Science.gov

Sample records for adsorption thermodynamic parameters

  1. Thermodynamic parameters for adsorption equilibrium of heavy metals and dyes from wastewaters.

    PubMed

    Liu, Xiang; Lee, Duu-Jong

    2014-05-01

    This meta-analysis evaluates adsorption studies that report thermodynamic parameters for heavy metals and dyes from wastewaters. The adsorbents were derived from agricultural waste, industrial wastes, inorganic particulates, or some natural products. The adsorption mechanisms, derivation of thermodynamic relationships, and possible flaws made in such evaluation are discussed. This analysis shows that conclusions from the examined standard enthalpy and entropy changes are highly contestable. The reason for this flaw may be the poor physical structure of adsorbents tested, such that pore transport controlled the solute flux, leaving a surface reaction process near equilibrium. PMID:24461254

  2. Removal of Anionic Dyes from Water by Potash Alum Doped Polyaniline: Investigation of Kinetics and Thermodynamic Parameters of Adsorption.

    PubMed

    Patra, Braja N; Majhi, Deola

    2015-06-25

    Polyaniline was synthesized by the oxidative polymerization method by using ammonium persulfate as an oxidant. The positive charge in the backbone of the polymer was generated by using Potash alum as a dopant. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X-ray fluorescence (XRF), and X-ray diffraction (XRD) techniques were used for characterization of doped polyaniline. The doped polyaniline can be used for selective adsorption of various dyes (selectively sulfonated dyes) from aqueous solution. Adsorption studies regarding the effect of contact time, initial dye concentration, pH, doses of adsorbent, and temperature on adsorption kinetics were investigated. The influence of other anions like Cl(-), NO3(-), and SO4(2-) on the adsorption density of dyes onto doped polyaniline was also explored. Langmuir isotherm and pseudo-second-order kinetics were found to be the most appropriate models to describe the removal of anionic dyes from water through adsorption. Thermodynamic parameters such as free energy (ΔG(0)), enthalpy (ΔH(0)), and entropy (ΔS(0)) changes were also evaluated. The interaction of dyes with doped polyaniline was also investigated by FTIR and UV spectroscopy. PMID:26079693

  3. 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.

  4. Thermodynamic analysis of adsorption refrigeration cycles

    SciTech Connect

    Saha, B.B.; Akisawa, Atsushi; Kashiwagi, Takao

    1997-12-31

    High- and mid-temperature waste heat can be recovered by using existing heat pump technologies. However, heat utilization near environmental temperatures still faces technical hurdles. Silica gel-water adsorption cycles have a distinct advantage over other systems in their ability to be driven by near-ambient temperature heat. Waste heat (above 60 C) can be exploited by using conventional silica gel-water adsorption chiller. The advanced silica gel-water adsorption chiller can operate effectively by utilizing low-grade waste heat ({approximately}50 C) as the driving source with a cooling source of 30 C. In this paper, the effect of operating temperatures on cycle performance is discussed from the thermodynamic viewpoint. The temperature effectiveness and the entropy generation number on cycle time are analyzed. For a comparatively short cycle time, adsorber/desorber heat exchanger temperature effectiveness reaches up to 92% after only 200 sec. The entropy generation number N{sub s} is defined by the ratio between irreversibility generated during a cycle and availability of the heat transfer fluid. The result showed that for the advanced adsorption cycle the entropy generation number N{sub s} is smaller for hot water temperature between 45 to 55 C with a cooling source of 30 C, while for the conventional cycle N{sub s} is smaller for hot water temperature between 65 to 75 C /with the same cooling source temperature.

  5. A thermodynamic model for gas adsorption isotherms

    SciTech Connect

    Riazi, M.R.; Khan, A.R.

    1999-02-15

    In this paper based on the principle of solution thermodynamics for gas-solid equilibrium, a relation is developed to express gas adsorption isotherms. An activity coefficient model based on weight fraction of sorbate in the solid phase has been derived that well describes the behavior of various gases on different types of adsorbents. The proposed model has been evaluated and compared with four other models commonly used for gas adsorption isotherms in the literature. For 12 different systems at various isotherms for the temperature range {minus}128 to 100 C and the pressure range 0.02 to 1219 kPa for 689 data points, the proposed model predicts equilibrium pressure with an average deviation of 5.3%, which is about half of the error obtained from other methods. The proposed model clearly outperforms other available methods such as the vacancy solution theory, the ideal adsorption solution model, and other various modified forms of the Langmuir isotherm. Unique features of the proposed model are its simplicity, generality, and accuracy over the entire pressure and temperature ranges.

  6. 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. PMID:27391585

  7. 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

  8. 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.

  9. Adsorption kinetics and thermodynamics of acid Bordeaux B from aqueous solution by graphene oxide/PAMAMs.

    PubMed

    Zhang, Fan; He, Shengfu; Zhang, Chen; Peng, Zhiyuan

    2015-01-01

    Graphene oxide/polyamidoamines dendrimers (GO/PAMAMs) composites were synthesized via modifying GO with 2.0 G PAMAM. The adsorption behavior of the GO/PAMAMs for acid Bordeaux B (ABB) was studied and the effects of media pH, adsorption time and initial ABB concentration on adsorption capacity of the adsorbent were investigated. The optimum pH value of the adsorption of ABB onto GO/PAMAMs was 2.5. The maximum adsorption capacity increased from 325.78 to 520.83 mg/g with the increase in temperature from 298 to 328 K. The equilibrium data followed the Langmuir isotherm model better than the Freundlich model. The kinetic study illustrated that the adsorption of ABB onto GO/PAMAMs fit the pseudo-second-order model. The thermodynamic parameters indicated that the adsorption process was physisorption, and also an endothermic and spontaneous process. PMID:26398038

  10. 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.

  11. 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. PMID:21481893

  12. 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. PMID:26683820

  13. 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. PMID:27039361

  14. [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. PMID:21250454

  15. On the thermodynamics of refrigerant + heterogeneous solid surfaces adsorption.

    PubMed

    Ismail, Azhar Bin; Li, Ang; Thu, Kyaw; Ng, K C; Chun, Wongee

    2013-11-26

    This Article presents a theoretical framework for the understanding of pressurized adsorption systems using the statistical rate methodology. Utilizing results from the statistical rate theory, basic thermodynamic variables including enthalpy (h(a)), entropy (s(a)), and the specific heat capacity (c(p,a)) of the adsorbed phase are derived using the thermodynamic requirements of chemical equilibrium, Gibbs law, as well as Maxwell relations. A built-in constant (K) describes the adsorbed molecular partition function (q(s)), and it captures the heterogeneous properties of the adsorbent + adsorbate pair at equilibrium states. Improved adsorbed-phase volume considerations were incorporated in the formulations of these variables where they could be utilized with relative ease for analyzing the energetic performances of any practical adsorption system. In this Article, we have demonstrated how derived thermodynamic quantities can bridge the information gap with respect to the states of adsorbed phase, as well as resolved some theoretical inconsistencies that were found in previously derived quantities. Experimentally, the adsorption isotherms of propane (refrigerant) on activated carbon powder (Maxsorb III) for temperatures from 5 to 75 °C and pressures up to 8 bar are presented, and they are used to illustrate the behaviors of the adsorbed-phase during uptakes, temperatures, and pressure excursions or changes. PMID:24191669

  16. 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. PMID:20817346

  17. Adsorption of copper ions by ion-imprinted simultaneous interpenetrating network hydrogel: Thermodynamics, morphology and mechanism

    NASA Astrophysics Data System (ADS)

    Wang, Jingjing; Ding, Liang; Wei, Jun; Liu, Fang

    2014-06-01

    Cu(II) ion-imprinted hydrogel [Cu(II)-IIH] with interpenetrating polymer network (IPN) structure was prepared and its application to adsorb Cu(II) ions from aqueous solution was studied. The Cu(II)-IIH was prepared by UV-initiated simultaneous free radical/cationic hybrid polymerization. The adsorption capacity of the Cu(II)-IIH increased with the initial pH value of the solution, but decreased as the temperature rose from 303 to 323 K. Thermodynamic parameters such as the Gibbs free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) for the Cu(II) ions adsorption were evaluated. It was suggested that the adsorption was a spontaneous, exothermic process with further decrease in the degree of freedom at the solid-solution interface due to the negative ΔS° value. The morphology study indicated that the copper adsorption caused significant changes to the hydrogel structure. Finally the adsorption mechanism was studied by Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The results indicated that copper adsorption was mainly through interactions with the amide and ether groups.

  18. Partial solvation parameters and mixture thermodynamics.

    PubMed

    Panayiotou, Costas

    2012-06-21

    The recently introduced partial solvation parameters (PSPs) are molecular descriptors that combine elements from quantum mechanics with the QSPR/LSER/solvatochromic and solubility parameter approaches. Basic regularities and universalities exhibited by PSPs are examined in this work and the concepts of homosolvation, heterosolvation and solvation energy density are quantified. A simple consistent thermodynamic framework is developed, through which the validity of the PSP approach is tested. The predictions are compared with experimental phase equilibrium data that span the full composition range from the pure fluid state to infinite dilution. They include vapor-liquid equilibria of fluids interacting with strong specific forces, dissolution of solids/liquids in various solvents and probe/oligomer or probe/polymer interactions as typically determined by inverse gas-chromatography. These applications show the potential of the PSP approach not only to reasonably predict a variety of properties of classes of complex systems but, also, to shed light to challenging aspects of intermolecular interactions. The perspectives of this unified approach to solution thermodynamics are discussed. PMID:22642662

  19. Adsorption of fluoride to UiO-66-NH2 in water: Stability, kinetic, isotherm and thermodynamic studies.

    PubMed

    Lin, Kun-Yi Andrew; Liu, Yu-Ting; Chen, Shen-Yi

    2016-01-01

    To provide safe drinking water, fluoride in water must be removed and adsorption processes appear to be the most widely used method. Metal organic frameworks (MOFs) represent a new class of adsorbents that have been used in various adsorption applications. To study the adsorption mechanism of fluoride to MOFs in water and obtain related adsorption parameters, we synthesized a zirconium-based MOF with a primary amine group on its ligand, named UiO-66-NH2. The kinetics, adsorption isotherm and thermodynamics of fluoride adsorption to UiO-66-NH2 were investigated. The crystalline structure of UiO-66-NH2 remained intact and the local structure of zirconium in UiO-66-NH2 did not change significantly after being exposed to fluoride. The kinetics of the fluoride adsorption in UiO-66-NH2 could be well represented by the pseudo second order rate law. The enthalpy of the adsorption indicates that the F(-) adsorption to UiO-66-NH2 was classified as a physical adsorption. However, the comparison between the adsorption capacities of UiO-66-NH2 and UiO-66 suggests that the fluoride adsorption to UiO-66-NH2 might primarily involve a strong interaction between F(-) and the metal site. The fluoride adsorption capacity of UiO-66-NH2 was found to decrease when pH>7. While the presence of chloride/bromide ions did not noticeably change the adsorption capacity of UiO-66-NH2, the ionic surfactants slightly affected the adsorption capacity of UiO-66-NH2. These findings provide insights to further optimize the adsorption process for removal of fluoride using zirconium-based MOFs. PMID:26397913

  20. 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

  1. Integrated 3-parameter diagram for determining thermodynamic properties of fluids

    NASA Astrophysics Data System (ADS)

    Zhao, Guochang; Deng, Xiaoxue; Zhu, Mingshan

    1987-04-01

    The importance of thermodynamic properties of fluids has motivated recent studies in developing methods of calculating thermodynamic properties. Among the various methods, the use of computational diagrams is a commonly used engineering method. Conventional diagrams do not take into consideration the internal relationships among the various thermodynamic properties. The internal relationships of various thermodynamic properties are considered. The Lee-Kessler three-parameter equations were used to construct an integrated three-parameter diagram for determining the thermodynamic properties of fluids; the curves were generated using an ai-M/6 microcomputer with an attached Sr 6602 plotter. The diagram is considered sufficiently accurate for engineering calculations.

  2. 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.

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

    SciTech Connect

    Sun, Baichuan; Chakraborty, Anutosh

    2014-05-19

    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.

  5. Thermodynamic characteristics of the adsorption of isomeric molecules of fluoroadamantanes on the surface of the basal face of graphite

    NASA Astrophysics Data System (ADS)

    Yashkin, S. N.; Svetlov, D. A.; Klimochkin, Yu. N.

    2011-10-01

    The thermodynamic characteristics of adsorption (TCA) for isomeric molecules of mono-, di-, tri-, and tetrafluoroadamantanes were determined for the first time experimentally and by molecular statistics on the surface of graphitized thermal black (GTB). The parameters of atom-atom potential function of pair intermolecular interaction (φ( r)) for F atoms included in fluoroadamantanes with C atoms on the basal face of graphite were calculated for the first time within an atom-atom approximation of the semi-empirical molecular statistical theory of adsorption. The adsorption non-equivalence of F atoms in various positions of an adamantane framework, a consequence of the mutual effect of atoms in a framework molecule, was determined. On the basis of the definite TCA values, the conclusion was drawn as to the possibility of isolation of isomeric fluoroadamantanes under the conditions of gas-adsorption chromatography on GTB.

  6. 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. PMID:26414422

  7. 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.

  8. 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.

  9. Thermodynamics of the adsorption of flexible polymers on nanowires

    DOE PAGESBeta

    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

  10. Diagnostics of gas turbines based on changes in thermodynamics parameters

    NASA Astrophysics Data System (ADS)

    Hocko, Marián; Klimko, Marek

    2016-03-01

    This article is focused on solving the problems of determining the true state of gas turbine based on measured changes in thermodynamic parameters. Dependence between the real individual parts for gas turbines and changing the thermodynamic parameters were experimentally verified and confirmed on a small jet engine MPM-20 in the laboratory of the Department of Aviation Engineering at Technical University in Košice. The results of experiments confirm that the wear and tear of basic parts for gas turbines (turbo-compressor engines) to effect the change of thermodynamic parameters of the engine.

  11. Kinetic and thermodynamic studies of Hg(II) adsorption onto MCM-41 modified by ZnCl2

    NASA Astrophysics Data System (ADS)

    Raji, Foad; Pakizeh, Majid

    2014-05-01

    Kinetics and thermodynamics of mercury ions sorption onto ZnCl2-MCM-41 sorbent were studied. Several rate models in the form of two main classes of mathematic kinetic models (adsorption reaction models and adsorption diffusion models) were investigated. Pseudo-first-order, pseudo-second-order, Elovich, film and intraparticle diffusion models were used to analyze the kinetic data. Results showed that the pseudo-second order model can well describe the adsorption kinetic data. The thermodynamic parameters, such as Gibb's free energy change (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°) were also evaluated. Negative value of free energy at temperature range of 20-55 °C, indicates the spontaneous nature of Hg(II) sorption by ZnCl2-MCM-41 sorbent. The adsorption capacity which was found to decrease with temperature showed the exothermic nature of the mercury sorption process (ΔH° = -49.4 kJ mol-1). The negative ΔS° value (-148.9 J mol-1 K-1) revealed a decrease in the randomness at the solid/solution interface and also indicated the fast adsorption of the Hg(II) onto active sites.

  12. 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. PMID:19773115

  13. Magnetic vinylphenyl boronic acid microparticles for Cr(VI) adsorption: kinetic, isotherm and thermodynamic studies.

    PubMed

    Kara, Ali; Demirbel, Emel; Tekin, Nalan; Osman, Bilgen; Beşirli, Necati

    2015-04-01

    Magnetic vinylphenyl boronic acid microparticles, poly(ethylene glycol dimethacrylate(EG)-vinylphenyl boronic acid(VPBA)) [m-poly(EG-VPBA)], produced by suspension polymerization and characterized, was found to be an efficient solid polymer for Cr(VI) adsorption. The m-poly(EG-VPBA) microparticles were prepared by copolymerizing of ethylene glycol dimethylacrylate (EG) with 4-vinyl phenyl boronic acid (VPBA). The m-poly(EG-VPBA) microparticles were characterized by N2 adsorption/desorption isotherms, electron spin resonance (ESR), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), elemental analysis, scanning electron microscope (SEM) and swelling studies. The m-poly(EG-VPBA) microparticles were used at adsorbent/Cr(VI) ion ratios. The influence of pH, Cr(VI) initial concentration, temperature of the removal process was investigated. The maximum removal of Cr(VI) was observed at pH 2. Langmuir isotherm and Dubinin-Radushkvich isotherm were found to better fit the experiment data rather than Fruendlich isotherm. The kinetics of the adsorption process of Cr(VI) on the m-poly(EG-VPBA) microparticles were investigated using the pseudo first-order, pseudo-second-order, Ritch-second-order and intraparticle diffusion models, results showed that the pseudo-second order equation model provided the best correlation with the experimental results. The thermodynamic parameters (free energy change, ΔG(0) enthalpy change, ΔH(0); and entropy change, ΔS(0)) for the adsorption have been evaluated. PMID:25666882

  14. Kinetic, equilibrium and thermodynamic studies of cadmium (II) adsorption by modified agricultural wastes.

    PubMed

    Othman, Zeid A Al; Hashem, Ali; Habila, Mohamed A

    2011-01-01

    Agricultural wastes have great potential for the removal of heavy metal ions from aqueous solution. The contamination of water by toxic heavy metals is a worldwide environmental problem. Unlike organic pollutants, the majority of which are susceptible to biological degradation, heavy metals do not degrade into harmless end products. Discharges containing cadmium, in particular, are strictly controlled because of the highly toxic nature of this element and its tendency to accumulate in the tissues of living organisms. This work aims to develop inexpensive, highly available, effective metal ion adsorbents from natural wastes as alternatives to existing commercial adsorbents. In particular, Tamrix articulata wastes were modified chemically by esterification with maleic acid to yield a carboxyl-rich adsorbent. The adsorption behavior of treated Tamrix articulata wastes toward cadmium ions in aqueous solutions in a batch system has been studied as a function of equilibration time, adsorbent dose, temperature and pH. Results showed that the maximum adsorption capacity was 195.5 mg/g in a pH 4 solution at 30 °C with a contact time of 120 min, an initial concentration of 400 mg/L and an adsorbent dose of 0.3 g/L. The kinetic data were analyzed using pseudo-first-order and pseudo-second-order kinetic models. It was shown that the adsorption of cadmium could be described by a pseudo-second-order equation. The experimental data were also analyzed using the Langmuir and Freundlich models of adsorption. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° have been evaluated and it has been found that the sorption process was spontaneous and exothermic in nature. From all of our data, we conclude that the treated Tamrix articulata wastes investigated in this study showed good potential for cadmium removal from aqueous solutions. PMID:22173337

  15. 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. PMID:24410681

  16. Electronic Parameters of Mesoporous Silicon Upon Adsorption of Plant Viruses

    NASA Astrophysics Data System (ADS)

    Vashpanov, Yuriy; Son, Jung-Young; Kwack, Kae-Dal; Shin, Seung-Jung

    2008-06-01

    Changes in the electronic parameters of mesoporous silicon upon adsorption of nematodetransmitted polyhedral (NEPO) viruses of plant [tomato ringspot virus (TORSV), grapevine virus A (GVA), and grapevine fan leaf virus (GFLV)] measured at room temperature are investigated. The adsorption of these viruses affected essentially on the electronic characteristic of the porous material. The measurement of the electronic characteristics of porous silicon can be applied to the creation of detectors for the presence of viruses in a given environment.

  17. 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. PMID:26136159

  18. 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

  19. Adsorptive removal of heavy metals by magnetic nanoadsorbent: an equilibrium and thermodynamic study

    NASA Astrophysics Data System (ADS)

    Shirsath, D. S.; Shirivastava, V. S.

    2015-11-01

    An efficient and new magnetic nanoadsorbent photocatalyst was fabricated by co-precipitation technique. This research focuses on understanding metal removal process and developing a cost-effective technology for treatment of heavy metal-contaminated industrial wastewater. In this investigation, magnetic nanoadsorbent has been employed for the removal of Zn(II) ions from aqueous solutions by a batch adsorption technique. The adsorption equilibrium data fitted very well to Langmuir and Freundlich adsorption isotherm models. The thermodynamics of Zn(II) ions adsorption onto the magnetic nanoadsorbents indicated that the adsorption was spontaneous, endothermic and physical in nature. Surface morphology of magnetic nanoadsorbent by scanning electron microscopy (SEM) and elemental analysis by EDX technique. The structural and photocatalytic properties of magnetic nanoadsorbent were characterized using X-ray diffraction (XRD) and FTIR techniques. Also, the magnetic properties of synthesized magnetic nanoadsorbent were determined by vibrating spinning magnetometer (VSM).

  20. 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. PMID:22097045

  1. 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.

  2. 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. PMID:26945716

  3. Quartz Crystal Microbalance Study of Kinetics and Thermodynamics of IgG Adsorption on the Polystyrene Surface

    NASA Astrophysics Data System (ADS)

    Feng, Bo; Feng, Xi; Xie, Xiaomei; Wang, Caiyun; Zhang, Mengxue; Zhang, Xiaoyun

    2015-03-01

    Polystyrene (PS) is a common substrate material for protein adsorption on biosensors and bioassays. By employing a quartz crystal microbalance (QCM) technique, we studied the kinetics and thermodynamics of anti-HBeAg adsorption on this substrate in situ. First, a thin PS film was deposited on the interface between the liquid and the quartz crystal wafer. Second, a solution containing anti-HBeAg was introduced into the holding tank. Third, we measured the change in the oscillation frequency of the quartz that was induced by the antibody-PS binding, which in turn depended on macroscopic parameters, such as antibody concentration and solution temperature, as well as on microscopic parameters, such as the diffusion type and the change in Gibb's free energy. The adsorption rate and capacity of anti-HBeAg on the PS surface were quantified and fitted using the conventional Langmuir model. It was shown that this model was applicable to protein-PS interface system. Approximately 250 nm2 of the surface area was occupied by a single antibody molecule at 298 K when the concentration was 90 μg/mL. The adsorption process might have been controlled by both liquid film and particle diffusions.

  4. 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.

  5. Assessment of thermodynamic parameters of plasma shock wave

    NASA Astrophysics Data System (ADS)

    Vasileva, O. V.; Isaev, Yu N.; Budko, A. A.; Filkov, A. I.

    2014-11-01

    The work is devoted to the solution of the one-dimensional equation of hydraulic gas dynamics for the coaxial magneto plasma accelerator by means of Lax-Wendroff modified algorithm with optimum choice of the regularization parameter artificial viscosity. Replacement of the differential equations containing private derivatives is made by finite difference method. Optimum parameter of regularization artificial viscosity is added using the exact known decision of Soda problem. The developed algorithm of thermodynamic parameter calculation in a braking point is proved. Thermodynamic parameters of a shock wave in front of the plasma piston of the coaxial magneto plasma accelerator are calculated on the basis of the offered algorithm. Unstable high-frequency fluctuations are smoothed using modeling and that allows narrowing the ambiguity area. Results of calculation of gas dynamic parameters in a point of braking coincide with literary data. The chart 3 shows the dynamics of change of speed and thermodynamic parameters of a shock wave such as pressure, density and temperature just before the plasma piston.

  6. Adsorption interaction parameter of polyethers in ternary mobile phases: the critical adsorption line.

    PubMed

    Nguyen, V Cuong; Trathnigg, Bernd

    2010-04-01

    It is shown that in LC of polymers, the interaction parameter in ternary mobile phases can be described by a plane, which is determined by the dependencies in binary mobile phases. Instead of a critical adsorption point, critical conditions are observed along a straight line of composition between the two critical points in binary mobile phases. Consequently, a separation of block copolymers under critical conditions for one block by an adsorption mechanism for the other block can be achieved in ternary mobile phases of different compositions, which allows an adjustment of the retention of the adsorbing block. PMID:20222074

  7. 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. PMID:24882703

  8. 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.

  9. 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. PMID:27539563

  10. Adsorption of surfactants on sand surface in enhanced oil recovery: Isotherms, kinetics and thermodynamic studies

    NASA Astrophysics Data System (ADS)

    Bera, Achinta; Kumar, T.; Ojha, Keka; Mandal, Ajay

    2013-11-01

    Adsorption of surfactants onto reservoir rock surface may result in the loss and reduction of their concentrations in surfactant flooding, which may render them less efficient or ineffective in practical applications of enhanced oil recovery (EOR) techniques. Surfactant flooding for EOR received attraction due to its ability to increase the displacement efficiency by lowering the interfacial tension between oil and water and mobilizing the residual oil. This article highlights the adsorption of surfactants onto sand surface with variation of different influencing factors. It has been experimentally found that adsorption of cationic surfactant on sand surface is more and less for anionic surfactant, while non-ionic surfactant shows intermediate behaviour. X-ray diffraction (XRD) study of clean sand particles has been made to determine the main component present in the sand particles. The interaction between sand particles and surfactant has been studied by Fourier Transform Infrared (FTIR) Spectroscopy of the sand particles before and after aging with surfactant. Salinity plays an important role in adsorption of anionic surfactant. Batch experiments were also performed to understand the effects of pH and adsorbent dose on the sorption efficiency. The sand particles exhibited high adsorption efficiency at low pH for anionic and nonionic surfactants. But opposite trend was found for cationic surfactant. Adsorption data were analyzed by fitting with Langmuir, Freundlich, Redlich-Peterson, and Sips isotherm models. Results show that the Langmuir isotherm and pseudo-second order kinetics models suit the equilibrium and kinetics of adsorption on sand surface. Thermodynamics feasibility of the adsorption process was also studied to verify the spontaneity of the process.

  11. 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. PMID:26921544

  12. 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.

  13. 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.

  14. 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

    2015-07-01

    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). PMID:26055623

  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. Thermodynamics of Iodide Adsorption at the Instantaneous Air-Water Interface.

    SciTech Connect

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

    2013-03-21

    We perform 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 the adsorption is measured as the distance from the instantaneous interface, which is defined by a coarse-graining scheme proposed recently by Willard and Chandler.\\cite{chandler1} 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 layer water.

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

    PubMed

    Vilvanathan, Sowmya; Shanthakumar, S

    2016-10-01

    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. PMID:27185382

  18. 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.

  19. 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. PMID:25732332

  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. 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.

  2. Global parameter estimation for thermodynamic models of transcriptional regulation.

    PubMed

    Suleimenov, Yerzhan; Ay, Ahmet; Samee, Md Abul Hassan; Dresch, Jacqueline M; Sinha, Saurabh; Arnosti, David N

    2013-07-15

    Deciphering the mechanisms involved in gene regulation holds the key to understanding the control of central biological processes, including human disease, population variation, and the evolution of morphological innovations. New experimental techniques including whole genome sequencing and transcriptome analysis have enabled comprehensive modeling approaches to study gene regulation. In many cases, it is useful to be able to assign biological significance to the inferred model parameters, but such interpretation should take into account features that affect these parameters, including model construction and sensitivity, the type of fitness calculation, and the effectiveness of parameter estimation. This last point is often neglected, as estimation methods are often selected for historical reasons or for computational ease. Here, we compare the performance of two parameter estimation techniques broadly representative of local and global approaches, namely, a quasi-Newton/Nelder-Mead simplex (QN/NMS) method and a covariance matrix adaptation-evolutionary strategy (CMA-ES) method. The estimation methods were applied to a set of thermodynamic models of gene transcription applied to regulatory elements active in the Drosophila embryo. Measuring overall fit, the global CMA-ES method performed significantly better than the local QN/NMS method on high quality data sets, but this difference was negligible on lower quality data sets with increased noise or on data sets simplified by stringent thresholding. Our results suggest that the choice of parameter estimation technique for evaluation of gene expression models depends both on quality of data, the nature of the models [again, remains to be established] and the aims of the modeling effort. PMID:23726942

  3. Thermodynamic Considerations in Solid Adsorption of Bound Solutes for Patient Support in Liver Failure

    PubMed Central

    Patzer, John F.

    2008-01-01

    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 (SSR) and microspheres-based detoxification system (MDS). Primary results from the thermodynamic analysis are that: (1) the solute-albumin binding constant is of minor importance to equilibrium once it exceeds about 105 L mol−1; (2) the Prometheus approach requires larger solid adsorbent columns than calculated by adsorbent solute capacity alone; and (3) 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. PMID:18638303

  4. 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

  5. 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. PMID:18446250

  6. Thermodynamic properties of hydrogen-water adsorption at terraces and steps of Pt(111) vicinal surface electrodes

    NASA Astrophysics Data System (ADS)

    Gómez-Marín, Ana M.; Feliu, Juan M.

    2016-04-01

    In this work, the effect of temperature on the adsorption states of Pt(111) vicinal surface electrodes in perchloric acid is studied through a thermodynamic analysis. The method allows calculating thermodynamic properties of the interface. In this framework, the concept of the generalized isotherm and the statistical thermodynamics description are applied to calculate formal entropies, enthalpies and Gibbs energies, ΔGbari0, of the adsorption processes at two-dimensional terraces and one-dimensional steps. These values are compared with data from literature. Additionally, the effect of the step density on ΔGbari0 and on the lateral interactions between adsorbed species, ωij, at terraces and steps is also determined. Calculated ΔGbari0, entropies and enthalpies are almost temperature-independent, especially at steps, but they depend on the step orientation. In contrast, ΔGbari0 and ωij at terraces depend on the step density, following a linear tendency for terrace lengths larger than 5 atoms. However, while ΔGbari0 increases with the step density, ωij decreases. Results were explained by considering the modification in the energetic surface balance by hydrogen, Hads, and water, H2Oads, co-adsorption on the electrode, which in turn determines the whole adsorption processes on terraces and steps.

  7. Adsorption behavior of EE2 (17 alpha-ethinylestradiol) onto the inactivated sewage sludge: kinetics, thermodynamics and influence factors.

    PubMed

    Feng, Yujie; Zhang, Zhaohan; Gao, Peng; Su, Hui; Yu, Yanling; Ren, Nanqi

    2010-03-15

    The adsorption behavior of 17 alpha-ethinylestradiol (EE(2)) onto inactivated sludge was investigated to assess the function of adsorption on EE(2) removal in activated sludge system. The adsorption equilibrium of EE(2) can be achieved in 5.0 h at the research temperature and the adsorption process could be well described by pseudo-second-order model. The equilibrium data at different temperatures were fitted by a linear regression. The thermodynamics analysis revealed that EE(2) adsorption onto inactivated sludge was spontaneous (Delta G=-15.18 to -16.35 kJ/mol), enthalpy-driven (Delta H=-27.2 kJ/mol), entropy-retarded (DeltaS=-39.18 J/(mol K)), and mainly physical adsorption. Effects of pH, ionic strength and coexisting organic matters (methanol and bisphenol A) on EE(2) adsorption onto inactivated sludge were also examined. The amounts of EE(2) equilibrium adsorption ability were unchanged as the pH values increasing from 2.0 to 6.0, but decreased from 2.14 to 1.43 mg/g MLSS when the initial EE(2) concentration was 5.0mg/L as pH above 6.0. The adsorption capacities were first increased from 2.19 to 2.50mg/g MLSS, then sharply decreased and stabilized at 1.12 mg/g MLSS during the ionic strength was adjusted from 0 to 1 mol/L. Methanol (0.4-5%, v/v) and bisphenol A (0-200mg/L) in the mixed liquor can decrease the adsorption capacity of EE(2) from 2.19 to 1.39 and 0.75 mg/g MLSS, respectively. PMID:19945220

  8. 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)

  9. 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

  10. 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. PMID:23653315

  11. 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. PMID:25409587

  12. Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

    NASA Astrophysics Data System (ADS)

    Moon, Ellen M.; Peacock, Caroline L.

    2011-11-01

    Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ˜2-7), with adsorption increasing with pH to a maximum at pH ˜6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO 5H n) n-8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1p K basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere tbnd RCOOCu + surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K tbnd RCOOCu + = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.

  13. Dye adsorption behavior of Luffa cylindrica fibers.

    PubMed

    Demir, H; Top, A; Balköse, D; Ulkü, S

    2008-05-01

    Using natural Luffa cylindrica fibers as adsorbent removal of methylene blue dye from aqueous solutions at different temperatures and dye concentrations was investigated in this study. Thermodynamics and kinetics of adsorption were also investigated. The adsorption isotherms could be well defined with Langmuir model instead of Freundlich model. The thermodynamic parameters of methylene blue (MB) adsorption indicated that the adsorption is exothermic and spontaneous. The average MB adsorption capacity was found out as 49 mg/g and average BET surface area of fibers was calculated as 123 m(2)/g. PMID:17919814

  14. Exploring the role of model parameters and regularization procedures in the thermodynamics of the PNJL model

    SciTech Connect

    Ruivo, M. C.; Costa, P.; Sousa, C. A. de; Hansen, H.

    2010-08-05

    The equation of state and the critical behavior around the critical end point are studied in the framework of the Polyakov-Nambu-Jona-Lasinio model. We prove that a convenient choice of the model parameters is crucial to get the correct description of isentropic trajectories. The physical relevance of the effects of the regularization procedure is insured by the agreement with general thermodynamic requirements. The results are compared with simple thermodynamic expectations and lattice data.

  15. A theoretical analysis of the thermodynamic contributions for the adsorption of individual protein residues on functionalized surfaces.

    PubMed

    Latour, Robert A; Hench, Larry L

    2002-12-01

    Although the denaturing of adsorbed proteins on biomaterials surfaces is believed to lead to adverse tissue reactions to implanted materials, very little is currently known of the actual mechanisms involved. These mechanisms must be understood if surfaces are to be proactively designed to control protein adsorption behavior. Concepts widely employed in rational drug design and in protein and RNA folding predictions provide a means to approach this problem. Accordingly, a theoretical analysis has been conducted to estimate the thermodynamic contributions (changes in enthalpy, entropy, and Gibbs free energy) for the adsorption of selected individual mid-chain protein residues to functionalized surfaces. Enthalpic contributions from residue-surface interactions were calculated using semi-empirical quantum mechanical-based computational chemistry methods in a simulated aqueous environment (MOPAC/COSMO), and enthalpic and entropic contributions due to water restructuring effects assumed to occur during adsorption were estimated from experimental data for functional group wetting and calculated changes in solvent accessible surface area as each protein residue approached each surface. When combined with intraprotein residue-residue interactions, the understanding of residue-surface adsorption energy relationships provides a means to begin to predict protein adsorption behavior as a function of biomaterials surface chemistry. It is recognized that several assumptions have been made in this approach that could be challenged, and that truncations necessary due to programming limitations have been applied that may neglect potentially important interactions. Therefore, it must be understood that the modeling predictions may not be directly applicable to biomaterials for surface design under actual physiologic conditions at this stage. However, this attempt at modeling fundamental components of protein adsorption is presented as an initial approach to understanding these

  16. The adsorption of C4 unsaturated hydrocarbons on highly dehydrated silica. An IR-spectroscopic and thermodynamic study.

    PubMed

    Magnacca, Giuliana; Morterra, Claudio

    2005-04-26

    The adsorptive interaction of 1-butyne and 1-butene with a highly dehydrated pyrogenic silica system has been studied to understand the thermodynamic behavior of the adsorption process by the application of the Langmuir model and of the Van't Hoff equation. In situ FTIR spectroscopy allowed the characterization of the adsorption phenomenon in terms of involved surface sites, gas-volumetric determinations yielded quantitative information relative to the adsorption process, and microcalorimetric results allowed the comparison between calculated and experimental data. K(eq) and Delta(ads)G degrees were obtained from Langmuir's model application; Delta(ads)H data were obtained from the Van't Hoff equation and by the isosteric heats method and were compared with experimental values. The virtual constancy of Delta(ads)H with equilibrium pressure and surface coverage (Langmuir model) allowed us to obtain the Delta(ads)H degrees values and, consequently, the Delta(ads)S degrees values for the systems of interest. PMID:15835958

  17. The determination of oxide surface charging parameters for a predictive metal adsorption model.

    PubMed

    Schreier, Marc; Feltes, Theresa E; Schaal, Melanie T; Regalbuto, John R

    2010-08-15

    The procurement of oxide surface charging parameters has been a widely researched topic in recent years [1-30]. In this study, a one-site, two-pK surface charging mechanism is used in combination with a diffuse double-layer description of the electric double-layer to fit pH shift data over silica and alumina. From these fits of pH data, with no further adjustment of parameters, metal adsorption can be predicted over both supports to a reasonable degree of accuracy. A multi-dimensional optimization procedure employing a Nelder-Mead simplex algorithm is used to optimize the DeltapK (pK(2)-pK(1)) parameter to obtain a best fit of the pH shift data with fixed PZC and hydroxyl density (N(s)). The resulting set of parameters is then used with no adjustment in a purely electrostatic adsorption model (the Revised Physical Adsorption or RPA model) in order to predict anionic chloroplatinic acid (CPA, [PtCl(6)](-2)) adsorption on alumina and cationic platinum tetraammine (PTA, [Pt(NH(3))(4)](+2)) adsorption on alumina and silica. The optimization procedure developed in this study gives reasonable values of the DeltapK compared to other values reported in the literature, with fits to the pH shift data at various oxide loadings with relative errors below 2.8%. PMID:20478569

  18. Thermodynamic investigation of trichloroethylene adsorption in water-saturated microporous adsorbents

    SciTech Connect

    Farrell, J.; Hauck, B.; Jones, M.

    1999-08-01

    Adsorption of trichloroethylene (TCE) in adsorbents containing hydrophilic and hydrophobic micropores was investigated in order to determine the mechanisms responsible for TCE adsorption on mineral solids. A high-pressure liquid chromatography method was used to measure TCE adsorption isotherms on three microporous adsorbents. Silica gel and zeolite type NaX were used as hydrophilic model adsorbents, and hexamethyldisilazane (HMDS)-treated silica gel was used as a model hydrophobic adsorbent. Batch uptake and desorption isotherms were also measured on the hydrophilic silica gel. Uptake of TCE by all three adsorbents was linear over the concentration range investigated. However, the silica gel desorption isotherm was highly nonlinear, as indicated by its Freundlich isotherm exponent of 0.58. Capillary phase separation into hydrophobic micropores was postulated as being responsible for the isotherm hysteresis. Supporting this hypothesis was the conformance of the TCE adsorption isotherm to Dubinin-Radushkevitch volume filling of micropores theory. The enthalpies for TCE adsorption on all three solids were determined by van't Hoff analysis of distribution coefficients measured over a temperature range from 5 to 90 C. The TCE adsorption enthalpies on the silica gel and HMDS silica gel were exothermic, but on the zeolite adsorption was endothermic. High exothermic adsorption enthalpies on the silica gel adsorbents indicated that TCE adsorption was occurring in hydrophobic micropores, and that adsorption on surfaces with large radii of curvature contributed only minimally to the total uptake. This indicates that the predominant mechanism for TCE adsorption on these mineral solids is not partitioning into the vicinal water layer.

  19. 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.

  20. Thermodynamic scaling of dynamic properties of liquid crystals: verifying the scaling parameters using a molecular model.

    PubMed

    Satoh, Katsuhiko

    2013-08-28

    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(γτ) , 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 γ(τ) 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. PMID:24007031

  1. Influence of elastic strains on the adsorption process in porous materials. Thermodynamics and experiment

    NASA Astrophysics Data System (ADS)

    Grosman, A.; Ortega, C.

    2010-06-01

    If we disregard the shape of the boundary hysteresis loop, H1 for SBA-15, MCM-41 and KIT-6, H2 for p +-type porous silicon and porous glass, the hysteretic features inside the loop are qualitatively the same for all these systems and show that none of them are composed of independent pores whether the pores are interconnected or not. We hence believe that the physical parameter which couples the pores is not the interconnectivity but the elastic deformation of the porous matrix. The thermodynamic approach we develop includes the elastic energy of the solid. We show that the variation of the surface free energy, which is proportional to the deformation of the porous matrix, is an important component of the total free energy. With porous silicon, we experimentally show that a stress external to the porous matrix exerted by the substrate on which it is supported significantly increases the total free energy and the adsorbed amount and decreases the condensation pressure compared to that of the same porous matrix detached from its substrate which is the relaxed state of the supported layer. This stress can be partly relaxed by making thicker porous layers due to the breaking of Si-Si bonds. This results in the shift of the isotherms towards that of the membrane. We propose a new interaction mechanism occurring through the pore wall elastic deformation in which the external mechanical stress is imposed on a given pore by its neighbours.

  2. 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).

  3. 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. PMID:24838985

  4. 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

  5. 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.

  6. Equilibrium and Kinetic Adsorption of Bacteria on Alluvial Sand and Surface Thermodynamic Interpretation

    SciTech Connect

    Chen, Gang; Rockhold, Mark L.; Strevett, Keith A.

    2003-05-15

    Equilibrium and kinetic adsorption of Escherichia coli HB 101, E. coli JM 109, Pseudomonas fluorescens, Pseudomonas putida and Pseudomonas sp. on alluvial sand from the Canadian River alluvium (Norman, OK) was investigated through column experiments. Equilibrium adsorption of these five bacterial strains followed the Freundlich expression and was a function of zero energy points, an indication of the zero energy buffer zone. Among the microorganisms studied, P. putida had the greatest equilibrium adsorption (162.4 x 108 cell/g sediment with a microbial injectate concentration of 108 cell/mL), followed by Pseudomonas sp. (127.9 x 108 cell/g sediment), E. coli HB 101 (62.8 x 108 cell/g sediment), E. coli JM 109 (58.4 x 108 cell/g sediment), and P. fluorescens (42.6 x 108 cell/g sediment). The first-order kinetic adsorption rate coefficient was an exponential function of the total interaction free energy between bacteria and sediment evaluated at the primary minimum, (PM). E. coli HB 101 had the greatest kinetic adsorption rate coefficient on the sediment (5.10 h-1), followed by E. coli JM 109 (4.52 h-1), P. fluorescens (2.12 h-1), P. putida (2.04 h-1), and Pseudomonas sp. (1.34 h-1).

  7. 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.

  8. Thermodynamics and kinetics of adsorption of selected monoalkylbenzenes in H-ZSM-5

    SciTech Connect

    Schumacher, R.; Karge, H.G.

    1999-03-04

    In this study, the authors present the first systematic investigation of the adsorption of n-propylbenzene, isopropylbenzene, and n-butylbenzene in H-ZSM-5. Both the sorption isotherms and the rate of sorption uptake were investigated at temperatures between 315 and 425 K. The adsorption isotherms are of type 1 and are reasonably well described by the Langmuir-Freundlich model. It is shown that the heat of adsorption of the longer sorbate molecules depends significantly on the concentration, thus indicating an increased influence of sorbate-sorbate interaction. The uptake rates are determined by Fickian diffusion. The activation energies for the diffusion process are identical for all systems (32--36 kJ/mol). The diffusivities are also in the same order of magnitude decreasing noticeably for sorbates with longer or more complex substituents. A tentative explanation based on a simple jump-rate model for intracrystalline diffusion is given.

  9. A study of the thermodynamic properties of surfactant mixtures: Mixed micelle formation and mixed surfactant adsorption

    SciTech Connect

    Lopata, J.J.

    1992-12-31

    The volumetric mixing in anionic/nonionic, cationic/nonionic, and anionic/cationic mixed micelles was determined by examining the total surfactant apparent molar volumes at total surfactant concentrations much greater than the mixture critical micelle concentration. The mixed surfactant systems investigated were: sodium dodecyl sulfate and a polyethoxylated nonylphenol, at 0.15 M NaCl and with no added NaCl; cetyl pyridinium chloride and polyethoxylated nonylphenol, at 0.03 M NaCl; and sodium dodecyl sulfate and dodecyl pyridinium chloride, at 0.15 M NaCl. The results of this study suggest that the electrostatic interactions in the mixed micelles do no significantly effect the molar volume of the mixed micelle. Therefore, the micelle hydrophobic core dominates the volumetric mixing in mixed micelles. The adsorption of sodium dodecyl sulfate and a polyethoxylated nonylphenol and well defined mixtures thereof was measured on gamma alumina. A pseudo-phase separation model to describe mixed anionic/nonionic admicelle (adsorbed surfactant aggregate) formation was developed. In this model, regular solution theory was used to describe the anionic/nonionic surfactant interactions in the mixed admicelle and a patch-wise adsorption model was used to describe surfactant adsorption on a heterogeneous surface. Regular solution theory was tested on specific homogeneous surface patches by examining constant total surfactant adsorption levels. For the adsorption of binary surfactant mixtures adsorbing at total equilibrium concentrations above the mixture critical micelle concentration, simultaneous solution of the pseudo-phase separation models for mixed admicelle and mixed micelle formation predicts that the surfactant compositions in the monomer, micelle, and admicelle pseudo-phases are constant at a constant total adsorption level.

  10. 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

    2016-02-01

    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, (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. PMID:26520475

  11. 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.

  12. 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.

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

    DOE PAGESBeta

    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 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

  14. 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). PMID:22339031

  15. Melanoidin Removal Mechanism in An Aqueous Adsorption System: An Equilibrium, Kinetic and Thermodynamic Study.

    PubMed

    Nunes, Diego L; Oliveira, Leandro S; Franca, Adriana S

    2015-01-01

    Melanoidins are colored products that can be found in food and drinks, formed by Maillard reactions. Sometimes these compounds are considered undesirable in certain food products, because they impart a brownish color and must be removed. An overview of recent patents related to melanoidin removal indicates that it can be performed by chemical/biological degradation or by adsorption processes. Therefore, in the present study, the adsorption mechanism for synthetic melanoidin removal from aqueous solutions was studied using different Raphanus sativus press-cake sorbents, with the precursor material being carbonized in a microwave oven, either with direct heating or after a chemical activation process with phosphoric acid, nitric acid or potassium hydroxide. Physical and chemical modifications were evaluated by FTIR, pHPZC, thermogravimetry and BET. The adsorption kinetics was better described by a pseudo-second order model for all activated carbons (ACs). Evaluation of the diffusion process showed dependence on the initial melanoidin concentration due to the wide range of sizes of the adsorbed molecules. The equilibrium data were best fitted by the Langmuir model for the acid-treated AC and by the Freundlich model for the base-treated and non-chemically treated ACs. Melanoidin adsorption was characterized as a spontaneous, favorable and endothermic process involving hydrogen bonds and π-π interactions between the adsorbents surfaces and the adsorbed molecules. PMID:26013772

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

    PubMed

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

    2015-07-01

    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. PMID:26266715

  17. 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. PMID:23736740

  18. Thermodynamic relation between voltage-concentration dependence and salt adsorption in electrochemical cells.

    PubMed

    Rica, R A; Ziano, R; Salerno, D; Mantegazza, F; Brogioli, D

    2012-10-12

    Electrochemical cells containing two electrodes dipped in an ionic solution are widely used as charge accumulators, either with polarizable (supercapacitor) or nonpolarizable (battery) electrodes. Recent applications include desalination ("capacitive deionization") and energy extraction from salinity differences ("capacitive mixing"). In this Letter, we analyze a general relation between the variation of the electric potential as a function of the concentration and the salt adsorption. This relation comes from the evaluation of the electrical and mechanical energy exchange along a reversible cycle, which involves salt adsorption and release by the electrodes. The obtained relation thus describes a connection between capacitive deionization and capacitive mixing. We check this relation with experimental data already reported in the literature, and moreover by some classical physical models for electrodes, including polarizable and nonpolarizable electrodes. The generality of the relation makes it very useful in the study of the properties of the electric double layer. PMID:23102339

  19. 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.

  20. Thermodynamic parameters of CdTe crystals in the cubic phase

    NASA Astrophysics Data System (ADS)

    Freik, Dmytro; Parashchuk, Taras; Volochanska, Bohdana

    2014-09-01

    Based on the analysis of the crystal and electronic structures of CdTe crystals in the cubic phase cluster models have been built for calculation of the geometric and thermodynamic parameters. According to density functional theory (DFT) and by using the hybrid B3LYP functional the temperature dependences of formation energy ∆E, formation enthalpy ∆H, Gibbs free energy ∆G, entropy ∆S, specific heat capacity at constant volume CV and pressure CP have been defined. Also, in the work analytical expressions of temperature dependences of the presented thermodynamic parameters have been derived, which have been approximated by quantum-chemical calculation data using the mathematical package Maple 14. The results of ab initio calculations are compared with experimental data.

  1. 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.

  2. 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.

  3. The role of test parameters on the kinetics and thermodynamics of glass leaching. [None

    SciTech Connect

    Jantzen, C M

    1988-01-01

    The relative durabilities of nuclear waste, natural, and ancient glasses have been assessed by standard laboratory leach tests. Different test conditions result in different glass surface areas (SA), leachant volumes (V), and test durations (t). Leachate concentrations are known to be a parabolic function of the kinetic test parameter SAV/center dot/t. Based on durability experiments of glass monoliths at low (SAV)/center dot/ glass durability has been shown to be a logarithmic function of the thermodynamic hydration free energy, ..delta..G/sub hyd/. The thermodynamic hydration free energy, ..delta..G/sub hyd/, can be calculated from glass composition and solution pH. In the repository environment high effective glass surface areas to solution volume ratios may occur as a result of slow groundwater flow rates. The application of hydration thermodynamics to crushed glass, high (SAV)/center dot/t, durability tests has been demonstrated. The relative contributions of the kinetic test parameters, (SAV)/center dot/t, and the thermodynamic parameter, ..delta..G/sub hyd/, have been shown to define a plane in ..delta..G/sub hyd/-concentration-(SAV)/center dot/t space. At constant test conditions, e.g. constant (SAV/center dot/t, the intersection with this surface indicates that all /delta G//sub hyd/-concentration plots should have similar slopes and predict the same relative durabilities for various glasses as a function of glass composition. Using this approach, the durability of nuclear waste glasses has been interpolated to be -- 10/sup 6/ years and no less than 10/sup 3/ years. 28 refs., 24 figs.

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

    PubMed

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

    2004-08-01

    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. PMID:15225927

  5. Determination of thermodynamic gas parameters in branched pipes in internal combustion engines

    NASA Astrophysics Data System (ADS)

    Mitianiec, W.

    2014-08-01

    The paper presents theoretical and experimental results of calculation of basic gas parameters in the branched pipes. These parameters are required in one-dimensional computer models for prediction of non-steady gas flow in complicated multi-cylinder engine ducts. The gas flow near the junction is described with assumption of compressed and unsteady flow. Mathematical equations describing the gas flow are given in the paper on basis of mass, energy balance in the junction, pressure drop between pipes and conservation of energy in the section of supplied pipe. Equation systems enable to solve values of pressure, gas velocity, sound speed, density and concentration of gas components in every pipe connected to the joint. The different cases of the flow area are considered. The obtained parameters at the junction outflow are needed as initial values for calculation of unsteady gas flow in the outflow pipes. Verification of the method was conducted experimentally and pressure loss coefficients are given in the paper. Additionally by using Fluent program with high mesh density of the T-pipe junction the thermodynamic parameters (pressure, velocity, temperature) are compared with those obtained from 0D model. The model enables calculation the thermodynamic parameters of inflow and outflow systems in multi-cylinder IC engines in computer program.

  6. Rapid Computation of Thermodynamic Properties over Multidimensional Nonbonded Parameter Spaces Using Adaptive Multistate Reweighting.

    PubMed

    Naden, Levi N; Shirts, Michael R

    2016-04-12

    We show how thermodynamic properties of molecular models can be computed over a large, multidimensional parameter space by combining multistate reweighting analysis with a linear basis function approach. This approach reduces the computational cost to estimate thermodynamic properties from molecular simulations for over 130,000 tested parameter combinations from over 1000 CPU years to tens of CPU days. This speed increase is achieved primarily by computing the potential energy as a linear combination of basis functions, computed from either modified simulation code or as the difference of energy between two reference states, which can be done without any simulation code modification. The thermodynamic properties are then estimated with the Multistate Bennett Acceptance Ratio (MBAR) as a function of multiple model parameters without the need to define a priori how the states are connected by a pathway. Instead, we adaptively sample a set of points in parameter space to create mutual configuration space overlap. The existence of regions of poor configuration space overlap are detected by analyzing the eigenvalues of the sampled states' overlap matrix. The configuration space overlap to sampled states is monitored alongside the mean and maximum uncertainty to determine convergence, as neither the uncertainty or the configuration space overlap alone is a sufficient metric of convergence. This adaptive sampling scheme is demonstrated by estimating with high precision the solvation free energies of charged particles of Lennard-Jones plus Coulomb functional form with charges between -2 and +2 and generally physical values of σij and ϵij in TIP3P water. We also compute entropy, enthalpy, and radial distribution functions of arbitrary unsampled parameter combinations using only the data from these sampled states and use the estimates of free energies over the entire space to examine the deviation of atomistic simulations from the Born approximation to the solvation free

  7. Order parameter, correlation functions, and fidelity susceptibility for the BCS model in the thermodynamic limit

    NASA Astrophysics Data System (ADS)

    El Araby, Omar; Baeriswyl, Dionys

    2014-04-01

    The exact ground state of the reduced BCS Hamiltonian is investigated numerically for large system sizes and compared with the BCS ansatz. A "canonical" order parameter is found to be equal to the largest eigenvalue of Yang's reduced density matrix in the thermodynamic limit. Moreover, the limiting values of the exact analysis agree with those obtained for the BCS ground state. Exact results for the ground-state energy, level occupations, and a pseudospin-pseudospin correlation function are also found to converge to the BCS values already for relatively small system sizes. However, discrepancies persist for a pair-pair correlation function, for interlevel correlations of occupancies and for the fidelity susceptibility, even for large system sizes where these quantities have visibly converged to well-defined limits. Our results indicate that there exist nonperturbative corrections to the BCS predictions in the thermodynamic limit.

  8. 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.

  9. Redefinition of the mode Grüneisen parameter for polyatomic substances and thermodynamic implications

    PubMed Central

    Hofmeister, Anne M.; Mao, Ho-kwang

    2002-01-01

    Although the value of the thermal Grüneisen parameter (γth) should be obtained by averaging spectroscopic measurements of mode Grüneisen parameters [γi ≡ (KT/νi)∂νi/∂P, where KT is isothermal bulk modulus, ν is frequency, and P is pressure], in practice, the average 〈γi〉 is up to 25% lower than γth. This discrepancy limits the accuracy of inferring physical properties from spectroscopic data and their application to geophysics. The problem arises because the above formula is physically meaningful only for monatomic or diatomic solids. We redefine γi to allow for the presence of functional groups in polyatomic crystal structures, and test the formula against spinel- and olivine-group minerals that have well-constrained spectra at pressure, band assignments, thermodynamic properties, and elastic moduli, and represent two types of functional groups. Our revised formula [γi ≡ (KX/νi)∂νi/∂P] uses polyhedral bulk moduli (KX) appropriate to the particular atomic motion associated with each vibrational mode, which results in equal values for 〈γi〉, γth, and γLA (the Grüneisen parameter of the longitudinal acoustic mode). Similar revisions lead to the pressure derivatives of these parameters being equal. Accounting for differential compression intrinsic to structures with functional groups improves the accuracy with which spectroscopic models predict thermodynamic properties and link to elastic properties. PMID:11805314

  10. Thermodynamic integration to monitor parameter convergence in molecular dynamics: application to liquid water

    NASA Astrophysics Data System (ADS)

    Soler, Jose M.; Fritz, Michelle; Fernandez-Serra, Marivi

    Checking the convergence of accuracy parameters (e.g. basis set), in ab initio molecular dynamics, is complicated and computationally expensive. This is because entire simulations are required for each new parameter set, and comparing two simulations is subject to large statistical errors in structural (pair correlation functions) and thermodynamic (pressure, compressibility) properties. In this work we propose a method to evaluate parameter convergence without these costly simulations. In the spirit of thermodynamic integration approaches, the average change of a given property is computed with different parameters in the same geometries, extracted from a given MD trajectory or set of trajectories. This same approach can be used to explore tendencies for new exchange-correlation functionals, so that only the most promising ones need to be thoroughly evaluated with entire simulations. This work is supported by DOE Grants No. DE-FG02-09ER16052, No. DE-SC0003871 and the Grant FIS2012-37549-C05 from the Spanish Ministry of Economy and Competitiveness.

  11. Thermodynamic characterization of metal dissolution and inhibitor adsorption processes in the low carbon steel/mimosa tannin/sulfuric acid system

    NASA Astrophysics Data System (ADS)

    Martinez, Sanja; Stern, Ivica

    2002-10-01

    The corrosion rates in the presence of mimosa tannin as a low carbon steel corrosion inhibitor in sulfuric acid media, were measured by the weight loss method, in the range of temperatures from 20 to 60 °C. The Temkin, Frumkin and Freundlich isotherms were tested for their fit to the experimental data. The free energies and enthalpies for the adsorption process and the apparent activation energies, enthalpies and entropies of the dissolution process were determined. The fundamental thermodynamic functions were used to glean important information about the mimosa tannin inhibitory behavior. The results were explained in terms of chemical thermodynamics.

  12. Anchored thiol smectite clay-kinetic and thermodynamic studies of divalent copper and cobalt adsorption

    SciTech Connect

    Guerra, Denis Lima Airoldi, Claudio

    2008-09-15

    A natural smectite clay sample from Serra de Maicuru, Para State, Brazil, had aluminum and zirconium polyoxycations inserted within the interlayer space. The precursor and pillarized smectites were organofunctionalized with the silyating agent 3-mercaptopropyltrimethoxysilane. The basal spacing of 1.47 nm for natural clay increased to 2.58 and 2.63 nm, for pillared aluminum, S{sub Al/SH}, and zirconium, S{sub Zr/SH}, and increases in the surface area from 44 to 583 and 585 m{sup 2} g{sup -1}, respectively. These chemically immobilized clay samples adsorb divalent copper and cobalt cations from aqueous solutions of pH 5.0 at 298{+-}1 K. The Langmuir, Redlich-Peterson and Toth adsorption isotherm models have been applied to fit the experimental data with a nonlinear approach. From the cation/basic center interactions for each smectite at the solid-liquid interface, by using van't Hoff methodology, the equilibrium constant and exothermic thermal effects were calculated. By considering the net interactive number of moles for each cation and the equilibrium constant, the enthalpy, {delta}{sub int}H{sup 0} (-9.2{+-}0.2 to -10.2{+-}0.2 kJ mol{sup -1}) and negative Gibbs free energy, {delta}{sub int}G{sup 0} (-23.9{+-}0.1 to -28.7{+-}0.1 kJ mol{sup -1}) were calculated. These values enabled the positive entropy, {delta}{sub int}S{sup 0} (51.3{+-}0.3 to 55.0{+-}0.3 JK{sup -1} mol{sup -1}) determination. The cation-sulfur interactive process is spontaneous in nature, reflecting the favorable enthalpic and entropic results. The kinetics of adsorption demonstrated that the fit is in agreement with a second-order model reaction with rate constant k{sub 2}, varying from 4.8x10{sup -2} to 15.0x10{sup -2} and 3.9x10{sup -2} to 12.2x10{sup -2} mmol{sup -1} min{sup -1} for copper and cobalt, respectively. - Graphical abstract: A natural smectite clay sample from Serra de Maicuru, Para State, Brazil, had aluminum and zirconium polyoxycations inserted within the interlayer space. The

  13. 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. PMID:27219463

  14. 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

    2015-07-01

    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. PMID:26023813

  15. Design of a new integrated chitosan-PAMAM dendrimer biosorbent for heavy metals removing and study of its adsorption kinetics and thermodynamics.

    PubMed

    Zarghami, Zabihullah; Akbari, Ahmad; Latifi, Ali Mohammad; Amani, Mohammad Ali

    2016-04-01

    In this research, different generations of PAMAM-grafted chitosan as integrated biosorbents were successfully synthesized via step by step divergent growth approach of dendrimer. The synthesized products were utilized as adsorbents for heavy metals (Pb(2+) in this study) removing from aqueous solution and their reactive Pb(2+) removal potential was evaluated. The results showed that as-synthesized products with higher generations of dendrimer, have more adsorption capacity compared to products with lower generations of dendrimer and sole chitosan. Adsorption capacity of as-prepared product with generation 3 of dendrimer is 18times more than sole chitosan. Thermodynamic and kinetic studies were performed for understanding equilibrium data of the uptake capacity and kinetic rate uptake, respectively. Thermodynamic and kinetic studies showed that Langmuir isotherm model and pseudo second order kinetic model are more compatible for describing equilibrium data of the uptake capacity and kinetic rate of the Pb(2+) uptake, respectively. PMID:26836608

  16. Determination of kinetic and thermodynamic parameters that describe isothermal seed germination: A student research project

    NASA Astrophysics Data System (ADS)

    Hageseth, Gaylord T.

    1982-02-01

    Students under the supervision of a faculty member can collect data and fit the data to the theoretical mathematical model that describes the rate of isothermal seed germination. The best-fit parameters are interpreted as an initial substrate concentration, product concentration, and the autocatalytic reaction rate. The thermodynamic model enables one to calculate the activation energy for the substrate and product, the activation energy for the autocatalytic reaction, and changes in enthalpy, entropy, and the Gibb's free energy. Turnip, lettuce, soybean, and radish seeds have been investigated. All data fit the proposed model.

  17. 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. PMID:26198014

  18. 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. PMID:27114109

  19. Redefinition of the mode Grüneisen parameter for polyatomic substances and thermodynamic implications.

    PubMed

    Hofmeister, Anne M; Mao, Ho-kwang

    2002-01-22

    Although the value of the thermal Grüneisen parameter (gamma(th)) should be obtained by averaging spectroscopic measurements of mode Grüneisen parameters [gamma(i) identical with (K(T)/nu(i)) delta nu(i)/ delta P, where K(T) is isothermal bulk modulus, nu is frequency, and P is pressure], in practice, the average is up to 25% lower than gamma(th). This discrepancy limits the accuracy of inferring physical properties from spectroscopic data and their application to geophysics. The problem arises because the above formula is physically meaningful only for monatomic or diatomic solids. We redefine gamma(i) to allow for the presence of functional groups in polyatomic crystal structures, and test the formula against spinel- and olivine-group minerals that have well-constrained spectra at pressure, band assignments, thermodynamic properties, and elastic moduli, and represent two types of functional groups. Our revised formula [gamma(i) identical with (K(X)/nu(i)) delta nu(i)/ delta P] uses polyhedral bulk moduli (K(X)) appropriate to the particular atomic motion associated with each vibrational mode, which results in equal values for , gamma(th), and gamma(LA) (the Grüneisen parameter of the longitudinal acoustic mode). Similar revisions lead to the pressure derivatives of these parameters being equal. Accounting for differential compression intrinsic to structures with functional groups improves the accuracy with which spectroscopic models predict thermodynamic properties and link to elastic properties. PMID:11805314

  20. Adsorption of C.I. Reactive Red 228 and Congo Red dye from aqueous solution by amino-functionalized Fe3O4 particles: kinetics, equilibrium, and thermodynamics.

    PubMed

    Yan, Ting-guo; Wang, Li-Juan

    2014-01-01

    A magnetic adsorbent was synthesized by γ-aminopropyltriethoxysilane (APTES) modification of Fe(3)O(4) particles using a two-step process. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and vibration sample magnetometry were used to characterize the obtained magnetic adsorbent. EDS and XPS showed that APTES polymer was successfully introduced onto the as-prepared Fe(3)O(4)/APTES particle surfaces. The saturation magnetization of the magnetic adsorbent was around 65 emu g(-1), which indicated that the dye can be removed fast and efficiently from aqueous solution with an external magnetic field. The maximum adsorption capacities of Fe(3)O(4)/APTES for C.I. Reactive Red 228 (RR 228) and Congo Red (CR) were 51.4 and 118.8 mg g(-1), respectively. The adsorption of C.I. Reactive Red 228 (RR 228) and Congo Red (CR) on Fe(3)O(4)/APTES particles corresponded well to the Langmuir model and the Freundlich model, respectively. The adsorption processes for RR 228 and CR followed the pseudo-second-order model. The Boyd's film-diffusion model showed that film diffusion also played a major role in the studied adsorption processes for both dyes. Thermodynamic study indicated that both of the adsorption processes of the two dyes are spontaneous exothermic. PMID:24552735

  1. Kinetic, isotherm and thermodynamic investigations of phosphate adsorption onto core-shell Fe₃O₄@LDHs composites with easy magnetic separation assistance.

    PubMed

    Yan, Liang-guo; Yang, Kun; Shan, Ran-ran; Yan, Tao; Wei, Jing; Yu, Shu-jun; Yu, Hai-qin; Du, Bin

    2015-06-15

    In this study, three different magnetic core-shell Fe3O4@LDHs composites, Fe3O4@Zn-Al-, Fe3O4@Mg-Al-, and Fe3O4@Ni-Al-LDH were prepared via a rapid coprecipitation method for phosphate adsorptive removal. The composites were characterized by XRD, FTIR, TEM, VSM and BET analyses. Characterization results proved the successful synthesis of core-shell Fe3O4@LDHs composites with good superparamagnetisms. Batch experiments were conducted to study the adsorption efficiency of phosphate. Optimal conditions for the phosphate adsorption were obtained: 0.05 g of adsorbent, solution pH of 3, and contact time of 60 min. Proposed mechanisms for the removal of phosphate species onto Fe3O4@LDHs composites at different initial solution pH were showed. The kinetic data were described better by the pseudo-second-order kinetic equation and KASRA model. The adsorption isotherm curves showed a three-region behavior in the ARIAN model. It had a good fit with Langmuir model and the maximum adsorption capacity followed the order of Fe3O4@Zn-Al-LDH>Fe3O4@Mg-Al-LDH>Fe3O4@Ni-Al-LDH. Thermodynamic analyses indicated that the phosphate adsorption process was endothermic and spontaneous in nature. The three Fe3O4@LDHs composites could be easily separated from aqueous solution by the external magnetic field in 10s. These novel magnetic core-shell Fe3O4@LDHs adsorbents may offer a simple single step adsorption treatment option to remove phosphate from water without the requirement of pre-/post-treatment for current industrial practice. PMID:25778739

  2. Application of novel Polypyrrole/thiol-functionalized zeolite Beta/MCM-41 type mesoporous silica nanocomposite for adsorption of Hg2+ from aqueous solution and industrial wastewater: Kinetic, isotherm and thermodynamic studies

    NASA Astrophysics Data System (ADS)

    Javadian, Hamedreza; Taghavi, Mehdi

    2014-01-01

    Hierarchical zeolite consists of both microporous and unordered mesoporous structures. A composite of Polypyrrole/thiol-functionalized Beta/MCM-41 (PPy/SH-Beta/MCM-41) was prepared, characterized by FE-SEM, FT-IR, XRD, TGA and BET analysis and applied in the investigation of its adsorption characteristics for the removal of Hg2+ ions from aqueous solutions. Thiol-functionalized Beta/MCM-41 (SH-Beta/MCM-41) was prepared by 3-mercaptopropyltrimethoxysilane (MPTMS) in the presence of aerosil-200 as a silica source by two-step hydrothermal crystallization procedure. Batch mode experiments were conducted and three kinetic models were used to describe the adsorption process. The experimental data fitted very well with the Pseudo-second-order kinetic model. The calculated thermodynamic parameters (ΔH, ΔS and ΔG) revealed that the adsorption of Hg2+ onto PPy/SH-Beta/MCM-41 is an endothermic and spontaneous process. It was found that temperature has a positive effect on the removal efficiency and that PPy/SH-Beta/MCM-41 is potentially able to remove Hg2+ ions from aqueous solutions at even high concentrations (400 mg L-1). The recovery of Hg2+ from the PPy/SH-Beta/MCM-41 adsorbent was found to be more than 90% using 0.5 M H2SO4, and the ability of the absorbent to be reused for removal of Hg2+ was investigated.

  3. 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.

  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. 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.

  6. 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. PMID:24013063

  7. Synthesis, molecular structure, spectroscopic analysis, thermodynamic parameters and molecular modeling studies of (2-methoxyphenyl)oxalate

    NASA Astrophysics Data System (ADS)

    Şahin, Zarife Sibel; Kantar, Günay Kaya; Şaşmaz, Selami; Büyükgüngör, Orhan

    2015-05-01

    The aim of this study is to find out the molecular characteristic and structural parameters that govern the chemical behavior of a new (2-methoxyphenyl)oxalate compound and to compare predictions made from theory with experimental observations. The title compound, (2-methoxyphenyl)oxalate, (I), (C16H14O6), has been synthesized. The compound has been characterized by elemental analysis, IR, 1H NMR, 13C NMR spectroscopies and single crystal X-ray diffraction techniques. Optimized molecular structure, harmonic vibrational frequencies, 1H and 13C NMR chemical shifts have been investigated by B3LYP/6-31G(d,p) method using density functional theory (DFT). The calculated results show that the predicted geometry can well reproduce structural parameters. In addition, global chemical reactivity descriptors, molecular electrostatic potential map (MEP), frontier molecular orbitals (FMOs), Mulliken population method and natural population analysis (NPA) and thermodynamic properties have also been studied. The energetic behavior of title compound has been examined in solvent media using polarizable continuum model (PCM).

  8. 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. PMID:26151482

  9. 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. PMID:26849187

  10. Predicting Selenite Adsorption by Soils Using Soil Chemical Parameters in the Constant Capacitance Model

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The constant capacitance model, a chemical surface complexation model, was applied to selenite, Se(IV), adsorption on 36 soils selected for variation in soil chemical properties. The constant capacitance model was able to fit Se(IV) adsorption by optimizing one monodentate Se(IV) surface complexati...

  11. Adsorption-desorption and leaching behavior of kresoxim-methyl in different soils of India: kinetics and thermodynamic studies.

    PubMed

    Sabale, Rupali P; Shabeer T P, Ahammed; Dasgupta, Soma; Utture, Sagar C; Banerjee, Kaushik; Oulkar, Dasharath P; Adsule, Pandurang G; Deshmukh, Madhukar B

    2015-07-01

    The sorption and leaching behavior of kresoxim-methyl was explored in four different soils, viz., clay, sandy loam, loamy sand, and sandy loam (saline), representing vegetables and fruits growing regions of India. Adsorption of kresoxim-methyl in all the soils reached equilibrium within 48 h. The rate constants for adsorption and desorption at two different temperatures were obtained from the Lindstrom model, which simultaneously evaluated adsorption and desorption kinetics. The data for rate constants, activation energies, enthalpy of activation, entropy of activation, and free energy indicated physical adsorption of kresoxim-methyl on soil. The relative adsorptivity of the test soils could be attributed to different organic matter and clay contents of the soils. A good fit to the linear and Freundlich isotherms was observed for both adsorption as well as desorption. The groundwater ubiquity score (GUS) for different soils varied between 0 and 2.26. The GUS and leaching study indicated moderately low leaching potential of kresoxim-methyl. The adsorption on four soil types largely depended on the soil physicochemical properties such as organic carbon content, cation-exchange capacity, and texture of the soil. PMID:26082423

  12. Thermodynamic parameters and counterion binding to the micelle in binary anionic surfactant systems.

    PubMed

    Maneedaeng, Atthaphon; Haller, Kenneth J; Grady, Brian P; Flood, Adrian E

    2011-04-15

    Competitive counterion binding of sodium and calcium to micelles, and mixed micellization have been investigated in the systems sodium dodecylsulfate (NaDS)/sodium decylsulfate (NaDeS) and NaDS/sodium 4-octylbenzenesulfonate (NaOBS) in order to accurately model the activity of the relevant species in solution. The critical micelle concentration (CMC) and equilibrium micelle compositions of mixtures of these anionic surfactants, which is necessary for determining fractional counterion binding measurements, is thermodynamically modeled by regular solution theory. The mixed micelle is ideal (the regular solution parameter β(M)=0) for the NaDS/NaOBS system, while the mixed micelle for NaDS/NaDeS has β(M)=-1.05 indicating a slight synergistic interaction. Counterion binding of sodium to the micelle is influenced by the calcium ion concentration, and vice versa. However, the total degree of counterion binding is essentially constant at approximately 0.65 charge negation at the micelle's surface. The counterion binding coefficients can be quantitatively modeled using a simple equilibrium model relating concentrations of bound and unbound counterions. PMID:21292278

  13. 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.

  14. 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

  15. 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.

  16. 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. PMID:26512858

  17. Kinetics, equilibrium, and thermodynamics investigation on the adsorption of lead(II) by coal-based activated carbon.

    PubMed

    Yi, Zhengji; Yao, Jun; Zhu, Mijia; Chen, Huilun; Wang, Fei; Liu, Xing

    2016-01-01

    The goal of this research is to investigate the feasibility of using activated coal-based activated carbon (CBAC) to adsorb Pb(II) from aqueous solutions through batch tests. Effects of contact time, pH, temperature and initial Pb(II) concentration on the Pb(II) adsorption were examined. The Pb(II) adsorption is strongly dependent on pH, but insensitive to temperature. The best pH for Pb(II) removal is in the range of 5.0-5.5 with more than 90 % of Pb(II) removed. The equilibrium time was found to be 60 min and the adsorption data followed the pseudo-second-order kinetics. Isotherm data followed Langmuir isotherm model with a maximum adsorption capacity of 162.33 mg/g. The adsorption was exothermic and spontaneous in nature. The Fourier transform infrared spectroscopy and scanning electron microscopy analysis suggested that CBAC possessed a porous structure and was rich in carboxyl and hydroxyl groups on its surface, which might play a major role in Pb(II) adsorption. These findings indicated that CBAC has great potential as an alternative adsorbent for Pb(II) removal. PMID:27504258

  18. Using Isothermal Titration Calorimetry to Determine Thermodynamic Parameters of Protein–Glycosaminoglycan Interactions

    PubMed Central

    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. PMID:25325962

  19. 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. PMID:21179969

  20. 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.

  1. Thermodynamic parameters of scandium trifluoride and triiodide in the condensed state

    NASA Astrophysics Data System (ADS)

    Aristova, N. M.; Belov, G. V.

    2015-06-01

    The thermodynamic properties of new classes of compounds, particularly scandium trihalides ScF3, ScCl3, ScBr3, and ScI3, are added to the IVTANTHERMO software package. A critical analysis and processing of the entire array of primary data available in the literature is performed. An equation approximating the temperature dependence of heat capacity in the temperature range 298.15- T m (K) is derived for each crystalline scandium trihalide. The resulting equations C {/p po}( T) for the solid state and the data for the liquid phase are used to calculate the thermodynamic functions of entropy, the reduced Gibbs free energies, and the enthalpy increments. Both the experimental data available in literature and the missing estimated thermodynamic data are used in calculations. The error of the recommended values is estimated in all cases. In the first part of this work, we describe the thermodynamic properties of ScF3 and ScI3 used as the reference data for calculating the thermodynamic functions of ScCl3 and ScBr3, for which experimental data are either very scarce or missing altogether. The resulting data are added to the database of the IVTANTHERMO software package.

  2. Superposition-additive approach: thermodynamic parameters of clusterization of monosubstituted alkanes at the air/water interface.

    PubMed

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

    2011-12-21

    The applicability of the superposition-additive approach for the calculation of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole electric polarisabilities, molecular diamagnetic susceptibilities, π-electron circular currents, as well as for the estimation of the thermodynamic parameters of substituted alkanes, was demonstrated earlier. Now the applicability of the superposition-additive approach for the description of clusterization of fatty alcohols, thioalcohols, amines, carboxylic acids at the air/water interface is studied. Two superposition-additive schemes are used that ensure the maximum superimposition of the graphs of the considered molecular structures including the intermolecular CH-HC interactions within the clusters. The thermodynamic parameters of clusterization are calculated for dimers, trimers and tetramers. The calculations are based on the values of enthalpy, entropy and Gibbs' energy of clusterization calculated earlier using the semiempirical quantum chemical PM3 method. It is shown that the proposed approach is capable of the reproduction with sufficiently enough accuracy of the values calculated previously. PMID:22042000

  3. Adsorption of Cd(II) by Mg-Al-CO3- and magnetic Fe3O4/Mg-Al-CO3-layered double hydroxides: Kinetic, isothermal, thermodynamic and mechanistic studies.

    PubMed

    Shan, Ran-ran; Yan, Liang-guo; Yang, Kun; Hao, Yuan-feng; Du, Bin

    2015-12-15

    Understanding the adsorption mechanisms of metal cations on the surfaces of solids is important for determining the fate of these metals in water and wastewater treatment. The adsorption kinetic, isothermal, thermodynamic and mechanistic properties of cadmium (Cd(II)) in an aqueous solution containing Mg-Al-CO3- and magnetic Fe3O4/Mg-Al-CO3-layered double hydroxide (LDH) were studied. The results demonstrated that the adsorption kinetic and isotherm data followed the pseudo-second-order model and the Langmuir equation, respectively. The adsorption process of Cd(II) was feasible, spontaneous and endothermic in nature. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to explain the adsorption mechanisms. The characteristic XRD peaks and FTIR bands of CdCO3 emerged in the LDH spectra after Cd(II) adsorption, which indicated that the adsorption of Cd(II) by LDHs occurred mainly via CdCO3 precipitation, surface adsorption and surface complexation. Furthermore, the magnetic Fe3O4/Mg-Al-CO3-LDH can be quickly and easily separated using a magnet before and after the adsorption process. PMID:26073520

  4. Effect of the adsorbate (Bromacil) equilibrium concentration in water on its adsorption on powdered activated carbon. Part 1. Equilibrium parameters.

    PubMed

    Al Mardini, Fadi; Legube, Bernard

    2009-10-30

    This study was carried out to investigate the adsorption equilibrium and kinetics of a pesticide of the uracil group on powdered activated carbon (PAC). The experiments were conducted at a wide range of initial pesticide concentrations (approximately 5 microg L(-1) to approximately 500 microg L(-1) at pH 7.8), corresponding to equilibrium concentrations of less than 0.1 microg L(-1) for the weakest, which is compatible with the tolerance limits of drinking water. Such a very broad range of initial solute concentrations resulting powdered activated carbon (PAC) concentrations (0.1-5 mg L(-1)) is the main particularity of our study. The application of several monosolute equilibrium models (two, three or more parameters) has generally shown that Bromacil adsorption is probably effective on two types of sites. High reactivity sites (K(L) approximately 10(3) Lmg(-1)) which are 10-20 less present in a carbon surface than lower reactivity sites (K(L) approximately 10 Lmg(-1)), according to the q(m) values calculated by two- or three-parameter models. The maximum capacity of the studied powdered activated carbon (PAC), corresponding to monolayer adsorption, compared to the Bromacil molecule surface, would be between 170 mg g(-1) and 190 mg g(-1). This theoretical value is very close to the experimental q(m) values obtained when using linearized forms of Langmuir, Tóth and Fritz-Schluender models. PMID:19539425

  5. 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.

  6. Internal ballistics of small arms: Particular problems. Part 2: Thermodynamic model, powder parameters, initiation

    NASA Astrophysics Data System (ADS)

    Celens, E.

    1986-01-01

    The applicability of the thermodynamic model was studied in small caliber weapons. The use of appropriate computer algorithms for optimal exploitation of closed vessel trials was examined. To better understand the initiation phase, the working of primary high explosive compounds was studied by visualizing the ignition phenomenon in a transparent chamber. The results obtained in these studies are summarized.

  7. 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

  8. Applying thermodynamic and kinetic parameters to predict the physical stability of two differently prepared amorphous forms of simvastatin.

    PubMed

    Graeser, Kirsten A; Patterson, James E; Rades, Thomas

    2009-08-01

    Converting drugs from the crystalline to the amorphous state has gained increasing interest in the past decades as a potential method to overcome solubility issues of poorly water soluble drugs. A variety of techniques exist to convert the crystalline state of a drug to its amorphous form, including solution based, heat based and solid - solid conversion based methods. Inherent to the amorphous state, regardless of its preparation technique, is its physical instability and tendency to recrystallize. In this study, quench-cooled and cryo-milled simvastatin were compared with regards to their configurational thermodynamic parameters (entropy, enthalpy and Gibbs free energy) and mobility (relaxation times calculated using the Adam-Gibbs and Kohlrausch-Williams-Watts method). Stability studies showed quench-cooled simvastatin to be more stable than cryo-milled simvastatin. This was reflected in the calculated parameters although their absolute values did not agree with the stability behaviour. Relaxation time parameters of tau = 6.9 x 10(4) s for quench-cooled and tau = 1.7 x 10(4) s for cryo-milled simvastatin were calculated. The results from this study suggested that differences in the physical stability of amorphous forms prepared by different techniques are reflected in their mobility and thermodynamic parameters. Even though the predictive capabilities of these parameters for a set of different drugs may be limited, they can serve as a predictive tool for physical stability assessment if differently prepared amorphous forms of the same drug are investigated. PMID:19534709

  9. Insight into both coverage and surface structure dependent CO adsorption and activation on different Ni surfaces from DFT and atomistic thermodynamics.

    PubMed

    Hao, Xiaobin; Wang, Baojun; Wang, Qiang; Zhang, Riguang; Li, Debao

    2016-06-29

    CO adsorption and activation on Ni(100), (110) and (111) surfaces have been systematically investigated to probe the effect of coverage and surface structure on CO adsorption and activation. Herein, dispersion-corrected density functional theory calculations (DFT-D) were employed, and the related thermodynamic energies at 523 K were calculated by including the zero-point energy, thermal energy and entropic corrections; the results show that the saturated coverage of CO on the Ni(111), (100) and (110) surfaces correspond to 8/9, 9/12 and 9/9 ML, respectively. As the coverage increases, the stepwise adsorption free energies decrease on the flat (111) and (100) surfaces, whereas small changes occur on the corrugated (110) surface. CO migrates from the three-fold hollow site to the top site on the (111) surface, and from the four-fold hollow to the two-fold bridge site on the (100) surface, while all the CO molecules remain at the short-bridge site on the (110) surface. As a result, the obtained intermolecular CO-CO repulsive interactions on the flat surface are stronger than the interactions on the corrugated surface. Furthermore, the computed CO vibrational frequencies at different levels of coverage over the Ni surfaces agree well with the experimental results. On the other hand, kinetic analyses were utilized to compare the stepwise CO desorption with the dissociation at different degrees of coverage on the three Ni surfaces. CO desorption is more favorable than its dissociation at all coverage levels on the most exposed Ni(111) surface. Analogously, CO desorption becomes more favorable than its dissociation on the Ni(110) surface at higher coverage, except for coverage of 1/9 ML, in which CO desorption competes with its dissociation. However, on the Ni(100) surface, CO dissociation is more favorable than its desorption at 1/12 ML; when the coverage increases from 2/12 to 3/12 ML, equilibrium states exist between dissociation and desorption over the surface; when

  10. The thermodynamic parameters of the step dissociation of L-phenylalanyl in aqueous solution

    NASA Astrophysics Data System (ADS)

    Kochergina, L. A.; Emel'Yanov, A. V.; Krutova, O. N.; Gorboletova, G. G.

    2007-10-01

    The heats of interaction of L-phenylalanine with solutions of nitric acid and potassium and lithium hydroxides were determined calorimetrically at 288.15, 298.15, and 308.15 K and solution ionic strengths of 0.5, 0.75, and 1.0 in the presence of LiNO3 and KNO3. The standard thermodynamic characteristics (Δr H°, Δr G°, Δr S°, and Δ C {/p °} of acid-base interactions in aqueous solutions of L-phenylalanine were calculated. The influence of the concentration of background electrolytes and temperature on the heats of dissociation of L-phenylalanine was considered. A comparative analysis of the standard thermodynamic characteristics of step dissociation of L-phenylalanine and alanine was performed in terms of the modern concepts of the structure and physicochemical properties of these compounds and their solutions.

  11. 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.

  12. 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. PMID:26306913

  13. 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. PMID:24377740

  14. Adsorption of chromium(VI) and Rhodamine B by surface modified tannery waste: kinetic, mechanistic and thermodynamic studies.

    PubMed

    Anandkumar, J; Mandal, B

    2011-02-28

    In this study, various activation methods have been employed to examine the potential reuse of tannery residual biomass (TRB) obtained from vegetable tanning process for the removal of Cr(VI) and Rhodamine B (RB) from aqueous solution. The maximum BET surface area (10.42 m(2)/g), honey comb pore distribution and uptake of both Cr(VI) and RB were achieved when only 3-fold volume of HCl was used to activate the biomass. The pH and temperature experiment showed that they have considerable impact on the adsorption capacity of the used adsorbent. The presence of other ions (Na(+), Ca(2+) and NH(4)(+)) significantly reduces the metal uptake but marginal enhancement in the dye removal was observed when Na(+) and NH(4)(+) ions were present in the solution. The equilibrium data fitted satisfactorily with the Langmuir model and monolayer sorption capacity obtained as 177-217 and 213-250 mg/g for Cr(VI) and RB at 30-50°C, respectively. The sorption kinetics was found to follow the pseudo-second-order kinetic model. The increase in adsorption capacity for both metal and dye with increase in temperature indicates that the uptake was endothermic in nature. The results indicate that the HCl modified TRB (A-TRB) could be employed as a low cost adsorbent for the removal of both Cr(VI) and RB from the aqueous solution including industrial wastewater. PMID:21168268

  15. 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

  16. Thermodynamic order parameters and statistical-mechanical measures for characterization of the burst and spike synchronizations of bursting neurons

    NASA Astrophysics Data System (ADS)

    Kim, Sang-Yoon; Lim, Woochang

    2015-11-01

    We are interested in characterization of population synchronization of bursting neurons which exhibit both the slow bursting and the fast spiking timescales, in contrast to spiking neurons. Population synchronization may be well visualized in the raster plot of neural spikes which can be obtained in experiments. The instantaneous population firing rate (IPFR) R(t) , which may be directly obtained from the raster plot of spikes, is often used as a realistic collective quantity describing population behaviors in both the computational and the experimental neuroscience. For the case of spiking neurons, realistic thermodynamic order parameter and statistical-mechanical spiking measure, based on R(t) , were introduced in our recent work to make practical characterization of spike synchronization. Here, we separate the slow bursting and the fast spiking timescales via frequency filtering, and extend the thermodynamic order parameter and the statistical-mechanical measure to the case of bursting neurons. Consequently, it is shown in explicit examples that both the order parameters and the statistical-mechanical measures may be effectively used to characterize the burst and spike synchronizations of bursting neurons.

  17. Control of phase boundary evolution in metal solidification for new thermodynamic parameters of the metal

    NASA Astrophysics Data System (ADS)

    Albu, A. F.

    2016-05-01

    The problem of controlling the phase boundary evolution in the course of solidification of metals with different thermodynamic properties is studied. The underlying mathematical model of the process is based on a three-dimensional nonstationary two-phase initial-boundary value problem of the Stefan type. The control functions are determined by optimal control problems, which are solved numerically with the help of gradient optimization methods. The gradient of the cost function is exactly computed by applying the fast automatic differentiation technique. The research results are described and analyzed. Some of them are illustrated.

  18. Simultaneous determination of kinetic and thermodynamic parameters from fast-reaction kinetic measurements.

    PubMed

    Trimm, H H; Ushio, H; Patel, R C

    1981-10-01

    A combined stopped-flow temperature-jump apparatus interfaced with a dedicated microcomputer has been used to study the complexation reaction of iron(III) with thiocyanate in aqueous solution. Kinetic rate-constants (k(f) = 143 l.mole(-1) .sec(-1) from T-jump, k(f) = 150 l.mole(-1) .sec(-1) from stopped flow), equilibrium constants (K = 143 from T-jump, K = 150 from stopped flow) and the thermodynamic enthalpy change (DeltaH(c) = -6.7 kJ/mole) could be independently determined from the simultaneous application of the two techniques. PMID:18962997

  19. 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

    2014-07-01

    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. PMID:24760757

  20. 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. PMID:26364074

  1. 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). PMID:27449668

  2. Comparison of multifractal parameters form adsorption isotherms, desorption isotherms and mercury intrusion curves

    NASA Astrophysics Data System (ADS)

    Paz-Ferreiro, Jorge; Mon, Rodolfo; Vidal Vázquez, Eva

    2013-04-01

    The soil pore space is composed of a continuum of pores extremely variable in size, which range from equivalent diameter sizes smaller than nanometers to an upper limit of the order of centimeters. So, it is quite typical for soil pore space to display a size range of more than a factor of 106 in scale. Nitrogen sorption and mercury injection provide pores size distributions in the range from about 0.1 to 0.001 μm and 150 to 0.005 μm, respectively. The aims of this study were to evaluate the scaling properties of nitrogen adsorption isotherms (NAI), nitrogen desorption isotherms (NDI) and mercury intrusion porosimetry (MIP) curves of agricultural soils from "La Pampa húmeda", in the north of Buenos Aires and south of Santa Fé provinces, Argentina. Both NAIs, NDIs and MIPs exhibited multifractal behavior but its scaling properties were different so that the multifractality index, assessed by the width of the generalized dimension and the singularity spectra ranked as follows: NAI > NDI > MIP. Also, parameterization by the Hurst exponent indicates NAIs were less persistent than NDIs and in turn, these were less persistent than MIPs. The multfractal approach was useful to characterize the heterogeneity of various domains of the soil nano- micro- and mesopore system at the scale of small aggregates.

  3. Study of thermodynamic parameters for solubilization of plant sterol and stanol in bile salt micelles.

    PubMed

    Matsuoka, Keisuke; Nakazawa, Tomomi; Nakamura, Ai; Honda, Chikako; Endo, Kazutoyo; Tsukada, Masamichi

    2008-08-01

    We investigated the difference between the molecular structures of plant sterols and stanols that affect the solubilization of cholesterol in bile salt micelles (in vitro study). First, the aqueous solubility of beta-sitosterol, beta-sitostanol, and campesterol was determined by considering the specific radioactivity by using a fairly small quantity of each radiolabeled compound. The order of their aqueous solubilities was as follows: cholesterol > campesterol > beta-sitostanol > beta-sitosterol. The maximum solubility of cholesterol and the above mentioned sterol/stanol in sodium taurodeoxycholate and sodium taurocholate solutions (single solubilizate system) was measured. Moreover, the preferential solubilization of cholesterol in bile salt solutions was systematically studied by using different types of plant sterols/stanols. The solubilization results showed that the cholesterol-lowering effect was similar for sterols and stanol. Thermodynamic analysis was applied to these experimental results. The Gibbs energy change (Delta G degrees ) for the solubilization of plant sterols/stanols showed a negative value larger than that for cholesterol. PMID:18544343

  4. 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.

  5. 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. PMID:26239502

  6. 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...

  7. 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

  8. The role of lattice parameter in water adsorption and wetting of a solid surface.

    PubMed

    Massey, A; McBride, F; Darling, G R; Nakamura, M; Hodgson, A

    2014-11-21

    Ice formation is a complex cooperative process that is almost invariably catalysed by the presence of an interface on which ice crystals nucleate. As yet there is no clear picture of what factors make a surface particularly good at nucleating ice, but the importance of having a template with a suitable lattice parameter has often been proposed. Here we report the contrasting wetting behaviour of a series of pseudomorphic surfaces, designed to form an ordered template that matches the arrangement of water in a bulk ice Ih(0001) bilayer. The close-packed M(111) surfaces (M = Pt, Pd, Rh, Cu and Ni) form a (√3 × √3) R30° Sn substitutional alloy surface, with Sn atoms occupying sites that match the symmetry of an ice bilayer. The lattice constant of the alloy changes from 4% smaller to 7% greater than the lateral spacing of ice across the series. We show that only the PtSn surface, with a lattice parameter some 7% greater than that of a bulk ice layer, forms a stable water layer, all the other surfaces being non-wetting and instead forming multilayer ice clusters. This observation is consistent with the idea that the repeat spacing of the surface should ideally match the O-O spacing in ice, rather than the bulk ice lattice parameter, in order to form a continuous commensurate water monolayer. We discuss the role of the lattice parameter in stabilising the first layer of water and the factors that lead to formation of a simple commensurate structure rather than an incommensurate or large unit cell water network. We argue that lattice match is not a good criteria for a material to give low energy nucleation sites for bulk ice, and that considerations such as binding energy and mobility of the surface layer are more relevant. PMID:25286238

  9. The effect of quaternary element on the thermodynamic parameters and structure of CuAlMn shape memory alloys

    NASA Astrophysics Data System (ADS)

    Aksu Canbay, C.; Karagoz, Z.

    2013-10-01

    In this study, the Cu-based shape memory alloys were produced by arc melting. We have investigated the effects of the alloying elements on the characteristic transformation temperatures, enthalpy, entropy values, and the structure of Cu-Al-Mn ternary system. The evolution of the transformation temperatures was studied by the differential scanning calorimetry. The characteristic transformation temperatures can be controlled by the variations in the aluminum and manganese content. Additionally, the effect of magnesium and iron on the transformation temperatures and thermodynamic parameters was investigated in the Cu-Al-Mn ternary system. The addition of the magnesium decreases the characteristic transformation temperatures of the Cu-Al-Mn system, but that of the iron increases. The structural changes of the samples were studied by X-ray diffraction measurements and optical microscope observations. Due to the low solubility of the magnesium, the magnesium addition into the Cu-Al-Mn system forms precipitates in the matrix. It is evaluated that the transformation parameters of the CuAlMn shape memory alloys can be controlled by the change of the alloying elements and the weight percentages of alloying elements.

  10. [Adsorption of Cr (VI) on magnetic graphene from aqueous solution].

    PubMed

    Liu, Wei; Yang, Qi; Li, Bo; Chen, Hai; Nie, Lan-Yu

    2015-02-01

    Chemical deposition method was applied to prepare magnetic graphene composites using graphite oxide and ferric salt (FeCl2 - 4H2O and FeCl3 x 6H2O) as starting materials. The static experiments were performed to study kinetics, thermodynamic, adsorption isotherm and effects of various parameters, such as pH, temperature and time on Cr(VI) adsorption. The results showed that adsorption kinetics followed the pseudo-second-order model. Compared with Freundlich isotherm, Langmuir isotherm could better describe the adsorption process. The parameters of thermodynamics were ΔHθ = 33.89 kJ x mol(-1), ΔSθ = 120.15 J x (mol x K)(-1), ΔGθ = -2.51 kJ x mol(-1) (303 K), it demonstrated that the adsorption was a spontaneously endothermic process. It also indicated that the optimal pH was 2. Higher temperature and extension of time were in favor of adsorption. When used repeatedly for three times, the adsorption capacity decreased from 3.9 mg x g(-1) to 2.1 mg x g(-1) with an initial concentration of 5 mg x L(-1). By using a permanent magnet, the recycling process of adsorbent was easy to be operated and adsorbent could be regenerated by sodium hydrate solution. Hence, the composites is a promising adsorbent for efficient removal of Cr(VI) from wastewater. PMID:26031080

  11. Transfer of antioxidants at the interfaces of model food emulsions: distributions and thermodynamic parameters.

    PubMed

    Losada-Barreiro, Sonia; Sánchez-Paz, Verónica; Bravo-Díaz, Carlos

    2015-01-21

    Knowledge on the driving force for the hydrophobic effect that partitions antioxidants (AOs) between the oil (O), aqueous (W) and interfacial (I) regions of food emulsions is crucial to predict their efficiency in inhibiting lipid oxidation and to preserve the organoleptic properties of lipid-based foods. Here, we have investigated the effects of temperature and surfactant volume fraction (ΦI) on the distribution of two representative AOs, the water insoluble α-tocopherol (TOC) and the oil insoluble caffeic acid (CA), in a model food emulsion composed of stripped corn oil, acidic water and the nonionic surfactant Tween 20. The distribution of the AOs is assessed in the intact emulsions by employing a well-established kinetic method based on the reaction between a hydrophobic arenediazonium ion and the AOs. The variations of the observed rate constant, kobs, with ΦI are interpreted on the grounds of the pseudophase kinetic model, which provides values for the interfacial rate constant kI and the partition constants between the aqueous-interfacial (P) and oil-interfacial (P) regions of the emulsions. From the variations of P, P and kI at a series of temperatures, we determined the Gibbs free energy, enthalpy and entropy values for the transfer of CA from the water to the interfacial (W → I) region and of TOC from the oil to the interfacial (O → I) regions of the emulsions, and the activation parameters for the reaction in the interfacial region. Activation energy values are in line with those expected for a bimolecular reaction. Results show that the W → I and O → I transfer processes are spontaneous and entropy driven. PMID:25408193

  12. 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.

  13. 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.

  14. 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.

  15. 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.

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

    DOE PAGESBeta

    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 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

  17. 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.

  18. 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. PMID:25980560

  19. Study the adsorption of phenol from aqueous solution on hydroxyapatite nanopowders.

    PubMed

    Lin, Kaili; Pan, Jiayong; Chen, Yiwei; Cheng, Rongming; Xu, Xuecheng

    2009-01-15

    In this study, the hydroxyapatite (HAp) nanopowders prepared by chemical precipitation method were used as the adsorbent, and the potential of HAp nanopowders for phenol adsorption from aqueous solution was studied. The effect of contact time, initial phenol concentration, pH, adsorbent dosage, solution temperature and adsorbent calcining temperature on the phenol adsorption, and the adsorption kinetic, equilibrium and thermodynamic parameters were investigated. The results showed that the HAp nanopowders possessed good adsorption ability to phenol. The adsorption process was fast, and it reached equilibrium in 2h of contact. The initial phenol concentration, pH and the adsorbent calcining temperature played obvious effects on the phenol adsorption capacity onto HAp nanopowders. Increase in the initial phenol concentration could effectively increase the phenol adsorption capacity. At the same time, increase in the pH to high-acidity or to high-alkalinity also resulted in the increase in the phenol adsorption capacity. Increase in the HAp dosage could effectively increase the phenol adsorption percent. However, the higher calcining temperature of HAp nanopowders could obviously decrease the adsorption capacity. The maximum phenol adsorption capacity was obtained as 10.33mg/g for 400mg/L initial phenol concentrations at pH 6.4 and 60 degrees C. The adsorption kinetic and the isotherm studies showed that the pseudo-second-order model and the Freundlich isotherm were the best choices to describe the adsorption behaviors. The thermodynamic parameters suggested that the adsorption of phenol onto HAp was physisorption, spontaneous and endothermic in nature. PMID:18573599

  20. 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

  1. Thermodynamic holography

    PubMed Central

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

    2015-01-01

    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. PMID:26478214

  2. Thermodynamic holography.

    PubMed

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

    2015-01-01

    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. PMID:26478214

  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. PMID:27497348

  4. 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. PMID:19295102

  5. 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. PMID:27191572

  6. Effect of the adsorbate (Bromacil) equilibrium concentration in water on its adsorption on powdered activated carbon. Part 2: Kinetic parameters.

    PubMed

    Al Mardini, Fadi; Legube, Bernard

    2009-10-30

    The application of several monosolute equilibrium models has previously shown that Bromacil adsorption on SA-UF (Norit) powdered activated carbon (PAC) is probably effective on two types of sites. High reactivity sites were found to be 10-20 less present in a carbon surface than lower reactivity sites, according to the q(m) values calculated by isotherm models. The aims of this work were trying, primarily, to identify the kinetic-determinant stage of the sorption of Bromacil at a wide range of initial pesticide concentrations (approximately 5 to approximately 500 microg L(-1) at pH 7.8), and secondly, to specify the rate constants and other useful design parameters for the application in water treatment. It was therefore not possible to specify a priori whether the diffusion or surface reaction is the key step. It shows that many of the tested models which describe the stage of distribution or the surface reaction are correctly applied. However, the diffusivity values (D and D(0)) were found to be constant only constants for some specific experimental concentrations. The HSDM model of surface diffusion in pores was also applied but the values of the diffusion coefficient of surface (D(s)) were widely scattered and reduce significantly with the initial concentration or the equilibrium concentration in Bromacil. The model of surface reaction of pseudo-second order fitted particularly well and led to constant values which are independent of the equilibrium concentration, except for the low concentrations where the constants become significantly more important. This last observation confirms perfectly the hypothesis based on two types of sites as concluded by the equilibrium data (part 1). PMID:19560269

  7. Determination of Arrhenius and Thermodynamic Parameters for the Aqueous Reaction of the Hydroxyl Radical with Lactic Acid

    SciTech Connect

    Leigh R. Martin; Stephen P. Mezyk; Bruce J. Mincher

    2009-01-01

    Lactic acid is a major component of the TALSPEAK process planned for use in the separation of trivalent lanthanide and actinide elements. This acid acts both as a buffer, and also to protect the actinide complexant from radiolytic damage. However, there is little kinetic information on the reaction of water radiolysis species with lactic acid, particularly under the anticipated process conditions of aerated aqueous solution at pH~3, where oxidizing reactions are expected to dominate. Here we have determined temperature-dependent reaction rate constants for the reactions of the hydroxyl radical with lactic acid and the lactate ion. For lactic acid this rate constant is given by the equation: ln k1 = (23.85 ± 0.19) – (1120 ± 54) / T, corresponding to an activation energy of 9.31 ± 0.45 kJ mol-1 and a room temperature reaction rate constant of (5.24 ± 0.09) x 108 M-1 s-1 (24.0oC). For the lactate ion, the temperature-dependent rate constant is given by: ln k2 = (24.83 ± 0.14) – (1295 ± 42) / T, for an activation energy of 10.76 ± 0.35 kJ mol-1 and a room temperature value of (7.77 ± 0.11) x 108 M-1 s-1 (22.2oC). These kinetic data have been combined with autotitration measurements to determine the temperature-dependent behavior of the lactic acid pKa value, allowing thermodynamic parameters for the acid dissociation to be calculated as ?Hº = -10.75 ± 1.77 kJ mol-1, ?Sº = -103.9 ± 6.0 J K-1 mol-1 and ?Gº = 20.24 ± 2.52 kJ mol-1 at low ionic strength.

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

    PubMed

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

    2016-10-01

    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 [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. PMID:27494384

  9. Adsorption of ferrous ions onto montmorillonites

    NASA Astrophysics Data System (ADS)

    Qin, Dawei; Niu, Xia; Qiao, Min; Liu, Gang; Li, Hongxin; Meng, Zhenxiao

    2015-04-01

    The adsorption of Fe (II) onto montmorillonites was investigated through initial concentration, contact time, pH and temperature. During the whole adsorption process, the ascorbic acid (Vitamin C) was added as a kind of antioxidant, at the same time, deionized water (after boiling) and nitrogen protection were also used to avoid oxidation. The Fe2+/Fetotal ratio of the iron exists in the Fe-montmorillonites was found more than 95%. Two kinetic models, including pseudo-first-order and pseudo-second-order model, were used to analyze the adsorption process of Fe (II) on montmorillonites. The results of our study showed that adsorption process fitted with pseudo-second-order well. Adsorption isotherms showed that Langmuir model was better than Freundlich model. The thermodynamic parameters ΔG0 and ΔH0 were 3.696 kJ/mol and 6.689 kJ/mol (we just gave the values at 298 K), respectively. The positive values at different temperatures showed that the adsorption process was non-spontaneous and endothermic. The characteristics of materials were determined by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Surface area and porosity analyzer, Thermogravimetric analysis (TGA), Differential scanning calorimeter (DSC) and Zeta potential distribution.

  10. Adsorption isotherms, kinetics, thermodynamics and desorption studies for uranium and thorium ions from aqueous solution by novel microporous composite P(HEMA-EP)

    NASA Astrophysics Data System (ADS)

    Akkaya, Recep; Akkaya, Birnur

    2013-03-01

    In this research, a novel composite, poly(2-hydroxyethylmethacrylate-expanded perlite) [P(HEMA-EP)], was synthesized and its adsorptive features were investigated. P(HEMA-EP)'s adsorptive features were evaluated for UO22+ and Th4+ ions in terms of the dependency upon the ion concentration, pH, temperature, and time. P(HEMA-EP) was able to bind UO22+ and Th4+ ions with strong chemical affinity. The adsorption results were fitted to the classical Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) sorption models. P(HEMA-EP) was also used to study the removal of UO22+ and Th4+ ions from aqueous solutions in a batch system. The adsorption capacity (XL) of UO22+ and Th4+ ions was found to be 0.29 and 0.44 mol kg-1, respectively. The kinetic data corresponds well to the pseudo-second-order equation. Changes in the enthalpy and entropy values demonstrated that the overall adsorption process was spontaneous (ΔG < 0), endothermic (ΔH > 0), and had increased entropy (ΔS > 0), as expected. The reusability of the composites was confirmed for five sequential reuses.

  11. Kinetic studies of the sucrose adsorption onto an alumina interface

    NASA Astrophysics Data System (ADS)

    Singh, Kaman; Mohan, Sudhanshu

    2004-01-01

    An account is given of an experimental kinetic study of adsorption of analar reagent sucrose (ARS) onto an alumina interface spectrometrically ( λmax=570 nm) at pH 8.0 and at room temperature. The adsorption isotherm is a typical Langmuirian isotherm (S-type) and adsorption parameters have been deduced according to the Langmuir's model. The adsorption coefficient evaluated from the Langmuir's equation was found to be 2.52×10 2 l mol -1. Adsorption mechanism has been interpreted on the basis of metal-saccharide interaction as found in organometallic compounds and interaction due to negatively charged ends on the disaccharide molecules and positively charge groups on the surface on alumina which depends on the pH value. The effects of variation in experimental conditions of the adsorption system have also been investigated. The adsorption exhibited a typical response to the pH effect and on going towards the PZC the net charge decreases and any reaction making dependence on charge and maximum adsorption (amount) was found near the isoelectric point of alumina (pH 9.0). The presence of ions like Cl -, SO 42- and PO 43- affect the adsorbed amount quantitatively and it seems that these anions compete with sucrose for the positively charged surface sites. The addition of similar concentration of cations was found to reduce the adsorbed amount. The temperature was found to have an inverse effect on adsorption. The additions of catonic and anionic detergents influence both the adsorbed amount and the adsorption rate. The thermodynamics of the titled adsorption model indicates the spontaneous and exothermic nature. The negative value of entropy is an indication of probability of favorable and complex nature of the adsorption.

  12. 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.

  13. [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. PMID:24191561

  14. 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. PMID:24373983

  15. [Adsorption Characteristics of Norfloxacin by Biochars Derived from Reed Straw and Municipal Sludge].

    PubMed

    Zhang, Han-yu; Wang, Zhao-wei; Gao, Jun-hong; Zhu, Jun-min; Xie, Chao-ran; Xie, Xiao-yun

    2016-02-15

    Two types of biochars were prepared by pyrolyzing reed straw and municipal sludge at the temperature of 500 degrees C. The structure and properties of biochars were characterized by BET, scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and fourier transform infrared spectroscopy ( FTIR ). The effects of pH value, adsorption time, temperature and initial concentration of norfloxacin (NOR) on the adsorption behaviors were determined by single factor experiments, which were used to preliminarily discuss adsorption mechanism. The results showed that the adsorption of NOR onto biochars derived from reed straw and municipal sludge could reach 70% and 60% of the total adsorption within 12 h, respectively; the maximum adsorption capacities of the two biochars were 2.13 mg x g(-1) (biochar derived from reed straw) and 2.09 mg x g(-1) (biochar derived from municipal sludge). The quantities of both absorptions increased with the decreasing solution pH. The two adsorption kinetics of NOR onto biochars followed the pseudo second order kinetic equations, and adsorption isotherms fitted well with the Langmuir equations. Adsorption thermodynamics parameters such as Gibbs free energy (AG), enthalpy (AH) and entropy (AS) indicated that the two adsorptions were endothermic reactions. Infrared spectroscopy analysis indicated that oxygen-containing functional groups on biochars provided NOR molecules with adsorptive sites, which facilitated the formation of hydrogen bonds between NOR and the biochars. PMID:27363161

  16. Adsorption modeling for off-gas treatment

    SciTech Connect

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

    2013-07-01

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

  17. 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. PMID:22050840

  18. 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)

  19. 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

  20. 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.

  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. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

    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. 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.

  5. Arsenic adsorption from aqueous solutions by activated red mud.

    PubMed

    Altundoğan, H Soner; Altundoğan, Sema; Tümen, Fikret; Bildik, Memnune

    2002-01-01

    Heat treatment and acid treatment methods have been tested on red mud to increase its arsenic adsorption capability. The results indicate that the adsorptive capacity of red mud can be increased by acid treatment. This treatment causes sodalite compounds to leach out. As(III) and As(V) adsorption characteristics of activated red mud have similar tendencies with raw red mud. Batch adsorption studies have shown that activated red mud in dosages ranging from 20 to 100 g l(-1) can be used effectively to remove arsenic from aqueous solutions. The process is pH dependent, the optimum range being 5.8-7.5 for As(III) and 1.8-3.5 for As(V). The maximum removals are 96.52% for As(V) and 87.54% for As(III) for solutions with a final pH of 7.25 and 3.50, respectively, for the initial arsenic concentration of 133.5 micromol l(-1) (10 mg l(-1)), activated red mud dosage of 20 g l(-1), contact time of 60 min and temperature of 25 degrees C. The adsorption data obtained follow a first-order rate expression and fit the Langmuir isotherm well. Isotherms have been used to obtain the thermodynamic parameters. It was found that the adsorption of As(III) was exothermic, whereas As(V) adsorption was endothermic. PMID:11952183

  6. 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). PMID:23399273

  7. Studies of gas adsorption in flexible Metal-Organic frameworks

    NASA Astrophysics Data System (ADS)

    Sircar, Sarmishtha

    minutes to >60 hours, and this in turn, led to a ˜300 fold increase in capacity, convergence of capacities at similar reduced temperatures (critical temperature being the reducing parameter), discontinuities in the isotherms, lowering of gate-opening pressures, changes in the isotherm shapes as well as width of hysteresis loops. Although an experimental time effect was also seen for H2 adsorption at 77K, H2 showed no discontinuity in the adsorption isotherm, adsorption-desorption hysteresis was much less pronounced, and equilibration required significantly less time. The significant difference in rates of adsorption by different gases was attributed to an activated configurational diffusion regime in which the diffusing species moves through a corrugated surface potential when the diameter of the adsorbate approaches that of the pore. A concentration-dependent diffusion model coupled with insufficient equilibration time provides an alternate explanation to describe the stepwise adsorption behavior in GO-MOFs and the changes in capacities. A sigmoid shape of adsorption rate data at cryogenic temperatures is atypical of simple Fickian diffusion, suggesting a more complex mechanistic explanation is required to explain adsorption kinetics to GO-MOFs. Extending the unreacted shrinking core model from the field of catalyst deactivation suggests that relaxation will be much faster relative to diffusion when temperature is increased even by just 10K. From a thermodynamic perspective, adsorption isotherms on (2) demonstrate universality when pressure and temperature are scaled/reduced according to those at critical conditions. At similar reduced conditions, isotherms of gases on (2) converged and both capacity and pressure points of discontinuities showed a predictive behavior. Discrete levels of capacities were found which decrease in temperature. Existence of a universal parameter of heat of gate-opening is calculated and the heats of adsorption and structural expansion are

  8. 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

  9. 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. PMID:21482279

  10. Entanglement thermodynamics

    NASA Astrophysics Data System (ADS)

    Schliemann, John

    2014-09-01

    We investigate further the relationship between the entanglement spectrum of a composite many-body system and the energy spectrum of a subsystem making use of concepts of canonical thermodynamics. In many important cases the entanglement Hamiltonian is, in the limit of strong coupling between subsystems, proportional to the energy Hamiltonian of the subsystem. The proportionality factor is an appropriately defined coupling parameter, suggesting to interpret the latter as a inverse temperature. We identify a condition on the entanglement Hamiltonian which rigorously guarantees this interpretation to hold and removes any ambiguity in the definition of the entanglement Hamiltonian regarding contributions proportional to the unit operator. Illustrations of our findings are provided by spin ladders of arbitrary spin length, and by bilayer quantum Hall systems at total filling factor ν = 2. Within mean-field description, the latter system realizes an entanglement spectrum of free fermions with just two levels of equal modulus where the analogies to canonical thermodynamics are particularly close.

  11. 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 EHOMO, ELUMO and ELUMO-EHOMO for degradability exploration at the same level. The influence of the chlorination degree (NCl) 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 NCl, while the reported NCl-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 ELUMO-EHOMO values. The chlorination effect and the conclusions were further checked with appropriate density functional theory (DFT) calculations. PMID:26899657

  12. 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. PMID:26745178

  13. 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

    2008-12-01

    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. PMID:18989918

  14. 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. PMID:27416513

  15. Interfacial solvation thermodynamics.

    PubMed

    Ben-Amotz, Dor

    2016-10-19

    Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air-water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute-solvent) and indirect (solvent-solvent) contributions to adsorption thermodynamics, of relevance to solvation at air-water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies. PMID:27545849

  16. How hottest geometries and adsorptive parameters influence the SER(R)S spectra of Methylene Blue molecules adsorbed on nanocolloidal gold particles of varied sizes?

    PubMed

    Roy, Sannak Dutta; Ghosh, Manash; Chowdhury, Joydeep

    2015-12-01

    The SER(R)S spectra of Methylene Blue (MB) molecule adsorbed on gold nanocolloidal particles (AuNCs) have been investigated. The adsorptive parameters of the molecule adsorbed on AuNCs have been evaluated with the aid of Fluorescence Spectroscopy study. Fluorescence spectroscopic studies have been further applied to understand the concentration of probe molecule actually adsorbed on AuNC surfaces. Gigantic enhancements ∼10(6)-10(16) orders of magnitude have been recorded for the enhanced Raman bands in the SER(R)S spectra. Three-dimensional Finite Difference Time Domain (3D-FDTD) simulations studies have been carried out to predict the distributions of electric fields around the possible nanoaggregated hot geometries considered to be responsible for the huge enhancements of SER(R)S bands of the MB molecule. PMID:26172467

  17. [Removal of Sulfate Ions from Aqueous Solution by Adsorption with Hydrotalcite- like Composite].

    PubMed

    Gu, Yi-bing; Ma, Yong-wen; Wan, Jin-quan; Wang, Yan; Guan, Ze-yu

    2016-03-15

    Hydrotalcite-like composite synthesized by co-precipitation method was used as an adsorbent to remove the sulfate ions in aqueous solution. XRD, FT-IR , SEM and EDS elemental analysis were used to clarify the structure and composition of the hydrotalcite- like composite. The influences of time, initial pH value and coexisting ions on adsorption performance were investigated. The result showed the material was the composite of zinc aluminum nitrate hydrotalcite-like compounds and zinc aluminum phenylalanine hydrotalcite-like compounds. Hydrotalcite-like composite had a good performance in adsorption of sulfate ions, and the maximum adsorption capacity was 52.75 mg · g⁻¹. The data fitted pseudo-second order kinetic model best, which indicated that chemical adsorption was the rate-limiting step. Freundlich isotherm was more suitable to describe the adsorption process, and this meant the adsorption of sulfate ions by hydrotalcite-like composite was multilayered adsorption. Thermodynamic parameters showed that the adsorption process was endothermic and spontaneous at room temperature. Hydrotalcite-like composite adsorbed sulfate ions mainly through ion exchange, electrostatic force and physical adsorption. The experimental results showed that the hydrotalcite-like composite had potential for sulfate ion removal in the aqueous solution. PMID:27337893

  18. A comprehensive investigation on adsorption of Ca (II), Cr (III) and Mg (II) ions by 3D porous nickel films.

    PubMed

    Lai, Chuan; Guo, Xiaogang; Xiong, Zhongshu; Liu, Changlu; Zhu, Hui; Wu, Mei; Zhang, Daixiong

    2016-02-01

    The present study reports the removal of Ca (II), Cr (III), Mg (II) ions from aqueous solution using 3D-porous nickel films (3DNFs) as a novel adsorbent material prepared by hydrogen bubble dynamic template (HBDT) method at room temperature. The structure morphology and the phase constitution of 3DNFs were characterized by FESEM, EDS and XRD. Adsorption process of Ca (II), Cr (III), Mg (II) ions was fast as the equilibrium was established within 30min, and the maximum adsorption at equilibrium was 44.1mg/g, 46.4mg/g and 32.7mg/g, respectively. The adsorption kinetics well fitted using a pseudo second-order kinetic model. The adsorption isotherm data of all the three metals fit well the Langmuir and Freundlich adsorption isotherm model. It was found out that kinetics of adsorption varies with initial concentration of metal ions. Thermodynamic parameters (i.e., the standard Gibbs free energies (ΔG), enthalpy change (ΔH), standard entropy change (ΔS)) were also evaluated. Thermodynamic analysis indicated that a high temperature is favored for the adsorption of metal ions by 3DNFs. These results suggest that 3DNFs have good potential application in effective adsorption of metal ions with satisfactory results. PMID:26520822

  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. PMID:22508113

  20. Adsorption of sodium lauryl sulfate onto arsenic-bearing ferrihydrite.

    PubMed

    Quan, C; Khoe, G; Bagster, D

    2001-02-01

    Ferrihydrite is an excellent adsorbent for binding trace toxic contaminants such as arsenic, and precipitate flotation of the arsenic-bearing ferrihydrite has been studied. Anionic surfactants such as sodium lauryl sulfate (SLS) and sodium oleate (NaOL) are suitable collectors for the flotation. The adsorption of SLS both alone and after the subsequent addition of NaOL on these precipitates at pH 4-5 was measured. It has been shown that the synergistic effect of the two surfactants on flotation is dependent on their addition order. The presence of NaOL before SLS in the conditioning stage can prevent the adsorption of SLS because of the electrostatic shielding of adsorption sites on the precipitates. The post addition of NaOL to the SLS-bearing precipitates can promote the flocculation of the precipitates and enhance entrainment of SLS for better flotation. The SLS adsorption data fit better with the modified Frumkin isotherm than the Langmuir isotherm. Thermodynamic parameters (-delta Gads0,delta Hads0, and delta Sads0) have been derived from the analysis of the adsorption isotherms. The results suggest that the adsorption of SLS on AFH is physical and exothermic. PMID:11229002

  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. 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. PMID:16083768

  3. Highly effective adsorption of cationic and anionic dyes on magnetic Fe/Ni nanoparticles doped bimodal mesoporous carbon.

    PubMed

    Liu, Yuanyuan; Zeng, Guangming; Tang, Lin; Cai, Ye; Pang, Ya; Zhang, Yi; Yang, Guide; Zhou, Yaoyu; He, Xiaoxiao; He, Yan

    2015-06-15

    Magnetic Fe/Ni nanoparticles doped bimodal mesoporous carbon (MBMC) was prepared for highly effective adsorption of cationic dye methylene blue (MB) and anionic dye methyl orange (MO). Structure characterization demonstrated that Fe/Ni nanoparticles were embedded into the interior of the mesoprous carbon, and MBMC maintained ordered and bimodal mesopores. The effects of several parameters such as contact time, pH, temperature, ionic strength and dye molecular structure on the adsorption were investigated. Alkaline pH was better for MB adsorption, while acidic pH was more favorable for MO uptake. The adsorption capacity was slightly enhanced when existing ion concentrations increased. Adsorption on MBMC was affected by the molecular structures of different dyes, and both primary and secondary pores of MBMC were involved in dye adsorption. The adsorption kinetics fitted well with pseudo-second-order model and exhibited 3-stage intraparticle diffusion mode. Equilibrium data were best described by Langmuir model, and the estimated maximum adsorption capacity for MB and MO was 959.5mg/g and 849.3mg/g, respectively. Thermodynamic studies indicated that the adsorption process was spontaneous and endothermic. Moreover, the adsorbent could be regenerated using ethanol, and the regenerated adsorbent after seven cycles could retain over 80% of the adsorption capacity for the fresh adsorbent. The results suggested that MBMC could be considered as very effective and promising materials for both anionic and cationic dyes removal from wastewater. PMID:25765736

  4. Generalized gas-solid adsorption modeling: Single-component equilibria

    DOE PAGESBeta

    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 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

  5. 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

  6. 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

  7. The significant role of the rare earth ions on the elastic and thermodynamic parameters of LiCoDy- and ZnCoCe-ferrites

    NASA Astrophysics Data System (ADS)

    Bishay, Samiha T.

    2006-06-01

    Two types of rare earth ferrites [Li 0.6Co 0.1Dy xFe 2.3-xO 4; 0.0⩽ x⩽0.2] and [Zn 0.5Co 0.5Ce yFe 2-yO 4; 0.0⩽ y⩽0.2] were prepared by standard ceramic technique with a view to investigate their elastic behavior and some essential thermodynamic parameters. The elastic properties were studied by measuring the ultrasonic velocities by adopting the pulse transmission technique. Longitudinal ( V) and shear ( V) velocities, Young's modulus ( E), Debye temperature ( θ) and specific heat capacity ( C) have been evaluated for all the investigated samples. The rare earth content as well as its ionic radius plays a significant role in the evaluated parameters. According to the experimental results, the two investigated types of rare earth ferrite are considered as insulator magnetic solids. It was found that for each composition there exists a characteristic temperature, down to which the resonance frequency of the investigated samples drops smoothly, but above this temperature the resonance frequency stays constant. Accordingly, these samples seem to be of importance in industrial applications especially in the field of electronics.

  8. Theoretical study on stability, mechanical properties and thermodynamic parameters of the orthorhombic-A2N2O (A=C, Si and Ge)

    NASA Astrophysics Data System (ADS)

    Ding, Yingchun

    2012-06-01

    The structural stability, mechanical properties and thermodynamic parameters such as Debye temperature, minimum thermal conductivities of orthorhombic-A2N2O (A=C, Si and Ge) are calculated by first principles calculations based on density functional theory. The calculated lattice parameters, elastic constants of Si2N2O and Ge2N2O using PBEsol function are consisted with the experimental data and other calculated values. The full set elastic constants of the orthorhombic-A2N2O (A=C, Si and Ge) are calculated by stress-strain method. The mechanical moduli (bulk modulus, shear modulus and Young's modulus) are evaluated by the Voigt-Reuss-Hill approach. The orthorhombic-C2N2O exhibits larger mechanical moduli than the other two structures. The hardness of orthorhombic-A2N2O (A=C, Si and Ge) is evaluated according to the intrinsic hardness calculation theory of covalent crystal relying on Mulliken overlap population. The results indicate that the orthorhombic-C2N2O is a super hard material. Furthermore, the mechanical anisotropy, Debye temperature and minimum thermal conductivity of the orthorhombic-A2N2O (A=C, Si and Ge) have been estimated by empirical methods. The orthorhombic-Ge2N2O shows the lowest thermal conductivity, which may have useful applications as gas turbine engines and diesel engines.

  9. Effect of organic matter and calcium carbonate on behaviors of cadmium adsorption-desorption on/from purple paddy soils.

    PubMed

    Zhao, Xiulan; Jiang, Tao; Du, Bin

    2014-03-01

    Batch experiments and sequential extraction analysis were employed to investigate the effects of soil organic matter and CaCO3 on the adsorption and desorption of cadmium (Cd(2+)) onto and from two purple paddy soils, an acidic purple paddy soil (APPS) and a calcareous purple paddy soil (CPPS). The Cd(2+) adsorption isotherms on both soils could be well-described by the Langmuir and Freundlich equations. CPPS had a higher capacity and a stronger affinity for Cd(2+) adsorption compared with APPS. The adsorption process of Cd(2+) on APPS was dominated by electrostatic attractions, whereas the adsorption mechanism varied depending on the Cd(2+) concentrations in equilibrium solutions on CPPS. At low equilibrium concentrations, the adsorption process was primarily specific adsorption, but nonspecific adsorption dominated at high equilibrium concentrations. Removal of organic matter decreased the amount of Cd(2+) adsorption on both of the soils, slightly affected the Cd(2+) desorption rate and exchangeable Cd (EXC-Cd) in APPS and increased the desorption rate and EXC-Cd in CPPS, suggesting that the effect of organic matter on Cd(2+) adsorption-desorption depends on the soils. CPPS and APPS containing CaCO3 exhibited higher adsorption amounts but lower desorption rates and lower proportions of EXC-Cd than those of their corresponding soils without CaCO3, demonstrating that CaCO3 played an important role in Cd(2+) specific adsorption on soil. The changes in the thermodynamic parameters, including free energy (ΔG(0)), enthalpy (ΔH(0)) and entropy (ΔS(0)), as evaluated by the Van't Hoff equations, indicated that the adsorption was a spontaneous and endothermic process with the primary interaction forces of dipole interactions and hydrogen bonds on APPS, whereas both physical and chemical interactions dominated the adsorption on CPPS. PMID:24289979

  10. 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.

  11. 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. PMID:18448244

  12. Removal of aqueous uranyl ions by magnetic functionalized carboxymethylcellulose and adsorption property investigation

    NASA Astrophysics Data System (ADS)

    Gao, Yangyang; Yuan, Yali; Ma, Dandan; Li, Le; Li, Yuhui; Xu, Wenhui; Tao, Wei

    2014-10-01

    Magnetic carboxymethylcellulose (CMC/Fe3O4) was used as a framework adsorption material to remove uranium ions from aqueous solutions. Carboxyl functional groups were grafted onto the CMC/Fe3O4. The maximum adsorption capacity of the magnetic composite toward U(VI) was 122.48 mg/g. Kinetic and thermodynamic parameters of the adsorption process were estimated. The pseudo-second-order model was more suitable and it proved to be an endothermic and spontaneous process. The Langmuir and Freundlich models were applied to evaluate the adsorption isotherm. The data matched well with Langmuir model after equilibrium was reached and with Freundlich model before equilibrium was reached.

  13. 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.

  14. Adsorption of 2,4-Dichlorophenoxyacetic Acid from an Aqueous Solution on Fly Ash.

    PubMed

    Kuśmierek, Krzysztof; Świątkowski, Andrzej

    2016-03-01

    The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) on fly ash was studied. The effects of adsorbent dose, contact time, pH, ionic strength, and temperature on the adsorption were investigated. Adsorption kinetic data were analyzed using pseudo-first and pseudo-second order models, and results showed that adsorption kinetics were better represented by the pseudo-second order model. Adsorption isotherms of 2,4-D on fly ash were analyzed using the Freundlich and Langmuir models. Thermodynamic parameters (ΔG°, ΔH°, and ΔS°) indicated that the adsorption process was spontaneous and endothermic. The negative values of ΔG° and the positive value of ΔH° indicate the spontaneous nature of 2,4-D adsorption on fly ash, and that the adsorption process was endothermic. Results showed that fly ash is an efficient, low-cost adsorbent for removal of 2,4-D from water. PMID:26931534

  15. Critical conditions of polymer adsorption and chromatography on non-porous substrates.

    PubMed

    Cimino, Richard T; Rasmussen, Christopher J; Brun, Yefim; Neimark, Alexander V

    2016-07-15

    We present a novel thermodynamic theory and Monte Carlo simulation model for adsorption of macromolecules to solid surfaces that is applied for calculating the chain partition during separation on chromatographic columns packed with non-porous particles. We show that similarly to polymer separation on porous substrates, it is possible to attain three chromatographic modes: size exclusion chromatography at very weak or no adsorption, liquid adsorption chromatography when adsorption effects prevail, and liquid chromatography at critical conditions that occurs at the critical point of adsorption. The main attention is paid to the analysis of the critical conditions, at which the retention is chain length independent. The theoretical results are verified with specially designed experiments on isocratic separation of linear polystyrenes on a column packed with non-porous particles at various solvent compositions. Without invoking any adjustable parameters related to the column and particle geometry, we describe quantitatively the observed transition between the size exclusion and adsorption separation regimes upon the variation of solvent composition, with the intermediate mode occurring at a well-defined critical point of adsorption. A relationship is established between the experimental solvent composition and the effective adsorption potential used in model simulations. PMID:27089017

  16. 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. PMID:24936305

  17. Removal of tetracycline from wastewater using pumice stone: equilibrium, kinetic and thermodynamic studies

    PubMed Central

    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 Cu2+ 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. PMID:24936305

  18. 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. PMID:19744839

  19. Size dependent adsorption on nanocrystal surfaces

    NASA Astrophysics Data System (ADS)

    Lu, H. M.; Wen, Z.; Jiang, Q.

    2005-03-01

    A quantitative thermodynamic correlation method to describe the size dependent Langmuir adsorption isotherm is developed. According to the model, the equilibrium adsorption constant increases as material size decreases, which is in agreement with the literature data of acetic acid, valeric acid, oxalic acid, and adipic acid on anatase nanoparticles.

  20. Column Experiments for Radionuclide Adsorption Studies of the Culebra Dolomite: Retardation Parameter Estimation for Non-Eluted Actinide Species

    SciTech Connect

    Brown, G.O.; Lucero, D.A.; Perkins, W.G.

    1999-01-01

    The U.S. Department of Energy (DOE) has been developing a nuclear waste disposal facility, the Waste Isolation Pilot Plant (WIPP), located approximately 42 km east of Carlsbad, New Mexico. The WIPP is designed to demonstrate the safe disposal of transuranic wastes produced by the defense nuclear-weapons program. Performance assessment analyses (U.S. DOE, 1996) indicate that human intrusion by inadvertent and intermittent drilling for resources provide the only credible mechanisms for significant releases of radionuclides horn the disposal system. These releases may occur by five mechanisms: (1) cuttings, (2) cavings, (3) spallings, (4) direct brine releases, and (5) long-term brine releases. The first four mechanisms could result in immediate release of contaminant to the accessible environment. For the last mechanism, migration pathways through the permeable layers of rock above the Salado are important, and major emphasis is placed on the Culebra Member of the Rustler Formation because this is the most transmissive geologic layer in the disposal system. For reasons of initial quantity, half-life, and specific radioactivity, certain isotopes of Th, U, Am, and Pu would dominate calculated releases from the WIPP. In order to help quanti~ parameters for the calculated releases, radionuclide transport experiments have been carried out using five intact-core columns obtained from the Culebra dolomite member of the Rustler Formation within the Waste Isolation Pilot Plant (WIPP) site in southeastern New Mexico. This report deals primarily with results of mathematical analyses related to the retardation of %J%, 24%, and 24'Am in two of these cores (B-Core - VPX26-11A and C-Core - VPX28-6C). All B-Core transport experiments were done using Culebra-simukmt brine relevant to the core recovery location (the WIPP air-intake shaft - AIS). Most experiments with C-Core were done with AIS brine with some admixture of a brine composition (ERDA-6) that simulated deeper formation

  1. 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. PMID:22689095

  2. 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. PMID:25643962

  3. 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.

  4. Molecular structure, spectroscopy (FT-IR, FT-Raman), thermodynamic parameters, molecular electrostatic potential and HOMO-LUMO analysis of 2, 6-dichlorobenzamide

    NASA Astrophysics Data System (ADS)

    Tao, Yaping; Han, Ligang; Li, Xiaofeng; Han, Yunxia; Liu, Zhaojun

    2016-03-01

    2, 6-dichlorobenzamide is the degradation product of 2, 6-dichlorobenzonitrile, which is often used as herbicide and can cause groundwater pollution. The FT-IR and FT-Raman spectra of 2, 6-dichlorobenzamide at room temperature were recorded and analyzed in the range 4000-400 and 3700-100 cm-1, respectively. In order to obtain the most stable structure, a potential energy surface (PES) scan for internal rotations was carried out at the B3LYP/6-31G(d) level. The optimized geometry, structural parameters energies, theoretical IR and Raman spectra for the title compound have been obtained by employing B3LYP exchange-correlation functional with high-quality aug-cc-pVTZ basis-set. Detailed vibrational assignments of vibrational spectra have been made on the basis of the potential energy distributions (PED) analysis. In addition, the HOMO-LUMO gap and molecular electrostatic potential (MEP) were studied theoretically. Finally, the thermodynamic functions (heat capacity, entropy, enthalpy, and Gibbs free energy) of 2, 6-dichlorobenzamide were obtained in the range of 100-1000 K.

  5. [Heat resistance of "Bacillus subtilis" and "Bacillus stearothermophilus" spores in ethylene glycol, propylene glycol and butylene glycol solutions. Criticism of the use of thermodynamic parameters (author's transl)].

    PubMed

    Cerf, O; L'Haridon, R; Hermier, J

    1975-01-01

    Increasing concentrations of ethylene glycol (EG), 1,2-propylene glycol (PG) or 2,3-butylene glycol (BG) lower the heat resistance of B. subtilis SJ2 and B. stearothermophilus 1518 spores, and there is a linear relationship between logarithm of decimal reduction time (D) and glycol concentration. D120 degreesc values of B. subtilis spores in 0.02M, pH 7.0 phosphate buffer containing 20 per cent (w/w) EG, PG and BG are respectively 1, 0.7 and 1.1 min compared to 1.5 min in buffer alone. Corresponding values for B. stearothermophilus spores are 2, 2.4 and 3 min compared to 3.2 min. The type of glycol has little effect upon temperature coefficient z for destruction of the B. subtilis spores (average 6.9 degrees C). On the contrary, in the case of B. stearothermophilus, z increases when the number of carbons increases in the glycol molecule (from 7 to 15 degrees). The thermodynamic parameters which characterize the activation of the spore destruction reaction cannot lead to a general conclusion about a possible mechanism of destruction in the presence of chemical compounds belonging to an homologous series: the two behave diversely, and there is no "isokinetic temperature". PMID:811145

  6. 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

  7. 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.

  8. Modeling of adsorption isotherms of water vapor on Tunisian olive leaves using statistical mechanical formulation

    NASA Astrophysics Data System (ADS)

    Knani, S.; Aouaini, F.; Bahloul, N.; Khalfaoui, M.; Hachicha, M. A.; Ben Lamine, A.; Kechaou, N.

    2014-04-01

    Analytical expression for modeling water adsorption isotherms of food or agricultural products is developed using the statistical mechanics formalism. The model developed in this paper is further used to fit and interpret the isotherms of four varieties of Tunisian olive leaves called “Chemlali, Chemchali, Chetoui and Zarrazi”. The parameters involved in the model such as the number of adsorbed water molecules per site, n, the receptor sites density, NM, and the energetic parameters, a1 and a2, were determined by fitting the experimental adsorption isotherms at temperatures ranging from 303 to 323 K. We interpret the results of fitting. After that, the model is further applied to calculate thermodynamic functions which govern the adsorption mechanism such as entropy, the free enthalpy of Gibbs and the internal energy.

  9. A generalized adsorption-phase transition model to describe adsorption rates in flexible metal organic framework RPM3-Zn.

    PubMed

    Lueking, Angela D; Wang, Cheng-Yu; Sircar, Sarmishtha; Malencia, Christopher; Wang, Hao; Li, Jing

    2016-03-14

    Flexible gate-opening metal organic frameworks (GO-MOFs) expand or contract to minimize the overall free energy of the system upon accommodation of an adsorbate. The thermodynamics of the GO process are well described by a number of models, but the kinetics of the process are relatively unexplored. A flexible GO-MOF, RPM3-Zn, exhibits a significant induction period for opening by N2 and Ar at low temperatures, both above and below the GO pressure. A similar induction period is not observed for H2 or O2 at comparable pressures and temperatures, suggesting the rate of opening is strongly influenced by the gas-surface interaction rather than an external stress. The induction period leads to severe mass transfer limitations for adsorption and over-prediction of the gate-opening pressure. After review of a number of existing adsorption rate models, we find that none adequately describe the experimental rate data and similar timescales for diffusion and opening invalidate prior reaction-diffusion models. Statistically, the rate data are best described by a compressed exponential function. The resulting fitted parameters exceed the expectations for adsorption but fall within those expected for phase transition. By treating adsorption as a phase transition, we generalize the Avrami theory of phase transition kinetics to describe adsorption in both rigid and flexible hosts. The generalized theory is consistent with observed experimental trends relating to induction period, temperature, pressure, and gas-substrate interaction. PMID:26563399

  10. 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.

  11. 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.

  12. 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. PMID:16006123

  13. Kinetic and equilibrium studies of adsorptive removal of phenol onto eggshell waste.

    PubMed

    Daraei, H; Mittal, A; Noorisepehr, M; Daraei, F

    2013-07-01

    The aim of the present research is to develop economic, fast, and versatile method for the removal of toxic organic pollutant phenol from wastewater using eggshell. The batch experiments are conducted to evaluate the effect of pH, phenol concentration, dosage of adsorbent, and contact time on the removal of phenol. The paper includes in-depth kinetic studies of the ongoing adsorption process. Attempts have also been made to verify Langmuir and Freundlich adsorption isotherms. The morphology and characteristics of eggshell have also been studied using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and X-ray fluorescence analysis. At ambient temperature, the maximum adsorption of phenol onto eggshells has been achieved at pH 9 and the contact time, 90 min. The experimental data give best-fitted straight lines for pseudo-first-order as well as pseudo-second-order kinetic models. Furthermore, the adsorption process verifies Freundlich and Langmuir adsorption isotherms, and on the basis of mathematical expressions of these models, various necessary adsorption constants have been calculated. Using adsorption data, various thermodynamic parameters like change in enthalpy (∆H(0)), change in entropy (∆S(0)), and change in free energy ∆G(0) have also been evaluated. Results clearly reveal that the solid waste material eggshell acts as an effective adsorbent for the removal of phenol from aqueous solutions. PMID:23274804

  14. 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

  15. Thermodynamic Diagrams

    NASA Astrophysics Data System (ADS)

    Chaston, Scot

    1999-02-01

    Thermodynamic data such as equilibrium constants, standard cell potentials, molar enthalpies of formation, and standard entropies of substances can be a very useful basis for an organized presentation of knowledge in diverse areas of applied chemistry. Thermodynamic data can become particularly useful when incorporated into thermodynamic diagrams that are designed to be easy to recall, to serve as a basis for reconstructing previous knowledge, and to determine whether reactions can occur exergonically or only with the help of an external energy source. Few students in our chemistry-based courses would want to acquire the depth of knowledge or rigor of professional thermodynamicists. But they should nevertheless learn how to make good use of thermodynamic data in their professional occupations that span the chemical, biological, environmental, and medical laboratory fields. This article discusses examples of three thermodynamic diagrams that have been developed for this purpose. They are the thermodynamic energy account (TEA), the total entropy scale, and the thermodynamic scale diagrams. These diagrams help in the teaching and learning of thermodynamics by bringing the imagination into the process of developing a better understanding of abstract thermodynamic functions, and by allowing the reader to keep track of specialist thermodynamic discourses in the literature.

  16. 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. PMID:20670360

  17. Fluoride adsorption onto amorphous aluminum hydroxide: Roles of the surface acetate anions.

    PubMed

    Zhang, Yong-Xing; Jia, Yong

    2016-12-01

    Amorphous aluminum hydroxide with hydroxyl groups, acetate anions and chlorine anions enriched surface was synthesized, and was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption-desorption isotherms. Batch experiments were performed to study the influence of various experimental parameters such as contact time, initial fluoride concentration, temperature, pH value and the presence of competing anions on the adsorption of fluoride on amorphous aluminum hydroxide. The kinetic data was well fitted to pseudo-second-order model. The fluoride adsorption on the amorphous aluminum hydroxide can be well described by the Langmuir model, and the maximum adsorption capacity was 63.94mgg(-1) at pH 7.0. Thermodynamic parameters including the Gibbs free energy, standard enthalpy and standard entropy were calculated, and the results suggested that the adsorption of fluoride on the amorphous aluminum hydroxide was a feasible, spontaneous and exothermic process. The adsorption mechanism was revealed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis. The results suggested that the surface acetate anions and surface chlorine anions played important roles in the fluoride removal process. PMID:27565961

  18. Free energy calculation using molecular dynamics simulation combined with the three dimensional reference interaction site model theory. I. Free energy perturbation and thermodynamic integration along a coupling parameter

    NASA Astrophysics Data System (ADS)

    Miyata, Tatsuhiko; Ikuta, Yasuhiro; Hirata, Fumio

    2010-07-01

    This article proposes a free energy calculation method based on the molecular dynamics simulation combined with the three dimensional reference interaction site model theory. This study employs the free energy perturbation (FEP) and the thermodynamic integration (TDI) along the coupling parameters to control the interaction potential. To illustrate the method, we applied it to a complex formation process in aqueous solutions between a crown ether molecule 18-Crown-6 (18C6) and a potassium ion as one of the simplest model systems. Two coupling parameters were introduced to switch the Lennard-Jones potential and the Coulomb potential separately. We tested two coupling procedures: one is a "sequential-coupling" to couple the Lennard-Jones interaction followed by the Coulomb coupling, and the other is a "mixed-coupling" to couple both the Lennard-Jones and the Coulomb interactions together as much as possible. The sequential-coupling both for FEP and TDI turned out to be accurate and easily handled since it was numerically well-behaved. Furthermore, it was found that the sequential-coupling had relatively small statistical errors. TDI along the mixed-coupling integral path was to be carried out carefully, paying attention to a numerical behavior of the integrand. The present model system exhibited a nonmonotonic behavior in the integrands for TDI along the mixed-coupling integral path and also showed a relatively large statistical error. A coincidence within a statistical error was obtained among the results of the free energy differences evaluated by FEP, TDI with the sequential-coupling, and TDI with the mixed-coupling. The last one is most attractive in terms of the computer power and is accurate enough if one uses a proper set of windows, taking the numerical behavior of the integrands into account. TDI along the sequential-coupling integral path would be the most convenient among the methods we tested, since it seemed to be well-balanced between the computational

  19. 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. PMID:25499502

  20. Microwave assisted preparation of n-butylacrylate grafted chitosan and its application for Cr(VI) adsorption.

    PubMed

    Santhana Krishna Kumar, A; Uday Kumar, Chinta; Rajesh, Vidya; Rajesh, N

    2014-05-01

    Biopolymers such as chitosan possess excellent properties suited for varied applications. In this work, we describe a novel microwave assisted method for the preparation of n-butylacrylate grafted chitosan adsorbent and its utility for the adsorption of chromium(VI). A 3 min irradiation time was enough to prepare the adsorbent, and techniques such as FT-IR, powder XRD, SEM and EDS were used for comprehensive characterization. The adsorption was effective at pH 3.5 with 25 mL of 20 ppm Cr(VI) solution. Langmuir, Freundlich, Dubinin-Radushkevich, Temkin, Elovich and Redlich isotherms were studied in detail. The ΔG, ΔH and ΔS parameters were evaluated to understand the adsorption thermodynamics. The adsorption involves the interaction of Cr(VI) with the hydroxyl and amino groups in chitosan. PMID:24530325

  1. 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.

  2. 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. PMID:24144367

  3. 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. PMID:26465269

  4. Removal of cadmium(II) ions from aqueous solution using Ni (15 wt.%)-doped α-Fe2O3 nanocrystals: equilibrium, thermodynamic, and kinetic studies.

    PubMed

    OuldM'hamed, Mohamed; Khezami, L; Alshammari, Abdulrahman G; Ould-Mame, S M; Ghiloufi, I; Lemine, O M

    2015-01-01

    The present publication investigates the performance of nanocrystalline Ni (15 wt.%)-doped α-Fe2O3 as an effective nanomaterial for the removal of Cd(II) ions from aqueous solutions. The nanocrystalline Ni-doped α-Fe2O3 powders were prepared by mechanical alloying, and characterized by X-ray diffraction and a vibrating sample magnetometer. Batch-mode experiments were realized to determine the adsorption equilibrium, kinetics, and thermodynamic parameters of toxic heavy metal ions by Ni (15 wt.%)-doped α-Fe2O3. The adsorption isotherms data were found to be in good agreement with the Langmuir model. The adsorption capacity of Cd(II) ion reached a maximum value of about 90.91 mg g(-1) at 328 K and pH 7. The adsorption process kinetics was found to comply with pseudo-second-order rate law. Thermodynamic parameters related to the adsorption reaction, free energy change, enthalpy change and entropy change, were evaluated. The found values of free energy and enthalpy revealed a spontaneous endothermic adsorption-process. Moreover, the positive entropy suggests an increase of randomness during the process of heavy metal removal at the adsorbent-solution interface. PMID:26247760

  5. Adsorption studies on fruits of Gular (Ficus glomerata): removal of Cr(VI) from synthetic wastewater.

    PubMed

    Rao, Rifaqat A K; Rehman, Fouzia

    2010-09-15

    The adsorption of Cr(VI) was studied in batch system using fruits of Ficus glomerata as adsorbent. The effect of temperature, pH, initial Cr(VI) concentration and time was investigated. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) was used to investigate surface morphology and active functional groups present on the adsorbent surface. Thermodynamic parameters like free energy change (DeltaG(0)), enthalpy (DeltaH(0)) and entropy (DeltaS(0)) indicate the spontaneous, endothermic and increased randomness nature of Cr(VI) adsorption. Equilibrium data were fitted well with Langmuir isotherm at 50 degrees C. The magnitude of mean free energy indicates chemical nature of adsorption. The breakthrough and exhaustive capacities were found to be 5 and 23.1 mg g(-1) respectively. The applicability of the adsorbent has been demonstrated by removing Cr(VI) from electroplating wastewater. PMID:20605325

  6. Hydration thermodynamics of the SWy-1 montmorillonite saturated with alkali and alkaline-earth cations: A predictive model

    NASA Astrophysics Data System (ADS)

    Vieillard, Philippe; Blanc, Philippe; Fialips, Claire I.; Gailhanou, Hélène; Gaboreau, Stéphane

    2011-10-01

    The aim of the present work was to study the thermodynamic equilibria between water and a homo-ionic montmorillonite SWy-1 saturated by different cations. The choice of this smectite is justified by the large set of experimental data available from the literature for eight different interlayer cations: Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, Sr 2+, and Ba 2+. In particular, studies by Cases et al. (1992, 1997) and Bérend et al. (1995) are providing heat of adsorption data, pairs of desorption-adsorption isotherms, and information about the partition of adsorption-desorption water molecules between external surfaces and internal spaces. By calculating the effective amount of hydration water as the difference between the so-called gravimetric water and the surface covering water, a thermodynamic model was then developed, based on the concept of Ransom and Helgeson (1994) considering an asymmetric subregular binary solid solution between a fully hydrated and a anhydrous smectite. A set of six thermodynamic parameters ( ΔH∘hyd,S∘hyd and four Margules parameters) was extracted by a least square method from measurements of enthalpies of adsorption and paired adsorption-desorption isotherms for each interlayer cation. These six initial parameters were then used to determine a complete set of standard thermodynamic hydration parameters ( ΔH∘hyd,ΔG∘hyd,ΔS∘hyd, heat capacity, molar volume, and number of interlayer H 2O) and quantify, for each cation, the number of moles of hydration water molecules as a function of relative humidity and temperature. The validation of the standard state thermodynamic properties of hydration for each end member was carried out using three approaches: (1) a comparison with experimental isotherms obtained on hetero-ionic and homo-ionic SWy-1 smectite at different temperatures; (2) a comparison with the experimental integral enthalpy and entropy of hydration of the SWy-1 smectite; and (3) a comparison with experimental isotherms

  7. Removal of uranium(VI) from aqueous solutions by manganese oxide coated zeolite: discussion of adsorption isotherms and pH effect.

    PubMed

    Han, Runping; Zou, Weihua; Wang, Yi; Zhu, Lu

    2007-01-01

    This paper discusses the adsorption properties for uranium(VI) by manganese oxide coated zeolite (MOCZ). The removal of uranium(VI) from aqueous solution by adsorption onto MOCZ in a single-component system with various contact times, pH, competitive ions, temperatures and initial concentrations of uranium(VI) was investigated. The experimental results were fitted to the Langmuir, Freundlich and the three-parameter Redlich-Peterson model isotherms to obtain the characteristic parameters of each model. Both the Langmuir and Redlich-Peterson isotherms were found to best represent the measured adsorption data. According to the evaluation using the Langmuir equation, the maximum adsorption capacity of uranium(VI) ions onto MOCZ was 15.1 mg g(-1) at 293K and pH 4.0. Using the thermodynamic equilibrium constants obtained at different temperatures, various thermodynamic parameters, such as DeltaG(0), DeltaH(0) and DeltaS(0), have been calculated. The thermodynamics of uranium(VI) ion/MOCZ system indicates the spontaneous and endothermic nature of the process. It was noted that an increase in temperature resulted in a higher uranium loading per unit weight of the adsorbent. PMID:17258360

  8. 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. PMID:25559496

  9. 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

  10. 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. PMID:26871732

  11. Physical Adsorption of Gases on Heterogeneous Solids and Equilibrium Studies of the Pressure Swing Adsorption Process.

    NASA Astrophysics Data System (ADS)

    Lu, Xiaochun

    1990-01-01

    isotherm equation based on benzene adsorption isotherms. We extended further the TVFM to derive thermodynamic functions, such as the adsorption entropy, the adsorption enthalpy, and the adsorption energy distribution, and constructed these functions for various adsorption systems based on their adsorption isotherms. To explore the energetic heterogeneity of the adsorbent, we used two approaches. First, we used the overall integral isotherm equation to obtain the Langmuir -Freundlich isotherm; and second, we used the Gibb's relation to obtain an exponential isotherm equation. The adsorption energy-distribution function can be obtained from these isotherm equations. The pressure swing adsorption (PSA) process was studied based on Shandalman and Mitchell's equilibrium theory for a PSA system with a linear isotherm. This theory was extended to a PSA system with a non-linear isotherm. Relationships were established between the isotherms and process parameters, such as the enrichment factor, the critical recycle ratio, and the extent of the recovery.

  12. Adsorption of cinnabarinic acid from culture fluid with magnetic microbeads.

    PubMed

    Göçenoğlu Sarıkaya, Aslı; Osman, Bilgen; Kara, Ali; Pazarlioglu, Nurdan; Beşirli, Necati

    2016-02-01

    In this study, antimicrobial pigment cinnabarinic acid (CA) was produced from Pycnoporus cinnabarinus in laboratory-scale batch cultures. Magnetic poly(ethylene glycol dimethacrylate-N-methacryloyl-l-tryptophan methyl ester) [m-poly(EGDMA-MATrp)] beads (average diameter = 53-103 µm) were synthesized by copolymerizing of N-methacryloyl-l-tryptophan methyl ester (MATrp) with ethylene glycol dimethacrylate (EGDMA) in the presence of magnetite (Fe3O4) and used for the adsorption of CA. The m-poly(EGDMA-MATrp) beads were characterized by N2 adsorption/desorption isotherms (Brunauer Emmet Teller), X-ray photoelecron spectroscopy, scanning electron microscopy, infrared spectroscopy, thermal gravimetric analysis, electron spin resonance and swelling studies. The efficiency of m-poly(EGDMA-MATrp) beads for separation of CA from culture fluid was evaluated. The effects of pH, initial concentration, contact time and temperature on adsorption were analyzed. The maximum CA adsorption capacity of the m-poly(EGDMA-MATrp) beads was 272.9 mg g(-1) at pH 7.0, 25 °C. All the isotherm data can be fitted with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The adsorption process obeyed pseudo-second-order kinetic model. Thermodynamic parameters ΔH = 5.056 kJ mol(-1), ΔS = 52.44 J K(-1)  mol(-1) and ΔG = -9.424 kJ mol-(1) to -11.27 kJ mol-(1) with the rise in temperature from 4 to 40 °C indicated that the adsorption process was endothermic and spontaneous. PMID:25994378

  13. Studies of gas adsorption in flexible Metal-Organic frameworks

    NASA Astrophysics Data System (ADS)

    Sircar, Sarmishtha

    minutes to >60 hours, and this in turn, led to a ˜300 fold increase in capacity, convergence of capacities at similar reduced temperatures (critical temperature being the reducing parameter), discontinuities in the isotherms, lowering of gate-opening pressures, changes in the isotherm shapes as well as width of hysteresis loops. Although an experimental time effect was also seen for H2 adsorption at 77K, H2 showed no discontinuity in the adsorption isotherm, adsorption-desorption hysteresis was much less pronounced, and equilibration required significantly less time. The significant difference in rates of adsorption by different gases was attributed to an activated configurational diffusion regime in which the diffusing species moves through a corrugated surface potential when the diameter of the adsorbate approaches that of the pore. A concentration-dependent diffusion model coupled with insufficient equilibration time provides an alternate explanation to describe the stepwise adsorption behavior in GO-MOFs and the changes in capacities. A sigmoid shape of adsorption rate data at cryogenic temperatures is atypical of simple Fickian diffusion, suggesting a more complex mechanistic explanation is required to explain adsorption kinetics to GO-MOFs. Extending the unreacted shrinking core model from the field of catalyst deactivation suggests that relaxation will be much faster relative to diffusion when temperature is increased even by just 10K. From a thermodynamic perspective, adsorption isotherms on (2) demonstrate universality when pressure and temperature are scaled/reduced according to those at critical conditions. At similar reduced conditions, isotherms of gases on (2) converged and both capacity and pressure points of discontinuities showed a predictive behavior. Discrete levels of capacities were found which decrease in temperature. Existence of a universal parameter of heat of gate-opening is calculated and the heats of adsorption and structural expansion are

  14. 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. PMID:27468818

  15. 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.

  16. 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.

  17. Emerging adsorptive removal of azo dye by metal-organic frameworks.

    PubMed

    Ayati, Ali; Shahrak, Mahdi Niknam; Tanhaei, Bahareh; Sillanpää, Mika

    2016-10-01

    Adsorptive removal of toxic compounds using advanced porous materials is one of the most attractive approaches. In recent years, the metal-organic frameworks (MOFs), a subset of advanced porous nano-structured materials, due to their unique characteristics are showing great promise for better adsorption/separation of various water contaminants. Given the importance of azo dye removal, as an important class of pollutants, this paper aims to review and summarize the recently published research on the effectiveness of various MOFs adsorbents under different physico-chemical process parameters in dyes adsorption. The effect of pH, the adsorption mechanism and the applicability of various adsorption kinetic and thermodynamic models are briefly discussed. Most of the results observed showed that the adsorption kinetic and isotherm of azo dyes onto the MOFs mostly followed the pseudo-second order and Langmuir models respectively. Also, the optimum pH value for the removal of majority of azo dyes by MOFs was observed to be in the range of ∼5-7. PMID:27355417

  18. 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. PMID:26282775

  19. Studies on adsorption, reaction mechanisms and kinetics for photocatalytic degradation of CHD, a pharmaceutical waste.

    PubMed

    Sarkar, Santanu; Bhattacharjee, Chiranjib; Curcio, Stefano

    2015-11-01

    The photocatalytic degradation of chlorhexidine digluconate (CHD), a disinfectant and topical antiseptic and adsorption of CHD catalyst surface in dark condition has been studied. Moreover, the value of kinetic parameters has been measured and the effect of adsorption on photocatalysis has been investigated here. Substantial removal was observed during the photocatalysis process, whereas 40% removal was possible through the adsorption route on TiO2 surface. The parametric variation has shown that alkaline pH, ambient temperature, low initial substrate concentration, high TiO2 loading were favourable, though at a certain concentration of TiO2 loading, photocatalytic degradation efficiency was found to be maximum. The adsorption study has shown good confirmation with Langmuir isotherm and during the reaction at initial stage, it followed pseudo-first-order reaction, after that Langmuir Hinshelwood model was found to be appropriate in describing the system. The present study also confirmed that there is a significant effect of adsorption on photocatalytic degradation. The possible mechanism for adsorption and photocatalysis has been shown here and process controlling step has been identified. The influences of pH and temperature have been explained with the help of surface charge distribution of reacting particles and thermodynamic point of view respectively. PMID:25956186

  20. 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.

  1. 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. PMID:27283701

  2. Studies on Vapor Adsorption Systems

    NASA Technical Reports Server (NTRS)

    Shamsundar, N.; Ramotowski, M.

    1998-01-01

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

  3. 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.

  4. Adsorption of branched and dendritic polymers onto flat surfaces: A Monte Carlo study

    SciTech Connect

    Sommer, J.-U.; Kłos, J. S.; Mironova, O. N.

    2013-12-28

    Using Monte Carlo simulations based on the bond fluctuation model we study the adsorption of starburst dendrimers with flexible spacers onto a flat surface. The calculations are performed for various generation number G and spacer length S in a wide range of the reduced temperature τ as the measure of the interaction strength between the monomers and the surface. Our simulations indicate a two-step adsorption scenario. Below the critical point of adsorption, τ{sub c}, a weakly adsorbed state of the dendrimer is found. Here, the dendrimer retains its shape but sticks to the surface by adsorbed spacers. By lowering the temperature below a spacer-length dependent value, τ*(S) < τ{sub c}, a step-like transition into a strongly adsorbed state takes place. In the flatly adsorbed state the shape of the dendrimer is well described by a mean field model of a dendrimer in two dimensions. We also performed simulations of star-polymers which display a simple crossover-behavior in full analogy to linear chains. By analyzing the order parameter of the adsorption transition, we determine the critical point of adsorption of the dendrimers which is located close to the critical point of adsorption for star-polymers. While the order parameter for the adsorbed spacers displays a critical crossover scaling, the overall order parameter, which combines both critical and discontinuous transition effects, does not display simple scaling. The step-like transition from the weak into the strong adsorbed regime is confirmed by analyzing the shape-anisotropy of the dendrimers. We present a mean-field model based on the concept of spacer adsorption which predicts a discontinuous transition of dendrimers due to an excluded volume barrier. The latter results from an increased density of the dendrimer in the flatly adsorbed state which has to be overcome before this state is thermodynamically stable.

  5. Evaluation of Adsorption Capacity of Montmorillonite and Aluminium-pillared Clay for Pb2+, Cu2+ and Zn2.

    PubMed

    Humelnicu, Doina; Ignat, Maria; Suchea, Mirela

    2015-01-01

    Adsorption capacity of the two adsorbents was investigated as a function of contact time between adsorbent and heavy metal ions solutions, the initial heavy metals concentration of the synthetic wastewater, pH value, temperature and adsorbent mass. Preliminary experiments at different pH values between 2.0 and 7.0 were performed, and were observed that maximum adsorption occurs at pH 5 for copper (q(max) = 92.59 mg · g(–1)), 6.0 for lead (qmax = 97.08 mg · g(–1)) and 6.5 for zinc ions (q(max) = 73.52 mg · g(–1)), respectively. The sorption capacity of studied adsorbents for Pb(2+), Cu(2+) and Zn(2+) was calculated using Langmuir and Freundlich models. Thermodynamic parameters – enthalpy change (ΔH(0)), entropychange (ΔS(0)) and free energy (ΔG(0)) – were calculated for predicting the nature of adsorption. Scanning electron micrograph(SEM) revealed changes in the surface morphology of the adsorbent as a result of heavy metal ions adsorption.EDS characterization confirmed qualitatively the presence of adsorbed species in the samples. On the basis of the obtained results the adsorption it was proposed an ordered adsorption: Pb(2+), Cu(2+) and Zn(2+), on the sorbents we investigated. PMID:26680724

  6. 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.

  7. Preparation, characterization and dye adsorption properties of γ-Fe 2O 3/SiO 2/chitosan composite

    NASA Astrophysics Data System (ADS)

    Zhu, H. Y.; Jiang, R.; Fu, Y.-Q.; Jiang, J.-H.; Xiao, L.; Zeng, G.-M.

    2011-12-01

    A γ-Fe2O3/SiO2/chitosan composite was prepared by water-in-oil emulsification, and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM). Effects of various factors, including adsorbent dosage, initial dye concentration, solution pH, and competing anions, on the adsorption of methyl orange from aqueous solutions by the resulting composite were studied by batch adsorption experiments. The adsorption kinetics was found to follow the pseudo-second-order kinetic model, and intraparticle diffusion was related to the adsorption, but not as a sole rate-controlling step. The equilibrium adsorption data were well described by the Freundlich isotherm model. Evaluation of the thermodynamic parameters ΔG°, ΔH°, and ΔS° revealed that the adsorption process was naturally feasible, spontaneous, and exothermic. The composite was proven to be efficient, suitable and promising for the removal of methyl orange from aqueous solutions since it has a relatively higher adsorption capacity than other low-cost adsorbents.

  8. 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

  9. The role of particle-size soil fractions in the adsorption of heavy metals

    NASA Astrophysics Data System (ADS)

    Mandzhieva, Saglara; Minkina, Tatiana; Pinsky, David; Batukaev, Abdulmalik; Kalinitchenko, Valeriy; Sushkova, Svetlana; Chaplygin, Viktor; Dikaev, Zaurbek; Startsev, Viktor; Bakoev, Serojdin

    2014-05-01

    Ion-exchange adsorption phenomena are important in the immobilization of heavy metals (HMs) by soils. Numerous works are devoted to the study of this problem. However, the interaction features of different particle-size soil fractions and their role in the immobilization of HMs studied insufficiently. Therefore, the assessment of the effect of the particle-size distribution on the adsorption properties of soils is a vital task. The parameters of Cu2+, Pb2+ and Zn2+ adsorption by chernozems of the south of Russia and their particle-size fractions were studied. In the particle-size fractions separated from the soils, the concentrations of Cu2+, Pb2+, and Zn2 decreased with the decreasing particle size. The parameters of the adsorption values of k (the constant of the affinity)and Cmax.(the maximum adsorption of the HMs) characterizing the adsorption of HMs by the southern chernozem and its particle-size fractions formed the following sequence: silt > clay > entire soil. The adsorption capacity of chernozems for Cu2+, Pb2+, and Zn2+ depending on the particle-size distribution decreased in the following sequence: clay loamy ordinary chernozem clay loamy southern chernozem> loamy southern chernozem> loamy sandy southern chernozem. According to the parameters of the adsorption by the different particle-size fractions, the heavy metal cations form a sequence analogous to that obtained for the entire soils: Cu2+ ≥ Pb2+ > Zn2+. The parameters of the heavy metal adsorption by similar particle-size fractions separated from different soils decreased in the following order: clay loamy chernozem> loamy chernozem> loamy sandy chernozem. The analysis of the changes in the parameters of the Cu2+, Pb2+, and Zn2+ adsorption by the studied soils and their particle-size fractions showed that the extensive adsorption characteristic - the maximum adsorption (Cmax.) - is a less sensitive parameter characterizing the adsorption capacity of the soils than the intensive characteristic of

  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. PMID:26819399

  11. 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.

  12. 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

  13. Critical adsorption and critical Casimir forces in the canonical ensemble.

    PubMed

    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. PMID:27627242

  14. 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.

  15. 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. PMID:19167162

  16. Adsorption of Cu(II), Cd(II) and Ni(II) ions by cross-linked magnetic chitosan-2-aminopyridine glyoxal Schiff's base.

    PubMed

    Monier, M; Ayad, D M; Abdel-Latif, D A

    2012-06-01

    The adsorption of Cu(II), Cd(II) and Ni(II) ions from aqueous solution by cross-linked magnetic chitosan-2-aminopyridine glyoxal Schiff's base resin (CSAP) was studied in a batch adsorption system. Cu(II), Cd(II) and Ni(II) removal is pH dependent and the optimum adsorption was observed at pH 5.0. The adsorption was fast with estimated initial rate of 2.7, 2.4 and 1.4 mg/(g min) for Cu(2+), Cd(2+) and Ni(2+) respectively. The adsorption data could be well interpreted by the Langmuir, Freundlich and Temkin model. The maximum adsorption capacities obtained from the Langmuir model were 124±1, 84±2 and 67±2 mg g(-1) for Cu(2+), Cd(2+) and Ni(2+) respectively. The adsorption process could be described by pseudo-second-order kinetic model. Thermodynamic parameters revealed the feasibility, spontaneity and exothermic nature of adsorption. The sorbents were successfully regenerated using EDTA and HCl solutions. PMID:22386793

  17. Thermodynamics and transport in microporous media

    SciTech Connect

    Glandt, E.D.

    1992-09-01

    Focus of this report is on the thermodynamic properties/behavior of fluids contained or adsorbed on the random microporus materials (disordered solids). The Madden-Glandt formalism for fluids in disordered matrices is applied to realistic systems (gas adsorption in carbons, polymer partitioning). Work on microgeometry of solids and their percolation and connectedness properties was continued; a study of the simplest model for microporous materials (random-pore or ''Swiss cheese'' model) was completed. Work on irreversible adsorption was continued; a simple model for correlated adsorption was studied.

  18. 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.

    2014-03-01

    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.

  19. 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.

  20. 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.

  1. 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.

  2. Application of 'waste' wood-shaving bottom ash for adsorption of azo reactive dye.

    PubMed

    Leechart, Piyawan; Nakbanpote, Woranan; Thiravetyan, Paitip

    2009-02-01

    The utilization of wood-shaving bottom ash (WBA) for the removal of Red Reactive 141 (RR141), an azo reactive dye, was investigated. WBA/H(2)O and WBA/H(2)SO(4) were made by treating WBA with water and 0.1M H(2)SO(4), respectively, to increase adsorption capacity. Adsorption of RR141 from reactive dye solution (RDS) and reactive dye wastewater (RDW) by WBA/H(2)O and WBA/H(2)SO(4) involved the BET surface area and pore size diameter. Properties of adsorbents, effect of contact time, initial pH of solution, dissolved metals and elution studies indicated that the decolorisation mechanism involved both chemical adsorption and precipitation with calcium ions. In addition, the WBA/H(2)SO(4) surface might contain sulphate-cation complexes that were specific to enhancing dye adsorption from RDW. The adsorption isotherm had a best fit by the Freundlich model. Freundlich parameters showed that WBA/H(2)O used more heterogeneous surface than WBA/H(2)SO(4) and activated carbon for RDW adsorption. A thermodynamic study indicated that RDW adsorption was an endothermic process. The maximum dye adsorption capacities of WBA/H(2)O, WBA/H(2)SO(4) and activated carbon obtained from a Langmuir model at 30 degrees C were 24.3, 29.9, and 41.5mgl(-1), respectively. In addition, WBA/H(2)O and WBA/H(2)SO(4) could reduce colour and high chemical oxygen demand (COD) of real textile wastewater. According to the difficulty in the elution study, it was an environmentally safe disposal of this waste. Therefore, WBA, a waste from combustion of wood shavings, was suitable to be used as an effective adsorbent for azo reactive dye removal. PMID:18436367

  3. 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.

  4. 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. PMID:24645464

  5. 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

  6. 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.

  7. Adsorption of methyl violet onto mesoporous MCM-48 from aqueous solution.

    PubMed

    Gu, Xingxing; Xu, Hong; Luo, Lingling; Wu, Jun; Lin, Hongjun; Chen, Jianrong

    2014-06-01

    In this study, hexadecyltrimethyl ammonium bromide and triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) were used as co-templates and tetraethoxysilane was used as silica source to synthesize mesoporous MCM-48, which was employed to adsorb methyl violet dye from water. The prepared MCM-48, after calcination at 550 degrees C, was found to have a high surface area of 1072 m2/g and a pore volume of 1.08 cm3/g. The MCM-48 adsorption of methyl violet in aqueous solution was studied using UV-visible spectrophotometry. Experimental conditions, including initial pH of sample solution, initial concentration, MCM-48 amount, adsorption time and temperature, were also investigated. Results showed that the adsorption behavior could well be depicted by Langmuir equations and pseudo-second-order kinetic model. The maximum adsorption capacity of 193.82 mg/g was obtained at 20 degrees C. The values for thermodynamic parameters deltaG0, deltaS0 and deltaH0 were all negative, showing that the MCM-48 adsorption of methyl violet was spontaneous and exothermic. PMID:24738444

  8. Modeling investigation of membrane biofouling phenomena by considering the adsorption of protein, polysaccharide and humic acid.

    PubMed

    Demneh, Seyedeh Marzieh Ghasemi; Nasernejad, Bahram; Modarres, Hamid

    2011-11-01

    The importance of solute adsorption in the biofouling membrane has been clearly verified for the performance of membrane bioreactor (MBR). In order to quantify the mechanism of static adsorption in biofouling during of MBR process, we characterize membrane biofouling caused by model solutions containing a protein (bovine serum albumin, BSA), a humic substance (humic acid, HA) and a polysaccharide (alginic acid, Alg) on commercial hydrophilic polyethersulfone (PES) membrane. For static adsorption experiments, membranes were immersed in well-defined model solutions in three temperatures (298, 308 and 318 K) to obtain equilibrium data. To determine the characteristic parameters for this process, 7 isotherm models were applied to the experimental data. Three error analysis methods; the coefficient of nonlinear regression (R(2)), the sum of the squared errors (SSE) and standard deviation of residuals (S(yx)), were used to evaluate the data and determine the best fit isotherm for each model solutions. The error values demonstrated that the Sips isotherm model provided the best fit to the experimental data. AFM images were used for determination of changes in membrane surface after adsorption. These images confirmed the results obtained from adsorption isotherm study. Thermodynamic parameters such as standard free energy (Δ(r)G(θ)), enthalpy (Δ(r)H(θ)) and entropy (Δ(r)S(θ)) changes were determined; these adsorption processes were found to be feasible and endothermic but not spontaneous. The distribution of the substances adsorbed on PES surface were more chaotic than that in the aqueous solutions. Parameters obtained in this study can be used to determine the "fouling potential" of a given feed stream and a membrane. PMID:21798726

  9. Thermodynamic analysis of nanoparticle size effect on kinetics in Fischer-Tropsch synthesis by lanthanum promoted iron catalyst

    NASA Astrophysics Data System (ADS)

    Nakhaei Pour, Ali; Housaindokht, Mohammad Reza; Behroozsarand, Alireza; Khodagholi, Mohammad Ali

    2014-08-01

    The kinetic parameters of the Fischer-Tropsch synthesis (FTS) on iron catalyst are analyzed by size-dependent thermodynamic method. A Langmuir-Hinshelwood kinetic equation is considered for evaluation of catalytic activity of lanthanum promoted iron catalyst. A series of unsupported iron catalysts with different particle sizes were prepared via microemulsion method. The experimental results showed that catalyst activity pass from a maximum value by increasing the iron particle size. Also, data presented that iron particle size has considerable effects on adsorption parameters and FTS rates. The ratio of surface tension ( σ) to nanoparticle radius ( r) is important in FTS reaction on iron catalyst. Finally, the results showed that by increasing of iron particle size from 18 to 45 nm the activation energies of catalysts and heats of adsorption of catalysts as two main parameters of FTS reaction increased from 89 to 114 kJ/mol and from 51 to 71 kJ/mol, respectively.

  10. Adsorption of organic molecules on silica surface.

    PubMed

    Parida, Sudam K; Dash, Sukalyan; Patel, Sabita; Mishra, B K

    2006-09-13

    The adsorption behaviour of various organic adsorbates on silica surface is reviewed. Most of the structural information on silica is obtained from IR spectral data and from the characteristics of water present at the silica surface. Silica surface is generally embedded with hydroxy groups and ethereal linkages, and hence considered to have a negative charged surface prone to adsorption of electron deficient species. Adsorption isotherms of the adsorbates delineate the nature of binding of the adsorbate with silica. Aromatic compounds are found to involve the pi-cloud in hydrogen bonding with silanol OH group during adsorption. Cationic and nonionic surfactants adsorb on silica surface involving hydrogen bonding. Sometimes, a polar part of the surfactants also contributes to the adsorption process. Styryl pyridinium dyes are found to anchor on silica surface in flat-on position. On modification of the silica by treating with alkali, the adsorption behaviour of cationic surfactant or polyethylene glycol changes due to change in the characteristics of silica or modified silica surface. In case of PEG-modified silica, adsolubilization of the adsorbate is observed. By using a modified adsorption equation, hemimicellization is proposed for these dyes. Adsorptions of some natural macromolecules like proteins and nucleic acids are investigated to study the hydrophobic and hydrophilic binding sites of silica. Artificial macromolecules like synthetic polymers are found to be adsorbed on silica surface due to the interaction of the multifunctional groups of the polymers with silanols. Preferential adsorption of polar adsorbates is observed in case of adsorbate mixtures. When surfactant mixtures are considered to study competitive adsorption on silica surface, critical micelle concentration of individual surfactant also contributes to the adsorption isotherm. The structural study of adsorbed surface and the thermodynamics of adsorption are given some importance in this review

  11. Volumetric interpretation of protein adsorption kinetics

    NASA Astrophysics Data System (ADS)

    Barnthip, Naris

    Protein adsorption is believed to be a very important factor ultimately leading to a predictive basis for biomaterials design and improving biocompatibility. Standard adsorption theories are modified to accommodate experimental observations. Adsorption from single-protein solutions and competitive adsorption from binary solutions are mainly considered. The standard solution-depletion method of measuring protein adsorption is implemented with SDS-gel electrophoresis as a multiplexing, separation-and-quantification tool to measure protein adsorption to hydrophobic octyl sepharose (OS) adsorbent particles. Standard radiometric methods have also been used as a further check on the electrophoresis method mentioned above for purified-protein cases. Experimental results are interpreted in terms of an alternative kinetic model called volumetric interpretation of protein adsorption. A partitioning process between bulk solution and a three-dimensional interphase region that separates bulk solution from the physical adsorbent surface is the concept of the model. Protein molecules rapidly diffuse into an inflating interphase that is spontaneously formed by bringing a protein solution into contact with a physical surface, then follows by rearrangement of proteins within this interphase to achieve the maximum interphase concentration (dictated by energetics of interphase dehydration) within the thinnest (lowest volume) interphase possible. An important role of water in protein adsorption is emphasized and supported by this model. The fundamental aspects including the reversibility/irreversibility of protein adsorption, the multilayer adsorption, the applicability of thermodynamic/computational models, the capacity of protein adsorption, and the mechanism of so called Vroman effect are discussed and compared to the conventional theories. Superhydrophobic effect on the adsorption of human serum albumin is also examined.

  12. Study on adsorption properties of QCS/PS-G8-2-8 anion exchange membrane for Rhodamine B

    NASA Astrophysics Data System (ADS)

    Zhang, Yang; Wang, Jilin; Wang, Lulu; Feng, Ruijiang; Zhang, Fan

    2015-06-01

    A series of novel anion exchange composite membrane (QCS/PS-G8-2-8) were synthesized based on the quaternized chitosan (QCS, DQ = 89.20 (±3.50)%) blended with block polymer of polystyrene (PS) and G8-2-8 (maleic acid diethyl brace base pairs [octyl dimethyl chloride/ammonium bromide]). Then the QCS was cross-linked by glutaraldehyde (GA). The parameters including adsorption time (t), pH, and initial concentration of Rhodamine B (C0), temperature (T), the mass fraction of G8-2-8 and GA (WGA) on the adsorption were investigated to determine the optimum condition for the removal of RB. The kinetic and thermodynamic properties of the adsorption process were also discussed. The optimum adsorption condition was that the adsorption time was 100 min, pH was 4, the initial concentration of RB was 100 mg L-1, the mass fraction of G8-2-8 was 5.0 wt%, the mass fraction of GA was 2.0 wt%, the temperature was 40 °C. Thus, RB optimum adsorption capacity (q) of the composite membrane QCS/PS-G8-2-8 (5.0%) (G8-2-8 mass content (wt.%) was 5.0%) was 17.04 mg g-1. The adsorption isotherm of the RB on the composite membrane can be well fitted with the Temkin equation. The adsorption kinetics can be well described by the pseudo-second-order kinetics model. The values of ΔG, ΔH and ΔS indicated that the adsorption of RB onto QCS/PS-G8-2-8 was spontaneous and exothermic.

  13. Thermodynamics of diffusion

    NASA Astrophysics Data System (ADS)

    Matuszak, Daniel

    Diffusion is the migration of molecules in the reference frame of a system's center of mass and it is a physical process that occurs in all chemical and biological systems. Diffusion generally involves intermolecular interactions that lead to clustering, adsorption, and phase transitions; as such, it is difficult to describe theoretically on a molecular level in systems containing both intermolecular repulsions and attractions. This work describes a simple thermodynamic approach that accounts for intermolecular attractions and repulsions (much like how the van der Waals equation does) to model and help provide an understanding of diffusion. The approach is an extension of the equilibrium Lattice Density Functional Theory of Aranovich and Donohue; it was developed with Mason and Lonsdale's guidelines on how to construct and test a transport theory. In the framework of lattice fluids, this new approach gives (a) correct equilibrium limits, (b) Fickian behavior for non-interacting systems, (c) correct departures from Fickian behavior in non-ideal systems, (d) the correct Maxwell-Stefan formulation, (e) symmetry behavior upon re-labeling species, (f) reasonable non-equilibrium phase behavior, (g) agreement with Molecular Dynamics simulations, (h) agreement with the theory of non-equilibrium thermodynamics, (i) a vanishing diffusive flux at the critical point, and (j) other qualitatively-correct behaviors when applied to problems in porous membranes and in packed beds.

  14. 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. PMID:25629452

  15. 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. PMID:26322940

  16. The effects of acid and alkali modification on the adsorption performance of fuller's earth for basic dye.

    PubMed

    Hisarli, G

    2005-01-01

    The objective of this work was to prepare modified adsorbents from fuller's earth (FE) by acid and alkali treatment for enhancement cationic dye adsorption. Toluidine blue (TB) was selected as adsorbate for evaluating the adsorption performance of fuller's earth samples, which was affected significantly by acid and alkali modification. The adsorption of TB was studied by visible spectra. The absorption band of the monomer at low loading of TB in FE suspension with respect to its maximum in aqueous solution is red-shifted, which is related to accessibility of dye interlamellar space in the presence of positively charged surface sites. Since all surfaces are negatively charged under experimental conditions, this effect has not been observed in acid- and alkali-treated FE suspensions. It was seen that the adsorption capacity of alkali-treated surface (FEAl) for TB was higher than these of acid-treated adsorbent (FEAc) and FE. Scanning electron micrographs (SEM) and X-ray diffraction (XRD) and fluorescence (XRF) spectra were applied to analyze the structure of the raw and modified FE samples. Absence of any identifiable amount of a crystalline compound in the solid reaction products after acid treatment was confirmed by XRD and SEM, whereas the crystalline form of FEAl was preserved. Experimental data for high-concentration regions were well described by Freundlich and Langmuir adsorption equations. The thermodynamic parameters were estimated for FE, FEAc, and FEAl by using temperature dependence of adsorption equilibrium constants. PMID:15567375

  17. The influence of hydrothermal temperature and time toward crystallinity of zeolite X supported on glass wool for CO2 adsorption

    NASA Astrophysics Data System (ADS)

    Anggita, R. K. Wardani; Yuniar, V. T. P.; Aini, W. T.; Nurul, W.

    2016-04-01

    In this study, the influence of hydrothermal temperature and time at zeolite X supported on glasswool were investigated. The results of characterization using XRD showed that a single phase zeolite X with highest crystallinity was obtained when hydrothermal temperature and time at 100°C during 24 hours (ZXF100-24H). The CO2 adsorption capacity of ZXF100-24H has reached up to 10.15 wt. %. Kinetics of CO2 adsorption onto zeolite X supported on glasswool was investigated using pseudo-first-order, pseudo-second-order and intra-particle diffusion kinetic models. After evaluating three kinetic models for CO2 adsorption at adsorption temperatures of 30°C, 40°C and 50°C, it was found that intra-particle diffusion kinetic model provided the best fitting for the adsorption data. Furthermore, the thermodynamic parameters of CO2 adsorption were obtained as follows, Gibbs free energy change (ΔG°) are -0.409 kJ/mol at 30°C, -0.274 kJ/mol at 40°C and -0.138 kJ/mol at 50 °C, whereas the enthalpy change (ΔH°) is -4.53 kJ/mol and the entropy change (ΔS°) is -0.0135 kJ/(mol K).

  18. 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. PMID:27451112

  19. 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

  20. 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

  1. 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.

  2. 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.

  3. Thermodynamic Properties of HCFC-124

    NASA Astrophysics Data System (ADS)

    Fukushima, Masato; Watanabe, Naohiro

    Thermodynamic properties of HCFC-124, such as saturated densities, vapor pressures and PVT properties, were measured and the critical parameters were determined through those experimental results. The correlations for vapor pressure, saturated liquid density and PVT properties deduced from those experimental results were compared with the measured data and also with the estimates of the other correlations published in literatures. The thermodynamic functions, such as enthalpy, entropy, heat capacity, etc., can reasonably be calculated from the correlation equations in this paper.

  4. 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.

  5. Adsorption of Ponceau S from aqueous solution by MgO nanoparticles

    NASA Astrophysics Data System (ADS)

    Venkatesha, T. G.; Nayaka, Y. Arthoba; Chethana, B. K.

    2013-07-01

    Ponceau S or Acid Red 112 is a widely used dye with versatile applications whose biotransformation products are toxic and is a suspected carcinogen. In the present work, magnesium oxide (MgO) nanoparticles were synthesized by precipitation method and used for the sorption of Ponceau S from aqueous solution. The effects of parameters like contact time, pH and temperature on the adsorption capacity were studied. The adsorption isotherm studies were carried out using Langmuir, Freundlich and Temkin models, of which Langmuir model was found more suitable. Pseudo-second-order model fitted well with good agreement with the experimental values of qe (equilibrium adsorption capacity). The values of thermodynamic parameters like enthalpy (ΔH°) and entropy (ΔS°) were found to be 35.71 kJ/mol and 0.127 J/K/mol, respectively. The negative values of standard free energy (ΔG°) suggested that the adsorption process is spontaneous with the energy of activation equal to 28.58 kJ/mol.

  6. Uranium and thorium adsorption from aqueous solution using a novel polyhydroxyethylmethacrylate-pumice composite.

    PubMed

    Akkaya, Recep

    2013-06-01

    Poly(hydroxyethylmethacrylate-pumice), [P(HEMA-Pum)], composite was synthesized by free radical polymerization in aqueous solution. The adsorptive features of P(HEMA-Pum) composite were investigated for UO2(2+) and Th(4+) using a range of pH, concentration, time (kinetics), temperature (thermodynamics), ionic strength and selectivity, and the related parameters were derived from the obtained results. These results indicated that all adsorbents had high affinity to the uranium and thorium ions. The parameters obtained from Langmuir, Freundlich and Dubinin-Radsushkevich models fit the data well. The values of enthalpy and entropy changes showed that the overall adsorption process was endothermic (ΔH > 0) and increasing entropy (ΔS > 0), and it was spontaneous (ΔG < 0) as expected. The adsorption kinetics following the pseudo-second order model indicated that the rate-controlling step was chemical adsorption that occurred by ion exchange process. Reusability of P(HEMA-Pum) was also investigated, and it was found that the composite could be used at least 5 times. PMID:23416761

  7. Assessment of Ethidium bromide and Ethidium monoazide bromide removal from aqueous matrices by adsorption on cupric oxide nanoparticles.

    PubMed

    Fakhri, Ali

    2014-06-01

    The present study was undertaken to develop an effective adsorbent and to study the adsorption of Ethidium bromide and Ethidium monoazide bromide from aqueous solution using the CuO nanoparticles. The characteristics of CuO nanoparticles were determined and found to have a surface area 89.59m(2)/g. Operational parameters such as pH, contact time and adsorbent concentration, initial concentration and temperature were also studied. The amount of removal increases with the increase in pH from one to seven and reaches the maximum when the pH is nine. Adsorption data fitted well with the Langmuir, Freundlich and Florry-Huggins models. The results show that the best fit was achieved with the Langmuir isotherm equation with maximum adsorption capacities of 0.868 and 0.662mg/g for Ethidium bromide and Ethidium monoazide bromide, respectively. The adsorption process was found to follow pseudo-second-order kinetics. The calculated thermodynamic parameters, namely ΔG, ΔH and ΔS showed that adsorption of Ethidium bromide and Ethidium monoazide bromide was spontaneous and endothermic under examined conditions. PMID:24630576

  8. 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. PMID:19810739

  9. Competitive adsorption of Cd(II), Zn(II) and Ni(II) from their binary and ternary acidic systems using tourmaline.

    PubMed

    Liu, Haibin; Wang, Cuiping; Liu, Jingting; Wang, Baolin; Sun, Hongwen

    2013-10-15

    The adsorption of Cd(II), Zn(II) and Ni(II) from aqueous solutions in binary and ternary component systems by tourmaline was investigated. Kinetic data were accurately fitted to pseudo-second order and internal diffusion models, which indicated that the adsorption of heavy metals occurred on the interior surface of the sorbent and internal diffusion was the controlling mechanism during heavy metal ion adsorption but was not the only rate-controlling step. Additionally, tourmaline had a very good adsorption capacity for Cd(II), Zn(II) and Ni(II) in multi-component aqueous solutions at strongly acidic pH values (in contrast to industrial wastewater pH values). This good adsorption capacity is attributed to the fact that tourmaline can automatically adjust the pH values of acidic (except pH 2.0 and 3.0), neutral or alkaline aqueous solutions to 6.0. Adsorption isotherms and separation factors showed that tourmaline displays a high selectivity toward one metal in a two-component or a three-component system with an affinity order of Cd(II) > Zn(II) > Ni(II). Thermodynamic parameters indicated that heavy metal adsorption was feasible, spontaneous, and endothermic. Therefore, tourmaline should be explored as a material for removing pollutants from the strongly acidic wastewater. PMID:23851318

  10. Powdered activated carbon adsorption of two fishy odorants in water: Trans,trans-2,4-heptadienal and trans,trans-2,4-decadienal.

    PubMed

    Li, Xin; Wang, Jun; Zhang, Xiaojian; Chen, Chao

    2015-06-01

    Powdered activated carbon (PAC) adsorption of two fishy odorants, trans,trans-2,4-heptadienal (HDE) and trans,trans-2,4-decadienal (DDE), was investigated. Both the pseudo first-order and the pseudo second-order kinetic models well described the kinetics curves, and DDE was more readily removed by PAC. In isotherm tests, both Freundlich and Modified Freundlich isotherms fitted the experimental data well. PAC exhibited a higher adsorption capacity for DDE than for HDE, which could be ascribed to the difference in their hydrophobicity. The calculated thermodynamic parameters (ΔG0, ΔH0, and ΔS0) indicated an exothermic and spontaneous adsorption process. PAC dosage, pH, and natural organic matter (NOM) presence were found to influence the adsorption process. With increasing PAC dosage, the pseudo first-order and pseudo second-order rate constants both increased. The value of pH had little influence on HDE or DDE molecules but altered the surface charge of PAC, and the maximum adsorption capacity occurred at pH9. The presence of NOM, especially the fraction with molecular weight less than 1k Dalton, hindered the adsorption. The study showed that preloaded NOM impaired the adsorption capacity of HDE or DDE more severely than simultaneously fed NOM did. PMID:26040727

  11. Preparation of cross-linked magnetic chitosan-phenylthiourea resin for adsorption of Hg(II), Cd(II) and Zn(II) ions from aqueous solutions.

    PubMed

    Monier, M; Abdel-Latif, D A

    2012-03-30

    In this study, cross-linked magnetic chitosan-phenylthiourea (CSTU) resin were prepared and characterized by means of FTIR, (1)H NMR, SEM high-angle X-ray diffraction (XRD), magnetic properties and thermogravimetric analysis (TGA). The prepared resin were used to investigate the adsorption properties of Hg(II), Cd(II) and Zn(II) metal ions in an aqueous solution. The extent of adsorption was investigated as a function of pH and the metal ion removal reached maximum at pH 5.0. Also, the kinetic and thermodynamic parameters of the adsorption process were estimated. These data indicated that the adsorption process is exothermic and followed the pseudo-second-order kinetics. Equilibrium studies showed that the data of Hg(II), Cd(II) and Zn(II) adsorption followed the Langmuir model. The maximum adsorption capacities for Hg(II), Cd(II) and Zn(II) were estimated to be 135 ± 3, 120 ± 1 and 52 ± 1 mg/g, which demonstrated the high adsorption efficiency of CSTU toward the studied metal ions. PMID:22277339

  12. Protein Adsorption in Three Dimensions

    PubMed Central

    Vogler, Erwin A.

    2011-01-01

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

  13. Kinetics and equilibrium adsorption study of p-nitrophenol onto activated carbon derived from walnut peel.

    PubMed

    Liu, Xiaohong; Wang, Fang; Bai, Song

    2015-01-01

    An original activated carbon prepared from walnut peel, which was activated by zinc chloride, was modified with ammonium hydroxide or sodium hydroxide in order to contrast the adsorption property of the three different activated carbons. The experiment used a static adsorption test for p-nitrophenol. The effects of parameters such as initial concentration, contact time and pH value on amount adsorbed and removal are discussed in depth. The thermodynamic data of adsorption were analyzed by Freundlich and Langmuir models. The kinetic data of adsorption were measured by the pseudo-first-order kinetics and the pseudo-second-order kinetics models. The results indicated that the alkalized carbon samples derived from walnut peel had a better performance than the original activated carbon treated with zinc chloride. It was found that adsorption equilibrium time was 6 h. The maximum removal rate of activated carbon treated with zinc chloride for p-nitrophenol was 87.3% at pH 3,whereas the maximum removal rate of the two modified activated carbon materials was found to be 90.8% (alkalized with ammonium hydroxide) and 92.0% (alkalized with sodium hydroxide) at the same pH. The adsorption data of the zinc chloride activated carbon were fitted to the Langmuir isotherm model. The two alkalized activated carbon samples were fitted well to the Freundlich model. The pseudo-second-order dynamics equation provided better explanation of the adsorption dynamics data of the three activated carbons than the pseudo-first-order dynamics equation. PMID:26676011

  14. Extracorporeal adsorption of endotoxin.

    PubMed

    Staubach, K H; Rosenfeldt, J A; Veit, O; Bruch, H P

    1997-02-01

    In a porcine endotoxin shock model using a continuous intravenous endotoxin infusion of 250 ng/kg body weight per hour, the cardiorespiratory and hematologic parameters were studied while applying a new on-line polymyxin B immobilized adsorption system. This preliminary report shows that the new adsorbent can remove endotoxin selectively from the circulation and confers a good amount of protection from endotoxin-induced cardiopulmonary decompensation as well as hematologic alterations. Survival time could be extended from 216 min to 313 min. Whereas cardiac output and mean arterial pressure declined critically after 3 h in the controls, the treated group remained stable for another 3 h. These data show that endotoxin adsorption by polymyxin B coupled covalently to acrylic spheres as an adjunctive on-line measure in the septic syndrome seems feasible. PMID:10225785

  15. 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.

  16. Hydrogen adsorption on functionalized nanoporous activated carbons.

    PubMed

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

    2005-05-12

    There is considerable interest in hydrogen adsorption on carbon nanotubes and porous carbons as a method of storage for transport and related energy applications. This investigation has involved a systematic investigation of the role of functional groups and porous structure characteristics in determining the hydrogen adsorption characteristics of porous carbons. Suites of carbons were prepared with a wide range of nitrogen and oxygen contents and types of functional groups to investigate their effect on hydrogen adsorption. The porous structures of the carbons were characterized by nitrogen (77 K) and carbon dioxide (273 K) adsorption methods. Hydrogen adsorption isotherms were studied at 77 K and pressure up to 100 kPa. All the isotherms were Type I in the IUPAC classification scheme. Hydrogen isobars indicated that the adsorption of hydrogen is very temperature dependent with little or no hydrogen adsorption above 195 K. The isosteric enthalpies of adsorption at zero surface coverage were obtained using a virial equation, while the values at various surface coverages were obtained from the van't Hoff isochore. The values were in the range 3.9-5.2 kJ mol(-1) for the carbons studied. The thermodynamics of the adsorption process are discussed in relation to temperature limitations for hydrogen storage applications. The maximum amounts of hydrogen adsorbed correlated with the micropore volume obtained from extrapolation of the Dubinin-Radushkevich equation for carbon dioxide adsorption. Functional groups have a small detrimental effect on hydrogen adsorption, and this is related to decreased adsorbate-adsorbent and increased adsorbate-adsorbate interactions. PMID:16852056

  17. The Influence of Adsorption on PVT Measurements in the Gaseous Phase

    NASA Astrophysics Data System (ADS)

    Chernyak, Y.; Zhelezny, V. P.; Yokozeki, A.

    1999-11-01

    PVT measurements of 1,1,1,2-tetrafluoroethane (C2H2F4, HFC-134a) and its blend with octofluoropropane (C3F8, FC-218) have been performed in the gas phase near the dew curve. The experimental data were obtained by variable-volume and vibrating tube methods. Discrepancies in the behavior of isotherms from their classical behavior were experimentally observed. It was found that the phase transition does not go to completion at a single point of the thermodynamic surface but extends over a limited range of conditions. Obtained results are in accordance with a concept of adsorption of the vapor sample on the surface of the experimental cell. An increase in adsorption under the conditions close to condensation is caused by capillary condensation of the sample at the walls of the cell that initiates an early phase transition. The ranges of diffuse phase transitions were determined for 1,1,1,2-tetrafluoroethane as well as for its mixture with octofluoropropane at different thermodynamic parameters. The influence of selective adsorption on the change in the conditions of phase transition of the 1,1,1,2-tetrafluoroethane/octofluoropropane mixture was also experimentally studied.

  18. Stochastic deformation of a thermodynamic symplectic structure

    NASA Astrophysics Data System (ADS)

    Kazinski, P. O.

    2009-01-01

    A stochastic deformation of a thermodynamic symplectic structure is studied. The stochastic deformation is analogous to the deformation of an algebra of observables such as deformation quantization, but for an imaginary deformation parameter (the Planck constant). Gauge symmetries of thermodynamics and corresponding stochastic mechanics, which describes fluctuations of a thermodynamic system, are revealed and gauge fields are introduced. A physical interpretation to the gauge transformations and gauge fields is given. An application of the formalism to a description of systems with distributed parameters in a local thermodynamic equilibrium is considered.

  19. Stochastic deformation of a thermodynamic symplectic structure.

    PubMed

    Kazinski, P O

    2009-01-01

    A stochastic deformation of a thermodynamic symplectic structure is studied. The stochastic deformation is analogous to the deformation of an algebra of observables such as deformation quantization, but for an imaginary deformation parameter (the Planck constant). Gauge symmetries of thermodynamics and corresponding stochastic mechanics, which describes fluctuations of a thermodynamic system, are revealed and gauge fields are introduced. A physical interpretation to the gauge transformations and gauge fields is given. An application of the formalism to a description of systems with distributed parameters in a local thermodynamic equilibrium is considered. PMID:19256999

  20. A novel zerovalent manganese for removal of copper ions: synthesis, characterization and adsorption studies

    NASA Astrophysics Data System (ADS)

    Dada, A. O.; Adekola, F. A.; Odebunmi, E. O.

    2015-11-01

    Synthesis of nanoscale zerovalent manganese (nZVMn) by chemical reduction was carried out in a single pot system under inert environment. nZVMn was characterized using a combination of analytical techniques: Ultraviolet-Visible Spectroscopy, Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Transmission Electron Microscopy, Energy Dispersive X-ray, BET surface area and Point of Zero Charge. The adsorption physicochemical factors: pH, contact time, adsorbent dose, agitation speed, initial copper ion concentration and temperature were optimized. The kinetic data fitted better to Pseudo second-order, Elovich, fractional power and intraparticle diffusion models and their validity was tested by three statistical models: sum of square error, Chi-square (χ 2) and normalized standard deviation (Δq). Seven of the two-parameter isotherm models [Freundlich, Langmuir, Temkin, Dubinin-Kaganer-Raduskevich (DKR), Halsey, Harkin-Jura and Flory-Huggins] were used to analyse the equilibrium adsorption data. The Langmuir monolayer adsorption capacity (Q max = 181.818 mg/g) obtained is greater than other those of nano-adsorbents utilized in adsorption of copper ions. The equilibrium adsorption data were better described by Langmuir, Freundlich, Temkin, DKR and Halsey isotherm models considering their coefficient of regression (R 2 > 0.90). The values of the thermodynamic parameters: standard enthalpy change ∆H° (+50.27848 kJ mol-1), standard entropy change ∆S° (203.5724 J mol-1 K-1) and the Gibbs free energy change ∆G° revealed that the adsorption process was feasible, spontaneous, and endothermic in nature. The performance of this novel nanoscale zerovalent manganese (nZVMn) suggested that it has a great potential for effective removal of copper ions from aqueous solution.

  1. 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. PMID:20194017

  2. Nanoporous chalcogenides for adsorption and gas separation.

    PubMed

    Ori, Guido; Massobrio, Carlo; Pradel, Annie; Ribes, Michel; Coasne, Benoit

    2016-05-21

    The adsorption and gas separation properties of amorphous porous chalcogenides such as GeS2 are investigated using statistical mechanics molecular simulation. Using a realistic molecular model of such amorphous adsorbents, we show that they can be used efficiently to separate different gases relevant to environmental and energy applications (H2, CO2, CH4, N2). In addition to shedding light on the microscopic adsorption mechanisms, we show that coadsorption in this novel class of porous materials can be described using the ideal adsorbed solution theory (IAST). Such a simple thermodynamic model, which allows avoiding complex coadsorption measurements, describes the adsorption of mixture from pure component adsorption isotherms. Our results, which are found to be in good agreement with available experimental data, paves the way for the design of gas separation membranes using the large family of porous chalcogenides. PMID:27126718

  3. 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

  4. [Adsorption and Desorption Characteristics of Endosulfan in Purple Soil].

    PubMed

    Zhao, Yan; Zheng, Guo-can; Zhu, Heng; Zhang, Jin-zhong; Zhu, Xiu-ying; Hu, Shu-chun; Wu, Ya-lin

    2015-09-01

    In order to reveal the residual process of endosulfan in purple soil and protect soil ecological environment, the adsorption and desorption characteristics of endosulfan in purple soil were investigated, and effects of temperature, adsorbent amount, and initial pH of adsorption solution on the adsorption capacity were also examined by static adsorption and desorption experiments. The results showed that the adsorption kinetic process could be well described by the second-order kinetic equation with the initial rate constants of α-, β-endosulfan as 0. 157 and 0. 115 mg.(g.min)-1, respectively. The adsorption thermodynamic process could be well described by the Langmuir isotherm with the maximum adsorption capacities of α-, β-endosulfan as 0. 257 mg . g -1 and 0. 155 mg . g -1, respectively. The adsorption process of endosulfan in purple soil may be an exothermic physicochemical process, and is dominated by physical adsorption. Under the experimental conditions examined in this study, the initial pH of adsorption solution had a relative great influence on the adsorption capacity, whereas the temperature and adsorbent amount had no significant influence. The desorption experiments found that the maximum desorption capacities of α-, β-endosulfan adsorbed in purple soil were 0. 029 mg . g -1 and 0. 017 mg . g -1 at 6 and 4 h, and accounted for 10. 5% and 16. 1% in the maximum adsorption capacities, respectively. PMID:26717711

  5. [Adsorption Properties of Fluorine onto Fulvic Acid-Bentonite Complex].

    PubMed

    Fang, Dun; Tian, Hua-jing; Ye, Xin; He, Ci-li; Dan, You-meng; Wei, Shi-yong

    2016-03-15

    Fulvic Acid-Bentonite (FA-BENT) complex was prepared using coprecipitation method, and basic properties of the complex and sorption properties of fluorine at different environmental conditions were studied. XRD results showed that the d₀₀₁ spacing of FA- BENT complex had no obvious change compared with the raw bentonite, although the diffraction peak intensity of smectite in FA-BENT complex reduced, and indicated that FA mainly existed as a coating on the external surface of bentonite. Some functional groups (such as C==O, −OH, etc. ) of FA were observed in FA-BENT FTIR spectra, thus suggesting ligand exchange-surface complexation between FA and bentonite. Higher initial pH values of the reaction system were in favor of the adsorption of fluorine onto FA-BENT, while the equilibrium capacity decreased with the increase of pH at initial pH ≥ 4.50. The adsorption of fluorine onto FA-BENT was also affected by ionic strength, and the main reason might be the "polarity" effect. The adsorption of fluorine onto FA-BENT followed pseudo-second-order kinetic model and was controlled by chemical process ( R² = 0.999 2). Compared with the Freundlich model, Langmuir model was apparently of a higher goodness of fit (R² > 0.994 9) for absorption of fluorine onto FA-BENT. Thermodynamic parameters indicated that the adsorption process of fluorine was an spontaneously endothermic reaction, and was an entropy-driven process (ΔH 32.57 kJ · mol⁻¹, ΔS 112.31 J · (mol · K)⁻¹, ΔG −0.65- −1.76 kJ · mol⁻¹). PMID:27337896

  6. Removal of radio nuclides of the U- and Th- series from aqueous solutions by adsorption onto Polyacryamide-expanded perlite: Effects of pH, concentration and temperature

    NASA Astrophysics Data System (ADS)

    Akkaya, Recep

    2012-10-01

    Poly (Acryamide-expanded perlite) [P(AAm-EP)], was synthesized. The influence of process parameters: initial pH and five radio nuclides of the U- and Th- series (TI+, Ra2+, Bi3+, Ac3+ and Pb2+ in a leaching solution) concentration, on sorption thermodynamic was studied and discussed. The five natural radio nuclides were counted by gamma spectrometer using a type NAI (Tl) detector. The amounts of five radio nuclides sorbed at equlibrium were well represented by Langmuir and Freundlich type isotherms. The Langmuir adsorption capacities (XL) were in the order of 208Tl (0.4 MBq kg-1)>212Pb and 212Bi (0.3 MBq kg-1)>228Ac and (0.1 MBq kg-1)>226Ra (0.04 MBq kg-1). These results demonstrated that P(AAm-EP) had high affinity to the five natural radio nuclides. In order to specify the type of adsorption reaction, thermodynamic parameters such as the standard enthalpy, entropy, and Gibbs free energy were also determined. It was also demonstrated that the adsorption mechanism was spontaneous (ΔG<0), the process was exothermic (ΔH<0) thus increasing entropy (ΔS>0). The composite was reused for four more times after regeneration without any detectable changes either in its structure or adsorptive capability.

  7. Selective adsorption of cationic dyes from aqueous solution by polyoxometalate-based metal-organic framework composite

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoxia; Gong, Wenpeng; Luo, Jing; Zou, Chentao; Yang, Yun; Yang, Shuijin

    2016-01-01

    A novel environmental friendly adsorbent H6P2W18O62/MOF-5 was synthesized by a simple one-step reaction under solvothermal conditions and characterized by XRD, FTIR, thermogravimetric analyses (TGA) and N2 adsorption-desorption isotherms. The removal rate of H6P2W18O62/MOF-5 was quite greater (85%) than that of MOF-5 (almost zero), showing that the adsorption performance of porous MOF-5 can be improved through the modification of H6P2W18O62. Further study revealed that H6P2W18O62/MOF-5 exhibited a fast adsorption rate and selective adsorption ability towards the cationic dyes in aqueous solution. The removal rate was up to 97% for cationic dyes methylene blue (MB) and 68% for rhodamine B(Rhb) within 10 min. However, anionicdye methyl orange(MO) can only reach to 10%. The influences including initial concentration, contact time, initial solution pH and temperature of MB adsorption onto H6P2W18O62/MOF-5 were investigated in detail. The kinetic study indicated that the adsorption of MB onto H6P2W18O62/MOF-5 followed the pseudo second-order model well. The isotherm obtained from experimental data fitted the Langmuir model, yielding maximum adsorption capacity of 51.81 mg/g. The thermodynamic parameters analysis illustrated that the MB adsorption onto H6P2W18O62 immobilized MOF-5 was spontaneous and endothermic process. Besides, these results implied that designing a novel material polyoxometalate-based metal-organic frameworks is great potential for removing cationic organic pollutants and even extended to improve other specific application.

  8. Adsorption of water vapor on reservoir rocks

    SciTech Connect

    Not Available

    1993-07-01

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

  9. Natural thermodynamics

    NASA Astrophysics Data System (ADS)

    Annila, Arto

    2016-02-01

    The principle of increasing entropy is derived from statistical physics of open systems assuming that quanta of actions, as undividable basic build blocks, embody everything. According to this tenet, all systems evolve from one state to another either by acquiring quanta from their surroundings or by discarding quanta to the surroundings in order to attain energetic balance in least time. These natural processes result in ubiquitous scale-free patterns: skewed distributions that accumulate in a sigmoid manner and hence span log-log scales mostly as straight lines. Moreover, the equation for least-time motions reveals that evolution is by nature a non-deterministic process. Although the obtained insight in thermodynamics from the notion of quanta in motion yields nothing new, it accentuates that contemporary comprehension is impaired when modeling evolution as a computable process by imposing conservation of energy and thereby ignoring that quantum of actions are the carriers of energy from the system to its surroundings.

  10. Advances in thermodynamics

    SciTech Connect

    Sieniutycz, S. ); Salamon, P. )

    1990-01-01

    This book covers: nonequilibrium thermodynamics for solar energy applications; finite-time thermodynamics as applied to solar power conversion; thermodynamics and economics; exergy analysis; and an analysis of cumulative exergy consumption and exergy losses.

  11. Fluorescent intercalator displacement replacement (FIDR) assay: determination of relative thermodynamic and kinetic parameters in triplex formation—a case study using triplex-forming LNAs

    PubMed Central

    Sau, Sujay P.; Kumar, Pawan; Sharma, Pawan K.; Hrdlicka, Patrick J.

    2012-01-01

    Triplex forming oligonucleotides (TFOs) are the most commonly used approach for site-specific targeting of double stranded DNA (dsDNA). Important parameters describing triplex formation include equilibrium binding constants (Keq) and association/dissociation rate constants (kon and koff). The ‘fluorescent intercalator displacement replacement’ (FIDR) assay is introduced herein as an operationally simple approach toward determination of these parameters for triplexes involving TC-motif TFOs. Briefly described, relative rate constants are determined from fluorescence intensity changes upon: (i) TFO-mediated displacement of pre-intercalated and fluorescent ethidium from dsDNA targets (triplex association) and (ii) Watson–Crick complement-mediated displacement of the TFO and replacement with ethidium (triplex dissociation). The assay is used to characterize triplexes between purine-rich dsDNA targets and TC-motif TFOs modified with six different locked nucleic acid (LNA) monomers, i.e. conventional and C5-alkynyl-functionalized LNA and α-L-LNA pyrimidine monomers. All of the studied monomers increase triplex stability by decreasing the triplex dissociation rate. LNA-modified TFOs form more stable triplexes than α-L-LNA-modified counterparts owing to slower triplex dissociation. Triplexes modified with C5-(3-aminopropyn-1-yl)-LNA-U monomer Z are particularly stable. The study demonstrates that three affinity-enhancing features can be combined into one high-affinity TFO monomer: conformational restriction of the sugar ring, expansion of the pyrimidine π-stacking surface and introduction of an exocyclic amine. PMID:22855561

  12. Fluorescent intercalator displacement replacement (FIDR) assay: determination of relative thermodynamic and kinetic parameters in triplex formation--a case study using triplex-forming LNAs.

    PubMed

    Sau, Sujay P; Kumar, Pawan; Sharma, Pawan K; Hrdlicka, Patrick J

    2012-11-01

    Triplex forming oligonucleotides (TFOs) are the most commonly used approach for site-specific targeting of double stranded DNA (dsDNA). Important parameters describing triplex formation include equilibrium binding constants (K(eq)) and association/dissociation rate constants (k(on) and k(off)). The 'fluorescent intercalator displacement replacement' (FIDR) assay is introduced herein as an operationally simple approach toward determination of these parameters for triplexes involving TC-motif TFOs. Briefly described, relative rate constants are determined from fluorescence intensity changes upon: (i) TFO-mediated displacement of pre-intercalated and fluorescent ethidium from dsDNA targets (triplex association) and (ii) Watson-Crick complement-mediated displacement of the TFO and replacement with ethidium (triplex dissociation). The assay is used to characterize triplexes between purine-rich dsDNA targets and TC-motif TFOs modified with six different locked nucleic acid (LNA) monomers, i.e. conventional and C5-alkynyl-functionalized LNA and α-L-LNA pyrimidine monomers. All of the studied monomers increase triplex stability by decreasing the triplex dissociation rate. LNA-modified TFOs form more stable triplexes than α-L-LNA-modified counterparts owing to slower triplex dissociation. Triplexes modified with C5-(3-aminopropyn-1-yl)-LNA-U monomer Z are particularly stable. The study demonstrates that three affinity-enhancing features can be combined into one high-affinity TFO monomer: conformational restriction of the sugar ring, expansion of the pyrimidine π-stacking surface and introduction of an exocyclic amine. PMID:22855561

  13. Adsorption of crystal violet with diatomite earth&carbon by a modification of hydrothermal carbonization process.

    PubMed

    Zhang, Yanzhuo; Li, Jun; Chen, Guanghui; Bian, Wei; Lu, Yun; Li, Wenjing; Zheng, Zhaoming; Cheng, Xiaojie

    2016-01-01

    The high colority and difficulty of decolorization are the most important tasks on printing and dyeing wastewater. This study investigates the ability of diatomite earth&carbon (DE&C) as an adsorbent to removal crystal violet (CV) from aqueous solutions. Fourier transform infrared spectroscopy results indicate the importance of functional groups during the adsorption of CV. The obtained N2 adsorption-desorption isotherm values accord with well IUPAC type II. Our calculations determined a surface area of 73.15 m(2) g(-1) for DE&C and an average pore diameter of 10.56 nm. Equilibrium data of the adsorption process fitted very well to the Langmuir model (R(2) > 0.99). The results of kinetics study showed that the pseudo-second-order model fitted to the experimental data well. The thermodynamic parameters were also evaluated. ΔH° <0, ΔS° > 0 and ΔG° < 0 demonstrated that the adsorption process was spontaneous and exothermic for dye. Furthermore the positive value of ΔS° reflected good affinity of the CV dye. PMID:27003089

  14. Nitrate adsorption from aqueous solution using granular chitosan-Fe3+ complex

    NASA Astrophysics Data System (ADS)

    Hu, Qili; Chen, Nan; Feng, Chuanping; Hu, WeiWu

    2015-08-01

    In the present study, In order to efficiently remove nitrate, granular chitosan-Fe3+ complex with high chemical stability and good environmental adaptation was synthesized through precipitation method and characterized using SEM, XRD, BET and FTIR. The nitrate adsorption performance was evaluated by batch experiments. The results indicated that granular chitosan-Fe3+ complex was an amorphous and mesoporous material. The BET specific surface area and average pore size were 8.98 m2 g-1 and 56.94 Å, respectively. The point of zero charge was obtained at pH 5. The maximum adsorption capacity reached 8.35 mg NO3--N g-1 based on Langmuir-Freundlich model. Moreover, no significant change in the nitrate removal efficiency was observed in the pH range of 3.0-10.0. The adverse influence of sulphate on nitrate removal was the most significant, followed by bicarbonate and fluoride, whereas chloride had slightly adverse effect. Adsorption process followed the pseudo-second-order kinetic model, and the experimental equilibrium data were fitted well with the Langmuir-Freundlich and D-R isotherm models. Thermodynamic parameters revealed that nitrate adsorption was a spontaneous and exothermic process. Granular chitosan-Fe3+ complex could be effectively regenerated by NaCl solution.

  15. Proton and Cd adsorption onto natural bacterial consortia: Testing universal adsorption behavior

    NASA Astrophysics Data System (ADS)

    Borrok, David; Fein, Jeremy B.; Kulpa, Charles F.

    2004-08-01

    Bacterial surface adsorption can control metal distributions in some natural systems, yet it is unclear whether natural bacterial consortia differ in their adsorption behaviors. In this study, we conduct potentiometric titration and metal adsorption experiments to measure proton and Cd adsorption onto a range of bacterial consortia. We model the experimental data using a surface complexation approach to determine thermodynamic stability constants. Our results indicate that these consortia adsorb similar extents of protons and Cd and that the adsorption onto all of the consortia can be modeled using a single set of stability constants. Consortia of bacteria cultured from natural environments also adsorb metals to lesser extents than individual strains of laboratory-cultivated species. This study suggests that a wide range of bacterial species exhibit similar adsorption behaviors, potentially simplifying the task of modeling the distribution and speciation of metals in bacteria-bearing natural systems. Current models for bacteria-metal adsorption that rely on pure strains of laboratory-cultivated species likely overpredict the amount of bacteria-metal adsorption in natural systems.

  16. Magnetic hydrogel beads based on PVA/sodium alginate/laponite RD and studying their BSA adsorption.

    PubMed

    Mahdavinia, Gholam Reza; Mousanezhad, Sedigheh; Hosseinzadeh, Hamed; Darvishi, Farshad; Sabzi, Mohammad

    2016-08-20

    In this study double physically crosslinked magnetic hydrogel beads were developed by a simple method including solution mixing of sodium alginate and poly(vinyl alcohol) (PVA) containing magnetic laponite RD (Rapid Dispersion). Sodium alginate and PVA were physically crosslinked by Ca(2+) and freezing-thawing cycles, respectively. Magnetic laponite RD nanoparticles were incorporated into the system to create magnetic response and strengthen the hydrogels. All hybrids double physically crosslinked hydrogel beads were stable under different pH values without any disintegration. Furthermore, adsorption of bovine serum albumin (BSA) on the hydrogel beads was investigated on the subject of pH, ion strength, initial BSA concentration, and temperature. Nanocomposite beads exhibited maximum adsorption capacity for BSA at pH=4.5. The experimental adsorption isotherm data were well followed Langmuir model and based on this model the maximum adsorption capacity was obtained 127.3mgg(-1) at 308K. Thermodynamic parameters revealed spontaneous and monolayer adsorption of BSA on magnetic nanocomposites beads. PMID:27178944

  17. Preparation and adsorption behavior of berberine hydrochloride imprinted polymers by using silica gel as sacrificed support material

    NASA Astrophysics Data System (ADS)

    Li, Hui; Li, Yuzhuo; Li, Zhiping; Peng, Xiyang; Li, Yanan; Li, Gui; Tan, Xianzhou; Chen, Gongxi

    2012-03-01

    Preparation of berberine hydrochloride (B-Cl) imprinted polymers (MIPs) based on surface imprinting technique with silica gel as sacrificial support material was performed successfully by using B-Cl as template, methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) as functional monomer and cross-linker, respectively. The prepared polymers were characterized by Fourier transmission infrared spectrometry (FTIR) and scanning electron microscopy (SEM). Adsorption behavior of the MIPs for the template and its structural analogues was investigated. Sites distribution on the surface of MIPs was explored by using different isotherm adsorption models and thermodynamic parameters for the adsorption of B-Cl on the MIPs determined. Sample application and reusability for the MIPs was also evaluated. Results indicated the strong adsorption and high selectivity of the MIPs for B-Cl. Saturated adsorption capacity reached 27.2 μmol g-1 and the selectivity coefficient of the MIPs for B-Cl relative to jatrorrhizine hydrochloride (J-Cl) and palmatine palmatus hydrochloride (P-Cl) are 3.70 and 6.03, respectively. In addition, the MIPs were shown with good reusability and selectively retention ability in sample application.

  18. Towards an integrated determination of thermodynamic density and gravity parameters using accelerometer measurements on board of low-orbit satellite missions

    NASA Astrophysics Data System (ADS)

    Kusche, Jürgen; Forootan, Ehsan; Löcher, Anno; Henze, Christina; Börger, Klaus; Schall, Judith

    2015-04-01

    The aim of this study is to develop an integrated approach, which allows a) to measure the neutral density of the thermosphere using orbit and accelerometer information from various satellite missions and b) to relate them to operational atmospheric models. The satellite missions to be considered will include low-orbit satellites CHAMP, GRACE, GOCE and SWARM; laser-ranging satellites such as LAGEOS; as well as altimetry satellites such as Topex/Poseidon and Jason 1-2. On the other hand different atmospheric models, including Jacchia-Bowman, MSIS 86, MSISE 90, and NRLMSISE-00 models, will be investigated with respect to their sensitivity to geomagnetic activity and sunspot cycle etc. and they will be used to determine a theoretical acceleration due to air drag. Subsequently, we will compare the "computed" atmospheric density with the total mass density ("observed" atmospheric density) retrieved from accelerometer measurements made on board the satellites during their operational period. Based on these results we finally will develop a method - a so called "integrated approach" - that allows the joint determination of thermospherical, instrumental, and gravitational parameters, as well as their respective errors and correlations.

  19. Simulating Metabolism with Statistical Thermodynamics

    SciTech Connect

    Cannon, William R.

    2014-08-04

    Kinetic probabilities of state are usually based on empirical measurements, while thermodynamic state probabilities are based on the assumption that chemical species are distributed to according to a multinomial Boltzmann distribution. While the use of kinetic simulations is desirable, obtaining all the mass action rate constants necessary to carry out kinetic simulations is an overwhelming challenge. Here, the kinetic probability of a state is compared in depth to the thermodynamic probability of a state for sets of coupled reactions. The entropic and energetic contributions to thermodynamic stable states are described and compared to entropic and energetic contributions of kinetic steady states. It is shown that many kinetic steady states are possible for a system of coupled reactions depending on the relative values of the mass action rate constants, but only one of these corresponds to a thermodynamically stable state. Furthermore, the thermodynamic stable state corresponds to a minimum free energy state. The use of thermodynamic simulations of state to model metabolic processes is attractive, since metabolite levels and energy requirements of pathways can be evaluated using only standard free energies of formation as parameters in the probability distribution. In chemical physics, the assumption of a Boltzmann distribution is the basis of transition state theory for modeling transitory species. Application to stable species, such as those found in metabolic processes, is a less severe assumption that would enable the use of simulations of state.

  20. Adsorption of toxic metal ion Cr(VI) from aqueous state by TiO2-MCM-41: equilibrium and kinetic studies.

    PubMed

    Parida, Kulamani; Mishra, Krushna Gopal; Dash, Suresh Kumar

    2012-11-30

    This paper deals with the immobilization of various weight percentage of TiO(2) on mesoporous MCM-41, characterization of the materials by X-ray diffraction (XRD), nitrogen adsorption-desorption, Fourier Transform Infrared (FTIR) analysis, UV-vis diffuse reflectance spectroscopy (DRS) and evaluation of the adsorption capacity toward Cr(VI) removal. It is found that the MCM-41 structure retained after loading of TiO(2) but the surface area and pore diameter decreased due to pore blockage. Adsorption of Cr(VI) from aqueous state was investigated on TiO(2)-MCM-41 by changing various parameters such as pH, metal ion concentration, and the temperature. When TiO(2) loading was more than 20 wt.%, the adsorption activity (25)TiO(2)-MCM-41 reduced significantly due to considerable decrease in the surface area. It is also observed that TiO(2) and neat MCM-41 exhibits very less Cr(VI) adsorption compared to TiO(2)-MCM-41. The adsorption of Cr(VI) onto (20)TiO(2)-MCM-41 at pH~5.5 and temperature 323 K was 91% at 100mg/L Cr(VI) metal ion concentration in 80 min. The experimental data fitted well to Langmuir and Freundlich isotherms. The adsorption of Cr(VI) on TiO(2)-MCM-41 followed a second order kinetics with higher values of intra-particle diffusion rate. Thermodynamic parameters suggested that the adsorption process is endothermic in nature and desorption studies indicated a chemisorption mode. PMID:23092612

  1. Rapid adsorptive removal of toxic Pb(2+) ion from aqueous solution using recyclable, biodegradable nanocomposite derived from templated partially hydrolyzed xanthan gum and nanosilica.

    PubMed

    Ghorai, Soumitra; Sarkar, Amit Kumar; Pal, Sagar

    2014-10-01

    This work studied the application of a novel biodegradable nanocomposite based on partially hydrolyzed polyacrylamide grafted xanthan gum and nanosilica (h-XG/SiO2) towards efficient and rapid removal of toxic Pb(2+) ions from aqueous environment. The uptake ability of Pb(2+) using h-XG/SiO2 has been studied in batch adsorption experiments with variation of adsorption parameters. The excellent removal rate (99.54% adsorption within 25min) and superior adsorption capacity (Qmax=1012.15mgg(-1)) of the composite material have been explained on the basis of synergistic and chelating effects of h-XG/SiO2 with Pb(2+) ion through electrostatic interactions. The kinetics, isotherm and thermodynamics studies reveal that Pb(2+) adsorb rapidly on nanocomposite surface, which is in agreement with pseudo-second-order kinetics and Langmuir adsorption isotherm models. In consequence of excellent adsorption as well as regeneration characteristics of nanocomposite, it has been found to be a promising adsorbent towards removal of Pb(2+) ions from battery industry wastewater. PMID:25164955

  2. Investigation of the effect of magnetic particles on the Crystal Violet adsorption onto a novel nanocomposite based on κ-carrageenan-g-poly(methacrylic acid).

    PubMed

    Gholami, Mostafa; Vardini, Mohammad Taghi; Mahdavinia, Gholam Reza

    2016-01-20

    A novel nanocomposite hydrogel prepared by incorporating Fe3O4 magnetic nanoparticles into the κ-carrageenan-g-poly (methacrylic acid) with in situ polymerization and was characterized by FT-IR, XRD, SEM, TEM and VSM. Synthesized nanocomposite was used to adsorb Crystal Violet (CV) (cationic dye) in aqueous solution in a batch system. The research studies showed that the adsorption of CV can be impressed as a function of contact time, initial concentration of CV, pH and molar ratio of κ-carrageenan to poly(methacrylic acid). CV adsorption tests disclosed that it only takes 15 min to reach the equilibrium and adsorption capacity for this dye was 28.24 mg g(-1). Langmuir isotherm for equilibrium adsorption data was fitted well and the pseudo-second-order model can describe the adsorption kinetics. Thermodynamic parameters of ΔG°, ΔH° and ΔS° showed the endothermic nature of adsorption and a spontaneous process. PMID:26572412

  3. Thermodynamic interpolation

    SciTech Connect

    Maiden, D E

    1998-10-01

    A method for constructing bicubic interpolation polynomials for the pressure P and internal energy E that are thermodynamically consistent at the mesh ponts and continuous across mesh boundaries is presented. The slope boundary conditions for the pressure and energy are derived from finite differences of the data and from Maxwell's consistency relation. Monotonicity of the sound speed and the specific heat is obtained by a bilinear interpolation of the slopes of the tabulated data. Monotonicity of the functions near steep gradients may be achieved by mesh refinement or by using a non-consistent bilinear to the data. Mesh refinement is very efficient for uniform-linear or uniform-logarithmic spaced data because a direct table lookup can be used. The direct method was compared to binary search and was 37 percent faster for logarithmic-spaced data and 106 percent faster for linear-spaced data. This improvement in speed is very important in the radiation-transport opacity-lookup part of the calculation. Interpolation in P-E space, with mesh refinement, can be made simple, robust, and conserve energy. In the final analysis the interpolation of the free energy and entropy (Maiden and Cook) remains a competitor.

  4. Novel sandwich structure adsorptive membranes for removal of 4-nitrotoluene from water.

    PubMed

    Guo, Yuexin; Jia, Zhiqian

    2016-11-01

    Novel sandwich PES-SPES/PS-PDVB/PTFE adsorptive membranes were prepared by a filtration/immersion precipitation method and employed for the removal of 4-nitrotoluene from water. The static adsorption thermodynamics, kinetics, dynamic adsorption/desorption and membrane reusability were investigated. The results showed that the Freundlich model describes the adsorption isotherm satisfactorily. With increased PS-PDVB content, the maximum static adsorption capacity, partition coefficient, apparent adsorption rate constant, and dynamic adsorption capacity all significantly increased. The sandwich membranes showed much higher removal efficiency and adsorption capacity than those of mixed matrix membranes. With respect to dynamics adsorption/desorption, the sandwich membranes exhibited excellent reusability, with a removal efficiency greater than 95% even after five recycles. PMID:27322899

  5. Efficient adsorption of phenanthrene by simply synthesized hydrophobic MCM-41 molecular sieves

    NASA Astrophysics Data System (ADS)

    Hu, Yun; He, Yinyun; Wang, Xiaowen; Wei, Chaohai

    2014-08-01

    Hydrophobic molecular sieve MCM-41 including surfactant template was synthesized by a simple method. The adsorption properties of this material toward phenanthrene were studied. The effects of adsorbent dose and pH value on the adsorption process as well as the adsorption mechanism and reuse performance were investigated. The template-containing MCM-41 showed a significant adsorption for phenanthrene, due to its hydrophobicity created by the surfactant template in MCM-41. The solution pH had little effect on the adsorption capacity. The adsorption kinetic could be fitted well with pseudo-second-order kinetic model. The adsorption equilibrium was fitted well by the linear model, and the adsorption process followed the liquid/solid phase distribution mechanism. The thermodynamic results indicated that the adsorption was a spontaneous and exothermic process.

  6. RNA Thermodynamic Structural Entropy

    PubMed Central

    Garcia-Martin, Juan Antonio; Clote, Peter

    2015-01-01

    Conformational entropy for atomic-level, three dimensional biomolecules is known experimentally to play an important role in protein-ligand discrimination, yet reliable computation of entropy remains a difficult problem. Here we describe the first two accurate and efficient algorithms to compute the conformational entropy for RNA secondary structures, with respect to the Turner energy model, where free energy parameters are determined from UV absorption experiments. An algorithm to compute the derivational entropy for RNA secondary structures had previously been introduced, using stochastic context free grammars (SCFGs). However, the numerical value of derivational entropy depends heavily on the chosen context free grammar and on the training set used to estimate rule probabilities. Using data from the Rfam database, we determine that both of our thermodynamic methods, which agree in numerical value, are substantially faster than the SCFG method. Thermodynamic structural entropy is much smaller than derivational entropy, and the correlation between length-normalized thermodynamic entropy and derivational entropy is moderately weak to poor. In applications, we plot the structural entropy as a function of temperature for known thermoswitches, such as the repression of heat shock gene expression (ROSE) element, we determine that the correlation between hammerhead ribozyme cleavage activity and total free energy is improved by including an additional free energy term arising from conformational entropy, and we plot the structural entropy of windows of the HIV-1 genome. Our software RNAentropy can compute structural entropy for any user-specified temperature, and supports both the Turner’99 and Turner’04 energy parameters. It follows that RNAentropy is state-of-the-art software to compute RNA secondary structure conformational entropy. Source code is available at https://github.com/clotelab/RNAentropy/; a full web server is available at http

  7. Thermodynamic Studies for Drug Design and Screening

    PubMed Central

    Garbett, Nichola C.; Chaires, Jonathan B.

    2012-01-01

    Introduction A key part of drug design and development is the optimization of molecular interactions between an engineered drug candidate and its binding target. Thermodynamic characterization provides information about the balance of energetic forces driving binding interactions and is essential for understanding and optimizing molecular interactions. Areas covered This review discusses the information that can be obtained from thermodynamic measurements and how this can be applied to the drug development process. Current approaches for the measurement and optimization of thermodynamic parameters are presented, specifically higher throughput and calorimetric methods. Relevant literature for this review was identified in part by bibliographic searches for the period 2004 – 2011 using the Science Citation Index and PUBMED and the keywords listed below. Expert opinion The most effective drug design and development platform comes from an integrated process utilizing all available information from structural, thermodynamic and biological studies. Continuing evolution in our understanding of the energetic basis of molecular interactions and advances in thermodynamic methods for widespread application are essential to realize the goal of thermodynamically-driven drug design. Comprehensive thermodynamic evaluation is vital early in the drug development process to speed drug development towards an optimal energetic interaction profile while retaining good pharmacological properties. Practical thermodynamic approaches, such as enthalpic optimization, thermodynamic optimization plots and the enthalpic efficiency index, have now matured to provide proven utility in design process. Improved throughput in calorimetric methods remains essential for even greater integration of thermodynamics into drug design. PMID:22458502

  8. Adsorption of heavy metal ions from aqueous solutions by bio-char, a by-product of pyrolysis

    NASA Astrophysics Data System (ADS)

    Kılıç, Murat; Kırbıyık, Çisem; Çepelioğullar, Özge; Pütün, Ayşe E.

    2013-10-01

    Bio-char, a by-product of almond shell pyrolysis, was used as an alternative adsorbent precursor for the removal of heavy metal ions from aqueous solutions. The adsorption potential of almond shell bio-char for Ni(II) and Co(II) removal was investigated. Adsorption experiments were carried out by varying pH, adsorbent dosage, initial metal ion concentrations, contact time and temperature to determine the optimum conditions. To describe the equilibrium isotherms the experimental data were analyzed by the Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherm models. Pseudo-first order, pseudo-second order, and intraparticle diffusion kinetic models were used to find out the kinetic parameters and mechanism of adsorption process. The thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated for predicting the nature of adsorption. The results showed that bio-char derived from pyrolysis of biomass can be used as a low-cost and effective adsorbent for removal of heavy metal ions from aqueous solutions.

  9. Thermodynamics of Radiation Modes

    ERIC Educational Resources Information Center

    Pina, Eduardo; de la Selva, Sara Maria Teresa

    2010-01-01

    We study the equilibrium thermodynamics of the electromagnetic radiation in a cavity of a given volume and temperature. We found three levels of description, the thermodynamics of one mode, the thermodynamics of the distribution of frequencies in a band by summing over the frequencies in it and the global thermodynamics by summing over all the…

  10. Adsorption analysis of ammonia in an aqueous solution

    SciTech Connect

    Arman, B.; Panchal, C.B.

    1993-08-01

    An analysis is carried out to determine the effects of the diffusional resistance on the rate of the adsorption of ammonia in an aqueous solution. A performance prediction model is developed to calculate the local rate of heat and mass transfer, including physical and thermodynamic property calculations of the mixture. An algorithm is developed for calculating the interfacial conditions. The local heat- and mass-transfer calculation is then incorporated into the performance prediction method for adsorption for a given geometry.

  11. Fabrication of hybrid magnetic Sr5xBa3x(PO4)3(OH)/Fe3O4 nanorod and its highly efficient adsorption performance for acid fuchsin dye

    NASA Astrophysics Data System (ADS)

    Yin, Xiaoju; Zhang, Fan; Zhang, Weihua

    2015-12-01

    The hybrid magnetic Sr5xBa3x(PO4)3(OH)/Fe3O4 (SBPF) nanorod was prepared and characterized using different techniques, such as SEM, EDS, TEM, SAED, HRTEM, XRD, and FT-IR. Adsorption studies of acid fuchsin (AF) from aqueous solution with respect to the pH, temperature, time, initial dye concentration, and sorbent dosage were investigated. The Freundlich adsorption model was applied to describe the equilibrium isotherms. The maximal AF uptake by SBPF was 1590 mg/g in the test. Kinetics parameters of the adsorption process indicated that it followed the pseudo-second order equation, and the maximum sorption capacity calculated from the pseudo-second-order rate equation was 909 mg/g which was close to the experimental value. Adsorption thermodynamics study indicated the spontaneous nature and exothermic of the adsorption process. The removal of AF was attributed to the hydrogen bond and ionic interactions. Moreover, SBPF was easily recovered, and the adsorption capacity was approximately 97.7% of the initial saturation adsorption capacity after being used five times.

  12. Preparation and characterization of chitosan/graphene oxide composites for the adsorption of Au(III) and Pd(II).

    PubMed

    Liu, Li; Li, Cui; Bao, Changli; Jia, Qiong; Xiao, Pengfei; Liu, Xiaoting; Zhang, Qiuping

    2012-05-15

    In this work, graphene oxide (GO) was firstly prepared, following by element analysis. Glutaraldehyde cross-linked chitosan (GCCS) and chitosan/graphene oxide (CSGO) composite with three different amounts of GO (5 wt%, 10 wt% and 15 wt%) were also prepared for the adsorption of Au(III) and Pd(II) in aqueous solution. The properties of the adsorbents were investigated by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and surface area analysis. Batch adsorption studies were carried out. The adsorption of Au(III) and Pd(II) onto CSGO composites was optimum at pH 3.0-5.0 for Au(III) and pH 3.0-4.0 for Pd(II), which was much wider than that of GCCS. The adsorption isotherms obeyed the Langmuir isotherm models for the adsorption of Au(III) and Pd(II). Chitosan with 5 wt% graphene oxide (CSGO(5)) composite had the largest adsorption capacity for Au(III) and Pd(II) compared with the other prepared adsorbents, where the maximum adsorption capacity were 1076.649 mg/g for Au(III) and 216.920 mg/g for Pd(II), respectively. The adsorption kinetics of Au(III) and Pd(II) onto CSGO(5) followed a pseudo-second-order kinetic model, indicating that the chemical adsorption was the rate-limiting step. Thermodynamic parameters, such as Gibbs energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°), were calculated, showing that the adsorption of Au(III) and Pd(II) onto CSGO(5) were spontaneous, endothermic and feasible. The desorption studies of Au(III) and Pd(II) onto CSGO(5) showed that CSGO(5) can be used repeatedly without significantly changing its adsorption capacity and desorption percentage after 3 cycles. Besides CSGO(5) was successfully applied for the determination and separation of Au(III) and Pd(II) in ore samples. PMID:22483922

  13. Solvothermal synthesis of MnFe2O4-graphene composite-Investigation of its adsorption and antimicrobial properties

    NASA Astrophysics Data System (ADS)

    Chella, Santhosh; Kollu, Pratap; Komarala, Eswara Vara P. R.; Doshi, Sejal; Saranya, Murugan; Felix, Sathiyanathan; Ramachandran, Rajendran; Saravanan, Padmanapan; Koneru, Vijaya Lakshmi; Venugopal, Velmurugan; Jeong, Soon Kwan; Nirmala Grace, Andrews

    2015-02-01

    Graphene manganese ferrite (MnFe2O4-G) composite was prepared by a solvothermal process. The as-prepared graphene manganese ferrite composite was tested for the adsorption of lead (Pb(II)) and cadmium (Cd(II)) ions by analytical methods under diverse experimental parameters. With respect to contact time measurements, the adsorption of Pb and Cd ions increased and reached equilibrium within 120 and 180 min at 37 °C with a maximum adsorption at pH 5 and 7 respectively. The Langmuir model correlates to the experimental data showing an adsorption capacity of 100 for Pb(II) and 76.90 mg g-1 for Cd(II) ions. Thermodynamic studies revealed that the adsorption of Pb and Cd ions onto MnFe2O4-G was spontaneous, exothermic and feasible in the range of 27-47 °C. Cytotoxicity behavior of graphene against bacterial cell membrane is well known. To better understand its antimicrobial mechanism, the antibacterial activity of graphene and MnFe2O4-G nanocomposite was compared. Under similar concentration and incubation conditions, nanocomposite MnFe2O4-G dispersion showed the highest antibacterial activity of 82%, as compared to graphene showing 37% cell loss. Results showed that the prepared composite possess good adsorption efficiency and thus could be considered as an excellent material for removal of toxic heavy metal ions as explained by adsorption isotherm. Hence MnFe2O4-G can be used as an adsorbent as well as an antimicrobial agent.

  14. Microscopic Theory of Hysteretic Hydrogen Adsorption in Nanoporous Materials

    SciTech Connect

    Kang, J.; Wei, S. H.; Kim, Y. H.

    2010-01-01

    Understanding gas adsorption confined in nanoscale pores is a fundamental issue with broad applications in catalysis and gas storage. Recently, hysteretic H{sub 2} adsorption was observed in several nanoporous metal-organic frameworks (MOFs). Here, using first-principles calculations and simulated adsorption/desorption isotherms, we present a microscopic theory of the enhanced adsorption hysteresis of H{sub 2} molecules using the MOF Co(1,4-benzenedipyrazolate) [Co(BDP)] as a model system. Using activated H{sub 2} diffusion along the small-pore channels as a dominant equilibration process, we demonstrate that the system shows hysteretic H{sub 2} adsorption under changes of external pressure. For a small increase of temperature, the pressure width of the hysteresis, as well as the adsorption/desorption pressure, dramatically increases. The sensitivity of gas adsorption to temperature changes is explained by the simple thermodynamics of the gas reservoir. Detailed analysis of transient adsorption dynamics reveals that the hysteretic H{sub 2} adsorption is an intrinsic adsorption characteristic in the diffusion-controlled small-pore systems.

  15. Molecular surface area based predictive models for the adsorption and diffusion of disperse dyes in polylactic acid matrix.

    PubMed

    Xu, Suxin; Chen, Jiangang; Wang, Bijia; Yang, Yiqi

    2015-11-15

    Two predictive models were presented for the adsorption affinities and diffusion coefficients of disperse dyes in polylactic acid matrix. Quantitative structure-sorption behavior relationship would not only provide insights into sorption process, but also enable rational engineering for desired properties. The thermodynamic and kinetic parameters for three disperse dyes were measured. The predictive model for adsorption affinity was based on two linear relationships derived by interpreting the experimental measurements with molecular structural parameters and compensation effect: ΔH° vs. dye size and ΔS° vs. ΔH°. Similarly, the predictive model for diffusion coefficient was based on two derived linear relationships: activation energy of diffusion vs. dye size and logarithm of pre-exponential factor vs. activation energy of diffusion. The only required parameters for both models are temperature and solvent accessible surface area of the dye molecule. These two predictive models were validated by testing the adsorption and diffusion properties of new disperse dyes. The models offer fairly good predictive ability. The linkage between structural parameter of disperse dyes and sorption behaviors might be generalized and extended to other similar polymer-penetrant systems. PMID:26197108

  16. Optimum conditions for adsorptive storage.

    PubMed

    Bhatia, Suresh K; Myers, Alan L

    2006-02-14

    The storage of gases in porous adsorbents, such as activated carbon and carbon nanotubes, is examined here thermodynamically from a systems viewpoint, considering the entire adsorption-desorption cycle. The results provide concrete objective criteria to guide the search for the "Holy Grail" adsorbent, for which the adsorptive delivery is maximized. It is shown that, for ambient temperature storage of hydrogen and delivery between 30 and 1.5 bar pressure, for the optimum adsorbent the adsorption enthalpy change is 15.1 kJ/mol. For carbons, for which the average enthalpy change is typically 5.8 kJ/mol, an optimum operating temperature of about 115 K is predicted. For methane, an optimum enthalpy change of 18.8 kJ/mol is found, with the optimum temperature for carbons being 254 K. It is also demonstrated that for maximum delivery of the gas the optimum adsorbent must be homogeneous, and that introduction of heterogeneity, such as by ball milling, irradiation, and other means, can only provide small increases in physisorption-related delivery for hydrogen. For methane, heterogeneity is always detrimental, at any value of average adsorption enthalpy change. These results are confirmed with the help of experimental data from the literature, as well as extensive Monte Carlo simulations conducted here using slit pore models of activated carbons as well as atomistic models of carbon nanotubes. The simulations also demonstrate that carbon nanotubes offer little or no advantage over activated carbons in terms of enhanced delivery, when used as storage media for either hydrogen or methane. PMID:16460092

  17. Adsorption and subsequent partial photodegradation of methyl violet 2B on Cu/Al layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Guzmán-Vargas, Ariel; Lima, Enrique; Uriostegui-Ortega, Gisselle A.; Oliver-Tolentino, Miguel A.; Rodríguez, Esaú E.

    2016-02-01

    Uncalcined Cu/Al LDH was studied as adsorbent and photocatalyst in the adsorption and subsequent photodegradation of methyl violet 2B dye (MV2B). Physicochemical characterization was carried out by XRD, FTIR, UV-vis, including photoactive properties, DSC/TGA and SEM. Kinetic and thermodynamic models showed great affinity and sorption capacity, the maximum adsorption capacity was 361.0 mg g-1 obtained by Langmuir model, in addition, the results showed that the dye was adsorbed on the LDH surface. Photocatalytic activity was evaluated in the MV2B dye photodegradation process, and it was confirmed by the presence rad OH radicals monitored by EPR spin trapping technique, additionally, COD and TOC parameters were measured, 13C NMR showed differences for the adsorbed and photodegraded samples.

  18. Thermodynamics. II - The extended thermodynamic system

    NASA Technical Reports Server (NTRS)

    Zeleznik, F. J.

    1981-01-01

    The algebraic theory of thermodynamics developed in a previous paper is extended to include the algebraic structure that arises from the introduction of a physical body into the theory. The extension is based on very general definitions of both the thermodynamic states of a body and subsystems of that body. The algebraic analysis, which includes bodies in nonuniform states, shows that the set of all thermodynamic states of a body has the same algebraic structure as the set of thermodynamic states and that composite systems are induced by the algebraic structure of thermodynamic states. The analysis also justifies a variational treatment of thermodynamic bodies in uniform as well as nonuniform states. The variational calculation includes all conventional methods of calculation as special cases and helps to illuminate the origin and interpretation of the electrochemical potential.

  19. Rethinking Critical Adsorption

    NASA Astrophysics Data System (ADS)

    Franck, Carl; Peach, Sarah; Polak, Robert D.

    1996-03-01

    Recent reflectivity experiments on near-critical mixtures of carbon disulfide and nitromethane contained in glass cells footnote Niraj S. Desai, Sarah Peach, and Carl Franck, Phys. Rev. E 52, 4129 (1995) have shown that preferential adsorption of one liquid component onto the wall can be controlled by chemical modification of the glass. The glass was treated with varying amounts of hexamethyldisilazane to decrease surface polarity and therefore enhance the adsorption of carbon disulfide in a surprisingly continuous way. The effect of the glass wall on the local liquid composition can be described by two different scaling hypotheses: using a short range field on the liquid closest to the wall, or pinning the amplitude of the order parameter at the surface. We have found that only the second approach is consistent with the experimental data, although this is difficult to reconcile with observed wetting critical phenomena. We also have reexamined the issue of substrate inhomogeneity and conclude that the substrates were indeed homogeneous on relevant length scales. Supported by the NSF under DMR-9320910 and the central facilities of the Materials Science Center at Cornell University.

  20. Adsorption of xenon and krypton on shales

    NASA Technical Reports Server (NTRS)

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

    1981-01-01

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

  1. Thermodynamics and transport in microporous media. Progress report

    SciTech Connect

    Glandt, E.D.

    1992-09-01

    Focus of this report is on the thermodynamic properties/behavior of fluids contained or adsorbed on the random microporus materials (disordered solids). The Madden-Glandt formalism for fluids in disordered matrices is applied to realistic systems (gas adsorption in carbons, polymer partitioning). Work on microgeometry of solids and their percolation and connectedness properties was continued; a study of the simplest model for microporous materials (random-pore or ``Swiss cheese`` model) was completed. Work on irreversible adsorption was continued; a simple model for correlated adsorption was studied.

  2. I. Gas adsorption properties and porosity of transition metal-based cyanogels. II. Novel energy transfer processes in organic light-emitting devices

    NASA Astrophysics Data System (ADS)

    Deshpande, Rahul Shrikant

    The gas adsorption properties and porosity of cyanide-bridged transition metal-based gels are investigated in the first part of this dissertation. The cyanide bridges, connecting two transition metal centers, are characteristic of these gels; hence, these gels are termed cyanogels. Aerogel versus xerogel structures have a profound effect, both, on the thermodynamics and kinetics of gas adsorption on these cyanogels. Carbon dioxide is selectively adsorbed on palladium-cobalt-based cyanogels; the adsorption is fully reversible on both types of gels discussed. The thermodynamics and kinetics of the gas adsorption processes on these gels are analyzed here. From the ease and reproducibility of the CO2 desorption and the associated enthalpy values, it is concluded that CO2 is physisorbed on these gels. Both the adsorption and desorption processes are first-order in the gels. Adsorption of carbon monoxide on the palladium-cobalt cyanogels is also investigated. Unlike CO 2 physisorption, carbon monoxide is chemisorbed on these gels. An uptake of CO brings about a profound change in the xerogel morphology. The palladium-cobalt-based aerogels possess both micro- and mesoporosity; the xerogels are predominantly microporous with a narrow microporosity. The aerogel surfaces are found to be fractal as analyzed by gas adsorption. Unlike the aerogels, the xerogels do not possess surface fractality. The mechanism of adsorption of different gases on these gels is analyzed based on the gel morphologies. These transition metal-based gels are promising for a variety of applications such as heterogeneous catalysts, gas filters and magnetic materials. The porosity of these gels can be exploited to make gel-embedded filters to separate mixtures of gases based on the their differential adsorption propensities. The reversible adsorption of CO2 can be harnessed practically by using these gels as CO2 storage reservoirs. In the second part of this dissertation, the first, balanced, white

  3. Study of polyethyleneimine- and amidoxime-functionalized hybrid biomass of Spirulina (Arthrospira) platensis for adsorption of uranium (VI) ion.

    PubMed

    Bayramoglu, Gulay; Akbulut, Aydin; Arica, M Yakup

    2015-11-01

    This study investigates the potential application of the polyethyleneimine- (PEI) and amidoxime-modified Spirulina (Arthrospira) platensis biomasses for the removal of uranium ion in batch mode using the native biomass as a control system. The uranium ion adsorption was also characterized by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra, zeta potential analysis, and surface area measurement studies. The effects of pH, biomass amount, contact time, initial uranium ion concentration, and ionic strength were evaluated by using native and modified algal biomass preparations. The uranium ion removal was rapid, with more than 70% of total adsorption taking place in 40 min, and equilibrium was established within 60 min. From the experimental data, it was found that the amount of adsorption uranium ion on the algal preparations decreased in the following series: amidoxime-modified algal biomass > PEI-modified algal biomass > native algal biomass. Maximum adsorption capacities of amidoxime- and PEI-modified, and native algal biomasses were found to be 366.8, 279.5, and 194.6 mg/g, respectively, in batchwise studies. The adsorption rate of U(VI) ion by amidoxime-modified algal biomass was higher than those of the native and PEI-modified counterparts. The adsorption processes on all the algal biomass preparations followed by the Dubinin-Radushkevitch (D-R) and Temkin isotherms and pseudo-second-order kinetic models. The thermodynamic parameters were determined at four different temperatures (i.e., 15, 25, 35, and 45 °C) using the thermodynamics constant of the Temkin isotherm model. The ΔH° and ΔG° values of U(VI) ion adsorption on algal preparations show endothermic heat of adsorption; higher temperatures favor the process. The native and modified algal biomass preparations were regenerated using 10 mM HNO3. These results show that amidoxime-modified algal biomass can be a potential candidate for effective removal of U(VI) ion from

  4. Adsorption properties of. cap alpha. -modification of boron nitride

    SciTech Connect

    Gavrilova, T.B.; Kiselev, A.V.; Parshina, I.V.; Roshchina, T.M.

    1986-11-01

    The adsorption properties of four samples of ..cap alpha..-BN were studied by means of gas chromatography. The particles of ..cap alpha..-BN particles, according to data obtained by electron microscopy, have the shape of thin platelets. A sample of ..cap alpha..-BN prepared from magnesium polyboride was found to be the most nearly homogeneous adsorbent. For a number of n-alkanes, benzene, and alkylbenzenes, data have been obtained on the retention volumes (Henry constants) and the differential heats of adsorption for surface coverages approaching zero. These thermodynamic data on the adsorption showed that ..cap alpha..-BN, like graphitized thermal carbon black, is a nonspecific adsorbent.

  5. Thermodynamic and activation parameters for dissociation of [CpCr(CO){sub 3}]{sub 2} and [Cp*Cr(CO){sub 3}]{sub 2} into paramagnetic monomers from {sup 1}H NMR shift and line width measurements

    SciTech Connect

    Woska, D.C.; Ni, Y.; Wayland, B.B.

    1999-09-06

    Substitution of pentamethyl cyclopentadienide (Cp*) for cyclopentadienide (Cp) is commonly used as an approach for increasing ligand steric requirements that can enhance dissociation of M-M bonded complexes. {sup 1}H NMR spectra for solutions prepared by dissolution of [CpCr(CO){sub 3}]{sub 2} and [Cp*Cr(CO){sub 3}]{sub 2} in toluene in the temperature range 190--390 K are interpreted in terms of thermodynamic and kinetic parameters for dissociation of the diamagnetic dimers into the paramagnetic monomers CpCr(CO){sub 3} and Cp*Cr(CO){sub 3}. There is no evidence in this temperature range for thermally populated excited states or non-Curie magnetic behavior of the monomers making a significant contribution to the NMR. An expression for the temperature dependence of the NMR chemical shift at limiting fast interchange of monomer and dimer in terms of the {Delta}H{degree} and {Delta}S{degree} for dimer dissociation is applied in determining the thermodynamic parameters for Cr-Cr bond homolysis of [CpCr(CO){sub 3}]{sub 2} ({Delta}H{sub 1}{degree} = 15.3 {+-} 0.6 kcal mol{sup {minus}1}; {Delta}S{sub 1}{degree} = 39 {+-} 2 cal K{sup {minus}1} mol{sup {minus}1}) and [Cp*Cr(CO){sub 3}]{sub 2} ({Delta}H{sub 2}{degree} = 14.2 {+-} 0.4 kcal mol{sup {minus}1}; {Delta}S{sub 2}{degree} = 47 {+-} 2 cal K{sup {minus}1}mol{sup {minus}1}). Rate constants and activation parameters have been evaluated from {sup 1}H NMR line broadening in the region of slow dimer-monomer interchange for dissociation of [CpCr(CO){sub 3}]{sub 2} ({kappa}{sub 1} (240 K) {approx} 59 s{sup {minus}1}; {Delta}H{sub 1}{double{underscore}dagger} = 17 {+-} 2 kcal mol{sup {minus}1}; {Delta}S{sub 1}{double{underscore}dagger} = 21 {+-} 6 cal K{sup {minus}1} mol{sup {minus}1}) and [Cp*Cr(CO){sub 3}]{sub 2} ({kappa}{sub 2} (240 K) {approx} 1.4 x 10{sup 4} s{sup {minus}1}; {Delta}H{sub 2}{double{underscore}dagger} = 16 {+-} 1 kcal mol{sup {minus}1}; {Delta}S{sub 2}{double{underscore}dagger} = 30 {+-} 6 cal K

  6. Measuring Thermodynamic Length

    SciTech Connect

    Crooks, Gavin E

    2007-09-07

    Thermodynamic length is a metric distance between equilibrium thermodynamic states. Among other interesting properties, this metric asymptotically bounds the dissipation induced by a finite time transformation of a thermodynamic system. It is also connected to the Jensen-Shannon divergence, Fisher information, and Rao's entropy differential metric. Therefore, thermodynamic length is of central interestin understanding matter out of equilibrium. In this Letter, we will consider how to denethermodynamic length for a small system described by equilibrium statistical mechanics and how to measure thermodynamic length within a computer simulation. Surprisingly, Bennett's classic acceptance ratio method for measuring free energy differences also measures thermodynamic length.

  7. Surfactant adsorption to soil components and soils.

    PubMed

    Ishiguro, Munehide; Koopal, Luuk K

    2016-05-01

    Soils are complex and widely varying mixtures of organic matter and inorganic materials; adsorption of surfactants to soils is therefore related to the soil composition. We first discuss the properties of surfactants, including the critical micelle concentration (CMC) and surfactant adsorption on water/air interfaces, the latter gives an impression of surfactant adsorption to a hydrophobic surface and illustrates the importance of the CMC for the adsorption process. Then attention is paid to the most important types of soil particles: humic and fulvic acids, silica, metal oxides and layered aluminosilicates. Information is provided on their structure, surface properties and primary (proton) charge characteristics, which are all important for surfactant binding. Subsequently, the adsorption of different types of surfactants on these individual soil components is discussed in detail, based on mainly experimental results and considering the specific (chemical) and electrostatic interactions, with hydrophobic attraction as an important component of the specific interactions. Adsorption models that can describe the features semi-quantitatively are briefly discussed. In the last part of the paper some trends of surfactant adsorption on soils are briefly discussed together with some complications that may occur and finally the consequences of surfactant adsorption for soil colloidal stability and permeability are considered. When we seek to understand the fate of surfactants in soil and aqueous environments, the hydrophobicity and charge density of the soil or soil particles, must be considered together with the structure, hydrophobicity and charge of the surfactants, because these factors affect the adsorption. The pH and ionic strength are important parameters with respect to the charge density of the particles. As surfactant adsorption influences soil structure and permeability, insight in surfactant adsorption to soil particles is useful for good soil management. PMID

  8. Thermodynamics of geothermal fluids

    SciTech Connect

    Rogers, P.S.Z.

    1981-03-01

    A model to predict the thermodynamic properties of geothermal brines, based on a minimum amount of experimental data on a few key systems, is tested. Volumetric properties of aqueous sodium chloride, taken from the literature, are represented by a parametric equation over the range 0 to 300{sup 0}C and 1 bar to 1 kbar. Density measurements at 20 bar needed to complete the volumetric description also are presented. The pressure dependence of activity and thermal properties, derived from the volumetric equation, can be used to complete an equation of state for sodium chloride solutions. A flow calorimeter, used to obtain heat capacity data at high temperatures and pressures, is described. Heat capacity measurements, from 30 to 200{sup 0}C and 1 bar to 200 bar, are used to derive values for the activity coefficient and other thermodynamic properties of sodium sulfate solutions as a function of temperature. Literature data on the solubility of gypsum in mixed electrolyte solutions have been used to evaluate model parameters for calculating gypsum solubility in seawater and natural brines. Predictions of strontium and barium sulfate solubility in seawater also are given.

  9. The investigation of kinetic and isotherm of fluoride adsorption onto functionalize pumice stone.

    PubMed

    Asgari, Ghorban; Roshani, Babak; Ghanizadeh, Ghader

    2012-05-30

    In this research work, pumice that is functionalized by the cationic surfactant, hexadecyltrimethyl ammonium (HDTMA), is used as an adsorbent for the removal of fluoride from drinking water. This work was carried out in two parts. The effects of HDTMA loading, pH (3-10), reaction time (5-60 min) and the adsorbent dosage (0.15-2.5 g L(-1)) were investigated on the removal of fluoride as a target contaminate from water through the design of different experimental sets in the first part. The results from this first part revealed that surfactant-modified pumice (SMP) exhibited the best performance at dose 0.5 g L(-1), pH 6, and it adsorbs over 96% of fluoride from a solution containing 10 mg L(-1) fluoride after 30 min of mixing time. The four linear forms of the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms model were applied to determine the best fit of equilibrium expressions. Apart from the regression coefficient (R(2)), four error functions were used to validate the isotherm and kinetics data. The experimental adsorption isotherm complies with Langmuir equation model type 1. The maximum amount of adsorption (Q(max)) was 41 mg g(-1). The kinetic studies indicated that the adsorption of fluoride best fitted with the pseudo-second-order kinetic type 1. Thermodynamic parameters evaluation of fluoride adsorption on SMP showed that the adsorption process under the selected conditions was spontaneous and endothermic. The suitability of SMP in defluoridation at field condition was investigated with natural groundwater samples collected from a nearby fluoride endemic area in the second part of this study. Based on this study's results, SMP was shown to be an affordable and a promising option for the removal of fluoride in drinking water. PMID:22476092

  10. Towards elucidation of the drug release mechanism from compressed hydrophilic matrices made of cellulose ethers. III. Critical use of thermodynamic parameters of activation for modeling the water penetration and drug release processes.

    PubMed

    Ferrero, Carmen; Massuelle, Danielle; Jeannerat, Damien; Doelker, Eric

    2013-09-10

    The two main purposes of this work were: (i) to critically consider the use of thermodynamic parameters of activation for elucidating the drug release mechanism from hydroxypropyl methylcellulose (HPMC) matrices, and (ii) to examine the effect of neutral (pH 6) and acidic (pH 2) media on the release mechanism. For this, caffeine was chosen as model drug and various processes were investigated for the effect of temperature and pH: caffeine diffusion in solution and HPMC gels, and drug release from and water penetration into the HPMC tablets. Generally, the kinetics of the processes was not significantly affected by pH. As for the temperature dependence, the activation energy (E(a)) values calculated from caffeine diffusivities were in the range of Fickian transport (20-40 kJ mol⁻¹). Regarding caffeine release from HPMC matrices, fitting the profiles using the Korsmeyer-Peppas model would indicate anomalous transport. However, the low apparent E(a) values obtained were not compatible with a swelling-controlled mechanism and can be assigned to the dimensional change of the system during drug release. Unexpectedly, negative apparent E(a) values were calculated for the water uptake process, which can be ascribed to the exothermic dissolution of water into the initially dry HPMC, the expansion of the matrix and the polymer dissolution. Taking these contributions into account, the true E(a) would fall into the range valid for Fickian diffusion. Consequently, a relaxation-controlled release mechanism can be dismissed. The apparent anomalous drug release from HPMC matrices results from a coupled Fickian diffusion-erosion mechanism, both at pH 6 and 2. PMID:23727289

  11. Thermodynamics of an accelerated expanding universe

    SciTech Connect

    Wang Bin; Gong Yungui; Abdalla, Elcio

    2006-10-15

    We investigate the laws of thermodynamics in an accelerating universe driven by dark energy with a time-dependent equation of state. In the case we consider that the physically relevant part of the Universe is that enveloped by the dynamical apparent horizon, we have shown that both the first law and second law of thermodynamics are satisfied. On the other hand, if the boundary of the Universe is considered to be the cosmological event horizon the thermodynamical description based on the definitions of boundary entropy and temperature breaks down. No parameter redefinition can rescue the thermodynamics laws from such a fate, rendering the cosmological event horizon unphysical from the point of view of the laws of thermodynamics.

  12. Utilization of activated carbon produced from fruit juice industry solid waste for the adsorption of Yellow 18 from aqueous solutions.

    PubMed

    Angin, Dilek

    2014-09-01

    The use of activated carbon obtained from sour cherry (Prunus cerasus L.) stones for the removal of a basic textile dye, which is Yellow 18, from aqueous solutions at different contact times, pH values and solution temperatures was investigated. The surface area and micropore volume of chemically modified activated carbon were 1704 m(2) g(-1) and 0.984 cm(3) g(-1), respectively. The experimental data indicated that the adsorption isotherms were well described by the Langmuir equilibrium isotherm equation and the calculated adsorption capacity was 75.76 mg g(-1) at 318 K. The adsorption kinetic of Yellow 18 obeys the pseudo-second-order kinetic model. The thermodynamic parameters were calculated to estimate the nature of adsorption. The activation energy of the system was calculated as 0.71-2.36 kJ/mol. According to these results, prepared activated carbon could be used as a low-cost adsorbent to compare with the commercial activated carbon for the removal of Yellow 18 from wastewater. PMID:24656549

  13. Microcystin-LR Adsorption by Activated Carbon.

    PubMed

    Pendleton, Phillip; Schumann, Russell; Wong, Shiaw Hui

    2001-08-01

    We use a selection of wood-based and coconut-based activated carbons to investigate the factors controlling the removal of the hepatotoxin microcystin-LR (m-LR) from aqueous solutions. The wood carbons contain both micropores and mesopores. The coconut carbons contain micropores only. Confirming previously published observations, we also find that the wood-based carbons adsorb more microcystin than the coconut-based carbons. From a combination of a judicious modification of a wood-based carbon's surface chemistry and of the solution chemistry, we demonstrate that both surface and solution chemistry play minor roles in the adsorption process, with the adsorbent surface chemistry exhibiting less influence than the solution chemistry. Conformational changes at low solution pH probably contribute to the observed increase in adsorption by both classes of adsorbent. At the solution pH of 2.5, the coconut-based carbons exhibit a 400% increased affinity for m-LR compared with 100% increases for the wood-based carbons. In an analysis of the thermodynamics of adsorption, using multiple temperature adsorption chromatography methods, we indicate that m-LR adsorption is an entropy-driven process for each of the carbons, except the most hydrophilic and mesoporous carbon, B1. In this case, exothermic enthalpy contributions to adsorption also exist. From our overall observations, since m-LR contains molecular dimensions in the secondary micropore width range, we demonstrate that it is important to consider both the secondary micropore and the mesopore volumes for the adsorption of m-LR from aqueous solutions. Copyright 2001 Academic Press. PMID:11446779

  14. Preparation of activated carbon from a renewable bio-plant of Euphorbia rigida by H 2SO 4 activation and its adsorption behavior in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Gerçel, Özgül; Özcan, Adnan; Özcan, A. Safa; Gerçel, H. Ferdi

    2007-03-01

    The use of activated carbon obtained from Euphorbia rigida for the removal of a basic textile dye, which is methylene blue, from aqueous solutions at various contact times, pHs and temperatures was investigated. The plant material was chemically modified with H 2SO 4. The surface area of chemically modified activated carbon was 741.2 m 2 g -1. The surface characterization of both plant- and activated carbon was undertaken using FTIR spectroscopic technique. The adsorption process attains equilibrium within 60 min. The experimental data indicated that the adsorption isotherms are well described by the Langmuir equilibrium isotherm equation and the calculated adsorption capacity of activated carbon was 114.45 mg g -1 at 40° C. The adsorption kinetics of methylene blue obeys the pseudo-second-order kinetic model and also followed by the intraparticle diffusion model up to 60 min. The thermodynamic parameters such as Δ G°, Δ H° and Δ S° were calculated to estimate the nature of adsorption. The activation energy of the system was calculated as 55.51 kJ mol -1. According to these results, prepared activated carbon could be used as a low-cost adsorbent to compare with the commercial activated carbon for the removal textile dyes from textile wastewater processes.

  15. A study of interaction potentials for H2 adsorption in Single Walled Nano Tubes: a possible way to more realistic predictions.

    PubMed

    Lerario, Marco; Magalhães, Alexandre L

    2014-06-01

    A comparative analysis of interaction potentials, classified according to the parametrization method, namely Lorentz-Berthelot rules, semi-empirical or ab initio calculations, found their energy depths to scale, respectively, to ca 30K, ca 40K, and ca 60K. We draw the Potential Energy Surfaces (PESs) for a hydrogen probe molecule inside a Carbon Nano-Tube (CNT): it is shown that the adsorption energy increases with the hard radius of the interaction potential and decreases as the CNT pore enlarges. This is valid just for low-medium pressures, when hydrogen repulsions are negligible. If not, adsorption is driven by H2-H2 hard radius despite all other parameters. Monte Carlo (MC) simulations, following the Gibbs Ensemble (GE) in high density conditions, confirm that the thermodynamic equilibrium of an order-disorder phase transition show no changes throughout any of the studied potentials. We also analyse, in the Grand Canonical (GC) ensemble, the geometric and structural characteristics of square lattice bundles of Single Walled Nano Tubes (SWNTs) with regard to their influence on adsorption storage. To do so, we develop a method for independently simulate inner or outer adsorption in infinitely long nanotube lattice systems. Our results suggest a pressure range for convenient H2 storage and enlighten the influence of CNT size on adsorption performance. In addition, larger CNTs are capable to host further hydrogen layers, but only at very high pressures. PMID:24893959

  16. Adsorption and excess fission xenon

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

    The adsorption of Xe and Kr on lunar soil 10084 was measured by a method that employs only very low fractions of monolayer coverage. Results are presented as parameters for calculation of the Henry constant for adsorption as a function of temperature. The adsorption potentials are about 3 kcal/mole for Kr and 5 kcal/mole for Xe; heating the sample in vacuum increased the Xe potential to nearly 7 kcal/mole. Henry constants at the characteristic lunar temperature are about 0.3 cu cm STP/g-atm. These data were applied to consider whether adsorption is important in producing the excess fission Xe effect characteristic of highland breccias. Sorption equilibrium with a transient lunar atmosphere vented fission Xe produces concentrations seven orders of magnitude lower than observed concentrations. Higher concentrations result because of the resistance of the regolith to upward diffusion of Xe. A diffusion coefficient of 0.26 sq cm/sec is estimated for this process.

  17. Impact of Adsorption on Scanning Electrochemical Microscopy Voltammetry and Implications for Nanogap Measurements.

    PubMed

    Tan, Sze-yin; Zhang, Jie; Bond, Alan M; Macpherson, Julie V; Unwin, Patrick R

    2016-03-15

    Scanning electrochemical microscopy (SECM) is a powerful tool that enables quantitative measurements of fast electron transfer (ET) kinetics when coupled with modeling predictions from finite-element simulations. However, the advent of nanoscale and nanogap electrode geometries that have an intrinsically high surface area-to-solution volume ratio realizes the need for more rigorous data analysis procedures, as surface effects such as adsorption may play an important role. The oxidation of ferrocenylmethyl trimethylammonium (FcTMA(+)) at highly oriented pyrolytic graphite (HOPG) is used as a model system to demonstrate the effects of reversible reactant adsorption on the SECM response. Furthermore, the adsorption of FcTMA(2+) species onto glass, which is often used to encapsulate ultramicroelectrodes employed in SECM, is also found to be important and affects the voltammetric tip response in a nanogap geometry. If a researcher is unaware of such effects (which may not be readily apparent in slow to moderate scan voltammetry) and analyzes SECM data assuming simple ET kinetics at the substrate and an inert insulator support around the tip, the result is the incorrect assignment of tip-substrate heights, kinetics, and thermodynamic parameters. Thus, SECM kinetic measurements, particularly in a nanogap configuration where the ET kinetics are often very fast (only just distinguishable from reversible), require that such effects are fully characterized. This is possible by expanding the number of experimental variables, including the voltammetric scan rate and concentration of redox species, among others. PMID:26877069

  18. Optimizing adsorption of fluoride from water by modified banana peel dust using response surface modelling approach

    NASA Astrophysics Data System (ADS)

    Bhaumik, Ria; Mondal, Naba Kumar

    2016-06-01

    The present work highlighted the effective application of banana peel dust (BPD) for removal of fluoride (F-) from aqueous solution. The effects of operating parameters such as pH, initial concentration, adsorbent dose, contact time, agitation speed and temperature were analysed using response surface methodology. The significance of independent variables and their interactions were tested by the analysis of variance and t test statistics. Experimental results revealed that BPD has higher F- adsorption capacity (17.43, 26.31 and 39.5 mg/g). Fluoride adsorption kinetics followed pseudo-second-order model with high correlation of coefficient value (0.998). On the other hand, thermodynamic data suggest that adsorption is favoured at lower temperature, exothermic in nature and enthalpy driven. The adsorbents were characterised through scanning electron microscope, Fourier transform infrared spectroscopy and point of zero charges (pHZPC) ranges from pH 6.2-8.2. Finally, error analysis clearly demonstrates that all three adsorbents are well fitted with Langmuir isotherm compared to the other isotherm models. The reusable properties of the material support further development for commercial application purpose.

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

    SciTech Connect

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

    2013-10-15

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

  20. Adsorption of thorium(IV) from simulated radioactive solutions using a novel electrospun PVA/TiO2/ZnO nanofiber adsorbent functionalized with mercapto groups: Study in single and multi-component systems

    NASA Astrophysics Data System (ADS)

    Alipour, Dariush; Keshtkar, Ali Reza; Moosavian, Mohammad Ali

    2016-03-01

    The novel polyvinyl alcohol/titanium oxide/zinc oxide (PVA/TiO2/ZnO) nanofiber adsorbent functionalized with 3-mercaptopropyltrimethoxysilane (TMPTMS) was prepared by electrospinning method and its potential was investigated for the adsorption of thorium from single and multi-metal aqueous solutions. The prepared adsorbent was characterized by FTIR, SEM and BET analysis. The influences of different operational parameters such as pH, ionic strength, equilibrium time, initial concentration and temperature were studied in batch mode. Investigation of ionic strength effect showed that the addition of NaNO3 to metal solution has a slight effect on the thorium adsorption, whereas pH value has a serious effect on the thorium adsorption at pH values lower than 4. The double-exponential model described the adsorption of Th(IV) ions much better than other kinetic models within both the single and multi-component systems. Among various isotherm models used, the equilibrium data of Th(IV) conformed the Langmuir isotherm in the single system, while those were best fitted by Dubinin-Radushkevich (D-R) isotherm in multi-component system. Thermodynamic parameters such as ΔH°, ΔS°, and ΔG° indicated that the nature of adsorption process was spontaneous, endothermic and thermodynamically favored. The inhibitory effect of other metal ions on the adsorption capacity of Th(IV) was in order of Al(III) > Cu(II) > Cd(II) > Ni(II) > U(VI) > Fe(II).

  1. Thermodynamics: Frontiers and Foundations.

    2009-07-27

    Version 00 Dr. J.D. Lewins has now released the following new book for free distribution: Thermodynamics: Frontiers and Foundations, Preface by Sir Alan Cottrell Introduction 1. Four-Square Foundations: The Laws of Thermodynamics 2. Maximum Entropy and Minimum Energy: The Master Functions and Equations 3. Ideal Gases and their Applications 4. Real Fluids and Some Applications 5. Van der Waals: A Model for Real Fluids 6. Surface Tension: Bubbles and Drops 7. Inert and Reactive Mixtures;more » An introduction to Chemical Thermodynamics 8. Radiation Thermodynamics: Solar Power Potential 9. Outposts of the Empire 10. A Glimpse into Statistical Thermodynamics Envoi« less

  2. Thermodynamics: Frontiers and Foundations.

    SciTech Connect

    JEFFERY,; LEWINS, D.

    2009-07-27

    Version 00 Dr. J.D. Lewins has now released the following new book for free distribution: Thermodynamics: Frontiers and Foundations, Preface by Sir Alan Cottrell Introduction 1. Four-Square Foundations: The Laws of Thermodynamics 2. Maximum Entropy and Minimum Energy: The Master Functions and Equations 3. Ideal Gases and their Applications 4. Real Fluids and Some Applications 5. Van der Waals: A Model for Real Fluids 6. Surface Tension: Bubbles and Drops 7. Inert and Reactive Mixtures; An introduction to Chemical Thermodynamics 8. Radiation Thermodynamics: Solar Power Potential 9. Outposts of the Empire 10. A Glimpse into Statistical Thermodynamics Envoi

  3. Thermodynamics of Metal Composites Based on Polyvinylchloride

    NASA Astrophysics Data System (ADS)

    Kolupaev, B. B.; Lyashuk, T. G.; Kolupaev, B. S.

    2014-03-01

    We present the results of experimental investigations of the thermodynamic properties of composites based on polyvinylchloride and copper nanoparticles obtained by electrical explosion of the conductor. It has been established that the thermodynamic potentials H and G in determining the system parameters (s, T, p, V) depend nonlinearly on the temperature and content of the filler. β- and α-relaxation transitions as a general phenomenon characteristic of the fluctuation structure of polyvinylchloride are observed thereby. The introduction of a nanodispersed metal filler into polyvinylchloride increases the amount of activation energy and the time of "settled" life of the structural elements, changing the thermodynamic stability of the composite.

  4. Assessing the Adsorption Properties of Shales

    NASA Astrophysics Data System (ADS)

    Pini, R.

    2014-12-01

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

  5. Thermodynamic Entropy as a Noether Invariant.

    PubMed

    Sasa, Shin-Ichi; Yokokura, Yuki

    2016-04-01

    We study a classical many-particle system with an external control represented by a time-dependent extensive parameter in a Lagrangian. We show that thermodynamic entropy of the system is uniquely characterized as the Noether invariant associated with a symmetry for an infinitesimal nonuniform time translation t→t+ηℏβ, where η is a small parameter, ℏ is the Planck constant, β is the inverse temperature that depends on the energy and control parameter, and trajectories in the phase space are restricted to those consistent with quasistatic processes in thermodynamics. PMID:27104690

  6. Thermodynamic Entropy as a Noether Invariant

    NASA Astrophysics Data System (ADS)

    Sasa, Shin-ichi; Yokokura, Yuki

    2016-04-01

    We study a classical many-particle system with an external control represented by a time-dependent extensive parameter in a Lagrangian. We show that thermodynamic entropy of the system is uniquely characterized as the Noether invariant associated with a symmetry for an infinitesimal nonuniform time translation t →t +η ℏβ , where η is a small parameter, ℏ is the Planck constant, β is the inverse temperature that depends on the energy and control parameter, and trajectories in the phase space are restricted to those consistent with quasistatic processes in thermodynamics.

  7. Equilibrium, Thermodynamics, and Kinetic Sorption Studies for the Removal of Coomassie Brilliant Blue on Wheat Bran as a Low-Cost Adsorbent

    PubMed Central

    Ata, Sadia; Imran Din, Muhammad; Rasool, Atta; Qasim, Imran; Ul Mohsin, Ijaz

    2012-01-01

    The sorption studies of coomassie brilliant blue (CBB) from aqueous solution have been carried out on wheat bran (WB). Coomassie brilliant blue on wheat bran was used to study the adsorption behavior under various parameters such as pH, dosage amount, and contact time. It was observed that under optimized conditions up to 95.70% dye could be removed from solution onto WB. Langmuir and Freundlich adsorption isotherms were used to elaborate the results. Freundlich model was found to be fitted well and favored multilayer adsorption. The Freundlich constants n and KF were determined as 0.53 and 2.5 × 10−4. Thermodynamic parameters such as ΔG, ΔH, and ΔS studied were taking into account, showed spontaneous and favorable reaction for coomassie brilliant blue on wheat bran. The maximum adsorption capacity qm was found to be 6.410 mg/g. The investigations show that non treated WB is a low-cost adsorbent for the removal of dyes from textile industry effluents. PMID:22567559

  8. Synthesis and properties of Fe3O4-activated carbon magnetic nanoparticles for removal of aniline from aqueous solution: equilibrium, kinetic and thermodynamic studies

    PubMed Central

    2013-01-01

    In this study, powder activated carbon (PAC) and magnetic nanoparticles of iron (III) oxide were used for synthesis of Fe3O4-activated carbon magnetic nanoparticles (AC-Fe3O4 MNPs) as an adsorbent for the removal of aniline. The characteristics of adsorbent were evaluated by SEM, TEM, XRD and BET. Also, the impact of different parameters such as pH, contact time, adsorbent dosage, aniline initials concentration and solution temperature were studied. The experimental data investigated by Langmuir and Freundlich adsorption isotherms and two models kinetically of pseudo first-order and pseudo second-order. The results indicated that the adsorption followed Langmuir and pseudo second-order models with correlation r2 > 0.98 and r2 > 0.99, respectively. The equilibrium time was obtained after 5 h. According to Langmuir model, the maximum adsorption capacity was 90.91 mg/g at pH = 6, and 20°C. The thermodynamic parameters indicated that adsorption of aniline on magnetic activated carbon was exothermic and spontaneous. This synthesized AC-Fe3O4 MNPs due to have advantages such as easy and rapid separation from solution could be applied as an adsorbent effective for removal of pollutants such as aniline from water and wastewater. PMID:23414171

  9. Thermodynamics of the Earth

    NASA Astrophysics Data System (ADS)

    Stacey, Frank D.

    2010-04-01

    Applications of elementary thermodynamic principles to the dynamics of the Earth lead to robust, quantitative conclusions about the tectonic effects that arise from convection. The grand pattern of motion conveys deep heat to the surface, generating mechanical energy with a thermodynamic efficiency corresponding to that of a Carnot engine operating over the adiabatic temperature gradient between the heat source and sink. Referred to the total heat flux derived from the Earth's silicate mantle, the efficiency is 24% and the power generated, 7.7 × 1012 W, causes all the material deformation apparent as plate tectonics and the consequent geological processes. About 3.5% of this is released in seismic zones but little more than 0.2% as seismic waves. Even major earthquakes are only localized hiccups in this motion. Complications that arise from mineral phase transitions can be used to illuminate details of the motion. There are two superimposed patterns of convection, plate subduction and deep mantle plumes, driven by sources of buoyancy, negative and positive respectively, at the top and bottom of the mantle. The patterns of motion are controlled by the viscosity contrasts (>104 : 1) at these boundaries and are self-selected as the least dissipative mechanisms of heat transfer for convection in a body with very strong viscosity variation. Both are subjects of the thermodynamic efficiency argument. Convection also drives the motion in the fluid outer core that generates the geomagnetic field, although in that case there is an important energy contribution by compositional separation, as light solute is rejected by the solidifying inner core and mixed into the outer core, a process referred to as compositional convection. Uncertainty persists over the core energy balance because thermal conduction is a drain on core energy that has been a subject of diverse estimates, with attendant debate over the need for radiogenic heat in the core. The geophysical approach to

  10. Adsorption Refrigeration System

    SciTech Connect

    Wang, Kai; Vineyard, Edward Allan

    2011-01-01

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

  11. Adsorption equilibrium of binary methane/ethane mixtures in BPL activated carbon: isotherms and calorimetric heats of adsorption.

    PubMed

    He, Yufeng; Yun, Jeong-Ho; Seaton, Nigel A

    2004-08-01

    The adsorption of pure methane and ethane in BPL activated carbon has been measured at temperatures between 264 and 373 K and at pressures up to 3.3 MPa with a bench-scale high-pressure open-flow apparatus. The same apparatus was used to measure the adsorption of binary methane/ethane mixtures in BPL at 301.4 K and at pressures up to 2.6 MPa. Thermodynamic consistency tests demonstrate that the data are thermodynamically consistent. In contrast to two sets of data previously published, we found that the adsorption of binary methane/ethane in BPL behaves ideally (in the sense of obeying ideal adsorbed solution theory, IAST) throughout the pressure and gas-phase composition range studied. A Tian-Calvet type microcalorimeter was used to measure low-pressure isotherms, the isosteric heats of adsorption of pure methane and ethane in BPL activated carbon, and the individual heats of adsorption in binary mixtures, at 297 K and at pressures up to 100 kPa. The mixture heats of adsorption were consistent with IAST. PMID:15274571

  12. Highly selective and efficient removal of lead with magnetic nano-adsorbent: Multivariate optimization, isotherm and thermodynamic studies.

    PubMed

    Khani, Rouhollah; Sobhani, Sara; Beyki, Mostafa Hossein

    2016-03-15

    2-Hydroxyethylammonium sulfonate immobilized on γ-Fe2O3 nanoparticles (γ-Fe2O3-2-HEAS) was synthesized by the reaction of n-butylsulfonated γ-Fe2O3 with ethanolamine. The structure of the resulting product was confirmed by fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD) spectrometry, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), elemental analysis, N2 adsorption-desorption and vibrating sample magnetometer (VSM) techniques. The supported ionic liquid on γ-Fe2O3 was applied as a new and green adsorbent to remove Pb(II) from aqueous solution. The effect of adsorption parameters such as pH, shaking time and amount of the adsorbent were investigated using two level three factor (2(3)) full factorial central composite design with the help of Design-Expert, Stat-Ease Inc. version 9.0 software. The significance of independent variables and their interactions were tested by means of the analysis of variance (ANOVA) with 95% confidence limits (α=0.05). The thermodynamic parameters of the adsorption process are estimated. It is found that the process is exothermic and spontaneous. The Langmuir and Freundlich models have been also applied to evaluate the removal efficiency and the data were correlated well with the Freundlich model. PMID:26724702

  13. Adsorption treatment and recovery of the hazardous dye, Brilliant Blue FCF, over bottom ash and de-oiled soya.

    PubMed

    Gupta, V K; Mittal, Alok; Krishnan, Lisha; Mittal, Jyoti

    2006-01-01

    Two waste materials-bottom ash, a power plant waste, and de-oiled soya, an agricultural waste-are meticulously and successfully used as adsorbent for the removal and recovery of a hazardous triphenylmethane dye, Brilliant Blue FCF. Both the materials were characterized by chemical analysis, IR, DTA, SEM and XRD studies. Their physical characteristics like surface area, porosity, density and loss on ignition were also determined. The adsorption of the dye over both materials was achieved under different pH, adsorbate concentration, sieve size, adsorbent dosage, contact time and temperature, etc. conditions. For both the systems Langmuir and Freundlich adsorption isotherm models were applied and, based on these models, useful thermodynamic parameters were calculated. For both the adsorbents, the kinetic measurements indicate that the adsorption process follows first order kinetics and film diffusion and particle diffusion mechanisms are operative at lower and higher concentrations, respectively, in each case. By percolating the dye solution through fixed-bed columns the bulk removal of the Brilliant Blue FCF was carried out and necessary parameters were determined to find out the percentage saturation of both the columns. Recovery of Brilliant Blue FCF was made by eluting dilute NaOH of pH 11 through each column. PMID:16040036

  14. Experimental and Quantum Studies on Adsorption and Corrosion Inhibition Effect of Imidazole Derivatives on N80 Steel in Hydrochloric Acid

    NASA Astrophysics Data System (ADS)

    Yadav, M.; Kumar, Sumit; Sharma, Dipti; Yadav, P. N.

    2013-12-01

    The inhibition effect of synthesized N‧-(phenylmethylidene)-2-(2-methyl-1H-benzimidazol-1-yl)acetohydrazides, N‧-(4-methylphenylmethylidene)-2-(2-methyl-1H-benzimidazol-1-yl)acetohydrazides, and N‧-(4-methoxyphenylmethylidene)-2-(2-methyl-1H-benzimidazol-1-yl)acetohydrazides on the corrosion behaviour of N80 steel in 15% hydrochloric acid solution was investigated using weight loss, potentiostatic polarization and electrochemical impedance spectroscopy methods. The inhibition efficiency increased as the concentration of the inhibitors was increased. The effect of temperature on corrosion inhibition was investigated by weight loss method and thermodynamic parameters were calculated. Potentiodynamic polarization measurements show that all the three studied inhibitors act as mixed inhibitor. The adsorption of inhibitors on N80 steel surface obeys Langmuir adsorption isotherm. The structure of inhibitors was optimized using semiemperical AM1 method. Theoretical parameters such as the highest occupied molecular orbital (EHOMO), lowest unoccupied molecular orbital (ELUMO) energy levels, energy gap (ΔE = ELUMO - EHOMO), dipole moment (μ), global hardness (γ), softness (σ), binding energy, molecular surface area and the fraction of electrons transferred (ΔN) were calculated and the adsorption mechanism was discussed. Scanning electron microscopy was used to characterize the surface marphology of the N80 steel.

  15. Uniform Cu{sub 2}Cl(OH){sub 3} hierarchical microspheres: A novel adsorbent for methylene blue adsorptive removal from aqueous solution

    SciTech Connect

    Wei, Wei; Gao, Pin; Xie, Jimin Zong, Sekai; Cui, Henglv; Yue, Xuejie

    2013-08-15

    Using the solution phase method without any surfactants or templates, the hierarchical of Cu{sub 2}Cl(OH){sub 3} microspheres were synthesized by freeze drying. The size and surface area of the microspheres are ca. 1–2 µm and 76.61 m{sup 2} g{sup −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. - Graphical abstract: The single-crystalline hierarchical Cu{sub 2}Cl(OH){sub 3} spheres can be prepared for the first time by using a template-free process through freeze-drying. Meanwhile, the hierarchical spheres exhibited high adsorption capacity to methylene blue. Display Omitted - Highlights: • Cu{sub 2}Cl(OH){sub 3} microspheres were successfully synthesized through a freeze drying process. • A possible formation mechanism of hierarchical microspheres was presented. • The Cu{sub 2}Cl(OH){sub 3} microspheres have high methylene blue adsorption capacity. • Methylene blue adsorption is a spontaneous and exothermic process. • The adsorption mechanism of microspheres onto dye was proposed in detail.

  16. Adsorption and Quantum Chemical Studies on the Inhibition Potentials of Some Thiosemicarbazides for the Corrosion of Mild Steel in Acidic Medium

    PubMed Central

    Ebenso, Eno E.; Isabirye, David A.; Eddy, Nnabuk O.

    2010-01-01

    Three thiosemicarbazides, namely 2-(2-aminophenyl)-N phenylhydrazinecarbothioamide (AP4PT), N,2-diphenylhydrazinecarbothioamide (D4PT) and 2-(2-hydroxyphenyl)-N-phenyl hydrazinecarbothioamide (HP4PT), were investigated as corrosion inhibitors for mild steel in H2SO4 solution using gravimetric and gasometric methods. The results revealed that they all inhibit corrosion and their % inhibition efficiencies (%IE) follow the order: AP4PT > HP4PT > D4PT. The %IE obtained from the gravimetric and gasometric experiments were in good agreement. The thermodynamic parameters obtained support a physical adsorption mechanism and the adsorption followed the Langmuir adsorption isotherm. Some quantum chemical parameters were calculated using different methods and correlated with the experimental %IE. Quantitative structure activity relationship (QSAR) approach was used on a composite index of some quantum chemical parameters to characterize the inhibition performance of the studied molecules. The results showed that the %IE were closely related to some of the quantum chemical parameters, but with varying degrees. The calculated/theoretical %IE of the molecules were found to be close to their experimental %IE. The local reactivity has been studied through the Fukui and condensed softness indices in order to predict both the reactive centers and to know the possible sites of nucleophilic and electrophilic attacks. PMID:20640164

  17. One-step synthesized calcium phosphate-based material for the removal of alizarin S dye from aqueous solutions: isothermal, kinetics, and thermodynamics studies

    NASA Astrophysics Data System (ADS)

    Adeogun, Abideen Idowu; Babu, Ramesh Balakrishnan

    2015-07-01

    Calcium phosphate hydroxyapatite (Ca-Hap) synthesized from CaCO3 and H3PO5, it was characterized by scanning electron microscopy, Fourier transform infrared, and X-ray diffraction. The Ca-Hap was used for the removal of Alizarin Red S dye from its aqueous solution. The kinetics, equilibrium, and thermodynamic of the adsorption of the dye onto the Ca-Hap were investigated. The effects of contact time, initial dye concentration, pH as well as temperature on adsorption capacity of Ca-Hap were studied. Experimental data were analyzed using six model equations: Langmuir, Freudlinch, Redlich-Peterson, Temkin, Dubinin-Radushkevich, and Sips isotherms and it was found that the data fitted well with Sips and Dubinin-Radushkevich isotherm models. Pseudo-first-order, pseudo-second-order, Elovic, and Avrami kinetic models were used to test the experimental data in order to elucidate the kinetic adsorption process and it was found that pseudo-second-order model best fit the data. The calculated thermodynamics parameters (∆G°, ∆H° and ∆S°) indicated that the process is spontaneous and endothermic in nature.

  18. Rapid adsorption of toxic Pb(II) ions from aqueous solution using multiwall carbon nanotubes synthesized by microwave chemical vapor deposition technique.

    PubMed

    Mubarak, Nabisab Mujawar; Sahu, Jaya Narayan; Abdullah, Ezzat Chan; Jayakumar, Natesan Subramanian

    2016-07-01

    Multiwall carbon nanotubes (MWCNTs) were synthesized using a tubular microwave chemical vapor deposition technique, using acetylene and hydrogen as the precursor gases and ferrocene as catalyst. The novel MWCNT samples were tested for their performance in terms of Pb(II) binding. The synthesized MWCNT samples were characterized using Fourier Transform Infrared (FT-IR), Brunauer, Emmett and Teller (BET), Field Emission Scanning Electron Microscopy (FESEM) analysis, and the adsorption of Pb(II) was studied as a function of pH, initial Pb(II) concentration, MWCNT dosage, agitation speed, and adsorption time, and process parameters were optimized. The adsorption data followed both Freundlich and Langmuir isotherms. On the basis of the Langmuir model, Qmax was calculated to be 104.2mg/g for the microwave-synthesized MWCNTs. In order to investigate the dynamic behavior of MWCNTs as an adsorbent, the kinetic data were modeled using pseudo first-order and pseudo second-order equations. Different thermodynamic parameters, viz., ∆H(0), ∆S(0) and ∆G(0) were evaluated and it was found that the adsorption was feasible, spontaneous and endothermic in nature. The statistical analysis revealed that the optimum conditions for the highest removal (99.9%) of Pb(II) are at pH5, MWCNT dosage 0.1g, agitation speed 160r/min and time of 22.5min with the initial concentration of 10mg/L. Our results proved that microwave-synthesized MWCNTs can be used as an effective Pb(II) adsorbent due to their high adsorption capacity as well as the short adsorption time needed to achieve equilibrium. PMID:27372128

  19. Predicting RNA pseudoknot folding thermodynamics.

    PubMed

    Cao, Song; Chen, Shi-Jie

    2006-01-01

    Based on the experimentally determined atomic coordinates for RNA helices and the self-avoiding walks of the P (phosphate) and C4 (carbon) atoms in the diamond lattice for the polynucleotide loop conformations, we derive a set of conformational entropy parameters for RNA pseudoknots. Based on the entropy parameters, we develop a folding thermodynamics model that enables us to compute the sequence-specific RNA pseudoknot folding free energy landscape and thermodynamics. The model is validated through extensive experimental tests both for the native structures and for the folding thermodynamics. The model predicts strong sequence-dependent helix-loop competitions in the pseudoknot stability and the resultant conformational switches between different hairpin and pseudoknot structures. For instance, for the pseudoknot domain of human telomerase RNA, a native-like and a misfolded hairpin intermediates are found to coexist on the (equilibrium) folding pathways, and the interplay between the stabilities of these intermediates causes the conformational switch that may underlie a human telomerase disease. PMID:16709732

  20. Coal surface structure and thermodynamics. Final report

    SciTech Connect

    Larsen, J.W.; Wernett, P.C.; Glass, A.S.; Quay, D.; Roberts, J.

    1994-05-01

    Coals surfaces were studied using static surface adsorption measurements, low angle x-ray scattering (LAXS), inverse gas chromatography (IGC) and a new {sup 13}C NMR relaxation technique. A comparison of surface areas determined by hydrocarbon gas adsorption and LAXS led to the twin conclusions that the hydrocarbons had to diffuse through the solid to reach isolated pores and that the coal pores do not form interconnected networks, but are largely isolated. This conclusion was confirmed when IGC data for small hydrocarbons showed no discontinuities in their size dependence as usually observed with porous solids. IGC is capable of providing adsorption thermodynamics of gases on coal surfaces. The interactions of non-polar molecules and coal surfaces are directly proportioned to the gas molecular polarizability. For bases, the adsorption enthalpy is equal to the polarizability interaction plus the heat of hydrogen bond formation with phenol. Amphoteric molecules have more complex interactions. Mineral matter can have highly specific effects on surface interactions, but with most of the molecules studied is not an important factor.

  1. Removal of Direct Red 12B by garlic peel as a cheap adsorbent: Kinetics, thermodynamic and equilibrium isotherms study of removal

    NASA Astrophysics Data System (ADS)

    Asfaram, A.; Fathi, M. R.; Khodadoust, S.; Naraki, M.

    2014-06-01

    The removal of dyes from industrial waste is very important from health and hygiene point of view and for environmental protection. In this work, efficiency and performance of garlic peel (GP) adsorbent for the removal of Direct Red 12B (DR12B) from wastewater was investigated. The influence of variables including pH, concentration of the dye and amount of adsorbent, particle size, contact time and temperature on the dye removal has been investigated. It was observed that the pseudo-second-order kinetic model fits better with good correlation coefficient and the equilibrium data fitted well with the Langmuir model. More than 99% removal efficiency was obtained within 25 min at adsorbent dose of 0.2 g per 50 ml for initial dye concentration of 50 mg L-1. 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 DR12B adsorption.

  2. Modeling the Adsorption of Oxalate onto Montmorillonite.

    PubMed

    Ramos, M Elena; Emiroglu, Caglayan; García, David; Sainz-Díaz, C Ignacio; Huertas, F Javier

    2015-11-01

    In this work, a multiscale modeling of the interaction of oxalate with clay mineral surfaces from macroscale thermodynamic equilibria simulations to atomistic calculations is presented. Previous results from macroscopic adsorption data of oxalate on montmorillonite in 0.01 M KNO3 media at 25 °C within the pH range from 2.5 to 9 have been used to develop a surface complexation model. The experimental adsorption edge data were fitted using the triple-layer model (TLM) with the aid of the FITEQL 4.0 computer program. Surface complexation of oxalate is described by two reactions: >AlOH + Ox(2-) + 2H(+) = >AlOxH + H2O (log K = 14.39) and >AlOH + Ox(2-) + H(+) = >AlOx(-) + H2O (log K = 10.39). The monodentate complex >AlOxH dominated adsorption below pH 4, and the bidentate complex >AlOx(-) was predominant at higher pH values. Both of the proposed inner-sphere oxalate species are qualitatively consistent with previously published diffuse reflectance FTIR spectroscopic results for oxalate on montmorillonite edge surface (Chem. Geol. 2014, 363, 283-292). Atomistic computational studies have been performed to understand the interactions at the molecular level between adsorbates and mineral surface, showing the atomic structures and IR frequency shifts of the adsorption complexes of oxalate with the edge surface of a periodic montmorillonite model. PMID:26444928

  3. Exhaustively sampling peptide adsorption with metadynamics.

    PubMed

    Deighan, Michael; Pfaendtner, Jim

    2013-06-25

    Simulating the adsorption of a peptide or protein and obtaining quantitative estimates of thermodynamic observables remains challenging for many reasons. One reason is the dearth of molecular scale experimental data available for validating such computational models. We also lack simulation methodologies that effectively address the dual challenges of simulating protein adsorption: overcoming strong surface binding and sampling conformational changes. Unbiased classical simulations do not address either of these challenges. Previous attempts that apply enhanced sampling generally focus on only one of the two issues, leaving the other to chance or brute force computing. To improve our ability to accurately resolve adsorbed protein orientation and conformational states, we have applied the Parallel Tempering Metadynamics in the Well-Tempered Ensemble (PTMetaD-WTE) method to several explicitly solvated protein/surface systems. We simulated the adsorption behavior of two peptides, LKα14 and LKβ15, onto two self-assembled monolayer (SAM) surfaces with carboxyl and methyl terminal functionalities. PTMetaD-WTE proved effective at achieving rapid convergence of the simulations, whose results elucidated different aspects of peptide adsorption including: binding free energies, side chain orientations, and preferred conformations. We investigated how specific molecular features of the surface/protein interface change the shape of the multidimensional peptide binding free energy landscape. Additionally, we compared our enhanced sampling technique with umbrella sampling and also evaluated three commonly used molecular dynamics force fields. PMID:23706011

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

    PubMed

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

    2016-01-01

    Adsorption plays a significant role in removing hydrophobic 17β-estradiol (E2) from wastewater. Batch experiments were conducted to compare the adsorption of E2 onto activated aerobic granular sludge (AGS) and activated sludge (AS), and features evaluated included the adsorption kinetics, thermodynamics, and influence of other environmental factors. By using a non-chemical wet-heat technique, both AGS and AS were treated to inactivated status. Then, after loading E2, the adsorption equilibrium capacity of the AGS was found to be greater than that of the AS at the same initial concentration of E2. Moreover, both the adsorption processes corresponded to a pseudo-second-order kinetic model; the adsorption rate constant of AGS was found to be higher and the half-adsorption time was shorter than that of AS. Next, evaluations of adsorption isotherms and thermodynamics indicated that the adsorption process was mainly a physical process. Lower temperatures facilitated a higher equilibrium adsorption capacity. However, the adsorption binding sites of AGS were distributed more uniformly at higher temperature, in contrast to the distribution found for AS. Finally, acidic conditions and an appropriate ionic strength (0.4 mol/L) were found to be particularly conducive to the adsorption process. Overall, the results showed that AGS has the potential to adsorb E2 with significant efficiency, thereby offering a new and more efficient means of treating E2 and trace oestrogens in wastewater. PMID:26209151

  5. Adsorption of n-alkane vapours at the water surface.

    PubMed

    Biscay, Frédéric; Ghoufi, Aziz; Malfreyt, Patrice

    2011-06-21

    Monte Carlo simulations are reported here to predict the surface tension of the liquid-vapour interface of water upon adsorption of alkane vapours (methane to hexane). A decrease of the surface tension has been established from n-pentane. A correlation has been evidenced between the decrease of the surface tension and the absence of specific arrangement at the water surface for n-pentane and n-hexane. The thermodynamic stability of the adsorption layer and the absence of film for longer alkanes have been checked through the calculation of a potential of mean force. This complements the work recently published [Ghoufi et al., Phys. Chem. Chem. Phys., 2010, 12, 5203] concerning the adsorption of methane at the water surface. The decrease of the surface tension has been interpreted in terms of the degree of hydrogen bonding of water molecules at the liquid-vapour interface upon adsorption. PMID:21584320

  6. Dissipation Bound for Thermodynamic Control

    NASA Astrophysics Data System (ADS)

    Machta, Benjamin B.

    2015-12-01

    Biological and engineered systems operate by coupling function to the transfer of heat and/or particles down a thermal or chemical gradient. In idealized deterministically driven systems, thermodynamic control can be exerted reversibly, with no entropy production, as long as the rate of the protocol is made slow compared to the equilibration time of the system. Here we consider fully realizable, entropically driven systems where the control parameters themselves obey rules that are reversible and that acquire directionality in time solely through dissipation. We show that when such a system moves in a directed way through thermodynamic space, it must produce entropy that is on average larger than its generalized displacement as measured by the Fisher information metric. This distance measure is subextensive but cannot be made small by slowing the rate of the protocol.

  7. Dissipation Bound for Thermodynamic Control.

    PubMed

    Machta, Benjamin B

    2015-12-31

    Biological and engineered systems operate by coupling function to the transfer of heat and/or particles down a thermal or chemical gradient. In idealized deterministically driven systems, thermodynamic control can be exerted reversibly, with no entropy production, as long as the rate of the protocol is made slow compared to the equilibration time of the system. Here we consider fully realizable, entropically driven systems where the control parameters themselves obey rules that are reversible and that acquire directionality in time solely through dissipation. We show that when such a system moves in a directed way through thermodynamic space, it must produce entropy that is on average larger than its generalized displacement as measured by the Fisher information metric. This distance measure is subextensive but cannot be made small by slowing the rate of the protocol. PMID:26764981

  8. Probing protein adsorption on a nanoparticle surface using second harmonic light scattering.

    PubMed

    Das, A; Chakrabarti, A; Das, P K

    2016-09-21

    A new application of second harmonic light scattering to probe protein physisorption on a gold nanoparticle surface in aqueous buffer is reported. The free energies of adsorption, the number of protein molecules adsorbed on the surface and the binding affinity of a moderate size protein, alcohol dehydrogenase (ADH), and a small protein, insulin, have been determined using the change in the second harmonic scattered light signal as a function of binding. Four different size gold nanoparticles from 15 to 60 nm were used to determine the effect of size on the free energy change, the affinity constant and the number of protein molecules adsorbed on the surface. All were shown to increase with an increase in size. The binding can be reversed by centrifugation, and the protein molecules can be desorbed quantitatively. The application of this method for studying thermodynamic parameters of weakly interacting biomolecules with nanoparticles for nanoparticle based diagnostic and therapeutic formulations is important. PMID:27530608

  9. Simulation of a High Efficiency Multi-bed Adsorption Heat Pump

    SciTech Connect

    TeGrotenhuis, Ward E.; Humble, Paul H.; Sweeney, J. B.

    2012-05-01

    Attaining high energy efficiency with adsorption heat pumps is challenging due to thermodynamic losses that occur when the sorbent beds are thermally cycled without effective heat recuperation. The multi-bed concept described here effectively transfers heat from beds being cooled to beds being heated, which enables high efficiency in thermally driven heat pumps. A simplified lumped-parameter model and detailed finite element analysis are used to simulate the performance of an ammonia-carbon sorption compressor, which is used to project the overall heat pump coefficient of performance. The effects of bed geometry and number of beds on system performance are explored, and the majority of the performance benefit is obtained with four beds. Results indicate that a COP of 1.24 based on heat input is feasible at AHRI standard test conditions for residential HVAC equipment. When compared on a basis of primary energy input, performance equivalent to SEER 13 or 14 are theoretically attainable with this system.

  10. Statistical physics studies of multilayer adsorption isotherm in food materials and pore size distribution

    NASA Astrophysics Data System (ADS)

    Aouaini, F.; Knani, S.; Ben Yahia, M.; Ben Lamine, A.

    2015-08-01

    Water sorption isotherms of foodstuffs are very important in different areas of food science engineering such as for design, modeling and optimization of many processes. The equilibrium moisture content is an important parameter in models used to predict changes in the moisture content of a product during storage. A formulation of multilayer model with two energy levels was based on statistical physics and theoretical considerations. Thanks to the grand canonical ensemble in statistical physics. Some physicochemical parameters related to the adsorption process were introduced in the analytical model expression. The data tabulated in literature of water adsorption at different temperatures on: chickpea seeds, lentil seeds, potato and on green peppers were described applying the most popular models applied in food science. We also extend the study to the newest proposed model. It is concluded that among studied models the proposed model seems to be the best for description of data in the whole range of relative humidity. By using our model, we were able to determine the thermodynamic functions. The measurement of desorption isotherms, in particular a gas over a solid porous, allows access to the distribution of pore size PSD.

  11. ARSENIC TREATMENT BY ADSORPTIVE TECHNOLOGY

    EPA Science Inventory

    Presentation will discuss the removal of arsenic from drinking water using the adsorptive media treatment process. Fundamental information is provided on the design and operation of adsorptive media technology including the selection of the adsorptive media. The information cites...

  12. A Simple Adsorption Experiment

    ERIC Educational Resources Information Center

    Guirado, Gonzalo; Ayllon, Jose A.

    2011-01-01

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

  13. A Computational Framework for Mineralogical Thermodynamics

    NASA Astrophysics Data System (ADS)

    Chust, Thomas Christian; Steinle-Neumann, Gerd; Bunge, Hans-Peter

    2013-04-01

    Determining the compositional, thermodynamic and mechanical properties of the polycrystalline aggregates in the mantle is an essential tool for geodynamic and seismological applications. We have developed an efficient, object-oriented, extensible software framework to facilitate such computations: Taking a database of thermodynamic model parameters for different minerals, a stable phase assemblage can be determined using Gibbs energy minimization at any given pressure and temperature. The program also computes densities, elastic moduli, heat capacities and thermal expansivities to name a few possibilities. These outputs can be transferred to control parameters of the mass and energy balance equations of a mantle convection model or of the propagation equation for seismic waves.

  14. Predictive thermodynamics for ionic solids and liquids.

    PubMed

    Glasser, Leslie; Jenkins, H Donald Brooke

    2016-08-21

    The application of thermodynamics is simple, even if the theory may appear intimidating. We describe tools, developed over recent years, which make it easy to estimate often elusive thermodynamic parameter values, generally (but not exclusively) for ionic materials, both solid and liquid, as well as for their solid hydrates and solvates. The tools are termed volume-based thermodynamics (VBT) and thermodynamic difference rules (TDR), supplemented by the simple salt approximation (SSA) and single-ion values for volume, Vm, heat capacity, , entropy, , formation enthalpy, ΔfH°, and Gibbs formation energy, ΔfG°. These tools can be applied to provide values of thermodynamic and thermomechanical properties such as standard enthalpy of formation, ΔfH°, standard entropy, , heat capacity, Cp, Gibbs function of formation, ΔfG°, lattice potential energy, UPOT, isothermal expansion coefficient, α, and isothermal compressibility, β, and used to suggest the thermodynamic feasibility of reactions among condensed ionic phases. Because many of these methods yield results largely independent of crystal structure, they have been successfully extended to the important and developing class of ionic liquids as well as to new and hypothesised materials. Finally, these predictive methods are illustrated by application to K2SnCl6, for which known experimental results are available for comparison. A selection of applications of VBT and TDR is presented which have enabled input, usually in the form of thermodynamics, to be brought to bear on a range of topical problems. Perhaps the most significant advantage of VBT and TDR methods is their inherent simplicity in that they do not require a high level of computational expertise nor expensive high-performance computation tools - a spreadsheet will usually suffice - yet the techniques are extremely powerful and accessible to non-experts. The connection between formula unit volume, Vm, and standard thermodynamic parameters represents a

  15. Thermodynamic Reassessment of the Nd-Fe-B Ternary System

    NASA Astrophysics Data System (ADS)

    Zhou, G. J.; Luo, Y.; Zhou, Y.

    2016-01-01

    The Nd-B binary system and Nd-Fe-B ternary system were thermodynamically reassessed with the aim of obtaining more reasonable thermodynamic parameters and more accurate phase relations. Based on the metastable experimental information, a reasonable, self-consistent, and comprehensive thermodynamic description of the Nd-Fe-B ternary system considering the metastable phases Fe3B, Fe23Nd2B3, and Fe17Nd2B has been developed.

  16. Neon and CO2 adsorption on open carbon nanohorns.

    PubMed

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

    2013-07-30

    We present the results of a thermodynamics and kinetics study of the adsorption of neon and carbon dioxide on aggregates of chemically opened carbon nanohorns. Both the equilibrium adsorption characteristics, as well as the dependence of the kinetic behavior on sorbent loading, are different for these two adsorbates. For neon the adsorption isotherms display two steps before reaching the saturated vapor pressure, corresponding to adsorption on strong and on weak binding sites; the isosteric heat of adsorption is a decreasing function of sorbent loading (this quantity varies by about a factor of 2 on the range of loadings studied), and the speed of the adsorption kinetics increases with increasing loading. By contrast, for carbon dioxide there are no substeps in the adsorption isotherms; the isosteric heat is a nonmonotonic function of loading, the value of the isosteric heat never differs from the bulk heat of sublimation by more than 15%, and the kinetic behavior is opposite to that of neon, with equilibration times increasing for higher sorbent loadings. We explain the difference in the equilibrium properties observed for neon and carbon dioxide in terms of differences in the relative strengths of adsorbate-adsorbate to adsorbate-sorbent interaction for these species. PMID:23802764

  17. Modeling adsorption of liquid mixtures on porous materials.

    PubMed

    Monsalvo, Matias A; Shapiro, Alexander A

    2009-05-01

    The multicomponent potential theory of adsorption (MPTA), which was previously applied to adsorption from gases, is extended onto adsorption of liquid mixtures on porous materials. In the MPTA, the adsorbed fluid is considered as an inhomogeneous liquid with thermodynamic properties that depend on the distance from the solid surface (or position in the porous space). The theory describes the two kinds of interactions present in the adsorbed fluid, i.e. the fluid-fluid and fluid-solid interactions, by means of an equation of state and interaction potentials, respectively. The proposed extension of the MPTA onto liquids has been tested on experimental binary and ternary adsorption data. We show that, for the set of experimental data considered in this work, the MPTA model is capable of correlating binary adsorption equilibria. Based on binary adsorption data, the theory can then predict ternary adsorption equilibria. Good agreement with the theoretical predictions is achieved in most of the cases. Some limitations of the model are also discussed. PMID:19243781

  18. Adsorption of Ar on individual carbon nanotubes, graphene, and graphite

    NASA Astrophysics Data System (ADS)

    Dzyubenko, Boris; Kahn, Joshua; Vilches, Oscar; Cobden, David

    2015-03-01

    We compare and contrast results of adsorption measurements of Ar on single-walled carbon nanotubes, graphene, and graphite. Adsorption isotherms on individual suspended nanotubes were obtained using both the mechanical resonance frequency shift (sensitive to mass adsorption) and the electrical conductance. Isotherms on graphene mounted on hexagonal boron nitride were obtained using only the conductance. New volumetric adsorption isotherms on bulk exfoliated graphite were also obtained, paying special attention to the very low coverage region (less than 2% of a monolayer). This allowed us to compare the degree of heterogeneity on the three substrate types, the binding energies, and the van der Waals 2D parameters. Research supported by NSF DMR 1206208.

  19. Thermodynamics and combustion modeling

    NASA Technical Reports Server (NTRS)

    Zeleznik, Frank J.

    1986-01-01

    Modeling fluid phase phenomena blends the conservation equations of continuum mechanics with the property equations of thermodynamics. The thermodynamic contribution becomes especially important when the phenomena involve chemical reactions as they do in combustion systems. The successful study of combustion processes requires (1) the availability of accurate thermodynamic properties for both the reactants and the products of reaction and (2) the computational capabilities to use the properties. A discussion is given of some aspects of the problem of estimating accurate thermodynamic properties both for reactants and products of reaction. Also, some examples of the use of thermodynamic properties for modeling chemically reacting systems are presented. These examples include one-dimensional flow systems and the internal combustion engine.

  20. Factors affecting the adsorption of chromium (VI) on activated carbon

    SciTech Connect

    Yavuz, R.; Orbak, I.; Karatepe, N.

    2006-09-15

    The aim of this investigation was to determine the adsorption behavior of chromium (VI) on two different activated carbon samples produced from Tuncbilek lignite. The effects of the initial chromium (VI) concentration (250-1000 mg/L), temperature (297-323 K) and pH (2.0-9.5) on adsorption were investigated systematically. The effectiveness of the parameters on chromium adsorption was found to be in the order of pH, the initial Cr(VI) concentration and the temperature. Increasing the pH from 2.0 to 9.5 caused a decrease in adsorption. However, the adsorption was increased by increasing the initial Cr(VI) concentration and temperature. The multilinear mathematical model was also developed to predict the Cr(VI) adsorption on activated carbon samples within the experimental conditions.

  1. Adsorption studies of methylene blue dye on tunisian activated lignin

    NASA Astrophysics Data System (ADS)

    Kriaa, A.; Hamdi, N.; Srasra, E.

    2011-02-01

    Activated carbon prepared from natural lignin, providing from a geological deposit, was used as the adsorbent for the removal of methylene blue (MB) dye from aqueous solutions. Batch adsorption studies were conducted to evaluate various experimental parameters like pH and contact time for the removal of this dye. Effective pH for MB removal was 11. Kinetic study showed that the adsorption of dye was gradual process. Quasi equilibrium reached in 4 h. Pseudo-first-order, pseudo-second-order were used to fit the experimental data. Pseudo-second-order rate equation was able to provide realistic description of adsorption kinetics. The experimental isotherms data were also modelled by the Langmuir and Freundlich equation of adsorption. Equilibrium data fitted well with the Langmuir model with maximum monolayer adsorption capacity of 147 mg/g. Activated lignin was shown to be a promising material for adsorption of MB from aqueous solutions.

  2. Adsorption of isopropanol and cyclohexane on zinc oxide

    NASA Astrophysics Data System (ADS)

    Bratchikova, I. G.; Pylinina, A. I.; Platonov, E. A.; Danilova, M. N.; Isaeva, N. Yu.; Yagodovskii, V. D.

    2015-01-01

    Adsorption isotherms of isopropanol and cyclohexane are obtained in the range of 234-303 K on an initial surface of zinc oxide and after its treatment with glow-discharge plasma in O2 and high-frequency plasma in Ar. The values of isosteric heat and adsorption entropy are shown to be only slightly affected by these treatments. It is found that the acidity of the surface increases by 38 and 97%, respectively, and the acidic sites are not adsorption sites for either adsorbate. At low degrees of occupation, the adsorption isotherms of (CH3)2CHOH are described by an equation of induced adsorption whose parameters are dependent on the plasma-chemical treatments. It is concluded that adsorbed isopropanol particles exist in positively and negatively charged forms. The adsorption of cyclohexane is described by the Hill-de Boer equation for the initial ZnO surface, and by the Langmuir equation after plasma-chemical treatments.

  3. A molecular-thermodynamic framework for asphaltene-oil equilibria

    SciTech Connect

    Wu, J.; Prausnitz, J.M. |; Firoozabadi, A.

    1997-02-01

    Asphaltene precipitation is a perennial problem in production and refinery of crude oils. To avoid precipitation, it is useful to predict the solubility of asphaltenes in petroleum liquids as a function of temperature, pressure and liquid-phase composition. In the molecular-thermodynamic model presented here, both asphaltenes and resins are represented by pseudo-pure components, and all other components in the solution are represented by a continuous medium which affects interactions among asphaltene and resin particles. The effect of the medium on asphaltene-asphaltene, resin-asphaltene, resin-resin pair interactions is taken into account through its density and molecular-dispersion properties. To obtain expressions for the chemical potential of asphaltene and for the osmotic pressure of an asphaltene-containing solution, the authors use the integral theory of fluids coupled with the SAFT model to allow for asphaltene aggregation and for adsorption of resin on asphaltene particles. With these expressions, a variety of experimental observations can be explained including the effects of temperature, pressure and composition on the phase behavior of asphaltene-containing fluids. For engineering application, the molecular parameters in this model must be correlated to some macroproperties of oil such as density and molecular weight. When such correlations are established, it will be possible to calculate asphaltene-precipitation equilibria at a variety of conditions for realistic systems.

  4. Modelling of CO2 Adsorption from Exhaust Gases

    NASA Astrophysics Data System (ADS)

    Panowski, Marcin; Klainy, Roman; Sztelder, Karol

    World tendencies in environmental protection points out necessity of reduction of CO2 emission to atmosphere. The one of the main sources of CO2 emission is placed in energy sector where electric energy and heat are produced based on fossil fuels combustion. Therefore, it seems to be necessary to perform research on CO2 emission reduction in this sector. The main aim of work presented in this paper was focused on the analysis and assessment of CO2 separation from flue gases on the total efficiency of conventional power station. The paper shows the numerical calculations performed with IPSEpro simulation software by SimTech.For the CO2 separation the PTSA (pressure-Temperature Swing Adsorption) process was chosen and the numerical as well as simulation model of such process was formulated. The calculations were made for few different adsorbents taking into account varying values of such thermodynamic parameters of separation process like temperature or pressure. Results obtained from calculations point out that mixed PTSA technology is not very energy consuming process. Owing to utilisation of waste heat for sorbent regeneration, it does not decrease the total efficiency for more than 0.6%. However, that is caused by separation only, while after that CO2 must be compressed for further treatment.

  5. Mechanisms and factors affecting the adsorption of sodium alginate onto modified clays

    NASA Astrophysics Data System (ADS)

    Lin, Yongxin; Cao, Xihua; Song, Xiuxian; Wang, Nan; Yu, Zhiming

    2013-07-01

    Algal organic materials (AOMs) are one critical factor affecting the efficiency of modified clays used for the mitigation of harmful algal blooms (HABs). This study was conducted to develop a deeper understanding of the mechanisms and factors affecting the adsorption of AOMs onto modified clays. Sodium alginate (polysaccharide) and kaolinite modified with polyaluminium chloride (PACl) were used as AOMs and modified clay model substances, respectively, and the effects of modifier dosage, contact time, solution pH and ionic strength were investigated through batch adsorption experiments. Kinetics revealed that the alginate adsorption rate was described well by a pseudo-second order model. PACl effectively enhanced the adsorption capacity of kaolinite and increased the adsorption rate, and the optimum additive amount of PACl was 5%. The experimental data fitted both the Freundlich and Langmuir adsorption equations well. The adsorption thermodynamics for alginate onto modified clays suggests that alginate adsorption is a spontaneous process. The adsorption of alginate onto modified clays was highly dependent on pH, with a decrease in adsorption observed with increased pH to 9.48, but the opposite was true above pH 9.48. Finally, adsorption increased with increasing ionic strength.

  6. Adsorptive removal of 2-chlorophenol by low-cost coir pith carbon.

    PubMed

    Namasivayam, C; Kavitha, D

    2003-03-17

    Adsorption of 2-chlorophenol (2-CP) by coir pith carbon was carried out by varying the parameters such as agitation time, 2-CP concentration, adsorbent dose, pH and temperature. Adsorption equilibrium reached at 40, 60, 80 and 100 min for 2-CP concentration of 10, 20, 30 and 40 mg/l, respectively. Adsorption followed second-order kinetics. The adsorption equilibrium data obeyed Freundlich isotherm. Acidic pH was favorable for the adsorption of 2-CP. Desorption studies showed that chemisorption plays a major role in the adsorption process. PMID:12628792

  7. Thermodynamic and kinetic aspects of surface acidity

    SciTech Connect

    Dumesic, J.A.

    1992-01-01

    Our research in the general area of acid catalysis involves the characterization of solid acidity and the corresponding assessment of catalytic performance of acidic materials. Acid characterization studies are required to provide essential information about the type of acid site (i.e., Lewis versus Bronsted), the strength of the sites, and the mobility of molecules adsorbed on the acid sites. An accurate measure of acid strength is given by the heat of adsorption of a basic probe molecule on the acid site. A thermodynamic representation of the mobility of adsorbed species on these sites is given by the entropy of adsorption. Important techniques used in these acid site characterization studies include microcalorimetry, thermogravimetric measurements, temperature programmed desorption, infrared spectroscopy and solid state nuclear magnetic resonance. The combination of these acid site characterization studies with reaction kinetics measurements of selected catalytic processes allows the elucidation of possible relationships between surface thermodynamic and kinetic properties of acidic sites. Such relationships are important milestones in formulating effective strategies for the effective utilization of solid acid catalysts. Current work in this direction involves methylamine syntheses over various zeolites, and the basic probe molecules employed include ammonia, methanol, water and mono-, di- and tri-methylamines. 31 refs., 18 figs., 1 tab.

  8. Can the Gibbs free energy of adsorption be predicted efficiently and accurately: an M05-2X DFT study.

    PubMed

    Michalkova, A; Gorb, L; Hill, F; Leszczynski, J

    2011-03-24

    This study presents new insight into the prediction of partitioning of organic compounds between a carbon surface (soot) and water, and it also sheds light on the sluggish desorption of interacting molecules from activated and nonactivated carbon surfaces. This paper provides details about the structure and interactions of benzene, polycyclic aromatic hydrocarbons, and aromatic nitrocompounds with a carbon surface modeled by coronene using a density functional theory approach along with the M05-2X functional. The adsorption was studied in vacuum and from water solution. The molecules studied are physisorbed on the carbon surface. While the intermolecular interactions of benzene and hydrocarbons are governed by dispersion forces, nitrocompounds are adsorbed also due to quite strong electrostatic interactions with all types of carbon surfaces. On the basis of these results, we conclude that the method of prediction presented in this study allows one to approach the experimental level of accuracy in predicting thermodynamic parameters of adsorption on a carbon surface from the gas phase. The empirical modification of the polarized continuum model leads also to a quantitative agreement with the experimental data for the Gibbs free energy values of the adsorption from water solution. PMID:21361266

  9. Adsorptive removal of Lead from water by the effective and reusable magnetic cellulose nanocomposite beads entrapping activated bentonite.

    PubMed

    Luo, Xiaogang; Lei, Xiaojuan; Xie, Xiuping; Yu, Bo; Cai, Ning; Yu, Faquan

    2016-10-20

    Many efforts have been driven to decontaminate the drinking water, and the development of efficient adsorbents with the advantages of cost-effectiveness and operating convenience for the removal of Pb(2+) from water is a major challenge. This work was aimed to explore the possibility of using cellulose-based adsorbents for efficient adsorption of Pb(2+). The millimeter-scale magnetic cellulose-based nanocomposite beads were fabricated via an optimal extrusion dropping technology by blending cellulose with the carboxyl-functionalized magnetite nanoparticles and acid-activated bentonite in NaOH/urea aqueous solution, and then they had been tested to evaluate the effectiveness in the removal of Pb(2+) from water. The effects of contact time, initial heavy metal ion concentrations, adsorption isotherms and solution pH on the sorption behavior were studied. The thermodynamic parameters (ΔG, ΔH and ΔS) indicated that the adsorption processes were feasible, spontaneous, endothermic and mainly controlled by chemical mechanisms. The reusability of the adsorbent was also studied. PMID:27474609

  10. Equilibrium adsorption and self-assembly of patchy colloids in microchannels

    NASA Astrophysics Data System (ADS)

    Marshall, Bennett D.

    2016-07-01

    A theory is developed to describe the equilibrium adsorption and self-assembly of patchy colloids in microchannels. The adsorption theory is developed in classical density functional theory, with the adsorbed phase and fluid phase chemical potentials modeled using thermodynamic perturbation theory. Adsorption of nonpatchy colloids in microchannels is typically achieved through nonequilibrium routes such as spin coating and evaporation. These methods are required due to the entropic penalty of adsorption. In this work we propose that the introduction of patches on the colloids greatly enhances the temperature dependent and reversible adsorption of colloids in microchannels. It is shown how bulk fluid density, temperature, patch size, and channel diameter can be manipulated to achieve the adsorption and self-assembly of patchy colloids in microchannels.

  11. Equilibrium adsorption and self-assembly of patchy colloids in microchannels.

    PubMed

    Marshall, Bennett D

    2016-07-01

    A theory is developed to describe the equilibrium adsorption and self-assembly of patchy colloids in microchannels. The adsorption theory is developed in classical density functional theory, with the adsorbed phase and fluid phase chemical potentials modeled using thermodynamic perturbation theory. Adsorption of nonpatchy colloids in microchannels is typically achieved through nonequilibrium routes such as spin coating and evaporation. These methods are required due to the entropic penalty of adsorption. In this work we propose that the introduction of patches on the colloids greatly enhances the temperature dependent and reversible adsorption of colloids in microchannels. It is shown how bulk fluid density, temperature, patch size, and channel diameter can be manipulated to achieve the adsorption and self-assembly of patchy colloids in microchannels. PMID:27575187

  12. Mesoporous magnetic activated carbon: Effect of preparation route on texture and surface properties and on effect for Reactive Black 5 adsorption.

    NASA Astrophysics Data System (ADS)

    Giannakoudakis, Dimitrios; Saroyan, Hayarpi; Lazaridis, Nikolaos; Deliyanni, Eleni

    2016-04-01

    Mesoporous magnetic activated carbon: Effect of preparation route on texture and surface properties and on effect for Reactive Black 5 adsorption. Dimitrios Giannakoudakis1, Hayarpi Saroyan2, Nikolaos Lazaridis2, Eleni Deliyanni2 1 City College of New York, Chemistry Department, 160 Convent Avenue, New York, United States 2 Laboratory of General and oInorganic Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Greece In this study, the effect of preparation route of a mesoporous magnetic activated carbon on Reactive Black 5 (RB5) adsorption was investigated. The synthesis of the magnetic activated carbon was achieved both with (i) impregnation method (Bmi), and (ii) co-precipitation with two precipitation agents: NaOH (Bm) and NH4OH (Bma). After synthesis, the full characterization with various techniques (SEM, FTIR, XRD, DTA, DTG, VSM) was achieved in order to testify the effect of the preparation route on its textural and surface properties. It was shown that after the precipitation method the prepared carbon presented a collapsed texture and small magnetic properties. Effects of initial solution pH, effect of temperature, adsorption isotherms and kinetics were investigated in order to conclude about the aforementioned effect of the preparation method on dye adsorption performance of the magnetic carbons. The adsorption evaluation of the magnetic activated carbon presented higher adsorption capacity of Bmi carbon (350 mg/g) and lower of Bm (150 mg/g). Equilibrium experiments are also performed studying the effect of contact time (pseudo-first and -second order equations) and temperature (isotherms at 25, 45 and 65 °C fitted to Langmuir and Freundlich model). A full thermodynamic evaluation was carried out, calculating the parameters of enthalpy, free energy and entropy (ΔHο, ΔGο and ΔSο). The characterization with various techniques revealed the possible interactions/forces of dye-composite system.

  13. Hybrid adsorptive membrane reactor

    DOEpatents

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

    2011-03-01

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

  14. Hybrid adsorptive membrane reactor

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

  15. Thermodynamic functions and intraparticle mass transfer kinetics of structural analogues of a template on molecularly imprinted polymers in liquid chromatography

    SciTech Connect

    Kim, Hyunjung; Guiochon, Georges A

    2005-08-01

    The parameters of the thermodynamics and mass transfer kinetics of the structural analogues (L-enantiomers) of the template were measured on an Fmoc-L-tryptophan (Fmoc-L-Trp) imprinted polymer, at different temperatures. The equilibrium isotherm data and the overloaded band profiles of these compounds were measured at temperatures of 298, 313, 323, and 333 K. The isotherm data were modeled. The thermodynamic functions of the different adsorption sites were derived from the isotherm parameters, using van't Hoff plots. The mass transfer parameters were derived by comparing the experimental peak profiles and profiles calculated using the lumped pore diffusion (POR) model for chromatography. These data show that (1) the strength between the substrate molecules and the MIP increases with increasing number of functional groups on the substrates; (2) enthalpy is the driving force for the affinity of the substrates for the MIP; (3) surface diffusion is the dominant mass transfer mechanism of the substrates through the porous MIP. For those substrate molecules that have the same stereochemistry as the template, the energetic surface heterogeneity needs to be incorporated into the surface diffusion coefficients. Heterogeneous surface diffusivities decrease with increasing affinity of the substrates for the MIP.

  16. Thermodynamics: A Stirling effort

    NASA Astrophysics Data System (ADS)

    Horowitz, Jordan M.; Parrondo, Juan M. R.

    2012-02-01

    The realization of a single-particle Stirling engine pushes thermodynamics into stochastic territory where fluctuations dominate, and points towards a better understanding of energy transduction at the microscale.

  17. The Thermodynamics of Portfolios

    NASA Astrophysics Data System (ADS)

    Piotrowski, E. W.; Sladkowski, J.

    2001-02-01

    We propose a new method of valuation of portfolios and their respective investing strategies. To this end we define a canonical ensemble of portfolios that allows to use the formalism of thermodynamics.

  18. Thermodynamics and Frozen Foods.

    ERIC Educational Resources Information Center

    Kerr, William L.; Reid, David S.

    1993-01-01

    The heat content of a food at a given temperature can be described by the thermodynamic property of enthalpy. Presents a method to construct a simple calorimeter for measuring the enthalpy changes of different foods during freezing. (MDH)

  19. Aqueous mercury adsorption by activated carbons.

    PubMed

    Hadi, Pejman; To, Ming-Ho; Hui, Chi-Wai; Lin, Carol Sze Ki; McKay, Gordon

    2015-04-15

    Due to serious public health threats resulting from mercury pollution and its rapid distribution in our food chain through the contamination of water bodies, stringent regulations have been enacted on mercury-laden wastewater discharge. Activated carbons have been widely used in the removal of mercuric ions from aqueous effluents. The surface and textural characteristics of activated carbons are the two decisive factors in their efficiency in mercury removal from wastewater. Herein, the structural properties and binding affinity of mercuric ions from effluents have been presented. Also, specific attention has been directed to the effect of sulfur-containing functional moieties on enhancing the mercury adsorption. It has been demonstrated that surface area, pore size, pore size distribution and surface functional groups should collectively be taken into consideration in designing the optimal mercury removal process. Moreover, the mercury adsorption mechanism has been addressed using equilibrium adsorption isotherm, thermodynamic and kinetic studies. Further recommendations have been proposed with the aim of increasing the mercury removal efficiency using carbon activation processes with lower energy input, while achieving similar or even higher efficiencies. PMID:25644627

  20. The adsorption of plutonium IV and V on goethite

    NASA Astrophysics Data System (ADS)

    Sanchez, Arthur L.; Murray, James W.; Sibley, Thomas H.

    1985-11-01

    The adsorption of Pu(IV) and Pu(V) on goethite (αFeOOH) from NaNO 3 solution shows distinct differences related to the different hydrolytic character of these two oxidation states. Under similar solution conditions, the adsorption edge of the more strongly hydrolyzable Pu(IV) occurs in the pH range 3 to 5 while that for Pu(V) is at pH 5 to 7. The adsorption edge for Pu(V) shifts with time to lower pH values and this appears to be due to the reduction of Pu(V) to Pu(IV) in the presence of the goethite surface. These results suggest that redox transformations may be an important aspect of Pu adsorption chemistry and the resulting scavenging of Pu from natural waters. Increasing ionic strength (from 0.1 M to 3 M NaCl or NaNO 3 and 0.03 M to 0.3 M Na 2SO 4) did not influence Pu(IV) or Pu(V) adsorption. In the presence of dissolved organic carbon (DOC), Pu(V) reduction to Pu(IV) occurred in solution. Pu(IV) adsorption on goethite decreased by 30% in the presence of 240 ppm natural DOC found in Soap Lake, Washington waters. Increasing concentrations of carbonate ligands decreased Pu(IV) and Pu(V) adsorption on goethite, with an alkalinity of 1000 meq/l totally inhibiting adsorption. The Pu-goethite adsorption system provides the data base for developing a thermodynamic model of Pu interaction with an oxide surface and with dissolved ligands, using the MINEQL computer program. From the model calculations we determined equilibrium constants for the adsorption of Pu(IV) hydrolysis species. The model was then applied to Pu adsorption in carbonate media to see how the presence of CO 3-2 could influence the mobility of Pu. The decrease in adsorption appears to be due to formation of a Pu-CO 3 complex. Model calculations were used to predict what the adsorption curves would look like if Pu-CO 3 complexes formed.

  1. Assessing the adsorption properties of shales

    NASA Astrophysics Data System (ADS)

    Pini, Ronny

    2015-04-01

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

  2. Adsorption of aqueous copper on peanut hulls

    NASA Astrophysics Data System (ADS)

    Davis, Kanika Octavia

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

  3. Thermodynamics of Bioreactions.

    PubMed

    Held, Christoph; Sadowski, Gabriele

    2016-06-01

    Thermodynamic principles have been applied to enzyme-catalyzed reactions since the beginning of the 1930s in an attempt to understand metabolic pathways. Currently, thermodynamics is also applied to the design and analysis of biotechnological processes. The key thermodynamic quantity is the Gibbs energy of reaction, which must be negative for a reaction to occur spontaneously. However, the application of thermodynamic feasibility studies sometimes yields positive Gibbs energies of reaction even for reactions that are known to occur spontaneously, such as glycolysis. This article reviews the application of thermodynamics in enzyme-catalyzed reactions. It summarizes the basic thermodynamic relationships used for describing the Gibbs energy of reaction and also refers to the nonuniform application of these relationships in the literature. The review summarizes state-of-the-art approaches that describe the influence of temperature, pH, electrolytes, solvents, and concentrations of reacting agents on the Gibbs energy of reaction and, therefore, on the feasibility and yield of biological reactions. PMID:27276551

  4. Simulating the effects of adsorption and capillary forces in geothermal reservoirs

    SciTech Connect

    Sta. Maria, Roman B.; Pingol, Alponso S.

    1996-01-24

    Until recently, geothermal reservoir simulators use flat interface thermodynamics to determine the thermodynamic state of the reservoir. Development of new simulators and the modification of existing ones has now incorporated the physics of curved interface thermodynamics. These simulators account for the effects of sorption and capillary forces. The simulators GSS and TETRAD were used to simulate the performance of a hypothetical vapordominated geothermal reservoir. GSS is a simulator specifically developed to account for adsorption by using adsorption isotherms. On the other hand, TETRAD is a commercial simulator that was modified to account for vapor pressure lowering by using capillary pressure relations. GSS and TETRAD yielded similar results. Thus, the two formulations being used to account for curved interface thermodynamics are practically equivalent. Areas for improvement of both GSS and TETRAD were identified. The hysteresis and temperature dependence of sorption and capillary properties are issues that are needed to be addressed.

  5. Dimer adsorption on a (100) nanotube of arbitrary diameter, with first- and second-neighbor interactions.

    PubMed

    Phares, Alain J; Grumbine, David W

    2014-06-17

    Dimer adsorption on an infinitely long (100) or square lattice nanotube of fixed lattice constant and arbitrary number M of sites in its normal cross section is considered with first- and second-neighbor interaction energies, V and W, respectively. An increase in M keeping the lattice constant fixed corresponds to a nanotube with increasing diameter. The system is at thermodynamic equilibrium and relatively low temperature in order to determine all of the possible crystallization patterns or phases that may exist. Under these conditions, the energy phase space diagram is two-dimensional, and the dimensionless parameters are u = W/|V| and v = μ/|V|, where μ is the sum of the chemical potential energy, μ', of a dimer and the dimer-substrate interaction energy V0. The low temperature energy phase diagram is numerically generated using a transfer matrix method adapted to the present problem. For both attractive and repulsive first-neighbors, it is M-independent for M even, and its M-dependence when M is odd is established. As a consistency check, the infinite odd-M limit matches exactly the M-independent phase diagram for even M. The knowledge of the boundaries of the regions in the phase diagram where these phases occur and the knowledge of their respective occupational configurations are particularly useful information when experimental data on dimer adsorption on square nanotubes become available. PMID:24897920

  6. Adsorption Kinetics and Binding Studies of Protein Quantum Dots Interaction: A Spectroscopic Approach.

    PubMed

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

    2016-05-01

    Protein Quantum dots interaction is crucial to investigate for better understanding of the biological interactions of QDs. Here in, the model protein Bovine serum albumin (BSA) was used to evaluate the process of protein QDs interaction and adsorption on QDs surface. The modified Stern-Volmer quenching constant (Ka), number of binding sites (n) at different temperatures (298 308 and 318 K ± 1) and corresponding thermodynamic parameters (ΔG < 0, ΔH < 0, and ΔS > 0) were calculated. The quenching constant (Ks) and number of binding sites (n) is found to be inversely proportional to temperature. It signified that static quenching mechanism is dominant over dynamic quenching. The standard free energy change (ΔG < 0) implies that the binding process is spontaneous, while the enthalpy change (ΔH < 0) suggest that the binding of QDs to BSA is an enthalpy-driven process. The standard entropy change (ΔS > 0) suggest that hydrophobic force played a pivotal role in the interaction process. The adsorption process were assessed and evaluated by pseudofirst-order, pseudosecond-order kinetic model, and intraparticle diffusion model. PMID:26825079

  7. Adsorptive treatment of brewery effluent using activated Chrysophyllum albidium seed shell carbon.

    PubMed

    Menkiti, Matthew Chukwudi; Aneke, Mathew Chidiebere; Ejikeme, Paul Madus; Onukwuli, Okechukwu Dominic; Menkiti, Nwasinachi Uzoma

    2014-01-01

    Chrysophyllum albidium seed shell, an abundant, biodegradable and inexpensive natural resource was used as a precursor to bioadsorbent production for the removal of suspended and dissolved particles (SDP) from initially coagulated Brewery Effluent (BRE). Influence of key parameters such as contact time, bioadsorbent dose, pH and temperature were investigated using batch mode. The thermal behavior studies were evaluated using Thermogravimetric and Differential scanning calorimetric analyses. The morphological observations and functional groups of the bioadsorbents were determined using scanning electron microscopy and Fourier transform infrared spectroscopy, respectively. The adsorption equilibrium, thermodynamics and kinetic of SDP adsorption on H3PO4-treated shell and NH4Cl-treated shell were examined at specified temperatures. Equilibrium data sufficiently fitted the Langmuir isotherm model (R (2) > 0.99; SSE < 0.09). The pseudo-second order kinetic model provided the best correlation (R (2) > 0.99; SSE < 0.14) with the experimental data. The values of ΔG° and ΔH° indicated the spontaneous and endothermic nature of the process. This study demonstrated that C. albidium seed shell could be utilized as low cost, renewable, ecofriendly bioadsorbent for the uptake of SDP from BRE. PMID:24877028

  8. Interactions of xanthines with activated carbon. I. Kinetics of the adsorption process

    NASA Astrophysics Data System (ADS)

    Navarrete Casas, R.; García Rodriguez, A.; Rey Bueno, F.; Espínola Lara, A.; Valenzuela Calahorro, C.; Navarrete Guijosa, A.

    2006-06-01

    Because of their pharmaceutical and industrial applications, we have studied the adsorption of xanthine derivates (caffeine and theophylline) by activated carbon. To this end, we examined kinetic, equilibrium and thermodynamic aspects of the process. This paper reports the kinetics results. The experimental results indicate that the process was first order in C and the overall process was assumed to involve a single, reversible adsorption-desorption process obeying a kinetic law postulated by us.

  9. Unitary Thermodynamics from Thermodynamic Geometry II: Fit to a Local-Density Approximation

    NASA Astrophysics Data System (ADS)

    Ruppeiner, George

    2015-10-01

    Strongly interacting Fermi gasses at low density possess universal thermodynamic properties that have recently seen very precise PVT measurements by a group at MIT. This group determined local thermodynamic properties of a system of ultracold atoms tuned to Feshbach resonance. In this paper, I analyze the MIT data with a thermodynamic theory of unitary thermodynamics based on ideas from critical phenomena. This theory was introduced in the first paper of this sequence and characterizes the scaled thermodynamics by the entropy per particle and the energy per particle Y( z), in units of the Fermi energy. Y( z) is in two segments, separated by a second-order phase transition at : a "superfluid" segment for and a "normal" segment for . For small z, the theory obeys a series where is a constant exponent and () are constant series coefficients. For large z, the theory obeys a perturbation of the ideal gas , where is a constant exponent and () are constant series coefficients. This limiting form for large z differs from the series used in the first paper and was necessary to fit the MIT data. I fit the MIT data by adjusting four free independent theory parameters: . This fit process was augmented by trap integration and comparison with earlier thermal data taken at Duke University. The overall match to both the data sets was good and had , , , scaled critical temperature , where is the Fermi temperature, and Bertsch parameter . I also discuss the virial expansion in the context of this thermodynamic geometric theory.

  10. Phase diagram of oxygen adsorbed on Ni(111) and thermodynamic properties from first-principles

    NASA Astrophysics Data System (ADS)

    Lazo, C.; Keil, F. J.

    2009-06-01

    The thermodynamic properties and the surface phase diagram of O/Ni(111) have been calculated from Metropolis and Wang-Landau Monte Carlo simulations based on lateral interactions derived from density-functional theory (DFT) calculations. The DFT energies were mapped onto an Ising-like Hamiltonian according to the cluster expansion technique formalism. Both fcc and hcp adsorption sites were included in the Hamiltonian. Different criteria were used to evaluate competing parameter sets: cross-validation score CV, Mallow’s Cp statistics, and adjusted R2 statistics. The parameter space was searched using genetic algorithms in order to find optimum parameter sets. The different parameter sets obtained from different criteria lead essentially to the same transition temperatures. Excellent agreement is found when comparing the shape and the stability regions of the theoretical and the experimental (from the literature) phase diagrams. We investigate the nature of the p(2×2) and (3×3)R30° phase transitions at Θ=1/4 and 1/3 ML, respectively. Differences arise when comparing the values of the calculated and the experimental transition temperatures owing to imprecision in present-day DFT calculations.

  11. Selective adsorption and separation of organic dyes from aqueous solution on polydopamine microspheres.

    PubMed

    Fu, Jianwei; Xin, Qianqian; Wu, Xuechen; Chen, Zhonghui; Yan, Ya; Liu, Shujun; Wang, Minghuan; Xu, Qun

    2016-01-01

    Polydopamine (PDA) microspheres, synthesized by a facile oxidation polymerization route, were evaluated as a potential adsorbent for selective adsorption and separation of organic dyes. The adsorption processes towards nine water-soluble dyes (anionic dyes: methyl orange (MO), eosin-Y (EY), eosin-B (EB), acid chrome blue K (ACBK), neutral dye: neutral red (NR), and cationic dyes: rhodamine B (RhB), malachite green (MG), methylene blue (MB), safranine T (ST)) were thoroughly investigated. The adsorption selectivity of organic dyes onto PDA microspheres was successfully applied for the separation of dyes mixtures. Various influential factors such as solution pH, temperature, and contact time were employed to ascertain the optimal condition for adsorption of representative organic dyes including MB, MG and NR. The pseudo-first-order and pseudo-second-order kinetics models were used to fit the adsorption kinetics process. Five isothermal adsorption models (Langmuir, Dubnin-Radushkevich, Temkin, Freundlich and Harkins-Jura) were used to investigate the adsorption thermodynamics properties. The results showed that the PDA microspheres owned good selective adsorption ability towards cationic dyes. The adsorption kinetics process conformed to the pseudo-second-order kinetics model and the Langmuir isotherm model was more appropriate for tracing the adsorption behavior than other isotherm models. Thus, we can conclude PDA microspheres may be a high-efficiency selective adsorbent towards some cationic dyes. PMID:26407057

  12. Atrazine adsorption removal with nylon6/polypyrrole core-shell nanofibers mat: possible mechanism and characteristics

    NASA Astrophysics Data System (ADS)

    Yang, Bi-Yi; Cao, Yang; Qi, Fei-Fei; Li, Xiao-Qing; Xu, Qian

    2015-05-01

    A functionalized nylon6/polypyrrole core-shell nanofibers mat (PA6/PPy NFM) was prepared via situ polymerization on nylon6 electrospun nanofibers mat (PA6 NFM) template and used as an adsorbent to remove atrazine from aqueous solutions. The core-shell structure of PA6/PPy NFM can be clearly proved under scanning electron microscope (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The effects of initial solution pH and ionic strength, as well as the comparison of the adsorption capacity of functionalized (PA6/PPy NFM) and non-functionalized (PA6 NFM) adsorbent, were examined to reveal the possible adsorption mechanism. The results indicated that π-π interaction and electrostatic interaction should play a key role in the adsorption process. The kinetics and thermodynamics studies also further elucidated the detailed adsorption characteristics of atrazine removal by PA6/PPy NFM. The adsorption of atrazine could be well described by the pseudo-second-order equation. The adsorption equilibrium data was well fitted with the Freundlich isotherm model with a maximum adsorption capacity value of 14.8 mg/g. In addition, the increase of adsorption rate caused by a temperature increase could be felicitously explained by the endothermic reaction. The desorption results showed that the adsorption capacity remained almost unchanged after six adsorption/desorption cycles. These results suggest that PA6/PPy NFM could be employed as an efficient adsorbent for removing atrazine from contaminated water sources.

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

    PubMed

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

    2003-03-17

    Investigations on the adsorption of ammonium dinitramide (NH(4)N(NO(2))(2)) (ADN) from aqueous solutions on powdered activated charcoal (PAC) were carried out in order to find out an effective and easier method of separating ADN from aqueous solutions. The effectiveness of PAC in the selective adsorption of ADN from aqueous solutions of ADN (ADN-F) and ADN in presence of sulfate (SO(4)(2-)) and nitrate (NO(3)(-)) ions (ADN-PS) was examined and compared using batch and column methods. The adsorption process follows both Langmuir and Freundlich adsorption isotherms and the isotherm parameters for the models were determined. The observed data favor the formation of monolayer adsorption. The adsorption capacities were found to be 63.3, 119, 105.3 and 82 mg of ADN per g of PAC for ADN-F (batch), ADN-PS (batch), ADN-F (column) and ADN-PS (column), respectively. Break-through curves for ADN-F and ADN-PS were obtained for the optimization of separation of ADN from aqueous solutions. Elution curves were generated for the desorption of ADN from PAC using hot water as eluent. PMID:12628781

  14. Universal thermodynamics in different gravity theories: Conditions for generalized second law of thermodynamics and thermodynamical equilibrium on the horizons

    NASA Astrophysics Data System (ADS)

    Mitra, Saugata; Saha, Subhajit; Chakraborty, Subenoy

    2015-04-01

    The present work deals with a detailed study of universal thermodynamics in different modified gravity theories. The validity of the generalized second law of thermodynamics (GSLT) and thermodynamical equilibrium (TE) of the Universe bounded by a horizon (apparent/event) in f(R) -gravity, Einstein-Gauss-Bonnet gravity, RS-II brane scenario and DGP brane model has been investigated. In the perspective of recent observational evidences, the matter in the Universe is chosen as interacting holographic dark energy model. The entropy on the horizons is evaluated from the validity of the unified first law and as a result there is a correction (in integral form) to the usual Bekenstein entropy. The other thermodynamical parameter namely temperature on the horizon is chosen as the recently introduced corrected Hawking temperature. The above thermodynamical analysis is done for homogeneous and isotropic flat FLRW model of the Universe. The restrictions for the validity of GSLT and the TE are presented in tabular form for each gravity theory. Finally, due to complicated expressions, the validity of GSLT and TE are also examined from graphical representation, using three Planck data sets.

  15. From thermodynamic cell models to partitioning cellular automata for diffusion in zeolites. I. Structure of the algorithm

    NASA Astrophysics Data System (ADS)

    Pazzona, Federico G.; Demontis, Pierfranco; Suffritti, Giuseppe B.

    2009-12-01

    In the study of adsorption of simple adsorbates in microporous materials like zeolites, thermodynamic models of small grand-canonical cells with very local interactions [e.g., see K. G. Ayappa, J. Chem. Phys. 111, 4736 (1999)] have been proven to be able to produce thermodynamic properties in very good agreement with the results of experiments and atomistic simulations. In this paper we present in details the structure and implementation of a thermodynamic partitioning cellular automaton (PCA) devised as a dynamical version of thermodynamic cell models and proposed as an easy environment to perform coarse-grained simulations of adsorption/diffusion of simple interacting molecules in microporous materials. Local evolution rules and memory effects are introduced to make our PCA able to complete the static picture provided by thermodynamic cell models with the simulation of transport properties.

  16. Introducing thermodynamics through energy and entropy

    NASA Astrophysics Data System (ADS)

    de Abreu, Rodrigo; Guerra, Vasco

    2012-07-01

    We suggest a simple approach to introducing thermodynamics, beginning with the concept of internal energy of deformable bodies. From a series of thought experiments involving ideal gases, we show that the internal energy depends on the volume and on a second parameter, leading to the development of the concept of entropy. By introducing entropy before the notions of temperature and heat, the proposed approach avoids some of the major conceptual difficulties with the traditional presentation. The relationship between mechanics and thermodynamics naturally emerges, mechanics corresponding to isentropic thermodynamics. The questions of evolution to equilibrium and irreversibility are studied under the light of the action of the "dynamic force" and its dissipative character, evincing the benefits of keeping in mind the microscopic picture.

  17. Adsorption of CO2 on Cu2O (1 1 1) oxygen-vacancy surface: First-principles study

    NASA Astrophysics Data System (ADS)

    Wu, Huanwen; Zhang, Ning; Wang, Hongming; Hong, Sanguo

    2013-05-01

    The adsorption of CO2 on Cu2O (1 1 1) oxygen-vacancy surface has been investigated by using the first-principles calculations based on the density functional theory (DFT). The geometry, adsorption energy, charge population and projected density of states (PDOS) were calculated. The results show dissociative adsorption of CO2 on the surface is thermodynamically unfeasible. The oxygen vacancy has the negative effects on the adsorption of CO2 at the coordinately unsaturated surface copper and oxygen (CuCUS and OCUS) sites. Oxygen vacancies are the active sites. CO2 can be directly adsorbed and converted into CO2δ- radical anion species at these sites.

  18. New findings on the influence of carbon surface curvature on energetics of benzene adsorption from gaseous phase

    NASA Astrophysics Data System (ADS)

    Terzyk, Artur P.; Furmaniak, Sylwester; Wiśniewski, Marek; Werengowska, Karolina; Gauden, Piotr A.; Kowalczyk, Piotr

    2016-02-01

    In this Letter, new results of calorimetric study on benzene adsorption from the gaseous phase are presented. According to some of recently published reports, the energy of solid-fluid, interactions increases with the rise in carbon nanotube curvature during adsorption. The recent considerations [Chem. Phys. Lett. 619 (2015) 219] on thermodynamics of adsorption from aqueous solutions on a series of carbon nanotubes have confirmed this observation. Although comparable 'energy-tube diameter' relations for benzene adsorption from the solution and from the gaseous phase are observed, remarkable differences between the mechanisms of the both processes caused by surface heterogeneity are noticeable.

  19. The adsorption enthalpy of nitrogen oxides on crystalline ice

    NASA Astrophysics Data System (ADS)

    Bartels-Rausch, T.; Eichler, B.; Zimmermann, P.; Gäggeler, H. W.; Ammann, M.

    2002-09-01

    The partitioning of nitrogen oxides between ice and air is of importance to the ozone budget in the upper troposphere. In the present study, adsorption of nitrogen oxides on ice was investigated at atmospheric pressure using a chromatographic technique with radioactively labelled nitrogen oxides at low concentrations. The measured retentions solely depended on molecular adsorption and were not influenced by dimerisation, formation of encapsulated hydrates on the ice surface, dissociation of the acids, nor by migration into a quasi-liquid layer or grain boundaries. Based on the chromatographic retention and the model of thermo-chromatography, the standard adsorption enthalpy of -20 kJ mol-1 for NO, -22kJ mol-1 for NO2, -30kJ mol-1 for peroxyacetyl nitrate, -32kJ mol-1 for HON} and -44 kJ mol-1 for HNO3 was calculated. To perform those calculations within the model of thermo-chromatography, the standard adsorption entropy was calculated based on statistical thermodynamics. In this work, two different choices of standard states were applied, and consequently different values of the standard adsorption entropy, of either between -39 kJ mol-1 and -45kJ mol-1, or -164 kJ mol-1 and -169 kJ mol-1 for each nitrogen oxide were derived. The standard adsorption enthalpy was identical for both standard adsorption entropies and thus shown to be independent of the choice of standard state. A brief outlook on environmental implications of our findings indicates that adsorption on ice might be an important removal process of HNO3. In addition, it might be of some importance for HONO and peroxyacetyl nitrate and irrelevant for NO and NO2.

  20. Adsorption of reactive dyes from aqueous solutions by fly ash: kinetic and equilibrium studies.

    PubMed

    Dizge, N; Aydiner, C; Demirbas, E; Kobya, M; Kara, S

    2008-02-11

    Adsorption kinetic and equilibrium studies of three reactive dyes namely, Remazol Brillant Blue (RB), Remazol Red 133 (RR) and Rifacion Yellow HED (RY) from aqueous solutions at various initial dye concentration (100-500 mg/l), pH (2-8), particle size (45-112.5 microm) and temperature (293-323 K) on fly ash (FA) were studied in a batch mode operation. The adsorbent was characterized with using several methods such as SEM, XRD and FTIR. Adsorption of RB reactive dye was found to be pH dependent but both RR and RY reactive dyes were not. The result showed that the amount adsorbed of the reactive dyes increased with increasing initial dye concentration and contact time. Batch kinetic data from experimental investigations on the removal of reactive dyes from aqueous solutions using FA have been well described by external mass transfer and intraparticle diffusion models. It was found that external mass transfer and intraparticle diffusion had rate limiting affects on the removal process. This was attributed to the relatively simple macropore structure of FA particles. The adsorption data fitted well with Langmuir and Freundlich isotherm models. The optimum conditions for removal of the reactive dyes were 100mg/l initial dye concentration, 0.6g/100ml adsorbent dose, temperature of 293 K, 45 microm particle size, pH 6 and agitation speed of 250 rpm, respectively. The values of Langmuir and Freundlich constants were found to increase with increasing temperature in the range 135-180 and 15-34 mg/g for RB, 47-86 and 1.9-3.7 mg/g for RR and 37-61 and 3.0-3.6 mg/g for RY reactive dyes, respectively. Different thermodynamic parameters viz., changes in standard free energy, enthalpy and entropy were evaluated and it was found that the reaction was spontaneous and endothermic in nature. PMID:17574338

  1. Thermodynamics of the variable modified Chaplygin gas

    NASA Astrophysics Data System (ADS)

    Panigrahi, D.; Chatterjee, S.

    2016-05-01

    A cosmological model with a new variant of Chaplygin gas obeying an equation of state(EoS), P = Aρ ‑ B/ρα where B= B0an is investigated in the context of its thermodynamical behaviour. Here B0 and n are constants and a is the scale factor. We show that the equation of state of this `Variable Modified Chaplygin gas' (VMCG) can describe the current accelerated expansion of the universe. Following standard thermodynamical criteria we mainly discuss the classical thermodynamical stability of the model and find that the new parameter, n introduced in VMCG plays a crucial role in determining the stability considerations and should always be negative. We further observe that although the earlier model of Lu explains many of the current observational findings of different probes it fails the desirable tests of thermodynamical stability. We also note that for 0n < our model points to a phantom type of expansion which, however, is found to be compatible with current SNe Ia observations and CMB anisotropy measurements. Further the third law of thermodynamics is obeyed in our case. Our model is very general in the sense that many of earlier works in this field may be obtained as a special case of our solution. An interesting point to note is that the model also apparently suggests a smooth transition from the big bang to the big rip in its whole evaluation process.

  2. Irreversible adsorption of particles on heterogeneous surfaces.

    PubMed

    Adamczyk, Zbigniew; Jaszczółt, Katarzyna; Michna, Aneta; Siwek, Barbara; Szyk-Warszyńska, Lilianna; Zembala, Maria

    2005-12-30

    Methods of theoretical and experimental evaluation of irreversible adsorption of particles, e.g., colloids and globular proteins at heterogeneous surfaces were reviewed. The theoretical models were based on the generalized random sequential adsorption (RSA) approach. Within the scope of these models, localized adsorption of particles occurring as a result of short-ranged attractive interactions with discrete adsorption sites was analyzed. Monte-Carlo type simulations performed according to this model enabled one to determine the initial flux, adsorption kinetics, jamming coverage and the structure of the particle monolayer as a function of the site coverage and the particle/site size ratio, denoted by lambda. It was revealed that the initial flux increased significantly with the site coverage theta(s) and the lambda parameter. This behavior was quantitatively interpreted in terms of the scaled particle theory. It also was demonstrated that particle adsorption kinetics and the jamming coverage increased significantly, at fixed site coverage, when the lambda parameter increased. Practically, for alpha = lambda2theta(s) > 1 the jamming coverage at the heterogeneous surfaces attained the value pertinent to continuous surfaces. The results obtained prove unequivocally that spherically shaped sites were more efficient in binding particles in comparison with disk-shaped sites. It also was predicted that for particle size ratio lambda < 4 the site multiplicity effect plays a dominant role, affecting significantly the structure of particle monolayers and the jamming coverage. Experimental results validating main aspects of these theoretical predictions also have been reviewed. These results were derived by using monodisperse latex particles adsorbing on substrates produced by covering uniform surface by adsorption sites of a desired size, coverage and surface charge. Particle deposition occurred under diffusion-controlled transport conditions and their coverage was

  3. Interlamellar adsorption of organic pollutants from water on hydrophobic clay minerals

    SciTech Connect

    Dekany, I.; Farkas, A.; Kiraly, Z.; Klumpp, E.; Narres, H.D.

    1995-12-01

    The adsorption excess isotherms of n-pentanol and nitrobenzene were determined with surfactant-modified (hexadecylanimonium ions) layered silicates. Both liquids intercalate into the silicate layers and increase the basal spacing, determined by X-ray diffraction measurements, depending on the equilibrium concentration in the bulk phase. To control the entropy change due to the intercalation, flow microcalorimetric experiments were made and enthalpy of displacement isotherms (adsorption and desorption) were determined. The information obtained from these three different measurements permitted the assessment of the composition of the interlarnellar space (in volume fraction of the intercalated molecules) and the thermodynamics of adsorption.

  4. Optimization by Response Surface Methodology of the adsorption of Coomassie Blue dye on natural and acid-treated clays.

    PubMed

    de Sales, Priscila F; Magriotis, Zuy M; Rossi, Marco A L S; Resende, Ricardo F; Nunes, Cleiton A

    2013-11-30

    The effect of acid treatment on natural agalmatolite (AN) and natural kaolinite (KN) was investigated, together with the influence of those modifications on the removal of Coomassie Blue (CB) dye. The process was optimized using the Response Surface Methodology (RSM) developed by the application of the quadratic model associated with the Central Composite Design. Adsorption was promoted by initial CB concentration of 25 mg L(-1), pH 2 and adsorbent mass of 0.1 g. The adsorption kinetics study carried out in optimized conditions established that the equilibrium times were 1 h for AN and AA (treated agalmatolite), 4 h for KN and 2 h for KA (treated kaolinite). The kinetics data for AN, KN and KA were best fitted to the pseudo second order model, whilst for AA, the result pointed to the pseudo first order model. In the isotherm of adsorption the maximum quantities were obtained with reference to 11.29 mg g(-1), 9.84 mg g(-1), 22.89 mg g(-1) and 30.08 mg g(-1) for the samples AN, AA, KN and KA respectively. The data fitting showed that the Sips model was the most satisfactory for all the adsorbents. The calculated thermodynamic parameters showed that the process was spontaneous in all the adsorbents, endothermic for the KN and KA samples, exothermic for AN and AA, involved the disorganization of the adsorption system for the KN and KA and its organization for the AN and AA samples. The results showed that the KN and KA samples were more appropriate for use as adsorbents. PMID:24141066

  5. Thermodynamics of Biological Processes

    PubMed Central

    Garcia, Hernan G.; Kondev, Jane; Orme, Nigel; Theriot, Julie A.; Phillips, Rob

    2012-01-01

    There is a long and rich tradition of using ideas from both equilibrium thermodynamics and its microscopic partner theory of equilibrium statistical mechanics. In this chapter, we provide some background on the origins of the seemingly unreasonable effectiveness of ideas from both thermodynamics and statistical mechanics in biology. After making a description of these foundational issues, we turn to a series of case studies primarily focused on binding that are intended to illustrate the broad biological reach of equilibrium thinking in biology. These case studies include ligand-gated ion channels, thermodynamic models of transcription, and recent applications to the problem of bacterial chemotaxis. As part of the description of these case studies, we explore a number of different uses of the famed Monod–Wyman–Changeux (MWC) model as a generic tool for providing a mathematical characterization of two-state systems. These case studies should provide a template for tailoring equilibrium ideas to other problems of biological interest. PMID:21333788

  6. Thermodynamics of Nonadditive Systems

    NASA Astrophysics Data System (ADS)

    Latella, Ivan; Pérez-Madrid, Agustín; Campa, Alessandro; Casetti, Lapo; Ruffo, Stefano

    2015-06-01

    The usual formulation of thermodynamics is based on the additivity of macroscopic systems. However, there are numerous examples of macroscopic systems that are not additive, due to the long-range character of the interaction among the constituents. We present here an approach in which nonadditive systems can be described within a purely thermodynamics formalism. The basic concept is to consider a large ensemble of replicas of the system where the standard formulation of thermodynamics can be naturally applied and the properties of a single system can be consequently inferred. After presenting the approach, we show its implementation in systems where the interaction decays as 1 /rα in the interparticle distance r , with α smaller than the embedding dimension d , and in the Thirring model for gravitational systems.

  7. Thermodynamics of Nitinol

    NASA Astrophysics Data System (ADS)

    McNichols, J. L., Jr.; Cory, J. S.

    1987-02-01

    A self-consistent macroscopic thermodynamics is developed for the calculation of work, heat, and dissipation for thermodynamic paths of the shape memory alloy, Nitinol. The thermodynamic system analyzed is a Nitinol helix for which extensive force-length-temperature (FLT) equation of state measurements have been made. The Nitinol system exhibits significant hysteresis and is determined to be a nonequilibrium thermostatic system. A set of equations of state are provided which correlate all reversible and irreversible Nitinol thermodynamic paths to both the set of helix (FLT) thermodynamic state variables and to new ``history'' state variables. It is shown that these equations predict observed cyclic behaviors not previously interpreted. In the absence of calorimetric measurements for the Nitinol helix system, a physical assumption is made that reversible paths are of constant phase. This assumption is used to estimate the reversible path thermal and mechanical heat capacities for the Nitinol system. With the state equations and the estimated reversible path heat capacities, the nonequilibrium thermostatic formalism is employed to derive expressions for the heat flow for any Nitinol thermodynamic path. It is shown that predicted calorimetric quantities are in good qualitative agreement with measurements. It is also shown that the calorimetric quantities are sensitive to state equation coefficients, which in turn are sensitive to cold-working or ``conditioning'' of the material. The large heat of transformation, ˜2.4 cal/g, an estimated isentropic temperature change of 22 °C and the large dimensional changes associated with the shape memory effect, imply that Nitinol may be useful for many applications, including use as a working medium for low-grade thermal-energy conversion (i.e., heat engines).

  8. [Application of classical isothermal adsorption models in heavy metal ions/ diatomite system and related problems].

    PubMed

    Zhu, Jian; Wu, Qing-Ding; Wang, Ping; Li, Ke-Lin; Lei, Ming-Jing; Zhang, Wei-Li

    2013-11-01

    In order to fully understand adsorption nature of Cu2+, Zn2+, Pb2+, Cd2+, Mn2+, Fe3+ onto natural diatomite, and to find problems of classical isothermal adsorption models' application in liquid/solid system, a series of isothermal adsorption tests were conducted. As results indicate, the most suitable isotherm models for describing adsorption of Pb2+, Cd2+, Cu2+, Zn2+, Mn2+, Fe3+ onto natural diatomite are Tenkin, Tenkin, Langmuir, Tenkin, Freundlich and Freundlich, respectively, the adsorption of each ion onto natural diatomite is mainly a physical process, and the adsorption reaction is favorable. It also can be found that, when using classical isothermal adsorption models to fit the experimental data in liquid/solid system, the equilibrium adsorption amount q(e) is not a single function of ion equilibrium concentration c(e), while is a function of two variables, namely c(e) and the adsorbent concentration W0, q(e) only depends on c(e)/W(0). Results also show that the classical isothermal adsorption models have a significant adsorbent effect, and their parameter values are unstable, the simulation values of parameter differ greatly from the measured values, which is unhelpful for practical use. The tests prove that four-adsorption-components model can be used for describing adsorption behavior of single ion in nature diatomite-liquid system, its parameters k and q(m) have constant values, which is favorable for practical quantitative calculation in a given system. PMID:24455943

  9. Viscoplasticity: A thermodynamic formulation

    NASA Technical Reports Server (NTRS)

    Freed, A. D.; Chaboche, J. L.

    1989-01-01

    A thermodynamic foundation using the concept of internal state variables is given for a general theory of viscoplasticity, as it applies to initially isotropic materials. Three fundamental internal state variables are admitted. They are: a tensor valued back stress for kinematic effects, and the scalar valued drag and yield strengths for isotropic effects. All three are considered to phenomenologically evolve according to competitive processes between strain hardening, strain induced dynamic recovery, and time induced static recovery. Within this phenomenological framework, a thermodynamically admissible set of evolution equations is put forth. This theory allows each of the three fundamental internal variables to be composed as a sum of independently evolving constituents.

  10. Thermodynamics of lattice OCD

    SciTech Connect

    Matsuoka, H.

    1985-01-01

    The thermodynamic consequences of QCD are explored in the framework of lattice gauge theory. Attention is focused upon the nature of the chiral symmetry restoration transition at finite temperature and at finite baryon density, and possible strategies for identifying relevant thermodynamic phases are discussed. Some numerical results are presented on the chiral symmetry restoration in the SU(2) gauge theory at high baryon density. The results suggest that with T approx. = 110 MeV there is a second order restoration transition at the critical baryon density n/sub B//sup c/ approx. = 0.62 fm/sup -3/.

  11. Conformational stab