonoid derivatives studied and ds.DNA. The binding constant values lie in the enhanced-binding range. Thermodynamic parameters obtained from UV studies also point to strong spontaneous binding of Fl with ds.DNA. Viscometric studies complimented the UV results where a small linear increase in relative viscosity of the DNA solution was observed with added optimal flavonoid concentration. An overall mixed mode of interaction (intercalative plus groove binding) is proposed between DNA and flavonoids. Conclusively, investigated flavonoid derivatives are found to be strong DNA binders and seem to be promising drug candidates like their natural analogues.

  8. Mechanism of Arsenic Adsorption on Magnetite Nanoparticles from Water: Thermodynamic and Spectroscopic Studies.

    PubMed

    Liu, Cheng-Hua; Chuang, Ya-Hui; Chen, Tsan-Yao; Tian, Yuan; Li, Hui; Wang, Ming-Kuang; Zhang, Wei

    2015-07-07

    Removal of arsenic (As) from water supplies is needed to reduce As exposure through drinking water and food consumption in many regions of the world. Magnetite nanoparticles (MNPs) are promising and novel adsorbents for As removal because of their great adsorption capacity for As and easy separation. This study aimed to investigate the adsorption mechanism of arsenate, As(V), and arsenite, As(III), on MNPs by macroscopic adsorption experiments in combination with thermodynamic calculation and microspectroscopic characterization using synchrotron-radiation-based X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). Adsorption reactions are favorable endothermic processes as evidenced by increased adsorption with increasing temperatures, and high positive enthalpy change. EXAFS spectra suggested predominant formation of bidentate binuclear corner-sharing complexes ((2)C) for As(V), and tridentate hexanuclear corner-sharing ((3)C) complexes for As(III) on MNP surfaces. The macroscopic and microscopic data conclusively identified the formation of inner-sphere complexes between As and MNP surfaces. More intriguingly, XANES and XPS results revealed complex redox transformation of the adsorbed As on MNPs exposed to air: Concomitant with the oxidation of MNPs, the oxidation of As(III) and MNPs was expected, but the observed As(V) reduction was surprising because of the role played by the reactive Fe(II).

  9. Experimental studies on equilibrium adsorption isosteres and determination of the thermodynamic quantities of polar media on alumina Al2O3

    NASA Astrophysics Data System (ADS)

    Yonova, Albena

    2017-03-01

    The present work is a revieif of theoretical and experimental study on the adsorption performance of the adsorbent Alumina (Al2O3) used in the adsorption system. An experimental investigation on the equilibrium adsorption isosteres at low pressure (< 1 atm) of working pairs Al2O3/H2O and Al2O3/C2H6O2 is carried out. The isovolume measurement method is adopted in the test setup to directly measure the saturated vapor pressures of working pairs at vapor-liquid equilibrium (dG=0 and dμi=0). Quantity adsorbed is determined from pressure, volume and temperature using gas law. The isosteric heat of adsorption is calculated from the slope of the plot of lnP versus 1/T different amounts of adsorbate onto adsorbent as follows: 0,01 vol% Al2O3/H2O; 0,03 vol% Al2O3/H2O; 0,1 vol% Al2O3/H2O; 0,01 vol% Al2O3/C2H6O2; 0,03 vol% Al2O3/C2H6O2; 0,1 vol% Al2O3/C2H6O2. This study shows that adsorption working pair Al2O3 C2H6O2 has better adsorption performances than those of the A2O3/H2O. Surface acidity! is a most important property! far both adsorption and catalysis and therefore is examined structure of active sites of alumina surface. Thermodynamic parameters such as isosteric heat of adsorption, isosteric enthalpy and entropy of adsorption are critical design variables in estimating the performance and predicting the mechanism of an adsorption process and are also one of the basic requirements for the characterization and optimization of an adsorption process

  10. Enhanced fluoride adsorption by nano crystalline γ-alumina: adsorption kinetics, isotherm modeling and thermodynamic studies

    NASA Astrophysics Data System (ADS)

    Chinnakoti, Prathibha; Chunduri, Avinash L. A.; Vankayala, Ranganayakulu K.; Patnaik, Sandeep; Kamisetti, Venkataramaniah

    2016-06-01

    Nano materials in particular nano oxides with enhanced surface area and an excellent catalytic surface serve as potential adsorbents for defluoridation of water. In the present study nano γ-alumina was synthesized through a simple and low cost, surfactant assisted solution combustion method. As synthesized material was characterized by XRD and FESEM for its phase, size and morphological characteristics. Surface properties have been investigated by BET method. Nano γ-alumina was further used for a detailed adsorption study to remove fluoride from water. Batches of experiments were performed at various experimental conditions such as solution pH, adsorbent dose, initial fluoride concentration and contact time to test the defluoridation ability of γ-alumina. Fluoride Adsorption by nano sized γ-alumina was rapid and reached equilibrium within two hours. The adsorption worked well at pH 4.0, where ˜96 % of fluoride was found to be adsorbed on adsorbent. It was possible to reduce fluoride levels to as low as 0.3 mg/L (within the safe limit of WHO: ≤1.5 mg/L) from an initial fluoride levels of 10 mg/L. This could be achieved using a very small quantity, 1 g/L of γ-alumina at pH 4 within 1 h of contact time. Defluoridation capacity of nano γ-alumina was further investigated by fitting the equilibrium data to various isotherm as well as kinetic models. The present study revealed that γ-alumina could be an efficient adsorbent for treating fluoride contaminated water.

  11. Kinetics and thermodynamics of textile dye adsorption from aqueous solutions using babassu coconut mesocarp.

    PubMed

    Vieira, Adriana P; Santana, Sirlane A A; Bezerra, Cícero W B; Silva, Hildo A S; Chaves, José A P; de Melo, Júlio C P; da Silva Filho, Edson C; Airoldi, Claudio

    2009-07-30

    Extracted babassu coconut (Orbignya speciosa) mesocarp (BCM) was applied as a biosorbent for aqueous Blue Remazol R160 (BR 160), Rubi S2G (R S2G), Red Remazol 5R (RR 5), Violet Remazol 5R (VR 5) and Indanthrene Olive Green (IOG) dye solutions. The natural sorbent was processed batchwise while varying several system parameters such as stirring time, pH and temperature. The interactions were assayed with respect to both pseudo-first-order and second-order reaction kinetics, with the latter the more suitable kinetic model. The maximum adsorption was obtained at pH 1.0 for all dyes due to available anionic groups attached to the structures, which can be justified by pH(pzc) 6.7 for the biosorbent BCM. The ability of babassu coconut mesocarp to adsorb dyes gave the order R S2G>VR 5>BR 160>IOG>RR 5, which data were best fit to Freundlich model, but did not well-adjusted for all dyes. The dye/biopolymer interactions at the solid/liquid interface are all spontaneous as given by free Gibbs energy, with exothermic enthalpic values of -26.1, -15.8, -17.8, -15.8 and -23.7 kJ mol(-1) for BR 160, R S2G, RR 5, IOG and VR 5, respectively. In spite of the negative entropic values contribution, the set of thermodynamic data is favorable for all dyes removal. However, the results pointed to the effectiveness of the mesocarp of babassu coconut as a biosorbent for removing textile dyes from aqueous solutions.

  12. Kinetic, equilibrium isotherm and thermodynamic studies of Cr(VI) adsorption onto low-cost adsorbent developed from peanut shell activated with phosphoric acid.

    PubMed

    ALOthman, Zeid A; Naushad, Mu; Ali, Rahmat

    2013-05-01

    A particular agricultural waste, peanut shell, has been used as precursor for activated carbon production by chemical activation with H₃PO₄. Unoxidized activated carbon was prepared in nitrogen atmosphere which was then heated in air at a desired temperature to get oxidized activated carbon. The prepared carbons were characterized for surface area, surface morphology, and pore volume and utilized for the removal of Cr(VI) from aqueous solution. Batch mode experiments were conducted to study the effects of pH, contact time, particle size, adsorbent dose, initial concentration of adsorbate, and temperature on the adsorption of Cr(VI). Cr(VI) adsorption was significantly dependent on solution pH, and the optimum adsorption was observed at pH 2. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to analyze the kinetic data obtained at different initial Cr(VI) concentrations. The adsorption kinetic data were described very well by the pseudo-second-order model. Equilibrium isotherm data were analyzed by the Langmuir, Freundlich, and Temkin models. The results showed that the Langmuir adsorption isotherm model fitted the data better in the temperature range studied. The adsorption capacity which was found to increase with temperature showed the endothermic nature of Cr(VI) adsorption. The thermodynamic parameters, such as Gibb's Free energy change (ΔG°), standard enthalpy change (ΔH°), and standard entropy change (ΔS°) were evaluated.

  13. Adsorption equilibrium, kinetics and thermodynamics of α-amylase on poly(DVB-VIM)-Cu(+2) magnetic metal-chelate affinity sorbent.

    PubMed

    Osman, Bilgen; Kara, Ali; Demirbel, Emel; Kök, Senay; Beşirli, Necati

    2012-09-01

    Designing an immobilised metal ion affinity process on large-scale demands that a thorough understanding be developed regarding the adsorption behaviour of proteins on metal-loaded gels and the characteristic adsorption parameters to be evaluated. In view of this requirement, interaction of α-amylase as a model protein with newly synthesised magnetic-poly(divinylbenzene-1-vinylimidazole) [m-poly(DVB-VIM)] microbeads (average diameter, 53-212 μm) was investigated. The m-poly(DVB-VIM) microbeads were prepared by copolymerising of divinylbenzene (DVB) with 1-vinylimidazole (VIM). The m-poly(DVB-VIM) microbeads were characterised by N(2) adsorption/desorption isotherms, electron spin resonance, elemental analysis, scanning electron microscope and swelling studies. Cu(2+) ions were chelated on the m-poly(DVB-VIM) beads and used in adsorption of α-amylase in a batch system. The maximum α-amylase adsorption capacity of the m-poly(DVB-VIM)-Cu(2+) beads was determined as 10.84 mg/g at pH 6.0, 25 °C. The adsorption data were analyzed using three isotherm models, which are the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The pseudo-first-order, pseudo-second-order, modified Ritchie's-second-order and intraparticle diffusion models were used to test dynamic experimental data. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy and entropy changes.

  14. Synthesis, characterization, and thermodynamic parameters of vanadium dioxide

    SciTech Connect

    Qi Ji; Ning Guiling Lin Yuan

    2008-08-04

    A novel process was developed for synthesizing pure thermochromic vanadium dioxide (VO{sub 2}) by thermal reduction of vanadium pentoxide (V{sub 2}O{sub 5}) in ammonia gas. The process of thermal reduction of V{sub 2}O{sub 5} was optimized by both experiments and modeling of thermodynamic parameters. The product VO{sub 2} was characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectrometry (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TG), and differential scanning calorimetry (DSC). The experimental results indicated that pure thermochromic VO{sub 2} crystal particles were successfully synthesized. The phase transition temperature of the VO{sub 2} is approximately 342.6 K and the enthalpy of phase transition is 44.90 J/g.

  15. Thermodynamics of iodide adsorption at the instantaneous air-water interface

    NASA Astrophysics Data System (ADS)

    Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.

    2013-03-01

    We performed molecular dynamics simulations using both polarizable and non-polarizable force fields to study the adsorption of iodide to the air-water interface. A novel aspect of our analysis is that the progress of ion adsorption is measured as the distance from the instantaneous interface, which is defined by a coarse-graining scheme proposed recently by Willard and Chandler ["Instantaneous liquid interfaces," J. Phys. Chem. B 114, 1954-1958 (2010), 10.1021/jp909219k]. Referring structural and thermodynamic quantities to the instantaneous interface unmasks molecular-scale details that are obscured by thermal fluctuations when the same quantities are referred to an average measure of the position of the interface, such as the Gibbs dividing surface. Our results suggest that an ion adsorbed at the interface resides primarily in the topmost water layer, and the interfacial location of the ion is favored by enthalpy and opposed by entropy.

  16. Kinetics and thermodynamics of protein adsorption: a generalized molecular theoretical approach.

    PubMed Central

    Fang, F; Szleifer, I

    2001-01-01

    The thermodynamics and kinetics of protein adsorption are studied using a molecular theoretical approach. The cases studied include competitive adsorption from mixtures and the effect of conformational changes upon adsorption. The kinetic theory is based on a generalized diffusion equation in which the driving force for motion is the gradient of chemical potentials of the proteins. The time-dependent chemical potentials, as well as the equilibrium behavior of the system, are obtained using a molecular mean-field theory. The theory provides, within the same theoretical formulation, the diffusion and the kinetic (activated) controlled regimes. By separation of ideal and nonideal contributions to the chemical potential, the equation of motion shows a purely diffusive part and the motion of the particles in the potential of mean force resulting from the intermolecular interactions. The theory enables the calculation of the time-dependent surface coverage of proteins, the dynamic surface tension, and the structure of the adsorbed layer in contact with the approaching proteins. For the case of competitive adsorption from a solution containing a mixture of large and small proteins, a variety of different adsorption patterns are observed depending upon the bulk composition, the strength of the interaction between the particles, and the surface and size of the proteins. It is found that the experimentally observed Vroman sequence is predicted in the case that the bulk solution is at a composition with an excess of the small protein, and that the interaction between the large protein and the surface is much larger than that of the smaller protein. The effect of surface conformational changes of the adsorbed proteins in the time-dependent adsorption is studied in detail. The theory predicts regimes of constant density and dynamic surface tension that are long lived but are only intermediates before the final approach to equilibrium. The implications of the findings to the

  17. Ni (II) adsorption onto Chrysanthemum indicum: Influencing factors, isotherms, kinetics, and thermodynamics.

    PubMed

    Vilvanathan, Sowmya; Shanthakumar, S

    2016-10-02

    The study explores the adsorption potential of Chrysanthemum indicum biomass for nickel ion removal from aqueous solution. C. indicum flowers in raw (CIF-I) and biochar (CIF-II) forms were used as adsorbents in this study. Batch experiments were conducted to ascertain the optimum conditions of solution pH, adsorbent dosage, contact time, and temperature for varying initial Ni(II) ion concentrations. Surface area, surface morphology, and functionality of the adsorbents were characterized by Brunauer, Emmett, and Teller (BET) surface analysis, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier transform infrared spectroscopy (FTIR). Adsorption kinetics were modeled using pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion, Bangham's, and Boyd's plot. The equilibrium data were modeled using Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich (D-R) isotherm models. Experimental data provided the best fit to pseudo-second-order kinetic model and Langmuir isotherm model for the adsorption of Ni(II) ion on both CIF-I and CIF-II with maximum adsorption capacities of 23.97 and 44.02 mg g(-1), respectively. Thermodynamic analysis of the data proved the process to be spontaneous and endothermic in nature. Desorption studies were conducted to evaluate the possibility of reusing the adsorbents. Findings of the present study provide substantial evidence for the use of C. indicum flower as an eco-friendly and potential adsorbent for the removal of Ni(II) ions from aqueous solution.

  18. A procedure to find thermodynamic equilibrium constants for CO2 and CH4 adsorption on activated carbon.

    PubMed

    Trinh, T T; van Erp, T S; Bedeaux, D; Kjelstrup, S; Grande, C A

    2015-03-28

    Thermodynamic equilibrium for adsorption means that the chemical potential of gas and adsorbed phase are equal. A precise knowledge of the chemical potential is, however, often lacking, because the activity coefficient of the adsorbate is not known. Adsorption isotherms are therefore commonly fitted to ideal models such as the Langmuir, Sips or Henry models. We propose here a new procedure to find the activity coefficient and the equilibrium constant for adsorption which uses the thermodynamic factor. Instead of fitting the data to a model, we calculate the thermodynamic factor and use this to find first the activity coefficient. We show, using published molecular simulation data, how this procedure gives the thermodynamic equilibrium constant and enthalpies of adsorption for CO2(g) on graphite. We also use published experimental data to find similar thermodynamic properties of CO2(g) and of CH4(g) adsorbed on activated carbon. The procedure gives a higher accuracy in the determination of enthalpies of adsorption than ideal models do.

  19. Investigation of mono/competitive adsorption of environmentally relevant ionized weak acids on graphite: impact of molecular properties and thermodynamics.

    PubMed

    Moustafa, Ahmed M A; McPhedran, Kerry N; Moreira, Jesús; Gamal El-Din, Mohamed

    2014-12-16

    The thermodynamics of adsorption and competitive interactions of five weak acids on a graphite surface was assessed in alkaline solutions. Adsorption of the acids in mono- and multicompound solutions followed their Freundlich isotherms which suggest a diversity of graphite adsorption sites as confirmed by the presence of carboxylic and phenolic groups observed on graphite surfaces. Thermodynamic calculations assigned the formation of the negatively charged assisted hydrogen bond (-CAHB) between ionized solutes and adsorbent surface groups as the possible adsorption mechanism. However, the similar pKa values of current acids resulted in comparable free energies for -CAHB formation (ΔG(-CAHB)) being less than solvation free energies (ΔGSolv). Thus, additional ΔG is supplemented by increased hydrophobicity due to proton exchange of ionized acids with water (ΔΔG Hydrophobicity). Adsorption capacities and competition coefficients indicated that ΔΔG Hydrophobicity values depend on the neutral and ionized acid Kow. Competitive adsorption implies that multilayer adsorption may occur via hydrophobic bonding with the CH3 ends of the self-assembled layer which affects the acid adsorption capacities in mixtures as compared to monocompound solutions. The determination of adsorption mechanisms will assist in understanding of the fate and bioavailability of emerging and classical weak acids released into natural waters.

  20. Kinetics, equilibrium and thermodynamics of adsorption of 2-biphenylamine and dibenzylamine from aqueous solutions by Fe3O4/bentonite nanocomposite

    NASA Astrophysics Data System (ADS)

    Vasheghani F., B.; Rajabi, F. H.; Omidi, M. H.; Shabanian, S.

    2015-05-01

    Magnetic Fe3O4/bentonite nanocomposite is synthesized by chemical co-precipitation method. Experimental data are modelled by Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherms. Freundlich and Langmuir isotherm model fitted the equilibrium data for the dibenzylamine (DBA) and 2-biphenylamine (BPA) respectively, compared to the other isotherm models. The calculated thermodynamic parameters, Δ G°, Δ H°, and Δ S° showed that the DBA and BPA adsorption on bentonite nanocomposite is spontaneous and endothermic under examined conditions. Experimental data were also modeled using the adsorption kinetic models. The results show that the adsorption processes of DBA and BPA followed well the pseudo-second-order kinetics. Results indicated that Fe3O4/bentonite nanocomposite could be an alternative for more costly adsorbents used for organic toxicants removal.

  1. Automation of data processing and calculation of retention parameters and thermodynamic data for gas chromatography

    NASA Astrophysics Data System (ADS)

    Makarycheva, A. I.; Faerman, V. A.

    2017-02-01

    The analyses of automation patterns is performed and the programming solution for the automation of data processing of the chromatographic data and their further information storage with a help of a software package, Mathcad and MS Excel spreadsheets, is developed. The offered approach concedes the ability of data processing algorithm modification and does not require any programming experts participation. The approach provides making a measurement of the given time and retention volumes, specific retention volumes, a measurement of differential molar free adsorption energy, and a measurement of partial molar solution enthalpies and isosteric heats of adsorption. The developed solution is focused on the appliance in a small research group and is tested on the series of some new gas chromatography sorbents. More than 20 analytes were submitted to calculation of retention parameters and thermodynamic sorption quantities. The received data are provided in the form accessible to comparative analysis, and they are able to find sorbing agents with the most profitable properties to solve some concrete analytic issues.

  2. Influence of adsorption thermodynamics on guest diffusivities in nanoporous crystalline materials.

    PubMed

    Krishna, Rajamani; van Baten, Jasper M

    2013-06-07

    Published experimental data, underpinned by molecular simulations, are used to highlight the strong influence of adsorption thermodynamics on diffusivities of guest molecules inside ordered nanoporous crystalline materials such as zeolites, metal-organic frameworks (MOFs), and zeolitic imidazolate frameworks (ZIFs). For cage-type structures (e.g. LTA, CHA, DDR, and ZIF-8), the variation of the free energy barrier for inter-cage hopping across the narrow windows, -δFi, provides a rationalization of the observed strong influence of pore concentrations, ci, on diffusivities. In open structures with large pore volumes (e.g. FAU, IRMOF-1, CuBTC) and within channels (MFI, BEA, MgMOF-74, MIL-47, MIL-53), the pore concentration (ci) dependence of the self- (Di,self), Maxwell-Stefan (Đi), and Fick (Di) diffusivities are often strongly dictated by the inverse thermodynamic correction factor, 1/Γi≡∂ln ci/∂ln pi; the magnitudes of the diffusivities are dictated by the binding energies for adsorption. For many guest-host combinations Đi-ci dependence is directly related to the 1/Γivs. ci variation. When molecular clustering occurs, we get 1/Γi > 1, causing unusual Đivs. ci dependencies. The match, or mis-match, between the periodicity of the pore landscape and the conformations of adsorbed chain molecules often leads to non-monotonic variation of diffusivities with chain lengths.

  3. Kinetics and thermodynamics of adsorption of azinphosmethyl from aqueous solution onto pyrolyzed (at 600 degrees C) ocean peat moss (Sphagnum sp.).

    PubMed

    Aroguz, A Z

    2006-07-31

    The removal of azinphosmethyl from aqueous solution onto pyrolyzed ocean peat moss (Sphagnum sp.), as a residue, from the Rhode Island coast (USA), has been investigated at different temperatures and initial concentrations. The ocean peat moss had been pyrolyzed at 600 degrees C in nitrogen atmosphere before the adsorption process. The kinetic data obtained from batch studies have been analyzed using pseudo-first order kinetic model. The rate constants were evaluated at different temperatures. The thermodynamic parameters (DeltaG degrees , DeltaH degrees , DeltaS degrees ) for the adsorption process were calculated and the results suggest that the nature of adsorption is endothermic and the process is spontaneous and favorable. The activation energy for adsorption process was estimated, about 18.3 kJ mol(-1). According to this value the adsorption of azinphosmethyl onto pyrolyzed ocean peat moss is in the range of physical adsorption. The experimental data have been modeled using Langmuir, Freundlich and Temkin isotherms. It was found that Langmuir and Freundlich isotherms give the best correlation with the experimental data.

  4. Corrosion Mechanism of Low-Carbon Steel in Industrial Water and Adsorption Thermodynamics in the Presence of Some Plant Extracts

    NASA Astrophysics Data System (ADS)

    Badiea, A. M.; Mohana, K. N.

    2009-12-01

    The effects of radish leaves and black cumin as plant extracts on the corrosion behavior of low-carbon steel in industrial water in the temperature range of 30 to 80 °C and velocity range of 1.44 to 2.02 m s-1 using potentiodynamic polarization, electrochemical impedance spectroscopy, and mass loss measurements have been investigated. The inhibition efficiency increased with increasing concentration of the plant extracts up to a critical value but it slightly decreased with increasing temperature. Inhibition efficiency values obtained from mass loss and potentiodynamic data were in reasonable agreement. Potentiodynamic polarization clearly indicated that radish leaves and black cumin extracts acted as anodic inhibitors. The adsorption behavior was found to obey the Flory-Huggins isotherm model. The associated activation parameters and thermodynamic data of adsorption were evaluated and discussed. The results show that radish leaves and black cumin could serve as effective inhibitors for low-carbon steel in industrial water media, with black cumin providing better protection than radish leaves.

  5. Adsorption equilibrium and thermodynamics of CO2 and CH4 on carbon molecular sieves

    NASA Astrophysics Data System (ADS)

    Song, Xue; Wang, Li'ao; Ma, Xu; Zeng, Yunmin

    2017-02-01

    Carbon molecular sieves (CMS) are widely used in the separation of dioxide carbon and methane. In this research, three commercial CMS were utilized to analyze the pore structure and chemical properties. The adsorption isotherms of CO2 and CH4 were studied at 298 K, 308 K and 318 K over the pressure range of 0-1 MPa by an Intelligent Gravimetric analysis (IGA-100B, UK). Langmuir model was adopted to fit the experimental data. The working capacity and selectivity were employed to evaluate the adsorbents. The adsorption thermodynamics were discussed. The adsorbed amounts of both CO2 and CH4 are found to be highly related with the BET specific surface area and the volume of micropores, and also are interrelated with the total pore volume and micropore surface area. The standard enthalpy change (ΔHΘ), standard Gibbs free energy (ΔGΘ) and standard entropy change (ΔSΘ) at zero surface loading are negative, manifesting the adsorption process is exothermic and spontaneous, and the system tends to be ordered. With the increasing surface coverage, the absolute values of Gibbs free energy (ΔG) decrease whereas the absolute values of enthalpy change (ΔH) and entropy change(ΔS) increase. This indicates that as the adsorbed amount increases, the degree of the spontaneity reduces, the intermolecular forces among the adsorbate molecules increase, the orderliness of the system improves and the adsorbed amount approaches the maximum adsorbed capacity.

  6. Mechanical properties of protein adsorption layers at the air/water and oil/water interface: a comparison in light of the thermodynamical stability of proteins.

    PubMed

    Mitropoulos, Varvara; Mütze, Annekathrin; Fischer, Peter

    2014-04-01

    Over the last decades numerous studies on the interfacial rheological response of protein adsorption layers have been published. The comparison of these studies and the retrieval of a common parameter to compare protein interfacial activity are hampered by the fact that different boundary conditions (e.g. physico-chemical, instrumental, interfacial) were used. In the present work we review previous studies and attempt a unifying approach for the comparison between bulk protein properties and their adsorption films. Among many common food grade proteins we chose bovine serum albumin, β-lactoglobulin and lysozyme for their difference in thermodynamic stability and studied their adsorption at the air/water and limonene/water interface. In order to achieve this we have i) systematically analyzed protein adsorption kinetics in terms of surface pressure rise using a drop profile analysis tensiometer and ii) we addressed the interfacial layer properties under shear stress using an interfacial shear rheometer under the same experimental conditions. We could show that thermodynamically less stable proteins adsorb generally faster and yield films with higher shear rheological properties at air/water interface. The same proteins showed an analog behavior when adsorbing at the limonene/water interface but at slower rates.

  7. Adsorptive removal of acrylonitrile by commercial grade activated carbon: kinetics, equilibrium and thermodynamics.

    PubMed

    Kumar, Arvind; Prasad, B; Mishra, I M

    2008-04-01

    The potential of activated carbons--powdered (PAC) and granular (GAC), for the adsorption of acrylonitrile (AN) at different initial AN concentrations (50adsorption was studied. The Langmuir, Freundlich, Tempkin, and Redlich-Peterson (R-P) isotherm equations were used to test their fit with the experimental data, and the model parameters were determined for different temperatures. The Langmuir and R-P models were found to be the best to describe the equilibrium isotherm data of AN adsorption on PAC and GAC, respectively. Error analysis also confirmed the efficacy of the R-P isotherm to best fit the experimental data. The pseudo-second order kinetic model best represents the kinetics of the adsorption of AN onto PAC and GAC. Maximum adsorption capacity of PAC and GAC at optimum conditions of AN removal (adsorbent dose approximately 20 g/l of solution, and equilibrium time approximately 5 h) was found to be 51.72 and 46.63 mg/g, respectively.

  8. Thermodynamic, Kinetic, and Equilibrium Parameters for the Removal of Lead and Cadmium from Aqueous Solutions with Calcium Alginate Beads

    PubMed Central

    Alfaro-Cuevas-Villanueva, Ruth; Hidalgo-Vázquez, Aura Roxana; Cortés Penagos, Consuelo de Jesús; Cortés-Martínez, Raúl

    2014-01-01

    The sorption of cadmium (Cd) and lead (Pb) by calcium alginate beads (CAB) from aqueous solutions in batch systems was investigated. The kinetic and thermodynamic parameters, as well as the sorption capacities of CAB in each system at different temperatures, were evaluated. The rate of sorption for both metals was rapid in the first 10 minutes and reached a maximum in 50 minutes. Sorption kinetic data were fitted to Lagergren, pseudo-second-order and Elovich models and it was found that the second-order kinetic model describes these data for the two metals; comparing kinetic parameters for Cd and Pb sorption a higher kinetic rate (K2) for Pb was observed, indicating that the interaction between lead cations and alginate beads was faster than for cadmium. Similarly, isotherm data were fitted to different models reported in literature and it was found that the Langmuir-Freundlich (L-F) and Dubinin-Radushkevich (D-R) models describe the isotherms in all cases. CAB sorption capacity for cadmium was 27.4 mg/g and 150.4 mg/g for lead, at 25°C. Sorption capacities of Cd and Pb increase as temperature rises. According to the thermodynamic parameters, the cadmium and lead adsorption process was spontaneous and endothermic. It was also found that pH has an important effect on the adsorption of these metals by CAB, as more were removed at pH values between 6 and 7. PMID:24587740

  9. Surface adsorption of lattice HP proteins: Thermodynamics and structural transitions using Wang-Landau sampling

    NASA Astrophysics Data System (ADS)

    Li, Ying Wai; Wüst, Thomas; Landau, David P.

    2012-12-01

    Wang-Landau sampling has been applied to investigate the thermodynamics and structural properties of a lattice hydrophobic-polar heteropolymer (the HP protein model) interacting with an attractive substrate. For simplicity, we consider a short HP sequence consisting of only 36 monomers interacting with a substrate which attracts all monomers in the sequence. The conformational “phase transitions” have been identified by a canonical analysis of the specific heat and suitable structural observables. Three major “transitions”, namely, adsorption, hydrophobic core formation and “flattening” of adsorbed structures, are observed. Depending on the surface attractive strength relative to the intra-protein attraction among the H monomers, these processes take place in different sequences upon cooling.

  10. Ammonium Removal from Aqueous Solutions by Clinoptilolite: Determination of Isotherm and Thermodynamic Parameters and Comparison of Kinetics by the Double Exponential Model and Conventional Kinetic Models

    PubMed Central

    Tosun, İsmail

    2012-01-01

    The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R2) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients. PMID:22690177

  11. Ammonium removal from aqueous solutions by clinoptilolite: determination of isotherm and thermodynamic parameters and comparison of kinetics by the double exponential model and conventional kinetic models.

    PubMed

    Tosun, Ismail

    2012-03-01

    The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R(2)) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients.

  12. Thermodynamic considerations in solid adsorption of bound solutes for patient support in liver failure.

    PubMed

    Patzer, John F

    2008-07-01

    New detoxification modes of treatment for liver failure that use solid adsorbents to remove toxins bound to albumin in the patient bloodstream are entering clinical evaluations, frequently in head-to-head competition. While generally effective in reducing toxin concentration beyond that obtainable by conventional dialysis procedures, the solid adsorbent processes are largely the result of heuristic development. Understanding the principles and limitations inherent in competitive toxin binding, albumin versus solid adsorbent, will enhance the design process and, possibly, improve detoxification performance. An equilibrium thermodynamic analysis is presented for both the molecular adsorbent recirculating system (MARS) and fractionated plasma separation, adsorption, and dialysis system (Prometheus), two advanced systems with distinctly different operating modes but with similar equilibrium limitations. The Prometheus analysis also applies to two newer approaches: sorbent suspension reactor and microsphere-based detoxification system. Primary results from the thermodynamic analysis are that: (i) the solute-albumin binding constant is of minor importance to equilibrium once it exceeds about 10(5) L/mol; (ii) the Prometheus approach requires larger solid adsorbent columns than calculated by adsorbent solute capacity alone; and (iii) the albumin-containing recycle stream in the MARS approach is a major reservoir of removed toxin. A survey of published results indicates that MARS is operating under mass transfer control dictated by solute-albumin equilibrium in the recycle stream, and Prometheus is approaching equilibrium limits under current clinical protocols.

  13. Thermodynamic analysis of framework deformation in Na,Cs-RHO zeolite upon CO2 adsorption.

    PubMed

    Pera-Titus, M; Palomino, M; Valencia, S; Rey, F

    2014-11-28

    Fully dehydrated and partially sodium-cesium containing RHO zeolite (Na,Cs-RHO) shows a genuine inflection in the CO2 isotherms in the temperature range 293-333 K that can be attributed to a sorbate-induced framework deformation from an acentric (A) to a centric (C) phase due to a partial cation rearrangement. This peculiar sorption pattern can be captured by the formulation of thermodynamic isotherms, providing a direct enthalpic and entropic signature of the CO2 adsorption-desorption process during deformation. Using this formulation, the energy barrier between the acentric and centric phases for CO2 adsorption-desorption was estimated in the range 4.7-9.6 J g(-1) of solid (15-32 kJ mol(-1)), reflecting a higher CO2 affinity for the acentric phase, whereas the elastic energy involved during framework distortion was estimated in the range 6-12 J g(-1) of solid (19-39 kJ mol(-1)) with a relative maximum at 303 K and showing a dominant entropic contribution.

  14. Adsorption behavior of levulinic acid onto microporous hyper-cross-linked polymers in aqueous solution: Equilibrium, thermodynamic, kinetic simulation and fixed-bed column studies.

    PubMed

    Lin, Xiaoqing; Huang, Qianlin; Qi, Gaoxiang; Xiong, Lian; Huang, Chao; Chen, Xuefang; Li, Hailong; Chen, Xinde

    2017-03-01

    The recovery of levulinic acid (LA) from aqueous solution and actual biomass hydrolysate by a microporous hyper-cross-linked polymer, SY-01, was investigated for the first time under batch and fixed-bed column conditions. The results showed that the optimum pH should be in the acidic range (pH < 3.0) without adjusting the pH. In the single-component system equilibrium study, the Langmuir isotherm model fits the LA adsorption onto SY-01 resin better than the Freundlich isotherm model, indicating that LA adsorption onto SY-01 resin under the concentration range studied is a monolayer homogeneous adsorption process. The maximum adsorption capacity of LA onto SY-01 resin decreased with increasing temperature, ranging from 103.74 to 95.70 mg/g. The obtained thermodynamic parameters suggested that the adsorption of LA on SY-01 was spontaneous (ΔG(0)<-3.788 kJ/mol), and exothermic (ΔH(0) = -11.764 kJ/mol). For kinetic study, the adsorption of LA onto SY-01 resin at various operating conditions follows the pore diffusion model and the intraparticle diffusion is the rate-limiting step for the adsorption of LA onto SY-01 resin. The effective pore diffusivity was dependent upon temperature, but independent of initial LA concentration, and were 3.306 × 10(-10), 5.274 × 10(-10) and 7.707 × 10(-10) m(2)/s at 298, 318 and 338 K, respectively. In desorption process, the recovery efficiency of LA from SY-01 resin was 99.39%, and LA concentration in the eluent was raised 2.97-fold. In conclusion, our results show that the SY-01 resin has potential application in product recovery of LA from biomass hydrolysate.

  15. ZnS:Cu nanoparticles loaded on activated carbon as novel adsorbent for kinetic, thermodynamic and isotherm studies of Reactive Orange 12 and Direct yellow 12 adsorption.

    PubMed

    Ghaedi, Mehrorang; Ansari, Amin; Sahraei, Reza

    2013-10-01

    The objective of this work is the study of adsorption of Reactive Orange 12 (RO-12) and Direct yellow 12 (DY 12) by zinc sulfide:copper (ZnS-Cu-NP-AC) nanoparticles loaded on activated carbon. This new material with high efficiency in a routine manner was synthesized in our laboratory and its surface properties viz surface area, pore volume and functional groups was characterized with different techniques such FT-IR, SEM, and BET analysis. Generally, in batch adsorption procedure variables including amount of adsorbent, initial dyes concentration, contact time, temperature on dyes removal percentage has great effect on removal percentage that their influence was optimized. The kinetic of proposed adsorption processes efficiently followed, pseudo-second-order, and intra-particle diffusion kinetic models. The equilibrium data the removal strongly follow Langmuir monolayer adsorption with high adsorption capacity in short time. This novel adsorbent by small amount (0.08 g) really is applicable for removal of high amount of both dyes (RO 12 and DY 12) in short time (<20 min). Based on the calculated thermodynamic parameters such as enthalpy (ΔH), entropy (ΔS), activation energy (Ea), sticking probability (S*) and Gibb's free energy changes (ΔG), it is noticeable that the sorption of both dyes onto ZnS:Cu-AC was spontaneous and endothermic process. At optimum values all variables the effect of contact time on adsorption was investigated and the dependency of adsorption data to different kinetic model such as pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion was assessed and it was found that the removal processes follow pseudo second order kinetics and interparticle diffusion mechanism.

  16. Coverage-dependent adsorption thermodynamics of oxygen on ZnO(0001)

    NASA Astrophysics Data System (ADS)

    Li, Ming; Seebauer, Edmund G.

    2017-03-01

    The equilibrium behavior of oxygen adsorbed on metal oxide surfaces such as ZnO(0001) often affects their behavior in applications such as gas sensing. The present work attempts to bridge this distinct gap to applications from an alternate perspective by employing the optical technique of photoreflectance (PR) to measure the enthalpy ΔHads and entropy ΔSads of oxygen adsorption as a function of coverage on Zn-terminated ZnO(0001). The large and strongly coverage-dependent parameters, stemming from a multiplicity of sites, chemical species and reconstructions, lead to a nonmonotonic coverage variation in both ΔHads and ΔSads. The entropic contribution to the free energy is comparable to the enthalpic contribution even near room temperature, so that temperature effects on oxygen adsorption may be uncommonly large.

  17. Microcomputer Calculation of Thermodynamic Properties from Molecular Parameters of Gases.

    ERIC Educational Resources Information Center

    Venugopalan, Mundiyath

    1990-01-01

    Described in this article is a problem-solving activity which integrates the application of microcomputers with the learning of physical chemistry. Students use the program with spectroscopic data to calculate the thermodynamic properties and compare them with the values from the thermochemical tables. (Author/KR)

  18. Adsorption of fibrinogen on a biomedical-grade stainless steel 316LVM surface: a PM-IRRAS study of the adsorption thermodynamics, kinetics and secondary structure changes.

    PubMed

    Desroches, Marie-Josee; Omanovic, Sasha

    2008-05-14

    Polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) was employed to investigate the interaction of serum protein fibrinogen with a biomedical-grade 316LVM stainless steel surface, in terms of the adsorption thermodynamics, kinetics and secondary structure changes of the protein. Apparent Gibbs energy of adsorption values indicated a highly spontaneous and strong adsorption of fibrinogen onto the surface. The kinetics of fibrinogen adsorption were successfully modeled using a pseudo first-order kinetic model. Deconvolution of the amide I bands indicated that the adsorption of fibrinogen on 316LVM results in significant changes in the protein's secondary structure that occur predominantly within the first minute of adsorption. Among the investigated structures, the alpha-helix structure undergoes the smallest changes, while the beta-sheet and beta-turns structures undergo significant changes. It was shown that lateral interactions between the adsorbed molecules do not play a role in controlling the secondary structure changes. An increase in temperature induced changes in the secondary structure of the protein, characterized by a loss of the alpha-helical content and its transformation into the beta-turns structure.

  19. Relationship between thermodynamic parameter and thermodynamic scaling parameter for orientational relaxation time for flip-flop motion of nematic liquid crystals.

    PubMed

    Satoh, Katsuhiko

    2013-03-07

    Thermodynamic parameter Γ and thermodynamic scaling parameter γ for low-frequency relaxation time, which characterize flip-flop motion in a nematic phase, were verified by molecular dynamics simulation with a simple potential based on the Maier-Saupe theory. The parameter Γ, which is the slope of the logarithm for temperature and volume, was evaluated under various conditions at a wide range of temperatures, pressures, and volumes. To simulate thermodynamic scaling so that experimental data at isobaric, isothermal, and isochoric conditions can be rescaled onto a master curve with the parameters for some liquid crystal (LC) compounds, the relaxation time was evaluated from the first-rank orientational correlation function in the simulations, and thermodynamic scaling was verified with the simple potential representing small clusters. A possibility of an equivalence relationship between Γ and γ determined from the relaxation time in the simulation was assessed with available data from the experiments and simulations. In addition, an argument was proposed for the discrepancy between Γ and γ for some LCs in experiments: the discrepancy arises from disagreement of the value of the order parameter P2 rather than the constancy of relaxation time τ1(*) on pressure.

  20. Kinetics, thermodynamics and surface heterogeneity assessment of uranium(VI) adsorption onto cation exchange resin derived from a lignocellulosic residue

    NASA Astrophysics Data System (ADS)

    Anirudhan, T. S.; Radhakrishnan, P. G.

    2009-02-01

    A new cation exchange resin (PGTFS-COOH) having a carboxylate functional group at the chain end was prepared by grafting poly(hydroxyethylmethacrylate) onto tamarind fruit shell, TFS (a lignocellulosic residue) using potassium peroxydisulphate-sodium thiosulphate redox initiator, and in the presence of N,N'-methylenebisacrylamide (MBA) as a crosslinking agent, followed by functionalisation. The adsorbent was characterized with the help of FTIR, XRD, scanning electron micrographs (SEM), and potentiometric titrations. The kinetic and isotherm data, obtained at optimum pH value 6.0 at different temperatures could be fitted with pseudo-second-order equation and Sips isotherm model, respectively. An increase in temperature induces positive effect on the adsorption process. The calculated activation energy of adsorption ( Ea, 18.67 kJ/mol) indicates that U(VI) adsorption was largely due to diffusion-controlled process. The values of adsorption enthalpy, Gibbs free energy, and entropy were calculated using thermodynamic function relationships. The decrease in adsorption enthalpy with increasing U(VI) uploading on the adsorbent, reflects the surface energetic heterogeneity of the adsorbent. The isosteric heat of adsorption was quantitatively correlated with the fractional loading for the U(VI) ions adsorption onto PGTFS-COOH. The results showed that the PGTFS-COOH possessed heterogeneous surface with sorption sites having different activities.

  1. Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

    SciTech Connect

    Stout, R B

    2001-04-01

    A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

  2. A thermodynamic adsorption/entrapment model for selenium(IV) coprecipitation with calcite

    NASA Astrophysics Data System (ADS)

    Heberling, Frank; Vinograd, Victor L.; Polly, Robert; Gale, Julian D.; Heck, Stephanie; Rothe, Jörg; Bosbach, Dirk; Geckeis, Horst; Winkler, Björn

    2014-06-01

    Selenium is an environmentally relevant trace element, while the radioisotope 79Se is of particular concern in the context of nuclear waste disposal safety. Oxidized selenium species are relatively soluble and show only weak adsorption at common mineral surfaces. However, a possible sorption mechanism for selenium in the geosphere is the structural incorporation of selenium(IV) (selenite, SeO32-) into calcite (CaCO3). In this study we investigate the interactions between selenite and calcite by a series of experimental and computational methods with the aim to quantify selenite incorporation into calcite at standard conditions. We further seek to describe the thermodynamics of selenite-doped calcite, and selenite coprecipitation with calcite. The structure of the incorporated species is investigated using Se K-edge EXAFS (isotropic and polarization dependent) and results are compared to density functional theory (DFT) calculations. These investigations confirm structural incorporation of selenite into calcite by the substitution of carbonate for selenite, leading to the formation of a Ca(SeO3)X(CO3)(1-X) solid solution. Coprecipitation experiments at low supersaturation indicate a linear increase of the selenite to carbonate ratio in the solid with the increase of the selenite to carbonate ratio in the contact solution. This relationship can be described under the assumption of an ideal mixing between calcite and a virtual CaSeO3 endmember, whose standard Gibbs free energy (G0(CaSeO3_exp) = -953 ± 6 kJ/mol, log10(KSP(CaSeO3_exp)) = -6.7 ± 1.0) is defined by linear extrapolation of the excess free energy from the dilute Henry’s law domain to X(CaSeO3) = 1. In contrast to this experimental result, DFT and force field calculations predict the virtual bulk CaSeO3 endmember to be significantly less stable and more soluble: G0(CaSeO3 bulk) = -912 ± 10 kJ/mol and log10(KSP(CaSeO3_bulk)) = 0.5 ± 1.7. To explain this discrepancy we introduce a thermodynamic adsorption

  3. Estimation of kinetic and thermodynamic ligand-binding parameters using computational strategies.

    PubMed

    Deganutti, Giuseppe; Moro, Stefano

    2017-03-31

    Kinetic and thermodynamic ligand-protein binding parameters are gaining growing importance as key information to consider in drug discovery. The determination of the molecular structures, using particularly x-ray and NMR techniques, is crucial for understanding how a ligand recognizes its target in the final binding complex. However, for a better understanding of the recognition processes, experimental studies of ligand-protein interactions are needed. Even though several techniques can be used to investigate both thermodynamic and kinetic profiles for a ligand-protein complex, these procedures are very often laborious, time consuming and expensive. In the last 10 years, computational approaches have enormous potential in providing insights into each of the above effects and in parsing their contributions to the changes in both kinetic and thermodynamic binding parameters. The main purpose of this review is to summarize the state of the art of computational strategies for estimating the kinetic and thermodynamic parameters of a ligand-protein binding.

  4. Adsorption of methylene blue onto poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) nanotubes: kinetics, isotherm and thermodynamics analysis.

    PubMed

    Chen, Zhonghui; Zhang, Jianan; Fu, Jianwei; Wang, Minghuan; Wang, Xuzhe; Han, Runping; Xu, Qun

    2014-05-30

    Poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) (PZS) nanotubes, an excellent adsorbent, were successfully synthesized by an in situ template method and used for the removal of methylene blue (MB) from aqueous solution. The morphology and structures of as-synthesized PZS nanotubes were characterized by scanning electron microscopy, transmission electron microscope, Fourier transform infrared spectroscopy and N2 adsorption/desorption isotherms. The effects of temperature, concentration, pH and contact time on MB adsorption were studied. It was favorable for adsorption under the condition of basic and high temperature. The pseudo-first-order, pseudo-second-order and intraparticle diffusion models were used to fit adsorption data in the kinetic studies. And results showed that the adsorption kinetics were more accurately described by the pseudo-second-order model. The equilibrium isotherms were conducted using Freundlich and Langmuir models. It has been demonstrated that the better agreement was Langmuir isotherm with correlation coefficient of 0.9933, equilibrium absorption capacity of 69.16mg/g and the corresponding contact time of 15min. Thermodynamic analyses showed that MB adsorption onto the PZS nanotubes was endothermic and spontaneous and it was also a physisorption process.

  5. Application of zeolite-activated carbon macrocomposite for the adsorption of Acid Orange 7: isotherm, kinetic and thermodynamic studies.

    PubMed

    Lim, Chi Kim; Bay, Hui Han; Neoh, Chin Hong; Aris, Azmi; Abdul Majid, Zaiton; Ibrahim, Zaharah

    2013-10-01

    In this study, the adsorption behavior of azo dye Acid Orange 7 (AO7) from aqueous solution onto macrocomposite (MC) was investigated under various experimental conditions. The adsorbent, MC, which consists of a mixture of zeolite and activated carbon, was found to be effective in removing AO7. The MC were characterized by scanning electron microscopy (SEM), energy dispersive X-ray, point of zero charge, and Brunauer-Emmett-Teller surface area analysis. A series of experiments were performed via batch adsorption technique to examine the effect of the process variables, namely, contact time, initial dye concentration, and solution pH. The dye equilibrium adsorption was investigated, and the equilibrium data were fitted to Langmuir, Freundlich, and Tempkin isotherm models. The Langmuir isotherm model fits the equilibrium data better than the Freundlich isotherm model. For the kinetic study, pseudo-first-order, pseudo-second-order, and intraparticle diffusion model were used to fit the experimental data. The adsorption kinetic was found to be well described by the pseudo-second-order model. Thermodynamic analysis indicated that the adsorption process is a spontaneous and endothermic process. The SEM, Fourier transform infrared spectroscopy, ultraviolet-visible spectral and high performance liquid chromatography analysis were carried out before and after the adsorption process. For the phytotoxicity test, treated AO7 was found to be less toxic. Thus, the study indicated that MC has good potential use as an adsorbent for the removal of azo dye from aqueous solution.

  6. Enhancing adsorption capacity of toxic malachite green dye through chemically modified breadnut peel: equilibrium, thermodynamics, kinetics and regeneration studies.

    PubMed

    Chieng, Hei Ing; Lim, Linda B L; Priyantha, Namal

    2015-01-01

    Breadnut skin, in both its unmodified (KS) and base-modified (BM-KS) forms, was investigated for its potential use as a low-cost adsorbent for the removal of toxic dye, malachite green (MG). Characterization of the adsorbents was carried out using scanning electron microscope, X-ray fluorescence and Fourier transform infra-red spectroscopy. Batch adsorption experiments, carried out under optimized conditions, for the adsorption of MG were fitted using five isotherm models (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin and Sips) and six error functions to determine the best-fit model. The adsorption capacity was greatly enhanced when breadnut skin was chemically modified with NaOH, leading to an adsorption capacity of 353.0 mg g(-1), that was far superior to most reported adsorbents for the removal of MG. Thermodynamics studies indicated that the adsorption of MG was spontaneous on KS and BM-KS, and the reactions were endothermic and exothermic, respectively. Kinetics studies showed that both followed the pseudo-second order. Regeneration experiments on BM-KS indicated that its adsorption capacity was still maintained at>90% even after five cycles. It can be concluded that NaOH-modified breadfruit skin has great potential to be utilized in real-life application as a low-cost adsorbent for the removal of MG in wastewater treatment.

  7. Using isothermal titration calorimetry to determine thermodynamic parameters of protein-glycosaminoglycan interactions.

    PubMed

    Dutta, Amit K; Rösgen, Jörg; Rajarathnam, Krishna

    2015-01-01

    It has now become increasingly clear that a complete atomic description of how biomacromolecules recognize each other requires knowledge not only of the structures of the complexes but also of how kinetics and thermodynamics drive the binding process. In particular, such knowledge is lacking for protein-glycosaminoglycan (GAG) complexes. Isothermal titration calorimetry (ITC) is the only technique that can provide various thermodynamic parameters-enthalpy, entropy, free energy (binding constant), and stoichiometry-from a single experiment. Here we describe different factors that must be taken into consideration in carrying out ITC titrations to obtain meaningful thermodynamic data of protein-GAG interactions.

  8. Research on Thermodynamic Parameters of a Micro-Turbine for Standalone Cogeneration

    NASA Astrophysics Data System (ADS)

    Chekardovskiy, M. N.; Chekardovskiy, S. M.; Chekardovskaya, I. A.; Mihajlenko, A. I.

    2016-10-01

    In order to advance the heating and hot water systems in the Russian Federation we need to address the problem of introducing new sources of heat and electric energy. The paper overviews the relationship between the reliability, efficiency and diagnostic maintenance of the GMTU, the studies of rated and operating conditions of the GMTU, the development and improvement of methods for calculating rated and operating thermodynamic and diagnostic parameter of the unit. This resulted in developing a passport of thermodynamic parameters that can be compared to the parameters of the same units when they operate for the purpose of diagnosing their state.

  9. Predicting heavy metals' adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics.

    PubMed

    Hu, Qinghai; Xiao, Zhongjin; Xiong, Xinmei; Zhou, Gongming; Guan, Xiaohong

    2015-01-01

    Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics, edge, and isotherm data with one pH-independent parameter. A close inspection of the derivation process of Langmuir isotherm revealed that the equilibrium constant derived from the Langmuir kinetic model, KS-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, KS-Langmuir. The modified Langmuir kinetic model (MLK model) and modified Langmuir isotherm model (MLI model) incorporating pH factor were developed. The MLK model was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on MnO2 at pH3.2 or 3.3 to get the values of KS-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model (MMP model), and the values of KS-Langmuir were obtained. The values of KS-kinetic and KS-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with KS-kinetic constants could predict the adsorption edges of heavy metals on MnO2 very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on MnO2 at various pH levels could be predicted reasonably well by the MLI model with the KS-kinetic constants.

  10. Equilibrium, Kinetic, and Thermodynamic Studies on the Adsorption of Cadmium from Aqueous Solution by Modified Biomass Ash

    PubMed Central

    Zheng, Xuebo; Cui, Hongbiao; Zhu, Zhenqiu; Liang, Jiani

    2017-01-01

    Natural biomass ash of agricultural residuals was collected from a power plant and modified with hexagonal mesoporous silica and functionalized with 3-aminopropyltriethoxysilane. The physicochemical and morphological properties of the biomass ash were analyzed by ICP-OES, SEM, TEM-EDS, FTIR, and BET analysis. The adsorption behavior of the modified product for Cd2+ in aqueous solution was studied as a function of pH, initial metal concentration, equilibrium time, and temperature. Results showed that the specific surface area of the modified product was 9 times that of the natural biomass ash. The modified biomass ash exhibited high affinity for Cd2+ and its adsorption capacity increased sharply with increasing pH from 4.0 to 6.0. The maximum adsorption capacity was 23.95 mg/g in a pH 5 solution with an initial metal concentration of 50 mg/L and a contact time of 90 min. The adsorption of Cd2+ onto the modified biomass ash was well fitted to the Langmuir model and it followed pseudo-second-order kinetics. Thermodynamic analysis results showed that the adsorption of Cd2+ was spontaneous and endothermic in nature. The results suggest that the modified biomass ash is promising for use as an inexpensive and effective adsorbent for Cd2+ removal from aqueous solution. PMID:28348509

  11. Thermodynamic scaling of dynamic properties of liquid crystals: Verifying the scaling parameters using a molecular model

    NASA Astrophysics Data System (ADS)

    Satoh, Katsuhiko

    2013-08-01

    The thermodynamic scaling of molecular dynamic properties of rotation and thermodynamic parameters in a nematic phase was investigated by a molecular dynamic simulation using the Gay-Berne potential. A master curve for the relaxation time of flip-flop motion was obtained using thermodynamic scaling, and the dynamic property could be solely expressed as a function of TV^{γ _τ }, where T and V are the temperature and volume, respectively. The scaling parameter γτ was in excellent agreement with the thermodynamic parameter Γ, which is the logarithm of the slope of a line plotted for the temperature and volume at constant P2. This line was fairly linear, and as good as the line for p-azoxyanisole or using the highly ordered small cluster model. The equivalence relation between Γ and γτ was compared with results obtained from the highly ordered small cluster model. The possibility of adapting the molecular model for the thermodynamic scaling of other dynamic rotational properties was also explored. The rotational diffusion constant and rotational viscosity coefficients, which were calculated using established theoretical and experimental expressions, were rescaled onto master curves with the same scaling parameters. The simulation illustrates the universal nature of the equivalence relation for liquid crystals.

  12. Adsorption of Pb(II) ions from aqueous solution by native and activated bentonite: kinetic, equilibrium and thermodynamic study.

    PubMed

    Kul, Ali Riza; Koyuncu, Hülya

    2010-07-15

    In this study, the adsorption kinetics, equilibrium and thermodynamics of Pb(II) ions on native (NB) and acid activated (AAB) bentonites were examined. The specific surface areas, pore size and pore-size distributions of the samples were fully characterized. The adsorption efficiency of Pb(II) onto the NB and AAB was increased with increasing temperature. The kinetics of adsorption of Pb(II) ions was discussed using three kinetic models, the pseudo-first-order, the pseudo-second-order and the intra-particle diffusion model. The experimental data fitted very well the pseudo-second-order kinetic model. The initial sorption rate and the activation energy were also calculated. The activation energy of the sorption was calculated as 16.51 and 13.66 kJ mol(-1) for NB and AAB, respectively. Experimental results were also analysed by the Langmuir, Freundlich and Dubinin-Redushkevich (D-R) isotherm equations at different temperatures. R(L) separation factor for Langmuir and the n value for Freundlich isotherm show that Pb(II) ions are favorably adsorbed by NB and AAB. Thermodynamic quantities such as Gibbs free energy (DeltaG), the enthalpy (DeltaH) and the entropy change of sorption (DeltaS) were determined as about -5.06, 10.29 and 0.017 kJ mol(-1) K(-1), respectively for AAB. It was shown that the sorption processes were an endothermic reactions, controlled by physical mechanisms and spontaneously.

  13. Effect of the ionic strength of a mobile phase on the chromatographic retention and thermodynamic characteristics of the adsorption of enantiomers of α-phenylcarboxylic acids on a chiral adsorbent with grafted antibiotic eremomycin

    NASA Astrophysics Data System (ADS)

    Reshetova, E. N.

    2017-01-01

    The effect the ionic strength of an aqueous ethanol mobile phase containing buffer salt has the on retention and thermodynamics of adsorption of optical isomers of some α-phenylcarboxylic acids on chiral adsorbent Nautilus-E with grafted antibiotic eremomycin is investigated. It is shown that ion exchange processes participate in the adsorption of enantiomers of α-phenylcarboxylic acids. It is established that electrostatic interactions contribute to the retention of enantiomers of α-phenylcarboxylic acids and affect selectivity only slightly. The dependences of retention characteristics, selectivity, and thermodynamic parameters on the concentration of the buffer salt in the eluent are determined. A statistical analysis of enthalpy-entropy compensation is performed, and the compensation effect is shown to be true. It is found that the points corresponding to the investigated adsorbates are distributed over the compensation dependence according to the spatial structural characteristics of molecules.

  14. Thermodynamics of the adsorption of organic molecules on graphitized carbon black modified with a monolayer of 5-hydroxy-6-methyluracil

    NASA Astrophysics Data System (ADS)

    Gus'kov, V. Yu.; Ivanov, S. P.; Shaikhitdinova, Yu. F.; Kudasheva, F. Kh.

    2016-10-01

    Thermodynamic characteristics of the adsorption of alkanes, alcohols, arenes, and esters on graphitized carbon black with a deposited monolayer (0.17%) of 5-hydroxy-6-methyluracil are studied by means of inverse gas chromatography at infinite dilution. It is established that size effects (violation of the additivity of molar changes in internal energy and the entropy of adsorption for pairs of molecules of one homologous series that differ by one methyl group) are observed when organic molecules are adsorbed on the surface of the resulting adsorbent. The size effects are similar to those observed when 1% 5-hydroxy-6-methyluracil is deposited on graphitized carbon black. It is concluded that the observed violation of additivity is associated with cavities in the supramolecular structure.

  15. Thermodynamic and cloud parameter retrieval using infrared spectral data

    NASA Technical Reports Server (NTRS)

    Zhou, Daniel K.; Smith, William L., Sr.; Liu, Xu; Larar, Allen M.; Huang, Hung-Lung A.; Li, Jun; McGill, Matthew J.; Mango, Stephen A.

    2005-01-01

    High-resolution infrared radiance spectra obtained from near nadir observations provide atmospheric, surface, and cloud property information. A fast radiative transfer model, including cloud effects, is used for atmospheric profile and cloud parameter retrieval. The retrieval algorithm is presented along with its application to recent field experiment data from the NPOESS Airborne Sounding Testbed - Interferometer (NAST-I). The retrieval accuracy dependence on cloud properties is discussed. It is shown that relatively accurate temperature and moisture retrievals can be achieved below optically thin clouds. For optically thick clouds, accurate temperature and moisture profiles down to cloud top level are obtained. For both optically thin and thick cloud situations, the cloud top height can be retrieved with an accuracy of approximately 1.0 km. Preliminary NAST-I retrieval results from the recent Atlantic-THORPEX Regional Campaign (ATReC) are presented and compared with coincident observations obtained from dropsondes and the nadir-pointing Cloud Physics Lidar (CPL).

  16. Computational study of frontier orbitals, moments, chemical reactivity and thermodynamic parameters of sildenafil

    NASA Astrophysics Data System (ADS)

    Sachdeva, Ritika; Kaur, Prabhjot; Singh, V. P.; Saini, G. S. S.

    2016-05-01

    Analysis of frontier orbitals of sildenafil has been carried using Density Functional Theory. On the basis of HOMO-LUMO energy, values of global chemical reactivity descriptors such as electronegativity, chemical hardness, softness, chemical potential, electrophilicity index have been calculated. Calculated values of dipole moment, polarizability, hyperpolarizability have also been reported for sildenafil along with its thermodynamic parameters.

  17. Modeling Complex Equilibria in ITC Experiments: Thermodynamic Parameters Estimation for a Three Binding Site Model

    PubMed Central

    Le, Vu H.; Buscaglia, Robert; Chaires, Jonathan B.; Lewis, Edwin A.

    2013-01-01

    Isothermal Titration Calorimetry, ITC, is a powerful technique that can be used to estimate a complete set of thermodynamic parameters (e.g. Keq (or ΔG), ΔH, ΔS, and n) for a ligand binding interaction described by a thermodynamic model. Thermodynamic models are constructed by combination of equilibrium constant, mass balance, and charge balance equations for the system under study. Commercial ITC instruments are supplied with software that includes a number of simple interaction models, for example one binding site, two binding sites, sequential sites, and n-independent binding sites. More complex models for example, three or more binding sites, one site with multiple binding mechanisms, linked equilibria, or equilibria involving macromolecular conformational selection through ligand binding need to be developed on a case by case basis by the ITC user. In this paper we provide an algorithm (and a link to our MATLAB program) for the non-linear regression analysis of a multiple binding site model with up to four overlapping binding equilibria. Error analysis demonstrates that fitting ITC data for multiple parameters (e.g. up to nine parameters in the three binding site model) yields thermodynamic parameters with acceptable accuracy. PMID:23262283

  18. Determination of kinetic and equilibrium parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous solution by black carrot (Daucus carota L.) residues.

    PubMed

    Güzel, Fuat; Yakut, Hakan; Topal, Giray

    2008-05-30

    In this study, the effect of temperature on the adsorption of Mn(II), Ni(II), Co(II) and Cu(II) from aqueous solution by modified carrot residues (MCR) was investigated. The equilibrium contact times of adsorption process for each heavy metals-MCR systems were determined. Kinetic data obtained for each heavy metal by MCR at different temperatures were applied to the Lagergren equation, and adsorption rate constants (kads) at these temperatures were determined. These rate constants related to the adsorption of heavy metal by MCR were applied to the Arrhenius equation, and activation energies (Ea) were determined. In addition, the isotherms for adsorption of each heavy metal by MCR at different temperatures were also determined. These isothermal data were applied to linear forms of isotherm equations that they fit the Langmuir adsorption isotherm, and the Langmuir constants (qm and b) were calculated. b constants determined at different temperatures were applied to thermodynamic equations, and thermodynamic parameters such as enthalpy (Delta H), free energy (Delta G), and entropy (Delta S) were calculated and these values show that adsorption of heavy metal on MCR was an endothermic process and process of adsorption was favoured at high temperatures.

  19. Relations between structural parameters and adsorption characterization of templated nanoporous materials with cubic symmetry

    SciTech Connect

    Ravikovitch, P.I.; Neimark, A.V.

    2000-03-21

    A systematic approach is proposed to structural characterization of templated nanoporous materials with cubic symmetry by gas adsorption. The authors hypothesize that regular structures of these materials can be described in terms of triply periodic minimal surfaces (TPMS), similarly to bicontinuous mesophases observed in oil-water, lipid, block copolymer, and other amphiphilic systems. The authors relate topological characteristics of TPMS to the pore structure parameters evaluated from adsorption measurements, such as the specific surface area, pore volume, mean pore size, and also pore wall thickness. The relations obtained can be used for discrimination of possible TPMS morphologies. The method developed is used for characterization of newly synthesized MCM-48 mesoporous materials by low-temperature nitrogen adsorption. They show that adsorption data fully support the minimal gyroid model of MCM-48 structure (Ia3d space group) established earlier by the X-ray diffraction (XRD) and transmission electron microscopy studies. The mean pore size of MCM-48 can be accurately described by the hydraulic diameter calculated from the capillary condensation region of nitrogen adsorption isotherms by the nonlocal density functional theory method. Moreover, the adsorption method allows one to estimate the pore wall thickness, which cannot be done by XRD. For a series of high-quality MCM-48 materials reported recently in the literature, the calculated mean wall thickness varied from 0.8 to 1.2 nm. The adsorption method developed is recommended as a complement to X-ray diffraction and electron microscopy techniques for characterization of nanoporous materials.

  20. Studies on Pidotimod Enantiomers With Chiralpak-IA: Crystal Structure, Thermodynamic Parameters and Molecular Docking.

    PubMed

    Dou, Xiaorui; Su, Xin; Wang, Yue; Chen, Yadong; Shen, Weiyang

    2015-11-01

    Pidotimod, a synthetic dipeptide, has two chiral centers with biological and immunological activity. Its enantiomers were characterized by x-ray crystallographic analysis. A chiral stationary phase (CSP) Chiralpak-IA based on amylose derivatized with tris-(3, 5-dimethylphenyl carbamate) was used to separate pidotimod enantiomers. The mobile phase was prepared in a ratio of 35:65:0.2 of methyl-tert-butyl-ether and acetonitrile trifluoroaceticacid. In addition, thermodynamics and molecular docking methods were used to explain the enantioseparation mechanism by Chiralpak-IA. Thermodynamic studies were carried out from 10 to 45 °C. In general, both retention and enantioselectivity decreased as the temperature increased. Thermodynamic parameters indicate that the interaction force between the pidotimod enantiomer (4S, 2'R) and IA CSP is stronger and their complex model is more stable. According to GOLD molecular docking simulation, Van der Waals force is the leading cause of pidotimod enantiomers separation by IA CSP.

  1. Comparing three methods of simultaneous synthesis and stabilization of Fe3O4 nanoparticles: Changing physicochemical properties of products to improve kinetic and thermodynamic of dye adsorption

    NASA Astrophysics Data System (ADS)

    Rakhshaee, Roohan; Noorani, Yasaman

    2017-01-01

    Fe3O4 nanoparticles (FNPs) were synthesized by conventional heating (CH), co-precipitation (CP) and microwave heating (MH) methods in presence of pectin crosslinked by β-isopropylglutaric acid (-CP) to stabilize nanoparticles. The role of the cross-linked pectin and kinds of synthesis methods was appeared to increase the effective total surface of FNPs both simultaneously as the synergistic effects and separately. The effective role of the microwave irradiation to decrease FNPs mean size was seen, so that its size in FMH was smaller 21.5% and 38.2% than that of FCP and FCH, and in FMH-CP was smaller 27.2% and 58.9% than that of FCP-CP and FCH-CP, respectively. The various experiments were done on the structures, functional groups, and connection quantities of -CP to FNPs synthesized by CH, CP and MH methods. The different physical properties of the obtained composites containing magnetization, zeta potential and thermal analyses were determined. To study the adsorption of methylene blue (MB) from the aqueous and alkali solution, the role Fe-O- groups of FNPs was evaluated more effective than the role of -COO- and -O- of -CP in the stabilized nanoparticles. Fe3O4 NPs stabilized by -CP using microwave heating showed the highest capacity of MB adsorption due to having the most suitable thermodynamic and kinetic parameters.

  2. Adsorption of methylene blue onto activated carbon produced from tea (Camellia sinensis L.) seed shells: kinetics, equilibrium, and thermodynamics studies.

    PubMed

    Gao, Jun-Jie; Qin, Ye-Bo; Zhou, Tao; Cao, Dong-Dong; Xu, Ping; Hochstetter, Danielle; Wang, Yue-Fei

    2013-07-01

    Tea (Camellia sinensis L.) seed shells, the main byproduct of the manufacture of tea seed oil, were used as precursors for the preparation of tea activated carbon (TAC) in the present study. A high yield (44.1%) of TAC was obtained from tea seed shells via a one-step chemical method using ZnCl2 as an agent. The Brunauer-Emmett-Teller (BET) surface area and the total pore volumes of the obtained TAC were found to be 1530.67 mg(2)/g and 0.7826 cm(3)/g, respectively. The equilibrium adsorption results were complied with Langmuir isotherm model and its maximum monolayer adsorption capacity was 324.7 mg/g for methylene blue. Adsorption kinetics studies indicated that the pseudo-second-order model yielded the best fit for the kinetic data. An intraparticle diffusion model suggested that the intraparticle diffusion was not the only rate-controlling step. Thermodynamics studies revealed the spontaneous and exothermic nature of the sorption process. These results indicate that tea seed shells could be utilized as a renewable resource to develop activated carbon which is a potential adsorbent for methylene blue.

  3. Adsorption of methylene blue onto activated carbon produced from tea (Camellia sinensis L.) seed shells: kinetics, equilibrium, and thermodynamics studies*

    PubMed Central

    Gao, Jun-jie; Qin, Ye-bo; Zhou, Tao; Cao, Dong-dong; Xu, Ping; Hochstetter, Danielle; Wang, Yue-fei

    2013-01-01

    Tea (Camellia sinensis L.) seed shells, the main byproduct of the manufacture of tea seed oil, were used as precursors for the preparation of tea activated carbon (TAC) in the present study. A high yield (44.1%) of TAC was obtained from tea seed shells via a one-step chemical method using ZnCl2 as an agent. The Brunauer-Emmett-Teller (BET) surface area and the total pore volumes of the obtained TAC were found to be 1 530.67 mg2/g and 0.782 6 cm3/g, respectively. The equilibrium adsorption results were complied with Langmuir isotherm model and its maximum monolayer adsorption capacity was 324.7 mg/g for methylene blue. Adsorption kinetics studies indicated that the pseudo-second-order model yielded the best fit for the kinetic data. An intraparticle diffusion model suggested that the intraparticle diffusion was not the only rate-controlling step. Thermodynamics studies revealed the spontaneous and exothermic nature of the sorption process. These results indicate that tea seed shells could be utilized as a renewable resource to develop activated carbon which is a potential adsorbent for methylene blue. PMID:23825151

  4. Thermodynamic characteristics of the adsorption of 1,3,4-oxadiazoles and 1,2,4,5-tetrazines from methanol and water-methanol solutions onto hypercrosslinked polystyrene

    NASA Astrophysics Data System (ADS)

    Saifutdinov, B. R.; Davankov, V. A.; Il'in, M. M.

    2017-03-01

    The thermodynamic characteristics of the adsorption of several 1,3,4-oxadiazoles and 1,2,4,5- tetrazines from methanol and water-methanol solutions onto neutral hypercrosslinked polystyrene with a degree of crosslinking of 150% are determined via high performance liquid chromatography. It is shown how the obtained characteristics depend on the molecular structure of adsorbed substances and the composition of the liquid phase in which adsorption occurs.

  5. Determination of thermodynamic and transport parameters of naphthenic acids and organic process chemicals in oil sand tailings pond water.

    PubMed

    Wang, Xiaomeng; Robinson, Lisa; Wen, Qing; Kasperski, Kim L

    2013-07-01

    Oil sand tailings pond water contains naphthenic acids and process chemicals (e.g., alkyl sulphates, quaternary ammonium compounds, and alkylphenol ethoxylates). These chemicals are toxic and can seep through the foundation of the tailings pond to the subsurface, potentially affecting the quality of groundwater. As a result, it is important to measure the thermodynamic and transport parameters of these chemicals in order to study the transport behavior of contaminants through the foundation as well as underground. In this study, batch adsorption studies and column experiments were performed. It was found that the transport parameters of these chemicals are related to their molecular structures and other properties. The computer program (CXTFIT) was used to further evaluate the transport process in the column experiments. The results from this study show that the transport of naphthenic acids in a glass column is an equilibrium process while the transport of process chemicals seems to be a non-equilibrium process. At the end of this paper we present a real-world case study in which the transport of the contaminants through the foundation of an external tailings pond is calculated using the lab-measured data. The results show that long-term groundwater monitoring of contaminant transport at the oil sand mining site may be necessary to avoid chemicals from reaching any nearby receptors.

  6. Optimization, isotherm, kinetic and thermodynamic studies of Pb(II) ions adsorption onto N-maleated chitosan-immobilized TiO₂ nanoparticles from aqueous media.

    PubMed

    Shaker, Medhat A; Yakout, Amr A

    2016-02-05

    Chitosan, CS was chemically engineered by maleic anhydride via simple protocol to produce N-maleated chitosan, MCS which immobilized on anatase TiO2 to synthesize novel eco-friendly nanosorbent (51±3.8 nm), MCS@TiO2 for cost-effective and efficient removal of Pb(II) ions from aqueous media. The chemical structure, surface properties and morphology of MCS@TiO2 were recognized by FTIR, (1)H NMR, XRD, TEM, DLS and zeta-potential techniques. The relations between %removal of Pb(II) and different analytical parameters such as solution acidity (pH), MCS@TiO2 dosage, time of contact and initial Pb(II) concentration were optimized using response surface methodology (RSM) and Box-Behnken design (BBD) statistical procedures. The fitting of the experimental data to four different isotherm models at optimized conditions was carried out by various statistical treatments including the correlation coefficient (r), coefficient of determination (r(2)) and non-linear Chi-square (χ(2)) test analyses which all confirm the suitability of Langmuir model to explain the adsorption isotherm data. Also, statistics predicted that the pseudo-second-order model is the optimum kinetic model among four applied kinetic models to closely describe the rate equation of the adsorption process. Thermodynamics viewed the adsorption as endothermic and feasible physical process. EDTA could release the sorbed Pb(II) ions from MCS@TiO2 with a recovery above 92% after three sorption-desorption cycles. The novel synthesized nanosorbent is evidenced to be an excellent solid phase extractor for Pb(II) ions from wastewaters.

  7. Optimization, isotherm, kinetic and thermodynamic studies of Pb(II) ions adsorption onto N-maleated chitosan-immobilized TiO2 nanoparticles from aqueous media

    NASA Astrophysics Data System (ADS)

    Shaker, Medhat A.; Yakout, Amr A.

    2016-02-01

    Chitosan, CS was chemically engineered by maleic anhydride via simple protocol to produce N-maleated chitosan, MCS which immobilized on anatase TiO2 to synthesize novel eco-friendly nanosorbent (51 ± 3.8 nm), MCS@TiO2 for cost-effective and efficient removal of Pb(II) ions from aqueous media. The chemical structure, surface properties and morphology of MCS@TiO2 were recognized by FTIR, 1H NMR, XRD, TEM, DLS and zeta-potential techniques. The relations between %removal of Pb(II) and different analytical parameters such as solution acidity (pH), MCS@TiO2 dosage, time of contact and initial Pb(II) concentration were optimized using response surface methodology (RSM) and Box-Behnken design (BBD) statistical procedures. The fitting of the experimental data to four different isotherm models at optimized conditions was carried out by various statistical treatments including the correlation coefficient (r), coefficient of determination (r2) and non-linear Chi-square (χ2) test analyses which all confirm the suitability of Langmuir model to explain the adsorption isotherm data. Also, statistics predicted that the pseudo-second-order model is the optimum kinetic model among four applied kinetic models to closely describe the rate equation of the adsorption process. Thermodynamics viewed the adsorption as endothermic and feasible physical process. EDTA could release the sorbed Pb(II) ions from MCS@TiO2 with a recovery above 92% after three sorption-desorption cycles. The novel synthesized nanosorbent is evidenced to be an excellent solid phase extractor for Pb(II) ions from wastewaters.

  8. Kinetics and thermodynamics of adsorption of methylene blue by a magnetic graphene-carbon nanotube composite

    NASA Astrophysics Data System (ADS)

    Wang, Peifang; Cao, Muhan; Wang, Chao; Ao, Yanhui; Hou, Jun; Qian, Jin

    2014-01-01

    A solvothermal method was employed to prepare a novel magnetic composite adsorbent composed of graphene, multi-walled carbon nanotubes (MWCNTs) and Fe3O4 nanoparticles. The prepared adsorbents were characterized by X-ray diffraction, scanning electron microscopy and X-ray fluorescence spectrometry and Fourier transform infrared spectroscopy. Fourier transform infrared spectroscopy and the particle size distribution of the samples before and after adsorption was also carried out. The performance of as-prepared composites was investigated by the adsorption of dye methylene blue. Results showed that the maximum adsorption capacity of the samples was up to 65.79 mg g-1, which was almost equal to the sum of magnetic graphene and magnetic MWCNTs. The effect of pH and temperature on the adsorption performance of methylene blue onto the magnetic adsorbents was investigated. The kinetic was well-described by pseudo-second-order and intraparticle diffusion model, while the isotherm obeyed the Langmuir isotherm. Furthermore, the as-prepared composites were found to be regenerative and reusable. The application in the treatment of an artificial dye wastewater and its cost estimation were also discussed. Therefore, the as-prepared magnetic composites can be severed as a potential adsorbent for removal of dye pollutant, owing to its high adsorption performance, magnetic separability and efficient recyclable property.

  9. Spectrophotometric and some thermodynamic parameters of the charge transfer complexation between chloranilic acid and chlorpheniramine.

    PubMed

    Ofoefule, S I; Ajali, U

    2001-01-01

    The principle of charge transfer complexation involving a pi-acceptor (chloranilic acid) and an n-donor (chlorpheniramine) was utilized in the assay of the later in its pure form and in its tablet dosage forms. Some thermodynamic parameters of the complex such as association constant (Kc), molar absorptivity (epsilon c), free energy change (delta G degree), enthalpy (delta H degree) and entropy (delta S degree) changes were determined to establish the stability of the complex and the optimum conditions for the complex formation. The values obtained for these thermodynamic parameters indicated that the complex formed between this two chemical entities is highly stable. Assay of chlorpheniramine in its pure form and in its tablet dosage forms gave high percentage recoveries. The principle of charge transfer complexation could therefore be employed in the colorimetric assay of chlorpheniramine in its tablet dosage forms.

  10. Modeling oxyanion adsorption on ferralic soil, part 1: parameter validation with phosphate ion.

    PubMed

    Pérez, Claudio; Antelo, Juan; Fiol, Sarah; Arce, Florencio

    2014-10-01

    Surface complexation models have proved to be valuable tools for predicting processes that occur at the solid-solution interface. Use of such models has become more widespread and nowadays more complex systems are studied, in an attempt to explain processes such as the competition between different species for mineral surfaces and the effect of the presence of organic matter. The aim of the present study was to analyze the mobility of phosphate in ferralic soils. The charge distribution model parameters for phosphate-goethite adsorption were used to predict phosphate mobility on samples from 2 horizons of a ferralic soil containing large amounts of iron oxides. The soil reactivity was attributed to the iron oxides, and some specific parameters were determined by means of phosphate adsorption-desorption experiments and included in the model. Adsorption of phosphate in the upper horizon, which contained more organic carbon and phosphate than the deeper one, was modeled by using the information obtained for the soil and the charge distribution model parameters derived for phosphate-goethite interaction with no need of further optimization. In contrast, some extra fitting parameters were required to improve the modeling of the phosphate adsorption in the deeper horizon.

  11. Melting Line Parameters and Thermodynamic Properties of Methane at High Pressures

    NASA Astrophysics Data System (ADS)

    Yakub, L. N.; Bodiul, E. S.

    2017-04-01

    The location of the melting line in the phase diagram of methane was predicted using two theoretical equations of state: for solid and fluid phases. The equations of state for both phases are constructed in the framework of thermodynamic perturbation theory, considering the octupole-octupole interaction of methane molecules as a perturbation. The results of calculations of the melting line parameters are compared with experimental and computer simulation data.

  12. Thermodynamic parameters of mixtures with allowance for phase transition components under shock-wave loading

    NASA Astrophysics Data System (ADS)

    Kinelovskii, S. A.; Maevskii, K. K.

    2017-02-01

    The shock-wave synthesis and compaction using powder mixtures are the one of perspective directions of new materials creation. The results of numerical experiments on modeling of shock wave loading of mixtures with allowance for phase transition components in their composition are presented. The significant change in volume in the region of phase transition components included in the mixtures allows us to expand the range of variation of thermodynamic parameters of the mixtures under shock wave loading. The calculation model is based on the assumption that all components of mixture under shock-wave loading are in thermodynamic equilibrium (model TEC). The model TEC allows us to describe the region of the polymorphic phase transition, considering the material in the region of phase transition as a mixture of low-pressure phase and high-pressure phase. The good agreement of these model calculations with the data of different authors defined on the basis of experiments is obtained. Thermodynamic parameters of the nitrides mixture, solid and porous mixtures with quartz as component were reliably described. This model is useful for determining the compositions and volume fractions of the components of the mixture to obtain the specified parameters of solid and porous materials under shock-wave loading.

  13. A Thermodynamic Study of Heavy Metal Adsorption at the Biofilm/Mineral Interface: Comparison Between Thermodynamic Model Results and In-situ Measurements

    NASA Astrophysics Data System (ADS)

    Gelabert, A.; Ha, J.; Wang, Y.; Ona-Nguema, G.; Cordova-Ardy, C.; Gescher, J.; Bargar, J. R.; Rogers, J.; Eng, P. J.; Ghose, S. K.; Farges, F.; Spormann, A. M.; Brown, G. E.

    2007-12-01

    Fe- and Al-(oxyhydr)oxides are among the most reactive mineral surfaces in water-rock systems. Bacteria are effective adsorbents of metal ions and can form colonies on the surfaces of minerals. The resulting biofilm coatings may create local microenvironments that could change significantly trace metal ion sorption compared to biofilm-free mineral surfaces. In this study, ATR-FTIR spectroscopy were used to identify the different types of metal binding sites in Shewanella oneidensis strain MR-1 (wild type) as well as the nature of the functional groups involved in metal complexation. Adsorption affinities of these sites for Pb(II) and Zn(II) as well as site densities were determined by fitting metal adsorption data as a function of pH and ionic strength using a constant capacitance model in the FITEQL computer code. Electrokinetic techniques were used to determine the biofilm influence on the overall mineral surface charge. This influence was quantified by determining the in-situ partitioning of Pb(II) between S. oneidensis MR-1 biofilms and highly polished and oriented single crystal surfaces of α-alumina (1-102) and hematite (0001) using the long-period X-ray standing wave-fluorescent yield (XSW-FY) method. ATR-FTIR spectra of S. oneidensis strain MR-1 revealed the presence of carboxyl, amide, and phosphate groups, as well as carbohydrate moieties. Electrophoretic mobility measurements of S. oneidensis MR-1 cell surfaces indicate that the bacterial surfaces become negatively charged at pH ~ 3.5, suggesting a high Pb(II) and Zn(II) adsorption capacity of the biofilm. Changes in ionic strengths from 1M to 0.01M NaNO3 had no effect on the interactions of the metal ions with the bacteria, suggesting that the physical structure of the cell wall does not change over this range of electrolyte concentrations. The thermodynamic stability of metal complexes on S. oneidensis and the binding sites concentrations for these metal complexes have been determined by FITEQL

  14. Exact results for the behavior of the thermodynamic Casimir force in a model with a strong adsorption

    NASA Astrophysics Data System (ADS)

    Dantchev, Daniel M.; Vassilev, Vassil M.; Djondjorov, Peter A.

    2016-09-01

    When massless excitations are limited or modified by the presence of material bodies one observes a force acting between them generally called Casimir force. Such excitations are present in any fluid system close to its true bulk critical point. We derive exact analytical results for both the temperature and external ordering field behavior of the thermodynamic Casimir force within the mean-field Ginzburg-Landau Ising type model of a simple fluid or binary liquid mixture. We investigate the case when under a film geometry the boundaries of the system exhibit strong adsorption onto one of the phases (components) of the system. We present analytical and numerical results for the (temperature-field) relief map of the force in both the critical region of the film close to its finite-size or bulk critical points as well as in the capillary condensation regime below but close to the finite-size critical point.

  15. Classical nucleation theory of immersion freezing: sensitivity of contact angle schemes to thermodynamic and kinetic parameters

    NASA Astrophysics Data System (ADS)

    Ickes, Luisa; Welti, André; Lohmann, Ulrike

    2017-02-01

    Heterogeneous ice formation by immersion freezing in mixed-phase clouds can be parameterized in general circulation models (GCMs) by classical nucleation theory (CNT). CNT parameterization schemes describe immersion freezing as a stochastic process, including the properties of insoluble aerosol particles in the droplets. There are different ways to parameterize the properties of aerosol particles (i.e., contact angle schemes), which are compiled and tested in this paper. The goal of this study is to find a parameterization scheme for GCMs to describe immersion freezing with the ability to shift and adjust the slope of the freezing curve compared to homogeneous freezing to match experimental data. We showed in a previous publication that the resulting freezing curves from CNT are very sensitive to unconstrained kinetic and thermodynamic parameters in the case of homogeneous freezing. Here we investigate how sensitive the outcome of a parameter estimation for contact angle schemes from experimental data is to unconstrained kinetic and thermodynamic parameters. We demonstrate that the parameters describing the contact angle schemes can mask the uncertainty in thermodynamic and kinetic parameters. Different CNT formulations are fitted to an extensive immersion freezing dataset consisting of size-selected measurements as a function of temperature and time for different mineral dust types, namely kaolinite, illite, montmorillonite, microcline (K-feldspar), and Arizona test dust. We investigated how accurate different CNT formulations (with estimated fit parameters for different contact angle schemes) reproduce the measured freezing data, especially the time and particle size dependence of the freezing process. The results are compared to a simplified deterministic freezing scheme. In this context, we evaluated which CNT-based parameterization scheme able to represent particle properties is the best choice to describe immersion freezing in a GCM.

  16. Thermodynamics of methane adsorption on copper HKUST-1 at low pressure

    SciTech Connect

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-06-11

    Metal–organic frameworks (MOFs) can be engineered as natural gas storage materials by tuning the pore structures and surface properties. Here we report the direct measurement of CH₄ adsorption enthalpy on a paddlewheel MOF (Cu HKUST-1) using gas adsorption calorimetry at 25 °C at low pressures (below 1 bar). In this pressure region, the CH₄–CH₄ intermolecular interactions are minimized and the energetics solely reflects the CH₄–MOF interactions. Our results suggest moderately exothermic physisorption with an enthalpy of -21.1 ± 1.1 kJ/mol CH₄ independent of coverage. The calorimetric investigation complements previous computational and crystallographic studies by providing zero coverage enthalpies of CH₄ adsorption. The analysis of the new and literature data suggests that in initial stages of adsorption the CH₄–HKUST-1 interaction tends to be more sensitive to the pore dimension than to the guest polarizability, suggesting a less specific chemical binding role for the open Cu site.

  17. Thermodynamics of methane adsorption on copper HKUST-1 at low pressure

    DOE PAGES

    Wu, Di; Guo, Xiaofeng; Sun, Hui; ...

    2015-06-11

    Metal–organic frameworks (MOFs) can be engineered as natural gas storage materials by tuning the pore structures and surface properties. Here we report the direct measurement of CH₄ adsorption enthalpy on a paddlewheel MOF (Cu HKUST-1) using gas adsorption calorimetry at 25 °C at low pressures (below 1 bar). In this pressure region, the CH₄–CH₄ intermolecular interactions are minimized and the energetics solely reflects the CH₄–MOF interactions. Our results suggest moderately exothermic physisorption with an enthalpy of -21.1 ± 1.1 kJ/mol CH₄ independent of coverage. The calorimetric investigation complements previous computational and crystallographic studies by providing zero coverage enthalpies of CH₄more » adsorption. The analysis of the new and literature data suggests that in initial stages of adsorption the CH₄–HKUST-1 interaction tends to be more sensitive to the pore dimension than to the guest polarizability, suggesting a less specific chemical binding role for the open Cu site.« less

  18. Adsorption kinetics, isotherms and thermodynamics of atrazine removal using a banana peel based sorbent.

    PubMed

    Chaparadza, Allen; Hossenlopp, Jeanne M

    2012-01-01

    Atrazine removal from water by treated banana peels was studied. The effect of pH, contact time, initial atrazine concentration, and temperature were investigated. Batch experiments demonstrated that 15 g L(-1) adsorbent dosage removed 90-99% of atrazine from 1-150 ppm aqueous solutions. The removal was both pH and temperature dependent with the most atrazine removed between pH 7 and 8.2 and increased with increasing temperature. Equilibrium data fitted well to the Langmuir and Redlich-Peterson models in the concentration and temperature ranges investigated, with a maximum adsorption capacity of 14 mg g(-1). Simple mass transfer models were applied to the experimental data to examine the adsorption mechanism and it was found that both external mass transfer and intraparticle diffusion played important roles in the adsorption mechanisms. The enthalpy of atrazine adsorption was evaluated to be 67.8 ± 6.3 kJ mol(-l) with a Gibbs free energy of -5.7 ± 1.2 kJ mol(-1).

  19. Thermodynamics of Methane Adsorption on Copper HKUST-1 at Low Pressure.

    PubMed

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-07-02

    Metal-organic frameworks (MOFs) can be engineered as natural gas storage materials by tuning the pore structures and surface properties. Here we report the direct measurement of CH4 adsorption enthalpy on a paddlewheel MOF (Cu HKUST-1) using gas adsorption calorimetry at 25 °C at low pressures (below 1 bar). In this pressure region, the CH4-CH4 intermolecular interactions are minimized and the energetics solely reflects the CH4-MOF interactions. Our results suggest moderately exothermic physisorption with an enthalpy of -21.1 ± 1.1 kJ/mol CH4 independent of coverage. This calorimetric investigation complements previous computational and crystallographic studies by providing zero coverage enthalpies of CH4 adsorption. The analysis of the new and literature data suggests that in initial stages of adsorption the CH4-HKUST-1 interaction tends to be more sensitive to the pore dimension than to the guest polarizability, suggesting a less specific chemical binding role for the open Cu site.

  20. Computer simulation for prediction of performance and thermodynamic parameters of high energy materials.

    PubMed

    Muthurajan, H; Sivabalan, R; Talawar, M B; Asthana, S N

    2004-08-09

    A new code viz., Linear Output Thermodynamic User-friendly Software for Energetic Systems (LOTUSES) developed during this work predicts the theoretical performance parameters such as density, detonation factor, velocity of detonation, detonation pressure and thermodynamic properties such as heat of detonation, heat of explosion, volume of explosion gaseous products. The same code also assists in the prediction of possible explosive decomposition products after explosion and power index. The developed code has been validated by calculating the parameters of standard explosives such as TNT, PETN, RDX, and HMX. Theoretically predicated parameters are accurate to the order of +/-5% deviation. To the best of our knowledge, no such code is reported in literature which can predict a wide range of characteristics of known/unknown explosives with minimum input parameters. The code can be used to obtain thermochemical and performance parameters of high energy materials (HEMs) with reasonable accuracy. The code has been developed in Visual Basic having enhanced windows environment, and thereby advantages over the conventional codes, written in Fortran. The theoretically predicted HEMs performance can be directly printed as well as stored in text (.txt) or HTML (.htm) or Microsoft Word (.doc) or Adobe Acrobat (.pdf) format in the hard disk. The output can also be copied into the Random Access Memory as clipboard text which can be imported/pasted in other software as in the case of other codes.

  1. Mesoporous silica originating from a gaseous ammonia epoxide ring opening and the thermodynamic data on some divalent cation adsorptions.

    PubMed

    Sales, José A A; Petrucelli, Giovanni C; Oliveira, Fernando J V E; Airoldi, Claudio

    2007-11-15

    An organofunctionalized mesoporous HMS-like compound has been synthesized by reacting the silylating agent 3-glycidoxypropyltrimethoxysilane with gaseous ammonia. The reaction path leads to the opening of the three membered epoxide ring to incorporate ammonia to give the modified silylating agent. This new silylating agent was used to synthesize a mesostructure inorganic-organic hybrid through the neutral template directing agent, dodecylamine, using a co-condensation process, and exploring the ability of the silicon source tetraethoxysilane. The final solid named HMS-NH has been characterized through elemental analysis, X-ray powder diffraction, nitrogen gas adsorption, infrared spectroscopy and solid state NMR for the 29Si nucleus. An amount of 1.06+/-0.10 mmol of pendant groups is covalently bonded to the inorganic backbone. The attached basic centers adsorbed divalent cations to give the maxima adsorption capacity of 0.74+/-0.03, 0.55+/-0.06, 0.53+/-0.05 and 0.51+/-0.06 mmolg(-1) for copper, nickel, zinc and cobalt, respectively. From calorimetric determinations the quantitative thermal effects for all these cation/basic center interactions gave exothermic enthalpy, negative Gibbs free energy and positive entropy. These thermodynamic data confirmed the energetically favorable condition of such interactions at the solid/liquid interface for all systems.

  2. Application of physical adsorption thermodynamics to heterogeneous chemistry on polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Elliott, Scott; Turco, Richard P.; Toon, Owen B.; Hamill, Patrick

    1991-01-01

    Laboratory isotherms for the binding of several nonheterogeneously active atmospheric gases and for HCl to water ice are translated into adsorptive equilibrium constants and surface enthalpies. Extrapolation to polar conditions through the Clausius Clapeyron relation yields coverage estimates below the percent level for N2, Ar, CO2, and CO, suggesting that the crystal faces of type II stratospheric cloud particles may be regarded as clean with respect to these species. For HCl, and perhaps HF and HNO3, estimates rise to several percent, and the adsorbed layer may offer acid or proton sources alternate to the bulk solid for heterogeneous reactions with stratospheric nitrates. Measurements are lacking for many key atmospheric molecules on water ice, and almost entirely for nitric acid trihydrate as substrate. Adsorptive equilibria enter into gas to particle mass flux descriptions, and the binding energy determines rates for desorption of, and encounter between, potential surface reactants.

  3. Thermodynamic properties of adsorption and micellization of n-oktyl-β-D-glucopiranoside.

    PubMed

    Mańko, Diana; Zdziennicka, Anna; Jańczuk, Bronisław

    2014-02-01

    Measurements of the surface tension, density and viscosity of aqueous solutions of n-oktyl-β-D-glucopiranoside (OGP) were made at 293 K. From the obtained results the Gibbs surface excess concentration of OGP at the water-air interface and its critical micelle concentration were determined. The Gibbs surface excess concentration of OGP used in the Gu and Zhu isotherm equation allowed us to determine the Gibbs standard free energy of OGP adsorption at the water-air interface. The Gibbs standard free energy of OGP adsorption was also determined on the basis of the Langmuir, Szyszkowski, Gamboa and Olea equations as well the surface tension of "hydrophobic" part of OGP and "hydrophobic" part-water interface tension. It appeared that there is an agreement between the values of Gibbs standard free energy of OGP adsorption at the water-air interface determined by using all the above mentioned methods. It also proved that standard free energy of OGP micellization determined from CMC is consistent with that obtained on the basis of the free energy of the interactions between the "hydrophobic" part of the OPG through the water phase.

  4. An Electromagnetic and Thermodynamic Lumped Parameter Model of an Explosively Driven Regenerative Magnetohydrodynamic Generator.

    NASA Astrophysics Data System (ADS)

    Morrison, John Lawrence, Jr.

    1992-01-01

    The objective of this research is to develop a simple, yet accurate, lumped parameter mathematical model for an explosively driven magnetohydrodynamic generator that can predict the pulse power variables of voltage and current from startup through regenerative operation. The inputs to the model will be the plasma properties entering the generator as predicted by the explosive shock model of Reference (1). The strategy used was to simplify electromagnetic and thermodynamic three dimensional effects into a zero dimensional model. The model will provide a convenient tool for researchers to optimize designs to be used in pulse power applications. The model is validated using experimental data of Reference (1). An overview of the operation of the explosively driven generator is first presented. Then a simplified electrical circuit model that describes basic performance of the device is developed. Then a lumped parameter model that incorporates the coupled electromagnetic and thermodynamic effects that govern generator performance is described and developed. The model is based on fundamental physical principles and parameters that were either obtained directly from design data or estimated from experimental data. The model was used to obtain parameter sensitivities and predict beyond the limits observed in the experiments to the levels desired by the potential Department of Defense sponsors. The model identifies process limitations that provide direction for future research.

  5. An electromagnetic and thermodynamic lumped parameter model of an explosively driven regenerative magnetohydrodynamic generator

    SciTech Connect

    Morrison, J.L.

    1992-12-01

    The objective of this research is to develop a simple, yet accurate, lumped parameter mathematical model for an explosively driven magnetohydrodynamic generator that can predict the pulse power variables of voltage and current from startup through regenerative operation. The inputs to the model will be the plasma properties entering the generator as predicted by the explosive shock model of Reference [1]. The strategy used was to simplify electromagnetic and thermodynamic three dimensional effects into a zero dimensional model. The model will provide a convenient tool for researchers to optimize designs to be used in pulse power applications. The model is validated using experimental data of Reference [1]. An overview of the operation of the explosively driven generator is first presented. Then a simplified electrical circuit model that describes basic performance of the device is developed. Then a lumped parameter model that incorporates the coupled electromagnetic and thermodynamic effects that govern generator performance is described and developed. The model is based on fundamental physical principles and parameters that were either obtained directly from design data or estimated from experimental data. The model was used to obtain parameter sensitivities and predict beyond the limits observed in the experiments to the levels desired by the potential Department of Defense sponsors. The model identifies process limitations that provide direction for future research.

  6. Enhanced adsorptive removal of Safranine T from aqueous solutions by waste sea buckthorn branch powder modified with dopamine: Kinetics, equilibrium, and thermodynamics

    NASA Astrophysics Data System (ADS)

    Xu, Xiaohui; Bai, Bo; Wang, Honglun; Suo, Yourui

    2015-12-01

    Polydopamine coated sea buckthorn branch powder (PDA@SBP) was facilely synthesized via a one-pot bio-inspired dip-coating approach. The as-synthesized PDA@SBP was characterized using Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The adsorption progresses of Safranine T on the surface of PDA@SBP adsorbent were systematically investigated. More specifically, the effects of solution pH, contact time, initial concentration and temperature were evaluated, respectively. The experimental results showed the adsorption capacity of PDA@SBP at 293.15 K could reach up to 54.0 mg/g; the adsorption increased by 201.7% compared to that of native SBP (17.9 mg/g). Besides, kinetics studies showed that pseudo-second-order kinetic model adequately described the adsorption behavior. The adsorption experimental data could be fitted well a Freundlich isotherm model. Thermodynamic analyses showed that the ST adsorption was a physisorption endothermic process. Regeneration of the spent PDA@SBP adsorbent was conducted with 0.1 M HCl without significant reduction in adsorption capacity. On the basis of these investigations, it is believed that the PDA@SBP adsorbent could have potential applications in sewage disposal areas because of their considerable adsorption capacities, brilliant regeneration capability, and cost-effective and eco-friendly preparation and use.

  7. Modeling of adsorption isotherms of phenol and chlorophenols onto granular activated carbon. Part II. Models with more than two parameters.

    PubMed

    Hamdaoui, Oualid; Naffrechoux, Emmanuel

    2007-08-17

    The adsorption equilibrium isotherms of five phenolic compounds, phenol, 2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol, from aqueous solutions onto granular activated carbon were studied and modeled. In order to determine the best-fit isotherm, the experimental equilibrium data were analyzed using thirteen adsorption isotherm models with more than two-parameter; nine three-parameter equations - the Redlich-Peterson, Sips, Langmuir-Freundlich, Fritz-Schlunder, Radke-Prasnitz (three models), Tóth, and Jossens isotherms - three four-parameter equation - the Weber-van Vliet, Fritz-Schlunder, and Baudu isotherms - and one five-parameter equation - the Fritz-Schlunder isotherm. The results reveal that the adsorption isotherm models fitted the experimental data in the order: Baudu (four-parameter)>Langmuir-Freundlich (three-parameter)>Sips (three-parameter)>Fritz-Schlunder (five-parameter)>Tóth (three-parameter)>Fritz-Schlunder (four-parameter)>Redlich-Peterson (three-parameter). The influence of solution pH on the adsorption isotherms of 4-CP was investigated. It was shown that the solution pH has not an effect on the adsorption isotherms for pHadsorptive pKa and the pH(PZC).

  8. Thermodynamical and structural insights of orange II adsorption by Mg{sub R}AlNO{sub 3} layered double hydroxides

    SciTech Connect

    Mustapha Bouhent, Mohamed; Derriche, Zoubir; Denoyel, Renaud; Prevot, Vanessa; Forano, Claude

    2011-05-15

    [Mg{sub 1-x} Al{sub x}(OH){sub 2}][(NO{sub 3}){sub x}, nH{sub 2}O] Layered Double Hydroxide (LDH) sorbents with variable Mg/Al molar (R=(1-x)/x) ratios were investigated for adsorption of azo dye, orange II (OII) at various pH and temperature conditions. Mg{sub 2}AlNO{sub 3} displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg{sub 2}AlNO{sub 3} at 40 {sup o}C. Adsorption isotherms have been fitted using the Langmuir model and free energy of adsorption ({Delta}G{sup o}), enthalpy ({Delta}H{sup o}) and entropy ({Delta}S{sup o}) were calculated. The experimental values for {Delta}G{sup o} in temperature range between 10 and 40 {sup o}C were found to be negative indicating that a spontaneous process occurred. Positive calculated enthalpy values, characteristic of an endothermic process were found. Characterization of solids (PXRD, FTIR, UV-vis, TGA/DTA, adsorption isotherm BET analysis, SEM and Zetametry) before and after adsorption showed that adsorption proceeds in two steps. First, adsorption occurs at the LDH surface, followed by intercalation via anion exchange. -- Graphical Abstract: Structural and thermodynamical insight of adsorption/Intercalation of OII in Mg{sub R}Al LDH Display Omitted Highlights: {yields} The nitrate containing hydrotalcite-like compounds (Mg{sub R}AlNO{sub 3} LDH) were prepared by the coprecipitation method. {yields} Adsorption of anionic orange dye(OII) is studied on LDHs at different temperatures. {yields} The adsorption process is well described by the Langmuir isotherm model. {yields} Mg{sub 2}AlNO{sub 3} displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg{sub 2}AlNO{sub 3} at 40 {sup o}C. {yields} Adsorption process does not occur on the surface of the LDH only but an intercalation process is also occurring concomitantly according to the thermodynamical values.

  9. Kinetics and thermodynamics associated with Bi adsorption transitions at Cu and Ni grain boundaries

    SciTech Connect

    Tai, Kaiping; Feng, Lin; Dillon, Shen J.

    2013-05-21

    The grain boundary diffusivity of Au in Cu and Cu-Bi, and Cu in Ni and Ni-Bi are characterized by secondary ion mass spectroscopy depth profiling. Samples are equilibrated in a Bi containing atmosphere at temperatures above and below the onset of grain boundary adsorption transitions, sometimes called complexion transitions. A simple thermo-kinetic model is used to estimate the relative entropic contributions to the grain boundary energies. The results indicate that the entropy term plays a major role in promoting thermally and chemically induced grain boundary complexion transition.

  10. Distributed parameter heat transfer and thermodynamic model of a scroll pump

    SciTech Connect

    Sunder, S.; Smith, J.L. Jr.

    1997-07-01

    Heat transfer processes between gas and walls of a scroll pump strongly affect its thermodynamic performance. Hence, the authors present a new methodology for simulating gas and wall processes of a scroll pump, using the techniques of Computational Fluid Dynamics (CFD). They capture the spatial and temporal distribution of gas temperature and pressure by solving the energy and continuity equations for moving and deforming gas control volumes represents a column (pocket) of gas as it moves through the pump and gets compressed. The gas models incorporate heat transfer between gas and walls, as well as leakage phenomena, and thermodynamic effects. Simultaneously, they also capture the spatial distribution of wall temperatures in a scroll pump by modeling the heat transfer processes that characterize wall-gas and wall-wall interactions. Modes of heat transfer simulated for the wall side include conduction, convection and kissing heat transfer, which is a novel mechanism of heat transfer through transient contact between the wraps of a scroll pump. Gas and wall side calculations proceed iteratively in order to be consistent with each other. The results of the model were found to be in good agreement with experimentally observed scroll wall temperature data and experimentally measured pump thermodynamic parameters.

  11. Thermodynamics and Phase Transitions of Electrolytes on Lattices with Different Discretization Parameters

    NASA Astrophysics Data System (ADS)

    Kolomeisky, Anatoly; Artyomov, Maxim; Kobelev, Vladimir

    2004-03-01

    Lattice models are crucial for understanding the thermodynamics and phase transitions in many biological and chemical systems. We investigate Lattice Restricted Primitive Model (LRPM) of ionic systems with different discretization parameters in order to understand the deviations from continuum description of charged systems. Discretization parameter is defined as a number of lattice sites occupied by every ion. Explicit analytic and numerical calculations are performed using Debye-Hückel approach, which takes into account dipole formations, dipole-ion interactions and correct lattice Coulomb potentials. The gas-liquid phase separation is found at low densities. The increase in the discretization parameter lowers the critical temperature and increases the critical density, in agreement with Monte Carlo simulations results. In the limit of infinitely large discretization, our results approach the predictions from continuum RPM of electrolytes. However, when every particle can only occupy one lattice site, the gas-liquid phase transitions are suppressed by order-disorder phase transformations.

  12. Synthesis, characterization and thermodynamic study of carbon dioxide adsorption on akaganéite

    SciTech Connect

    Roque-Malherbe, R.; Lugo, F.; Rivera-Maldonado, C.; Polanco-Estrella, R.; Uwakweh, O.

    2015-04-01

    A mixture of akaganeite nanoparticles and sodium salts was synthesized and modi fied, first by washing, and then by Li exchange. The structural characterization of the produced materials was performed with: powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, thermogravimetric analysis, diffuse reflectance infrared Fourier transform spectrometry, Mossbauer spectros- € copy and magnetization measurements. Additionally low pressure nitrogen and high pressure carbon dioxide adsorption experiments were performed. The sum of the characterization information made possible to conclude that the produced akaganeite phases crystallized in a structure exhibiting the symmetry of the I2/m space group, where the measured equivalent spherical diameter of the akaganeite crystallites yielded 9 nm, as well, the tested phases exhibited a standard behaviour under heating and displayed a superparamagnetic behaviour. Finally the high pressure carbon dioxide adsorption experiments demonstrated a pressure-responsive framework opening event due to a structural transformation of the adsorbent framework induced by the guest molecules. This fact opens new applications for akaganeite as a high pressure adsorbent.

  13. Synthesis, characterization and thermodynamic study of carbon dioxide adsorption on akaganéite

    DOE PAGES

    Roque-Malherbe, R.; Lugo, F.; Rivera-Maldonado, C.; ...

    2015-04-01

    A mixture of akaganeite nanoparticles and sodium salts was synthesized and modi fied, first by washing, and then by Li exchange. The structural characterization of the produced materials was performed with: powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, thermogravimetric analysis, diffuse reflectance infrared Fourier transform spectrometry, Mossbauer spectros- € copy and magnetization measurements. Additionally low pressure nitrogen and high pressure carbon dioxide adsorption experiments were performed. The sum of the characterization information made possible to conclude that the produced akaganeite phases crystallized in a structure exhibiting the symmetry of the I2/m space group, where the measured equivalentmore » spherical diameter of the akaganeite crystallites yielded 9 nm, as well, the tested phases exhibited a standard behaviour under heating and displayed a superparamagnetic behaviour. Finally the high pressure carbon dioxide adsorption experiments demonstrated a pressure-responsive framework opening event due to a structural transformation of the adsorbent framework induced by the guest molecules. This fact opens new applications for akaganeite as a high pressure adsorbent.« less

  14. Influence of precipitating agents on thermodynamic parameters of protein crystallization solutions.

    PubMed

    Stavros, Philemon; Saridakis, Emmanuel; Nounesis, George

    2016-09-01

    X-ray crystallography is the most powerful method for determining three-dimensional structures of proteins to (near-)atomic resolution, but protein crystallization is a poorly explained and often intractable phenomenon. Differential Scanning Calorimetry was used to measure the thermodynamic parameters (ΔG, ΔH, ΔS) of temperature-driven unfolding of two globular proteins, lysozyme, and ribonuclease A, in various salt solutions. The mixtures were categorized into those that were conducive to crystallization of the protein and those that were not. It was found that even fairly low salt concentrations had very large effects on thermodynamic parameters. High concentrations of salts conducive to crystallization stabilized the native folded forms of proteins, whereas high concentrations of salts that did not crystallize them tended to destabilize them. Considering the ΔH and TΔS contributions to the ΔG of unfolding separately, high concentrations of crystallizing salts were found to enthalpically stabilize and entropically destabilize the protein, and vice-versa for the noncrystallizing salts. These observations suggest an explanation, in terms of protein stability and entropy of hydration, of why some salts are good crystallization agents for a given protein and others are not. This in turn provides theoretical insight into the process of protein crystallization, suggesting ways of predicting and controlling it. © 2016 Wiley Periodicals, Inc. Biopolymers 105: 642-652, 2016.

  15. Complex Thermodynamic Behavior of Single-Stranded Nucleic Acid Adsorption to Graphene Surfaces.

    PubMed

    Ranganathan, Srivathsan V; Halvorsen, Ken; Myers, Chris A; Robertson, Neil M; Yigit, Mehmet V; Chen, Alan A

    2016-06-21

    In just over a decade since its discovery, research on graphene has exploded due to a number of potential applications in electronics, materials, and medicine. In its water-soluble form of graphene oxide, the material has shown promise as a biosensor due to its preferential absorption of single-stranded polynucleotides and fluorescence quenching properties. The rational design of these biosensors, however, requires an improved understanding of the binding thermodynamics and ultimately a predictive model of sequence-specific binding. Toward these goals, here we directly measured the binding of nucleosides and oligonucleotides to graphene oxide nanoparticles using isothermal titration calorimetry and used the results to develop molecular models of graphene-nucleic acid interactions. We found individual nucleosides binding KD values lie in the submillimolar range with binding order of rG < rA < rC < dT < rU, while 5mer and 15mer oligonucleotides had markedly higher binding affinities in the range of micromolar and submicromolar KD values, respectively. The molecular models developed here are calibrated to quantitatively reproduce the above-mentioned experimental results. For oligonucleotides, our model predicts complex binding features such as double-stacked bases and a decrease in the fraction of graphene stacked bases with increasing oligonucleotide length until plateauing beyond ∼10-15 nucleotides. These experimental and computational results set the platform for informed design of graphene-based biosensors, further increasing their potential and application.

  16. Application of Statistical Thermodynamics To Predict the Adsorption Properties of Polypeptides in Reversed-Phase HPLC.

    PubMed

    Tarasova, Irina A; Goloborodko, Anton A; Perlova, Tatyana Y; Pridatchenko, Marina L; Gorshkov, Alexander V; Evreinov, Victor V; Ivanov, Alexander R; Gorshkov, Mikhail V

    2015-07-07

    The theory of critical chromatography for biomacromolecules (BioLCCC) describes polypeptide retention in reversed-phase HPLC using the basic principles of statistical thermodynamics. However, whether this theory correctly depicts a variety of empirical observations and laws introduced for peptide chromatography over the last decades remains to be determined. In this study, by comparing theoretical results with experimental data, we demonstrate that the BioLCCC: (1) fits the empirical dependence of the polypeptide retention on the amino acid sequence length with R(2) > 0.99 and allows in silico determination of the linear regression coefficients of the log-length correction in the additive model for arbitrary sequences and lengths and (2) predicts the distribution coefficients of polypeptides with an accuracy from 0.98 to 0.99 R(2). The latter enables direct calculation of the retention factors for given solvent compositions and modeling of the migration dynamics of polypeptides separated under isocratic or gradient conditions. The obtained results demonstrate that the suggested theory correctly relates the main aspects of polypeptide separation in reversed-phase HPLC.

  17. Thermodynamic investigations using molecular dynamics simulations with potential of mean force calculations for cardiotoxin protein adsorption on mixed self-assembled monolayers.

    PubMed

    Hung, Shih-Wei; Hsiao, Pai-Yi; Lu, Ming-Chang; Chieng, Ching-Chang

    2012-10-25

    Understanding protein adsorption onto solid surfaces is of critical importance in the field of bioengineering, especially for applications such as medical implants, diagnostic biosensors, drug delivery systems, and tissue engineering. This study proposed the use of molecular dynamics simulations with potential of mean force (PMF) calculations to identify and characterize the mechanisms of adsorption of a protein molecule on a designed surface. A set of model systems consisting of a cardiotoxin (CTX) protein and mixed self-assembled monolayer (SAM) surfaces were used as examples. The set of mixed SAM surfaces with varying topographies were created by mixing alkanethiol chains of different lengths. The results revealed that CTX proteins underwent similar conformal changes upon adsorption onto the various mixed SAMs but showed distinctive characteristics in free energy profiles. Enhancement of the adsorption affinity, i.e., the change in free energy of adsorption, for mixed SAMs was demonstrated by using atomic force microscopic measurements. A component analysis conducted to quantify the physical mechanisms that promoted CTX adsorption revealed contributions from both SAMs and the solvent. Further component analyses of thermodynamic properties, such as the free energy, enthalpy, and entropy, indicated that the contribution from SAMs was driven by enthalpy, and the contribution from the solvent was driven by entropy. The results indicated that CTX adsorption was an entropy-driven process, and the entropic component from the solvent, i.e., the hydrophobic interaction, was the major driving force for CTX adsorption onto SAMs. The study also concluded that the surfaces composed of mixtures of SAMs with different chain lengths promoted the adsorption of CTX protein.

  18. Thermodynamic analysis and optimization of the cycle parameters of regenerative gas-turbine converters for solar power stations /SGTS/

    NASA Astrophysics Data System (ADS)

    Drabkin, L. M.

    A thermodynamic analysis compares the efficiency of a simple solar-driven helium gas turbine generator with two improved schemes employing regeneration of heat from the recirculating working fluid. One scheme uses a recuperator based on direct heat exchange while the other recovers heat by thermoelectric conversion in addition to the recuperator. The specific area of the heat exchange surface is calculated along with other system parameters for maximum thermodynamic cycle efficiency. Gains of up to 15% are demonstrated.

  19. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation.

    PubMed

    Nugent, Patrick; Belmabkhout, Youssef; Burd, Stephen D; Cairns, Amy J; Luebke, Ryan; Forrest, Katherine; Pham, Tony; Ma, Shengqian; Space, Brian; Wojtas, Lukasz; Eddaoudi, Mohamed; Zaworotko, Michael J

    2013-03-07

    The energy costs associated with the separation and purification of industrial commodities, such as gases, fine chemicals and fresh water, currently represent around 15 per cent of global energy production, and the demand for such commodities is projected to triple by 2050 (ref. 1). The challenge of developing effective separation and purification technologies that have much smaller energy footprints is greater for carbon dioxide (CO2) than for other gases; in addition to its involvement in climate change, CO2 is an impurity in natural gas, biogas (natural gas produced from biomass), syngas (CO/H2, the main source of hydrogen in refineries) and many other gas streams. In the context of porous crystalline materials that can exploit both equilibrium and kinetic selectivity, size selectivity and targeted molecular recognition are attractive characteristics for CO2 separation and capture, as exemplified by zeolites 5A and 13X (ref. 2), as well as metal-organic materials (MOMs). Here we report that a crystal engineering or reticular chemistry strategy that controls pore functionality and size in a series of MOMs with coordinately saturated metal centres and periodically arrayed hexafluorosilicate (SiF(2-)(6)) anions enables a 'sweet spot' of kinetics and thermodynamics that offers high volumetric uptake at low CO2 partial pressure (less than 0.15 bar). Most importantly, such MOMs offer an unprecedented CO2 sorption selectivity over N2, H2 and CH4, even in the presence of moisture. These MOMs are therefore relevant to CO2 separation in the context of post-combustion (flue gas, CO2/N2), pre-combustion (shifted synthesis gas stream, CO2/H2) and natural gas upgrading (natural gas clean-up, CO2/CH4).

  20. Thermodynamics, interfacial pressure isotherms and dilational rheology of mixed protein-surfactant adsorption layers.

    PubMed

    Fainerman, V B; Aksenenko, E V; Krägel, J; Miller, R

    2016-07-01

    Proteins and their mixtures with surfactants are widely used in many applications. The knowledge of their solution bulk behavior and its impact on the properties of interfacial layers made great progress in the recent years. Different mechanisms apply to the formation process of protein/surfactant complexes for ionic and non-ionic surfactants, which are governed mainly by electrostatic and hydrophobic interactions. The surface activity of these complexes is often remarkably different from that of the individual protein and has to be considered in respective theoretical models. At very low protein concentration, small amounts of added surfactants can change the surface activity of proteins remarkably, even though no strongly interfacial active complexes are observed. Also small added amounts of non-ionic surfactants change the surface activity of proteins in the range of small bulk concentrations or surface coverages. The modeling of the equilibrium adsorption behavior of proteins and their mixtures with surfactants has reached a rather high level. These models are suitable also to describe the high frequency limits of the dilational viscoelasticity of the interfacial layers. Depending on the nature of the protein/surfactant interactions and the changes in the interfacial layer composition rather complex dilational viscoelasticities can be observed and described by the available models. The differences in the interfacial behavior, often observed in literature for studies using different experimental methods, are at least partially explained by a depletion of proteins, surfactants and their complexes in the range of low concentrations. A correction of these depletion effects typically provides good agreement between the data obtained with different methods, such as drop and bubble profile tensiometry.

  1. Swelling, diffusion, network parameters and adsorption properties of IPN hydrogel of chitosan and acrylic copolymer.

    PubMed

    Mandal, Bidyadhar; Ray, Samit Kumar

    2014-11-01

    Interpenetrating network (IPN) type hydrogels of a biopolymer and a synthetic polymer were prepared from chitosan and crosslink copolymer of acrylic acid, sodium acrylate and hydroxyethyl methacrylate. Acrylic acid, sodium acrylate, hydroxyethyl methacrylate and N'N'-methylenebisacrylamide (MBA) monomers were free radically copolymerized and crosslinked in aqueous solution of chitosan. Several IPN hydrogels were prepared by varying concentrations of initiator, crosslinker (MBA) and weight% of chitosan . These hydrogels were characterized by free acid content, pH at point of zero charge (PZC), FTIR, DTA-TGA, SEM and XRD. The swelling and diffusion characteristics, network parameters and adsorption of cationic methyl violet (MV) and anionic congo red (CR) dyes by these hydrogels were studied. The hydrogels showed high adsorption (9.5-119 mg/g for CR and 9.2-98 mg/g for MV) and removal% (98-73% for CR and 94-66% for MV) over the feed concentration of 10-140 mg/l dye in water. The isotherms and kinetics of dye adsorption by the hydrogels were also studied.

  2. Surface tension and related thermodynamic parameters of alcohols using the Traube stalagmometer

    NASA Astrophysics Data System (ADS)

    Dilmohamud, B. A.; Seeneevassen, J.; Rughooputh, S. D. D. V.; Ramasami, P.

    2005-11-01

    An apparatus was devised using the Traube Stalagmometer for the determination of the surface tension of the alcohols methanol, ethanol, propan-1-ol and butan-1-ol. Measurements were made under atmospheric pressure at temperatures between 288.15 K and 313.15 K. The surface tension values were correlated with temperature and surface thermodynamic parameters, namely surface entropy and surface enthalpy, were also calculated. The results obtained are in agreement with the literature and they are promising for the use of this low cost arrangement for accurate measurement of surface tension. Surface tension values were obtained with a maximum error of 0.5 mN m-1 and a maximum standard deviation of 0.8 mN m-1. We recommend this arrangement for students in advanced university courses and it can also be used for research work.

  3. The optical method for determining the thermodynamic parameters of hot gases

    NASA Astrophysics Data System (ADS)

    Egorov, O. V.; Voitsekhovskaya, O. K.; Kashirskii, D. E.; Tsvyk, R. Sh.; Sazanovich, V. M.; Sherstobitov, M. V.

    2014-11-01

    The research conducted on the thermodynamic parameters of a flame was based on its experimental transmission spectra in the 2.7 μm and 4.3 μm ranges. To produce the flame, alcohol was burned under atmospheric conditions. The hot gases resulting from the burning of ethanol (H2O, CO, and CO2) were accelerated and spun by the rotation of an impeller. The optical method developed by the authors was employed for predicting the temperature and partial pressure of the hot gases. The results demonstrate the practical significance of the method suggested. The spectroscopic database HITEMP 2010 was used for all line-by-line calculations presented in the article.

  4. Thermal equation of state and thermodynamic Grüneisen parameter of beryllium metal

    SciTech Connect

    Zhang, Jianzhong Zhu, Jinlong; Velisavljevic, Nenad; Wang, Liping; Zhao, Yusheng

    2013-11-07

    We conducted in-situ high-pressure synchrotron x-ray experiments on beryllium metal at pressures up to 7.9 GPa and temperatures up to 1373 K. A complete pressure (P)–volume (V)–temperature (T) equation of state (EOS) is determined based on the experiment, which includes temperature derivatives of elastic bulk modulus (at both constant pressure and constant volume) and pressure dependence of thermal expansivity. From this EOS, we calculate thermal pressure, heat capacity at constant volume, and thermodynamic Grüneisen parameter as a function of temperature. Above ∼600 K, our results show notable deviation from theoretical predictions using the quasiharmonic and local-density approximations, indicating that the free energy calculations need to be further improved within the current scheme of approximations.

  5. Electrochemistry of mammalian cytochrome P450 2B4 indicates tunable thermodynamic parameters in surfactant films.

    PubMed

    Hagen, Katharine D; Gillan, James M; Im, Sang-Choul; Landefeld, Sally; Mead, Griffin; Hiley, Megan; Waskell, Lucy A; Hill, Michael G; Udit, Andrew K

    2013-12-01

    Electrochemical methods continue to present an attractive means for achieving in vitro biocatalysis with cytochromes P450; however understanding fully the nature of electrode-bound P450 remains elusive. Herein we report thermodynamic parameters using electrochemical analysis of full-length mammalian microsomal cytochrome P450 2B4 (CYP 2B4) in didodecyldimethylammonium bromide (DDAB) surfactant films. Electronic absorption spectra of CYP 2B4-DDAB films on silica slides reveal an absorption maximum at 418nm, characteristic of low-spin, six-coordinate, water-ligated Fe(III) heme in P450. The Fe(III/II) and Fe(II/I) redox couples (E1/2) of substrate-free CYP 2B4 measured by cyclic voltammetry are -0.23V and -1.02V (vs. SCE, or 14mV and -776mV vs. NHE) at 21°C. The standard heterogeneous rate constant for electron transfer from the electrode to the heme for the Fe(III/II) couple was estimated at 170s(-1). Experiments indicate that the system is capable of catalytic reduction of dioxygen, however substrate oxidation was not observed. From the variation of E1/2 with temperature (18-40°C), we have measured entropy and enthalpy changes that accompany heme reduction, -151Jmol(-1)K(-1) and -46kJmol(-1), respectfully. The corresponding entropy and enthalpy values are less for the six-coordinate low-spin, imidazole-ligated enzyme (-59Jmol(-1)K(-1) and -18kJmol(-1)), consistent with limited conformational changes upon reduction. These thermodynamic parameters are comparable to those measured for bacterial P450 from Bacillus megaterium (CYP BM3), confirming our prior reports that the surfactant environment exerts a strong influence on the redox properties of the heme.

  6. Optimisation of process parameters for adsorption of metal ions on straw carbon by using response surface methodology.

    PubMed

    Kannan, N; Rajakumar, A; Rengasamy, G

    2004-05-01

    Optimisation of process parameters for adsorption of metal ions viz., Cu2+, Cd2+ and Ni2+ ions on Straw Carbon (SC) was carried out by using Box-Behnken statistics and analysis of variance methods. Response surface methodology with three levels of initial pH (4, 5, 6), dose (8, 10, 12 gl(-1)) and particle size (0.075, 0.090, 0.106m micron) were used in the identification of significance of the effects and interactions in adsorption studies. Response surface methodology requires no assumption and identifies the principal experimental variables and their interactions which have the greatest effect on adsorption. The optimum process parameters for maximum adsorption of Ni2+, Cu2+ and Cd2+ were obtained by this procedure.

  7. Elucidating thermodynamic parameters for electron transfer proteins using isothermal titration calorimetry: application to the nitrogenase Fe protein.

    PubMed

    Sørlie, Morten; Chan, Jeannine M; Wang, Haijang; Seefeldt, Lance C; Parker, Vernon D

    2003-05-01

    Establishing thermodynamic parameters for electron transfer reactions involving redox proteins is essential for a complete description of these important reactions. While various methods have been developed for measuring the Gibbs free energy change (Delta G(HR) or E(m)) for the protein half-reactions, deconvolution of the respective contributions of enthalpy (Delta H(HR)) and entropy (Delta S(HR)) changes is much more challenging. In the present work, an approach is developed using isothermal titration calorimetry (ITC) that allows accurate determination of all of these thermodynamic parameters for protein electron transfer half-reactions. The approach was validated for essentially irreversible and reversible electron transfer reactions between well-characterized mediators and between mediators and the protein cytochrome c. In all cases, the measured thermodynamic parameters were in excellent agreement with parameters determined by electrochemical methods. Finally, the calorimetry approach was used to determine thermodynamic parameters for electron transfer reactions of the nitrogenase Fe protein [4Fe-4S](2+/+) couple in the absence or presence of MgADP or MgATP. The E(m) value was found to change from -290 mV in the absence of nucleotides to -381 mV with MgATP and -423 mV with MgADP, consistent with earlier values. For the first time, the enthalpy (Delta H(HR)) and entropy (Delta S(HR)) contributions for each case were established, revealing shifts in the contribution of each thermodynamic parameter induced by nucleotide binding. The results are discussed in the context of current models for electron transfer in nitrogenase.

  8. Prediction of adsorption from multicomponent solutions by activated carbon using single-solute parameters.

    PubMed

    Wurster, D E; Alkhamis, K A; Matheson, L E

    2000-08-31

    The adsorption of 3 barbiturates--phenobarbital, mephobarbital, and primidone--from simulated intestinal fluid (SIF), without pancreatin, by activated carbon was studied using the rotating bottle method. The concentrations of each drug remaining in solution at equilibrium were determined with the aid of a high-performance liquid chromatography (HPLC) system employing a reversed-phase column. The competitive Langmuir-like model, the modified competitive Langmuir-like model, and the LeVan-Vermeulen model were each fit to the data. Excellent agreement was obtained between the experimental and predicted data using the modified competitive Langmuir-like model and the LeVan-Vermeulen model. The agreement obtained from the original competitive Langmuir-like model was less satisfactory. These observations are not surprising because the competitive Langmuir-like model assumes that the capacities of the adsorbates are equal, while the other 2 models take into account the differences in the capacities of the components. The results of these studies indicate that the adsorbates employed are competing for the same binding sites on the activated carbon surface. The results also demonstrate that it is possible to accurately predict multicomponent adsorption isotherms using only single-solute isotherm parameters. Such prediction is likely to be useful for improving in vivo/in vitro correlations.

  9. Effects of Zeolite Structural Confinement on Adsorption Thermodynamics and Reaction Kinetics for Monomolecular Cracking and Dehydrogenation of n-Butane.

    PubMed

    Janda, Amber; Vlaisavljevich, Bess; Lin, Li-Chiang; Smit, Berend; Bell, Alexis T

    2016-04-13

    The effects of zeolite structure on the kinetics of n-butane monomolecular cracking and dehydrogenation are investigated for eight zeolites differing in the topology of channels and cages. Monte Carlo simulations are used to calculate enthalpy and entropy changes for adsorption (ΔHads-H+ and ΔSads-H+) of gas-phase alkanes onto Brønsted protons. These parameters are used to extract intrinsic activation enthalpies (ΔHint‡), entropies (ΔSint‡), and rate coefficients (kint) from measured data. As ΔSads-H+ decreases (i.e., as confinement increases), ΔHint‡ and ΔSint‡ for terminal cracking and dehydrogenation decrease for a given channel topology. These results, together with positive values observed for ΔSint‡, indicate that the transition states for these reactions resemble products. For central cracking (an earlier transition state), ΔHint‡ is relatively constant, while ΔSint‡ increases as ΔSads-H+ decreases because less entropy is lost upon protonation of the alkane. Concurrently, selectivities to terminal cracking and dehydrogenation decrease relative to central cracking because ΔSint‡ decreases for the former reactions. Depending on channel topology, changes in the measured rate coefficients (kapp) with confinement are driven by changes in kint or by changes in the adsorption equilibrium constant (Kads-H+). Values of ΔSint‡ and ΔHint‡ are positively correlated, consistent with weaker interactions between the zeolite and transition state and with the greater freedom of movement of product fragments within more spacious pores. These results differ from earlier reports that ΔHint‡ and ΔSint‡ are structure-insensitive and that kapp is dominated by Kads-H+. They also suggest that ΔSads-H+ is a meaningful descriptor of confinement for zeolites having similar channel topologies.

  10. Adsorption of aluminum and lead from wastewater by chitosan-tannic acid modified biopolymers: Isotherms, kinetics, thermodynamics and process mechanism.

    PubMed

    Badawi, M A; Negm, N A; Abou Kana, M T H; Hefni, H H; Abdel Moneem, M M

    2017-06-01

    Chitosan was reacted by tannic acid to obtain three modified chitosan biopolymer. Their chemical structures were characterized by FTIR and elemental analysis. The prepared biopolymers were used to adsorb Al(III) and Pb(II) metal ions from industrial wastewater. The factors affecting the adsorption process were biosorbent amount, initial concentration of metal ion and pH of the medium. The adsorption efficiency increased considerably with the increase of the biosorbent amount and pH of the medium. The adsorption process of biosorbent on different metal ions was fitted by Freundlich adsorption model. The adsorption kinetics was followed Pseudo-second-order kinetic model. The adsorption process occurred according to diffusion mechanism which was confirmed by the interparticle diffusion model. The modified biopolymers were efficient biosorbents for removal of Pb(II) and Al(III) metal ions from the medium.

  11. Investigation of thermodynamic parameters in the thermal decomposition of plastic waste-waste lube oil compounds.

    PubMed

    Kim, Yong Sang; Kim, Young Seok; Kim, Sung Hyun

    2010-07-01

    Thermal decomposition properties of plastic waste-waste lube oil compounds were investigated under nonisothermal conditions. Polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET) were selected as representative household plastic wastes. A plastic waste mixture (PWM) and waste lube oil (WLO) were mixed with mixing ratios of 33, 50, and 67 (w/w) % on a PWM weight basis, and thermogravimetric (TG) experiments were performed from 25 to 600 degrees C. The Flynn-Wall method and the Ozawa-Flynn-Wall method were used for analyses of thermodynamic parameters. In this study, activation energies of PWM/WLO compounds ranged from 73.4 to 229.6 kJ/mol between 0.2 and 0.8 of normalized mass conversions, and the 50% PWM/WLO compound had lower activation energies and enthalpies among the PWM/WLO samples at each mass conversion. At the point of maximum differential mass conversion, the analyzed activation energies, enthalpies, entropies, and Gibbs free energies indicated that mixing PWM and WLO has advantages in reducing energy to decrease the degree of disorder. However, no difference in overall energy that would require overcoming both thermal decomposition reactions and degree of disorder was observed among PWM/WLO compounds under these experimental conditions.

  12. Vibrational and electronic investigations, thermodynamic parameters, HOMO and LUMO analysis on Lornoxicam by density functional theory

    NASA Astrophysics Data System (ADS)

    Suhasini, M.; Sailatha, E.; Gunasekaran, S.; Ramkumaar, G. R.

    2015-11-01

    The Fourier transform infrared (FT-IR) and FT-Raman spectra of Lornoxicam were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameters, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p) and 6-31++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the Vibrational modes calculated using Vibrational Energy Distribution Analysis (VEDA 4) program. The oscillator's strength calculated by TD-DFT and Lornoxicam is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis and the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like Entropy, Enthalpy, Specific heat capacity and zero vibrational energy have been calculated. Besides, molecular electrostatic potential (MEP) was investigated using theoretical calculations.

  13. Partition function and thermodynamic parameters of the all-particle cosmic-ray flux

    NASA Astrophysics Data System (ADS)

    Tomaschitz, Roman

    2016-11-01

    The all-particle cosmic-ray energy spectrum is studied in the 1 GeV-1011 GeV interval, the relativistic nuclei being treated as a free multi-component gas in stationary non-equilibrium. A phase-space derivation of the spectral number density, partition function and entropy is given, and an analytic expression for the flux density of the all-particle spectrum is semi-empirically obtained from a wideband spectral fit. The all-particle spectrum is the additive superposition of four strongly overlapping peaks with exponential cutoffs at the spectral breaks. The analytic flux density covers the mentioned interval ranging over eleven decades and accurately reproduces the spectral fine-structure, such as two weak spectral breaks between knee and ankle emerging in the IceTop-73 and KASCADE-Grande data sets. In the low-energy range below 104 GeV, the all-particle flux is approximated by adding the proton and helium flux densities obtained from fits to the AMS-02 and CREAM spectra, the contribution of heavier nuclei being negligible in this energy range. Estimates of the thermodynamic parameters (number count, internal energy, entropy and pressure) of the all-particle flux and the partial fluxes generating the spectral peaks are derived.

  14. Thermodynamic parameters of heterogeneous materials under shock-wave loading in presentation of equilibrium model

    NASA Astrophysics Data System (ADS)

    Maevskii, K. K.; Kinelovskii, S. A.

    2016-11-01

    The results of numerical experiments on modeling of shock wave loading of solid and porous heterogeneous materials on the example of molybdenum and some alloys included molybdenum as a component are presented. A thermodynamically equilibrium model is applied to describe the behavior of solid and porous materials. This model ensures good compliance with the experiment in a wide range of pressures. The gas in pores, which is a component of the medium, is taken into account in this model. The equation of state of the Mie-Grüneisen type with allowance for the dependence of the Grüneisen coefficient on temperature is used for condensed phases. The applied model allows the behavior of the molybdenum with porosity from 1 to 3 to be calculated under shock-wave loading at pressures above 5 GPa in the one-velocity and one-temperature approximations, as well as on the assumption of equal pressures for all the phases. Computational results are compared with the well-known experimental results obtained by different authors. The model permits the shock-wave loading of solid and porous alloys with molybdenum in their composition to be described reliably solely by using species parameters.

  15. Exogenous electron shuttle-mediated extracellular electron transfer of Shewanella putrefaciens 200: electrochemical parameters and thermodynamics.

    PubMed

    Wu, Yundang; Liu, Tongxu; Li, Xiaomin; Li, Fangbai

    2014-08-19

    Despite the importance of exogenous electron shuttles (ESs) in extracellular electron transfer (EET), a lack of understanding of the key properties of ESs is a concern given their different influences on EET processes. Here, the ES-mediated EET capacity of Shewanella putrefaciens 200 (SP200) was evaluated by examining the electricity generated in a microbial fuel cell. The results indicated that all the ESs substantially accelerated the current generation compared to only SP200. The current and polarization parameters were linearly correlated with both the standard redox potential (E(ES)(0)) and the electron accepting capacity (EAC) of the ESs. A thermodynamic analysis of the electron transfer from the electron donor to the electrode suggested that the EET from c-type cytochromes (c-Cyts) to ESs is a crucial step causing the differences in EET capacities among various ESs. Based on the derived equations, both E(ES)(0) and EAC can quantitatively determine potential losses (ΔE) that reflect the potential loss of the ES-mediated EET. In situ spectral kinetic analysis of ES reduction by c-Cyts in a living SP200 suspension was first investigated with the E(ES), E(c-Cyt), and ΔE values being calculated. This study can provide a comprehensive understanding of the role of ESs in EET.

  16. Removal of 2,4-dichlorophenol using cyclodextrin-ionic liquid polymer as a macroporous material: characterization, adsorption isotherm, kinetic study, thermodynamics.

    PubMed

    Raoov, Muggundha; Mohamad, Sharifah; Abas, Mohd Radzi

    2013-12-15

    Cyclodextrin-ionic liquid polymer (βCD-BIMOTs-TDI) was firstly synthesized using functionalized β-Cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using toluene diisocyanate (TDI) linker to form insoluble βCD-BIMOTs-TDI. SEM characterization result shows that βCD-BIMOTs-TDI exhibits macropore size while the BET result shows low surface area (1.254 m(2)g(-1)). The unique properties of the ILs allow us to produce materials with different morphologies. The adsorption isotherm and kinetics of 2,4-dichlorophenol (2,4-DCP) onto βCD-BIMOTs-TDI is studied. Freundlich isotherm and pseudo-second order kinetics are found to be the best to represent the data for 2,4-DCP adsorption on the βCD-BIMOTs-TDI. The presence of macropores decreases the mass transfer resistance and increases the adsorption process by reducing the diffusion distance. The change in entropy (ΔS°) and heat of adsorption (ΔH°) for 2,4-DCP on βCD-BIMOTs-TDI were estimated as -55.99 J/Kmol and -18.10 J/mol, respectively. The negative value of Gibbs free energy (ΔG°) indicates that the adsorption process is thermodynamically feasible, spontaneous and chemically controlled. Finally, the interactions between the cavity of βCD-BIMOTs and 2,4-DCP are investigated and the results shows that the inclusion of the complex formation and π-π interaction are the main processes involved in the adsorption process.

  17. Analysis of water sorption isotherms of amorphous food materials by solution thermodynamics with relevance to glass transition: evaluation of plasticizing effect of water by the thermodynamic parameters.

    PubMed

    Shimazaki, Eriko; Tashiro, Akiko; Kumagai, Hitomi; Kumagai, Hitoshi

    2017-04-01

    Relation between the thermodynamic parameters obtained from water sorption isotherms and the degree of reduction in the glass transition temperature (Tg), accompanied by water sorption, was quantitatively studied. Two well-known glassy food materials namely, wheat gluten and maltodextrin were used as samples. The difference between the chemical potential of water in a solution and that of pure water ([Formula: see text]), the difference between the chemical potential of solid in a solution and that of a pure solid ([Formula: see text]), and the change in the integral Gibbs free energy ([Formula: see text]) were obtained by analyzing the water sorption isotherms using solution thermodynamics. The parameter [Formula: see text] correlated well with ΔTg (≡Tg - Tg0; where Tg0 is the glass transition temperature of dry material), which had been taken to be an index of plasticizing effect. This indicates that plasticizing effect of water on foods can be evaluated through the parameter [Formula: see text].

  18. Physically-Retrieving Cloud and Thermodynamic Parameters from Ultraspectral IR Measurements

    NASA Technical Reports Server (NTRS)

    Zhou, Daniel K.; Smith, William L., Sr.; Liu, Xu; Larar, Allen M.; Mango, Stephen A.; Huang, Hung-Lung

    2007-01-01

    A physical inversion scheme has been developed, dealing with cloudy as well as cloud-free radiance observed with ultraspectral infrared sounders, to simultaneously retrieve surface, atmospheric thermodynamic, and cloud microphysical parameters. A fast radiative transfer model, which applies to the clouded atmosphere, is used for atmospheric profile and cloud parameter retrieval. A one-dimensional (1-d) variational multi-variable inversion solution is used to improve an iterative background state defined by an eigenvector-regression-retrieval. The solution is iterated in order to account for non-linearity in the 1-d variational solution. It is shown that relatively accurate temperature and moisture retrievals can be achieved below optically thin clouds. For optically thick clouds, accurate temperature and moisture profiles down to cloud top level are obtained. For both optically thin and thick cloud situations, the cloud top height can be retrieved with relatively high accuracy (i.e., error < 1 km). NPOESS Airborne Sounder Testbed Interferometer (NAST-I) retrievals from the Atlantic-THORPEX Regional Campaign are compared with coincident observations obtained from dropsondes and the nadir-pointing Cloud Physics Lidar (CPL). This work was motivated by the need to obtain solutions for atmospheric soundings from infrared radiances observed for every individual field of view, regardless of cloud cover, from future ultraspectral geostationary satellite sounding instruments, such as the Geosynchronous Imaging Fourier Transform Spectrometer (GIFTS) and the Hyperspectral Environmental Suite (HES). However, this retrieval approach can also be applied to the ultraspectral sounding instruments to fly on Polar satellites, such as the Infrared Atmospheric Sounding Interferometer (IASI) on the European MetOp satellite, the Cross-track Infrared Sounder (CrIS) on the NPOESS Preparatory Project and the following NPOESS series of satellites.

  19. Relationship between nonlinear pressure-induced chemical shift changes and thermodynamic parameters.

    PubMed

    Beck Erlach, Markus; Koehler, Joerg; Moeser, Beate; Horinek, Dominik; Kremer, Werner; Kalbitzer, Hans Robert

    2014-05-29

    NMR chemical shift analysis is a powerful method to investigate local changes in the environment of the observed nuclear spin of a polypeptide that are induced by application of high hydrostatic pressure. Usually, in the fast exchange regime, the pressure dependence of chemical shifts is analyzed by a second order Taylor expansion providing the first- and second-order pressure coefficient B1 and B2. The coefficients then are interpreted in a qualitative manner. We show here that in a two-state model, the ratio of B2/B1 is related to thermodynamic parameters, namely the ratio of the difference of compressibility factors Δβ' and partial molar volumes ΔV. The analysis is applied to the random-coil model peptides Ac-Gly-Gly-Xxx-Ala-NH2, with Xxx being one of the 20 proteinogenic amino acids. The analysis gives an average Δβ'/ΔV ratio of 1.6 GPa(-1) provided the condition |ΔG(0)| ≪ 2RT holds for the difference of the Gibbs free energies (ΔG(0)) of the two states at the temperature (T0) and the pressure (p0). The amide proton and nitrogen B2/B1 of a given amino acid Xxx are strongly correlated, indicating that their pressure-dependent chemical shift changes are due to the same thermodynamic process. As a possible physical mechanism providing a two-state model, the hydrogen bonding of water with the corresponding amide protein was simulated for isoleucine in position Xxx. The obtained free energy could satisfy the relation |ΔG(0)| ≪ 2RT. The derived relation was applied to the β-amyloid peptide Aβ and the phosphocarrier protein HPr from S. carnosus. For the transition of state 1 to state 2' of Aβ, the derived relation of B2/B1 to Δβ'/ΔV can be confirmed experimentally. The HPr protein is characterized by substantially higher negative B2/B1 values than those found in the tetrapeptides with an average value of approximately -5.1 GPa(-1) (Δβ'/ΔV of 5.1 GPa(-1) provided |ΔG(0)| ≪ 2RT holds). Qualitatively, the B2/B1 ratio can be used to predict

  20. Model-based analysis of coupled equilibrium-kinetic processes: indirect kinetic studies of thermodynamic parameters using the dynamic data.

    PubMed

    Emami, Fereshteh; Maeder, Marcel; Abdollahi, Hamid

    2015-05-07

    Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-dependent degradation of chemical compounds and tautomerization kinetics in micellar solutions. Model-based global analysis with the possibility of calculating and embedding the equilibrium and kinetic parameters into the fitting algorithm has allowed the complete analysis of the complex reaction mechanisms. After the fitting process, the optimal equilibrium and kinetic parameters together with an estimate of their standard deviations have been obtained. This work opens up a promising new avenue for obtaining equilibrium constants through the kinetic data analysis for the kinetic reactions that involve equilibrium processes.

  1. Application of AlMCM-41 for competitive adsorption of methylene blue and rhodamine B: Thermodynamic and kinetic studies.

    PubMed

    Eftekhari, S; Habibi-Yangjeh, A; Sohrabnezhad, Sh

    2010-06-15

    AlMCM-41 was applied for adsorption of methylene blue (MB) and rhodamine B (RB) in single and binary component systems. In the single component systems, AlMCM-41 represents higher adsorption capacity for MB than RB with the maximal adsorption capacity of 2.08x10(-4) and 8.74x10(-5)mol/g at 25 degrees C for MB and RB, respectively. In the binary component system, MB and RB exhibit competitive adsorption onto the adsorbent. The adsorption is approximately reduced to 94 and 79% of single component adsorption systems for MB and RB (initial concentration of 8x10(-6)M) at 25 degrees C. In single and binary component systems, kinetic and adsorption isotherm studies demonstrate that the data are following pseudo-second-order kinetic model and Langmuir isotherm. Effect of solution pH on the adsorption in single and binary component systems was studied and the results were described by electrostatic interactions.

  2. Thermodynamical and structural insights of orange II adsorption by Mg RAlNO 3 layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Mustapha Bouhent, Mohamed; Derriche, Zoubir; Denoyel, Renaud; Prevot, Vanessa; Forano, Claude

    2011-05-01

    [Mg 1- x Al x(OH) 2][(NO 3) x, nH 2O] Layered Double Hydroxide (LDH) sorbents with variable Mg/Al molar ( R=(1- x)/ x) ratios were investigated for adsorption of azo dye, orange II (OII) at various pH and temperature conditions. Mg 2AlNO 3 displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg 2AlNO 3 at 40 °C. Adsorption isotherms have been fitted using the Langmuir model and free energy of adsorption (Δ G°), enthalpy (Δ H°) and entropy (Δ S°) were calculated. The experimental values for Δ G° in temperature range between 10 and 40 °C were found to be negative indicating that a spontaneous process occurred. Positive calculated enthalpy values, characteristic of an endothermic process were found. Characterization of solids (PXRD, FTIR, UV-vis, TGA/DTA, adsorption isotherm BET analysis, SEM and Zetametry) before and after adsorption showed that adsorption proceeds in two steps. First, adsorption occurs at the LDH surface, followed by intercalation via anion exchange.

  3. Adsorption removal of tannic acid from aqueous solution by polyaniline: Analysis of operating parameters and mechanism.

    PubMed

    Sun, Chencheng; Xiong, Bowen; Pan, Yang; Cui, Hao

    2017-02-01

    Polyaniline (PANI) prepared by chemical oxidation was studied for adsorption removal of tannic acid (TA) from aqueous solution. Batch adsorption studies were carried out under different adsorbent dosages, pH, ionic strength, initial TA concentration and coexisting anions. Solution pH had an important impact on TA adsorption onto PANI with optimal removal in the pH range of 8-11. TA adsorption on PANI at three ionic strength levels (0.02, 0.2 and 2molL(-1) NaCl) could be well described by Langmuir model (monolayer adsorption process) and the maximum adsorption capacity was 230, 223 and 1023mgg(-1), respectively. Kinetic data showed that TA adsorption on PANI fitted well with pseudo-second-order model (controlled by chemical process). Among the coexisting anions tested, PO4(3-) significantly inhibited TA adsorption due to the enhancement of repulsive interaction. Continuous flow adsorption studies indicated good flexibility and adaptability of the PANI adsorbent under different flow rates and influent TA concentrations. The mechanism controlling TA adsorption onto PANI under different operating conditions was analyzed with the combination of electrostatic interactions, hydrogen bonding, π-π interactions and Van der Waals interactions.

  4. Thermodynamic and chemical parameters of the exhaust effluents from the HARPOON booster motor

    NASA Technical Reports Server (NTRS)

    Stephens, J. B.; Goldford, A. I.

    1978-01-01

    The exhaust products from the Harpoon booster motors were analyzed using both thermodynamic analysis and finite-rate chemistry. The resulting constituents are presented together with a discussion of the techniques employed.

  5. Adsorption isotherms, kinetics and thermodynamic studies towards understanding the interaction between cross-linked alginate-guar gum matrix and chymotrypsin.

    PubMed

    Woitovich Valetti, Nadia; Picó, Guillermo

    2016-02-15

    The adsorption kinetics of chymotrypsin, a pancreatic serine protease, onto an alginate-gum guar matrix cross-linked with epichlorohydrin has been performed using a batch-adsorption technique. The effect of various experimental parameters such as pH, salt presence, contact time and temperature were investigated. The pseudo-first-order and pseudo-second-order kinetic models were used to describe the kinetic data which shows that the adsorption of the enzyme followed the pseudo-second-order rate expression. The Langmuir, Freundlich and Hill adsorption isotherm models were applied to describe the equilibrium isotherms, and the isotherm constants were determined. It was found that Hill model was more suitable for our data because the isotherm data showed a sigmoidal behavior with the free enzyme concentration increasing in equilibrium. At 8°C and at pH 5.0, 1g hydrate matrix adsorbed about 7mg of chymotrypsin. In the desorption process 80% of the biological activity of chymotrypsin was recovered under the condition of 50mM phosphate buffer, pH 7.00-500mM NaCl. When successive cycles of adsorption/washing/desorption were performed, it was observed that the matrix remained functional until the fourth cycle of repeated batch enzyme adsorption. These results are important in terms of diminishing of cost and waste generation.

  6. Equilibrium, kinetic and thermodynamic studies on the adsorption of 2-nitroaniline onto activated carbon prepared from cotton stalk fibre.

    PubMed

    Li, Kunquan; Zheng, Zheng; Huang, Xingfa; Zhao, Guohua; Feng, Jingwei; Zhang, Jibiao

    2009-07-15

    Activated carbon prepared from cotton stalk fibre has been utilized as an adsorbent for the removal of 2-nitroaniline from aqueous solutions. The influence of adsorbent mass, contact time and temperature on the adsorption was investigated by conducting a series of batch adsorption experiments. The equilibrium data at different temperatures were fitted with the Langmuir, Freundlich, Tempkin, Redlich-Peterson and Langmuir-Freundlich models. The Langmuir-Freundlich isotherm was found to best describe the experimental data. The adsorption amount increased with increasing temperature. The maximum adsorption capacity of 2-nitroaniline was found to be 383 mg/g for initial 2-nitroaniline concentration of 200mg/L at 45 degrees C. The kinetic rates were modeled by using the Lagergren-first-order, pseudo-second-order and Elovich models. The pseudo-second-order model was found to explain the adsorption kinetics most effectively. It was also found that the pore diffusion played an important role in the adsorption, and intraparticle diffusion was the rate-limiting step at the first 30 min for the temperatures of 25, 35 and 45 degrees C. FTIR and (13)C NMR study revealed that the amino and isocyanate groups present on the surface of the adsorbent were involved in chemical interaction with 2-nitroaniline. The negative change in free energy (Delta G degrees) and positive change in enthalpy (Delta H degrees) indicated that the adsorption was a spontaneous and endothermic process.

  7. Optimization of thiamethoxam adsorption parameters using multi-walled carbon nanotubes by means of fractional factorial design.

    PubMed

    Panić, Sanja; Rakić, Dušan; Guzsvány, Valéria; Kiss, Erne; Boskovic, Goran; Kónya, Zoltán; Kukovecz, Ákos

    2015-12-01

    The aim of this work was to evaluate significant factors affecting the thiamethoxam adsorption efficiency using oxidized multi-walled carbon nanotubes (MWCNTs) as adsorbents. Five factors (initial solution concentration of thiamethoxam in water, temperature, solution pH, MWCNTs weight and contact time) were investigated using 2V(5-1) fractional factorial design. The obtained linear model was statistically tested using analysis of variance (ANOVA) and the analysis of residuals was used to investigate the model validity. It was observed that the factors and their second-order interactions affecting the thiamethoxam removal can be divided into three groups: very important, moderately important and insignificant ones. The initial solution concentration was found to be the most influencing parameter on thiamethoxam adsorption from water. Optimization of the factors levels was carried out by minimizing those parameters which are usually critical in real life: the temperature (energy), contact time (money) and weight of MWCNTs (potential health hazard), in order to maximize the adsorbed amount of the pollutant. The results of maximal adsorbed thiamethoxam amount in both real and optimized experiments indicate that among minimized parameters the adsorption time is one that makes the largest difference. The results of this study indicate that fractional factorial design is very useful tool for screening the higher number of parameters and reducing the number of adsorption experiments.

  8. Activated carbon derived from carbon residue from biomass gasification and its application for dye adsorption: Kinetics, isotherms and thermodynamic studies.

    PubMed

    Maneerung, Thawatchai; Liew, Johan; Dai, Yanjun; Kawi, Sibudjing; Chong, Clive; Wang, Chi-Hwa

    2016-01-01

    In this work, activated carbon (AC) as an effective and low-cost adsorbent was successfully prepared from carbon residue (or char, one of the by-products from woody biomass gasification) via physical activation. The surface area of char was significantly increased from 172.24 to 776.46m(2)/g after steam activation at 900°C. The obtained activated carbons were then employed for the adsorption of dye (Rhodamine B) and it was found that activated carbon obtained from steam activation exhibited the highest adsorption capability, which is mainly attributed to the higher surface area and the abundance of hydroxyl (-OH) and carboxyl (-COOH) groups on the activated carbon surface. Moreover, it was also found that the adsorption capability significantly increased under the basic condition, which can be attributed to the increased electrostatic interaction between the deprotonated (negatively charged) activated carbon and dye molecules. Furthermore, the equilibrium data were fitted into different adsorption isotherms and found to fit well with Langmuir model (indicating that dye molecules form monolayer coverage on activated carbon) with a maximum monolayer adsorption capability of 189.83mg/g, whereas the adsorption kinetics followed the pseudo-second-order kinetics.

  9. Determination of adsorption isotherm parameters for minor whey proteins by gradient elution preparative liquid chromatography.

    PubMed

    Faraji, Naeimeh; Zhang, Yan; Ray, Ajay K

    2015-09-18

    Ion-Exchange Chromatography (IEC) techniques have been extensively investigated in protein purification processes, due to the more selective and milder separation steps. To date, existing studies of minor whey proteins fractionation in IEC have primarily been conducted as batch uptake studies, which require more experimental search space, time and materials. In this work, the selected resin's (SP Sepharose FF) equilibrium and dynamic binding capacity were first investigated. Next, adsorption of the pure binary mixture of lactoperoxidase and lactoferrin was studied to calibrate steric mass action (SMA) model using a simplified approach with data from single column experiments. The calibrated model was then verified by performing factorial-design based experiments for various process operating conditions assessing process performance on a larger bed height column. The model predicted results demonstrated a realistic agreement with the experiments providing reproducible column elution profile and reduced experimental work. Finally, whey protein isolate was used to evaluate model parameters in real conditions. Results obtained herein are suitable for future large scale applications.

  10. On equivalence of high temperature series expansion and coupling parameter series expansion in thermodynamic perturbation theory of fluids

    SciTech Connect

    Sai Venkata Ramana, A.

    2014-04-21

    The coupling parameter series expansion and the high temperature series expansion in the thermodynamic perturbation theory of fluids are shown to be equivalent if the interaction potential is pairwise additive. As a consequence, for the class of fluids with the potential having a hardcore repulsion, if the hard-sphere fluid is chosen as reference system, the terms of coupling parameter series expansion for radial distribution function, direct correlation function, and Helmholtz free energy follow a scaling law with temperature. The scaling law is confirmed by application to square-well fluids.

  11. Prediction of equilibrium parameters of adsorption of lead (II) ions onto diatomite

    NASA Astrophysics Data System (ADS)

    Salman, Taylan; Ardalı, Yüksel; Gamze Turan, N.

    2013-04-01

    Heavy metals from industrial wastewaters are one of the most important environmental issues to be solved today. Due to their toxicity and nonbiodegradable nature, heavy metals cause environmental and public health problems. Various techniques have been developed to remove heavy metals from aqueous solutions. These include chemical precipitation, reverse osmosis, ion Exchange and adsorption. Among them, adsorption is considered to be a particularly competitive and effective process for the removal of heavy metals from aqueous solutions. There is growing interest in using low cost, commercially available materials for the adsorption of heavy metals. Diatomite is a siliceous sedimentary rock having an amorphous form of silica (SiO2. nH2O) containing a small amount of microcrystalline material. It has unique combination of physical and chemical properties such as high porosity, high permeability, small particle size, large surface area, and low thermal conductivity. In addition, it is available in Turkey and in various locations around the world. Therefore, diatomite has been successfully used as adsorbent for the removal of heavy metals. The aim of the study is to investigate the adsorption properties of diatomite. The equilibrium adsorption data were applied to the Langmuir, Freundlich and Dubinin-Radushkevic (D-R) isotherm models. Adsorption experiments were performed under batch process, using Pb (II) initial concentration, pH of solution and contact time as variables. The results demonstrated that the adsorption of Pb (II) was strongly dependent on pH of solution. The effect of pH on adsorption of Pb(II) on diatomite was conducted by varying pH from 2 to 12 at 20 oC. In the pH range of 2.0-4.0, the adsorption percentage increases slightly as the pH increasing. At pH>4, the adsorption percentage decreases with increasing pH because hydrolysis product and the precipitation begin to play an important role in the sorption of Pb (II). At pH4, the maximum adsorption

  12. Kinetics and equilibrium adsorption studies of dimethylamine (DMA) onto ion-exchange resin.

    PubMed

    Hu, Qinhai; Meng, Yuanyuan; Sun, Tongxi; Mahmood, Qaisar; Wu, Donglei; Zhu, Jianhang; Lu, George

    2011-01-30

    The fine grained resin ZGSPC106 was used to adsorb dimethylamine (DMA) from aqueous solution in the present research. Batch experiments were performed to examine the effects of initial pH of solution and agitation time on the adsorption process. The thermodynamics and kinetics of adsorption were also analyzed. The maximum adsorption was found at natural pH of DMA solution and equilibrium could be attained within 12 min. The equilibrium adsorption data were conformed satisfactorily to the Langmuir equation. The evaluation based on Langmuir isotherm gave the maximal static saturated adsorption capacity of 138.89 mg/g at 293K. Various thermodynamic parameters such as free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) showed that the adsorption was spontaneous, endothermic and feasible. DMA adsorption on ZGSPC106 fitted well to the pseudo-second-order kinetic model. Furthermore, the adsorption mechanism was discussed by Fourier transform infrared spectroscopy (FT-IR) analysis.

  13. Application of activated carbon derived from scrap tires for adsorption of Rhodamine B.

    PubMed

    Li, Li; Liu, Shuangxi; Zhu, Tan

    2010-01-01

    Activated carbon derived from solid hazardous waste scrap tires was evaluated as a potential adsorbent for cationic dye removal. The adsorption process with respect to operating parameters was investigated to evaluate the adsorption characteristics of the activated pyrolytic tire char (APTC) for Rhodamine B (RhB). Systematic research including equilibrium, kinetics and thermodynamic studies was performed. The results showed that APTC was a potential adsorbent for RhB with a higher adsorption capacity than most adsorbents. Solution pH and temperature exert significant influence while ionic strength showed little effect on the adsorption process. The adsorption equilibrium data obey Langmuir isotherm and the kinetic data were well described by the pseudo second-order kinetic model. The adsorption process followed intra-particle diffusion model with more than one process affecting the adsorption process. Thermodynamic study confirmed that the adsorption was a physisorption process with spontaneous, endothermic and random characteristics.

  14. 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.

  15. 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.

  16. Thermodynamic parameters for mixtures of quartz under shock wave loading in views of the equilibrium model

    SciTech Connect

    Maevskii, K. K. Kinelovskii, S. A.

    2015-10-27

    The numerical results of modeling of shock wave loading of mixtures with the SiO{sub 2} component are presented. The TEC (thermodynamic equilibrium component) model is employed to describe the behavior of solid and porous multicomponent mixtures and alloys under shock wave loading. State equations of a Mie–Grüneisen type are used to describe the behavior of condensed phases, taking into account the temperature dependence of the Grüneisen coefficient, gas in pores is one of the components of the environment. The model is based on the assumption that all components of the mixture under shock-wave loading are in thermodynamic equilibrium. The calculation results are compared with the experimental data derived by various authors. The behavior of the mixture containing components with a phase transition under high dynamic loads is described.

  17. Effects of quantum gravity on the inflationary parameters and thermodynamics of the early universe

    NASA Astrophysics Data System (ADS)

    Tawfik, A.; Magdy, H.; Farag Ali, Ahmed

    2013-06-01

    The effects of generalized uncertainty principle (GUP) on the inflationary dynamics and the thermodynamics of the early universe are studied. Using the GUP approach, the tensorial and scalar density fluctuations in the inflation era are evaluated and compared with the standard case. We find a good agreement with the Wilkinson Microwave Anisotropy Probe data. Assuming that a quantum gas of scalar particles is confined within a thin layer near the apparent horizon of the Friedmann-Lemaitre-Robertson-Walker universe which satisfies the boundary condition, the number and entropy densities and the free energy arising form the quantum states are calculated using the GUP approach. A qualitative estimation for effects of the quantum gravity on all these thermodynamic quantities is introduced.

  18. Rapid determination of thermodynamic parameters from one-dimensional programmed-temperature gas chromatography for use in retention time prediction in comprehensive multidimensional chromatography.

    PubMed

    McGinitie, Teague M; Ebrahimi-Najafabadi, Heshmatollah; Harynuk, James J

    2014-01-17

    A new method for estimating the thermodynamic parameters of ΔH(T0), ΔS(T0), and ΔCP for use in thermodynamic modeling of GC×GC separations has been developed. The method is an alternative to the traditional isothermal separations required to fit a three-parameter thermodynamic model to retention data. Herein, a non-linear optimization technique is used to estimate the parameters from a series of temperature-programmed separations using the Nelder-Mead simplex algorithm. With this method, the time required to obtain estimates of thermodynamic parameters a series of analytes is significantly reduced. This new method allows for precise predictions of retention time with the average error being only 0.2s for 1D separations. Predictions for GC×GC separations were also in agreement with experimental measurements; having an average relative error of 0.37% for (1)tr and 2.1% for (2)tr.

  19. Nanoparticle-protein interactions: a thermodynamic and kinetic study of the adsorption of bovine serum albumin to gold nanoparticle surfaces.

    PubMed

    Boulos, Stefano P; Davis, Tyler A; Yang, Jie An; Lohse, Samuel E; Alkilany, Alaaldin M; Holland, Lisa A; Murphy, Catherine J

    2013-12-03

    Investigating the adsorption process of proteins on nanoparticle surfaces is essential to understand how to control the biological interactions of functionalized nanoparticles. In this work, a library of spherical and rod-shaped gold nanoparticles (GNPs) was used to evaluate the process of protein adsorption to their surfaces. The binding of a model protein (bovine serum albumin, BSA) to GNPs as a function of particle shape, size, and surface charge was investigated. Two independent comparative analytical methods were used to evaluate the adsorption process: steady-state fluorescence quenching titration and affinity capillary electrophoresis (ACE). Although under favorable electrostatic conditions kinetic analysis showed a faster adsorption of BSA to the surface of cationic GNPs, equilibrium binding constant determinations indicated that BSA has a comparable binding affinity to all of the GNPs tested, regardless of surface charge. BSA was even found to adsorb strongly to GNPs with a pegylated/neutral surface. However, these fluorescence titrations suffer from significant interference from the strong light absorption of the GNPs. The BSA-GNP equilibrium binding constants, as determined by the ACE method, were 10(5) times lower than values determined using spectroscopic titrations. While both analytical methods could be suitable to determine the binding constants for protein adsorption to NP surfaces, both methods have limitations that complicate the determination of protein-GNP binding constants. The optical properties of GNPs interfere with Ka determinations by static fluorescence quenching analysis. ACE, in contrast, suffers from material compatibility issues, as positively charged GNPs adhere to the walls of the capillary during analysis. Researchers seeking to determine equilibrium binding constants for protein-GNP interactions should therefore utilize as many orthogonal techniques as possible to study a protein-GNP system.

  20. TI-205 nuclear magnetic resonance determination of the thermodynamic parameters for the binding of monovalent cations to gramicidins A and C.

    PubMed Central

    Hinton, J F; Fernandez, J Q; Shungu, D C; Whaley, W L; Koeppe, R E; Millett, F S

    1988-01-01

    Thermodynamic parameters for the binding of the monovalent cations, Li+, Na+, K+, Rb+, Cs+, NH4+, TI+, and Ag+, to gramicidin A and for the binding of TI+ to gramicidin C, incorporated into lysophosphatidylcholine, have been determined using a combination of TI-205 nuclear magnetic resonance spectroscopy and competition binding. The thermodynamic parameters, enthalpy and entropy, are discussed in terms of a process involving the transfer of cations from an aqueous to amide environment. PMID:2462930

  1. Removal of Bisphenol A aqueous solution using surfactant-modified natural zeolite: Taguchi's experimental design, adsorption kinetic, equilibrium and thermodynamic study.

    PubMed

    Genç, Nevim; Kılıçoğlu, Ödül; Narci, Ali Oğuzhan

    2017-02-01

    In this study, surfactant-modified natural zeolite was used to remove Bisphenol A (BPA) from aqueous solutions. Kinetics, equilibrium and thermodynamics of BPA adsorption on the adsorbent surfaces were investigated. The experimental data were described with the Temkin isotherm and the pseudo-second- order kinetic model. Taguchi's robust design approach was used to optimize adsorption of BPA. Experimentation was planned as per Taguchi's L27 orthogonal array. Tests were conducted with different adsorbate amount, pH, time, initial concentration of BPA, temperature and agitation speed. The optimum levels of control factors for maximum total organic carbon removal were defined (adsorbate amount at 0.25 g, pH at 7, time at 30 min, initial concentration of BPA at 50 mg/L, temperature at 30°C and agitation speed at 200 rpm). The ANOVA analysis shown that the most effective control factor is adsorbent dosage; its contribution is 56.4%. Contribution of pH and mixing rate are 7.5% and 7.6%, respectively. A confirmation experiment was conducted to verify the feasibility and effectiveness of the optimal combination. The observed value of S/N (ηobs = 39) ratio is compared with that of the predicted value (ηopt = 48). The prediction error, that is, ηopt - ηobs = 9, is within CI value.

  2. Application of activated carbon derived from 'waste' bamboo culms for the adsorption of azo disperse dye: kinetic, equilibrium and thermodynamic studies.

    PubMed

    Wang, Lianggui

    2012-07-15

    The utilization of activated carbon derived from 'waste' bamboo culms (BAC) for the removal of Disperse Red 167 (DR167), an azo disperse dye, was investigated. Studies of the properties of the adsorbent, the effect of contact time, the initial pH of the solution, the initial concentration of the dye solution and temperature indicated that a low initial pH or concentration of dye solution favors the adsorption process; temperature exerts a greater effect on the removal of azo disperse red 167 dye from aqueous solution. Kinetic and isotherm data were fitted to five non-linear kinetic and nine non-linear isotherm equations. In addition, the fits were evaluated in terms of the non-linear coefficient, Chi-square test, Marquardt's percent standard deviation error function and small-sample-corrected Akaike Information Criterion (AICc) methodology. The results showed that the AICc analysis was the best statistical tool for analyzing the data, the intra-particle diffusion and the pseudo-first-order models played important roles in the controlling rate step, and the Temkin equation best described the BAC isotherm data. Furthermore, the thermodynamic analysis indicated that the adsorption was a spontaneous, endothermic, entropy-increasing and physical process. Two types of commercial activated carbon, Filtrasorb 400 and Filtrasorb (F400 and F300), were used as contrast adsorbents. The contrast experiments revealed that BAC exhibits similar properties to F400 and F300. The utilization of bamboo wastes as carbon precursors is feasible.

  3. Computation of adsorption parameters for the removal of dye from wastewater by microwave assisted sawdust: Theoretical and experimental analysis.

    PubMed

    S, Suganya; P, Senthil Kumar; A, Saravanan; P, Sundar Rajan; C, Ravikumar

    2017-03-01

    In this research, the microwave assistance has been employed for the preparation of novel material from agro/natural bio-waste i.e. sawdust, for the effective removal of methylene blue (MB) dye from aqueous solution. The characterization of the newly prepared microwave assisted sawdust (MASD) material was performed by using FTIR, SEM and XRD analyses. In order to obtain the maximum removal of MB dye from wastewater, the adsorption experimental parameters such as initial dye concentration, contact time, solution pH and adsorbent dosage were optimized by trial and error approach. The obtained experimental results were applied to the different theoretical models to predict the system behaviour. The optimum conditions for the maximum removal MB dye from aqueous solution for an initial MB dye concentration of 25mg/L was calculated as: adsorbent dose of 3g/L, contact time of 90min, solution pH of 7.0 and at the temperature of 30°C. Freundlich and pseudo-second order models was best obeyed with the studied experimental data. Langmuir maximum monolayer adsorption capacity of MASD for MB dye removal was calculated as 58.14mg of MB dye/g of MASD. Adsorption diffusion model stated that the present adsorption system was controlled by intraparticle diffusion model. The obtained results proposed that, novel MASD was considered to be an effective and low-cost adsorbent material for the removal of dye from wastewater.

  4. Moisture sorption isotherms and thermodynamic properties of Oak wood (Quercus robur and Quercus canariensis): optimization of the processing parameters

    NASA Astrophysics Data System (ADS)

    Bahar, Rim; Azzouz, Soufien; Remond, Romain; Ouertani, Sahbi; Elaieb, Mohamed Taher; El Cafci, Mohamed Afif

    2016-09-01

    The aim of this paper was to determine the moisture desorption isotherms and essentials thermodynamic properties of two Oak wood varieties. Desorption isotherms were measured using a static gravimetric method at 50, 60, 70 and 80 °C within the range of 5-90 % relative humidity. The equilibrium moisture content decreased with increasing temperature and decreased with decreasing relative humidity at a constant temperature. The `Thermodynamic' sorption equation was found to be the best for describing the experimental moisture sorption isotherms of woods within the range of temperature and water activity investigated. The Fiber saturation point, deduced from the `Thermodynamic' model parameters, depends on the temperature and varying from 22.6 to 54.4 (% kg water/kg dry matter). Isosteric heat of desorption and differential entropy were calculated by applying Clausius-Clapeyron equation to the desorption data fitted by the `Thermodynamic' model. The isosteric heat of desorption and the differential entropy decreased with increasing moisture content according to an exponential law equation and varying from 2.03 to 31.14 kJ/mol and from 73.98 to 4.34 J/(mol K), respectively. The linear relationship between differential enthalpy and entropy satisfied the enthalpy-entropy compensation theory. The sign of Gibbs free energy was found to be positive (+283 J/mol) and (+97 J/mol) for Quercus robur and Quercus canariensis, respectively. The isokinetic temperature was found to be greater than the harmonic temperature. Based on the enthalpy-entropy compensation theory, it could be concluded that the moisture desorption isotherm of Oak wood is a non-spontaneous and enthalpy-controlled process.

  5. Adsorption of methyl orange and salicylic acid on a nano-transition metal composite: Kinetics, thermodynamic and electrochemical studies.

    PubMed

    Arshadi, M; Mousavinia, F; Amiri, M J; Faraji, A R

    2016-12-01

    In this work synthesis of Mn-nanoparticles (MnNPs) supported on the Schiff base modified nano-sized SiO2Al2O3 mixed-oxides (Si/Al) and its implementation as an adsorbent for the removal of organic pollutions such as methyl orange (MO) and salicylic acid (SA) was investigated. Si/Al were functionalized by grafting Schiff base ligand and in the next step, MnNPs were prepared over the modified nano sol-gel Si/Al. Structures and adsorption characteristics of the obtained organometallic-modified SiO2/Al2O3 mixed oxide were studied by several methods such as elemental analysis, diffuse reflectance UV-vis spectroscopy, FT-IR spectroscopy, nitrogen adsorption/desorption, scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive X-ray (EDX), inductively coupled plasma (ICP-AES), Electron Paramagnetic Resonance (EPR), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). EPR data of the immobilized manganese ions resulted that the transition state of active sites in the nano-adsorbent are in the form of Mn(II) ions at the surface. The adsorption properties of heterogeneous Mn(II) ions showed that this nano-adsorbent has very good potential to remove MO and SA ions from aqueous solution. The removal efficiency of the SAPAS@MnNPs towards MO reached out to 89.3 and 29.1% and for SA approached to 54.6 and 18.9% at 150 and 500mg/dm(3) initial organic pollution concentrations, respectively. To investigate the adsorption kinetic of Mn(II) ions onto the nano-sized support, pseudo first and pseudo second order kinetics, and the Freundlich, Langmuir and Langmuir-Freundlich isotherm models have also been applied to the equilibrium adsorption data. The contact time to obtain equilibrium for maximum adsorption capacity was 45min. The adsorption process was spontaneous and endothermic in nature and it was well explained with pseudo-second-order kinetic model. No remarkable loss of removal capacity even after 8th times regeneration

  6. Performance of DFT+U method for prediction of structural and thermodynamic parameters of monazite-type ceramics.

    PubMed

    Blanca Romero, Ariadna; Kowalski, Piotr M; Beridze, George; Schlenz, Hartmut; Bosbach, Dirk

    2014-07-05

    We performed a density functional theory (DFT) study of the monazite-type ceramics using DFT+U method, where the Hubbard U parameters are derived ab initio, with the main goal in testing the predictive power of this computational method for modeling of f-electron materials that are of interest in nuclear waste management. We show that DFT+U approach with PBEsol as the exchange-correlation functional significantly improves description of structures and thermodynamic parameters of lanthanide-bearing oxides and monazites over commonly used standard DFT (PBE) approach. We found that it is essential to use the Hubbard U parameter derived for a given element and a given structure to reproduce the structural parameters of the measured materials. We obtained exceptionally good description of the structural parameters with U parameter derived using the linear response approach of Cococcioni and de Gironcoli (Phys. Rev. B 2005, 71, 035105). This shows that affordable methods, such as DFT+U with a clever choice of exchange-correlation functional and the Hubbard U parameter can lead to a good description of f-electron materials.

  7. [The heavy ion irradiation influence on the thermodynamic parameters of liquids in human body].

    PubMed

    Vlasenko, T S; Bulavin, L A; Sysoev, V M

    2014-01-01

    In this manuscript a theoretical model describing the influence of the heavy ion radiotherapy on the liquid matter in the human body is suggested. Based on the fundamental equations of Bogoliubov chain the effective temperatures in the case of constant particles fluent are found in the context of single component model. An existence of such temperatures allows the use of equilibrium thermodynamics formalism to nonequilibrium stationary state. The obtained results provide the possibility of predicting the liquid matter structural changes in the biological systems in the area influenced by the heavy ion beams.

  8. Co-modified MCM-41 as an effective adsorbent for levofloxacin removal from aqueous solution: optimization of process parameters, isotherm, and thermodynamic studies.

    PubMed

    Jin, Ting; Yuan, Wenhua; Xue, Yujie; Wei, Hong; Zhang, Chaoying; Li, Kebin

    2016-12-21

    thermodynamic functions were also determined. The negative ΔH (0) (-33.50 kJ mol(-1)) and ΔS (0) (-43.57 J mol(-1) K(-1)) suggested that the adsorption was an exothermic process accompanied by decreasing disorder. This study may indicate that 3% Co-MCM-41 is a promising adsorbent for removing emerging pollutants of LVF from water.

  9. 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.

  10. Interaction of the protein transduction domain of HIV-1 TAT with heparan sulfate: binding mechanism and thermodynamic parameters.

    PubMed

    Ziegler, André; Seelig, Joachim

    2004-01-01

    The positively charged protein transduction domain of the HIV-1 TAT protein (TAT-PTD; residues 47-57 of TAT) rapidly translocates across the plasma membrane of living cells. This property is exploited for the delivery of proteins, drugs, and genes into cells. The mechanism of this translocation is, however, not yet understood. Recent theories for translocation suggest binding of the protein transduction domain (PTD) to extracellular glycosaminoglycans as a possible mechanism. We have studied the binding equilibrium between TAT-PTD and three different glycosaminoglycans with high sensitivity isothermal titration calorimetry and provide the first quantitative thermodynamic description. The polysulfonated macromolecules were found to exhibit multiple identical binding sites for TAT-PTD with only small differences between the three species as far as the thermodynamic parameters are concerned. Heparan sulfate (HS, molecular weight, 14.2 +/- 2 kDa) has 6.3 +/- 1.0 independent binding sites for TAT-PTD which are characterized by a binding constant K0 = (6.0 +/- 0.6) x 10(5) M(-1) and a reaction enthalpy deltaHpep0 = -4.6 +/- 1.0 kcal/mol at 28 degrees C. The binding affinity, deltaGpep0, is determined to equal extent by enthalpic and entropic contributions. The HS-TAT-PTD complex formation entails a positive heat capacity change of deltaCp0 = +135 cal/mol peptide, which is characteristic of a charge neutralization reaction. This is in contrast to hydrophobic binding reactions which display a large negative heat capacity change. The stoichiometry of 6-7 TAT-PTD molecules per HS corresponds to an electric charge neutralization. Light scattering data demonstrate a maximum scattering intensity at this stoichiometric ratio, the intensity of which depends on the order of mixing of the two components. The data suggest cross-linking and/or aggregation of HS-TAT-PTD complexes. Two other glycosaminoglycans, namely heparin and chondroitin sulfate B, were also studied with isothermal

  11. Isotherm, kinetic, and thermodynamic studies on Hg(II) adsorption from aqueous solution by silica- multiwall carbon nanotubes.

    PubMed

    Saleh, Tawfik A

    2015-11-01

    Silica combined with 2% multiwall carbon nanotubes (SiO2-CNT) was synthesized and characterized. Its sorption efficacy was investigated for the Hg(II) removal from an aqueous solution. The effect of pH on the percentage removal by the prepared material was examined in the range from 3 to 7. The adsorption kinetics were well fitted by using a pseudo-second-order model at various initial Hg(II) concentrations with R (2) of >0.99. The experimental data were plotted using the interparticle diffusion model, which indicated that the interparticle diffusion is not the only rate-limiting step. The data is well described by the Freundlich isotherm equation. The activation energy (Ea) for adsorption was 12.7 kJ mol(-1), indicating the process is to be physisorption. Consistent with an endothermic process, an increase in the temperature resulted in increasing mercury removal with a ∆H(o) of 13.3 kJ/mol and a ∆S(o) 67.5 J/mol K. The experimental results demonstrate that the combining of silica and nanotubes is a promising alternative material, which can be used to remove the mercury from wastewaters.

  12. 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 .

  13. Combined Yamamoto approach for simultaneous estimation of adsorption isotherm and kinetic parameters in ion-exchange chromatography.

    PubMed

    Rüdt, Matthias; Gillet, Florian; Heege, Stefanie; Hitzler, Julian; Kalbfuss, Bernd; Guélat, Bertrand

    2015-09-25

    Application of model-based design is appealing to support the development of protein chromatography in the biopharmaceutical industry. However, the required efforts for parameter estimation are frequently perceived as time-consuming and expensive. In order to speed-up this work, a new parameter estimation approach for modelling ion-exchange chromatography in linear conditions was developed. It aims at reducing the time and protein demand for the model calibration. The method combines the estimation of kinetic and thermodynamic parameters based on the simultaneous variation of the gradient slope and the residence time in a set of five linear gradient elutions. The parameters are estimated from a Yamamoto plot and a gradient-adjusted Van Deemter plot. The combined approach increases the information extracted per experiment compared to the individual methods. As a proof of concept, the combined approach was successfully applied for a monoclonal antibody on a cation-exchanger and for a Fc-fusion protein on an anion-exchange resin. The individual parameter estimations for the mAb confirmed that the new approach maintained the accuracy of the usual Yamamoto and Van Deemter plots. In the second case, offline size-exclusion chromatography was performed in order to estimate the thermodynamic parameters of an impurity (high molecular weight species) simultaneously with the main product. Finally, the parameters obtained from the combined approach were used in a lumped kinetic model to simulate the chromatography runs. The simulated chromatograms obtained for a wide range of gradient lengths and residence times showed only small deviations compared to the experimental data.

  14. The influence of the carbon surface chemical composition on Dubinin-Astakhov equation parameters calculated from SF6 adsorption data-grand canonical Monte Carlo simulation.

    PubMed

    Furmaniak, Sylwester; Terzyk, Artur P; Gauden, Piotr A; Kowalczyk, Piotr; Harris, Peter J F

    2011-10-05

    Using grand canonical Monte Carlo simulation we show, for the first time, the influence of the carbon porosity and surface oxidation on the parameters of the Dubinin-Astakhov (DA) adsorption isotherm equation. We conclude that upon carbon surface oxidation, the adsorption decreases for all carbons studied. Moreover, the parameters of the DA model depend on the number of surface oxygen groups. That is why in the case of carbons containing surface polar groups, SF(6) adsorption isotherm data cannot be used for characterization of the porosity.

  15. The study of adsorption characteristics of electrospun polymer nanofibers for benzenes in water.

    PubMed

    Sun, Jing; Kang, Xue-Jun; Ma, Yu-Qin; Chen, Li-Qin; Wang, Yu; Gu, Zhong-Ze

    2011-01-01

    The adsorption properties of benzene, p-dichlorobenzene and nitrobenzene on polymer nanofibers were studied. Compared with polyacrylonitrile nanofiber, polystyrene (PS) nanofiber presented better adsorption performance. Langmuir and Freundlich adsorption models were used for the mathematical description of adsorption equilibria, and Freundlich isotherms fitted better. Kinetic studies showed that the adsorption of PS nanofiber followed pseudo first-order model. Various thermodynamic parameters such as standard free energy (delta G), enthalpy (delta H) and entropy (delta S) were calculated for predicting the adsorption nature of PS nanofiber for three benzenes, which indicated that the adsorption was spontaneous and a physical process. The regeneration efficiency maintains over 80% after five cycles of adsorption/desorption tests. It showed that PS nanofibers are promising candidates for adsorption and removal of aromatic hydrocarbons from water.

  16. Removal of Ni (II) from aqueous solutions by adsorption onto Ricinus communis seed shell activated carbons.

    PubMed

    Thamilarasu, P; Karunakaran, K

    2011-01-01

    The adsorption studies on the removal of Ni(II) from aqueous solution using Ricinus communis seed shells activated carbon and polypyrrole coated Ricinus communis seed shells activated carbon were carried out under various experimental conditions. The effects of various process parameters have been investigated by following the batch adsorption technique. Adsorption data was modeled with Freundlich, Langmuir and tempkin adsorption isotherms. Thermodynamics parameters such as DeltaH0, DeltaS0, and DeltaG0 were calculated indicating that the adsorption was spontaneous and endothermic nature. A mechanism, involving intra particle diffusion and surface adsorption, has been proposed for the adsorption of Ni(II) onto the adsorbent. Adsorbent used in this study is characterized by FTIR and SEM before and after the adsorption of metal ions.

  17. Adsorptive performance of un-calcined sodium exchanged and acid modified montmorillonite for Ni2+ removal: equilibrium, kinetics, thermodynamics and regeneration studies.

    PubMed

    Ijagbemi, Christianah Olakitan; Baek, Mi-Hwa; Kim, Dong-Su

    2010-02-15

    The efficacy of un-calcined sodium exchanged (Na-MMT) and acid modified montmorillonite (A-MMT) has been investigated for adsorptive removal of Ni(2+) from aqueous solution. Physico-chemical parameters such as pH, initial Ni(2+) concentration, and equilibrium contact time were studied in a series of batch adsorption experiments. The equilibrium time of contact for both adsorbents was about 230 min. The Redlich-Peterson model best described the equilibrium sorption of Ni(2+) onto Na-MMT and the Dubinin-Radushkevich model was the best model in predicting the equilibrium sorption of Ni(2+) onto A-MMT. The kinetics of Ni(2+) uptake by Na-MMT and A-MMT followed the pseudo second-order chemisorption mechanism. Sorptions of Ni(2+) onto Na-MMT and A-MMT were spontaneous and endothermic. Regeneration was tried for several cycles with a view to recover the adsorbed Ni(2+) and also to restore Na-MMT and A-MMT to their original states. The un-calcined Na-MMT and A-MMT have adsorptive potentials for removal of Ni(2+) from aqueous bodies.

  18. Stabilization of lysozyme by benzyl alcohol: surface tension and thermodynamic parameters.

    PubMed

    Goyal, Monu Kumari; Roy, Ipsita; Amin, Aeshna; Banerjee, Uttam Chand; Bansal, Arvind Kumar

    2010-10-01

    The aim of the study was to understand the effect of benzyl alcohol on biological activity, aggregation behavior, denaturant and heat-induced unfolding of lysozyme. Compatibility studies of lysozyme carried out with a number of anti-microbial preservatives, indicated benzyl alcohol to be the best suppressor of protein aggregation against heat stress. The effect of this preservative was checked at various pH values ranging from 4.0 to 9.0. In spite of reducing the thermal denaturation temperature (T(m)) at all pH values, benzyl alcohol had a stabilizing effect on lysozyme in terms of retaining the biological activity when the enzyme was incubated at 75 degrees C. The reduction in T(m) with increasing benzyl alcohol concentration was correlated with decreasing surface tension of surrounding medium. A detailed thermodynamic study of lysozyme in the presence of benzyl alcohol was carried out at pH 6.2. Change in Gibb's free energy of thermal unfolding at 25 degrees C was found to remain constant in the presence of benzyl alcohol, indicating no interaction of benzyl alcohol with the native protein at room temperature. Both the enthalpy and entropy change at mid point of thermal unfolding were found to increase in the presence of benzyl alcohol indicating the stabilization of partially unfolded state.

  19. Generalized statistical model for multicomponent adsorption equilibria on zeolites

    SciTech Connect

    Rota, R.; Gamba, G.; Paludetto, R.; Carra, S.; Morbidelli, M. )

    1988-05-01

    The statistical thermodynamic approach to multicomponent adsorption equilibria on zeolites has been extended to nonideal systems, through the correction of cross coefficients characterizing the interaction between unlike molecules. Estimation of the model parameters requires experimental binary equilibrium data. Comparisons with the classical model based on adsorbed solution theory are reported for three nonideal ternary systems. The two approaches provide comparable results in the simulation of binary and ternary adsorption equilibrium data at constant temperature and pressure.

  20. Preparation and properties of ion-imprinted hollow particles for the selective adsorption of silver ions.

    PubMed

    Hou, Hongbin; Yu, Demei; Hu, Guohe

    2015-02-03

    Four kinds of silver ion-imprinted particles (Ag-IIPs) with different morphologies were prepared by the surface ion-imprinting technology (SIIT) and were used for the selective removal and concentration of silver ions from wastewater. The favorable adsorptivity and selectivity of Ag-IIPs for Ag(+) were confirmed by a series of adsorption experiments at a suitable pH value. The adsorption mechanism was elucidated by analyzing the adsorption isotherms, adsorption thermodynamics, and adsorption kinetics systematically. The Ag(+) adsorption onto the Ag-IIPs was well-described by the Langmuir isotherm model, and it was likely to be a monolayer chemical adsorption. This conclusion was also confirmed by the thermodynamic parameters. Moreover, the adsorption kinetics indicated that the adsorption rate would be controlled jointly by the intraparticle diffusion and the inner surface adsorption process, and the latter process was generally associated with the formation and breaking of chemical bonds. Finally, the effects of different morphologies of the Ag-IIPs for Ag(+) adsorption were also investigated. In aqueous solution, the adsorptivity of the Ag(+) ion-imprinting single-hole hollow particles (Ag-IISHPs) for Ag(+) was highest (80.5 mg g(-1)) because of a specific morphology that features a single hole in the shell. In an oil-water mixture, Ag(+) in the water phase could be adsorbed efficiently by the Ag(+) ion-imprinting Janus hollow particles (Ag-IIJHPs), with emulsifiability originating from the Janus structure.

  1. Joint interaction of ethidium bromide and methylene blue with DNA. The effect of ionic strength on binding thermodynamic parameters.

    PubMed

    Vardevanyan, Poghos O; Antonyan, Ara P; Parsadanyan, Marine A; Torosyan, Margarita A; Karapetian, Armen T

    2016-07-01

    Large amount of data of experimental and theoretical studies have shown that ethidium bromide (EtBr) and methylene blue (MB) may bind to nucleic acids via three modes: intercalation between two adjacent base pairs, insertion into the plane between neighboring bases in the same strand (semi-intercalation), and outside binding with negatively charged backbone phosphate groups. The aim of the given research is to examine the behavior of these two ligands at both separate and joint DNA binding. The obtained experimental data show that the effect of simultaneous binding of EtBr and MB on double-stranded DNA has a non-additive effect of separate binding. The analyses of the melting thermodynamic parameters of DNA complexes with two bound ligands suggest competitive mechanism of interaction.

  2. On the 2D-transition, hysteresis and thermodynamic equilibrium of Kr adsorption on a graphite surface.

    PubMed

    Diao, Rui; Fan, Chunyan; Do, D D; Nicholson, D

    2015-12-15

    The adsorption and desorption of Kr on graphite at temperatures in the range 60-88K, was systematically investigated using a combination of several simulation techniques including: Grand Canonical Monte Carlo (GCMC), Canonical kinetic-Monte Carlo (C-kMC) and the Mid-Density Scheme (MDS). Particular emphasis was placed on the gas-solid, gas-liquid and liquid-solid 2D phase transitions. For temperatures below the bulk triple point, the transition from a 2D-liquid-like monolayer to a 2D-solid-like state is manifested as a sub-step in the isotherm. A further increase in the chemical potential leads to another rearrangement of the 2D-solid-like state from a disordered structure to an ordered structure that is signalled by (1) another sub-step in the monolayer region and (2) a spike in the plot of the isosteric heat versus density at loadings close to the dense monolayer coverage concentration. Whenever a 2D transition occurs in a grand canonical isotherm it is always associated with a hysteresis, a feature that is not widely recognised in the literature. We studied in details this hysteresis with the analysis of the canonical isotherm, obtained with C-kMC, which exhibits a van der Waals (vdW) type loop with a vertical segment in the middle. We complemented the hysteresis loop and the vdW curve with the analysis of the equilibrium transition obtained with the MDS, and found that the equilibrium transition coincides exactly with the vertical segment of the C-kMC isotherm, indicating the co-existence of two phases at equilibrium. We also analysed adsorption at higher layers and found that the 2D-coexistence is also observed, provided that the temperature is well below the triple point. Finally the 2D-critical temperatures were obtained for the first three layers and they are in good agreement with the experimental data in the literature.

  3. Effects of the adsorption of alkali metal oxides on the electronic, optical, and thermodynamic properties of the Mg12O12nanocage: a density functional theory study.

    PubMed

    Mohammadi Hesari, Asghar; Shamlouei, Hamid Reza; Raoof Toosi, Ali

    2016-08-01

    The effect of alkali metal oxides M n O (M = Li, Na, K; n = 2, 3, 4) on the geometric, electronic, and linear and nonlinear optical properties of the Mg12O12 nanocage was investigated by density-functional-based methods. According to the computational results, these alkali metal oxides are adsorbed on the Mg12O12 nanocage because this adsorption reduces its energy gap. The static first hyperpolarizability (β 0) of the nanocage is dramatically increased in the presence of the alkali metal oxides, with the greatest increase seen in the presence of the superalkalis (i.e., M3O; M = Li, Na, and K). The highest first hyperpolarizability (β 0 ≈ 600,000 a.u.) was calculated for K3O@Mg12O12, which was considerably more than that for Mg12O12. The thermodynamic properties and relative stabilities of these inorganic compounds are discussed. Graphical Abstract Optimized structure and DOS spectrum of K3O(e@Mg12O12).

  4. Multi-criteria assessment of energy conversion systems by means of thermodynamic, economic and environmental parameters

    NASA Astrophysics Data System (ADS)

    Becerra Lopez, Humberto Ruben

    2007-12-01

    High expansion of power demand is expected in the Upper Rio Grande region (El Paso, Hudspeth, Culberson, Jeff Davis, Presidio and Brewster counties) as a result of both electrical demand growth and decommissioning of installed capacity. On the supply side a notable deployment of renewable power technologies can be projected owing to the recent introduction of a new energy policy in Texas, which attempts to reach 10,000 installed-MWe of renewable capacity for 2025. Power generation fueled by natural-gas might consistently expand due to the encouraged use of this fuel. In this context the array of participating technologies can be optimized, which, within a sustainability framework, translates into a multidimensional problem. The solution to the problem is presented through this dissertation in two main parts. The first part solves the thermodynamic-environmental problem through developing a dynamic model to project maximum allowable expansion of technologies. Predetermined alternatives include diverse renewable energy technologies (wind turbine, photovoltaic conversion, hybrid solar thermal parabolic trough, and solid oxide fuel cells), a conventional fossil-fuel technology (natural gas combined-cycle), and a breakthrough fossil-fuel technology (solid oxide fuel cells). The analysis is based on the concept of cumulative exergy consumption, expanded to include abatement of emissions. A Gompertz sigmoid growth is assumed and constrained by both exergetic self-sustenance and regional energy resource availability. This part of the analysis assumes that power demand expansion is met by full deployment of alternative technologies backed up by conventional technology. Results show that through a proper allowance for exergy reinvestment the power demand expansion may be met largely by alternative technologies minimizing the primary resource depletion. The second part of the study makes use of the dynamic model to support a multi-objective optimization routine, where the

  5. Thermodynamic Characterization of Five Key Kinetic Parameters that Define Neuronal Nitric Oxide Synthase Catalysis

    PubMed Central

    Haque, Mohammad Mahfuzul; Tejero, Jesús; Bayachou, Mekki; Wang, Zhi-Qiang; Fadlalla, Mohammed; Stuehr, Dennis J.

    2013-01-01

    NO synthase (NOS) enzymes convert L-arginine to NO in two sequential reactions whose rates (kcat1 and kcat2) are both limited by the rate of ferric heme reduction (kr). An enzyme ferric heme-NO complex forms as an immediate product complex and then undergoes either dissociation (at a rate that we denote as kd) to release NO in a productive manner, or reduction (kr) to form a ferrous heme-NO complex (FeIINO) that must react with O2 (at a rate that we denote as kox) in a NO dioxygenase reaction that regenerates the ferric enzyme. The interplay of these five kinetic parameters (kcat1, kcat2, kr, kd, and kox) determine NOS specific activity, O2 concentration response, and pulsatile versus steady-state NO generation. Here we utilized stopped-flow spectroscopy and single catalytic turnover methods to characterize the individual temperature dependencies of the five kinetic parameters of rat neuronal NOS (nNOS). We then incorporated the measured kinetic values into computer simulations of the nNOS reaction using a global kinetic model to comprehensively model its temperature-dependent catalytic behaviors. Our results provide new mechanistic insights and also reveal that the different temperature dependencies of the five kinetic parameters significantly alter nNOS catalytic behaviors and NO release efficiency as a function of temperature. PMID:23789902

  6. Relative importance of column and adsorption parameters on the productivity in preparative liquid chromatography II: Investigation of separation systems with competitive Langmuir adsorption isotherms.

    PubMed

    Forssén, Patrik; Samuelsson, Jörgen; Fornstedt, Torgny

    2014-06-20

    In this study we investigated how the maximum productivity for commonly used, realistic separation system with a competitive Langmuir adsorption isotherm is affected by changes in column length, packing particle size, mobile phase viscosity, maximum allowed column pressure, column efficiency, sample concentration/solubility, selectivity, monolayer saturation capacity and retention factor of the first eluting compound. The study was performed by generating 1000 random separation systems whose optimal injection volume was determined, i.e., the injection volume that gives the largest achievable productivity. The relative changes in largest achievable productivity when one of the parameters above changes was then studied for each system and the productivity changes for all systems were presented as distributions. We found that it is almost always beneficial to use shorter columns with high pressure drops over the column and that the selectivity should be greater than 2. However, the sample concentration and column efficiency have very limited effect on the maximum productivity. The effect of packing particle size depends on the flow rate limiting factor. If the pumps maximum flow rate is the limiting factor use smaller packing, but if the pressure of the system is the limiting factor use larger packing up to about 40μm.

  7. Thermodynamic parameters of phase transitions of perfluoro-N-(4-methylcyclohexyl)piperidine

    NASA Astrophysics Data System (ADS)

    Druzhinina, A. I.; Efimova, A. A.; Varushchenko, R. M.; Chelovskaya, N. V.

    2007-12-01

    The heat capacity of perfluoro-N-(4-methylcyclohexyl)piperidine (PMCP) was measured by low-temperature adiabatic calorimetry. The purity of the substance ( N 1 = 99.66 mol %), triple point temperature ( T tp = 293.26 K), and enthalpy of fusion (Δfus H {m/°} = 8.32 kJ/mol) were determined. The enthalpy of vaporization was measured by calorimetry at 298.15 K (Δvap H {m/°}(298.15 K) = 56.56 kJ/mol). The temperature dependence of the saturated vapor pressure of PMCP over the pressure range 6.2-101.6 kPa was determined by comparative ebulliometry. The normal boiling point ( T n.b. = 460.74 K), ehthalpies of vaporization (at various temperatures), and critical parameters of PMCP were calculated. The calculated and experimental values of Δvap H {m/°}(298.15 K) agree to within measurement errors, which proves the reliability of these values and pT parameters used in calculations.

  8. Thermodynamics of Polymer Adsorption onto Nanoporous Silica and its Application in the Large Scale Purification of Poly(styrene)-block-Poly(alkyl methacrylate) Diblock Copolymers

    NASA Astrophysics Data System (ADS)

    Abdulahad, Asem Irfan

    As a result of unavoidable inconsistencies in their synthesis via controlled radical polymerization techniques, block copolymers inherently have distributions in chemical composition and molecular weight in each block that can have significant impact on their viscoelastic properties as well as their ability to self-assemble into ordered phases. High performance liquid chromatography is routinely utilized for determining the average molecular weight distribution that exist in synthetic polymers and is becoming increasingly popular for the fractionation and purification of chemically diverse complex polymer materials such as diblock copolymers. However, the inability of HPLC fractionation to provide meaningful quantities of purified complex polymers makes this method extremely inefficient and limits the ability to characterize purified fractions further. Overall, this dissertation work can be digested in two distinct parts. In the first part, high performance liquid chromatography was used as a tool for studying the influential parameters affecting the critical adsorption point of poly(styrene) and poly(alkyl methacrylate) homopolymers. The understanding gained in the first portion was depended on for the development of large scale fractionation procedures. In the second part, a chemically diverse variety of poly(alkyl methacrylate)-block-poly(styrene) diblock copolymers synthesized by atom transfer radical polymerization and anionic polymerization were purified by large scale adsorption-based fractionation procedures that included chromatographic filtration and the sequential adsorption/desorption of bulk diblock copolymer materials. The impact of diblock copolymer purification is addressed by comparing the molecular weight distribution, chemical composition distribution, viscoelastic properties, and small-angle X-ray scattering profiles.

  9. Bayesian calibration of thermodynamic parameters for geochemical speciation modeling of cementitious materials

    SciTech Connect

    Sarkar, S.; Kosson, D.S.; Mahadevan, S.; Meeussen, J.C.L.; Sloot, H. van der; Arnold, J.R.; Brown, K.G.

    2012-07-15

    Chemical equilibrium modeling of cementitious materials requires aqueous-solid equilibrium constants of the controlling mineral phases (K{sub sp}) and the available concentrations of primary components. Inherent randomness of the input and model parameters, experimental measurement error, the assumptions and approximations required for numerical simulation, and inadequate knowledge of the chemical process contribute to uncertainty in model prediction. A numerical simulation framework is developed in this paper to assess uncertainty in K{sub sp} values used in geochemical speciation models. A Bayesian statistical method is used in combination with an efficient, adaptive Metropolis sampling technique to develop probability density functions for K{sub sp} values. One set of leaching experimental observations is used for calibration and another set is used for comparison to evaluate the applicability of the approach. The estimated probability distributions of K{sub sp} values can be used in Monte Carlo simulation to assess uncertainty in the behavior of aqueous-solid partitioning of constituents in cement-based materials.

  10. Estimation of adsorption isotherm and mass transfer parameters in protein chromatography using artificial neural networks.

    PubMed

    Wang, Gang; Briskot, Till; Hahn, Tobias; Baumann, Pascal; Hubbuch, Jürgen

    2017-03-03

    Mechanistic modeling has been repeatedly successfully applied in process development and control of protein chromatography. For each combination of adsorbate and adsorbent, the mechanistic models have to be calibrated. Some of the model parameters, such as system characteristics, can be determined reliably by applying well-established experimental methods, whereas others cannot be measured directly. In common practice of protein chromatography modeling, these parameters are identified by applying time-consuming methods such as frontal analysis combined with gradient experiments, curve-fitting, or combined Yamamoto approach. For new components in the chromatographic system, these traditional calibration approaches require to be conducted repeatedly. In the presented work, a novel method for the calibration of mechanistic models based on artificial neural network (ANN) modeling was applied. An in silico screening of possible model parameter combinations was performed to generate learning material for the ANN model. Once the ANN model was trained to recognize chromatograms and to respond with the corresponding model parameter set, it was used to calibrate the mechanistic model from measured chromatograms. The ANN model's capability of parameter estimation was tested by predicting gradient elution chromatograms. The time-consuming model parameter estimation process itself could be reduced down to milliseconds. The functionality of the method was successfully demonstrated in a study with the calibration of the transport-dispersive model (TDM) and the stoichiometric displacement model (SDM) for a protein mixture.

  11. Equation of State and Heat Capacity of Water over a Wide Range of Thermodynamic Parameters (Uravnenie Sostoyaniya i Teploemkost Vody v Shirokom Diapazone Termodinamicheskikh Parametrov),

    DTIC Science & Technology

    The equation of state and heat capacity obtained from this work make it possible to determine the energy and pressure of water from its temperature...and density over a wide range of thermodynamic parameters, with an error of 15-20%. The equation of state and heat capacity also determine, in

  12. Adsorption-desorption studies of indigocarmine from industrial effluents by using deoiled mustard and its comparison with charcoal.

    PubMed

    Gupta, Vinod K; Jain, Rajeev; Malathi, S; Nayak, Arunima

    2010-08-15

    Deoiled mustard obtained from local oil mills has been used as an inexpensive and effective adsorbent for the removal of indigocarmine dye from industrial effluents. The influence of various factors on the adsorption capacity has been studied by batch experiments. The adsorption studies validate both Langmuir and Freundlich adsorption isotherms. Thermodynamic parameters such as DeltaG degrees, DeltaH degrees, and DeltaS degrees for the adsorption process were calculated, which indicated the feasibility of the adsorption process. Desorption profiles revealed that a significant portion (85%) could be desorbed from deoiled mustard by using 30% glycerol as eluting agent.

  13. Thermodynamic characteristics of adsorption of some 1,3,4-oxadiazoles and 1,2,4,5-tetrazines from water-acetonitrile solutions on phenyl-bonded silica gel

    NASA Astrophysics Data System (ADS)

    Saifutdinov, B. R.; Pimerzin, A. A.

    2013-04-01

    Standard differential molar changes of the Gibbs energy, enthalpy, and entropy during adsorption in the Henry region of 17 derivatives of 1,3,4-oxadiazole and 1,2,4,5-tetrazine from water-acetonitrile solutions with acetonitrile concentrations of 20 to 80 vol % and a variation step of 5 vol % on silica gel with grafted phenyl groups at column temperatures of 313.15 to 333.15 K with at a step of 5 K are determined under dynamic conditions by high-performance liquid chromatography. The dependence of the thermodynamic characteristics of adsorption on the molecular structure of adsorbates is discussed. It is established that the absolute values of the changes in the Gibbs energy and enthalpy during adsorption as a whole increase with increasing Van der Waals surface area and volume of the adsorbate molecules, while the adsorption of most 1,3,4-oxadiazoles is characterized by a dependence close to isentropic. It is assumed that the determining role in the change of entropy during adsorption from solutions is played by the polarity of the adsorbate molecule and the conformational flexibility of its substituents.

  14. Removal of ibuprofen, naproxen and carbamazepine in aqueous solution onto natural clay: equilibrium, kinetics, and thermodynamic study

    NASA Astrophysics Data System (ADS)

    Khazri, Hassen; Ghorbel-Abid, Ibtissem; Kalfat, Rafik; Trabelsi-Ayadi, Malika

    2016-04-01

    This study aimed to describe the adsorption of three pharmaceuticals compounds (ibuprofen, naproxen and carbamazepine) onto natural clay on the basis of equilibrium parameters such as a function of time, effect of pH, varying of the concentration and the temperature. Adsorption kinetic data were modeled using the Lagergren's first-order and the pseudo-second-order kinetic equations. The kinetic results of adsorption are described better using the pseudo-second order model. The isotherm results were tested in the Langmuir, Freundlich and Dubinin-Radushkevich models. The thermodynamic parameters obtained indicate that the adsorption of pharmaceuticals on the clay is a spontaneous and endothermic process.

  15. 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.

  16. Thermodynamic holography

    NASA Astrophysics Data System (ADS)

    Wei, Bo-Bo; Jiang, Zhan-Feng; Liu, Ren-Bao

    2015-10-01

    The holographic principle states that the information about a volume of a system is encoded on the boundary surface of the volume. Holography appears in many branches of physics, such as optics, electromagnetism, many-body physics, quantum gravity, and string theory. Here we show that holography is also an underlying principle in thermodynamics, a most important foundation of physics. The thermodynamics of a system is fully determined by its partition function. We prove that the partition function of a finite but arbitrarily large system is an analytic function on the complex plane of physical parameters, and therefore the partition function in a region on the complex plane is uniquely determined by its values along the boundary. The thermodynamic holography has applications in studying thermodynamics of nano-scale systems (such as molecule engines, nano-generators and macromolecules) and provides a new approach to many-body physics.

  17. Bayesian and Frequentist Methods for Estimating Joint Uncertainty of Freundlich Adsorption Isotherm Fitting Parameters

    EPA Science Inventory

    In this paper, we present methods for estimating Freundlich isotherm fitting parameters (K and N) and their joint uncertainty, which have been implemented into the freeware software platforms R and WinBUGS. These estimates were determined by both Frequentist and Bayesian analyse...

  18. Facile and rapid thermo-regulated biomineralization of gold by pullulan and study of its thermodynamic parameters.

    PubMed

    Choudhury, Anirban Roy; Malhotra, Ankit; Bhattacharjee, Paramita; Prasad, G S

    2014-06-15

    A novel method for the production of gold nanoparticles (AuNPs) using pullulan as reducing and stabilizing agent has been developed. Quasi-spherical shaped AuNPs in the range of 50-100 nm were produced at three different temperature regimes 80°C, 90°C and 100°C as characterized using UV-vis spectrophotometer, TEM and DLS. Study of reaction kinetics and thermodynamic parameters indicated that the reaction between pullulan and chloroauric acid for AuNPs formation followed first order reaction kinetics and higher temperature was favorable for the synthesis of smaller sized AuNPs. FT-IR data analyses, provided an insight towards the mechanism of gold nanoparticle formation which suggested that, the free CH2OH groups of pullulan molecule were oxidized to carboxylate ions resulted in formation of AuNPs whereas the basic skeletal structure of pullulan remained unaltered. This study may open up new avenues for synthesis of tailor made biogenic AuNPs with possible application in biomedical field.

  19. Optimization of laccase fermentation and evaluation of kinetic and thermodynamic parameters of a partially purified laccase produced by Daedalea flavida.

    PubMed

    Singha, Siddhartha; Panda, Tapobrata

    2015-01-01

    Studies on laccase production by Daedalea flavida were carried out in static and low-speed shake cultures. The enzyme production was reduced drastically at a high speed of shaking. Optimal production conditions are necessary to assess the quality of laccase suitable for a specific application. Thus, the production of laccase was optimized by the application of response surface methodology. Laccase production was 8-fold and 7.5-fold more in static and low-speed shake conditions, respectively, in an optimal medium composition than in an unoptimized medium. Laccase obtained using the optimal culture medium of D. flavida was tested for its stability at different temperatures and pH conditions. The partially purified enzyme was most stable at 30°C and pH 5. The half-life of laccase is 87 min at 60°C and at pH 6. The kinetic and thermodynamic parameters were evaluated for the inactivation of the partially purified laccase. The entropy change of inactivation of the enzyme is least at pH 4.

  20. Vibrational and electronic investigations, thermodynamic parameters, HOMO and LUMO analysis on crotonaldehyde by ab initio and DFT methods

    NASA Astrophysics Data System (ADS)

    Jayaprakash, A.; Arjunan, V.; Jose, Sujin P.; Mohan, S.

    2011-12-01

    The energy, geometrical parameters and vibrational wavenumbers of crotonaldehyde were calculated by using ab initio and B3LYP with 6-31G(d,p) and 6-311G(d,p) basis sets. The FT-IR and FT-Raman spectra for liquid state crotonaldehyde have been recorded in the region 3400-400 cm -1 and 3400-100 cm -1, respectively and compared with the theoretical spectrographs constructed from the scaled harmonic vibrational frequencies calculated at HF and DFT levels. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. Detailed interpretations on vibrational modes have been made on the observed and theoretical spectra and PED for each mode was also reported more precisely. HOMO and LUMO energy levels are constructed and the corresponding theoretical frontier energy gaps are calculated to realise the charge transfer occurring in the molecule. The thermodynamic properties of the title compound have been calculated at different temperatures and the results reveals the standard heat capacities ( C0p), standard entropies ( S0) and standard enthalpy changes (Δ H0) increases with rise in temperature.

  1. Equation of state and thermodynamic Gruneisen parameter of monoclinic 1,1-diamino-2,2-dinitroethylene

    DOE PAGES

    Zhang, Jianzhong; Velisavljevic, Nenad; Zhu, Jinlong; ...

    2016-08-05

    In situ synchrotron x-ray diffraction experiments were conducted on 1,1-diamino-2,2 dinitroethylene (FOX-7) at pressures up to 6.8 GPa and temperatures up to 485 K. Within th resolution of the present diffraction data, our results do not reveal evidence for a pressureinduce structural phase transition near 2 GPa, previously observed in several vibrationa spectroscopy experiments. Based on unit-cell volume measurements, the least-squares fi using the third-order Birch–Murnaghan equation of state (EOS) yields K0 = 12.6 ± 1.4 GP and K0 = 11.3 ± 2.1 for the α-phase of FOX-7, which are in good agreement with recentl reported values for the deuteratedmore » sample, indicating that the effect of hydrogen–deuteriu substitution on the compressibility of FOX-7 is negligibly small. A thermal EOS is als obtained for the α-phase of FOX-7, including pressure dependence of thermal expansivity (∂α/∂P)T = -7.0 ± 2.0 × 10-5 K-1 GPa-1, and temperature derivative of the bulk modulus (∂KT/∂T)P = -1.1 × 10-2 GPa K-1. From these EOS parameters, we calculate heat capacit at constant volume (CV) and thermodynamic Grüneisen parameter (γTH) as a function o temperature. At ambient conditions, the calculated γTH is 1.055, which is in good agreemen with the value (1.09) previously obtained from density functional theory (DFT). The obtaine CV, however, is 13% larger than that calculated from the first-principles calculations indicating that the dispersion correction in the DFT calculations may need to be furthe improved for describing intermolecular interactions of molecular crystals.« less

  2. Studies on Thorium Adsorption Characteristics upon Activated Titanium Hydroxide Prepared from Rosetta Ilmenite Concentrate

    SciTech Connect

    Gado, M Zaki, S

    2016-01-01

    The titanium hydroxide prepared from Rosetta ilmenite concentrate has been applied for Th (IV) adsorption from its acid aqueous solutions. The prepared hydroxide is first characterized by both Fourier transform infrared (FT-IR) spectrum and thermogravimetric analysis. The relevant factors affecting the adsorption process have been studied. The obtained equilibrium data fits well with the Langmuir isotherm rather than Freundlich isotherm, while the adsorption kinetic data follow the pseudo-second order model. The different thermodynamic parameters have also been calculated and indicate that the adsorption process is spontaneous.

  3. Enhanced adsorptive removal of toxic dyes using SiO2 nanofibers

    NASA Astrophysics Data System (ADS)

    Batool, S. S.; Imran, Z.; Hassan, Safia; Rasool, Kamran; Ahmad, Mushtaq; Rafiq, M. A.

    2016-05-01

    Electrospinning method was used to synthesize porous SiO2 nanofibers. The adsorption of Methyl Orange and Safranin O by porous SiO2 nanofibers was carried out by varying the parameters such as pH, contact time, adsorbent dose, dye concentration, and temperature. Equilibrium adsorption data followed Langmuir isotherms. Kinetic adsorption followed second-order rate kinetics model. The maximum adsorption capacity for Methyl Orange and Safranin O was found to be 730.9 mg/g and 960.4 mg/g, respectively. Acidic pH was favorable for the adsorption of Methyl Orange while basic pH was favorable for the adsorptions of Safranin O. Modeling study suggested the major mode of adsorption, while thermodynamic study showed the endothermic reactions. This effort has pronounced impact on environmental applications of SiO2 nanofibers as auspicious adsorbent nanofibers for organic material from aqueous solution.

  4. 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.

  5. Adsorption potential of mercury(II) from aqueous solutions onto Romanian peat moss.

    PubMed

    Bulgariu, Laura; Ratoi, Mioara; Bulgariu, Dumitru; Macoveanu, Matei

    2009-06-01

    This study was undertaken to evaluate the adsorption potential of Romanian peat moss for the removal of mercury(II) from aqueous solutions. The batch system experiments carried out showed that this natural material was effective in removing mercury(II). The analysis of FT-IR spectra indicated that the mechanism involved in the adsorption can be mainly attributed to the binding of mercury(II) with the carboxylic groups of Romanian peat moss. Adsorption equilibrium approached within 60 min. The adsorption data fitted well the Langmuir isotherm model. The maximum adsorption capacity (qmax) was 98.94 mg g(-1). Pseudo-second-order kinetic model was applicable to the adsorption data. The thermodynamic parameters indicate that the adsorption process was spontaneous as the Gibbs free energy values were found to be negative (between -17.58 and -27.25 kJ mol(-1)) at the temperature range of 6-54 degrees C.

  6. 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.

  7. Impact of biochar produced from post-harvest residue on the adsorption behavior of diesel oil on loess soil.

    PubMed

    Jiang, Yu Feng; Sun, Hang; Yves, Uwamungu J; Li, Hong; Hu, Xue Fei

    2016-02-01

    The primary objective of this study was to investigate the effect of biochar, produced from wheat residue at different temperatures, on the adsorption of diesel oil by loess soil. Kinetic and equilibrium data were processed to understand the adsorption mechanism of diesel by biochar-affected loess soil; dynamic and thermodynamic adsorption experiments were conducted to characterize this adsorption. The surface features and chemical structure of biochar, modified at varying pyrolytic temperatures, were investigated using surface scanning electron microscopy and Fourier transform infrared analysis. The kinetic data showed that the adsorption of diesel oil onto loess soil could be described by a pseudo-second-order kinetic model, with the rate-controlling step being intraparticle diffusion. However, in the presence of biochar, boundary layer control and intraparticle diffusion were both involved in the adsorption. Besides, the adsorption equilibrium data were well described by the Freundlich isothermal model. The saturated adsorption capacity weakened as temperature increased, suggesting a spontaneous exothermic process. Thermodynamic parameter analysis showed that adsorption was mainly a physical process and was enhanced by chemical adsorption. The adsorption capacity of loess soil for diesel oil was weakened with increasing pH. The biochar produced by pyrolytic wheat residue increased the adsorption behavior of petroleum pollutants in loess soil.

  8. 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.

  9. 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

  10. Equation of state and thermodynamic Grüneisen parameter of monoclinic 1,1-diamino-2,2-dinitroethylene

    NASA Astrophysics Data System (ADS)

    Zhang, Jianzhong; Velisavljevic, Nenad; Zhu, Jinlong; Wang, Liping

    2016-10-01

    In situ synchrotron x-ray diffraction experiments were conducted on 1,1-diamino-2,2-dinitroethylene (FOX-7) at pressures up to 6.8 GPa and temperatures up to 485 K. Within the resolution of the present diffraction data, our results do not reveal evidence for a pressure-induced structural phase transition near 2 GPa, previously observed in several vibrational spectroscopy experiments. Based on unit-cell volume measurements, the least-squares fit using the third-order Birch-Murnaghan equation of state (EOS) yields K 0  =  12.6  ±  1.4 GPa and K0\\prime   =  11.3  ±  2.1 for the α-phase of FOX-7, which are in good agreement with recently reported values for the deuterated sample, indicating that the effect of hydrogen-deuterium substitution on the compressibility of FOX-7 is negligibly small. A thermal EOS is also obtained for the α-phase of FOX-7, including pressure dependence of thermal expansivity, (∂α/∂P)T  =  -7.0  ±  2.0  ×  10-5 K-1 GPa-1, and temperature derivative of the bulk modulus, (∂K T/∂T)P  =  -1.1  ×  10-2 GPa K-1. From these EOS parameters, we calculate heat capacity at constant volume (C V) and thermodynamic Grüneisen parameter (γ TH) as a function of temperature. At ambient conditions, the calculated γ TH is 1.055, which is in good agreement with the value (1.09) previously obtained from density functional theory (DFT). The obtained C V, however, is 13% larger than that calculated from the first-principles calculations, indicating that the dispersion correction in the DFT calculations may need to be further improved for describing intermolecular interactions of molecular crystals.

  11. Equation of state and thermodynamic Grüneisen parameter of monoclinic 1,1-diamino-2,2-dinitroethylene.

    PubMed

    Zhang, Jianzhong; Velisavljevic, Nenad; Zhu, Jinlong; Wang, Liping

    2016-10-05

    In situ synchrotron x-ray diffraction experiments were conducted on 1,1-diamino-2,2-dinitroethylene (FOX-7) at pressures up to 6.8 GPa and temperatures up to 485 K. Within the resolution of the present diffraction data, our results do not reveal evidence for a pressure-induced structural phase transition near 2 GPa, previously observed in several vibrational spectroscopy experiments. Based on unit-cell volume measurements, the least-squares fit using the third-order Birch-Murnaghan equation of state (EOS) yields K 0  =  12.6  ±  1.4 GPa and [Formula: see text]  =  11.3  ±  2.1 for the α-phase of FOX-7, which are in good agreement with recently reported values for the deuterated sample, indicating that the effect of hydrogen-deuterium substitution on the compressibility of FOX-7 is negligibly small. A thermal EOS is also obtained for the α-phase of FOX-7, including pressure dependence of thermal expansivity, (∂α/∂P)T  =  -7.0  ±  2.0  ×  10(-5) K(-1) GPa(-1), and temperature derivative of the bulk modulus, (∂K T/∂T)P  =  -1.1  ×  10(-2) GPa K(-1). From these EOS parameters, we calculate heat capacity at constant volume (C V) and thermodynamic Grüneisen parameter (γ TH) as a function of temperature. At ambient conditions, the calculated γ TH is 1.055, which is in good agreement with the value (1.09) previously obtained from density functional theory (DFT). The obtained C V, however, is 13% larger than that calculated from the first-principles calculations, indicating that the dispersion correction in the DFT calculations may need to be further improved for describing intermolecular interactions of molecular crystals.

  12. Equation of state and thermodynamic Gruneisen parameter of monoclinic 1,1-diamino-2,2-dinitroethylene

    SciTech Connect

    Zhang, Jianzhong; Velisavljevic, Nenad; Zhu, Jinlong; Wang, Liping

    2016-08-05

    In situ synchrotron x-ray diffraction experiments were conducted on 1,1-diamino-2,2 dinitroethylene (FOX-7) at pressures up to 6.8 GPa and temperatures up to 485 K. Within th resolution of the present diffraction data, our results do not reveal evidence for a pressureinduce structural phase transition near 2 GPa, previously observed in several vibrationa spectroscopy experiments. Based on unit-cell volume measurements, the least-squares fi using the third-order Birch–Murnaghan equation of state (EOS) yields K0 = 12.6 ± 1.4 GP and K0 = 11.3 ± 2.1 for the α-phase of FOX-7, which are in good agreement with recentl reported values for the deuterated sample, indicating that the effect of hydrogen–deuteriu substitution on the compressibility of FOX-7 is negligibly small. A thermal EOS is als obtained for the α-phase of FOX-7, including pressure dependence of thermal expansivity (∂α/∂P)T = -7.0 ± 2.0 × 10-5 K-1 GPa-1, and temperature derivative of the bulk modulus (∂KT/∂T)P = -1.1 × 10-2 GPa K-1. From these EOS parameters, we calculate heat capacit at constant volume (CV) and thermodynamic Grüneisen parameterTH) as a function o temperature. At ambient conditions, the calculated γTH is 1.055, which is in good agreemen with the value (1.09) previously obtained from density functional theory (DFT). The obtaine CV, however, is 13% larger than that calculated from the first-principles calculations indicating that the dispersion correction in the DFT calculations may need to be furthe improved for describing intermolecular interactions of molecular crystals.

  13. 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

    butene products. Theoretical calculations suggest that this effect originates from the adsorption of isobutene at channel intersections, indicating that dehydrogenation occurs with stronger preference for these locations than does cracking. In order to analyze the effects of zeolite structure on monomolecular alkane activation reactions, it is necessary to separate the contributions of the adsorption and reaction steps to observed kinetics. A method is developed in Chapter 3 for obtaining the enthalpy and entropy changes for adsorption of n-alkanes from the gas phase onto Bronsted protons (DeltaH ads·H+ and DeltaSads·H+) using configurational-bias Monte Carlo (CBMC) simulations. In Chapter 4 the effects of zeolite structural confinement on n-butane cracking and dehydrogenation are characterized for zeolites that differ predominately in the size and abundance of cavities. Values of DeltaHads·H+ and DeltaSads·H+ are obtained from CBMC simulations and used to extract intrinsic rates and activation parameters. As DeltaS ads·H+ (a proxy for confinement) becomes more negative, DeltaH ‡int and DeltaS‡int decrease for terminal cracking and dehydrogenation when the channel topology (e.g., straight, sinusoidal) is fixed. This observation, as well as positive values for DeltaS‡int, indicate that the transition states for these reactions resemble the products. Finally, in Chapter 5 the influence of channel and cage topology on n-alkane adsorption are characterized for zeolites and zeotypes with one-dimensional pore systems. When cages are not present, DeltaHads·H+ and DeltaSads·H+ at fixed pore-limiting diameter (PLD; the diameter of the largest sphere that can traverse the pores) decrease in magnitude as the ratio of the smallest to largest channel diameter decreases and the pore become less circular. The higher entropy of alkanes in non-circular pores is attributed to greater freedom of movement and can cause the free energy to be lower in these environments relative

  14. A New General Method for Simultaneous Fitting of Temperature- and Concentration-Dependence of Reaction Rates Yields Kinetic and Thermodynamic Parameters for HIV Reverse Transcriptase Specificity.

    PubMed

    Li, An; Ziehr, Jessica L; Johnson, Kenneth A

    2017-03-02

    Recent studies have demonstrated the dominant role of induced-fit in enzyme specificity of HIV reverse transcriptase and many other enzymes. However, relevant thermodynamic parameters are lacking and equilibrium thermodynamic methods are of no avail because the key parameters can only determined by kinetic measurement. By modifying KinTek Explorer software, we present a new general method for globally fitting data collected over a range of substrate concentrations and temperatures and apply it to HIV reverse transcriptase. Fluorescence stopped-flow methods were used to record the kinetics of enzyme conformational changes that monitor nucleotide binding and incorporation. The nucleotide concentration dependence was measured at temperatures ranging from 5 to 37C and the raw data were fit globally to derive a single set of rate constants at 37C and a set of activation enthalpy terms to account for the kinetics at all other temperatures. This comprehensive analysis afforded thermodynamic parameters for nucleotide binding (Kd, ΔG, ΔH, ΔS at 37C), and kinetic parameters for enzyme conformational changes and chemistry (rate constants and activation enthalpy). Comparisons between wild-type enzyme and a mutant resistant to nucleoside analogs used to treat HIV infections reveal that the ground state binding is weaker and the activation enthalpy for the conformational change step is significantly larger for the mutant. Further studies to explore the structural underpinnings of the observed thermodynamics and kinetics of the conformational change step may help to design better analogs to treat HIV infections and other diseases. Our new method is generally applicable to enzyme and chemical kinetics.

  15. Effects of surface treatment and process parameters on immobilization of recombinant yeast cells by adsorption to fibrous matrices.

    PubMed

    Kilonzo, Peter; Margaritis, Argyrios; Bergougnou, Maurice

    2011-02-01

    The effects of surface properties of Saccharomyces cerevisiae strains 468/pGAC9 and 468 on adhesion to polyethyleneimine (PEI) and/glutaraldehyde (GA) pre-treated cotton (CT), polyester (PE), polyester+cotton (PECT), nylon (NL), polyurethane foam (PUF), and cellulose re-enforced polyurethane (CPU) fibers were investigated. Process parameters (circulation velocity, pH, ionic strength, media composition and surfactants) were also examined. 80%, 90%, and 35% of the cells were adsorbed onto unmodified CT, PUF, and PE, respectively. PEI-GA pre-treated CT and alkali treated PE yielded 25% and 60% cell adhesion, respectively. Adsorption rate (K(a)) ranged from 0.06 to 0.17 for CT and 0.06-0.16 for PE at varied pH. Adhesion increased by 15% in the presence of ethanol, low pH and ionic strength, and decreased by 23% in the presence of yeast extract and glucose. Shear flow and 1% Triton X-100 detached 62% and 36% nonviable cells from PE and CT, respectively, suggesting that cell immobilization in fibrous-bed bioreactors can be controlled to optimize cell density for long-term stability.

  16. 2, 4 dichlorophenol (2, 4-DCP) sorption from aqueous solution using granular activated carbon and polymeric adsorbents and studies on effect of temperature on activated carbon adsorption.

    PubMed

    Ghatbandhe, A S; Yenkie, M K N

    2008-04-01

    Adsorption equilibrium, kinetics and thermodynamics of 2,4-dichlorophenol (2,4-DCP), one of the most commonly used chlorophenol, onto bituminous coal based Filtrasorb-400 grade granular activated carbon, were studied in aqueous solution in a batch system with respect to temperature. Uptake capacity of activated carbon found to increase with temperature. Langmuir isotherm models were applied to experimental equilibrium data of 2, 4-DCP adsorption and competitive studies with respect to XAD resin were carried out. Equilibrium data fitted very well to the Langmuir equilibrium model. Adsorbent monolayer capacity 'Q0, Langmuir constant 'b' and adsorption rate constant 'k(a)' were evaluated at different temperatures for activated carbon adsorption. This data was then used to calculate the energy of activation of adsorption and also the thermodynamic parameters, namely the free energy of adsorption, deltaG0, enthalpy of adsorption, deltaH0 and the entropy of adsorption deltaS0. The obtained results showed that the monolayer capacity increases with the increase in temperatures. The obtained values of thermodynamic parameters showed that adsorption of 2,4 DCP is an endothermic process. Synthetic resin was not found efficient to adsorb 2,4 DCP compared to activated carbon. The order of adsorption efficiencies of three resins used in the study found as XAD7HP > XAD4 > XAD1180.

  17. Protein selective adsorption properties of a polyethylene terephtalate artificial ligament grafted with poly(sodium styrene sulfonate) (polyNaSS): correlation with physicochemical parameters of proteins.

    PubMed

    Lessim, S; Oughlis, S; Lataillade, J J; Migonney, V; Changotade, S; Lutomski, D; Poirier, F

    2015-12-14

    Immediately after surgical placement of biomaterials, a first step consists in the adsorption of proteins from the biological environment on the artificial surfaces. Because the composition of the adsorbed protein layer modulates the cell response to the implanted material, researchers in the biomaterials field have focused on coating proteins or peptides onto surfaces to improve cell response and therefore the long-term compatibility of the implant. However, some materials used in tissue engineering, mainly synthetic polymers, are too hydrophobic to allow the optimal adsorption of proteins and have to be first submitted to physical or chemical treatments. In our laboratory, we have demonstrated that grafting of poly(sodium styrene sulfonate) (polyNaSS) onto biomaterials can strongly modulate the protein adsorption and the cellular response compared to unmodified surfaces. In this study, we used a liquid chromatography strategy coupled to proteomics to evaluate the adsorptive properties of a polyethylene terephtalate (PET) artificial ligament grafted with polyNaSS, and to identify and analyse proteins adsorbed on PET fibers. Results obtained with platelet rich plasma (PRP) proteins demonstrated that grafting significantly increases the protein adsorption of the PET and also selectively modulates the adsorption of proteins on PET fibers. Finally, regarding physicochemical parameters calculated from the amino acid sequence of identified proteins, we found that the aliphatic index is highly correlated with the selective adsorption of proteins onto the polyNaSS/PET surface. Therefore, the proteomic approach complemented with physicochemical property evaluation could provide a powerful tool for the elaboration of new biomaterials based on protein layer deposition.

  18. Complexation of DTPA and EDTA with Cd(2+): stability constants and thermodynamic parameters at the soil-water interface.

    PubMed

    Karak, Tanmoy; Paul, Ranjit Kumar; Das, Dilip Kumar; Boruah, Romesh Kumar

    2016-12-01

    Two alkaline soils collected from the surface horizon (0-15 cm) of two agricultural fields Lakshmikantapur (LKP; 22° 06' 03″ N and 88° 18' 19″ E) and Diamond Harbour (DHB; 22° 11' N and 88° 14' E) of West Bengal, India were studied to observe the stability of cadmium (Cd) chelate complexes with diethylenetriaminepentaacetatic acid (DTPA) and ethylenediaminetetraacetic acid (EDTA), removing organic matter (OM). The objective of the present study is "determination of the stability constants and the thermodynamic parameters of Cd-DTPA and Cd-EDTA complexes at different pH and temperatures at the soil-water interface". Complex formation of soil Cd with DTPA and EDTA at the soil-water interface was studied under different ligand-to-metal ratios, pHs and temperatures. Apparent conditional stability constants (log k´) were calculated from the concentrations of Cd chelates and free Cd(2+), estimated by solid phase extraction with an ion exchanger. Standard Gibbs energy (ΔG°), standard enthalpy (ΔH°) and standard entropy (ΔS°) of formation were calculated at three different temperatures. The higher stability constants of Cd-DTPA than Cd-EDTA indicated longer persistence of Cd-DTPA at the soil solution interface than Cd-EDTA complex. Increase of ΔG°, ΔH° and ΔS° with progress of temperature revealed that Cd-complex formation was facilitated by temperature. Highly negative ΔG° and positive ΔH° for Cd-complex formation indicated the reaction spontaneous and exothermic. In general, both ligands complexed high percentages of cadmium signalling their role in enhancing remobilization of Cd present in soil and preventing exchange of contaminated Cd from external source with soil mineral matrix; these phenomena may greatly reduce hazard for environment and human health. The result of this study support that DTPA increases solubility and more persistence of Cd in acidic soils within the range of temperature and mole fraction (MF = moles of Cd(2+)

  19. Adsorption of methylene blue onto sonicated sepiolite from aqueous solutions.

    PubMed

    Küncek, Ilknur; Sener, Savaş

    2010-01-01

    The aim of the present study is to enhance the methylene blue (MB) adsorption of sepiolite by ultrasonic treatment. The natural sepiolite was pretreated by sonication to improve the surface characteristics and enhance the dye uptake capacity. Sonication process resulted in a significant increase in the specific surface area (SSA) of sepiolite. The FTIR spectrum of the sonicated sepiolite indicates that the tetrahedral sheet is probably distorted after sonication process. The effect of various parameters such as sonication, pH, initial dye concentration and temperature on dye adsorption has been investigated. The adsorbed amount of MB on sepiolite increased after sonication as well as with increasing pH and temperature. The experimental data were evaluated by applying the pseudo-first- and second-order, and the intraparticle diffusion adsorption kinetic models. Adsorption process of MB onto sepiolite followed the pseudo-second-order rate expression. The experimental data were analyzed by Langmuir and Freundlich isotherms, and found that the isotherm data were reasonably well correlated by Langmuir isotherm. Maximum monolayer adsorption capacity of sepiolite for MB increased from 79.37 to 128.21 mg/g after the sonication. Various thermodynamic parameters, such as Delta G(0), Delta H(0) and DeltaS(0) were calculated. The thermodynamics of MB/sepiolite system indicated spontaneous and endothermic nature of the process. Adsorption measurements showed that the process was very fast and physical in nature.

  20. Proton magnetic relaxation study of the thermodynamic characteristics of water adsorbed by cellulose fibers

    NASA Astrophysics Data System (ADS)

    Grunin, Yu. B.; Grunin, L. Yu.; Masas, D. S.; Talantsev, V. I.; Sheveleva, N. N.

    2016-11-01

    The possibility of determining the thermodynamic parameters that characterize the sorption properties of cellulose and the state of water associated with its fibers is demonstrated using modern concepts of the structure of this vegetable polymer and methods based on theories of adsorption and NMR relaxation in heterogeneous systems.

  1. 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.

  2. The influence of the potassium promoter on the kinetics and thermodynamics of CO adsorption on a bulk iron catalyst applied in Fischer-Tropsch synthesis: a quantitative adsorption calorimetry, temperature-programmed desorption, and surface hydrogenation study.

    PubMed

    Graf, Barbara; Muhler, Martin

    2011-03-07

    The adsorption of carbon monoxide on an either unpromoted or potassium-promoted bulk iron catalyst was investigated at 303 K and 613 K by means of pulse chemisorption, adsorption calorimetry, temperature-programmed desorption and temperature-programmed surface reaction in hydrogen. CO was found to adsorb mainly molecularly in the absence of H(2) at 303 K, whereas the presence of H(2) induced CO dissociation at higher temperatures leading to the formation of CH(4) and H(2)O. The hydrogenation of atomic oxygen chemisorbed on metallic iron was found to occur faster than the hydrogenation of atomically adsorbed carbon. At 613 K CO adsorption occurred only dissociatively followed by recombinative CO(2) formation according to C(ads) + 2O(ads)→ CO(2(g)). The presence of the potassium promoter on the catalyst surface led to an increasing strength of the Fe-C bond both at 303 K and 613 K: the initial differential heat of molecular CO adsorption on the pure iron catalyst at 303 K amounted to 102 kJ mol(-1), whereas it increased to 110 kJ mol(-1) on the potassium-promoted sample, and the initial differential heat of dissociative CO adsorption on the unpromoted iron catalyst at 613 K amounted to 165 kJ mol(-1), which increased to 225 kJ mol(-1) in the presence of potassium. The calorimetric CO adsorption experiments also reveal a change of the energetic distribution of the CO adsorption sites present on the catalyst surface induced by the potassium promoter, which was found to block a fraction of the CO adsorption sites.

  3. A key parameter on the adsorption of diluted aniline solutions with activated carbons: The surface oxygen content.

    PubMed

    Pardo, Beatrice; Ferrer, Nabí; Sempere, Julià; Gonzalez-Olmos, Rafael

    2016-11-01

    A total of 11 different commercial activated carbons (AC) with well characterized textural properties and oxygen surface content were tested as adsorbents for the removal of aniline as a target water pollutant. The maximum adsorption capacity of aniline for the studied AC was from 138.9 to 257.9 mg g(-1) at 296.15 K and it was observed to be strongly related to the textural properties of the AC, mainly with the BET surface area and the micropore volume. It was not observed any influence of the oxygen surface content of the AC on the maximum adsorption capacity. However, it was found that at low aniline aqueous concentration, the presence of oxygen surface groups plays a dominant role during the adsorption. A high concentration of oxygen surface groups, mainly carboxylic and phenolic groups, decreases the aniline adsorption regardless of the surface area of the AC.

  4. 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

  5. Restricted primitive model for electrolyte solutions in slit-like pores with grafted chains: microscopic structure, thermodynamics of adsorption, and electric properties from a density functional approach.

    PubMed

    Pizio, Orest; Sokołowski, Stefan

    2013-05-28

    We apply a density functional theory to describe properties of a restricted primitive model of an ionic fluid in slit-like pores. The pore walls are modified by grafted chains. The chains are built of uncharged or charged segments. We study the influence of modification of the pore walls on the structure, adsorption, ion selectivity, and the electric double layer capacitance of ionic fluid under confinement. The brush built of uncharged segments acts as a collection of obstacles in the walls vicinity. Consequently, separation of charges requires higher voltages, in comparison to the models without brushes. At high grafting densities the formation of crowding-type structure is inhibited. The double layer structure becomes more complex in various aspects, if the brushes are built of charged segments. In particular, the evolution of the brush height with the bulk fluid density and with the charge on the walls depends on the length of the blocks of charged spheres as well as on the distribution of charged species along chains. We also investigated how the dependence of the double layer capacitance on the electrostatic potential (or on the charge on the walls) changes with grafting density, the chain length, distribution of charges along the chain, the bulk fluid density, and, finally, with the pore width. The shape of the electric double layer capacitance vs. voltage changes from a camel-like to bell-like shape, if the bulk fluid density changes from low to moderate and high. If the bulk density is appropriately chosen, it is possible to alter the shape of this curve from the double hump to single hump by changing the grafting density. Moreover, in narrow pores one can observe the capacitance curve with even three humps for a certain set of parameters describing brush. This behavior illustrates how strong the influence of brushes on the electric double layer properties can be, particularly for ionic fluids in narrow pores.

  6. Simulation of antimony adsorption on nano-zero valent iron and kaolinite and analyzing the influencing parameters.

    PubMed

    Saeidnia, Setareh; Asadollahfardi, Gholamreza; Darban, Ahmad Khodadadi; Mohseni, Mehdi

    2016-01-01

    Antimony is one of the most toxic pollutants in industrial and mineral wastewaters threatening the life of humans and other creatures. We simulated the adsorption of antimony in the presence of nano-zero valent iron (nZVI) adsorbent, on kaolinite and in the presence of nZVI coated on kaolinite from mineral wastewater using VISUAL MINTEQ 3.1 software. Our aim was to determine the factors affecting the adsorption of antimony by applying simulation. The simulation was performed using an adsorption model of a diffuse layer model. The results of the simulation indicated that the nZVI concentration, initial concentrations of antimony and pH factor are effective on the adsorption of antimony. In the conducted stimulation, the optimum pH was 2-5 and the highest adsorption occurred in an acidic state. With increasing initial concentrations of antimony in the simulation, we concluded that nZVI had absorbed various concentrations above 90% and, by increasing the concentration of nZVI, antimony adsorption rate increased. The increased surface area of nZVI and the expansion of more interchangeable surfaces available for reaction with antimony ions causes more antimony ions to be adsorbed. In all cases, the coefficient of determination between the laboratory results and the model predictions that was obtained was more than 0.9.

  7. 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.

  8. Influence of the pore structure and surface chemical properties of activated carbon on the adsorption of mercury from aqueous solutions.

    PubMed

    Lu, Xincheng; Jiang, Jianchun; Sun, Kang; Wang, Jinbiao; Zhang, Yanping

    2014-01-15

    Reactivation and chemical modification were used to obtain modified activated carbons with different pore structure and surface chemical properties. The samples were characterized by nitrogen absorption-desorption, Fourier transform infrared spectroscopy and the Bothem method. Using mercury chloride as the target pollutant, the Hg(2+) adsorption ability of samples was investigated. The results show that the Hg(2+) adsorption capacity of samples increased significantly with increases in micropores and acidic functional groups and that the adsorption process was exothermic. Different models and thermodynamic parameters were evaluated to establish the mechanisms. It was concluded that the adsorption occurred through a monolayer mechanism by a two-speed process involving both rapid adsorption and slow adsorption. The adsorption rate was determined by chemical reaction.

  9. Removal of Reactofix Navy Blue 2 GFN from aqueous solutions using adsorption techniques.

    PubMed

    Gupta, Vinod Kumar; Jain, Rajeev; Varshney, Shaily; Saini, Vipin Kumar

    2007-03-15

    The wheat husk, an agricultural by-product, has been activated and used as an adsorbent for the adsorption of Reactofix Navy Blue 2 GFN from aqueous solution. In this work, adsorption of Reactofix Navy Blue 2 GFN on wheat husk and charcoal has been studied by using batch studies. The equilibrium adsorption level was determined to be a function of the solution pH, adsorbent dosage, dye concentration and contact time. The equilibrium adsorption capacities of wheat husk and charcoal for dye removal were obtained using Freundlich and Langmuir isotherms. Thermodynamic parameters such as the free energies, enthalpies and entropies of adsorption were also evaluated. Adsorption process is considered suitable for removing color, COD from waste water.

  10. Nano-Bio Interactions of Porous and Nonporous Silica Nanoparticles of Varied Surface Chemistry: A Structural, Kinetic, and Thermodynamic Study of Protein Adsorption from RPMI Culture Medium.

    PubMed

    Lehman, Sean E; Mudunkotuwa, Imali A; Grassian, Vicki H; Larsen, Sarah C

    2016-01-26

    Understanding complex chemical changes that take place at nano-bio interfaces is of great concern for being able to sustainably implement nanomaterials in key applications such as drug delivery, imaging, and environmental remediation. Typical in vitro assays use cell viability as a proxy to understanding nanotoxicity but often neglect how the nanomaterial surface can be altered by adsorption of solution-phase components in the medium. Protein coronas form on the nanomaterial surface when incubated in proteinaceous solutions. Herein, we apply a broad array of techniques to characterize and quantify protein corona formation on silica nanoparticle surfaces. The porosity and surface chemistry of the silica nanoparticles have been systematically varied. Using spectroscopic tools such as FTIR and circular dichroism, structural changes and kinetic processes involved in protein adsorption were evaluated. Additionally, by implementing thermogravimetric analysis, quantitative protein adsorption measurements allowed for the direct comparison between samples. Taken together, these measurements enabled the extraction of useful chemical information on protein binding onto nanoparticles in solution. Overall, we demonstrate that small alkylamines can increase protein adsorption and that even large polymeric molecules such as poly(ethylene glycol) (PEG) cannot prevent protein adsorption in these systems. The implications of these results as they relate to further understanding nano-bio interactions are discussed.

  11. The thermodynamics of simple biomembrane mimetic systems

    PubMed Central

    Raudino, Antonio; Sarpietro, Maria Grazia; Pannuzzo, Martina

    2011-01-01

    Insight into the forces governing a system is essential for understanding its behavior and function. Thermodynamic investigations provide a wealth of information that is not, or is hardly, available from other methods. This article reviews thermodynamic approaches and assays to measure collective properties such as heat adsorption / emission and volume variations. These methods can be successfully applied to the study of lipid vesicles (liposomes) and biological membranes. With respect to instrumentation, differential scanning calorimetry, pressure perturbation calorimetry, isothermal titration calorimetry, dilatometry, and acoustic techniques aimed at measuring the isothermal and adiabatic processes, two- and three-dimensional compressibilities are considered. Applications of these techniques to lipid systems include the measurement of different thermodynamic parameters and a detailed characterization of thermotropic, barotropic, and lyotropic phase behavior. The membrane binding and / or partitioning of solutes (proteins, peptides, drugs, surfactants, ions, etc.) can also be quantified and modeled. Many thermodynamic assays are available for studying the effect of proteins and other additives on membranes, characterizing non-ideal mixing, domain formation, bilayer stability, curvature strain, permeability, solubilization, and fusion. Studies of membrane proteins in lipid environments elucidate lipid–protein interactions in membranes. Finally, a plethora of relaxation phenomena toward equilibrium thermodynamic structures can be also investigated. The systems are described in terms of enthalpic and entropic forces, equilibrium constants, heat capacities, partial volume changes, volume and area compressibility, and so on, also shedding light on the stability of the structures and the molecular origin and mechanism of the structural changes. PMID:21430953

  12. Microwave-assisted preparation and adsorption performance of activated carbon from biodiesel industry solid reside: influence of operational parameters.

    PubMed

    Foo, K Y; Hameed, B H

    2012-01-01

    Preparation of activated carbon has been attempted using KOH as activating agent by microwave heating from biodiesel industry solid residue, oil palm empty fruit bunch (EFBAC). The significance of chemical impregnation ratio (IR), microwave power and activation time on the properties of activated carbon were investigated. The optimum condition has been identified at the IR of 1.0, microwave power of 600 W and activation time of 7 min. EFBAC was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and nitrogen adsorption isotherm. The surface chemistry was examined by zeta potential measurement, determination of surface acidity/basicity, while the adsorptive property was quantified using methylene blue as dye model compound. The optimum conditions resulted in activated carbon with a monolayer adsorption capacity of 395.30 mg/g and carbon yield of 73.78%, while the BET surface area and total pore volume were corresponding to 1372 m2/g and 0.76 cm3/g, respectively.

  13. Characterizations of strontium(II) and barium(II) adsorption from aqueous solutions using dolomite powder.

    PubMed

    Ghaemi, Ahad; Torab-Mostaedi, Meisam; Ghannadi-Maragheh, Mohammad

    2011-06-15

    In this research, adsorption technique was applied for strontium and barium removal from aqueous solution using dolomite powder. The process has been investigated as a function of pH, contact time, temperature and adsorbate concentration. The experimental data was analyzed using equilibrium isotherm, kinetic and thermodynamic models. The isotherm data was well described by Langmuir isotherm model. The maximum adsorption capacity was found to be 1.172 and 3.958 mg/g for Sr(II) and Ba(II) from the Langmuir isotherm model at 293 K, respectively. The kinetic data was tested using first and pseudo-second order models. The results indicated that adsorption fitted well with the pseudo-second order kinetic model. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) were also determined using the equilibrium constant value obtained at different temperatures. The results showed that the adsorption for both ions was feasible and exothermic.

  14. Calculation of the aqueous thermodynamic properties of citric acid cycle intermediates and precursors and the estimation of high temperature and pressure equation of state parameters.

    PubMed

    Dalla-Betta, Peter; Schulte, Mitchell

    2009-06-22

    The citric acid cycle (CAC) is the central pathway of energy transfer for many organisms, and understanding the origin of this pathway may provide insight into the origins of metabolism. In order to assess the thermodynamics of this key pathway for microorganisms that inhabit a wide variety of environments, especially those found in high temperature environments, we have calculated the properties and parameters for the revised Helgeson-Kirkham-Flowers equation of state for the major components of the CAC. While a significant amount of data is not available for many of the constituents of this fundamental pathway, methods exist that allow estimation of these missing data.

  15. 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.

  16. Superposition-additive approach in the description of thermodynamic parameters of formation and clusterization of substituted alkanes at the air/water interface.

    PubMed

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Vasylyev, A O; Vollhardt, D; Fainerman, V B; Aksenenko, E V; Miller, R

    2012-12-01

    The superposition-additive approach developed previously was shown to be applicable for the calculations of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole polarizability, molecular diamagnetic susceptibility, π-electronic ring currents, etc. In the present work, the applicability of this approach for the calculation of the thermodynamic parameters of formation and clusterization at the water/air interface of alkanes, fatty alcohols, thioalcohols, amines, nitriles, fatty acids (C(n)H(2n+1)X, X is the functional group) and cis-unsaturated carboxylic acids (C(n)H(2n-1)COOH) is studied. Using the proposed approach the thermodynamic quantities determined agree well with the available data, either calculated using the semiempirical (PM3) quantum chemical method, or obtained in experiments. In particular, for enthalpy and Gibbs' energy of the formation of substituted alkane monomers from the elementary substances, and their absolute entropy, the standard deviations of the values calculated according to the superposition-additive scheme with the mutual superimposition domain C(n-2)H(2n-4) (n is the number of carbon atoms in the alkyl chain) from the results of PM3 calculations for alkanes, alcohols, thioalcohols, amines, fatty acids, nitriles and cis-unsaturated carboxylic acids are respectively: 0.05, 0.004, 2.87, 0.02, 0.01, 0.77, and 0.01 kJ/mol for enthalpy; 2.32, 5.26, 4.49, 0.53, 1.22, 1.02, 5.30 J/(molK) for absolute entropy; 0.69, 1.56, 3.82, 0.15, 0.37, 0.69, 1.58 kJ/mol for Gibbs' energy, whereas the deviations from the experimental data are: 0.52, 5.75, 1.40, 1.00, 4.86 kJ/mol; 0.52, 0.63, 1.40, 6.11, 2.21 J/(molK); 2.52, 5.76, 1.58, 1.78, 4.86 kJ/mol, respectively (for nitriles and cis-unsaturated carboxylic acids experimental data are not available). The proposed approach provides also quite accurate estimates of enthalpy, entropy and Gibbs' energy of boiling and melting, critical temperatures and standard heat

  17. [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.

  18. 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.

  19. 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.

  20. 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.

  1. Lysozyme immobilization via adsorption process using sulphonic acid functionalized silane grafted copolymer.

    PubMed

    Anirudhan, T S; Rauf, Tharun A

    2013-07-01

    A unique silane based adsorbent material, [stearyl alcohol (SA)-grafted-epichlorohydrin (E)]-grafted-aminoproypyl silanetriol (APST) was synthesized and functionalized with sulphonyl groups via sulphonation process [(SA-g-E)-g-APST/SO3H]. The adsorbent material characterization was done by FTIR, XRD, and TGA analysis. Immobilization of protein Lysozyme (LYZ) using batch adsorption process was carried out for studying the protein-particle interaction. The most suitable pH for maximum adsorption was found to be 7.0. Pseudo-second-order kinetic model was found to be the best fit and the adsorption equilibrium was attained within 3h. Studies on diffusion parameters explained that the adsorption mechanism was controlled by film diffusion mode. The adsorption process was then evaluated using the various isotherm models and the Sips isotherm model proved to be the best fit with a maximum adsorption capacity of 37.68 mg/g. The isotherm favorability of the adsorption process was calculated by calculating the separation factor (R(L)) and the values confirmed the favorability of the adsorption process. Studies on adsorption percentage with respect to temperature and thermodynamic studies revealed that adsorption process is exothermic, spontaneous with maximum entropy. Batch adsorption/desorption studies in acidic medium, for over six cycles showed the repeatability and regeneration capability of the adsorbent material (SA-g-E)-g-APST/SO3H.

  2. Investigation kinetics mechanisms of adsorption malachite green onto activated carbon.

    PubMed

    Onal, Y; Akmil-Başar, C; Sarici-Ozdemir, C

    2007-07-19

    Lignite was used to prepare activated carbon (T3K618) by chemical activation with KOH. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by t-plot based on N2 adsorption isotherm. BET surface area of activated carbon is determined as 1000 m2/g. Adsorption capacity of malachite green (MG) onto T3K618 activated carbon was investigated in a batch system by considering the effects of various parameters like initial concentration (100, 150 and 200 mg/L) and temperature (25, 40 and 50 degrees C). The adsorption process was relatively fast and equilibrium was reached after about 20 min for 100, 150 mg/L at all adsorption temperature. Equilibrium time for 200 mg/L was determined as 20 min and 40 min at 298, 313 and 323 K, respectively. Simple mass and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate controlling steps such as external mass transfer, intraparticle diffusion. Pseudo second-order model was found to explain the kinetics of MG adsorption most effectively. It was found that both mass transfer and pore diffusion are important in determining the adsorption rates. The intraparticle diffusion rate constant, external mass transfer coefficient, film and pore diffusion coefficient at various temperatures were evaluated. The activation energy (Ea) was determined as 48.56, 63.16, 67.93 kJ/mol for 100, 150, 200 mg/L, respectively. The Langmiur and Freundlich isotherm were used to describe the adsorption equilibrium studies at different temperatures. Langmiur isotherm shows better fit than Freundlich isotherm in the temperature range studied. The thermodynamic parameters, such as DeltaG degrees, DeltaS and DeltaH degrees were calculated. The thermodynamics of dyes-T3K618 system indicates endothermic process.

  3. Exact solution of the thermodynamics and size parameters of a polymer confined to a lattice of finite size: Large chain limit

    SciTech Connect

    Snyder, Chad R. Guttman, Charles M.; Di Marzio, Edmund A.

    2014-01-21

    We extend the exact solutions of the Di Marzio-Rubin matrix method for the thermodynamic properties, including chain density, of a linear polymer molecule confined to walk on a lattice of finite size. Our extensions enable (a) the use of higher dimensions (explicit 2D and 3D lattices), (b) lattice boundaries of arbitrary shape, and (c) the flexibility to allow each monomer to have its own energy of attraction for each lattice site. In the case of the large chain limit, we demonstrate how periodic boundary conditions can also be employed to reduce computation time. Advantages to this method include easy definition of chemical and physical structure (or surface roughness) of the lattice and site-specific monomer-specific energetics, and straightforward relatively fast computations. We show the usefulness and ease of implementation of this extension by examining the effect of energy variation along the lattice walls of an infinite rectangular cylinder with the idea of studying the changes in properties caused by chemical inhomogeneities on the surface of the box. Herein, we look particularly at the polymer density profile as a function of temperature in the confined region for very long polymers. One particularly striking result is the shift in the critical condition for adsorption due to surface energy inhomogeneities and the length scale of the inhomogeneities; an observation that could have important implications for polymer chromatography. Our method should have applications to both copolymers and biopolymers of arbitrary molar mass.

  4. Hold-up volume and its application in estimating effective phase ratio and thermodynamic parameters on a polysaccharide-coated chiral stationary phase.

    PubMed

    Lao, Wenjian; Gan, Jay

    2007-11-01

    As an "unretained" marker, 1,3,5-tri-tert-butylbenzene (TTBB) has been commonly used to measure the hold-up volume. Despite many racemates have been resolved on Chiralcel OJ column, the hold-up volume of the column is still not well characterized. The aim of this work was to evaluate the chromatographic behavior of TTBB on the OJ column, and its application in estimating the effective phase ratio and thermodynamic parameters. The hold-up volume was affected not only by the mobile phase composition but also the solvents used for dissolving TTBB. A higher concentration of TTBB (0.500 mg/mL) showed a better reproducibility than when used at a lower concentration. After correction for thermal expansion of the mobile phase, TTBB was found to have slight retention on the OJ phase. The effective phase ratio increased with an increase in the temperature and decrease in the strength of the mobile phase. The enthalpy and entropy of enantiomers of imidazolinone herbicides were independent of the temperature in a linear van't Hoff plot when the effective phase ratio was changed. This study shows that, based on the hold-up volume from TTBB, thermodynamic evaluation with parameters derived from the distribution constant is valuable for understanding chromatographic retention and enantioseparation mechanisms of chiral analytes.

  5. In search of the best match: probing a multi-dimensional cloud microphysical parameter space to better understand what controls cloud thermodynamic phase

    NASA Astrophysics Data System (ADS)

    Tan, Ivy; Storelvmo, Trude

    2015-04-01

    Substantial improvements have been made to the cloud microphysical schemes used in the latest generation of global climate models (GCMs), however, an outstanding weakness of these schemes lies in the arbitrariness of their tuning parameters, which are also notoriously fraught with uncertainties. Despite the growing effort in improving the cloud microphysical schemes in GCMs, most of this effort has neglected to focus on improving the ability of GCMs to accurately simulate the present-day global distribution of thermodynamic phase partitioning in mixed-phase clouds. Liquid droplets and ice crystals not only influence the Earth's radiative budget and hence climate sensitivity via their contrasting optical properties, but also through the effects of their lifetimes in the atmosphere. The current study employs NCAR's CAM5.1, and uses observations of cloud phase obtained by NASA's CALIOP lidar over a 79-month period (November 2007 to June 2014) guide the accurate simulation of the global distribution of mixed-phase clouds in 20∘ latitudinal bands at the -10∘ C, -20∘C and -30∘C isotherms, by adjusting six relevant cloud microphysical tuning parameters in the CAM5.1 via Quasi-Monte Carlo sampling. Among the parameters include those that control the Wegener-Bergeron-Findeisen (WBF) timescale for the conversion of supercooled liquid droplets to ice and snow in mixed-phase clouds, the fraction of ice nuclei that nucleate ice in the atmosphere, ice crystal sedimentation speed, and wet scavenging in stratiform and convective clouds. Using a Generalized Linear Model as a variance-based sensitivity analysis, the relative contributions of each of the six parameters are quantified to gain a better understanding of the importance of their individual and two-way interaction effects on the liquid to ice proportion in mixed-phase clouds. Thus, the methodology implemented in the current study aims to search for the combination of cloud microphysical parameters in a GCM that

  6. 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)

  7. Thermodynamic profiles at the solvated inorganic-organic interface: the case of gold-thiolate monolayers.

    PubMed

    Ravi, Venkataramanan; Binz, Jason M; Rioux, Robert M

    2013-09-11

    The thermodynamic adsorption profile at a solvated organic-inorganic interface is probed by following the binding and organization of carboxylic acid-terminated alkanethiols of varying chain lengths (C2, C3, and C6) to the surface of gold nanoparticles (NPs) (5.4 ± 0.7, 9.5 ± 0.6, and 19.4 ± 1.1 nm diameter) using isothermal titration calorimetry (ITC). We discuss the effect of alkyl chain length, temperature, and Au NP size on the energetics at an organic-inorganic interface. ITC allows for the quantification of the adsorption constant, enthalpy of adsorption, entropy of adsorption, and the binding stoichiometry in a single experiment. The thermodynamic parameters support a mechanism of stepwise adsorption of thiols to the surface of Au NPs and secondary ordering of the thiols at the organic-inorganic interface. The adsorption enthalpies are chain-length dependent; enthalpy becomes more exothermic as longer chains are confined, compensating for greater decreases in entropy with increasing chain length. We observe an apparent compensation effect: the negative ΔH is compensated by a negative ΔS as the thiols self-assemble on the Au NP surface. A comparison of the thermodynamic parameters indicates thiol-Au NP association is enthalpy-driven because of the large, exothermic enthalpies accompanied by an unfavorable entropic contribution associated with confinement of alkyl chains, reduced trans-gauche interconversion, and the apparent ordering of solvent molecules around the hydrophobic organic thiols (hydrophobic effect). Understanding the thermodynamics of adsorption at NP surfaces will provide critical insight into the role of ligands in directing size and shape during NP synthesis since thiols are a common ligand choice (i.e., Brust method). The ITC technique is applicable to a larger number of structure-directing ligands and solvent combinations and therefore should become an important tool for understanding reaction mechanisms in nanostructure synthesis.

  8. Adsorption of phenol onto activated carbon from Rhazya stricta: determination of the optimal experimental parameters using factorial design

    NASA Astrophysics Data System (ADS)

    Hegazy, A. K.; Abdel-Ghani, N. T.; El-Chaghaby, G. A.

    2014-09-01

    A novel activated carbon was prepared from Rhazya stricta leaves and was successfully used as an adsorbent for phenol removal from aqueous solution. The prepared activated carbon was characterized by FTIR and SEM analysis. Three factors (namely, temperature, pH and adsorbent dose) were screened to study their effect on the adsorption of phenol by R. stricta activated carbon. A 23 full factorial design was employed for optimizing the adsorption process. The removal of phenol by adsorption onto R. stricta carbon reached 85 % at a solution pH of 3, an adsorbent dose of 0.5 g/l and a temperature of 45 °C. The temperature and adsorbent weight had a positive effect on phenol removal percentage, when both factors were changed from low to high and the opposite is true for the initial solution pH. The results of the main effects showed that the three studied factors significantly affected phenol removal by R. stricta carbon with 95 % confidence level. The interaction effects revealed that the interaction between the temperature and pH had the most significant effect on the removal percentage of phenol by R. stricta activated carbon. The present work showed that the carbon prepared from a low-cost and natural material which is R. stricta leaves is a good adsorbent for the removal of phenol from aqueous solution.

  9. Evaluation of confinement effects in zeolites under Henry's adsorption regime

    NASA Astrophysics Data System (ADS)

    Pera-Titus, Marc; Llorens, Joan

    2010-06-01

    This paper provides a detailed thermodynamic analysis of gas/vapour adsorption in zeolites at low pressures. At these conditions, we show first that Henry's isotherm can be conveniently rewritten using the thermodynamic isotherm model developed in a previous study [J. Llorens, M. Pera-Titus, Description of gas adsorption on microporous materials: evaluation of energy heterogeneity, J. Colloid Interface Sci. 331, 2009, 302-311], linking the integral free energy of adsorption relative to saturation, Ψ/ RT, expressed as a Kiselev integral, with the variable Z = 1/-ln( Π), being Π the relative pressure. Relevant information about sorbate confinement effects in zeolites can be inferred using strong sorbates under Henry's adsorption regime using the thermodynamic formulation provided here. The confining level of zeolites can be characterized by a parameter ( m1), whose value depends on the zeolite framework, but remains essentially unchanged with the sorbate probe molecule and temperature. We illustrate the application of these concepts using a collection of MFI and MTW-type zeolites as model systems.

  10. Mechanism of adsorption of single and double stranded DNA on gold and silver nanoparticles: Investigating some important parameters in bio-sensing applications.

    PubMed

    Farkhari, Nahid; Abbasian, Sara; Moshaii, Ahmad; Nikkhah, Maryam

    2016-12-01

    The mechanism of adsorption of single and double stranded DNAs on colloidal gold and silver nanoparticles has been studied by measuring the resistance of the nanoparticles, surrounded by various oligonucleotides, against salt induced aggregation. It is shown that both single and double stranded DNAs can be adsorbed on the metal nanoparticles and the adsorption strength is determined by the interaction between various bases of DNA and the nanoparticles. By changing the salt concentration, the difference between adsorption of various DNA strands on the nanoparticles can be specified. The results indicate that a key parameter in success of a sensing assay of DNA hybridization is the salt concentration which should be greater than a minimum threshold depending on the nanoparticles characteristics. We have also investigated the interaction mechanism between various DNA bases with the metal nanoparticles. For both gold and silver nanoparticles, adenine has the highest and thymine has the lowest attachment to the nanoparticles. From surface enhanced Raman spectroscopy (SERS) data of various bases in the presence of gold nanoparticles, the probable interaction points in the bases with the nanoparticles have been determined, which are mainly the nitrogen sites of these oligonucleotides.

  11. 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)

  12. Chlorination pattern effect on thermodynamic parameters and environmental degradability for C₁₀-SCCPs: Quantum chemical calculation based on virtual combinational library.

    PubMed

    Sun, Yuzhen; Pan, Wenxiao; Lin, Yuan; Fu, Jianjie; Zhang, Aiqian

    2016-01-01

    Short-chain chlorinated paraffins (SCCPs) are still controversial candidates for inclusion in the Stockholm Convention. The inherent mixture nature of SCCPs makes it rather difficult to explore their environmental behaviors. A virtual molecule library of 42,720 C10-SCCP congeners covering the full structure spectrum was constructed. We explored the structural effects on the thermodynamic parameters and environmental degradability of C10-SCCPs through semi-empirical quantum chemical calculations. The thermodynamic properties were acquired using the AM1 method, and frontier molecular orbital analysis was carried out to obtain the E(HOMO), E(LUMO) and E(LUMO)-E(HOMO) for degradability exploration at the same level. The influence of the chlorination degree (N(Cl)) on the relative stability and environmental degradation was elucidated. A novel structural descriptor, μ, was proposed to measure the dispersion of the chlorine atoms within a molecule. There were significant correlations between thermodynamic values and N(Cl), while the reported N(Cl)-dependent pollution profile of C10-SCCPs in environmental samples was basically consistent with the predicted order of formation stability of C10-SCCP congeners. In addition, isomers with large μ showed higher relative stability than those with small μ. This could be further verified by the relationship between μ and the reactivity of nucleophilic substitution and OH attack respectively. The C10-SCCP congeners with less Cl substitution and lower dispersion degree are susceptible to environmental degradation via nucleophilic substitution and hydroxyl radical attack, while direct photolysis of C10-SCCP congeners cannot readily occur due to the large E(LUMO)-E(HOMO) values. The chlorination effect and the conclusions were further checked with appropriate density functional theory (DFT) calculations.

  13. Thermodynamics and kinetics parameters of co-combustion between sewage sludge and water hyacinth in CO2/O2 atmosphere as biomass to solid biofuel.

    PubMed

    Huang, Limao; Liu, Jingyong; He, Yao; Sun, Shuiyu; Chen, Jiacong; Sun, Jian; Chang, KenLin; Kuo, Jiahong; Ning, Xun'an

    2016-10-01

    Thermodynamics and kinetics of sewage sludge (SS) and water hyacinth (WH) co-combustion as a blend fuel (SW) for bioenergy production were studied through thermogravimetric analysis. In CO2/O2 atmosphere, the combustion performance of SS added with 10-40wt.% WH was improved 1-1.97 times as revealed by the comprehensive combustion characteristic index (CCI). The conversion of SW in different atmospheres was identified and their thermodynamic parameters (ΔH,ΔS,ΔG) were obtained. As the oxygen concentration increased from 20% to 70%, the ignition temperature of SW decreased from 243.1°C to 240.3°C, and the maximum weight loss rate and CCI increased from 5.70%·min(-1) to 7.26%·min(-1) and from 4.913%(2)·K(-3)·min(-2) to 6.327%(2)·K(-3)·min(-2), respectively, which corresponded to the variation in ΔS and ΔG. The lowest activation energy (Ea) of SW was obtained in CO2/O2=7/3 atmosphere.

  14. Synthesis and evaluation of a thiourea-modified chitosan derivative applied for adsorption of Hg(II) from synthetic wastewater.

    PubMed

    Wang, Lin; Xing, Ronge; Liu, Song; Cai, Shengbao; Yu, Huahua; Feng, Jinhua; Li, Rongfeng; Li, Pengcheng

    2010-06-01

    In this work, a thiourea-modified chitosan derivative (TMCD) was synthesized through two steps, O-carboxymethylated first and then modified by a polymeric Schiff's base of thiourea/glutaraldehyde. The adsorption behavior of mercury (II) ions onto TMCD was investigated through batch method. The maximum adsorption capacity for Hg(II) was found to be 6.29 mmol/g at pH 5.0 and both kinetic and thermodynamic parameters of the adsorption process were obtained. The results indicated that adsorption process was spontaneous exothermic reaction and kinetically followed pseudo-second-order model. The adsorption experiments also demonstrated TMCD had high adsorption selectivity towards Hg(II) ions when coexisted with Cu(II), Zn(II), Cd(II) and Ca(II) in solution and it could be easily regenerated and efficiently reused.

  15. Insight into the adsorption mechanisms of vanadium(V) on a high-efficiency biosorbent (Ti-doped chitosan bead).

    PubMed

    Liu, Xin; Zhang, Lingfan

    2015-08-01

    In this present study, a new chitosan bead modified with titanium ions (TiCB) was prepared and employed for the adsorption of vanadium ions from aqueous solutions. Batch adsorption experiments were performed to research the effect of various factors, including pH, temperature, contact time and initial concentration of vanadium(V) ions. The adsorption of vanadium was followed by the pseudo second-order kinetic and the Langmuir isotherm model, with a remarkable maximum adsorption capacity of 210 mg/g. The analysis of thermodynamic parameters (ΔG°, ΔH° and ΔS°) revealed that the nature of adsorption was feasible, spontaneous (ΔG°<0) and endothermic (ΔH°>0) process. FTIR, EDS, EMI and XPS studies suggested that the mechanisms of adsorption were possibly attributed to electrostatic attraction, ligand-exchange and redox reaction between TiCB and vanadium ions.

  16. Modeling studies: Adsorption of aniline blue by using Prosopis Juliflora carbon/Ca/alginate polymer composite beads.

    PubMed

    Kumar, M; Tamilarasan, R

    2013-02-15

    The research article describes the experimental and modeling study for the adsorptive removal of aniline blue dye (AB dye) from aqueous matrices using a Prosopis Juliflora modified carbon/Ca/alginate polymer bead as a low cost and eco-friendly adsorbent. The rate of adsorption was investigated under various experimental parameters such as contact time, adsorbent dose, dye concentration, pH and temperature. The kinetics, equilibrium and thermodynamic studies were assessed to find out the efficiency of the adsorption process. The equilibrium uptake capacity of the adsorption process was found with Freundlich and Langmuir adsorption isotherm equations and it was evaluated by dimensionless separation factor (R(L)). The dynamics of adsorption was predicted by pseudo-first order, pseudo-second order Lagergren's equation and intra particle diffusion model. Adsorption feasibility was assessed with thermodynamic parameters such as isosteric heat of adsorption (ΔH°), standard entropy (ΔS°) and Gibbs free energy (ΔG°) using VantHoff plot. The alginate bead was characterized with FTIR spectroscopy and Scanning Electron Microscopy (SEM).

  17. Protein nanoparticle interaction: A spectrophotometric approach for adsorption kinetics and binding studies

    NASA Astrophysics Data System (ADS)

    Vaishanav, Sandeep K.; Chandraker, Kumudini; Korram, Jyoti; Nagwanshi, Rekha; Ghosh, Kallol K.; Satnami, Manmohan L.

    2016-08-01

    Investigating the protein nanoparticle interaction is crucial to understand how to control the biological interactions of nanoparticles. In this work, Model protein Bovine serum albumin (BSA) was used to evaluate the process of protein adsorption to the gold nanoparticles (GNPs) surface. The binding of a model protein (BSA) to GNPs was investigated through fluorescence quenching measurements. The strong affinities of BSA for GNPs were confirmed by the high value of binding constant (Ks) which was calculated to be 2.2 × 1011 L/mol. In this consequence, we also investigated the adsorption behavior of BSA on GNPs surface via UV-Vis spectroscopy. The effect of various operational parameters such as pH, contact time, initial BSA concentration, and temperature on adsorption of BSA was investigated using batch adsorption experiments. Kinetics of adsorption was found to follow the pseudo-second order rate equation. The suitability of Freundlich and Langmuir adsorption models to the equilibrium data was investigated. The equilibrium adsorption was well described by the Freundlich isotherm model. The maximum adsorption capacity for BSA adsorbed on GNPs was 58.71 mg/g and equilibrium constant was 0.0058 calculated by the Langmuir model at 298 K and pH = 11.0. Thermodynamic parameters showed that the adsorption of BSA onto GNPs was feasible, spontaneous, and exothermic.

  18. 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

  19. Cr(VI) Adsorption on Red Mud Modified by Lanthanum: Performance, Kinetics and Mechanisms.

    PubMed

    Cui, You-Wei; Li, Jie; Du, Zhao-Fu; Peng, Yong-Zhen

    Water pollution caused by the highly toxic metal hexavalent chromium (Cr(VI)) creates significant human health and ecological risks. In this study, a novel adsorbent was used to treat Cr(VI)-containing wastewater; the adsorbent was prepared using red mud (RM) generated from the alumina production industry and the rare earth element lanthanum. This study explored adsorption performance, kinetics, and mechanisms. Results showed that the adsorption kinetics of the RM modified by lanthanum (La-RM), followed the pseudo-second-order model, with a rapid adsorption rate. Cr(VI) adsorption was positively associated with the absorbent dose, pH, temperature, and initial Cr(VI) concentration; coexisting anions had little impact. The maximum Cr(VI) adsorption capacity was 17.35 mg/g. Cr(VI) adsorption on La-RM was a mono-layer adsorption pattern, following the Langmuir isotherm model. Thermodynamic parameters showed the adsorption was spontaneous and endothermic. The adsorption of Cr(VI) on La-RM occurred as a result of LaOCl formation on the RM surface, which in turn further reacted with Cr(VI) in the wastewater. This study highlighted a method for converting industrial waste into a valuable material for wastewater treatment. The novel absorbent could be used as a potential adsorbent for treating Cr(VI)-contaminating wastewater, due to its cost-effectiveness and high adsorption capability.

  20. Cr(VI) Adsorption on Red Mud Modified by Lanthanum: Performance, Kinetics and Mechanisms

    PubMed Central

    Cui, You-Wei; Li, Jie; Du, Zhao-Fu; Peng, Yong-Zhen

    2016-01-01

    Water pollution caused by the highly toxic metal hexavalent chromium (Cr(VI)) creates significant human health and ecological risks. In this study, a novel adsorbent was used to treat Cr(VI)-containing wastewater; the adsorbent was prepared using red mud (RM) generated from the alumina production industry and the rare earth element lanthanum. This study explored adsorption performance, kinetics, and mechanisms. Results showed that the adsorption kinetics of the RM modified by lanthanum (La-RM), followed the pseudo-second-order model, with a rapid adsorption rate. Cr(VI) adsorption was positively associated with the absorbent dose, pH, temperature, and initial Cr(VI) concentration; coexisting anions had little impact. The maximum Cr(VI) adsorption capacity was 17.35 mg/g. Cr(VI) adsorption on La-RM was a mono-layer adsorption pattern, following the Langmuir isotherm model. Thermodynamic parameters showed the adsorption was spontaneous and endothermic. The adsorption of Cr(VI) on La-RM occurred as a result of LaOCl formation on the RM surface, which in turn further reacted with Cr(VI) in the wastewater. This study highlighted a method for converting industrial waste into a valuable material for wastewater treatment. The novel absorbent could be used as a potential adsorbent for treating Cr(VI)-contaminating wastewater, due to its cost-effectiveness and high adsorption capability. PMID:27658113

  1. Particle-scale CO2 adsorption kinetics modeling considering three reaction mechanisms

    SciTech Connect

    Suh, Dong-Myung; Sun, Xin

    2013-09-01

    In the presence of water (H2O), dry and wet adsorptions of carbon dioxide (CO2) and physical adsorption of H2O happen concurrently in a sorbent particle. The three reactions depend on each other and have a complicated, but important, effect on CO2 capturing via a solid sorbent. In this study, transport phenomena in the sorbent were modeled, including the tree reactions, and a numerical solving procedure for the model also was explained. The reaction variable distribution in the sorbent and their average values were calculated, and simulation results were compared with experimental data to validate the proposed model. Some differences, caused by thermodynamic parameters, were observed between them. However, the developed model reasonably simulated the adsorption behaviors of a sorbent. The weight gained by each adsorbed species, CO2 and H2O, is difficult to determine experimentally. It is known that more CO2 can be captured in the presence of water. Still, it is not yet known quantitatively how much more CO2 the sorbent can capture, nor is it known how much dry and wet adsorptions separately account for CO2 capture. This study addresses those questions by modeling CO2 adsorption in a particle and simulating the adsorption process using the model. As adsorption temperature changed into several values, the adsorbed amount of each species was calculated. The captured CO2 in the sorbent particle was compared quantitatively between dry and wet conditions. As the adsorption temperature decreased, wet adsorption increased. However, dry adsorption was reduced.

  2. Thermodynamics of hydrogen adsorption in slit-like carbon nanopores at 77 K. Classical versus path-integral Monte Carlo simulations.

    PubMed

    Kowalczyk, Piotr; Gauden, Piotr A; Terzyk, Artur P; Bhatia, Suresh K

    2007-03-27

    Hydrogen in slit-like carbon nanopores at 77 K represents a quantum fluid in strong confinement. We have used path-integral grand canonical Monte Carlo and classical grand canonical Monte Carlo simulations for the investigation of the "quantumness" of hydrogen at 77 K adsorbed in slit-like carbon nanopores up to 1 MPa. We find that classical simulations overpredict the hydrogen uptake in carbon nanopores due to neglect of the quantum delocalization. Such disagreement of both simulation methods depends on the slit-like carbon pore size. However, the differences between the final uptakes of hydrogen computed from both classical and quantum simulations are not large due to a similar effective size of quantum/classical hydrogen molecules in carbon nanospaces. For both types of molecular simulations, the volumetric density of stored energy in optimal carbon nanopores exceeds 6.4 MJ dm(-3) (i.e., 45 kg m(-3); Department of Energy target for 2010). In contrast to the hydrogen adsorption isotherms, we found a large reduction of isosteric enthalpy of adsorption computed from the quantum Feynman's path-integral simulations in comparison to the classical values at 77 K and pressures up to 1 MPa. Depression of the quantum isosteric enthalpy of adsorption depends on the slit-like carbon pore size. For the narrow pores (pore width H in [0.59-0.7] nm), the reduction of the quantum isosteric enthalpy of adsorption at zero coverage is around 50% in comparison to the classical one. We observed new phenomena called, by us, the quantum confinement-inducing polymer shrinking. In carbon nanospaces, the quantum cyclic polymers shrink, in comparison to its bulk-phase counterpart, due to a strong confinement effect. At considered storage conditions, this complex phenomenon depends on the size of the slit-like carbon nanopore and the density of hydrogen volumetric energy. For the smallest nanopores and a low density of hydrogen volumetric energy, the reduction of the polymer effective size

  3. Adsorption of copper from aqueous solution on Brassica cumpestris (mustard oil cake).

    PubMed

    Ajmal, Mohammad; Rao, Rifaqat Ali Khan; Khan, Moonis Ali

    2005-06-30

    The adsorption behavior of various heavy metals on mustard oil cake (MOC) was studied. The maximum adsorption of Cu(II) was observed followed by Zn(II), Cr(VI), Mn(II), Cd(II), Ni(II) and Pb(II). The adsorption of Cu(II) was found to be dependent on initial concentration of solution, pH, adsorbent dose, temperature and contact time. The adsorption followed pseudo-first-order and second-order kinetics but pseudo-second-order kinetic model was better obeyed since experimental data agreed well with theoretical data. Thermodynamic parameters were also evaluated. The adsorption process was found to be endothermic and spontaneous in nature. Attempts were also made to desorb Cu(II) from the adsorbent and regeneration of the spent adsorbent. The breakthrough and exhaustive capacities were found to be 5 and 10 mg g(-1), respectively.

  4. Removal of 8-quinolinecarboxylic acid pesticide from aqueous solution by adsorption on activated montmorillonites.

    PubMed

    Mekhloufi, M; Zehhaf, A; Benyoucef, A; Quijada, C; Morallon, E

    2013-12-01

    Sodium montmorillonite (Na-M), acidic montmorillonite (H-M), and organo-acidic montmorillonite (Org-H-M) were applied to remove the herbicide 8-quinolinecarboxylic acid (8-QCA). The montmorillonites containing adsorbed 8-QCA were investigated by transmission electron microscopy, FT-IR spectroscopy, X-ray diffraction analysis, X-ray fluorescence thermogravimetric analysis, and physical adsorption of gases. Experiments showed that the amount of adsorbed 8-QCA increased at lower pH, reaching a maximum at pH 2. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The Langmuir model provided the best correlation of experimental data for adsorption equilibria. The adsorption of 8-QCA decreased in the order Org-H-M > H-M > Na-M. Isotherms were also used to obtain the thermodynamic parameters. The negative values of ΔG indicated the spontaneous nature of the adsorption process.

  5. Modification of a magnetic carbon composite for ciprofloxacin adsorption.

    PubMed

    Mao, Haixin; Wang, Shikui; Lin, Jian-Ying; Wang, Zengshuang; Ren, Jun

    2016-11-01

    A magnetic carbon composite, Fe3O4/C composite, was fabricated by one-step hydrothermal synthesis, modified by heat treatment under an inert atmosphere (N2), and then used as an adsorbent for ciprofloxacin (CIP) removal. Conditions for the modification were optimized according to the rate of CIP removal. The adsorbent was characterized by Fourier transform infrared spectroscopy, X-ray diffraction measurements, vibrating-sample magnetometry, scanning electron microscopy, transmission electron microscopy, and N2 adsorption/desorption isotherm measurements. The results indicate that the modified adsorbent has substantial magnetism and has a large specific area, which favor CIP adsorption. The effects of solution pH, adsorbent dose, contact time, initial CIP concentration, ion strength, humic acid and solution temperature on CIP removal were also studied. Our results show that all of the above factors influence CIP removal. The Langmuir adsorption isotherm fits the adsorption process well, with the pseudo second-order model describing the adsorption kinetics accurately. The thermodynamic parameters indicate that adsorption is mainly physical adsorption. Recycling experiments revealed that the behavior of adsorbent is maintained after recycling for five times. Overall, the modified magnetic carbon composite is an efficient adsorbent for wastewater treatment.

  6. Adsorption and preconcentration of divalent metal ions in fossil fuels and biofuels: gasoline, diesel, biodiesel, diesel-like and ethanol by using chitosan microspheres and thermodynamic approach.

    PubMed

    Prado, Alexandre G S; Pescara, Igor C; Evangelista, Sheila M; Holanda, Matheus S; Andrade, Romulo D; Suarez, Paulo A Z; Zara, Luiz F

    2011-05-15

    Biodiesel and diesel-like have been obtained from soybean oil by transesterification and thermal cracking process, respectively. These biofuels were characterized as according to ANP standards by using specific ASTM methods. Ethanol, gasoline, and diesel were purchased from a gas station. Deacetylation degree of chitosan was determined by three distinct methods (conductimetry, FTIR and NMR), and the average degree was 78.95%. The chitosan microspheres were prepared from chitosan by split-coating and these spheres were crosslinked using glutaraldehyde. The surface area of microspheres was determined by BET method, and the surface area of crosslinked microspheres was 9.2m(2)g(-1). The adsorption isotherms of cooper, nickel and zinc on microspheres of chitosan were determined in petroleum derivatives (gasoline and diesel oil), as well as in biofuels (alcohol, biodiesel and diesel-like). The adsorption order in all fuels was: Cu>Ni>Zn. The elution tests presented the following preconcentration degrees: >4.5 to ethanol, >4.4 to gasoline, >4.0 to diesel, >3.8 to biodiesel and >3.6 to diesel-like. The application of chitosan microspheres in the metal ions preconcentration showed the potential of this biopolymer to enrich fuel sample in order to be analyzed by flame atomic absorption spectrometry.

  7. A review on zinc and nickel adsorption on natural and modified zeolite, bentonite and vermiculite: examination of process parameters, kinetics and isotherms.

    PubMed

    Malamis, S; Katsou, E

    2013-05-15

    Adsorption and ion exchange can be effectively employed for the treatment of metal-contaminated wastewater streams. The use of low-cost materials as sorbents increases the competitive advantage of the process. Natural and modified minerals have been extensively employed for the removal of nickel and zinc from water and wastewater. This work critically reviews existing knowledge and research on the uptake of nickel and zinc by natural and modified zeolite, bentonite and vermiculite. It focuses on the examination of different parameters affecting the process, system kinetics and equilibrium conditions. The process parameters under investigation are the initial metal concentration, ionic strength, solution pH, adsorbent type, grain size and concentration, temperature, agitation speed, presence of competing ions in the solution and type of adsorbate. The system's performance is evaluated with respect to the overall metal removal and the adsorption capacity. Furthermore, research works comparing the process kinetics with existing reaction kinetic and diffusion models are reviewed as well as works examining the performance of isotherm models against the experimental equilibrium data.

  8. Thermodynamics of micelle formation of the counterion coupled gemini surfactant Bis(4-(2-dodecyl)benzenesulfonate)-Jeffamine salt and its dynamic adsorption on sandstone.

    PubMed

    Páhi, Annamária B; Király, Zoltán; Mastalir, Agnes; Dudás, József; Puskás, Sándor; Vágó, Arpád

    2008-12-04

    A novel counterion-coupled gemini (cocogem) surfactant, DBSJ, was synthetized via the 2:1 coupling reaction between 4-(2-dodecyl)benzenesulfonic acid (Lutensit A-LBS) and polypropyleneglycol-bis(2-aminopropyl) ether (Jeffamine D230). The surfactant had a polydispersity index of Mw/Mn = 1.04, as determined by electrospray-ionization mass spectrometry. The micellar properties of DBSJ in water were investigated in the temperature range 283-348 K by conductometry and titration microcalorimetry. The critical micelle concentration (cmc) of the cocogem was found to be more than 1 order of magnitude less than that of monomeric sodium 4-(2-dodecyl)benzenesulfonate (SDBS). The mean degree of dissociation in the temperature range studied proved to be alpha = 0.39. The calorimetric enthalpies of micelle formation agreed well with the enthalpies calculated via the van't Hoff relation. The cmc versus T curve passes through a minimum just below room temperature, after which the micelle formation changes from endothermic to exothermic. The Gibbs free energy of micelle formation was nearly constant as the temperature was increased, due to enthalpy/entropy compensation. The isotherm for DBSJ adsorption from aqueous solution onto sandstone was determined by continuous flow frontal analysis solid/liquid chromatography at 298 K and 60 bar. The adsorption of DBSJ on sandstone followed an S-type isotherm. Surface aggregation occurred over an extended range of concentration. Surface saturation was reached at a solution concentration more than 1 order of magnitude less than for monomeric SDBS. This finding is a point of concern in the chemical flooding of oil reservoir rocks to enhance oil recovery.

  9. Kinetics and equilibrium adsorption study of lead(II) onto activated carbon prepared from coconut shell.

    PubMed

    Sekar, M; Sakthi, V; Rengaraj, S

    2004-11-15

    Removal of lead from aqueous solutions by adsorption onto coconut-shell carbon was investigated. Batch adsorption experiments were performed to find out the effective lead removal at different metal ion concentrations. Adsorption of Pb2+ ion was strongly affected by pH. The coconut-shell carbon (CSC) exhibited the highest lead adsorption capacity at pH 4.5. Isotherms for the adsorption of lead on CSC were developed and the equilibrium data fitted well to the Langmuir, Freundlich, and Tempkin isotherm models. At pH 4.5, the maximum lead adsorption capacity of CSC estimated with the Langmuir model was 26.50 mg g(-1) adsorbent. Energy of activation (Ea) and thermodynamic parameters such as DeltaG, DeltaH, and DeltaS were evaluated by applying the Arrhenius and van't Hoff equations. The thermodynamics of Pb(II) on CSC indicates the spontaneous and endothermic nature of adsorption. Quantitative desorption of Pb(II) from CSC was found to be 75% which facilitates the sorption of metal by ion exchange.

  10. Adsorptive removal of phenol from aqueous solution with zeolitic imidazolate framework-67.

    PubMed

    Pan, Yong; Li, Zhi; Zhang, Zhe; Tong, Xiong-Shi; Li, Hai; Jia, Chong-Zhi; Liu, Bei; Sun, Chang-Yu; Yang, Lan-Ying; Chen, Guang-Jin; Ma, De-Yun

    2016-03-15

    ZIF-67(zinc-methylimidazolate framework-67), one of the zeolitic imidazolate frameworks (ZIFs), was used for the removal of phenol from aqueous solutions via adsorption and shows high adsorption capacity for phenol. The thermodynamic and kinetic adsorption behavior of ZIF-67 for phenol in water with concentration ranging from 50 to 300 ppm were investigated in a batch reactor and a ZIF-67 packed column, respectively. The effects of pH, contact time, zeta potential of the adsorbent and temperature on the adsorption behavior were evaluated, and the results demonstrated that the adsorption is primarily brought about by a specific favorable interaction (electrostatic interaction) between phenol and ZIF-67 surface. The suitability of the Langmuir adsorption model to the equilibrium data was investigated for each phenol-adsorbent system, which the results showed that the equilibrium data for all the phenol-sorbent systems fitted the Langmuir model. Thermodynamic parameters such as Gibbs free energy are calculated from the experimental data at different temperatures. The adsorbent could be perfectly regenerated at 120 °C with little loss in the adsorption ability.

  11. Mechanism of ligand binding to alpha 1-acid glycoprotein (orosomucoid): correlated thermodynamic factors and molecular parameters of polarity.

    PubMed Central

    Urien, S; Giroud, Y; Tsai, R S; Carrupt, P A; Brée, F; Testa, B; Tillement, J P

    1995-01-01

    Eight ligands were used in this study, four basic, three neutral and one acidic. Their binding to serum alpha 1-acid glycoprotein (orosomucoid) was measured at several temperatures, and the data were analysed together by a general model with three unknowns, number of binding sites, delta H0 and delta S0. The partition coefficients of the ligands were measured in octanol/water and heptane/water systems (log Poct. and log Phep.), and their molecular volumes were calculated by molecular modelling techniques. These structural properties allow determination of polarity parameters (delta log Poct.-hep., lambda oct. and lambda hep.) which encode in different proportions the various polar interactions between the solute and the aqueous and organic phases, i.e. hydrogen-bonding capacity and dipolarity/polarizability. This study shows that good correlations exist between delta H0 or delta S0 and polarity parameters, such that the enthalpic contribution to binding increases with increasing polarity of the ligands, mainly hydrogen-bond-donor acidity, whereas their entropic contribution to binding decreases. PMID:7887909

  12. Thermodynamics of Cadmium Sorption on Different Soils of West Bengal, India

    PubMed Central

    Paul, Ranjit Kumar; Das, D. K.; Boruah, Romesh K.; Sonar, Indira

    2014-01-01

    A sorption study was conducted on different soils collected from five agroecological zones of West Bengal, India, to understand the soil environmental behavior and fate of cadmium. For this purpose batch adsorption experiments were carried out at the native soil pH and at three different temperatures (25°C, 35°C, and 45°C). The adsorption data fitted by a linear least squares technique to the different sorption isotherms. Most data obtained give the good fit to both Freundlich and modified Langmuir isotherms, but they are not consistent with the linear Langmuir adsorption model. Thermodynamic parameters, namely, thermodynamics equilibrium constant at a particular temperature T  (KT0), Gibbs free energy at a particular temperature T  (ΔGT0), and change of enthalpy (ΔH0) and change of entropy at temperature T  (ΔST0), were also determined by applying sorption value and concentrations of Cd in equilibrium solution within the temperature range. The thermodynamic parameters revealed that Cd sorption increases as the values of KT0, ΔGT0, ΔH0, and ΔST0 were increased on reaction temperatures. The spontaneous sorption reaction can be concluded due to high values of ΔGT0. The positive values of ΔH0 indicated that the Cd sorption is an endothermic one. Under these present conditions, the soil and its components possibly supply a number of sites having different adsorption energies for cadmium sorption. PMID:24683322

  13. Thermodynamic properties and vapor pressures of polar fluids from a four-parameter corresponding-states method

    SciTech Connect

    Wilding, W.V.; Johnson, J.K.; Rowley, R.L.

    1987-11-01

    A recently proposed extended Lee-Kesler corresponding-states method (ELK) for polar fluids which accurately predicts compressibility factors and departure functions is considered. Tables of polar deviation functions have been generated and values of the shape/size and polar parameters for 52 polar fluids have been calculated, allowing the method to be used for quick hand calculation in addition to the previous, more accurate, computer applications. Additionally, vapor pressures of 44 pure polar fluids were computed using the full version of the ELK and the equality of the Gibbs free energy criterion for phase equilibrium. An ELK vapor pressure correlation is proposed which is essentially numerically equivalent to, but computationally simpler than, the former method. Computed vapor pressures agree with experimental values as well or better than other vapor pressure equations designed exclusively for vapor pressure prediction of polar fluids.

  14. Adsorption kinetics of azinphosmethyl from aqueous solution onto pyrolyzed Horseshoe sea crab shell from the Atlantic Ocean.

    PubMed

    Gulen, J; Aroguz, A Z; Dalgin, D

    2005-07-01

    The adsorption behavior of azinphosmethyl on pyrolyzed Horseshoe Crab (Limulus polyphemus) outer shell, as a residue, from the Atlantic Ocean, collected along the Maine coast, USA, has been studied with regards to its kinetic and equilibrium conditions, taking into account adsorbate concentrations of 2 x 10(-3), 4 x 10(-3), 6 x 10(-3), and 8 x 10(-3), as well as temperatures of 30 degrees C, 40 degrees C, 50 degrees C, and 60 degrees C. The yield of adsorption of azinphosmethyl from aqueous solution ranged from 56.1% to 61% with temperature increasing. Kinetic studies showed that adsorption rate decreased as the initial azinphosmethyl concentration increased. It was found, that the adsorption reaction obeyed first-order kinetics. The overall rate constants were estimated for different temperatures. The activation energy for adsorption was about 1.52 kJmol(-1), which implies that azinphosmethyl mainly adsorbed physically onto Horseshoe Crab outer shell. Langmuir and Freundlich isotherms were applied to the experimental data and isotherm constants were calculated. The thermodynamic parameters DeltaG0, DeltaH0 and DeltaS0 for the adsorption reaction were evaluated based on equilibrium data and in connection with this result the thermodynamic aspects of adsorption reaction were discussed. The adsorption was found to be endothermic in nature. The adsorbent used in this study proved highly efficient for the removal of azinphosmethyl.

  15. Characteristic Evaluation of Graphene Oxide for Bisphenol A Adsorption in Aqueous Solution

    PubMed Central

    Phatthanakittiphong, Thatchaphong; Seo, Gyu Tae

    2016-01-01

    This paper investigates the characteristics of graphene oxide (GO) for Bisphenol A (BPA) adsorption in water. Batch experiments on the influence of significant parameters were performed. While an improvement of the adsorption capacity of BPA was obtained by the increment of contact time and the initial BPA concentration, the increment of pH above 8, GO dosage, and temperature showed the reverse results. The thermodynamic study suggested that BPA adsorption on GO was an exothermic and spontaneous process. The kinetics was explained by the pseudo-second-order model which covers all steps of adsorption. The fit of the results with the Langmuir isotherm indicated the monolayer adsorption. At 298 K, the adsorption reached equilibrium within 30 min with the maximum adsorption capacity of 49.26 mg/g. The low BPA adsorption capacity of GO can be interpreted by the occurrence of oxygen-containing functional groups (OCFGs) that are able to form hydrogen bonds with the surrounding OCFGs and water molecules. This effect inhibited the role of π–π interactions that are mainly responsible for the adsorption of BPA. PMID:28335257

  16. Sorption equilibrium, mechanism and thermodynamics studies of 1,3-propanediol on beta zeolite from an aqueous solution.

    PubMed

    Wang, Zhe; Wu, Zhe; Tan, Tianwei

    2013-10-01

    To identify the adsorption characteristics of 1,3-propanediol on beta zeolite, the effects of temperature, zeolite dose, and 1,3-propanediol concentration were studied through batch experiments. The results showed that the pseudo-second order model expressed the kinetic data better. The experimental and theoretical adsorption capacities were 116.2 and 119.0 mg/g at 293 K, respectively. The adsorption equilibrium data were observed to satisfy the Freundlich isotherm model. Based on the Boyd plot, intraparticle diffusion primarily governed the uptake process. Moreover, thermodynamic parameters, such as changes in standard free energy (ΔG(0)), standard enthalpy (ΔH(0)), and standard entropy, were estimated. The negative values of ΔG(0) and ΔH(0) (-9.4 kJ/mol) indicated that the adsorption process was spontaneous, exothermic, and feasible. Finally, the activation energy derived from the Arrhenius equation suggested that the interaction mainly constitute physical adsorption.

  17. Statistical Thermodynamics of Chain Molecular Fluids: Equation of State Parameters for PVT Scaling and Their Group Contributions

    NASA Astrophysics Data System (ADS)

    Yahsi, Ugur

    Extensive experimental studies of fluid hydrocarbons in the lubricating range of molar mass have been undertaken sometime ago by American Petroleum Institute Project 42, located in the Departments of Chemistry and Physics at Pennsylvania State University. In these studies systematic structural changes were introduced, so that the equation of state (e.o.s.) as well as the viscosities of linear paraffins, branched hydrocarbons, and various rings attached to n-alkanes tails are known. Hence this material became the basis for various semi-empirical or empirical structural correlations. We proceed here with the hole theory of Simha-Somcynsky (SS) which has proven quantitatively successful for low as well as high molar mass system and examine e.o.s. data. We demonstrate the success of the theory and obtain the characteristic volume (nu^*), energy ( varepsilon^*) and flexibility (c) parameters as functions of chain length for the different structures. For the short chains in question these represent averages over the terminal and internal units. By suitable generalization of the SS theory developed for physical mixtures we decompose these averages into the individual group contributions. The accuracy of the numerical procedures employed is tested by back computations. Sometime ago A. Bondi developed structural rules for the computation of Van der Waals excluded group volumes. Interesting correlations between these and the above nu ^* values, defined for a 6-12 potential, are obtained. In the same way we examine correlations between D. W. Van Krevelen's and P. J. Hoftyzer's cohesive group energies and varepsilon^* values.

  18. The adsorption of Cr(VI) on sulphuric acid-treated wheat bran.

    PubMed

    Ozer, A; Ozer, D

    2004-06-01

    Wheat bran, a by-product of wheat milling industries, was converted into a cheap and efficient material by treating with sulphuric acid and used for the adsorption of Cr(VI) from aqueous solution. Effects of various parameters such as initial pH of solution, contact time, initial Cr(VI) concentration and temperature were studied. The sulphuric acid-treated wheat bran (STWB) gave the highest adsorption efficiency at pH 1.5. The equilibrium data were fitted better to Langmuir isotherm model compared to Freundlich model at all the temperatures studied. The adsorption capacity increased from 91 to 133 mg gl(-1) with an increase in temperature from 20 degrees C to 50 degrees C. The adsorption process was found to be endothermic and Langmuir isotherm data were evaluated to determine the thermodynamic parameters for the process. Thermodynamic parameters showed that the process was feasible. The results indicated that the chromium removal process by STWB followed first-order rate expression and adsorption rate constants increased with increasing temperature.

  19. 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.

  20. Thermodynamic estimation: Ionic materials

    SciTech Connect

    Glasser, Leslie

    2013-10-15

    Thermodynamics establishes equilibrium relations among thermodynamic parameters (“properties”) and delineates the effects of variation of the thermodynamic functions (typically temperature and pressure) on those parameters. However, classical thermodynamics does not provide values for the necessary thermodynamic properties, which must be established by extra-thermodynamic means such as experiment, theoretical calculation, or empirical estimation. While many values may be found in the numerous collected tables in the literature, these are necessarily incomplete because either the experimental measurements have not been made or the materials may be hypothetical. The current paper presents a number of simple and relible estimation methods for thermodynamic properties, principally for ionic materials. The results may also be used as a check for obvious errors in published values. The estimation methods described are typically based on addition of properties of individual ions, or sums of properties of neutral ion groups (such as “double” salts, in the Simple Salt Approximation), or based upon correlations such as with formula unit volumes (Volume-Based Thermodynamics). - Graphical abstract: Thermodynamic properties of ionic materials may be readily estimated by summation of the properties of individual ions, by summation of the properties of ‘double salts’, and by correlation with formula volume. Such estimates may fill gaps in the literature, and may also be used as checks of published values. This simplicity arises from exploitation of the fact that repulsive energy terms are of short range and very similar across materials, while coulombic interactions provide a very large component of the attractive energy in ionic systems. Display Omitted - Highlights: • Estimation methods for thermodynamic properties of ionic materials are introduced. • Methods are based on summation of single ions, multiple salts, and correlations. • Heat capacity, entropy

  1. Adsorption of divalent metals to metal oxide nanoparicles: Competitive and temperature effects

    NASA Astrophysics Data System (ADS)

    Grover, Valerie Ann

    The presence of metals in natural waters is becoming a critical environmental and public health concern. Emerging nanotechnology and the use of metal oxide nanoparticles has been identified as a potential remediation technique in removing metals from water. However, practical applications are still being explored to determine how to apply their unique chemical and physical properties for full scale remediation projects. This thesis investigates the sorption properties of Cd(II), Cu(II), Pb(II) and Zn(II) to hematite (alpha-Fe2O3) and titanium dioxide (TiO2) nanoparticles in single- and binary-adsorbate systems. Competitive sorption was evaluated in 1L batch binary-metal systems with 0.05g/L nano-hematite at pH 8.0 and pH 6.0. Results indicate that the presence of a secondary metal can affect the sorption process depending upon the molar ratios, such as increased or reduced adsorption. Thermodynamic properties were also studied in order to better understand the effects of temperature on equilibrium and kinetic adsorption capabilities. Understanding the thermodynamic properties can also give insight to determine if the sorption process is a physical, chemical or ion exchange reaction. Thermodynamic parameters such as enthalpy (DeltaH), entropy (DeltaS), and Gibbs free energy (DeltaG) were evaluated as a function of temperature, pH, and metal concentration. Results indicate that Pb(II) and Cu(II) adsorption to nano-hematite was an endothermic and physical adsorption process, while Zn(II) and Cd(II) adsorption was dependent upon the adsorbed concentration evaluated. However, metal adsorptions to nano-titanium dioxide were all found to be endothermic and physical adsorption processes; the spontaneity of metal adsorption was temperature dependent for both metal oxide nanoparticles.

  2. Generalized gas-solid adsorption modeling: Single-component equilibria

    SciTech Connect

    Ladshaw, Austin; Yiacoumi, Sotira; Tsouris, Costas; DePaoli, David W.

    2015-01-07

    Over the last several decades, modeling of gas–solid adsorption at equilibrium has generally been accomplished through the use of isotherms such as the Freundlich, Langmuir, Tóth, and other similar models. While these models are relatively easy to adapt for describing experimental data, their simplicity limits their generality to be used with many different sets of data. This limitation forces engineers and scientists to test each different model in order to evaluate which one can best describe their data. Additionally, the parameters of these models all have a different physical interpretation, which may have an effect on how they can be further extended into kinetic, thermodynamic, and/or mass transfer models for engineering applications. Therefore, it is paramount to adopt not only a more general isotherm model, but also a concise methodology to reliably optimize for and obtain the parameters of that model. A model of particular interest is the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm. The GSTA isotherm has enormous flexibility, which could potentially be used to describe a variety of different adsorption systems, but utilizing this model can be fairly difficult due to that flexibility. To circumvent this complication, a comprehensive methodology and computer code has been developed that can perform a full equilibrium analysis of adsorption data for any gas-solid system using the GSTA model. The code has been developed in C/C++ and utilizes a Levenberg–Marquardt’s algorithm to handle the non-linear optimization of the model parameters. Since the GSTA model has an adjustable number of parameters, the code iteratively goes through all number of plausible parameters for each data set and then returns the best solution based on a set of scrutiny criteria. Data sets at different temperatures are analyzed serially and then linear correlations with temperature are made for the parameters of the model. The end result is a full set of

  3. Generalized gas-solid adsorption modeling: Single-component equilibria

    DOE PAGES

    Ladshaw, Austin; Yiacoumi, Sotira; Tsouris, Costas; ...

    2015-01-07

    Over the last several decades, modeling of gas–solid adsorption at equilibrium has generally been accomplished through the use of isotherms such as the Freundlich, Langmuir, Tóth, and other similar models. While these models are relatively easy to adapt for describing experimental data, their simplicity limits their generality to be used with many different sets of data. This limitation forces engineers and scientists to test each different model in order to evaluate which one can best describe their data. Additionally, the parameters of these models all have a different physical interpretation, which may have an effect on how they can bemore » further extended into kinetic, thermodynamic, and/or mass transfer models for engineering applications. Therefore, it is paramount to adopt not only a more general isotherm model, but also a concise methodology to reliably optimize for and obtain the parameters of that model. A model of particular interest is the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm. The GSTA isotherm has enormous flexibility, which could potentially be used to describe a variety of different adsorption systems, but utilizing this model can be fairly difficult due to that flexibility. To circumvent this complication, a comprehensive methodology and computer code has been developed that can perform a full equilibrium analysis of adsorption data for any gas-solid system using the GSTA model. The code has been developed in C/C++ and utilizes a Levenberg–Marquardt’s algorithm to handle the non-linear optimization of the model parameters. Since the GSTA model has an adjustable number of parameters, the code iteratively goes through all number of plausible parameters for each data set and then returns the best solution based on a set of scrutiny criteria. Data sets at different temperatures are analyzed serially and then linear correlations with temperature are made for the parameters of the model. The end result is a full set

  4. Kinetic studies of adsorption of thiocyanate onto ZnCl2 activated carbon from coir pith, an agricultural solid waste.

    PubMed

    Namasivayam, C; Sangeetha, D

    2005-09-01

    The adsorption of thiocyanate onto ZnCl2 activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of various parameters such as agitation time, thiocyanate concentration, adsorbent dose, pH and temperature has been studied. Adsorption followed second-order rate kinetics. Two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q0) was found to be 16.2 mg g(-1) of the adsorbent. The per cent adsorption was maximum in the pH range 3.0-7.0. pH effect and desorption studies showed that ion exchange and chemisorption mechanism are involved in the adsorption process. Thermodynamic parameters such as DeltaG0, DeltaH0 and DeltaS0 for the adsorption were evaluated. The negative values of DeltaH0 confirm the exothermic nature of adsorption. Effects of foreign ions on the adsorption of thiocyanate have been investigated. Removal of thiocyanate from ground water was also tested.

  5. Removal of tetracycline from wastewater using pumice stone: equilibrium, kinetic and thermodynamic studies.

    PubMed

    Guler, Ulker Asli; Sarioglu, Meltem

    2014-01-01

    In this study, pumice stone was used for the removal of tetracyline (TC) from aqueous solutions. It was characterized by XRD, FT-IR, SEM and BET analyses. Cation exchange capacity of pumice stone was found to be 9.9 meq/100 g. Effect of various parameters such as solution pH (2-11), adsorbent dosage (0.5-10 g/L), contact time (2.5-120 min), initial TC concentration (5-300 mg/L) and temperature (20-50°C) on TC adsorption onto pumice was investigated. Also the adsorption of TC on pumice stone was studied as a function of Na(+) and Cu(2+) cations changing pH from 2 to 11 using batch experiments. The best removal efficiency performance was exhibited at adsorbent dosage 10 g/L, pH 3, contact time 120 min. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models were applied to the equilibrium data. The result has shown that the adsorption was favorable, physicochemical in nature and agrees well with Langmuir and Freundlich models. The maximum Langmuir adsorption capacity was found to be 20.02 mg/g. The adsorption behavior of TC on pumices stone was fitted well in the pseudo-second order kinetics model. Thermodynamic parameters calculated from the adsorption data at different temperature showed that the adsorption reaction was feasible, spontaneous and exothermic.

  6. Thermodynamic assessment of Hg(II)-gibbsite interactions.

    PubMed

    Weerasooriya, Rohan; Seneviratne, Wasana; Kathriarachchi, Heasha A; Tobschall, Heinz J

    2006-09-15

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

  7. Electrochemical thermodynamic measurement system

    DOEpatents

    Reynier, Yvan; Yazami, Rachid; Fultz, Brent T.

    2009-09-29

    The present invention provides systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and electrochemical energy storage and conversion systems. Systems and methods of the present invention are configured for simultaneously collecting a suite of measurements characterizing a plurality of interconnected electrochemical and thermodynamic parameters relating to the electrode reaction state of advancement, voltage and temperature. Enhanced sensitivity provided by the present methods and systems combined with measurement conditions that reflect thermodynamically stabilized electrode conditions allow very accurate measurement of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and electrochemical systems, such as the energy, power density, current rate and the cycle life of an electrochemical cell.

  8. Kinetics of adsorption of dyes from aqueous solution using activated carbon prepared from waste apricot.

    PubMed

    Onal, Yunus

    2006-10-11

    Adsorbent (WA11Zn5) has been prepared from waste apricot by chemical activation with ZnCl(2). Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N(2) adsorption and DFT plus software. Adsorption of three dyes, namely, Methylene Blue (MB), Malachite Green (MG), Crystal Violet (CV), onto activated carbon in aqueous solution was studied in a batch system with respect to contact time, temperature. The kinetics of adsorption of MB, MG and CV have been discussed using six kinetic models, i.e., the pseudo-first-order model, the pseudo-second-order model, the Elovich equation, the intraparticle diffusion model, the Bangham equation, the modified Freundlich equation. Kinetic parameters and correlation coefficients were determined. It was shown that the second-order kinetic equation could describe the adsorption kinetics for three dyes. The dyes uptake process was found to be controlled by external mass transfer at earlier stages (before 5 min) and by intraparticle diffusion at later stages (after 5 min). Thermodynamic parameters, such as DeltaG, DeltaH and DeltaS, have been calculated by using the thermodynamic equilibrium coefficient obtained at different temperatures and concentrations. The thermodynamics of dyes-WA11Zn5 system indicates endothermic process.

  9. Porous and Magnetic Molecularly Imprinted Polymers via Pickering High Internal Phase Emulsions Polymerization for Selective Adsorption of λ-Cyhalothrin

    PubMed Central

    Wu, Yunlong; Ma, Yue; Pan, Jianming; Gu, Runxing; Luo, Jialu

    2017-01-01

    A novel macroporous magnetic molecularly imprinted polymer (MMIPs) of was prepared by W/O Pickering (high internal phase emulsions) HIPEs polymerization, and then it was adopted as adsorbent for selective adsorption of λ-cyhalothrin (LC). In static conditions, adsorption capacity of LC increased rapidly in the first 60 min and reached to equilibrium in ~2.0 h. Excellent conformity of the second-order model confirmed the chemical nature of the interaction between the LC and imprinted sites. The fitting adsorption isotherm was a Langmuir type, and the maximum monolayer adsorption capacity at 298 K was 404.4 μmol g−1. Thermodynamic parameters suggested the specific adsorption at 298 K was an exothermic, spontaneous, and entropy decreased process. Competitive recognition studies of the MMIPs were performed with diethyl phthalate (DEP) and the structurally similar compound fenvalerate (FL), and the MMIPs, which displayed high selectivity for LC.

  10. Contrasting pKa of protonated bis(3-aminopropyl)-terminated polyethylene glycol "Jeffamine" and the associated thermodynamic parameters in solution and covalently attached to graphite surfaces.

    PubMed

    Abiman, Poobalasingam; Wildgoose, Gregory G; Crossley, Alison; Jones, John H; Compton, Richard G

    2007-01-01

    The pKa value of protonated Jeffamine (bis(3-aminopropyl) terminated polyethylene glycol) in solution and attached as a monolayer to graphite surfaces has been determined using potentiometric titration. The protonated Jeffamine was found to have a pKa value of 9.7 in solution at 25 degrees C, whereas this value decreases to 7.1 when it is attached to a graphite surface. Potentiometric titrations from 25 to 40 degrees C allowed us to determine the surface pKa of the protonated Jeffamine at each temperature studied and hence to determine the enthalpy, entropy and Gibbs energy changes associated with the deprotonation of the amino-terminated surface bound Jeffamine groups. It was found that the enthalpic contribution is negligibly small and the evaluation of these thermodynamic parameters controlling the shift in surface pKa value indicates that this process is controlled by entropic contribution arising from the ordering/disordering of solvent molecules at the carbon-water interface. This suggests that the long chain Jeffamine molecules are oriented on the carbon surface rather than existing in the bulk solution.

  11. Dependence of the kinetic and thermodynamic parameters on hydrophilic-lipophilic character of alprazolam, clonazepam, diazepam, doxepin and haloperidol in alkaline environment.

    PubMed

    Maślanka, Anna; Krzek, Jan; Szlósarczyk, Marek; Żmudzki, Paweł; Wach, Katarzyna

    2013-10-15

    Examination of the stability of clonazepam, diazepam, alprazolam, haloperidol, and doxepin in basic solutions was performed, together with an assessment of the kinetic (k, t0.1i t0.5) and thermodynamic (Ea, ΔH(++)i ΔS(++)) stability-indicating parameters, which were compared with the lipophilicity (logP) of the studied drugs. It was observed that the calculated values of Ea, ΔH(++) and ΔS(++) for the studied drugs increased from 41.04 kJ/mol to 125.50 kJ/mol, from 37.82 kJ/mol to 122.24 kJ/mol and from -167.09 J/Kmol to 53.02 J/Kmol, respectively, along with an increase of lipophilicity (logP) from 2.12 to 4.30 for the most hydrophilic alprazolam to the most lipophilic haloperidol. The degradation products were identified using UPLC/MS/MS method.

  12. Adsorption of copper ion on magnetite-immobilised chitin.

    PubMed

    Wong, K S; Wong, K H; Ng, S; Chung, W K; Wong, P K

    2007-01-01

    The adsorption of Cu2+ from aqueous solution by magnetite-immobilised chitin (MC) was studied in batch mode. Two conventional adsorbents, cation exchange resin (CER) and activated carbon (AC) were used for the comparison. The physicochemical parameters including pH, concentration of adsorbent, temperature and initial Cu2+ concentration were optimised. Under the optimised conditions, the removal efficiencies of Cu2+ for MC, CER and AC were 91.67, 93.36 and 89.16%, respectively. In addition, the removal capacities of Cu2+ for MC, CER and AC were 56.71, 74.84 and 6.55 mg/g, respectively. The adsorption isotherm studies indicated that the adsorptive behaviour of Cu2+ on three adsorbents could be well described by the Langmuir model. The maximum adsorption capacities (qmax) for MC, CER and AC were 53.19, 89.29 and 5.82 mg/g, respectively. The applicability of the kinetic model has been investigated for MC. Experimental results indicated that a pseudo-second-order reaction model provided the best description of the data with a correlation coefficient 0.999 for different initial Cu2+ concentrations. The rate constants were also determined. Various thermodynamic parameters such as standard free energy (DeltaG 0), enthalpy (DeltaH 0) and entropy (DeltaS 0) were calculated for predicting the adsorption nature of MC. The results indicated that this system was a spontaneous and endothermic process.

  13. Errors in Sounding of the Atmosphere Using Broadband Emission Radiometry (SABER) Kinetic Temperature Caused by Non-Local Thermodynamic Equilibrium Model Parameters

    NASA Technical Reports Server (NTRS)

    Garcia-Comas, Maya; Lopez-Puertas, M.; Funke, B.; Bermejo-Pantaleon, D.; Marshall, Benjamin T.; Mertens, Christopher J.; Remsberg, Ellis E.; Mlynczak, Martin G.; Gordley, L. L.; Russell, James M.

    2008-01-01

    The vast set of near global and continuous atmospheric measurements made by the SABER instrument since 2002, including daytime and nighttime kinetic temperature (T(sub k)) from 20 to 105 km, is available to the scientific community. The temperature is retrieved from SABER measurements of the atmospheric 15 micron CO2 limb emission. This emission separates from local thermodynamic equilibrium (LTE) conditions in the rarefied mesosphere and thermosphere, making it necessary to consider the CO2 vibrational state non-LTE populations in the retrieval algorithm above 70 km. Those populations depend on kinetic parameters describing the rate at which energy exchange between atmospheric molecules take place, but some of these collisional rates are not well known. We consider current uncertainties in the rates of quenching of CO2 (v2 ) by N2 , O2 and O, and the CO2 (v2 ) vibrational-vibrational exchange to estimate their impact on SABER T(sub k) for different atmospheric conditions. The T(sub k) is more sensitive to the uncertainty in the latter two and their effects depend on altitude. The T(sub k) combined systematic error due to non-LTE kinetic parameters does not exceed +/- 1.5 K below 95 km and +/- 4-5 K at 100 km for most latitudes and seasons (except for polar summer) if the Tk profile does not have pronounced vertical structure. The error is +/- 3 K at 80 km, +/- 6 K at 84 km and +/- 18 K at 100 km under the less favourable polar summer conditions. For strong temperature inversion layers, the errors reach +/- 3 K at 82 km and +/- 8 K at 90 km. This particularly affects tide amplitude estimates, with errors of up to +/- 3 K.

  14. Removal of cesium ions from aqueous solution by adsorption onto local Taiwan laterite.

    PubMed

    Wang, Tsing-Hai; Li, Ming-Hsu; Yeh, Wen-Chun; Wei, Yuan-Yaw; Teng, Shi-Ping

    2008-12-30

    Utilization of local Taiwan laterite (LTL) to remove aqueous cesium was investigated in this work under the conditions of various contact time, cesium (Cs) loading and temperature. Experimental results show that adsorption is instantaneous. Freundlich and Langmuir simulation results demonstrate that local Taiwan laterite has high affinity and sorption capacity for Cs at low temperatures, which may be attributed to enhanced desorption as temperature increased. Thermodynamic parameters including DeltaH, DeltaG and DeltaS were calculated and it is indicated that Cs adsorption on LTL is an exothermic, spontaneous and physical adsorption reaction. Moreover, the adsorbed Cs is distributed evenly on the LTL surface, which is confirmed by SEM/EDS mapping images. Furthermore, the absence of apparent shifting or broadening of the kaolinite signal in XRD patterns after Cs adsorption is an indication of the non-expanding characteristic of kaolinite structure.

  15. A New Simplified Local Density Model for Adsorption of Pure Gases and Binary Mixtures

    NASA Astrophysics Data System (ADS)

    Hasanzadeh, M.; Dehghani, M. R.; Feyzi, F.; Behzadi, B.

    2010-12-01

    Adsorption modeling is an important tool for process simulation and design. Many theoretical models have been developed to describe adsorption data for pure and multicomponent gases. The simplified local density (SLD) approach is a thermodynamic model that can be used with any equation of state and offers some predictive capability with adjustable parameters for modeling of slit-shaped pores. In previous studies, the SLD model has been utilized with the Lennard-Jones potential function for modeling of fluid-solid interactions. In this article, we have focused on application of the Sutherland potential function in an SLD-Peng-Robinson model. The advantages and disadvantages of using the new potential function for adsorption of methane, ethane, carbon dioxide, nitrogen, and three binary mixtures on two types of activated carbon are illustrated. The results have been compared with previous models. It is shown that the new SLD model can correlate adsorption data for different pressures and temperatures with minimum error.

  16. Co-adsorption of perfluorooctane sulfonate and phosphate on boehmite: Influence of temperature, phosphate initial concentration and pH.

    PubMed

    Qian, Jin; Shen, Mengmeng; Wang, Peifang; Wang, Chao; Hu, Jing; Hou, Jun; Ao, Yanhui; Zheng, Hao; Li, Kun; Liu, Jingjing

    2017-03-01

    The co-presence of perfluorooctane sulfonate (PFOS) and phosphate in wastewater of various industries has been detected. Removing PFOS and phosphate simultaneously before discharging sewage into natural water can decrease effectively the environmental risk caused by the combined pollution of PFOS and phosphate. In this study, laboratory batch experiments were conducted for investigating the co-adsorption of PFOS and phosphate on boehmite and the influences of temperature, phosphate initial concentration and pH on the co-adsorption. The adsorption thermodynamics and kinetics of PFOS and phosphate on boehmite were also investigated completely and systematically. The results showed that lower temperature favored the co-adsorptions of PFOS and phosphate. The adsorption of PFOS and phosphate on boehmite agreed well with the Langmuir isotherm and the adsorption parameters of thermodynamics are ΔH=-16.9 and -20.0kJmol(-1) (PFOS and phosphate), ΔS=-5.69 and -7.63Jmol(-1) K(-1) (PFOS and phosphate) and ΔG <0 (PFOS and phosphate). It demonstrated that the co-adsorption of PFOS and phosphate on boehmite is a spontaneously exothermic process. Moreover, the co-adsorption process can be described well by a pseudo-second-order kinetic model. With increasing phosphate initial concentration, more phosphate could be adsorbed on boehmite, while the adsorption of PFOS decreased at phosphate initial concentration of less than 30mgL(-1) and increased at that of larger than 30mgL(-1). In the co-adsorption process, the adsorption amount of PFOS decreased with pH increasing, but that of phosphate changed little.

  17. Synthesis, characterization, and mercury adsorption properties of hybrid mesoporous aluminosilicate sieve prepared with fly ash

    NASA Astrophysics Data System (ADS)

    Liu, Minmin; Hou, Li-an; Xi, Beidou; Zhao, Ying; Xia, Xunfeng

    2013-05-01

    A novel hybrid mesoporous aluminosilicate sieve (HMAS) was prepared with fly ash and impregnated with zeolite A precursors. This improved the mercury adsorption of HMAS compared to original MCM-41. The HMAS was characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption, Fourier transform infrared (FTIR) analysis, transmission electron microscopy (TEM) images and 29Si and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra. These showed that the HMAS structure was still retained after impregnated with zeolite A. But the surface area and pore diameter of HMAS decreased due to pore blockage. Adsorption of mercury from aqueous solution was studied on untreated MCM-41and HMAS. The mercury adsorption rate of HMAS was higher than that of origin MCM-41. The adsorption of mercury was investigated on HMAS regarding the pH of mercury solution, initial mercury concentration, and the reaction temperature. The experimental data fit well to Langmuir and Freundlich isotherm models. The Dublin-Radushkevich isotherm and the characterization show that the mercury adsorption on HMAS involved the ion-exchange mechanisms. In addition, the thermodynamic parameters suggest that the adsorption process was endothermic in nature. The adsorption of mercury on HMAS followed the first order kinetics.

  18. Adsorption of Ag, Cu and Hg from aqueous solutions using expanded perlite.

    PubMed

    Ghassabzadeh, Hamid; Mohadespour, Ahmad; Torab-Mostaedi, Meisam; Zaheri, Parisa; Maragheh, Mohammad Ghannadi; Taheri, Hossein

    2010-05-15

    The aim of the present work was to investigate the ability of expanded perlite (EP) to remove of silver, copper and mercury ions from aqueous solutions. Batch adsorption experiments were carried out and the effect of pH, adsorbent dosage, contact time and temperature of solution on the removal process has been investigated. The optimum pH for the adsorption was found to be 6.5. Adsorption of these metal ions reached their equilibrium concentration in 120, 240 and 180 min for Ag (I), Cu (II) and Hg (II) ions, respectively. Experimental data were also evaluated in terms of kinetic characteristics of adsorption and it was found that adsorption process for these metal ions followed well pseudo-second-order kinetics. Using Langmuir isotherm model, maximum adsorption capacity of EP was found to be 8.46, 1.95 and 0.35 mg/g for Ag (I), Cu (II) and Hg (II) ions, respectively. Finally, the thermodynamic parameters including, the change of free energy (DeltaG degrees ), enthalpy (DeltaH degrees ) and entropy (DeltaS degrees ) of adsorption were calculated for each metal ion. The results showed that the adsorption of these metal ions on EP was feasible and exothermic at 20-50 degrees C.

  19. Synthesis, characterization, and mercury adsorption properties of hybrid mesoporous aluminosilicate sieve prepared with fly ash.

    PubMed

    Liu, Minmin; Hou, Li-An; Xi, Beidou; Zhao, Ying; Xia, Xunfeng

    2013-05-15

    A novel hybrid mesoporous aluminosilicate sieve (HMAS) was prepared with fly ash and impregnated with zeolite A precursors. This improved the mercury adsorption of HMAS compared to original MCM-41. The HMAS was characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption, Fourier transform infrared (FTIR) analysis, transmission electron microscopy (TEM) images and (29)Si and (27)Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra. These showed that the HMAS structure was still retained after impregnated with zeolite A. But the surface area and pore diameter of HMAS decreased due to pore blockage. Adsorption of mercury from aqueous solution was studied on untreated MCM-41and HMAS. The mercury adsorption rate of HMAS was higher than that of origin MCM-41. The adsorption of mercury was investigated on HMAS regarding the pH of mercury solution, initial mercury concentration, and the reaction temperature. The experimental data fit well to Langmuir and Freundlich isotherm models. The Dublin-Radushkevich isotherm and the characterization show that the mercury adsorption on HMAS involved the ion-exchange mechanisms. In addition, the thermodynamic parameters suggest that the adsorption process was endothermic in nature. The adsorption of mercury on HMAS followed the first order kinetics.

  20. Adsorption of cellulase Aspergillus niger on a commercial activated carbon: kinetics and equilibrium studies.

    PubMed

    Daoud, Fatima Boukraa-Oulad; Kaddour, Samia; Sadoun, Tahar

    2010-01-01

    The adsorption kinetics of cellulase Aspergillus niger on a commercial activated carbon has been performed using a batch-adsorption technique. The effect of various experimental parameters such as initial enzyme concentration, contact time and temperature were investigated. The pseudo-first-order and pseudo-second-order kinetic models were used to describe the kinetic data which shows that the adsorption of the enzyme followed the pseudo-second-order rate expression and the rate constants were evaluated. The Langmuir and Freundlich adsorption isotherm models were applied to describe the equilibrium isotherms, and the isotherm constants were determined. It was found that Langmuir model was more suitable for our data. The activation energy of adsorption was also evaluated for the adsorption of enzyme onto activated carbon. It was found 11.37 kJ mol(-1). Thermodynamic parameters Delta G(0), Delta H(0) and DeltaS(0) were calculated, indicating that this process can be spontaneous and endothermic. The adsorption enthalpy and entropy were found 11.12 kJ mol(-1) and 0.084 kJ mol(-1)K(-1), respectively. At 30 degrees C and at pH 4.8, 1g activated carbon adsorbed about 1565 mg of cellulase, with a retention of 70% of the native enzyme activity up to five cycles of repeated batch enzyme reactions.

  1. Removal of methylene blue from aqueous solution by adsorption onto pineapple leaf powder.

    PubMed

    Weng, Chih-Huang; Lin, Yao-Tung; Tzeng, Tai-Wei

    2009-10-15

    The ability of an unconventional bio-adsorbent, pineapple leaf powder (PLP) for the adsorption of methylene blue (MB) from aqueous solution was studied. It was observed that intra-particle diffusion was involved in the adsorption process and that the kinetic data fitted well with a pseudo-second-order equation. Fitting parameters revealed that the rate of adsorption increased with decrease in dye concentration and decrease in ionic strength while the mixing speed did not have a significant effect on adsorption. The adsorption was favorable at higher pH and lower temperature, and the equilibrium data were well fitted by the Langmuir isotherm. The maximum adsorption capacity varied from 4.68 x 10(-4) to 9.28 x 10(-4)mol/g when pH increases from 3.5 to 9.5. Thermodynamic parameters suggest that the adsorption is a typical physical process, spontaneous, and exothermic in nature. The results revealed that this agricultural waste has potential to be used as an economical adsorbent for the removal of methylene blue from aqueous solution.

  2. Kinetics and isotherm analysis of Tropaeoline 000 adsorption onto unsaturated polyester resin (UPR): a non-carbon adsorbent.

    PubMed

    Jain, Rajeev; Sharma, Pooja; Sikarwar, Shalini

    2013-03-01

    The presence of dyes in water is undesirable due to the toxicological impact of their entrance into the food chain. Owing to the recalcitrant nature of dyes to biological oxidation, a tertiary treatment like adsorption is required. In the present study, unsaturated polyester resin (UPR) has been used as a sorbent in the treatment of dye-contaminated water. Different concentrations of Tropaeoline 000 containing water were treated with UPR. The preliminary investigations were carried out by batch adsorption to examine the effects of pH, adsorbate concentration, adsorbent dosage, contact time, and temperature. A plausible mechanism for the ongoing adsorption process and thermodynamic parameters have also been obtained from Langmuir and Freundlich adsorption isotherm models. Thermodynamic parameter showed that the sorption process of Tropaeoline 000 onto activated carbon (AC) and UPR were feasible, spontaneous, and endothermic under studied conditions. The estimated values for (ΔG) are -10.48 × 10(3) and -6.098 × 10(3) kJ mol(-1) over AC and UPR at 303 K (30 °C), indicating towards a spontaneous process. The adsorption process followed pseudo-first-order model. The mass transfer property of the sorption process was studied using Lagergren pseudo-first-order kinetic models. The values of % removal and k (ad) for dye systems were calculated at different temperatures (303-323 K). The mechanism of the adsorption process was determined from the intraparticle diffusion model.

  3. Thermodynamic parameters monitoring the equilibrium shift of enzyme-catalyzed hydrolysis/synthesis reactions in favor of synthesis in mixtures of water and organic solvent.

    PubMed

    Deschrevel, Brigitte; Vincent, Jean-Claude; Ripoll, Camille; Thellier, Michel

    2003-01-20

    The main strategy developed to shift the equilibrium state of a hydrolase-catalyzed hydrolysis/synthesis reaction consists in reducing water activity by addition of organic solvents in the reaction medium. We have used several mixtures of water and 1,4-butanediol, ranging from pure water to pure 1,4-butanediol, to study the hydrolysis/synthesis reaction of the N-Cbz-L-tryptophanyl-glycineamide dipeptide, catalyzed by alpha-chymotrypsin. In the presence of 1,4-butanediol, alpha-chymotrypsin also catalyzed the esterification reaction between this diol and N-Cbz-L-tryptophan; this ester hydrolysis/synthesis reaction has thus also been examined. The dipeptide and ester equilibrium concentrations increase when the water content of the reaction medium is decreased. Using our experimental data, we have determined the equilibrium constants of the hydrolysis/synthesis equilibria involving the nonionized forms of the protected amino acids, the estimated values of which are Ksp = 8 10(5) for the dipeptide and Kse = 78 for the ester respectively. They are true thermodynamic equilibrium constants, each related to a single, well-defined reaction equilibrium and with water activity being taken into account. If an organic solvent is added to the reaction medium these equilibria can be shifted towards synthesis by decreasing the water activity but also by modifying the ionization/neutralization equilibrium constant of the ionizable groups. These two effects depend both on the water content and on the nature of the organic solvent used, and, in particular, on its dielectric constant. Because of the importance of this parameter in our study, we discuss using it as an indicator to select an appropriate organic solvent to perform an enzyme-catalyzed synthesis.

  4. Determination of thermodynamic parameters for complexation of calcium and magnesium with chondroitin sulfate isomers using isothermal titration calorimetry: Implications for calcium kidney-stone research

    NASA Astrophysics Data System (ADS)

    Rodgers, Allen L.; Jackson, Graham E.

    2017-04-01

    Chondroitin sulfate (CS) occurs in human urine. It has several potential binding sites for calcium and as such may play an inhibitory role in calcium oxalate and calcium phosphate (kidney stone disease by reducing the supersaturation (SS) and crystallization of these salts. Urinary magnesium is also a role player in determining speciation in stone forming processes. This study was undertaken to determine the thermodynamic parameters for binding of the disaccharide unit of two different CS isomers with calcium and magnesium. These included the binding constant K. Experiments were performed using an isothermal titration calorimeter (ITC) at 3 different pH levels in the physiological range in human urine. Data showed that interactions between the CS isomers and calcium and magnesium occur via one binding site, thought to be sulfate, and that log K values are 1.17-1.93 and 1.77-1.80 for these two metals respectively. Binding was significantly stronger in Mg-CS than in Ca-CS complexes and was found to be dependent on pH in the latter but not in the former. Furthermore, binding in Ca-CS complexes was dependent on the location of the sulfate binding site. This was not the case in the Mg-CS complexes. Interactions were shown to be entropy driven and enthalpy unfavourable. These findings can be used in computational modeling studies to predict the effects of the calcium and magnesium CS complexes on the speciation of calcium and the SS of calcium salts in real urine samples.

  5. Effects of different doses of low power continuous wave he-ne laser radiation on some seed thermodynamic and germination parameters, and potential enzymes involved in seed germination of sunflower (Helianthus annuus L.).

    PubMed

    Perveen, Rashida; Ali, Qasim; Ashraf, Muhammad; Al-Qurainy, Fahad; Jamil, Yasir; Raza Ahmad, Muhammad

    2010-01-01

    In this study, water-soaked seeds of sunflower were exposed to He-Ne laser irradiation of different energies to determine whether or not He-Ne laser irradiation caused changes to seed thermodynamic and germination parameters as well as effects on the activities of germination enzymes. The experiment comprised four energy levels: 0 (control), 100, 300 and 500mJ of laser energy and each treatment replicated four times arranged in a completely randomized design. The experimentation was performed under the greenhouse conditions in the net-house of the Department of Botany, University of Agriculture, Faisalabad. The seed thermodynamic parameters were calculated according to seed germination thermograms determined with a calorimeter at 25.8°C for 72h. Various thermodynamic parameters of seed (ΔH, (ΔS)(e), (ΔS)(c), (ΔS)(e) /Δt and (ΔS)(c) /Δt) were affected significantly due to presowing laser treatment. Significant changes in seed germination parameters and enzyme activities were observed in seeds treated with He-Ne laser. The He-Ne laser seed treatment resulted in increased activities of amylase and protease. These results indicate that the low power continuous wave He-Ne laser light seed treatment has considerable biological effects on seed metabolism. This seed treatment technique can be potentially employed to enhance agricultural productivity.

  6. Thermodynamics of graphene

    NASA Astrophysics Data System (ADS)

    Rusanov, A. I.

    2014-12-01

    The 21st century has brought a lot of new results related to graphene. Apparently, graphene has been characterized from all points of view except surface science and, especially, surface thermodynamics. This report aims to close this gap. Since graphene is the first real two-dimensional solid, a general formulation of the thermodynamics of two-dimensional solid bodies is given. The two-dimensional chemical potential tensor coupled with stress tensor is introduced, and fundamental equations are derived for energy, free energy, grand thermodynamic potential (in the classical and hybrid forms), enthalpy, and Gibbs energy. The fundamentals of linear boundary phenomena are formulated with explaining the concept of a dividing line, the mechanical and thermodynamic line tensions, line energy and other linear properties with necessary thermodynamic equations. The one-dimensional analogs of the Gibbs adsorption equation and Shuttleworth-Herring relation are presented. The general thermodynamic relationships are illustrated with calculations based on molecular theory. To make the reader sensible of the harmony of chemical and van der Waals forces in graphene, the remake of the classical graphite theory is presented with additional variable combinations of graphene sheets. The calculation of the line energy of graphene is exhibited including contributions both from chemical bonds and van der Waals forces (expectedly, the latter are considerably smaller than the former). The problem of graphene holes originating from migrating vacancies is discussed on the basis of the Gibbs-Curie principle. An important aspect of line tension is the planar sheet/nanotube transition where line tension acts as a driving force. Using the bending stiffness of graphene, the possible radius range is estimated for achiral (zigzag and armchair) nanotubes.

  7. An efficient removal of crystal violet dye from waste water by adsorption onto TLAC/Chitosan composite: A novel low cost adsorbent.

    PubMed

    Jayasantha Kumari, H; Krishnamoorthy, P; Arumugam, T K; Radhakrishnan, S; Vasudevan, D

    2017-03-01

    A composite of Typha latifolia activated carbon (TLAC) (a novel, low cost absorbent) and chitosan (TLAC/Chitosan composite) was prepared. The composite was characterised using IR spectra, XRD, FESEM and Pore size studies. Its effectivity was tested for the removal of crystal violet dye from aqueous solutions. The effect of pH, dose rate and initial dye concentration was evaluated. The adsorption isotherm, kinetics and thermodynamic parameters were studied. Langmuir and Freundlich isotherm models were found fit effectively for the dye adsorption data in the present study. The adsorption followed pseudo-second order kinetics. The evaluated thermodynamic parameters show a spontaneous and exothermic reaction. Overall, this study indicates TLAC/Chitosan composite as an effective adsorbent for the removal of crystal violet dye from aqueous solutions.

  8. Removal of Direct Red 23 from aqueous solution using corn stalks: Isotherms, kinetics and thermodynamic studies

    NASA Astrophysics Data System (ADS)

    Fathi, M. R.; Asfaram, A.; Farhangi, A.

    2015-01-01

    The objective of this study was to assess the suitability and efficiency of corn stalk (CS) for the removal of diazo dye Direct Red 23 (DR23) from aqueous solutions. The effect of different variables in the batch method as a function of solution pH, contact time, initial dye concentration, CS amount, temperature, and so forth by the optimization method has been investigated. The color reduction was monitored by spectrophotometry at 503 nm before and after DR23 adsorption on the CS, and the removal percentage was calculated using the difference in absorbance. The sorption processes followed the pseudo second order in addition to intraparticle diffusion kinetics models with a good correlation coefficient with the overall entire adsorption of DR23 on adsorbent. The experimental equilibrium data were tested by four widely used isotherm models namely, Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich (D-R). It was found that adsorption of DR23 on CS well with the Freindlich isotherm model, implying monolayer coverage of dye molecules onto the surface of the adsorbent. More than 99% removal efficiency was obtained within 10 min at adsorbent dose of 0.2 g for initial dye concentration of 10-90 mg L-1 at pH 3. Various thermodynamic parameters, such as Gibbs free energy, entropy, and enthalpy, of the ongoing adsorption process have been calculated. Judgment based on the obtained results of thermodynamic values shows the spontaneous and endothermic nature adsorption processes on adsorbent.

  9. Estimation of thermodynamic and Beyer's parameter ( B / A ) in liquid crystalline 5. m , 5O. m , 5.O m , 5O.O m compounds with m =5 and 16

    NASA Astrophysics Data System (ADS)

    Madhavi Latha, D.; Pisipati, V. G. K. M.; Ramakrishna Nanchara Rao, M.; Datta Prasad, P. V.

    2011-10-01

    The thermodynamic parameters such as Sharma parameter ( So), Huggins parameter ( F), reduced volume ( V˜), reduced compressibility ( V), etc. are studied using the volume expansion coefficient ( α), which is estimated from density for N-( p- n-pentyl benzylidene)- p- n-pentyl aniline (5.5), N-( p-n-pentyloxy benzylidene)- p-n-pentyl aniline (5O.5), N-( p-n-pentyl benzylidene)- p- n-pentyloxy aniline (5.O5), N-( p- n-pentyloxy benzylidene)- p- n-pentyloxy aniline (5O.O5), N-( p- n-pentyl benzylidene)- p- n-hexadecyl aniline (5.16), N-( p- n-pentyloxy benzylidene)- p- n-hexadecyl aniline (5O.16), N-( p- n-pentyl benzylidene)- p- n-hexadecyloxy aniline (5.O16) and N-( p- n-pentyloxy benzylidene)- p- n-hexadecyloxy aniline (5O.O16) compounds in isotropic and liquid crystalline phases. The parameters like intermolecular free length ( Lf), molecular radius ( mr) and Beyer's non-linearity parameter ( B/ A) are also computed from density data for the above compounds. The results are discussed in the light of these parameters variation with temperature in a particular phase in a liquid crystal molecule and with the position of oxygen atom. The thermodynamic parameter So exhibits a constant characteristic value 1.11±0.01 in all the compounds like other reported liquid crystalline compounds, liquids and polymers. The variation of other thermodynamic parameters in LC phases of these compounds with temperature is discussed in the light of the body of the data available.

  10. Highly enhanced adsorption for the removal of Hg(II) from aqueous solution by Mercaptoethylamine/Mercaptopropyltrimethoxysilane functionalized vermiculites.

    PubMed

    Tran, Lytuong; Wu, Pingxiao; Zhu, Yajie; Yang, Lin; Zhu, Nengwu

    2015-05-01

    Vermiculites modified with Mercaptoethylamine (MEA) and 3-Mercaptopropyltrimethoxysilane (MPTMS) were used as effective adsorbents for the removal of Hg(II) from aqueous solution. The physicochemical characteristics of the pristine and functionalized vermiculites were analyzed by XRD, BET, FTIR, SEM, TEM and Zeta potentials, confirming that the vermiculite was successfully functionalized by the organic ligands containing the thiol (SH) metal-chelating groups. Batch adsorption experiments demonstrated that the factors such as initial pH, contact time, temperature, coexisting cations and initial Hg(II) concentration could significantly influence the adsorption behaviors typically for VER and MEA-VER, whereas the adsorption capacity of MPTMS-VER showed negligible dependence on such factors. The maximum adsorption capacity of Hg(II) ions was greatly improved after functionalization, which was in the order of MPTMS-VER>MEA-VER>VER (286.29 μg g(-1), 176.33 μg g(-1), 99.95 μg g(-1), respectively). The adsorption isotherm could be well described with Langmuir model and the kinetic studies indicated that the adsorption process fitted well with the pseudo-second-order model. The calculated thermodynamic parameters suggested that the adsorption process was feasible and spontaneous. The adsorption mechanism of Hg(II) on thiol groups was studied through XPS analysis. Considering the favorable adsorption capacities, thiol-functionalized vermiculites show a promising application in the removal of Hg(II) from wastewater.

  11. Kinetic modeling of liquid-phase adsorption of Congo red dye using guava leaf-based activated carbon

    NASA Astrophysics Data System (ADS)

    Ojedokun, Adedamola Titi; Bello, Olugbenga Solomon

    2016-02-01

    Guava leaf, a waste material, was treated and activated to prepare adsorbent. The adsorbent was characterized using Scanning Electron Microscopy (SEM), Fourier Transform Infra Red (FTIR) and Energy-Dispersive X-ray (EDX) techniques. The carbonaceous adsorbent prepared from guava leaf had appreciable carbon content (86.84 %). The adsorption of Congo red dye onto guava leaf-based activated carbon (GLAC) was studied in this research. Experimental data were analyzed by four different model equations: Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms and it was found to fit Freundlich equation most. Adsorption rate constants were determined using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion model equations. The results clearly showed that the adsorption of CR dye onto GLAC followed pseudo-second-order kinetic model. Intraparticle diffusion was involved in the adsorption process. The mean energy of adsorption calculated from D-R isotherm confirmed the involvement of physical adsorption. Thermodynamic parameters were obtained and it was found that the adsorption of CR dye onto GLAC was an exothermic and spontaneous process at the temperatures under investigation. The maximum adsorption of CR dye by GLAC was found to be 47.62 mg/g. The study shows that GLAC is an effective adsorbent for the adsorption of CR dye from aqueous solution.

  12. Inflight thermodynamic properties

    NASA Technical Reports Server (NTRS)

    Brown, S. C.; Daniels, G. E.; Johnson, D. L.; Smith, O. E.

    1973-01-01

    The inflight thermodynamic parameters (temperature, pressure, and density) of the atmosphere are presented. Mean and extreme values of the thermodynamic parameters given here can be used in application of many aerospace problems, such as: (1) research and planning and engineering design of remote earth sensing systems; (2) vehicle design and development; and (3) vehicle trajectory analysis, dealing with vehicle thrust, dynamic pressure, aerodynamic drag, aerodynamic heating, vibration, structural and guidance limitations, and reentry analysis. Atmospheric density plays a very important role in most of the above problems. A subsection on reentry is presented, giving atmospheric models to be used for reentry heating, trajectory, etc., analysis.

  13. The adsorption of basic dye (Astrazon Blue FGRL) from aqueous solutions onto sepiolite, fly ash and apricot shell activated carbon: kinetic and equilibrium studies.

    PubMed

    Karagozoglu, B; Tasdemir, M; Demirbas, E; Kobya, M

    2007-08-17

    In this study, sepiolite, fly ash and apricot stone activated carbon (ASAC) were used as adsorbents for the investigation of the adsorption kinetics, isotherms and thermodynamic parameters of the basic dye (Astrazon Blue FGRL) from aqueous solutions at various concentrations (100-300 mg/L), adsorbent doses (3-12 g/L) and temperatures (303-323 K). The result showed that the adsorption capacity of the dye increased with increasing initial dye concentration, adsorbent dose and temperature. Three kinetic models, the pseudo-first-order, second-order, intraparticle diffusion, were used to predict the adsorption rate constants. The kinetics of adsorption of the basic dye followed pseudo-second-order kinetics. Equations were developed using the pseudo-second-order model which predicts the amount of the basic dye adsorbed at any contact time, initial dye concentration and adsorbent dose within the given range accurately. The adsorption equilibrium data obeyed Langmuir isotherm. The adsorption capacities (Q0) calculated from the Langmuir isotherm were 181.5 mg/g for ASAC, 155.5 mg/g for sepiolite and 128.2 mg/g for fly ash at 303 K. Thermodynamical parameters were also evaluated for the dye-adsorbent systems and revealed that the adsorption process was endothermic in nature.

  14. Efficient removal of cadmium using magnetic multiwalled carbon nanotube nanoadsorbents: equilibrium, kinetic, and thermodynamic study

    NASA Astrophysics Data System (ADS)

    Pashai Gatabi, Maliheh; Milani Moghaddam, Hossain; Ghorbani, Mohsen

    2016-07-01

    Adsorptive potential of maghemite decorated multiwalled carbon nanotubes (MWCNTs) for the removal of cadmium ions from aqueous solution was investigated. The magnetic nanoadsorbent was synthesized using a versatile and cost effective chemical route. Structural, magnetic and surface charge properties of the adsorbent were characterized using FTIR, XRD, TEM, VSM analysis and pHPZC determination. Batch adsorption experiments were performed under varied system parameters such as pH, contact time, initial cadmium concentration and temperature. Highest cadmium adsorption was obtained at pH 8.0 and contact time of 30 min. Adsorption behavior was kinetically studied using pseudo first-order, pseudo second-order, and Weber-Morris intra particle diffusion models among which data were mostly correlated to pseudo second-order model. Adsorbate-adsorbent interactions as a function of temperature was assessed by Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherm models from which Freundlich model had the highest consistency with the data. The adsorption capacity increased with increasing temperature and maximum Langmuir's adsorption capacity was found to be 78.81 mg g-1 at 298 K. Thermodynamic parameters and activation energy value suggest that the process of cadmium removal was spontaneous and physical in nature, which lead to fast kinetics and high regeneration capability of the nanoadsorbent. Results of this work are of great significance for environmental applications of magnetic MWCNTs as promising adsorbent for heavy metals removal from aqueous solutions.

  15. [Effect of SDS on the adsorption of Cd2+ onto amphoteric modified bentonites].

    PubMed

    Wang, Jian-Tao; Meng, Zhao-Fu; Yang, Ya-Ti; Yang, Shu-Ying; Li, Bin; Xu, Shao-e

    2014-07-01

    Under different modified ratios, temperatures, pH and ionic strengths, the effect of sodium dodecyl sulfonate (SDS) on the adsorption of Cd2+ onto bentonites which modified with amphoteric modifier dodecyl dimethyl betaine (BS-12) was studied by batch experiments, and the adsorption mechanism was also discussed. Results showed that the adsorption of Cd2+ on amphoteric bentonites can be enhanced significantly by SDS combined modification, Cd2+ adsorption decreases in the order: BS + 150SDS (BS-12 + 150% SDS) > BS + 100SDS (BS-12 + 100% SDS) > BS +50SDS(BS-12 + 50% SDS) > BS + 25SDS (BS-12 + 25% SDS) > BS (BS-12) > CK (unmodified soil). The adsorption isotherm can be described by the Langmuir equation. The change of temperature effect from positive on CK and amphoteric bentonites to negative on BS + 150SDS bentonites is observed with an increase of SDS modified ratio. The pH has little influence on Cd2+ adsorption on bentonites. The adsorption of Cd2+ on bentonites decreases with ionic strength rise, but the effect of ionic strength can be reduced with an increase of SDS modified ratio also. The adsorption thermodynamic parameters demonstrated that the adsorption of Cd2+ on modified bentonites was spontaneously controlled by entropy increment. When the SDS modified ratio is lower than 100% CEC, the adsorption of Cd2+ on modified bentonites is a process with characteristics of both enthalpy increment and entropy increment, while the SDS modified ratio is equal to or higher than 100% CEC, the adsorption of Cd2+ on modified bentonites becomes a process of enthalpy decrement and entropy increment.

  16. Potential Use of Molecular Sieves for the Removal of Ni2+ Metal Ion: Kinetics, Isotherms and Thermodynamic Studies

    NASA Astrophysics Data System (ADS)

    Gaddala, Babu Rao; Monditoka, Krishna Prasad; Challa, Venkata Ramachandra Murthy; Kadimpati, Kishore Kumar

    2016-10-01

    The potential of using molecular sieves as adsorbent for the removal of nickel from aqueous solution was investigated. The isotherms and kinetics of nickel adsorption using 3 Å molecular sieves were evaluated. The results indicated that equilibrium was established in about 5 h. The effect of the pH was examined in the range of 2-6. The maximum removal of nickel obtained is at pH value of 5. The effect of dosage also evaluated to get optimum adsorption of nickel. The maximum adsorption capacity at 25 °C is 18.25 mg/g. The effect of temperature has been carried out at 15, 25, 30, and 40 °C. The data obtained from adsorption isotherms of nickel at different temperatures fit to linear form of Freundlich adsorption equation followed by Langmuir equations. Adsorption kinetic data were modelled using the pseudo-first and pseudo-second-order equation models. The results indicated that the pseudo-second-order model was best described adsorption kinetic data. The thermodynamic parameters such as enthalpy (ΔH°), free energy (ΔG°), and entropy (ΔS°) were calculated. They show that adsorption of nickel onto molecular sieves is an exothermic process. These results show that molecular sieves are a good adsorbent for the removal of nickel from aqueous solutions and could be used as a purifier for water and wastewater.

  17. Adsorptive potential of cationic Basic Yellow 2 (BY2) dye onto natural untreated clay (NUC) from aqueous phase: Mass transfer analysis, kinetic and equilibrium profile

    NASA Astrophysics Data System (ADS)

    Öztürk, A.; Malkoc, E.

    2014-04-01

    In this work, natural untreated clay (NUC) was studied for the removal of Basic Yellow 2 (BY2) from aqueous solution in batch system. The effects of initial BY2 concentration, contact time, solution temperature and solution pH on BY2 adsorption were investigated. Nitrogen sorption measurements were employed to investigate the variation in surface and pore properties after dye adsorption. The adsorbent was characterized by means of FTIR, PSD, TEM, XRD and BET analysis. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin and Scatchard isotherm models. The maximum monolayer adsorption capacity was found to be 833.33 mg/g at 25 °C (at room temperature). The pseudo-second-order kinetic model provided the best fit to the experimental datas compared with pseudo-first-order kinetic adsorption models. To explain mass transfer mechanism of BY2 adsorption, obtained experimental datas were applied Weber and Morris model, Body and Frusawa and Smith models. The results show that the adsorption process is controlled by film diffusion. The thermodynamic parameters such as, Gibbs free energy changes (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°) were determined. Adsorption of BY2 on NUC is exothermic and spontaneous in nature. The calculated activation energy of adsorption was found to be 5.24 kJ/mol for BY2. This value indicates that the adsorption process is a physisorption.

  18. Fabrication and characterization of chitosan-crosslinked-poly(alginic acid) nanohydrogel for adsorptive removal of Cr(VI) metal ion from aqueous medium.

    PubMed

    Sharma, Gaurav; Naushad, Mu; Al-Muhtaseb, Ala'a H; Kumar, Amit; Khan, Mohammad Rizwan; Kalia, Susheel; Shweta; Bala, Manju; Sharma, Arush

    2017-02-01

    In this study, chitosan-crosslinked-poly (alginic acid) nanohydrogel (CN-cl-PL(AA)NHG) was synthesized by co-polymerization method. It was used an effective adsorbent for the exclusion of Cr(VI) metal ion from aqueous medium. The synthesized nanohydrogel was characterized by FTIR, SEM and TEM. The TEM images clearly indicated the appearance of smooth surface with average size of particles ranging from 30 to 80nm. The effect of different adsorption parameters like agitation time, temperature, initial metal ion concentration and adsorbent dosage was studied and optimized. The results demonstrated that the prepared chitosan-crosslinked-poly (alginic acid) nanohydrogel had high adsorption tendency for the removal of Cr(VI) from the aqueous solution. The pseudo-second-order equation represented the better adsorption kinetics for the adsorption process. The thermodynamic studies showed the adsorption of Cr(VI) onto CN-cl-PL(AA)NHG was spontaneous and chemical in nature.

  19. Removal of the hazardous dye rhodamine B through photocatalytic and adsorption treatments.

    PubMed

    Jain, Rajeev; Mathur, Megha; Sikarwar, Shalini; Mittal, Alok

    2007-12-01

    This paper reports on photocatalytic and adsorptive treatment of a hazardous xanthene dye, Rohdamine B, in wastewater. The photocatalytic degradation was carried out in the presence of the catalyst TiO(2) and the effects of pH, concentration of the dye, amount of TiO(2), temperature and electron acceptor H(2)O(2) on the degradation process were observed. It was found that photocatalytic degradation by TiO(2) is an effective, economical and faster mode of removing Rohdamine B from aqueous solutions. Attempts were also made to utilize activated carbon and rice husk as potential adsorbents to remove Rhodamine B from wastewater. The adsorption studies were carried out at 40, 50 and 60 degrees C, and the effects of pH, temperature, amount of adsorbents, concentration of adsorbate, etc., on the adsorption were measured. On the basis of adsorption data the Langmuir and Freundlich adsorption isotherm models were also confirmed. The adsorption isotherm constants thus obtained were employed to calculate thermodynamic parameters like Gibb's free energy, change in enthalpy and entropy. In order to observe the quality of wastewater COD measurements were also carried out before and after the treatments. A significant decrease in the COD values was observed, which clearly indicates that both photocatalytic and adsorption methods offer good potential to remove Rhodamine B from industrial effluents.

  20. Adsorption of Chrysoidine R by using fly ash in batch process.

    PubMed

    Matheswaran, Manickam; Karunanithi, Thirugnanam

    2007-06-25

    This investigation deals with effective utilization of fly ash as adsorbent for the removal of Chrysoidine R from the aqueous solution. The fly ash is a major byproduct generated in coal-based thermal power plants and has good potential for use as an adsorbent. A series of experiments were carried out in a batch adsorption technique to obtain the effect of process variables viz. contact time, pH (2, 4, 6 and 8) initial concentration of the dye (400, 600, 800 and 1000mgL(-1)), amount of the adsorbent (125, 250, 375 and 500mgL(-1)), and temperature (303, 313, 323 and 333K) on adsorption. The concentration of dye was determined by spectrophotometer. The results showed that as the amount of the adsorbent was increased, the percentage of dye removal increased accordingly; higher adsorption percentage was observed at lower concentration of chrysoidine. The adsorption data were analyzed using Langmuir and Freundlich isotherms. The adsorption was found to obey pseudo-first order kinetics. An intra particle diffusion model was used to fit the experimental data. The thermodynamic parameters such as standard change in free energy, enthalpy and entropy of adsorption have been calculated. Adsorption of Chrysoidine R on fly ash was found to be an exothermic reaction.

  1. Synthesis, characterization, and mercury adsorption properties of hybrid mesoporous aluminosilicate sieve prepared with fly ash

    PubMed Central

    Liu, Minmin; Hou, Li-an; Xi, Beidou; Zhao, Ying; Xia, Xunfeng

    2013-01-01

    A novel hybrid mesoporous aluminosilicate sieve (HMAS) was prepared with fly ash and impregnated with zeolite A precursors. This improved the mercury adsorption of HMAS compared to original MCM-41. The HMAS was characterized by X-ray diffraction (XRD), nitrogen adsorption–desorption, Fourier transform infrared (FTIR) analysis, transmission electron microscopy (TEM) images and 29Si and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra. These showed that the HMAS structure was still retained after impregnated with zeolite A. But the surface area and pore diameter of HMAS decreased due to pore blockage. Adsorption of mercury from aqueous solution was studied on untreated MCM-41and HMAS. The mercury adsorption rate of HMAS was higher than that of origin MCM-41. The adsorption of mercury was investigated on HMAS regarding the pH of mercury solution, initial mercury concentration, and the reaction temperature. The experimental data fit well to Langmuir and Freundlich isotherm models. The Dublin–Radushkevich isotherm and the characterization show that the mercury adsorption on HMAS involved the ion-exchange mechanisms. In addition, the thermodynamic parameters suggest that the adsorption process was endothermic in nature. The adsorption of mercury on HMAS followed the first order kinetics. PMID:23687400

  2. Adsorption character for removal Cu(II) by magnetic Cu(II) ion imprinted composite adsorbent.

    PubMed

    Ren, Yueming; Wei, Xizhu; Zhang, Milin

    2008-10-01

    A novel magnetic Cu(II) ion imprinted composite adsorbent (Cu(II)-MICA) was synthesized, characterized and applied for the selective removal Cu(II) from aqueous solution in the batch system. The adsorption-desorption and selectivity characteristics were investigated. The maximum adsorption occurred at pH 5-6. The equilibrium time was 6.0h, and a pseudo-second-order model could best describe adsorption kinetics. The adsorption equilibrium data fit Langmuir isotherm equation well with a maximum adsorption capacity of 46.25mg/g and Langmuir adsorption equilibrium constant of 0.0956L/mg at 298K. Thermodynamic parameters analysis predicted an exothermic nature of adsorption and a spontaneous and favourable process that could be mainly governed by physisorption mechanism. The relative selectivity coefficients of Cu(II)-MICA for Cu(II)/Zn(II) and Cu(II)/Ni(II) were 2.31, 2.66 times greater than the magnetic non-imprinted composite adsorbent (MNICA). Results suggested that Cu(II)-MICA was a material of efficient, low-cost, convenient separation under magnetic field and could be reused five times with about 14% regeneration loss.

  3. Adsorption characteristics and behaviors of graphene oxide for Zn(II) removal from aqueous solution

    NASA Astrophysics Data System (ADS)

    Wang, Hou; Yuan, Xingzhong; Wu, Yan; Huang, Huajun; Zeng, Guangming; Liu, Yan; Wang, Xueli; Lin, Ningbo; Qi, Yu

    2013-08-01

    In this study, graphene oxide (GO) was synthesized via modified Hummers’ method, and characterized by scanning electron microscopy (SEM), atomic force microscope (AFM), X-ray diffraction (XRD), and Fourier transform infrared spectrum (FT-IR), X-ray photoelectron spectroscopy (XPS). The adsorption of Zn(II) on GO as a function of pH, adsorbent dosage, foreign ions, contact time, and temperature was investigated using batch technique. Results showed that the suitable pH for Zn(II) removal was about 7.0, and the optimal dosage was 2 mg. The adsorption of Zn(II) onto GO increased sharply within 20 min and obtained equilibrium gradually. Meanwhile, foreign ion and temperature also affected the adsorption performance of GO. The adsorption process was found to be well described by the pseudo-second-order rate model. Equilibrium studies indicated that the data of Zn(II) adsorption followed the Langmuir model. The maximum adsorption capacity for Zn(II) was up to 246 mg/g with a Langmuir adsorption equilibrium constant of 5.7 L/g at 20 °C. The thermodynamic parameters calculated from temperature-dependent sorption isotherms suggested that Zn(II) sorption on GO was an exothermic and spontaneous process in nature. The possibility of Zn(II) recovery was investigated and the result revealed that the maximum Zn(II) recovery yield was achieved with hydrochloric acid.

  4. Adsorption of p-nitroaniline from aqueous solutions onto activated carbon fiber prepared from cotton stalk.

    PubMed

    Li, Kunquan; Zheng, Zheng; Feng, Jingwei; Zhang, Jibiao; Luo, Xingzhang; Zhao, Guohua; Huang, Xingfa

    2009-07-30

    Activated carbon fiber prepared from cotton stalk was used as an adsorbent for the removal of p-nitroaniline (PNA) from aqueous solutions. Liquid phase adsorption experiments were conducted and the maximum adsorptive capacity was determined. The effect of experimental parameters such as pH, salinity and temperature on the adsorption was studied. The obtained experimental data were then fitted with the Langmuir, Freundlich and Redlich-Peterson models to describe the equilibrium isotherms. The kinetics rates were modeled by using the pseudo-first-order and pseudo-second-order equations. The results indicated that cotton stalk activated carbon fiber (CS-ACF) is an effective adsorbent for the removal of PNA from aqueous solutions. The maximum adsorption capacity of 406 mg g(-1) was achieved at the initial PNA concentration of 200 mg L(-1). The optimum pH for the removal of PNA was found to be 7.6. The presence of ammonium chloride proved to be favorable for the process of adsorption. The adsorption amount decreased with increasing temperature. The Redlich-Peterson model was found to best represent the equilibrium data. The kinetic data followed closely the pseudo-second-order equation. Thermodynamic study showed the adsorption was a spontaneous exothermic physical process.

  5. Removal of molybdate from water by adsorption onto ZnCl2 activated coir pith carbon.

    PubMed

    Namasivayam, C; Sangeetha, D

    2006-07-01

    Removal and recovery of molybdate from aqueous solution was investigated using ZnCl2 activated carbon developed from coir pith. Studies were conducted to delineate the effects of contact time, adsorbent dose, molybdate concentration, pH and temperature. Two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q0) was found to be 18.9 mg molybdate/g of the adsorbent. Adsorption followed second order kinetics. Studies were performed at different pH values to find out the pH at which maximum adsorption occurred. The pH effect and desorption studies showed that ion exchange and chemisorption mechanism were involved in the adsorption process. Thermodynamic parameters such as DeltaG0, DeltaH0 and DeltaS0 for the adsorption were evaluated. Effect of foreign ions on adsorption of molybdate has been examined. The results showed that ZnCl2 activated coir pith carbon was effective for the removal and recovery of molybdate from water.

  6. Thermodynamics of adaptive molecular resolution

    NASA Astrophysics Data System (ADS)

    Delgado-Buscalioni, R.

    2016-11-01

    A relatively general thermodynamic formalism for adaptive molecular resolution (AMR) is presented. The description is based on the approximation of local thermodynamic equilibrium and considers the alchemic parameter λ as the conjugate variable of the potential energy difference between the atomistic and coarse-grained model Φ=U(1)-U(0). The thermodynamic formalism recovers the relations obtained from statistical mechanics of H-AdResS (Español et al., J. Chem. Phys. 142, 064115, 2015 (doi:10.1063/1.4907006)) and provides relations between the free energy compensation and thermodynamic potentials. Inspired by this thermodynamic analogy, several generalizations of AMR are proposed, such as the exploration of new Maxwell relations and how to treat λ and Φ as `real' thermodynamic variables. This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

  7. Synthesis of magnetic β-cyclodextrin-chitosan/graphene oxide as nanoadsorbent and its application in dye adsorption and removal.

    PubMed

    Fan, Lulu; Luo, Chuannan; Sun, Min; Qiu, Huamin; Li, Xiangjun

    2013-03-01

    Magnetic β-cyclodextrin-chitosan/graphene oxide materials (MCCG) were fabricated through a facile chemical route and their application as excellent adsorbents for dye removal were also demonstrated. The characteristics results of FTIR, SEM, TEM and XRD showed that MCCG was successfully prepared. The results showed that, benefiting from the surface property of graphene oxide, hydrophobicity of β-cyclodextrin, the abundant amino and hydroxyl functional groups of chitosan, and from the magnetic property of Fe(3)O(4), the adsorbent possesses quite a good and versatile adsorption capacity to the dye under investigation, and can be easily and rapidly extracted from water by magnetic attraction. Most importantly, the adsorbent can be easily and efficiently regenerated for reuse with hardly any compromise of the adsorption capacity. The adsorption kinetics, isotherms and thermodynamics were investigated to indicate that the kinetics and equilibrium adsorptions were well-described by pseudo-second-order kinetic and Langmuir isotherm model, respectively. The thermodynamic parameters suggested that the adsorption process was spontaneous and endothermic in nature. The inherent advantages of the nano-structured adsorbent, such as adsorption capacity, easy, handy operation, rapid extraction, and regeneration, may pave a new, efficient and sustainable way towards highly-efficient dye pollutant removal in water and wastewater treatment.

  8. Adsorption of chromium from aqueous solutions using crosslinked chitosan-diethylenetriaminepentaacetic acid.

    PubMed

    Bhatt, Ronak; Sreedhar, B; Padmaja, P

    2015-03-01

    Chitosan (CH) and its derivatives have been the focus of attention for researchers as potential adsorbents for heavy metal removal. The adsorption potential of chitosan cross-linked with diethylenetriaminepentaacetic acid (CD) for Cr6+ was investigated. CD was characterized by FTIR, XRD, TGA, XPS and ESR techniques. Batch experiments were conducted to optimize the parameters affecting the adsorption of chromium. The optimum pH was found to be 3 and the adsorption process was found to be exothermic. Adsorption isotherms were determined and the maximum adsorption capacity of CD for chromium was found to be 192.3 mg/g which was higher than the adsorption capacity of the adsorbents reported in literature. The thermodynamic parameters, such as Gibbs free energy, changes in enthalpy and changes in entropy change were also evaluated. XPS and ESR studies revealed that Cr6+ adsorbed onto CD was reduced to Cr3+. The efficacy of CD for removal of Cr6+ from chrome plating effluent was demonstrated.

  9. Preparation and characterization of chitosan-zirconium(IV) composite for adsorption of vanadium(V).

    PubMed

    Zhang, Lingfan; Liu, Xin; Xia, Wei; Zhang, Wenqing

    2014-03-01

    In this present study, an inorganic-biopolymer composite based on chitosan-zirconium(IV) was prepared and investigated as a biosorbent for the removal of vanadium(V) ions from aqueous solution. The resulting composite before and after adsorbed V(V) were characterized by using FT-IR, XRD, SEM and EDS, respectively. Various relevant parameters affecting the adsorption capacity such as pH, initial concentration, contact time, temperature and co-existing ions were evaluated. The results demonstrated that the optimum pH was found to be 4.0 and the equilibrium was achieved after 4h for V(V) adsorption. The Langmuir isotherm model could be well described the adsorption of V(V), with the maximum adsorption capacity of 208 mg g(-1) at 30 °C. The kinetics data were well fitted to pseudo-second-order equation, indicating that chemical sorption as the rate-limiting step of adsorption mechanism. The calculated thermodynamic parameters such as ΔG°, ΔH° and ΔS° indicated that the adsorption process was feasible, spontaneous and endothermic in nature. Moreover, co-existing ions including nitrate, chloride and sulfate had a certain effect on the uptake of V(V). The V(V) loaded chitosan-zirconium(IV) composite could be regenerated by 0.01 mol L(-1) sodium hydroxide, with efficiency greater than 95%.

  10. Adsorption behavior of Hg2+ in aqueous solutions on a novel chelating cross-linked chitosan microsphere.

    PubMed

    Xiong, Chunhua; Pi, Leilei; Chen, Xinyi; Yang, Liqun; Ma, Chunan; Zheng, Xuming

    2013-10-15

    In this study, cross-linked chitosan microspheres (CCTS) was synthesized from chitosan and epichlorohydrin (ECH), then, 2-(chloromethyl) benzimidazole (CBM) was introduced to modify CCTS as the ligand. The resulting CBM-chitosan was characterized by EA, FTIR and TGA, and tested for metal adsorption. Results showed that CBM-chitosan has a relatively high selectivity toward Hg(2+). Equilibrium data were fitted well with Langmuir isotherms with the maximum adsorption capacity of 257.8 mg/g for Hg(2+). Both kinetics and thermodynamic parameters of the adsorption process were obtained. The data indicated that adsorption process was exothermic spontaneous reaction and kinetically proceeded according to Second-order kinetics model. CBM-chitosan can be eluted effectively using 1.0 mol/L HCl solution and it has a potential use for separation and preconcentration of Hg(2+) ions from contaminated natural waters.

  11. A comparative study and evaluation of sulfamethoxazole adsorption onto organo-montmorillonites.

    PubMed

    Lu, Laifu; Gao, Manglai; Gu, Zheng; Yang, Senfeng; Liu, Yuening

    2014-12-01

    Three organo-montmorillonites were prepared using surfactants, and their adsorption behaviors toward sulfamethoxazole (SMX) were investigated. The surfactants used were cetyltrimethyl ammonium bromide (CTMAB), 3-(N,N-dimethylhexadecylammonio) propane sulfonate (HDAPS) and 1,3-bis(hexadecyldimethylammonio)-propane dibromide (BHDAP). The properties of the organo-montmorillonites were characterized by X-ray diffraction, scanning electron microscopy and N2 adsorption-desorption isotherm measurements. Results showed that the interlayer spacing of montmorillonite was increased and the surface area as well as the morphology were changed. Batch adsorption experiments showed that the surfactant loading amount had a great effect on the adsorption of SMX. The adsorption process was pH dependent and the maximum adsorption capacity was obtained at pH3 for HDAPS-Mt, while CTMAB-Mt and BHDAP-Mt showed a high removal efficiency at 3-11. The adsorption capacity increased with the initial SMX concentration and contact time but decreased with increasing solution ionic strength. Kinetic data were best described by the pseudo second-order model. Equilibrium data were best represented by the Langmuir model, and the Freundlich constant (n) indicated a favorable adsorption process. The maximum adsorption capacity of SMX was 235.29 mg/g for CTMAB-Mt, 155.28 mg/g for HDAPS-Mt and 242.72 mg/g for BHDAP-Mt. Thermodynamic parameters were calculated to evaluate the spontaneity and endothermic or exothermic nature. The adsorption mechanism was found to be dominated by electrostatic interaction, while hydrophobic interaction played a secondary role.

  12. A model for predicting contaminant removal by adsorption within the International Space Station water processor: 1. Multicomponent equilibrium modeling.

    PubMed

    Bulloch, J L; Hand, D W; Crittenden, J C

    1998-01-01

    A thermodynamic model is developed to predict adsorption equilibrium in the International Space Station water processor's multifiltration beds. The model predicts multicomponent adsorption equilibrium behavior using single-component isotherm parameters and fictitious components representing the background matrix. The fictitious components are determined by fitting total organic carbon and tracer isotherms with the ideal adsorbed solution theory. Multicomponent isotherms using a wastewater with high surfactant and organic compound concentrations are used to validate the equilibrium description on a coconut-shell-based granular activated carbon (GAC), coal-based GAC, and a polymeric adsorbent.

  13. Development of novel delivery system for warfarin based on mesoporous silica: adsorption characteristics of silica materials for the anticoagulant.

    PubMed

    Dolinina, Ekaterina S; Vorobyeva, Evgeniya V; Parfenyuk, Elena V

    2016-08-01

    The adsorption of the anticoagulant warfarin onto unmodified (UMS) and modified (phenyl (PhMS), methyl (MMS), mercaptopropyl (MPMS)) mesoporous silica materials was studied at pH 1.6 and 7.4 and in the temperature range of 293-325 K. The silica materials were prepared by sol-gel method for further characterization by FTIR spectroscopy, N2 adsorption/desorption method, transmission electron microscopy and zeta potential measurements. The effects of medium pH, temperature and surface modification of mesoporous silica material on their adsorption characteristics (adsorption capacity, thermodynamic parameters of adsorption) relative to anticoagulant warfarin were investigated. It was found that medium acid-base properties strongly affect the adsorption of warfarin due to the pH-dependent structural diversity of the drug and ionization state of the silica surfaces. The adsorption capacity of the silica materials at pH 1.6 decreases in the order: MMS > MPMS > UMS > PhMS. The influence of various non-covalent interactions on the adsorption capacity of the silica materials and energy of the drug-silica interactions is discussed. These results may be useful for the development of a novel delivery system of warfarin.

  14. Orange waste: A valuable carbohydrate source for the development of beads with enhanced adsorption properties for cationic dyes.

    PubMed

    Lessa, Emanuele F; Gularte, Matheus S; Garcia, Emanuel S; Fajardo, André R

    2017-02-10

    Eco-friendly pectin and pectin/cellulose microfibers beads (PB and PB-CF) were synthesized using compounds extracted from orange bagasse, a solid waste from the food industry. PB-CF beads showed remarkable differences regarding several properties as compared to the beads without CF. The adsorption capability of PB and PB-CF was tested towards the removal of methylene blue (MB) from aqueous solution. The effect of various parameters on the MB adsorption was investigated. The kinetics and mechanism of adsorption were explained by the pseudo-second-order kinetics and intra-particle diffusion models. Equilibrium adsorption data are explained by the Langmuir isotherm model, which revealed a maximum adsorption capacity of 1550.3mg/g for PB and 2307.9mg/g for PB-CF5. Thermodynamic analysis suggests that the adsorption of MB on the beads is spontaneous and favorable. Recycling study demonstrated that both PB and PB-CF5 can be implemented in 6 consecutive adsorption/desorption cycles without losing their adsorption capacity. These results enable the use of PB and PB-CF as potentially low-cost adsorbents for wastewater treatments.

  15. Salt-enhanced removal of 2-ethyl-1-hexanol from aqueous solutions by adsorption on activated carbon.

    PubMed

    Chang, Ganggang; Bao, Zongbi; Zhang, Zhiguo; Xing, Huabin; Su, Baogen; Yang, Yiwen; Ren, Qilong

    2013-12-15

    2-Ethyl-1-hexanol has extensive industrial applications in solvent extraction, however, in view of its potential pollution to environment, the removal and recovery of 2-ethyl-1-hexanol is considered an essential step toward its sustainable use in the future. In this work, we report the removal of 2-ethyl-1-hexanol from aqueous solutions containing salts in high concentrations by adsorption on a coal-based activated carbon. Adsorption thermodynamics showed that the experimental isotherms were conformed well to the Langmuir equation. Also it was found that inorganic salts, i.e. MgCl2 and CaCl2 in high concentration significantly enhanced the adsorption capacity from 223 mg/g in the deionized water to 277 mg/g in a saline water. This phenomenon of adsorption enhancement could be ascribed to the salt-out effect. Kinetic analysis indicated that adsorption kinetics follows the pseudo-second-order equation and the adsorption rate constants increase with the salt concentration. The dynamic breakthrough volume and adsorbed amount of 2-ethyl-1-hexanol were significantly elevated when the salt is present in the water. The dynamic saturated adsorption amount increased from 218.3mg/g in the deionized water to 309.5mg/g in a salt lake brine. The Tomas model was well applied to predict the breakthrough curves and determine the characteristics parameters of the adsorption column.

  16. Complexes between ovalbumin nanoparticles and linoleic acid: Stoichiometric, kinetic and thermodynamic aspects.

    PubMed

    Sponton, Osvaldo E; Perez, Adrián A; Carrara, Carlos R; Santiago, Liliana G

    2016-11-15

    Stoichiometric, kinetic and thermodynamic aspects of complex formation between heat-induced aggregates of ovalbumin (ovalbumin nanoparticles, OVAn) and linoleic acid (LA) were evaluated. Extrinsic fluorescence data were fitted to modified Scatchard model yielding the following results: n: 49±2 LA molecules bound per OVA monomer unit and Ka: 9.80±2.53×10(5)M. Kinetic and thermodynamic properties were analyzed by turbidity measurements at different LA/OVA monomer molar ratios (21.5-172) and temperatures (20-40°C). An adsorption approach was used and a pseudo-second-order kinetics was found for LA-OVAn complex formation. This adsorption process took place within 1h. Thermodynamic parameters indicated that LA adsorption on OVAn was a spontaneous, endothermic and entropically-driven process, highlighting the hydrophobic nature of the LA and OVAn interaction. Finally, Atomic Force Microscopy imaging revealed that both OVAn and LA-OVAn complexes have a roughly rounded form with size lower than 100nm.

  17. Stochastic thermodynamics

    NASA Astrophysics Data System (ADS)

    Eichhorn, Ralf; Aurell, Erik

    2014-04-01

    'Stochastic thermodynamics as a conceptual framework combines the stochastic energetics approach introduced a decade ago by Sekimoto [1] with the idea that entropy can consistently be assigned to a single fluctuating trajectory [2]'. This quote, taken from Udo Seifert's [3] 2008 review, nicely summarizes the basic ideas behind stochastic thermodynamics: for small systems, driven by external forces and in contact with a heat bath at a well-defined temperature, stochastic energetics [4] defines the exchanged work and heat along a single fluctuating trajectory and connects them to changes in the internal (system) energy by an energy balance analogous to the first law of thermodynamics. Additionally, providing a consistent definition of trajectory-wise entropy production gives rise to second-law-like relations and forms the basis for a 'stochastic thermodynamics' along individual fluctuating trajectories. In order to construct meaningful concepts of work, heat and entropy production for single trajectories, their definitions are based on the stochastic equations of motion modeling the physical system of interest. Because of this, they are valid even for systems that are prevented from equilibrating with the thermal environment by external driving forces (or other sources of non-equilibrium). In that way, the central notions of equilibrium thermodynamics, such as heat, work and entropy, are consistently extended to the non-equilibrium realm. In the (non-equilibrium) ensemble, the trajectory-wise quantities acquire distributions. General statements derived within stochastic thermodynamics typically refer to properties of these distributions, and are valid in the non-equilibrium regime even beyond the linear response. The extension of statistical mechanics and of exact thermodynamic statements to the non-equilibrium realm has been discussed from the early days of statistical mechanics more than 100 years ago. This debate culminated in the development of linear response

  18. Thermodynamic analysis of Bacillus subtilis endospore protonation using isothermal titration calorimetry

    NASA Astrophysics Data System (ADS)

    Harrold, Zoë R.; Gorman-Lewis, Drew

    2013-05-01

    Bacterial proton and metal adsorption reactions have the capacity to affect metal speciation and transport in aqueous environments. We coupled potentiometric titration and isothermal titration calorimetry (ITC) analyses to study Bacillus subtilis spore-proton adsorption. We modeled the potentiometric data using a four and five-site non-electrostatic surface complexation model (NE-SCM). Heats of spore surface protonation from coupled ITC analyses were used to determine site specific enthalpies of protonation based on NE-SCMs. The five-site model resulted in a substantially better model fit for the heats of protonation but did not significantly improve the potentiometric titration model fit. The improvement observed in the five-site protonation heat model suggests the presence of a highly exothermic protonation reaction circa pH 7 that cannot be resolved in the less sensitive potentiometric data. From the log Ks and enthalpies we calculated corresponding site specific entropies. Log Ks and site concentrations describing spore surface protonation are statistically equivalent to B. subtilis cell surface protonation constants. Spore surface protonation enthalpies, however, are more exothermic relative to cell based adsorption suggesting a different bonding environment. The thermodynamic parameters defined in this study provide insight on molecular scale spore-surface protonation reactions. Coupled ITC and potentiometric titrations can reveal highly exothermic, and possibly endothermic, adsorption reactions that are overshadowed in potentiometric models alone. Spore-proton adsorption NE-SCMs derived in this study provide a framework for future metal adsorption studies.

  19. Removal of Pb(II) from water by natural zeolitic tuff: kinetics and thermodynamics.

    PubMed

    Karatas, Mustafa

    2012-01-15

    The present study was aimed at examining the ability of a natural zeolitic volcanic tuff to remove Pb(II) ions from aqueous solutions under various conditions. The effects of various parameters such as optimum adsorbent mass, contact time, pH of the medium, Pb(II) concentration, and temperature were investigated. In addition, different adsorption isotherms were obtained using concentrations of Pb(II) ions ranging from 1mg/L to 200mg/L. The adsorption process follows second-order reaction kinetics and follows the Langmuir adsorption isotherm. The thermodynamic parameters are discussed in this article, including changes in Gibbs free energy, entropy, and enthalpy, for the adsorption of Pb(II) on tuff, and it is revealed that the adsorption process was spontaneous and exothermic under natural conditions. The maximum removal efficiency of 92% was obtained at a pH of 5 with a 25-min contact time for a 10 g/L solid-to-liquid ratio and an initial heavy metal concentration of 100mg/L.

  20. Comparative analysis of tropaeolin adsorption onto raw and acid-treated kaolinite: optimization by Response Surface Methodology.

    PubMed

    de Sales, Priscila F; Magriotis, Zuy M; Rossi, Marco A L S; Resende, Ricardo F; Nunes, Cleiton A

    2015-03-15

    The comparative adsorption of Tropaeolin (TP) onto raw kaolinite (RK) and kaolinite submitted to acid treatment (AK) was studied. RK and AK were characterized by zeta potential and energy dispersive X-ray spectroscopy (EDS). The adsorption was investigated using Composite Central Design (CCD) and the parameters evaluated were initial TP solution concentration, quantity of adsorbent and the pH of the solution. The optimized parameters were: initial TP solution concentration of 75 mg L(-1), pH 4 and 0.12 g adsorbent. Kinetic data were evaluated by pseudo-first order, pseudo-second order and Avrami models. The equilibrium adsorption was analyzed by Langmuir, Freundlich and Sips isotherms. The kinetic data were best fitted to the pseudo-second order model. The Sips isotherm model gives the better correlation to predict the adsorption equilibrium. The maximum adsorption capacities were 18.3 mg g(-1) and 23.2 mg g(-1) for RK and AK, respectively. The calculated thermodynamic parameters showed that the process was spontaneous, endothermic and involving the disorganization of the adsorption system for both adsorbents. The desorption step showed that the AK sample was more suitable as an adsorbent.

  1. Method transfer from high-pressure liquid chromatography to ultra-high-pressure liquid chromatography. I. A thermodynamic perspective.

    PubMed

    Åsberg, Dennis; Leśko, Marek; Samuelsson, Jörgen; Kaczmarski, Krzysztof; Fornstedt, Torgny

    2014-10-03

    This is the first investigation in a series that aims to enhance the scientific knowledge needed for reliable analytical method transfer between HPLC and UHPLC using the quality by design (QbD) framework. Here, we investigated the differences and similarities from a thermodynamic point of view between RP-LC separations conducted with 3.5μm (HPLC) and 1.7μm (UHPLC) C18 particles. Three different model solutes and one pharmaceutical compound were used: the uncharged cycloheptanone, the cationic benzyltriethylammonium chloride, the anionic sodium 2-naphatlene sulfonate and the pharmaceutical compound omeprazole, which was anionic at the studied pH. Adsorption data were determined for the four solutes at varying fractions of organic modifier and in gradient elution in both the HPLC and UHPLC system, respectively. From the adsorption data, the adsorption energy distribution of each compound was calculated and the adsorption isotherm model was estimated. We found that the adsorption energy distribution was similar, with only minor differences in degree of homogeneity, for HPLC and UHPLC stationary phases. The adsorption isotherm model did not change between HPLC and UHPLC, but the parameter values changed considerably especially for the ionic compounds. The dependence of the organic modifier followed the same trend in HPLC as in UHPLC. These results indicates that the adsorption mechanism of a solute is the same on HPLC and UHPLC stationary phases which simplifies design of a single analytical method applicable to both HPLC and UHPLC conditions within the QbD framework.

  2. 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.

  3. Adsorption of gold ions from industrial wastewater using activated carbon derived from hard shell of apricot stones - an agricultural waste.

    PubMed

    Soleimani, Mansooreh; Kaghazchi, Tahereh

    2008-09-01

    In this study, hard shell of apricot stones was selected from agricultural solid wastes to prepare effective and low cost adsorbent for the gold separation from gold-plating wastewater. Different adsorption parameters like adsorbent dose, particle size of activated carbon, pH and agitation speed of mixing on the gold adsorption were studied. The results showed that under the optimum operating conditions, more than 98% of gold was adsorbed onto activated carbon after only 3h. The equilibrium adsorption data were well described by the Freundlich and Langmuir isotherms. Isotherms have been used to obtain thermodynamic parameters. Gold desorption studies were performed with aqueous solution mixture of sodium hydroxide and organic solvents at ambient temperatures. Quantitative recovery of gold ions is possible by this method. As hard shell of apricot stones is a discarded as waste from agricultural and food industries, the prepared activated carbon is expected to be an economical product for gold ion recovery from wastewater.

  4. Removal of beta-blockers from aqueous media by adsorption onto graphene oxide.

    PubMed

    Kyzas, George Z; Koltsakidou, Anastasia; Nanaki, Stavroula G; Bikiaris, Dimitrios N; Lambropoulou, Dimitra A

    2015-12-15

    The aim of the present study is the evaluation of graphene oxide (GhO) as adsorbent material for the removal of beta-blockers (pharmaceutical compounds) in aqueous solutions. The composition and morphology of prepared materials were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Atenolol (ATL) and propranolol (PRO) were used as model drug molecules and their behavior were investigated in terms of GhO dosage, contact time, temperature and pH. Adsorption mechanisms were proposed and the pH-effect curves after adsorption were discussed. The kinetic behavior of GhO-drugs system was analyzed after fitting to pseudo-first and -second order equations. The adsorption equilibrium data were fitted to Langmuir, Freundlich and Langmuir-Freundlich model calculating the maximum adsorption capacity (67 and 116 mg/g for PRO and ATL (25 °C), respectively). The temperature effect on adsorption was tested carrying out the equilibrium adsorption experiments at three different temperatures (25, 45, 65 °C). Then, the thermodynamic parameters of enthalpy, free energy and entropy were calculated. Finally, the desorption of drugs from GhO was evaluated by using both aqueous eluants (pH2-10) and organic solvents.

  5. Enhanced adsorption of phenol from water by a novel polar post-crosslinked polymeric adsorbent.

    PubMed

    Zeng, Xiaowei; Fan, Yunge; Wu, Guolin; Wang, Chunhong; Shi, Rongfu

    2009-09-30

    A novel post-crosslinked polymeric adsorbent PDM-2 was prepared by Friedel-Crafts reaction of pendant vinyl groups without external crosslinking agent. Both the specific surface area and the pore volume of starting copolymer PDM-1 increased significantly after post-crosslinking. Batch adsorption runs of phenol from aqueous solution onto PDM-1 and PDM-2 were investigated. Commercial macroporous resins XAD-4 and AB-8 were chosen as the comparison. Experimental results showed that isotherms of phenol adsorption onto these four polymeric adsorbents could be represented by Freundlich model reasonably. PDM-2 exhibited higher adsorption capacity of phenol than other three adsorbents, which resulted from synergistic effect of larger specific surface area and polar groups on the network. The adsorption process for phenol was proved to be exothermic and spontaneous in nature. Thermodynamic parameters such as Gibb's free energy (DeltaG), change in enthalpy (DeltaH) and change in entropy (DeltaS) were calculated. Kinetics studies indicated that phenol uptake onto PDM-1 and PDM-2 followed the pseudo-second order model and the intraparticle diffusion process was a rate-controlling step. Column adsorption runs demonstrated that nearly 100% regeneration efficiency for PDM-2 by 3BV industrial alcohol and the adsorbate phenol can be easily recovered by further distilling. Continuous column adsorption-regeneration cycles indicated negligible capacity loss of PDM-2 during operation.

  6. Adsorption of an anionic azo dye by cross-linked chitosan/bentonite composite.

    PubMed

    Liu, Qian; Yang, Bingchao; Zhang, Lujie; Huang, Ruihua

    2015-01-01

    In this study, cross-linked chitosan (CCS)/bentonite (BT) composite was prepared by the intercalation of chitosan in bentonite and the cross-linking reaction between chitosan and glutaraldehyde. CCS/BT composite was characterized by using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD) and thermal gravimetric analyses (TGA). Their adsorption characteristics were assessed by using an azo dye (Amido Black 10B) as a model adsorbate. The adsorption of Amido Black 10B onto the CCS/BT composite was found to be optimal at pH 2. The adsorption isotherm was well described by the Langmuir model and the maximum adsorption capacity was 323.6 mg/g at 293K and pH 2. Amido Black 10B adsorption kinetics followed a pseudo-second-order kinetic model. The calculated thermodynamic parameters showed that the adsorption of Amido Black 10B by CCS/BT composite was spontaneous and endothermic in nature.

  7. Modification of bentonite with a cationic surfactant: An adsorption study of textile dye Reactive Blue 19.

    PubMed

    Ozcan, Adnan; Omeroğlu, Ciğdem; Erdoğan, Yunus; Ozcan, A Safa

    2007-02-09

    The utilization of modified bentonite with a cationic surfactant (dodecyltrimethylammonium (DTMA) bromide) as an adsorbent was successfully carried out to remove a synthetic textile dye (Reactive Blue 19 (RB19)) by adsorption, from aqueous solutions. Batch studies were carried out to address various experimental parameters such as pH, contact time and temperature. The surface modification of bentonite with a surfactant was examined using the FTIR spectroscopic technique and elemental analysis. Effective pH for the adsorption of RB19 onto DTMA-bentonite was around 1.5. The Langmuir isotherm model was found to be the best to represent the equilibrium with experimental data. The maximum adsorption capacity (q(max)) has been found to be 3.30x10(-4)molg(-1) or 206.58mgg(-1). The thermodynamic study indicated that the adsorption of RB19 onto DTMA-bentonite was favored with the negative Gibbs free energy values. The pseudo-second-order rate equation was able to provide the best description of adsorption kinetics and the intraparticle diffusion model was also applicable up to 40min for the adsorption of RB19 onto DTMA-bentonite.

  8. Microstructure-Dependent Gas Adsorption: Accurate Predictions of Methane Uptake in Nanoporous Carbons

    SciTech Connect

    Ihm, Yungok; Cooper, Valentino R; Gallego, Nidia C; Contescu, Cristian I; Morris, James R

    2014-01-01

    We demonstrate a successful, efficient framework for predicting gas adsorption properties in real materials based on first-principles calculations, with a specific comparison of experiment and theory for methane adsorption in activated carbons. These carbon materials have different pore size distributions, leading to a variety of uptake characteristics. Utilizing these distributions, we accurately predict experimental uptakes and heats of adsorption without empirical potentials or lengthy simulations. We demonstrate that materials with smaller pores have higher heats of adsorption, leading to a higher gas density in these pores. This pore-size dependence must be accounted for, in order to predict and understand the adsorption behavior. The theoretical approach combines: (1) ab initio calculations with a van der Waals density functional to determine adsorbent-adsorbate interactions, and (2) a thermodynamic method that predicts equilibrium adsorption densities by directly incorporating the calculated potential energy surface in a slit pore model. The predicted uptake at P=20 bar and T=298 K is in excellent agreement for all five activated carbon materials used. This approach uses only the pore-size distribution as an input, with no fitting parameters or empirical adsorbent-adsorbate interactions, and thus can be easily applied to other adsorbent-adsorbate combinations.

  9. Adsorption of neutral red and malachite green onto grapefruit peel in single and binary systems.

    PubMed

    Zou, Weihua; Gao, Shuaipeng; Zou, Xiuli; Bai, Hongjuan

    2013-05-01

    This study characterized the properties of NaOH-modified grapefruit peel (MGP) and investigated its adsorption properties, specifically the adsorption of the synthetic dyes neutral red (NR) and malachite green (MG) onto MGP, in single and binary systems by means of batch techniques. The adsorption equilibrium data of NR onto MGP fit well with both the Langmuir and Koble-Corrigan models, while the Koble-Corrigan and Dubinin-Radushkevich models seemed to agree better with MG adsorption. The maximum equilibrium quantities of NR and MG from the Langmuir model were 640.3 and 314.9 mg/g at 298 K, respectively. The Elovich model was a better fit with the kinetic process, which suggested that ion exchange was one of the main mechanisms at work. The thermodynamic parameters of adsorption systems indicated spontaneous and endothermic processes. In the binary system experiments, NR and MG exhibited competitive adsorption. The quantity of MG adsorbed was more strongly influenced by NR, due to the higher affinity of MGP for the latter.

  10. Liquid phase adsorption behavior of inulin-type fructan onto activated charcoal.

    PubMed

    Li, Kecheng; Liu, Song; Xing, Ronge; Yu, Huahua; Qin, Yukun; Li, Pengcheng

    2015-05-20

    This study describes liquid phase adsorption characteristics of inulin-type fructan onto activated charcoal. Batch mode experiments were conducted to study the effects of pH, contact time, temperature and initial concentration of inulin. Nearly neutral solution (pH 6-8) was favorable to the adsorption and the equilibrium was attained after 40 min with the maximum adsorption Qmax 0.182 g/g (adsorbate/adsorbent) at 298 K. The experimental data analysis indicated that the adsorption process fitted well with the pseudo-second-order kinetic model (R(2) = 1) and Langmuir isotherms model (R(2) > 0.99). Thermodynamic parameters revealed that the adsorption process was spontaneous and exothermic with a physical nature. Inulin desorption could reach 95.9% using 50% ethanol solution and activated charcoal could be reused without significant losses in adsorption capacity. These results are of practical significance for the application of activated charcoal in the production and purification of inulin-type fructan.

  11. An experimental design approach for modeling As(V) adsorption from aqueous solution by activated carbon.

    PubMed

    Bakkal Gula, C; Bilgin Simsek, E; Duranoglu, D; Beker, U

    2015-01-01

    The present paper discusses response surface methodology as an efficient approach for predictive model building and optimization of As(V) adsorption on activated carbon derived from a food industry waste: peach stones. The objectives of the study are application of a three-factor 2³ full factorial and central composite design technique for maximizing As(V) removal by produced activated carbon, and examination of the interactive effects of three independent variables (i.e., solution pH, temperature, and initial concentration) on As(V) adsorption capacity. Adsorption equilibrium was investigated by using Langmuir, Freundlich, and Dubinin-Radushkevich isotherm models. First-order and second-order kinetic equations were used for modeling of adsorption kinetics. Thermodynamic parameters (ΔG °, ΔH °, and ΔS °) were calculated and used to explain the As(V) adsorption mechanism. The negative value of ΔH (-7.778 kJ mol⁻¹) supported the exothermic nature of the sorption process and the Gibbs free energy values (ΔG°) were found to be negative, which indicates that the As(V) adsorption is feasible and spontaneous.

  12. Adsorption of Cd(II) and Pb(II) from aqueous solutions on activated alumina.

    PubMed

    Naiya, Tarun Kumar; Bhattacharya, Ashim Kumar; Das, Sudip Kumar

    2009-05-01

    The ability of activated alumina as synthetic adsorbent was investigated for adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions. Various physico-chemical parameters such as pH, initial metal ion concentration, and adsorbent dosage level and equilibrium contact time were studied. The optimum solution pH for adsorption of Cd(II) and Pb(II) from aqueous solutions was found to be 5. Kinetics data were best described by pseudo-second order model. The effective particle diffusion coefficient of Cd(II) and Pb(II) are of the order of 10(-10) m(2)/s. Values of mass transfer coefficient were estimated as 4.868x10(-6) cm/s and 6.85x10(-6) cm/s for Cd(II) and Pb(II) adsorption respectively. The equilibrium adsorption data for Cd(II) and Pb(II) were better fitted to Langmuir adsorption isotherm model. The thermodynamic studies indicated that the adsorption was spontaneous and exothermic for Cd(II) adsorption and endothermic for Pb(II). The sorption energy calculated from Dubinin-Radushkevich isotherm were 11.85 kJ/mol and 11.8 kJ/mol for the adsorption of Cd(II) and Pb(II) respectively which indicated that both the adsorption processes were chemical in nature. Desorption studies were carried out using dilute mineral acids. Application studies carried out using industrial waste water samples containing Cd(II) and Pb(II) showed the suitability of activated alumina in waste water treatment plant operation.

  13. The adsorption of Cd(II) ions on sulphuric acid-treated wheat bran.

    PubMed

    Ozer, A; Pirinççi, H B

    2006-09-21

    The adsorption of Cd(II) ions which is one of the most important toxic metals by using sulphuric acid-treated wheat bran (STWB) was investigated. The effects of solution pH and temperature, contact time and initial Cd(II) concentration on the adsorption yield were studied. The equilibrium time for the adsorption process was determined as 4 h. The adsorbent used in this study gave the highest adsorption capacity at around pH 5.4. At this pH, adsorption capacity for an initial Cd(II) ions concentration of 100 mg/L was found to be 43.1 mg/g at 25 degrees C for contact time of 4 h. The equilibrium data were analysed using Langmuir and Freundlich isotherm models to calculate isotherm constants. The maximum adsorption capacity (qmax) which is a Langmuir constant decreased from 101.0 to 62.5 mg/g with increasing temperature from 25 to 70 degrees C. Langmuir isotherm data were evaluated to determine the thermodynamic parameters for the adsorption process. The enthalpy change (deltaH(o)) for the process was found to be exothermic. The free energy change (deltaG(o)) showed that the process was feasible. The kinetic results indicated that the adsorption process of Cd(II) ions by STWB followed first-order rate expression and adsorption rate constant was calculated as 0.0081 l/min at 25 degrees C. It was observed that the desorption yield of Cd(II) was highly pH dependent.

  14. Adsorption characteristics of hexavalent chromium on HCB/TiO2

    NASA Astrophysics Data System (ADS)

    Zhang, Li; Zhang, Yonggang

    2014-10-01

    Sol-gel method was adopted to prepare HCB/TiO2 and its adsorption ability of hexavalent chromium, Cr(VI), and removal from aqueous solution were investigated. The samples were characterized by Power X-ray diffraction (XRD) and a transmission electron microscope (TEM) which showed that the TiO2 was deposited on the surface of HCB. FTIR was used to identify the changes of the surface functional groups before and after adsorption. Potentiometric titration method was used to characterize the zero charge (pHpzc) characteristics of the surface of HCB/TiO2 which showed more acidic functional groups containing. Batch experiments showed that initial pH, absorbent dosage, contact time and initial concentration of Cr(VI) were important parameters for the Cr(VI) adsorption studies. The Freundlich isotherm model better reflected the experimental data better. Cr(VI) adsorption process followed the pseudo-second order kinetic model, which illustrated chemical adsorption. The thermodynamic parameters, such as Gibbs free energy (ΔG), changes in enthalpy change (ΔH) and changes in entropy change (ΔS) were also evaluated. Negative value of free energy occurred at temperature range of 25-45 °C, so Cr(VI) adsorption by HCB/TiO2 is spontaneous. Desorption results showed that the adsorption capacity could maintain 80% after five cycles. The maximum adsorption capacity for Cr(VI) was at 27.33 mg g-1 in an acidic medium, of which the value is worth comparable with other low-cost adsorbents.

  15. 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.

  16. 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

  17. Efficacy of mangrove leaf powder for bioremediation of chromium (VI) from aqueous solutions: kinetic and thermodynamic evaluation

    NASA Astrophysics Data System (ADS)

    Sathish, Thadikamala; Vinithkumar, N. V.; Dharani, G.; Kirubagaran, R.

    2015-06-01

    Biosorption of heavy metals by bio-materials has been posited as a potential alternative to the existing physicochemical technologies for detoxification and recovery of toxic and valuable metals from wastewaters. In this context, the role of mangrove leaf powder (MLP) as biosorbent for chromium removal was investigated. In the present study, the effect of process parameters such as particle size, solution pH, initial concentration of Cr(VI) ion and adsorbent dose on chromium removal by MLP was investigated. The maximum sorption was observed at particle size 0.5 mm and pH 2.0. The adsorption data follow the pseudo second-order kinetics model. The isotherms denote that Langmuir model is the best fitted than Freundlich model. The maximum adsorption capacity ( Q 0) of 60.24 mg/g of Cr(VI) at 30 min on MLP was determined using the Langmuir model. The adsorption isotherm model indicates that the chromium is adsorbing as monolayer on the surface of MLP with heterogeneous energetic distribution of active sites. Various thermodynamic parameters, such as Gibb's free energy (∆ G °), enthalpy (∆ H °) and entropy (∆ S °) have been calculated. The thermodynamic data revealed that the adsorption of chromium ions onto MLP is endothermic in nature and a spontaneous process. The results of the present study suggest that MLP is an effective bioremediation measure for removal of high concentration of Cr(VI) in waste waters.

  18. He-Ne laser-induced changes in germination, thermodynamic parameters, internal energy, enzyme activities and physiological attributes of wheat during germination and early growth

    NASA Astrophysics Data System (ADS)

    Jamil, Yasir; Perveen, Rashida; Ashraf, Muhammad; Ali, Qasim; Iqbal, Munawar; Ahmad, Muhammad Raza

    2013-04-01

    Using low power continuous wave He-Ne laser irradiation of seeds, the germination characteristics, thermodynamic changes and enzyme activities as well as changes in morphological attributes were explored for wheat (Triticum aestivum L. cv. S-24) cultivar. The changes in thermodynamic properties such as change in enthalpy (ΔH), entropy generation [(ΔSe)], entropy flux [(ΔSc)], entropy generation ratio [(ΔS)e/Δt], and entropy flux ratio [(ΔS)c/Δt] showed significant (P < 0.05) changes at an energy level of 500 mJ. The germination energy (GE), germination percentage (G%), germination index (GI) as well as α-amylase and protease activities was also found to be higher at 500 mJ, while the mean emergence time (MET) and time for 50% germination (E50) decreased for 300 mJ irradiance. The internal energy of the seeds increased significantly at all laser energy levels, but was highest for 500 mJ 72 h after sowing. The enzyme activities increased up to 24 h after sowing and then declined. The activities of α-amylase and protease were found to be positively correlated with the plant physiological attributes. These results indicate that low power continuous wave He-Ne laser (632 nm) treatment has considerable biological effects on seed metabolism during germination as well as on later vegetative growth.

  19. Removal of Pb(II) ions from aqueous solution by a waste mud from copper mine industry: equilibrium, kinetic and thermodynamic study.

    PubMed

    Ozdes, Duygu; Gundogdu, Ali; Kemer, Baris; Duran, Celal; Senturk, Hasan Basri; Soylak, Mustafa

    2009-07-30

    The objective of this study was to assess the adsorption potential of a waste mud (WM) for the removal of lead (Pb(II)) ions from aqueous solutions. The WM was activated with NaOH in order to increase its adsorption capacity. Adsorption studies were conducted in a batch system as a function of solution pH, contact time, initial Pb(II) concentration, activated-waste mud (a-WM) concentration, temperature, etc. Optimum pH was specified as 4.0. The adsorption kinetic studies indicated that the overall adsorption process was best described by pseudo-second-order kinetics. The equilibrium adsorption capacity of a-WM was obtained by using Langmuir and Freundlich isotherm models and both models fitted well. Adsorption capacity for Pb(II) was found to be 24.4 mg g(-1) for 10 g L(-1) of a-WM concentration. Thermodynamic parameters including the Gibbs free energy (Delta G degrees), enthalpy (Delta H degrees), and entropy (DeltaS degrees) indicated that the adsorption of Pb(II) ions on the a-WM was feasible, spontaneous and endothermic, at temperature range of 0-40 degrees C. Desorption studies were carried out successfully with diluted HCl solutions. The results indicate that a-WM can be used as an effective and no-cost adsorbent for the treatment of industrial wastewaters contaminated with Pb(II) ions.

  20. 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.

  1. Adsorption studies of cadmium ions on alginate-calcium carbonate composite beads

    NASA Astrophysics Data System (ADS)

    Mahmood, Zahid; Amin, Athar; Zafar, Uzma; Raza, Muhammad Amir; Hafeez, Irfan; Akram, Adnan

    2015-07-01

    Alginate-calcium carbonate composite material was prepared in the form of beads and characterized using Fourier transform infra red (FT-IR) spectroscopy and scanning electron microscope (SEM) techniques. The adsorption of Cd2+ ions was studied through batch experiments. The adsorption parameters such as contact time (120 min), adsorbent dose (1.5 g), initial metal ion concentration(10 mg/L), pH (6) and agitation speed (150 rpm) were optimized at room temperature. Langmuir and Freundlich isotherms were applied to the data and it was noted that the adsorption of Cd2+ ions is better explained by Freundlich model. The kinetic studies showed that the adsorption of Cd2+ ions followed pseudo-first order kinetics. Thermodynamic parameters like ∆G 0, ∆H 0 and ∆S 0 were calculated and on the basis of these values it was established that the adsorption process is feasible and endothermic in nature. It was concluded from the study that the composite material of alginate and calcium carbonate can effectively be used to recover Cd2+ ions from wastewater.

  2. Biosorption studies on waste cotton seed for cationic dyes sequestration: equilibrium and thermodynamics

    NASA Astrophysics Data System (ADS)

    Sivarajasekar, N.; Baskar, R.; Ragu, T.; Sarika, K.; Preethi, N.; Radhika, T.

    2016-01-01

    The immature Gossypium hirsutum seeds—an agricultural waste was converted into a novel adsorbent and its effectiveness for cationic dyes removal was discussed in this study. Characterization revealed that sulfuric acid activated waste Gossypium hirsutum seed (WGSAB) contains surface area 496 m2 g-1. The ability of WGSAB to adsorb basic red 2 (BR2) and basic violet 3 (BV3) from aqueous solutions has been studied. Batch adsorption studies were carried out at different initial dye concentrations (100-300 mg l-1), contact time (1-5 h), pH (2-12) and temperature (293-323 K) to understand the adsorption mechanism. Adsorption data were modeled using Langmuir, Freundlich and Toth adsorption isotherms. Equilibrium data of the adsorption process fitted very well to the Toth model for both dyes. The Langmuir maximum adsorption capacity was 66.69 mg g-1 for BV3 and 50.11 mg g-1 for BR2 at optimum conditions. The near unity value of Toth isotherm constant (BR2: 0.999 and BV3: 1.0) indicates that WGSAB surface is heterogeneous in nature. The maximum adsorption capacity predicted by Toth isotherm of BV3 (66.699 mg g-1) is higher than BR2 (50.310 mg g-1). The kinetic investigation revealed that the BR2 and BV3 were chemisorbed on WGSAB surface following Avrami fractional order kinetics. Further, the fractional order and rate constant values are almost similar for every concentration in both the dyes. The thermodynamic parameters such as ΔH 0, ΔS 0 and ΔG 0 were evaluated. The dye adsorption process was found to be spontaneous and endothermic for the two dyes. Regeneration of WGSAB exhausted by the two dyes could be possible via acetic acid as elutant.

  3. Polydopamine-mediated surface functionalization of electrospun nanofibrous membranes: Preparation, characterization and their adsorption properties towards heavy metal ions

    NASA Astrophysics Data System (ADS)

    Wu, Chunlin; Wang, Heyun; Wei, Zhong; Li, Chuan; Luo, Zhidong

    2015-08-01

    In this paper, a simple and versatile approach for the fabrication of a polyethyleneimine (PEI)-functionalized nanofibrous membrane utilizing polydopamine (PDA) as a mediator is proposed. The morphology and structure of the PDA-coated and PEI-grafted nanofibrous membranes were confirmed using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Due to a large specific surface area and long fibrous morphology, the synthesized membranes were used as novel adsorbents for copper ion (Cu2+) removal from aqueous solutions. The adsorption of Cu2+ was investigated on the synthesized membranes regarding the membrane dosages, initial solution pH values, initial solution concentrations, contact times and temperatures. In addition, the adsorption equilibrium data of PEI-grafted membranes were well fitted with the Langmuir adsorption isotherm, and a maximum adsorption capacity value of 33.59 mg g-1 was determined (while it was 21.94 mg g-1 for the PDA-coated membranes). The thermodynamic parameters indicated that Cu2+ absorption was a spontaneous and exothermic adsorption process. In addition, XPS peak differentiation imitating analysis permitted the proposal of a copper-amine coordination adsorption mechanism that can be used to explain changes in the adsorption properties compared to PDA coating nanofibrous membranes.

  4. Adsorption and magnetic removal of neutral red dye from aqueous solution using Fe3O4 hollow nanospheres.

    PubMed

    Iram, Mahmood; Guo, Chen; Guan, Yueping; Ishfaq, Ahmad; Liu, Huizhou

    2010-09-15

    Fe(3)O(4) hollow nanospheres were prepared via a simple one-pot template-free hydrothermal method and were fully characterized. These magnetic spheres have been investigated for application as an adsorbant for the removal of dye contaminants from water. Because of the high specific surface area, nano-scale particle size, and hollow porous material, Fe(3)O(4) hollow spheres showed favorable adsorption behavior for Neutral red. Factors affecting adsorption, such as, initial dye concentration, pH and contact time were evaluated. Langmuir and the Freundlich adsorption isotherms were selected to explicate the interaction of the dye and magnetic adsorbant. The characteristic parameters for each isotherm have been determined. The overall trend followed an increase of the sorption capacity with increasing dye concentration with a maximum of 90% dye removal. The monolayer adsorption capacity of magnetic hollow spheres (0.05 g) for NR in the concentration range studied, as calculated from the Langmuir isotherm model at 25 degrees C and pH 6, was found to be 105 mg g(-1). Adsorption kinetic followed pseudo-second-order reaction kinetics. Thermodynamic study showed that the adsorption processes are spontaneous and endothermic. The combination of the superior adsorption and the magnetic properties of Fe(3)O(4) nanospheres can be useful as a powerful separation tool to deal with environmental pollution.

  5. Thermodynamic parameters of molecular complexes in aqueous solution: enthalpy-entropy compensation in a series of complexes of caffeine with beta- naphthoxyacetic acid and drug-related aromatic compounds.

    PubMed

    Donbrow, M; Sax, P

    1982-04-01

    Stability constants and thermodynamic parameters have been evaluated for the complexation reaction in aqueous solution of caffeine with beta-naphthoxy acetic acid. The values were higher than those previously reported for the complexation of other ligands with methyl xanthines. In nearly all aromatic ligands complexing with caffeine and theophylline for which data are available, both entropy and free energy of complexation were linearly related to the enthalpy, giving an isoequilibrium relationship. Salicylamide, sodium benzoate and cis-methyl cinnamate exhibited slight deviations on the delta G-delta H plot; the non-aromatic dehydroacetic acid showed the largest deviation. The isoequilibrium relationship was shown to be valid statistically (349-365 K, caffeine systems; 353-372 K, caffeine and theophylline systems) indicating underlying chemical causation. Thermodynamic equations are presented for analysis of the factor involved, which are attributed to a combination of substrate-ligand interactions and solvent effects. The substrate-ligand overlap area is considered as a common parameter through which the solvent and interaction forces might cooperate to give rise to linearity in the isoequilibrium relationship. The increasingly negative experimental values of the enthalpy and entropy with increase in ligand planar overlap area are discussed in relation to the underlying forces involved in the complexation.

  6. Optical Melting Measurements of Nucleic Acid Thermodynamics

    PubMed Central

    Turner, Douglas H.

    2014-01-01

    Optical melting experiments provide measurements of thermodynamic parameters for nucleic acids. These thermodynamic parameters are widely used in RNA structure prediction programs and DNA primer design software. This review briefly summarizes the theory and underlying assumptions of the method and provides practical details for instrument calibration, experimental design, and data interpretation. PMID:20946778

  7. 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.

  8. Thermodynamic Metrics and Optimal Paths

    SciTech Connect

    Sivak, David; Crooks, Gavin

    2012-05-08

    A fundamental problem in modern thermodynamics is how a molecular-scale machine performs useful work, while operating away from thermal equilibrium without excessive dissipation. To this end, we derive a friction tensor that induces a Riemannian manifold on the space of thermodynamic states. Within the linear-response regime, this metric structure controls the dissipation of finite-time transformations, and bestows optimal protocols with many useful properties. We discuss the connection to the existing thermodynamic length formalism, and demonstrate the utility of this metric by solving for optimal control parameter protocols in a simple nonequilibrium model.

  9. Actinide Thermodynamics at Elevated Temperatures

    SciTech Connect

    Friese, Judah I.; Rao, Linfeng; Xia, Yuanxian; Bachelor, Paula P.; Tian, Guoxin

    2007-11-16

    The postclosure chemical environment in the proposed Yucca Mountain repository is expected to experience elevated temperatures. Predicting migration of actinides is possible if sufficient, reliable thermodynamic data on hydrolysis and complexation are available for these temperatures. Data are scarce and scattered for 25 degrees C, and nonexistent for elevated temperatures. This collaborative project between LBNL and PNNL collects thermodynamic data at elevated temperatures on actinide complexes with inorganic ligands that may be present in Yucca Mountain. The ligands include hydroxide, fluoride, sulfate, phosphate and carbonate. Thermodynamic parameters of complexation, including stability constants, enthalpy, entropy and heat capacity of complexation, are measured with a variety of techniques including solvent extraction, potentiometry, spectrophotometry and calorimetry

  10. Comparative studies on adsorptive removal of heavy metal ions by biosorbent, bio-char and activated carbon obtained from low cost agro-residue.

    PubMed

    Kırbıyık, Çisem; Pütün, Ayşe Eren; Pütün, Ersan

    2016-01-01

    In this study, Fe(III) and Cr(III) metal ion adsorption processes were carried out with three adsorbents in batch experiments and their adsorption performance was compared. These adsorbents were sesame stalk without pretreatment, bio-char derived from thermal decomposition of biomass, and activated carbon which was obtained from chemical activation of biomass. Scanning electron microscopy and Fourier transform-infrared techniques were used for characterization of adsorbents. The optimum conditions for the adsorption process were obtained by observing the influences of solution pH, adsorbent dosage, initial solution concentration, contact time and temperature. The optimum adsorption efficiencies were determined at pH 2.8 and pH 4.0 for Fe(III) and Cr(III) metal ion solutions, respectively. The experimental data were modelled by different isotherm models and the equilibriums were well described by the Langmuir adsorption isotherm model. The pseudo-first-order, pseudo-second-order kinetic, intra-particle diffusion and Elovich models were applied to analyze the kinetic data and to evaluate rate constants. The pseudo-second-order kinetic model gave a better fit than the others. The thermodynamic parameters, such as Gibbs free energy change ΔG°, standard enthalpy change ΔH° and standard entropy change ΔS° were evaluated. The thermodynamic study showed the adsorption was a spontaneous endothermic process.

  11. Adsorption study of anionic reactive dye from aqueous solution to Mg-Fe-CO3 layered double hydroxide (LDH)

    NASA Astrophysics Data System (ADS)

    Ahmed, I. M.; Gasser, M. S.

    2012-10-01

    Mg-Fe-Cl Layered double hydroxides (LDHs) have been prepared using a method involving separate nucleation and aging steps with Mg/Fe = 3. The interlayer anions readily replaced by carbonate are characterized by X-ray diffraction (XRD) and FTIR. The effects of different parameters, such as pH, contact time, concentration of dye and temperature on the capacity and adsorption mechanism of Mg-Fe-CO3-LDH in removing an anionic dye (congo red, CR) from aqueous solution were separately investigated. The results show that Mg-Fe-CO3-LDH is particularly efficient in removing CR and the dye removal increases with decreasing pH. The adsorption of CR on Mg-Fe-CO3-LDH reached equilibrium after 15 min where 100 mg/L CR was removed. The equilibrium isotherm indicates that the adsorption of CR onto Mg-Fe-CO3-LDH fits to Langmuir and Freundlich equation as well. The adsorption data obtained from the Langmuir model gave good values of the determination coefficient and the saturated adsorption capacity of Mg-Fe-CO3-LDH for CR was found to be 104.6 mg/g. The regeneration study indicates that the prepared LDH could be used for several cycles. The thermodynamic parameters have been calculated, and the adsorption process was found to be spontaneous, endothermic in nature and follows a pseudo-second-order kinetic model.

  12. Descriptive thermodynamics

    NASA Astrophysics Data System (ADS)

    Ford, David; Huntsman, Steven

    2006-06-01

    Thermodynamics (in concert with its sister discipline, statistical physics) can be regarded as a data reduction scheme based on partitioning a total system into a subsystem and a bath that weakly interact with each other. Whereas conventionally, the systems investigated require this form of data reduction in order to facilitate prediction, a different problem also occurs, in the context of communication networks, markets, etc. Such “empirically accessible” systems typically overwhelm observers with the sort of information that in the case of (say) a gas is effectively unobtainable. What is required for such complex interacting systems is not prediction (this may be impossible when humans besides the observer are responsible for the interactions) but rather, description as a route to understanding. Still, the need for a thermodynamical data reduction scheme remains. In this paper, we show how an empirical temperature can be computed for finite, empirically accessible systems, and further outline how this construction allows the age-old science of thermodynamics to be fruitfully applied to them.

  13. Adsorption of Cu(II) on Oxidized Multi-Walled Carbon Nanotubes in the Presence of Hydroxylated and Carboxylated Fullerenes

    PubMed Central

    Wang, Jing; Li, Zhan; Li, Shicheng; Qi, Wei; Liu, Peng; Liu, Fuqiang; Ye, Yuanlv; Wu, Liansheng; Wang, Lei; Wu, Wangsuo

    2013-01-01

    The adsorption of Cu(II) on oxidized multi-walled carbon nanotubes (oMWCNTs) as a function of contact time, pH, ionic strength, temperature, and hydroxylated fullerene (C60(OH)n) and carboxylated fullerene (C60(C(COOH)2)n) were studied under ambient conditions using batch techniques. The results showed that the adsorption of Cu(II) had rapidly reached equilibrium and the kinetic process was well described by a pseudo-second-order rate model. Cu(II) adsorption on oMWCNTs was dependent on pH but independent of ionic strength. Compared with the Freundlich model, the Langmuir model was more suitable for analyzing the adsorption isotherms. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that Cu(II) adsorption on oMWCNTs was spontaneous and endothermic. The effect of C60(OH)n on Cu(II) adsorption of oMWCNTs was not significant at low C60(OH)n concentration, whereas a negative effect was observed at higher concentration. The adsorption of Cu(II) on oMWCNTs was enhanced with increasing pH values at pH < 5, but decreased at pH ≥ 5. The presence of C60(C(COOH)2)n inhibited the adsorption of Cu(II) onto oMWCNTs at pH 4–6. The double sorption site model was applied to simulate the adsorption isotherms of Cu(II) in the presence of C60(OH)n and fitted the experimental data well. PMID:24009683

  14. Adsorption of Candida rugosa lipase at water-polymer interface: The case of poly( DL)lactide

    NASA Astrophysics Data System (ADS)

    Kamel, Gihan; Bordi, Federico; Chronopoulou, Laura; Lupi, Stefano; Palocci, Cleofe; Sennato, Simona; Verdes, Pedro V.

    2011-12-01

    Insights into the interactions between biological macromolecules and polymeric surfaces are of great interest because of potential uses in developing biotechnologies. In this study we focused on the adsorption of a model lipolytic enzyme, Candida rugosa lipase (CRL), on poly-(D,L)-lactic acid (PDLLA) polymer with the aim to gain deeper insights into the interactions between the enzyme and the carrier. Such studies are of particular relevance in order to establish the optimal conditions for enzyme immobilization and its applications. We employed two different approaches; by analyzing the influence of adsorbed CRL molecules on the thermodynamic behavior of Langmuir films of PDLLA deposited at air-water interface, we gained interesting information on the molecular interactions between the protein and the polymer. Successively, by a systematic analysis of the adsorption of CRL on PDLLA nanoparticles, we showed that the adsorption of a model lipase, CRL, on PDLLA is described in terms of a Langmuir-type adsorption behavior. In this model, only monomolecular adsorption takes place (i.e. only a single layer of the protein adsorbs on the support) and the interactions between adsorbed molecules and surface are short ranged. Moreover, both the adsorption and desorption are activated processes, and the heat of adsorption (the difference between the activation energy for adsorption and desorption) is independent from the surface coverage of the adsorbing species. Finally, we obtained an estimate of the number of molecules of the protein adsorbed per surface unit on the particles, a parameter of a practical relevance for applications in biocatalysis, and a semi-quantitative estimate of the energies (heat of adsorption) involved in the adsorption process.

  15. Kinetics and thermodynamic studies for removal of acid blue 129 from aqueous solution by almond shell

    PubMed Central

    2014-01-01

    Efficiency and performance of Almond shell (AS) adsorbent for the removal and recovery of Acid Blue 129 (AB129) from wastewater is presented in this report. The influence of variables including pH, initial dye concentration, adsorbent dosage, particle size, contact time and temperature on the dye removal have been investigated in batch method by one at a time optimization method. The experimental equilibrium data were tested by four widely used isotherm models namely, Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich (D–R). It was found that adsorption of AB129 on AS well with the Langmuir isotherm model, implying monolayer coverage of dye molecules onto the surface of the adsorbent. More than 98% removal efficiency was obtained within 14 min at adsorbent dose of 0.4 g for initial dye concentration of 40 mg/L at pH 2. Kinetics of the adsorption process was tested by pseudo-first-order and pseudo-second-order kinetics, and intraparticle diffusion mechanism. Pseudo-second-order kinetic model provided a better correlation for the experimental data studied in comparison to the pseudo-first-order model. Calculation of various thermodynamic parameters such as, Gibb’s free energy, entropy and enthalpy of the on-going adsorption process indicate feasibility and endothermic nature of AB129 adsorption on all adsorbents. This work can be used in design of adsorption columns for dyes removal. PMID:24620822

  16. Critical adsorption and critical Casimir forces in the canonical ensemble

    NASA Astrophysics Data System (ADS)

    Gross, Markus; Vasilyev, Oleg; Gambassi, Andrea; Dietrich, S.

    2016-08-01

    Critical properties of a liquid film between two planar walls are investigated in the canonical ensemble, within which the total number of fluid particles, rather than their chemical potential, is kept constant. The effect of this constraint is analyzed within mean-field theory (MFT) based on a Ginzburg-Landau free-energy functional as well as via Monte Carlo simulations of the three-dimensional Ising model with fixed total magnetization. Within MFT and for finite adsorption strengths at the walls, the thermodynamic properties of the film in the canonical ensemble can be mapped exactly onto a grand canonical ensemble in which the corresponding chemical potential plays the role of the Lagrange multiplier associated with the constraint. However, due to a nonintegrable divergence of the mean-field order parameter profile near a wall, the limit of infinitely strong adsorption turns out to be not well-defined within MFT, because it would necessarily violate the constraint. The critical Casimir force (CCF) acting on the two planar walls of the film is generally found to behave differently in the canonical and grand canonical ensembles. For instance, the canonical CCF in the presence of equal preferential adsorption at the two walls is found to have the opposite sign and a slower decay behavior as a function of the film thickness compared to its grand canonical counterpart. We derive the stress tensor in the canonical ensemble and find that it has the same expression as in the grand canonical case, but with the chemical potential playing the role of the Lagrange multiplier associated with the constraint. The different behavior of the CCF in the two ensembles is rationalized within MFT by showing that, for a prescribed value of the thermodynamic control parameter of the film, i.e., density or chemical potential, the film pressures are identical in the two ensembles, while the corresponding bulk pressures are not.

  17. Fluoride adsorption from aqueous solution by magnetic core-shell Fe3O4@alginate-La particles fabricated via electro-coextrusion

    NASA Astrophysics Data System (ADS)

    Zhang, Yahui; Lin, Xiaoyan; Zhou, Quisheng; Luo, Xuegang

    2016-12-01

    The magnetic core-shell Fe3O4@Alg-La particles were fabricated successfully by a simple method of electro-coextrusion, and employed as an adsorbent for separation of fluoride from aqueous solution. Main factors affecting the removal of fluoride, including pH, adsorbent dosage, initial concentration, temperature and contact time were investigated. The adsorption isotherm and adsorption kinetics were studied to understand the adsorption process in detail. The experimental data were fitted well by the non-linear Freundlich isotherm and linear pseudo-second-order model, the maximum fluoride adsorption capacity was 45.230 mg/g at pH 4, 298.15 K. Thermodynamic parameters indicated that the fluoride adsorption process was feasible and spontaneous. The presence of other anions like Cl-, SO42-, HCO3- and PO43- had almost no effect on the fluoride adsorption. The adsorbent can be easily separated from the solution by a magnet. The magnetic core-shell Fe3O4@Alg-La particles before and after fluoride adsorption were studied by SEM, FTIR, EDX and XPS, which indicated that the adsorption mechanism may be related to electrostatic attraction and Lewis acid-base interaction.

  18. Study of the behaviour of thorium adsorption on PAN/zeolite composite adsorbent.

    PubMed

    Kaygun, A Kilincarslan; Akyil, S

    2007-08-17

    The adsorption behaviour of thorium from aqueous solutions by a composite adsorbent has been investigated by a batch technique. The thorium adsorption on composite adsorbent was studied as a function of initial concentration, pH, shaking time and temperature. The sorption of thorium at the determined optimum conditions follows Langmuir, Freundlich and D-R type isotherms. Langmuir constants Q=0.04 mmol g(-1) and b=64.94 L mol(-1) and of D-R parameter Xm = 0.04, beta=0.79 and of sorption energy E=0.80 and Freundlich constants 1/n=3.12 and cm = 0.012 mmol g(-1) were evaluated. Thermodynamic parameters such as DeltaH and DeltaS were found to be 37.32 kJ mol(-1) and 206.17 J mol(-1)K(-1), respectively.

  19. Removal of anionic dye Congo red from aqueous solution by raw pine and acid-treated pine cone powder as adsorbent: equilibrium, thermodynamic, kinetics, mechanism and process design.

    PubMed

    Dawood, Sara; Sen, Tushar Kanti

    2012-04-15

    Pine cone a natural, low-cost agricultural by-product in Australia has been studied for its potential application as an adsorbent in its raw and hydrochloric acid modified form. Surface study of pine cone and treated pine cone was investigated using Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The modification process leads to increases in the specific surface area and decreases mean particle sizes of acid-treated pine cone when compared to raw pine cone biomass. Batch adsorption experiments were performed to remove anionic dye Congo red from aqueous solution. It was found that the extent of Congo red adsorption by both raw pine cone biomass and acid-treated biomass increased with initial dye concentration, contact time, temperature but decreased with increasing solution pH and amount of adsorbent of the system. Overall, kinetic studies showed that the dye adsorption process followed pseudo-second-order kinetics based on pseudo-first-order and intra-particle diffusion models. The different kinetic parameters including rate constant, half-adsorption time, and diffusion coefficient were determined at different physico-chemical conditions. Equilibrium data were best represented by Freundlich isotherm model among Langmuir and Freundlich adsorption isotherm models. It was observed that the adsorption was pH dependent and the maximum adsorption of 32.65 mg/g occurred at pH of 3.55 for an initial dye concentration of 20 ppm by raw pine cone, whereas for acid-treated pine cone the maximum adsorption of 40.19 mg/g for the same experimental conditions. Freundlich constant 'n' also indicated favourable adsorption. Thermodynamic parameters such as ∆G(0), ∆H(0), and ∆S(0) were calculated. A single-stage batch absorber design for the Congo red adsorption onto pine cone biomass also presented based on the Freundlich isotherm model equation.

  20. Equilibrium and kinetic studies of C.I. Basic Blue 41 adsorption onto N, F-codoped flower-like TiO2 microspheres

    NASA Astrophysics Data System (ADS)

    Jiang, Yinhua; Luo, Yingying; Zhang, Fumei; Guo, Leiqun; Ni, Liang

    2013-05-01

    Three-dimensional (3D) N, F-codoped flower-like TiO2 microspheres were successfully synthesized by a hydrothermal method combined with calcination process. The as-prepared samples were characterized by XRD, FE-SEM and EDS. The adsorption abilities of prepared samples were investigated for the removal of C.I. Basic Blue 41(CB41) from aqueous solution. The FE-SEM and adsorption results showed that doping amount of NH4F affected the morphologies of samples and sample NFT-1 with the structure of 3D flower-like microsphere had the highest adsorption amount of CB41. The effects of varying parameters such as pH, contact time, initial dye concentration and temperature on the CB41 adsorption onto NFT-1 were further examined. Equilibrium data correlated with Langmuir, Freundlich and Temkin isotherms. The Langmuir isotherm showed the best fit to the equilibrium data. The kinetic experimental data were analyzed by three kinetic models including the pseudo-first-order model, the pseudo-second-order model and the intraparticle diffusion model to access the adsorption mechanism and the potential rate-controlling step. The pseudo-second-order kinetic model described best for the adsorption of CB41 on NFT-1 and the intraparticle diffusion was not the only rate-controlling step. The thermodynamics parameters as positive values of ΔH° and negative values of ΔG° showed that the adsorption process was endothermic and spontaneous in nature.

  1. Batch and fixed-bed adsorption of tartrazine azo-dye onto activated carbon prepared from apricot stones

    NASA Astrophysics Data System (ADS)

    Albroomi, H. I.; Elsayed, M. A.; Baraka, A.; Abdelmaged, M. A.

    2016-02-01

    This work describes the potential of utilizing prepared activated carbon from apricot stones as an efficient adsorbent material for tartrazine (TZ) azo-dye removal in a batch and dynamic adsorption system. The results revealed that activated carbons with well-developed surface area (774 m2/g) and pore volume (1.26 cm3/g) can be manufactured from apricot stones by H3PO4 activation. In batch experiments, effects of the parameters such as initial dye concentration and temperature on the removal of the dye were studied. Equilibrium was achieved in 120 min. Adsorption capacity was found to be dependent on the initial concentration of dye solution, and maximum adsorption was found to be 76 mg/g at 100 mg/L of TZ. The adsorption capacity at equilibrium (q e) increased from 22.6 to 76 mg/g with an increase in the initial dye concentrations from 25 to 100 mg/L. The thermodynamic parameters such as change in free energy (ΔG 0), enthalpy (ΔH 0) and entropy (ΔS 0) were determined and the positive value of (ΔH) 78.1 (K J mol-1) revealed that adsorption efficiency increased with an increase in the process temperature. In fixed-bed column experiments, the effect of selected operating parameters such as bed depth, flow rate and initial dye concentration on the adsorption capacity was evaluated. Increase in bed height of adsorption columns leads to an extension of breakthrough point as well as the exhaustion time of adsorbent. However, the maximum adsorption capacities decrease with increases of flow rate. The breakthrough data fitted well to bed depth service time and Thomas models with high coefficient of determination, R 2 ≥ 94.

  2. Quantum-mechanical parameters for the risk assessment of multi-walled carbon-nanotubes: A study using adsorption of probe compounds and its application to biomolecules.

    PubMed

    Chayawan; Vikas

    2016-11-01

    This work forwards new insights into the risk-assessment of multi-walled carbon-nanotubes (MWCNTs) while analysing the role of quantum-mechanical interactions between the electrons in the adsorption of probe compounds and biomolecules by MWCNTs. For this, the quantitative models are developed using quantum-chemical descriptors and their electron-correlation contribution. The major quantum-chemical factors contributing to the adsorption are found to be mean polarizability, electron-correlation energy, and electron-correlation contribution to the absolute electronegativity and LUMO energy. The proposed models, based on only three quantum-chemical factors, are found to be even more robust and predictive than the previously known five or four factors based linear free-energy and solvation-energy relationships. The proposed models are employed to predict the adsorption of biomolecules including steroid hormones and DNA bases. The steroid hormones are predicted to be strongly adsorbed by the MWCNTs, with the order: hydrocortisone > aldosterone > progesterone > ethinyl-oestradiol > testosterone > oestradiol, whereas the DNA bases are found to be relatively less adsorbed but follow the order as: guanine > adenine > thymine > cytosine > uracil. Besides these, the developed electron-correlation based models predict several insecticides, pesticides, herbicides, fungicides, plasticizers and antimicrobial agents in cosmetics, to be strongly adsorbed by the carbon-nanotubes. The present study proposes that the instantaneous inter-electronic interactions may be quite significant in various physico-chemical processes involving MWCNTs, and can be used as a reliable predictor for their risk assessment.

  3. Diethyl phthalate removal from aqueous phase using poly(EGDMA-MATrp) beads: kinetic, isothermal and thermodynamic studies.

    PubMed

    Özer, Elif Tümay; Osman, Bilgen; Kara, Ali; Demirbel, Emel; Beşirli, Necati; Güçer, Şeref

    2015-01-01

    In this study, poly(ethylene glycol dimethacrylate-N-methacryloyl-L-tryptophan methyl ester) [poly(EGDMA-MATrp)] beads (average diameter=106-300 µm), which were synthesized by co-polymerizing of N-methacryloyl-L-tryptophan methyl ester (MATrp) with ethylene glycol dimethacrylate (EGDMA), were used for diethyl phthalate (DEP) adsorption. The various factors affecting the adsorption of DEP from aqueous solutions such as pH, initial concentration, contact time and temperature were analysed. Adsorption behaviour of DEP on the poly(EGDMA-MATrp) beads was investigated by varying pH values of solution, contact time, initial concentration and temperature. An optimum adsorption capacity of 590.7 mg/g for DEP was obtained at 25 °C. The present adsorption process obeyed a pseudo-second-order kinetic model. All the isotherm data can be fitted with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. Thermodynamic parameters ΔH=7.745 kJ/mol, ΔS=81.92 J/K/mol and ΔG=-16.69 kJ/mol to -18.31 kJ/mol with the rise in temperature from 25 °C to 45 °C indicated that the adsorption process was endothermic and spontaneous.

  4. Removal of thorium (IV) ions from aqueous solution by a novel nanoporous ZnO: Isotherms, kinetic and thermodynamic studies.

    PubMed

    Kaynar, Ümit H; Ayvacıklı, Mehmet; Hiçsönmez, Ümran; Kaynar, Sermin Çam

    2015-12-01

    The adsorption of thorium (IV) from aqueous solutions onto a novel nanoporous ZnO particles prepared by microwave assisted combustion was studied using batch methods under different experimental conditions. The effect of contact time, solution pH, initial concentration and temperature on adsorption process was studied. The ability of this material to remove Th (IV) from aqueous solution was characterises by Langmuir, Freunlinch and Temkin adsorption isotherms. The adsorption percent and distribution coefficient for nanoporous ZnO powders in optimum conditions were 97% ± 1.02; 8080 L kg(-1)for Th (IV), respectively. Based on the Langmuir model, the maximum adsorption capacity of nanoporous ZnO for Th (IV) was found to be 1500 g kg(-1). Thermodynamic parameters were determined and discussed. The results indicated that nanoporous ZnO was suitable as sorbent material for recovery and adsorption of Th (IV) ions from aqueous solutions. The radioactive Th (VI) in surface water, sea water and waste waters from technologies producing nuclear fuels, mining (uranium and thorium) and laboratories working with radioactive materials (uranium and thorium) can be removed with this nanoporous ZnO.

  5. Adsorption of phenol from aqueous solution by using carbonised beet pulp.

    PubMed

    Dursun, Gülbeyi; Ciçek, Handan; Dursun, Arzu Y

    2005-10-17

    The beet pulp, a major low value by-product in sugar industry was used to prepare carbon for phenol adsorption. It was produced by carbonisation in N2 atmosphere at 600 degrees C for 1.5 h. The surface area of beet pulp carbon was measured as 47.5 m2g(-1) by using BET method. The adsorption studies of phenol from aqueous solution on beet pulp carbon (BPC) have been studied in the range of 25-500 mgdm(-3) initial phenol concentrations and at the temperatures of 25, 40 and 60 degrees C. The maximum phenol adsorption capacity was obtained as 89.5 mgg(-1)at the temperature of 60 degrees C at pH=6.0. The Freundlich and Langmuir adsorption models were used for the mathematical description of the adsorption equilibrium and it was reported that experimental data fitted very well to Freundlich model, although they could be modelled by the Langmuir equation. Batch adsorption models, based on the assumption of the pseudo-first order and pseudo-second order mechanism, were applied to examine the kinetics of the adsorption. The results showed that kinetic data were followed more closely the pseudo-second order model than the pseudo-first order. The thermodynamic parameters such as, equilibrium constant (K), Gibbs free energy changes (DeltaG degrees ), standard enthalpy change (DeltaH degrees ) and standard entropy change (DeltaS degrees ) had been determined. The results show that adsorption of phenol on BPC is an endothermic and spontaneous in nature.

  6. The effect of dependence between vapor heat capacity, specific heat of evaporation-condensation of irrigating liquid and temperature on thermodynamic parameters of processes gases

    NASA Astrophysics Data System (ADS)

    Khromova, Helen; Oparina, Irene

    2014-08-01

    The results of parameters calculations of the vapor-gas flow and droplets of irrigating liquid in application to the conditions of flue gas cooling in the reactors of the soda ash workshop at "Azot" limited company, Kemerovo, are compared.

  7. Nanoscopic Thermodynamics.

    PubMed

    Qi, Weihong

    2016-09-20

    Conventional thermodynamics for bulk substances encounters challenges when one considers materials on the nanometer scale. Quantities such as entropy, enthalpy, free energy, melting temperature, ordering temperature, Debye temperature, and specific heat no longer remain constant but change with the crystal dimension, size, and morphology. Often, one phenomenon is associated with a variety of theories from different perspectives. Still, a model that can reconcile the size and shape dependence of the thermal properties of the nanoscaled substances remains one of the goals of nanoscience and nanotechnology. This Account highlights the nanoscopic thermodynamics for nanoparticles, nanowires, and nanofilms, with particular emphasis on the bond energy model. The central idea is that the atomic cohesive energy determines the thermodynamic performance of a substance and the cohesive energy varies with the atomic coordination environment. It is the cohesive energy difference between the core and the shell that dictates the nanoscopic thermodynamics. This bond energy model rationalizes the following: (i) how the surface dangling bonds depress the melting temperature, entropy, and enthalpy; (ii) how the order-disorder transition of the nanoparticles depends on particle size and how their stability may vary when they are embedded in an appropriate matrix; (iii) predictions of the existence of face-centered cubic structures of Ti, Zr, and Hf at small size; (iv) how two elements that are immiscible in the bulk can form an alloy on the nanoscale, where the critical size can be predicted. The model has enabled us to reproduce the size and shape dependence of a number of physical properties, such as melting temperature, melting entropy, melting enthalpy, ordering temperature, Gibbs free energy, and formation heat, among others, for materials such as Pd, Au, Ag, Cu, Ni, Sn, Pb, In, Bi, Al, Ti, Zr, Hf, In-Al, Ag-Ni, Co-Pt, Cu-Ag, Cu-Ni, Au-Ni, Ag-Pt, and Au-Pt on the nanometer scale

  8. Adsorption studies of chromium (VI) removal from water by lanthanum diethanolamine hybrid material.

    PubMed

    Mandal, Sandip; Sahu, Manoj Kumar; Giri, Anil Kumar; Patel, Raj Kishore

    2014-01-01

    In the present research work, lanthanum diethanolamine hybrid material is synthesized by co-precipitation method and used for the removal of Cr(VI) from synthetic dichromate solution and hand pump water sample. The sorption experiments were carried out in batch mode to optimize various influencing parameters such as adsorbent dose, contact time, pH, competitive anions and temperature. The characterization of the material and mechanism of Cr(VI) adsorption on the material was studied by using scanning electron microscope, Fourier transform infrared, X-ray diffraction, Brunauer-Emmett-Teller and thermogravimetric analysis-differential thermal analysis. Adsorption kinetics studies reveal that the adsorption process followed first-order kinetics and intraparticle diffusion model with correlation coefficients (R2) of 0.96 and 0.97, respectively. The adsorption data were best fitted to linearly transformed Langmuir isotherm with correlation coefficient (R2) of 0.997. The maximum removal of Cr(VI) is found to be 99.31% at optimal condition: pH = 5.6 of the solution, adsorbent dose of 8 g L(-1) with initial concentration of 10mgL(-1) of Cr(VI) solution and an equilibrium time of 50 min. The maximum adsorption capacity of the material is 357.1 mg g(-1). Thermodynamic parameters were evaluated to study the effect of temperature on the removal process. The study shows that the adsorption process is feasible and endothermic in nature. The value of E (260.6 kJ mol(-1)) indicates the chemisorption nature of the adsorption process. The material is difficult to be regenerated. The above studies indicate that the hybrid material is capable of removing Cr(VI) from water.

  9. Statistical Thermodynamics of Biomembranes

    PubMed Central

    Devireddy, Ram V.

    2010-01-01

    An overview of the major issues involved in the statistical thermodynamic treatment of phospholipid membranes at the atomistic level is summarized: thermodynamic ensembles, initial configuration (or the physical system being modeled), force field representation as well as the representation of long-range interactions. This is followed by a description of the various ways that the simulated ensembles can be analyzed: area of the lipid, mass density profiles, radial distribution functions (RDFs), water orientation profile, Deuteurium order parameter, free energy profiles and void (pore) formation; with particular focus on the results obtained from our recent molecular dynamic (MD) simulations of phospholipids interacting with dimethylsulfoxide (Me2SO), a commonly used cryoprotective agent (CPA). PMID:19460363

  10. Uniform Cu2Cl(OH)3 hierarchical microspheres: A novel adsorbent for methylene blue adsorptive removal from aqueous solution

    NASA Astrophysics Data System (ADS)

    Wei, Wei; Gao, Pin; Xie, Jimin; Zong, Sekai; Cui, Henglv; Yue, Xuejie

    2013-08-01

    Using the solution phase method without any surfactants or templates, the hierarchical of Cu2Cl(OH)3 microspheres were synthesized by freeze drying. The size and surface area of the microspheres are ca. 1-2 μm and 76.61 m2 g-1, respectively. A possible formation mechanism is presented based on the experimental results. Methylene blue was chosen to investigate the adsorption capacity of the as-prepared adsorbent. The effects of various experimental parameters, such as pH, initial dye concentration, and contact time were investigated. The results showed that the dye removal increased with the increasing in the initial concentration of the dye and also increased in the amount of microspheres used and initial pH. Adsorption data fitted well with the Freundlich adsorption isotherm. The thermodynamic analysis presented the exothermic, spontaneous and more ordered arrangement process. The microspheres could be employed effective for removal of dyes from aqueous solution.

  11. Low density lipoprotein detection based on antibody immobilized self-assembled monolayer: investigations of kinetic and thermodynamic properties.

    PubMed

    Matharu, Zimple; Bandodkar, Amay Jairaj; Sumana, G; Solanki, Pratima R; Ekanayake, E M I Mala; Kaneto, Keiichi; Gupta, Vinay; Malhotra, B D

    2009-10-29

    Human plasma low density lipoprotein (LDL) immunosensor based on surface plasmon resonance (SPR) and quartz crystal microbalance (QCM) was fabricated by immobilizing antiapolipoprotein B (AAB) onto self-assembled monolayer (SAM) of 4-aminothiophenol (ATP). The AAB/ATP/Au immunosensor can detect LDL up to 0.252 microM (84 mg/dL) and 0.360 microM (120 mg/dL) with QCM and SPR, respectively. The SPR and QCM measurements were further utilized to study the reaction kinetics of the AAB-LDL interaction. The adsorption process involved was explored using Langmuir adsorption isotherm and Freundlich adsorption models. The thermodynamic parameters such as change in Gibb's free energy (DeltaG(ads)), change in enthalpy (DeltaH(ads)), and change in entropy (DeltaS(ads)) determined at 283, 298, and 308 K revealed that the AAB-LDL interaction is endothermic in nature and is governed by entropy. Kinetic, thermodynamic, and sticking probability studies disclosed that desorption of the water molecules from the active sites of AAB and LDL plays a key role in the interaction process and increase in temperature favors binding of LDL with the AAB/ATP/Au immunosensor. Thus, the studies were utilized to unravel the most important subprocess involved in the adsorption of LDL onto AAB-modified ATP/Au surface that may help in the fabrication of LDL immunosensors with better efficiency.

  12. Thermodynamic analysis of the heterogeneous binding sites of molecularly imprinted polymers

    SciTech Connect

    Kim, Hyunjung; Kaczmarski, Krzysztof; Guiochon, Georges A

    2005-11-01

    The thermodynamic interactions of two polymers, one Fmoc-L-Trp-imprinted (MIP), the other one an unimprinted reference (NIP), with the two Fmoc-tryptophan enantiomers were studied by frontal analysis, which allows accurate measurements of the adsorption isotherms. These isotherms were acquired at temperatures of 40, 50, 60, and 70 C, for sample concentrations ranging between 0.005 and 40 mM. The mobile phase used was acetonitrile with one percent acetic acid as an organic modifier. Within the measured concentration ranges, the tri-Langmuir isotherm model accounts best for the isotherm data of both enantiomers on the MIP, the bi-Langmuir model for the isotherm data of Fmoc-L-Trp on the NIP. These isotherm models were selected using three independent processes: statistical tests on the results from regression of the isotherm data to different isotherm models; calculation of the affinity energy distribution from the raw isotherm data; comparison of the experimental and the calculated band profiles. The isotherm parameters obtained from these best selected isotherm models showed that the enantiomeric selectivity does not change significantly with temperature, while the affinity of the substrates for both the MIP and the NIP decrease considerably with increasing temperatures. These temperature effects on the binding performance of the MIP were clarified by considering the thermodynamic functions (i.e., the standard molar Gibbs free energy, the standard molar entropy of adsorption, and the standard molar enthalpy of adsorption) for each identified type of adsorption sites, derived from the Van't Hoff equation. This showed that the entropy of transfer of Fmoc-L-Trp from the mobile to the MIP stationary phase is the dominant driving force for the selective adsorption of Fmoc-L-Trp onto the enantioselective binding sites. This entropy does not change significantly with increasing temperatures from 40 to 70 C.

  13. Magnetically recoverable Fe3O4/graphene nanocomposite towards efficient removal of triazine pesticides from aqueous solution: Investigation of the adsorption phenomenon and specific ion effect.

    PubMed

    Boruah, Purna K; Sharma, Bhagyasmeeta; Hussain, Najrul; Das, Manash R

    2017-02-01

    Spillage of effluents containing high concentration levels of pesticides into water has been considered as one of the serious environmental problems. In this study Fe3O4/reduced graphene oxide (rGO) nanocomposite has been efficiently utilized for the adsorption of five harmful pesticides namely ametryn, prometryn, simazine, simeton and atrazine in an aqueous medium. Electrostatic interaction between the pesticides and Fe3O4/rGO nanocomposite was analyzed by the zeta potential analysis, which is strongly related to the adsorption capacity of the adsorbent. The kinetics parameters of adsorption followed the pseudo second-order linear model. The adsorption isotherm studies show that, the maximum adsorption capacity of 54.8 mg g(-1) is achieved at pH 5 and it was enhanced in the presence of different ions (Mg(2+), Ca(2+), Na(+) and SO4(2)) and maximum (63.7 mg g(-1)) for ametryn adsorption was found in seawater medium. Thermodynamic parameter shows that, the adsorption process is physisorption and spontaneity in nature. The mechanism of the adsorption process was established by the DRIFT spectroscopy analysis. Efficient adsorption (93.61%) of pesticides was observed due to electrostatic, hydrophobic and π-π interactions of composite towards the heterocyclic conjugation of pesticide molecules. Further, Fe3O4/rGO nanocomposite was easily and rapidly separated from an aqueous medium using the external magnet for reuse and 88.66% adsorption efficiency was observed up to seven cycles.

  14. Robust estimation of thermodynamic parameters (ΔH, ΔS and ΔCp) for prediction of retention time in gas chromatography - Part II (Application).

    PubMed

    Claumann, Carlos Alberto; Wüst Zibetti, André; Bolzan, Ariovaldo; Machado, Ricardo A F; Pinto, Leonel Teixeira

    2015-12-18

    For this work, an analysis of parameter estimation for the retention factor in GC model was performed, considering two different criteria: sum of square error, and maximum error in absolute value; relevant statistics are described for each case. The main contribution of this work is the implementation of an initialization scheme (specialized) for the estimated parameters, which features fast convergence (low computational time) and is based on knowledge of the surface of the error criterion. In an application to a series of alkanes, specialized initialization resulted in significant reduction to the number of evaluations of the objective function (reducing computational time) in the parameter estimation. The obtained reduction happened between one and two orders of magnitude, compared with the simple random initialization.

  15. The quantum-chemical approach to calculations of thermodynamic and structural parameters of formation of fatty acid monolayers with hexagonal packing at the air/water interface.

    PubMed

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Vollhardt, D; Fainerman, V B; Miller, R

    2014-02-21

    The structural parameters of fatty acid (with formula CnH2n+1COOH, n = 7-16) monolayers at the air/water interface were modeled within quantum-chemical semiempirical program complex Mopac 2012 (PM3 method). On the basis of quantum-chemical calculations it was shown that molecules in the highly ordered monolayer can be oriented at the angle ∼16° (tilted monolayer), or at the angle ∼0° to the normal to the air/water interface (untilted monolayer). The structural parameters of both tilted and untilted monolayers correspond well to the experimental data. The parameters of the unit cell of the modelled tilted monolayer are: a = 8.0-8.2 Å and b = 4.2-4.5 Å (with the corresponding experimental data 8.4-8.7 Å and 4.9-5.0 Å). For the modelled untilted monolayer these parameters are: a = 7.7-8.0 Å; b = 4.6 Å (with the corresponding experimental data 8.4 Å and 4.8-4.9 Å). Enthalpy, entropy and Gibbs' energy of clusterization were calculated for both structures. The correlation dependencies of the calculated parameters on the number of pair intermolecular CHHC interactions in the clusters and the pair interactions between functional groups were obtained. It was shown that the spontaneous clusterization of the fatty carboxylic acids at the air/water interface under standard conditions is energetically preferable for molecules which have 13 or more carbon atoms in the alkyl chain and this result also agrees with the corresponding experimental parameters.

  16. Kinetic, equilibrium and thermodynamic studies for the removal of lead (II) and copper (II) ions from aqueous solutions by nanocrystalline TiO

    NASA Astrophysics Data System (ADS)

    Rashidi, Fatemeh; Sarabi, Reza Sadeghi; Ghasemi, Zinab; Seif, Ahmad

    2010-12-01

    Titanium dioxide nanocrystallites were synthesized as adsorbents through the hydrolysis of titanium tetrachloride as the precursor in hydrochloric acid. The product was analyzed by XRD, BET and SEM-EDX; analysis indicated that the particles were a mixture of 86.8% rutile and 13.2% anatase TiO 2 with spherical shapes. The adsorption of Pb (II) and Cu (II) metal ions from aqueous solution onto nano- TiO 2 were investigated with variations in pH, contact time, initial metal ion concentration and temperature. The kinetics, adsorption isotherm and adsorption thermodynamics of the heavy metals were studied. The kinetics data were analyzed by the pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models; the best correlation coefficients were obtained for the pseudo-second order kinetic model. The adsorption results obtained from equilibrium experiments were analyzed by Freundlich, Langmuir, Temkin and Dubinin-Radushkevich isotherms with the Freundlich isotherm giving the best fitting isotherm to the equilibrium data. The thermodynamic parameters ( ΔG°, ΔH° and ΔS°) were calculated and it was found that the adsorption process is spontaneous and endothermic and is favored at higher temperature.

  17. A comparative investigation on adsorption performances of mesoporous activated carbon prepared from waste rubber tire and activated carbon for a hazardous azo dye--Acid Blue 113.

    PubMed

    Gupta, V K; Gupta, Bina; Rastogi, Arshi; Agarwal, Shilpi; Nayak, Arunima

    2011-02-15

    A mesoporous carbon developed from waste tire rubber, characterized by chemical analysis, FTIR, and SEM studies, was used as an adsorbent for the removal and recovery of a hazardous azo dye, Acid Blue 113. Surface area, porosity, and density were determined. The adsorption of the dye over the prepared adsorbent and a commercial activated carbon was achieved under different pH, adsorbate concentration, sieve size, adsorbent dosage, contact time and temperature conditions. Langmuir and Freundlich adsorption isotherm models were applied and thermodynamic parameters were calculated. Kinetic studies indicated that the adsorption process follow first order kinetics and particle diffusion mechanisms are operative. By percolating the dye solution through fixed-bed columns the bulk removal of the Acid Blue 113 was carried out and necessary parameters were determined to find out the percentage saturation of both the columns. Recovery of the dye was made by eluting 0.1 M NaOH through the column.

  18. Optimizing adsorption of Pb(II) by modified litchi pericarp using the response surface methodology.

    PubMed

    Sun, Shujuan; Yang, Jili; Li, Yan; Wang, Kai; Li, Xiaochen

    2014-10-01

    Litchi pericarp was chemically modified as a novel bioadsorbent (MLP) for Pb(II) adsorption in this study. Operating parameters such as contact time, adsorbent dosage, and initial pH of solution were investigated using batch assays and further optimized using response surface methodology (RSM). The results showed that the MLP exhibited a high adsorption efficiency of 99.97% for Pb(II), which was optimal at a contact time of 71.56min, a initial pH of 6.81, and an adsorbent dose of 3.80g/L. Adsorption processes of Pb(II) by MLP could be well described with Langmuir or Freundlich isotherms and a pseudo-second-order kinetic model. The maximum adsorption capacity of Pb(II) by MLP was determined as 163.93mg/g, suggesting a highly promising potential for MLP to be used as a new bioadsorbent. Additionally, the thermodynamic study indicated that the adsorption process of Pb(II) by MLP was spontaneously and exothermic.

  19. Adsorption of indium(III) ions from aqueous solution using chitosan-coated bentonite beads.

    PubMed

    Calagui, Mary Jane C; Senoro, Delia B; Kan, Chi-Chuan; Salvacion, Jonathan W L; Futalan, Cybelle Morales; Wan, Meng-Wei

    2014-07-30

    Batch adsorption study was utilized in evaluating the potential suitability of chitosan-coated bentonite (CCB) as an adsorbent in the removal of indium ions from aqueous solution. The percentage (%) removal and adsorption capacity of indium(III) were examined as a function of solution pH, initial concentration, adsorbent dosage and temperature. The experimental data were fitted with several isotherm models, where the equilibrium data was best described by Langmuir isotherm. The mean energy (E) value was found in the range of 1-8kJ/mol, indicating that the governing type of adsorption of indium(III) onto CCB is essentially physical. Thermodynamic parameters, including Gibbs free energy, enthalpy, and entropy indicated that the indium(III) ions adsorption onto CCB was feasible, spontaneous and endothermic in the temperature range of 278-318K. The kinetics was evaluated utilizing the pseudo-first order and pseudo-second order model. The adsorption kinetics of indium(III) best fits the pseudo-second order (R(2)>0.99), which implies that chemical sorption as the rate-limiting step.

  20. Synthesis, characterization and adsorption performance of a novel post-crosslinked adsorbent.

    PubMed

    Zeng, Xiaowei; Yao, Hongjie; Ma, Ning; Fan, Yunge; Wang, Chunhong; Shi, Rongfu

    2011-02-01

    In this paper a post-crosslinked polymeric adsorbent PDHT-2 with high specific surface area was prepared by Friedel-Crafts reaction of the pendant vinyl groups without an externally added crosslinking agent. It was obvious that both the specific surface area and the pore volume of starting copolymer PDHT-1 increased significantly after post-crosslinking. Batch adsorption runs of phenol from aqueous solution onto adsorbent PDHT-1 and PDHT-2 were researched, and commercial macroporous resin XAD-4 was chosen for comparison purpose. Experimental results showed that the adsorption isotherms could be fitted by Langmuir model and Freundlich model and the adsorption capacity onto PDHT-2 was much larger than that onto PDHT-1 and XAD-4 with respect to phenol and phenolic compound, which possibly resulted from its larger specific surface area. The adsorption process for phenol onto the three adsorbents was proved to be exothermic and spontaneous in nature. The thermodynamic parameters such as Gibb's free energy (ΔG), change in enthalpy (ΔH) and change in entropy (ΔS) had been calculated. The adsorption kinetic curves obeyed the pseudo-second order model and the intraparticle diffusion process was the rate-controlling step.

  1. Transition state kinetics of Hg(II) adsorption at gibbsite-water interface.

    PubMed

    Weerasooriya, Rohan; Tobschall, Heinz J; Seneviratne, Wasana; Bandara, Atula

    2007-08-25

    Kinetics of adsorption plays a pivotal factor in determining the bio-availability and mobility of Hg(II) in the environment. The kinetics of Hg(II) adsorption on gibbsite was examined as a function of pH, temperature and electrolyte type. Adsorption of Hg(II) was highly non-linear where the rate of Hg(II) retention was rapid initially and was followed by gradual or somewhat slow retention behavior with increasing contact time. The respective rate constants designated as k(1) (S-1: fast step) and k(2) (S-2: slow step). Always k(1) follows the order: k(1)(CIO)(4) >/= k(1)(NO3)(4) > k(1)(Cl). Such a relationship was not observed for the S-2 route. A two-step reaction model with pseudo-first order kinetics successfully described the adsorption rates of Hg(II) on gibbsite. Arrhenius and Erying models determined the thermodynamic parameters at activation states, which correspond to S-1 and S-2 routes. In a given system, always the activation energies showed a decrease with the pH. Gibbs free energy (DeltaG(#)), enthalpy (DeltaH(#)), and entropy (DeltaS(#)) values of activation states were almost similar both in NaClO(4) and NaNO(3) which signal a similar Hg(II) adsorptive mechanism on gibbsite. The configurations of different Hg(II)-surface complexes were elucidated by transmission vibration spectroscopy.

  2. Adsorption mechanism of magnetically separable Fe3O4/graphene oxide hybrids

    NASA Astrophysics Data System (ADS)

    Ouyang, Ke; Zhu, Chuanhe; Zhao, Ya; Wang, Leichao; Xie, Shan; Wang, Qun

    2015-11-01

    A reclaimable Fe3O4/graphene oxide (GO) magnetic hybrid was successfully synthesized via a facile one-pot polyol approach and employed as a recyclable adsorbent for Bisphenol A (BPA) in aqueous solutions. The maximum adsorption capacity (qm) of the Fe3O4/GO hybrid for BPA was 72.80 mg/g at 273 K. The kinetics of the adsorption process and the adsorption isotherm data were fitted using the Freundlich equation and a pseudo-second-order kinetic model. The results of the thermodynamic parameters ΔH°, ΔS° and ΔG° showed that the adsorption process was exothermic and spontaneous. Furthermore, the reusability of the samples was investigated, and the results indicated that the samples exhibited high stability. The magnetic characterization demonstrated that hybrids were superparamagnetic and could be recovered conveniently by magnetic separation. The strong π-π interaction was determined to be the predominant driving force behind the adsorption of BPA onto the Fe3O4/GO hybrid. Therefore, the Fe3O4/GO hybrid could be regarded as a potential adsorbent for wastewater treatment and purification processes.

  3. Adsorption characteristics of sol gel-derived zirconia for cesium ions from aqueous solutions.

    PubMed

    Yakout, Sobhy M; Hassan, Hisham S

    2014-07-01

    Zirconia powder was synthesized via a sol gel method and placed in a batch reactor for cesium removal investigation. X-ray analysis and Fourier transform infrared spectroscopy were utilized for the evaluation of the developed adsorbent. The adsorption process has been investigated as a function of pH, contact time and temperature. The adsorption is strongly dependent on the pH of the medium whereby the removal efficiency increases as the pH turns to the alkaline range. The process was initially very fast and the maximum adsorption was attained within 60 min of contact. A pseudo-second-order model and homogeneous particle diffusion model (HPDM) were found to be the best to correlate the diffusion of cesium into the zirconia particles. Furthermore, adsorption thermodynamic parameters, namely the standard enthalpy, entropy, and Gibbs free energy, were calculated. The results indicate that cesium adsorption by zirconia is an endothermic (ΔH>0) process and good affinity of cesium ions towards the sorbent (ΔS>0) was observed.

  4. Dilution method study on the interfacial composition, thermodynamic properties and structural parameters of W/O microemulsions stabilized by 1-pentanol and surfactants in absence and presence of sodium chloride.

    PubMed

    Paul, Bidyut K; Nandy, Debdurlav

    2007-12-15

    The phase behaviors, interfacial composition, thermodynamic properties and structural characteristics of water-in-oil microemulsions under varied molar ratio of water to surfactant (omega) at 303 K and also by varying temperatures at a fixed omega(=40) by mixing with 1-pentanol and decane or dodecane in absence and presence of sodium chloride have been studied by the method of dilution. The surfactants used were cetyl pyridinium chloride (CPC), sodium dodecyl sulfate (SDS) and polyoxyethylene (23) lauryl ether (Brij-35). The compositions of 1-pentanol and the surfactant at the interfacial region, the distribution of 1-pentanol between the interfacial region and the continuous oil phase, and the effective packing parameter (P(eff)) at the threshold level of stability have been estimated. The thermodynamics of transfer of 1-pentanol from the continuous oil phase to the interface have been evaluated. The structural parameters viz. radii of the droplet (R(e)) and the waterpool (R(w)), effective thickness of the interfacial layer (d(I)), average aggregation numbers of surfactants (N (s)) and the cosurfactant (1-pentanol) (N (a)) and the number of droplets (N(d)) have also been estimated. The prospect of using these w/o microemulsions for the synthesis of nanoparticles with small size, have been discussed in the light of the radii of the droplet, and waterpool, the extent of variation of effective thickness of the droplet under varied molar ratio of water to surfactant and temperature. An attempt has been made to rationalize the results in a comprehensive manner.

  5. Equilibrium, kinetic and thermodynamic studies of acid Orange 52 dye biosorption by Paulownia tomentosa Steud. leaf powder as a low-cost natural biosorbent.

    PubMed

    Deniz, Fatih; Saygideger, Saadet D

    2010-07-01

    The biosorption of Acid Orange 52 onto the leaf powder of Paulownia tomentosa Steud. was studied in a batch adsorption system to estimate the equilibrium, kinetic and thermodynamic parameters as a function of solution pH, biosorbent concentration, dye concentration, biosorbent size, temperature and contact time. The Langmuir, Freundlich and Temkin isotherm models were used for modeling the biosorption equilibrium. The experimental equilibrium data could be well interpreted by the Temkin and Langmuir isotherms with maximum adsorption capacity of 10.5 mg g(-1). In order to state the sorption kinetics, the fits of pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion kinetic models were investigated. It was obtained that the biosorption process followed the pseudo-second order rate kinetics. Thermodynamic studies indicated that this system was exothermic process. The results revealed that P. tomentosa leaf powder could be an efficient biosorbent for the treatment of wastewater containing Acid Orange 52.

  6. Vibrational spectra, NBO analysis, first order hyperpolarizabilities, thermodynamic functions and NMR chemical shielding anisotropy (CSA) parameters of 5-nitro-2-furoic acid by ab initio HF and DFT calculations.

    PubMed

    Balachandran, V; Rajeswari, S; Lalitha, S

    2013-09-01

    In this work, FT-IR and FT-Raman spectra are recorded on the solid phase of 5-nitro-2-furoic acid (abbreviated as NFA) in the regions 4000-400 cm(-1) and 3500-100 cm(-1) respectively. The geometrical parameters, vibrational assignments, HOMO-LUMO energies and NBO calculations are obtained for the monomer and dimer of NFA from HF and DFT (B3LYP) with 6-311++G (d, p) basis set calculations. Second order perturbation energies and electron density (ED) transfer from filled lone pairs of Lewis base to unfilled Lewis acid sites of NFA are discussed on the basis of NBO analysis. Intermolecular hydrogen bonds exist through COOH groups; give the evidence for the formation of dimer entities in the title molecule. The theoretically calculated harmonic frequencies are scaled by common scale factor. The observed and the calculated frequencies are found to be in good agreement. The thermodynamic functions were obtained for the range of temperature 100-1000 K. The polarizability, first hyperpolarizability, anisotropy polarizability invariant has been computed using quantum chemical calculations. The chemical parameters were calculated from the HOMO and LUMO values. The NMR chemical shielding anisotropy (CSA) parameters were also computed for the title molecule.

  7. Modeling of thorium (IV) ions adsorption onto a novel adsorbent material silicon dioxide nano-balls using response surface methodology.

    PubMed

    Kaynar, Ümit H; Şabikoğlu, Israfil; Kaynar, Sermin Çam; Eral, Meral

    2016-09-01

    The silicon dioxide nano-balls (nano-SiO2) were prepared for the adsorption of thorium (IV) ions from aqueous solution. The synthesized silicon dioxide nano-balls were characterized by Scanning Electron Microscopy/Energy Dispersive X-ray, X-ray Diffraction, Fourier Transform Infrared and BET surface area measurement spectroscopy. The effects of pH, concentration, temperature and the solid-liquid ratio on the adsorption of thorium by nano-balls were optimized using central composite design of response surface methodology. The interaction between four variables was studied and modelled. Furthermore, the statistical analysis of the results was done. Analysis of variance revealed that all of the single effects found statistically significant on the sorption of Th(IV). Probability F-values (F=4.64-14) and correlation coefficients (R(2)=0.99 for Th(IV)) indicate that model fit the experimental data well. The ability of this material to remove Th(IV) from aqueous solution was characterized by Langmuir, Freunlinch and Temkin adsorption isotherms. The adsorption capacity of thorium (IV) achieved 188.2mgg(-1). Thermodynamic parameters were determined and discussed. The batch adsorption condition with respect to interfering ions was tested. The results indicated that silicon dioxide nano-balls were suitable as sorbent material for adsorption and recovery of Th(IV) ions from aqueous solutions.

  8. Synthesis of activated carbon-based amino phosphonic acid chelating resin and its adsorption properties for Ce(III) removal.

    PubMed

    Chen, Tao; Yan, Chunjie; Wang, Yixia; Tang, Conghai; Zhou, Sen; Zhao, Yuan; Ma, Rui; Duan, Ping

    2015-01-01

    This work aims to investigate the adsorption of Ce(III) onto chelating resin based on activated carbon (CRAC). The CRAC adsorbent was prepared from activated carbon (AC) followed by oxidation, silane coupling, ammoniation and phosphorylation, and characterized by Fourier transform-infrared spectrometry, nitrogen adsorption measurements and scanning electron microscopy. The effects of solution pH, adsorbent dosage and contact time were studied by batch technique. Langmuir and Freundlich isotherms were used to describe the adsorption behaviour of Ce(III) by CRAC, and the results showed that the adsorption behaviour well fitted the Langmuir model. The maximum uptake capacity (qmax) calculated by using the Langmuir equation for cerium ions was found to be 94.34 mg/g. A comparison of the kinetic models and the overall experimental data was best fitted with the type 1 pseudo second-order kinetic model. The calculated thermodynamic parameters (ΔG°, ΔH° and ΔS°) showed that the adsorption for Ce(III) was feasible, spontaneous and exothermic at 25-45 °C. The CRAC showed an excellent adsorptive selectivity towards Ce(III). Moreover, more than 82% of Ce(III) adsorbed onto CRAC could be desorbed with HCl and could be used several times.

  9. Preparation and Characterization of Chitosan/Feldspar Biohybrid as an Adsorbent: Optimization of Adsorption Process via Response Surface Modeling

    PubMed Central

    Yazdani, Maryam; Bahrami, Hajir; Arami, Mokhtar

    2014-01-01

    Chitosan/feldspar biobased beads were synthesized, characterized, and tested for the removal of Acid Black 1 dye from aquatic phases. A four-factor central composite design (CCD) accompanied by response surface modeling (RSM) and optimization was used to optimize the dye adsorption by the adsorbent (chitosan/feldspar composite) in 31 different batch experiments. Independent variables of temperature, pH, initial dye concentration, and adsorbent dose were used to change to coded values. To anticipate the responses, a quadratic model was applied. Analysis of variance (ANOVA) tested the significance of the process factors and their interactions. The adequacy of the model was investigated by the correlation between experimental and predicted data of the adsorption and the calculation of prediction errors. The results showed that the predicted maximum adsorption amount of 21.63 mg/g under the optimum conditions (pH 3, temperature 15°C, initial dye concentration 125 mg/L, and dose 0.2 g/50 mL) was close to the experimental value of 19.85 mg/g. In addition, the results of adsorption behaviors of the dye illustrated that the adsorption process followed the Langmuir isotherm model and the pseudo-second-order kinetic model. Langmuir sorption capacity was found to be 17.86 mg/g. Besides, thermodynamic parameters were evaluated and revealed that the adsorption process was exothermic and favourable. PMID:24587722

  10. Advances in thermodynamics