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Sample records for adsorption equilibrium kinetics

  1. 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

  2. Adsorption of leather dye onto activated carbon prepared from bottle gourd: equilibrium, kinetic and mechanism studies.

    PubMed

    Foletto, Edson Luiz; Weber, Caroline Trevisan; Paz, Diego Silva; Mazutti, Marcio Antonio; Meili, Lucas; Bassaco, Mariana Moro; Collazzo, Gabriela Carvalho

    2013-01-01

    Activated carbon prepared from bottle gourd has been used as adsorbent for removal of leather dye (Direct Black 38) from aqueous solution. The activated carbon obtained showed a mesoporous texture, with surface area of 556.16 m(2) g(-1), and a surface free of organic functional groups. The initial dye concentration, contact time and pH significantly influenced the adsorption capacity. In the acid region (pH 2.5) the adsorption of dye was more favorable. The adsorption equilibrium was attained after 60 min. Equilibrium data were analyzed by the Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models. The equilibrium data were best described by the Langmuir isotherm, with maximum adsorption capacity of 94.9 mg g(-1). Adsorption kinetic data were fitted using the pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The adsorption kinetic was best described by the second-order kinetic equation. The adsorption process was controlled by both external mass transfer and intraparticle diffusion. Activated carbon prepared from bottle gourd was shown to be a promising material for adsorption of Direct Black 38 from aqueous solution. PMID:23128640

  3. Equilibrium and kinetic data and process design for adsorption of Congo Red onto bentonite.

    PubMed

    Bulut, Emrah; Ozacar, Mahmut; Sengil, I Ayhan

    2008-06-15

    The adsorption of Congo Red onto bentonite in a batch adsorber has been studied. Four kinetic models, the pseudo first- and second-order equations, the Elovich equation and the intraparticle diffusion equation, were selected to follow the adsorption process. Kinetic parameters; rate constants, equilibrium adsorption capacities and correlation coefficients, for each kinetic equation were calculated and discussed. It was shown that the adsorption of Congo Red onto bentonite could be described by the pseudo second-order equation. The experimental isotherm data were analyzed using the Langmuir, Freundlich and Temkin equations. Adsorption of Congo Red onto bentonite followed the Langmuir isotherm. A single stage batch adsorber was designed for different adsorbent mass/treated effluent volume ratios using the Langmuir isotherm. PMID:18055111

  4. 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

  5. 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.

  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. 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

  8. Equilibrium and kinetics studies of arsenate adsorption by FePO(4).

    PubMed

    Hamayun, M; Mahmood, T; Naeem, A; Muska, M; Din, S U; Waseem, M

    2014-03-01

    The present work is focusing on removal of arsenate from aqueous solution using FePO4. The equilibrium study regarding the removal of arsenic by FePO4 was carried out at 298, 308, 318 and 328K. Langmuir parameters were found to increase with the increase in temperature indicating that the adsorption is favorable at high temperature. Kinetic study of arsenate adsorption on FePO4 was also carried out at different temperatures and at pH 6 and 8. Different kinetic models were used to the kinetic data amongst which pseudo second order model was best fitted. The mechanism of the adsorption kinetics was investigated by employing intraparticle diffusion and Richenberg models. The energy of activation (Ea) was found to be 30 and 35.52kJmol(-1) at pH 6 and pH 8, respectively, suggesting chemisorption nature of the adsorption process. The negative entropic values of activation signified the existence of entropy barrier while the positive ΔG(#) values indicated the existence of energy barrier to be crossed over for the occurrence of a chemical reaction. Both the spectroscopic studies and increase in equilibrium pH reveal the anion exchange removal of arsenate from aqueous solution to the solid surface. PMID:24280053

  9. Adsorption equilibrium and kinetics of monomer-dimer monoclonal antibody mixtures on a cation exchange resin.

    PubMed

    Reck, Jason M; Pabst, Timothy M; Hunter, Alan K; Wang, Xiangyang; Carta, Giorgio

    2015-07-10

    Adsorption equilibrium and kinetics are determined for a monoclonal antibody (mAb) monomer and dimer species, individually and in mixtures, on a macroporous cation exchange resin both under the dilute limit of salt gradient elution chromatography and at high protein loads and low salt based on batch adsorption equilibrium and confocal laser scanning microscopy (CLSM) experiments. In the dilute limit and weak binding conditions, the dimer/monomer selectivity in 10mM phosphate at pH 7 varies between 8.7 and 2.3 decreasing with salt concentration in the range of 170-230mM NaCl. At high protein loads and strong binding conditions (0-60mM NaCl), the selectivity in the same buffer is near unity with no NaCl added, but increases gradually with salt concentration reaching high values between 2 and 15 with 60mM added NaCl. For these conditions, the two-component adsorption kinetics is controlled by pore diffusion and is predicted approximately by a dual shrinking core model using parameters based on single component equilibrium and kinetics measurements. PMID:26028510

  10. 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

  11. Dye removal from textile industrial effluents by adsorption on exfoliated graphite nanoplatelets: kinetic and equilibrium studies.

    PubMed

    Carvallho, Marilda N; da Silva, Karolyne S; Sales, Deivson C S; Freire, Eleonora M P L; Sobrinho, Maurício A M; Ghislandi, Marcos G

    2016-01-01

    The concept of physical adsorption was applied for the removal of direct and reactive blue textile dyes from industrial effluents. Commercial graphite nanoplatelets were used as substrate, and the quality of the material was characterized by atomic force and transmission electron microscopies. Dye/graphite nanoplatelets water solutions were prepared varying their pH and initial dye concentration. Exceptionally high values (beyond 100 mg/L) for adsorptive capacity of graphite nanoplatelets could be achieved without complicated chemical modifications, and equilibrium and kinetic experiments were performed. Our findings were compared with the state of the art, and compared with theoretical models. Agreement between them was satisfactory, and allowed us to propose novel considerations describing the interactions of the dyes and the graphene planar structure. The work highlights the important role of these interactions, which can govern the mobility of the dye molecules and the amount of layers that can be stacked on the graphite nanoplatelets surface. PMID:27148721

  12. 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

  13. Adsorption of reactive blue BF-5G dye by soybean hulls: kinetics, equilibrium and influencing factors.

    PubMed

    Honorio, Jacqueline Ferandin; Veit, Márcia Teresinha; Gonçalves, Gilberto da Cunha; de Campos, Élvio Antonio; Fagundes-Klen, Márcia Regina

    2016-01-01

    The textile industry is known for the high use of chemicals, such as dyes, and large volumes of effluent that contaminate waters, a fact that has encouraged research and improved treatment techniques. In this study, we used unprocessed soybean hulls for the removal of reactive blue BF-5G dye. The point of zero charge of soybean hulls was 6.76. Regarding the speed of agitation in the adsorption process, the resistance to mass transfer that occurs in the boundary layer was eliminated at 100 rpm. Kinetics showed an experimental amount of dye adsorbed at equilibrium of 57.473 mg g(-1) obtained under the following conditions: dye initial concentration = 400 mg L(-1); diameter of particle = 0.725 mm; dosage = 6 g L(-1); pH 2; 100 rpm; temperature = 30 °C; and duration of 24 hours. The pseudo-second order best showed the dye removal kinetics. The adsorption isotherms performed at different temperatures (20, 30, 40 and 50 °C) showed little variation in the concentration range assessed, being properly adjusted by the Langmuir isotherm model. The maximum capacity of dye adsorption was 72.427 mg g(-1) at 30 °C. Since soybean hull is a low-cost industrial byproduct, it proved to be a potential adsorbent for the removal of the textile dye assessed. PMID:26942540

  14. 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

  15. Equilibrium and kinetic adsorption study of Basic Yellow 28 and Basic Red 46 by a boron industry waste.

    PubMed

    Olgun, Asim; Atar, Necip

    2009-01-15

    In this study, the adsorption characteristics of Basic Yellow 28 (BY 28) and Basic Red 46 (BR 46) onto boron waste (BW), a waste produced from boron processing plant were investigated. The equilibrium adsorption isotherms and kinetics were investigated. The adsorption equilibrium data were analyzed by using various adsorption isotherm models and the results have shown that adsorption behavior of two dyes could be described reasonably well by a generalized isotherm. Kinetic studies indicated that the kinetics of the adsorption of BY 28 and BR 46 onto BW follows a pseudo-second-order model. The result showed that the BW exhibited high-adsorption capacity for basic dyes and the capacity slightly decreased with increasing temperature. The maximum adsorption capacities of BY 28 and BR 46 are reported at 75.00 and 74.73mgg(-1), respectively. The dye adsorption depended on the initial pH of the solution with maximum uptake occurring at about pH 9 and electrokinetic behavior of BW. Activation energy of 15.23kJ/mol for BY 28 and 18.15kJ/mol for BR 46 were determined confirming the nature of the physisorption onto BW. These results indicate that BW could be employed as low-cost material for the removal of the textile dyes from effluents. PMID:18434000

  16. 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

  17. Equilibrium and kinetic studies of adsorption of phosphate onto ZnCl2 activated coir pith carbon.

    PubMed

    Namasivayam, C; Sangeetha, D

    2004-12-15

    Phosphate removal from aqueous solution was investigated using ZnCl(2)-activated carbon developed from coir pith, an agricultural solid waste. Studies were conducted to delineate the effect of contact time, adsorbent dose, phosphate concentration, pH, and temperature. The adsorption equilibrium data followed both Langmuir and Freundlich isotherms. Langmuir adsorption capacity was found to be 5.1 mg/g. Adsorption followed second-order kinetics. The removal was maximum in the pH range 3-10. pH effect and desorption studies showed that adsorption occurred by both ion exchange and chemisorption mechanisms. Adsorption was found to be spontaneous and endothermic. Effect of foreign ions on adsorption shows that perchlorate, sulfate, and selenite decreased the percent removal of phosphate. PMID:15533408

  18. 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.

  19. 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

  20. 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

  1. Adsorption kinetics and equilibrium study of nitrogen species onto radiata pine (Pinus radiata) sawdust.

    PubMed

    Harmayani, Kadek D; Faisal Anwar, A H M

    2016-01-01

    Nitrogen species (NH3-N, NO3-N, and NO2-N) are found as one of the major dissolved constituents in wastewater or stormwater runoff. In this research, laboratory experiments were conducted to remove these pollutants from the water environment using radiata pine (Pinus radiata) sawdust. A series of batch tests was conducted by varying initial concentration, dosage, particle size, pH, and contact time to check the removal performance. Test results confirmed the effectiveness of radiata pine sawdust for removing these contaminants from the aqueous phase (100% removal of NO3-N, and NO2-N; 55% removal of NH3-N). The adsorbent dosage and initial concentration showed a significantly greater effect on the removal process over pH or particle sizes. The optimum dosage for contaminant removal on a laboratory scale was found to be 12 g. Next, the adsorption kinetics were studied using intraparticle diffusion, liquid-film diffusion, and a pseudo-first order and pseudo-second order model. The adsorption of all species followed a pseudo-second order model but NO2-N adsorption followed both models. In addition, the kinetics of NO2-N adsorption showed two-step adsorption following intraparticle diffusion and liquid-film diffusion. The isotherm study showed that NO3-N and NO2-N adsorption fitted slightly better with the Freundlich model but that NH3-N adsorption followed both Freundlich and Langmuir models. PMID:27438245

  2. Adsorption and desorption of arsenate on sandy sediments from contaminated and uncontaminated saturated zones: Kinetic and equilibrium modeling.

    PubMed

    Hafeznezami, Saeedreza; Zimmer-Faust, Amity G; Dunne, Aislinn; Tran, Tiffany; Yang, Chao; Lam, Jacquelyn R; Reynolds, Matthew D; Davis, James A; Jay, Jennifer A

    2016-08-01

    Application of empirical models to adsorption of contaminants on natural heterogeneous sorbents is often challenging due to the uncertainty associated with fitting experimental data and determining adjustable parameters. Sediment samples from contaminated and uncontaminated portions of a study site in Maine, USA were collected and investigated for adsorption of arsenate [As(V)]. Two kinetic models were used to describe the results of single solute batch adsorption experiments. Piecewise linear regression of data linearized to fit pseudo-first order kinetic model resulted in two distinct rates and a cutoff time point of 14-19 h delineating the biphasic behavior of solute adsorption. During the initial rapid adsorption stage, an average of 60-80% of the total adsorption took place. Pseudo-second order kinetic models provided the best fit to the experimental data (R(2) > 0.99) and were capable of describing the adsorption over the entire range of experiments. Both Langmuir and Freundlich isotherms provided reasonable fits to the adsorption data at equilibrium. Langmuir-derived maximum adsorption capacity (St) of the studied sediments ranged between 29 and 97 mg/kg increasing from contaminated to uncontaminated sites. Solid phase As content of the sediments ranged from 3.8 to 10 mg/kg and the As/Fe ratios were highest in the amorphous phase. High-pH desorption experiments resulted in a greater percentage of solid phase As released into solution from experimentally-loaded sediments than from the unaltered samples suggesting that As(V) adsorption takes place on different reversible and irreversible surface sites. PMID:27218893

  3. Batch removal of malachite green from aqueous solutions by adsorption on oil palm trunk fibre: equilibrium isotherms and kinetic studies.

    PubMed

    Hameed, B H; El-Khaiary, M I

    2008-06-15

    Oil palm trunk fibre (OPTF)--an agricultural solid waste--was used as low-cost adsorbent to remove malachite green (MG) from aqueous solutions. The operating variables studied were contact time, initial dye concentration, and solution pH. Equilibrium adsorption data were analyzed by three isotherms, namely the Freundlich isotherm, the Langmuir isotherm, and the multilayer adsorption isotherm. The best fit to the data was obtained with the multilayer adsorption. The monolayer adsorption capacity of OPTF was found to be 149.35 mg/g at 30 degrees C. Adsorption kinetic data were modeled using the Lagergren pseudo-first-order, Ho's pseudo-second-order and Elovich models. It was found that the Lagergren's model could be used for the prediction of the system's kinetics. The overall rate of dye uptake was found to be controlled by external mass transfer at the beginning of adsorption, then for initial MG concentrations of 25, 50, 100, 150, and 300 mg/L the rate-control changed to intraparticle diffusion at a later stage, but for initial MG concentrations 200 and 250 mg/L no evidence was found of intraparticle diffusion at any period of adsorption. It was found that with increasing the initial concentration of MG, the pore-diffusion coefficient increased while the film-diffusion coefficient decreased. PMID:18022316

  4. Adsorption removal of tetracycline from aqueous solution by anaerobic granular sludge: equilibrium and kinetic studies.

    PubMed

    Li, Ke; Ji, Feng; Liu, Yuanlu; Tong, Zilin; Zhan, Xinmin; Hu, Zhenhu

    2013-01-01

    High concentration animal wastewater is often contaminated by tetracycline and an upflow anaerobic sludge bioreactor (UASB) with granular sludge is often used to treat the wastewater. The investigation of the adsorption process of tetracycline on anaerobic granular sludge during anaerobic digestion of animal wastewater will increase the understanding of antibiotics behavior in the UASB reactor. In this study, the effects of initial pH, humic acid concentration, and temperature on the removal of tetracycline by anaerobic granular sludge from aqueous solution were investigated using the batch adsorption technique in 100 mL flasks with 75 mL of work volume. The results show that the highest removal efficiency of 93.0% was achieved around pH 3.0 and the removal efficiency at the neutral pH range (pH 6.0-8.0) is about 91.5%. The thermodynamic analysis indicates that the adsorption is a spontaneous and endothermic process. The adsorption kinetics followed the pseudo-second-order equation. The adsorption isotherms analysis indicates that the Langmuir model is better than the Freundlich model for the description of the adsorption process and confirms the result of thermodynamics analysis. The maximum adsorption capacities were 2.984, 4.108 and 4.618 mg/g at 25, 35 and 45 °C, respectively. These results provide useful information for understanding the fate and transformation of tetracycline in a UASB digestion system and improving the management of tetracycline contaminated animal wastewater. PMID:23552236

  5. 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

  6. Adsorption behavior of direct red 80 and congo red onto activated carbon/surfactant: Process optimization, kinetics and equilibrium

    NASA Astrophysics Data System (ADS)

    Cheng, Zhengjun; Zhang, Lei; Guo, Xiao; Jiang, Xiaohui; Li, Tian

    2015-02-01

    Adsorptions of congo red and direct red 80 onto activated carbon/surfactant from aqueous solution were optimized. The Box-Behnken design (BBD) has been employed to analyze the effects of concentration of surfactant, temperature, pH, and initial concentration of the dye in the adsorption capacity. Their corresponding experimental data could be evaluated excellently by second order polynomial regression models and the two models were also examined based on the analysis of variance and t test statistics, respectively. The optimum conditions were obtained as follows: Cs = 34.10 μM, T = 50 °C, pH = 3.5, and CCR = 160 mg/L for the congo red system, and Cs = 34.10 μM, T = 50 °C, pH = 6.1, and CDR80 = 110 mg/L for the direct red 80 system. And in these conditions, the measured experimental maximum adsorption capacities for the congo red and direct red 80 removals were 769.48 mg/g and 519.90 mg/g, which were consistent with their corresponding predicted values, with small relative errors of -2.81% and -0.67%, respectively. The adsorption equilibrium and kinetics for the two dye adsorptions onto AC/DDAC were also investigated. The experimental data were fitted by four isotherm models, and Langmuir model presented the best fit. The kinetic studies indicated that the kinetic data followed the pseudo-second-order model.

  7. Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

    SciTech Connect

    Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

    2013-02-12

    Rates of contaminant U(VI) release from individual size fractions of a composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through batch reactors to maintain quasi-constant chemical conditions. Variability in equilibrium adsorption among the various size fractions was determined in static batch reactors and analyzed using the surface complexation modeling approach. The estimated stoichiometric coefficients of U(VI) surface complexation reactions with respect to pH and carbonate concentrations varied with size fractions. This source of variability significantly increased the uncertainty in U(VI) conditional equilibrium constants over that estimated from experimental errors alone. A minimum difference between conditional equilibrium constants was established in order to evaluate statistically significant differences between sediment adsorption properties. A set of equilibrium and kinetic expressions for cation exchange, calcite dissolution, aerobic respiration, and silica dissolution were incorporated in a reaction-rate model to describe the temporal evolution of solute concentrations observed during the flow-through batch experiments. Parameters in the reaction-rate model, calibrated using experimental data for select size fractions, predicted the changes in solute concentrations for the bulk, <2 mm, sediment sample. Kinetic U(VI) desorption was well described using a multi-rate surface complexation model with an assumed lognormal distribution for the rate constants. The estimated mean and standard deviation were the same for all < 2mm size fractions, but differed in the 2-8mm size fraction. Micropore volumes in the varied size fractions were also similar as assessed using t-plots to analyze N2 desorption data. These findings provide further support for the link between microporosity and particle-scale mass transfer rates controlling kinetic U(VI) adsorption/desorption and for the utility of N2 desorption

  8. 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

  9. 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

  10. Hydrous ferric oxide doped alginate beads for fluoride removal: Adsorption kinetics and equilibrium studies

    NASA Astrophysics Data System (ADS)

    Sujana, M. G.; Mishra, A.; Acharya, B. C.

    2013-04-01

    A new biopolymer beads, composite of hydrous ferric oxide (HFO) and alginate were synthesised, characterised and studied for its fluoride efficiency from water. The beads were characterised by chemical analysis, BET surface area, pHPZC and X-ray diffraction (XRD) analysis. The optimum conditions for fluoride removal were determined by studying operational variables viz. pH, contact time, initial F- concentration, bead dose and temperature. Presence of other anions like SO42-, PO43-, NO3-, Cl- and HCO3- effect on fluoride removal efficiency of prepared beads was also tested. The beads were 0.8-0.9 mm in size and contain 32-33% Fe (III) and showed specific surface area of 25.80 m2 g-1 and pHPZC of 5.15. Modified beads demonstrated Langmuir F- adsorption capacity of 8.90 mg g-1 at pH 7.0. The adsorption kinetics were best described by the pseudo-second order kinetic model followed by intra-particle diffusion as the rate determining step. It was found that about 80% of the adsorbed fluoride could be desorbed by using 0.05 M HCl. The FTIR, Raman and SEM-EDAX analysis were used to study the fluoride adsorption mechanisms on beads. Studies were also conducted to test the potential application of beads for F- removal from drinking water and the treated water quality.

  11. 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

  12. Adsorption of Rhodamine B on two novel polar-modified post-cross-linked resins: Equilibrium and kinetics.

    PubMed

    Jiang, Xiangfu; Huang, Jianhan

    2016-04-01

    We employed two polar monomers, triallyl isocyanurate (TAIC) and butyl acrylate (BA), to copolymerize with divinylbenzene (DVB), and synthesized two starting copolymers labeled PDT and PDB. Then, the Friedel-Crafts alkylation reaction was performed for the two starting copolymers, and the residual pendent vinyl groups were consumed, and hence we obtained two novel polar-modified post-cross-linked resins PDTpc and PDBpc. The surface polarity greatly improved due to introduction of the polar monomers, and the Brunauer-Emmett-Teller (BET) surface area and pore volume significantly increased after the Friedel-Crafts alkylation reaction. Compared with the starting copolymers, the non-polar post-cross-linked resin PDVBpc and some other adsorbents in the references, PDTpc and PDBpc possessed a much enhanced adsorption to Rhodamine B, and the equilibrium capacity reached 578.2mg/g and 328.7mg/g, respectively, at an equilibrium concentration of 100mg/L, and the Freundlich model characterized the equilibrium data very well. The adsorption was a fast process and the kinetic data obeyed the micropore diffusion model. These results confirmed that PDTpc and PDBpc had the potential superiority in adsorptive removal of Rhodamine B from aqueous solution. PMID:26803602

  13. Kinetics and equilibrium studies of adsorption of chromium(VI) ion from industrial wastewater using Chrysophyllum albidum (Sapotaceae) seed shells.

    PubMed

    Amuda, O S; Adelowo, F E; Ologunde, M O

    2009-02-01

    A new biosorbent has been prepared by coating Chrysophyllum albidum (Sapotaceae) seed shells with chitosan and/or oxidizing agents such as sulfuric acid. This study investigated the technical feasibility of activated and modified activated C. albidum seed shells carbons for the adsorption of chromium(VI) from aqueous solution. The sorption process with respect to its equilibria and kinetics as well as the effects of pH, contact time, adsorbent mass, adsorbate concentration and particle size on adsorption was also studied. The most effective pH range was found to be between 4.5 and 5 for the sorption of the metal ion. The pseudo-first-order rate equation by Lagergren and pseudo-second-order rate equation were tested on the kinetic data, the adsorption process followed pseudo-second-order rate kinetics, also, isotherm data was analyzed for possible agreement with the Langmuir and Freundlich adsorption isotherms, the Freundlich and Langmuir models for dynamics of metal ion uptake proposed in this work fitted the experimental data reasonably well. However, equilibrium sorption data were better represented by Langmuir model than Freundlich. The adsorption capacity calculated from Langmuir isotherm was 84.31, 76.23 and 59.63mgCr(VI)/g at initial pH of 3.0 at 30 degrees C for the particle size of 1.00-1.25mm with the use of 12.5, 16.5 and 2.1g/L of CACASC, CCASC and ACASC adsorbent mass, respectively. This readily available adsorbent is efficient in the uptake of Cr(VI) ion in aqueous solution, thus, it could be an excellent alternative for the removal of heavy metals and organic matter from water and wastewater. PMID:19022632

  14. 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

  15. Rapid Adsorption of Copper(II) and Lead(II) by Rice Straw/Fe3O4 Nanocomposite: Optimization, Equilibrium Isotherms, and Adsorption Kinetics Study

    PubMed Central

    Khandanlou, Roshanak; Ahmad, Mansor B.; Fard Masoumi, Hamid Reza; Shameli, Kamyar; Basri, Mahiran; Kalantari, Katayoon

    2015-01-01

    Rice straw/magnetic nanocomposites (RS/Fe3O4-NCs) were prepared via co-precipitation method for removal of Pb(II) and Cu(II) from aqueous solutions. Response surface methodology (RSM) was utilized to find the optimum conditions for removal of ions. The effects of three independent variables including initial ion concentration, removal time, and adsorbent dosage were investigated on the maximum adsorption of Pb (II) and Cu (II). The optimum conditions for the adsorption of Pb(II) and Cu(II) were obtained (100 and 60 mg/L) of initial ion concentration, (41.96 and 59.35 s) of removal time and 0.13 g of adsorbent for both ions, respectively. The maximum removal efficiencies of Pb(II) and Cu(II) were obtained 96.25% and 75.54%, respectively. In the equilibrium isotherm study, the adsorption data fitted well with the Langmuir isotherm model. The adsorption kinetics was best depicted by the pseudo-second order model. Desorption experiments showed adsorbent can be reused successfully for three adsorption-desorption cycles. PMID:25815470

  16. Adsorption of Pb(II) ions onto biomass from Trifolium resupinatum: equilibrium and kinetic studies

    NASA Astrophysics Data System (ADS)

    Athar, Makshoof; Farooq, Umar; Aslam, Muhammad; Salman, M.

    2013-09-01

    The present study provides information about the binding of Pb(II) ions on an eco-friendly and easily available biodegradable biomass Trifolium resupinatum. The powdered biomass was characterized by FTIR, potentiometric titration and surface area analyses. The FTIR spectrum showed the presence of hydroxyl, carbonyl and amino functional groups and Pb(II) ions bound with the oxygen- and nitrogen-containing sites (hydroxyl and amino groups). The acidic groups were also confirmed by titrations. Effects of various environmental parameters (time, pH and concentration) have been studied. The biosorption process achieved equilibrium in a very short period of time (25 min). Non-linear approach for Langmuir and Freundlich models was used to study equilibrium process and root mean-square error was used as an indicator to decide the fitness of the mathematical model. The biosorption process was found to follow pseudo-second-order kinetics and was very fast. Thus, the biomass can be cost-effectively used for the binding of Pb(II) ions from aqueous solutions.

  17. Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics.

    PubMed

    Anirudhan, T S; Divya, L; Suchithra, P S

    2009-01-01

    This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater

  18. 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

  19. Equilibrium and kinetic models on the adsorption of Reactive Black 5 from aqueous solution using Eichhornia crassipes/chitosan composite.

    PubMed

    El-Zawahry, Manal M; Abdelghaffar, Fatma; Abdelghaffar, Rehab A; Hassabo, Ahmed G

    2016-01-20

    New natural biopolymer composite was prepared using extracted cellulose from an environmentally problematic water hyacinth Eichhornia crassipes (EC). The extracted cellulose was functionalized by chitosan and TiO2 nanoparticles to form EC/Chitosan (EC/Cs) composite network. Surface characterization of EC/Cs natural biopolymer composite was examined by spectrum analysis FT-IR, specific surface area, micropore volume, pore width and SEM. Furthermore, the sorption experiments were carried out as a function of pH, various initial dye concentration and contact time. Experiment results showed that the EC/Cs composite have high ability to remove C.I. Reactive Black 5 from its dye-bath effluent. The equilibrium sorption evaluation of RB5 conformed and fitted well to Langmuir adsorption isotherm models and the maximum sorption capacity was 0.606 mg/g. The kinetic adsorption models followed pseudo-second order model and the dye intra-particle diffusion may suggesting a chemical reaction mechanism. Further, it was obvious from the investigation that this composite could be applied as a promising low cost adsorbent for anionic dye removal from aqueous solutions. PMID:26572382

  20. Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

    USGS Publications Warehouse

    Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

    2013-01-01

    Rates of U(VI) release from individual dry-sieved size fractions of a field-aggregated, field-contaminated composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through reactors to maintain quasi-constant chemical conditions. The principal source of variability in equilibrium U(VI) adsorption properties of the various size fractions was the impact of variable chemistry on adsorption. This source of variability was represented using surface complexation models (SCMs) with different stoichiometric coefficients with respect to hydrogen ion and carbonate concentrations for the different size fractions. A reactive transport model incorporating equilibrium expressions for cation exchange and calcite dissolution, along with rate expressions for aerobic respiration and silica dissolution, described the temporal evolution of solute concentrations observed during the flow-through reactor experiments. Kinetic U(VI) desorption was well described using a multirate SCM with an assumed lognormal distribution for the mass-transfer rate coefficients. The estimated mean and standard deviation of the rate coefficients were the same for all <2 mm size fractions but differed for the 2–8 mm size fraction. Micropore volumes, assessed using t-plots to analyze N2 desorption data, were also the same for all dry-sieved <2 mm size fractions, indicating a link between micropore volumes and mass-transfer rate properties. Pore volumes for dry-sieved size fractions exceeded values for the corresponding wet-sieved fractions. We hypothesize that repeated field wetting and drying cycles lead to the formation of aggregates and/or coatings containing (micro)pore networks which provided an additional mass-transfer resistance over that associated with individual particles. The 2–8 mm fraction exhibited a larger average and standard deviation in the distribution of mass-transfer rate coefficients, possibly caused by the abundance of

  1. 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.

  2. Equilibrium and kinetics study on the adsorption of perfluorooctanoic acid from aqueous solution onto powdered activated carbon.

    PubMed

    Qu, Yan; Zhang, Chaojie; Li, Fei; Bo, Xiaowen; Liu, Guangfu; Zhou, Qi

    2009-09-30

    Powdered activated carbon (PAC) was applied to remove perfluorooctanoic acid (PFOA) from the aqueous PFOA solution in this study. Contact time, adsorbent dose and temperature were analyzed as the effect factors in the adsorption reaction. The contact time of maximum PFOA uptake was around 1h while the sorption removal efficiency increased with the PAC concentrations. And the process of adsorption increased from 303 K to 313 K and then decreased from 313 K to 323 K. Among four applied models, the experimental isotherm data were discovered to follow Langmuir isotherm model more closely. Thermodynamically, adsorption was endothermic because enthalpy, entropy and Gibbs constants were 198.5 kJ/mol, 0.709 kJ/mol/K and negative, respectively, which also indicated that the adsorption process was spontaneous and feasible. From kinetic analysis, the adsorption was suggested to be pseudo-second-order model. The adsorption of PFOA on the PAC was mainly controlled by particle diffusion. PMID:19395160

  3. 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

  4. 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.

  5. 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

  6. A novel polar-modified post-cross-linked resin and its enhanced adsorption to salicylic acid: Equilibrium, kinetics and breakthrough studies.

    PubMed

    Wang, Xiaomei; Li, Guoqiang; Guo, Deping; Zhang, Yaling; Huang, Jianhan

    2016-05-15

    Improving the surface polarity is of significance for the post-cross-linked resins to enhance their adsorption to polar aromatic compounds. In the present study, we prepared a novel polar-modified post-cross-linked PDEpc_D by the Friedel-Crafts alkylation reaction and the amination reaction, the Brunauer-Emmett-Teller (BET) surface area and pore volume increased significantly after the Friedel-Crafts alkylation reaction and the surface polarity improved greatly after the amination reaction. Batch adsorption showed that PDEpc_D possessed a much enhanced adsorption to salicylic acid as compared the precursors PDE and PDEpc as well as the non-polar post-cross-linked PDVBpc. The equilibrium data was characterized by the Freundlich model, π-π stacking, hydrogen bonding and static interaction were the possible driving forces. The adsorption was a fast process and the kinetic data obeyed the micropore diffusion model. Column adsorption-desorption experiments suggested that PDEpc_D was a potential candidate for adsorptive removal of salicylic acid from aqueous solution. PMID:26928058

  7. Polar modified post-cross-linked resin and its adsorption toward salicylic acid from aqueous solution: Equilibrium, kinetics and breakthrough studies.

    PubMed

    Fu, Zhenyu; He, Chunlian; Huang, Jianhan; Liu, You-Nian

    2015-08-01

    A novel polar modified post-cross-linked resin PDMPA was synthesized, characterized and evaluated for adsorption of salicylic acid from aqueous solution. PDMPA was prepared by a suspension polymerization of methyl acrylate (MA) and divinylbenzene (DVB), a Friedel-Crafts reaction and an amination reaction. After characterization of the chemical and pore structure of PDMPA, the adsorption behaviors of salicylic acid on PDMPA were determined in comparison with the precursor resins. The equilibrium adsorption capacity of salicylic acid on PDMPA was much larger than the precursor resins and the equilibrium data were correlated by both of the Langmuir and Freundlich models. The pseudo-second-order rate equation fitted the kinetic data better than the pseudo-first-order rate equation, and the micropore diffusion model could characterize the kinetic data very well. The dynamic experimental results showed that the breakthrough point and saturated point of salicylic acid on PDMPA were 40.3 and 92.4BV (1BV=10mL) at a feed concentration of 995.8mg/L and a flow rate of 1.4mL/min, and the resin column could be regenerated by 16.0BV of a mixture desorption solvent containing 0.01mol/L of NaOH (w/v) and 50% of ethanol (v/v). PMID:25863446

  8. Removal of azo dye by a highly graphitized and heteroatom doped carbon derived from fish waste: Adsorption equilibrium and kinetics.

    PubMed

    Liu, Zhengang; Zhang, Fang; Liu, Tingting; Peng, Nana; Gai, Chao

    2016-11-01

    A highly graphitized and heteroatom doped porous carbon was prepared from fish waste in the present study. The morphology and chemical composition of the resultant porous carbon were characterized by SEM-EDS, TEM, BET, XRD and Raman measurement. The prepared porous carbon was employed as an adsorbent for acid orange 7, a typical azo dye, removal from aqueous solution. The results showed that the porous carbon had ultrahigh surface area of 2146 m(2)/g, a high degree of graphitization structure and naturally doped with nitrogen and phosphorous. The maximum adsorption capacity of acid orange 7 reached 285.71 mg/g due to unique property of the prepared porous carbon. In addition, acid orange 7 adsorption onto the porous carbon well followed pseudo-second-order kinetics model and acid orange 7 diffusion in micropores was the potential rate controlling step. PMID:27526082

  9. Study on an effective industrial waste-based adsorbent for the adsorptive removal of phosphorus from wastewater: equilibrium and kinetics studies.

    PubMed

    Xie, Ruzhen; Chen, Yao; Cheng, Ting; Lai, Yuguo; Jiang, Wenju; Yang, Zhishan

    2016-01-01

    In this work, an effective adsorbent for removing phosphate from aqueous solution was developed from modifying industrial waste--lithium silica fume (LSF). The characterization of LSF before and after modification was investigated using an N2 adsorption-desorption technique (Brunauer-Emmett-Teller, BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Studies were conducted to investigate the effect of adsorbent dose, initial solution pH, contact time, phosphate concentration, and temperature on phosphate removal using this novel adsorbent. The specific surface area for modified LSF (LLSF) is 24.4024 m(2)/g, improved 69.8% compared with unmodified LSF. XRD result suggests that the lanthanum phosphate complex was formed on the surface of LLSF. The maximum phosphate adsorption capacity was 24.096 mg P/g for LLSF, and phosphate removal was favored in the pH range of 3-8. The kinetic data fitted pseudo-second-order kinetic equation, intra-particle diffusion was not the only rate controlling step. The adsorption isotherm results illustrated that the Langmuir model provided the best fit for the equilibrium data. The change in free energy (△G(0)), enthalpy (△H(0)) and entropy (△S(0)) revealed that the adsorption of phosphate on LLSF was spontaneous and endothermic. It was concluded that by modifying with lanthanum, LSF can be turned to be a highly efficient adsorbent in phosphate removal. PMID:27120644

  10. Adsorption/desorption of Cd(II), Cu(II) and Pb(II) using chemically modified orange peel: Equilibrium and kinetic studies

    NASA Astrophysics Data System (ADS)

    Lasheen, Mohamed R.; Ammar, Nabila S.; Ibrahim, Hanan S.

    2012-02-01

    Waste materials from industries such as food processing may act as cost effective and efficient biosorbents to remove toxic contaminants from wastewater. This study aimed to establish an optimized condition and closed loop application of processed orange peel for metals removal. A comparative study of the adsorption capacity of the chemically modified orange peel was performed against environmentally problematic metal ions, namely, Cd 2+, Cu 2+ and Pb 2+, from aqueous solutions. Chemically modified orange peel (MOP) showed a significantly higher metal uptake capacity compared to original orange peel (OP). Fourier Transform Infrared (FTIR) Spectra of peel showed that the carboxylic group peak shifted from 1637 to 1644 cm -1 after Pb (II) ions binding, indicated the involvement of carboxyl groups in Pb(II) ions binding. The metals uptake by MOP was rapid and the equilibrium time was 30 min at constant temperature and pH. Sorption kinetics followed a second-order model. The mechanism of metal sorption by MOP gave good fits for Freundlich and Langmuir models. Desorption of metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after four cycles of adsorption-elution, the adsorption capacity was regained completely and adsorption efficiency of metal was maintained at around 90%.

  11. 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

  12. Development of facile property calculation model for adsorption chillers based on equilibrium adsorption cycle

    NASA Astrophysics Data System (ADS)

    Yano, Masato; Hirose, Kenji; Yoshikawa, Minoru; Thermal management technology Team

    Facile property calculation model for adsorption chillers was developed based on equilibrium adsorption cycles. Adsorption chillers are one of promising systems that can use heat energy efficiently because adsorption chillers can generate cooling energy using relatively low temperature heat energy. Properties of adsorption chillers are determined by heat source temperatures, adsorption/desorption properties of adsorbent, and kinetics such as heat transfer rate and adsorption/desorption rate etc. In our model, dependence of adsorption chiller properties on heat source temperatures was represented using approximated equilibrium adsorption cycles instead of solving conventional time-dependent differential equations for temperature changes. In addition to equilibrium cycle calculations, we calculated time constants for temperature changes as functions of heat source temperatures, which represent differences between equilibrium cycles and real cycles that stemmed from kinetic adsorption processes. We found that the present approximated equilibrium model could calculate properties of adsorption chillers (driving energies, cooling energies, and COP etc.) under various driving conditions quickly and accurately within average errors of 6% compared to experimental data.

  13. pH-responsive diblock copolymer micelles at the silica/aqueous solution interface: Adsorption kinetics and equilibrium studies.

    PubMed

    Sakai, Kenichi; Smith, Emelyn G; Webber, Grant B; Schatz, Christophe; Wanless, Erica J; Bütün, Vural; Armes, Steven P; Biggs, Simon

    2006-08-01

    The adsorption behavior of two examples of a weakly basic diblock copolymer, poly(2-(dimethylamino)ethyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate) (PDMA-PDEA), at the silica/aqueous solution interface has been investigated using a quartz crystal microbalance with dissipation monitoring and an optical reflectometer. Dynamic and static light scattering measurements have also been carried out to assess aqueous solution properties of such pH-responsive copolymers. In alkaline solution, core-shell micelles are formed above the critical micelle concentration (cmc) by both copolymers, whereas the chains are molecularly dissolved (as unimers) at all concentrations in acidic solution. As a result, the adsorption behavior of PDMA-PDEA diblock copolymers on silica is strongly dependent on both the copolymer concentration and the solution pH. Below the cmc at pH 9, the cationic PDMA-PDEA copolymers adsorb as unimers and the conformation of the adsorbed polymer is essentially flat. At concentrations just above the cmc, the initial adsorption of copolymer onto the silica is dominated by the unimers due to their faster diffusion compared to the much larger micelles. Rearrangement of the adsorbed unimers and/or their subsequent displacement by micelles from solution is then observed during an equilibration period, and the final adsorbed mass is greater than that observed below the cmc. At concentrations well above the cmc, the much higher proportion of micelles in solution facilitates more effective competition for the surface at all stages of the adsorption process and no replacement of initially adsorbed unimers by micelles is evident. However, the adsorbed layer undergoes gradual rearrangement after initial adsorption. This relaxation is believed to result from a combination of further copolymer adsorption and swelling of the adsorbed layer. PMID:16869582

  14. Phosphate Adsorption using Modified Iron Oxide-based Sorbents in Lake Water: Kinetics, Equilibrium, and Column Tests

    EPA Science Inventory

    Adsorption behavior of Bayoxide ® E33 (E33) and three E33-modified sorbents for the removal of phosphate from lake water was investigated in this study. E33-modified sorbents were synthesized by coating with manganese (E33/Mn) and silver (E33/AgI and E33/AgII) nanoparticles. Adso...

  15. 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.

  16. Investigation of equilibrium and kinetics of Cr(VI) adsorption by dried Bacillus cereus using response surface methodology.

    PubMed

    Yang, Kai; Zhang, Jing; Yang, Tao; Wang, Hongyu

    2016-01-01

    In this study, response surface methodology (RSM) based on three-variable-five-level central composite rotatable design was used to analyze the effects of combined and individual operating parameters (biomass dose, initial concentration of Cr(VI) and pH) on the Cr(VI) adsorption capacity of dried Bacillus cereus. A quadratic polynomial equation was obtained to predict the adsorbed Cr(VI) amount. Analysis of variance showed that the effect of biomass dose was the key factor in the removal of Cr(VI). The maximum adsorbed Cr(VI) amount (30.93 mg g(-1)) was found at 165.30 mg L(-1), 2.96, and 3.01 g L(-1) for initial Cr(VI) concentration, pH, and biosorbent dosage, respectively. The surface chemical functional groups and microstructure of unloaded and Cr(VI)-loaded dried Bacillus cereus were identified by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), respectively. Besides, the results gained from these studies indicated that Langmuir isotherm and the second-order rate expression were suitable for the removal of Cr(VI) from wastewater. The results revealed RSM was an effective method for optimizing biosorption process, and dried Bacillus cereus had a remarkable performance on the removal of Cr(VI) from wastewater. PMID:26877045

  17. Adsorption-Desorption Kinetics of Soft Particles

    NASA Astrophysics Data System (ADS)

    Osberg, Brendan; Nuebler, Johannes; Gerland, Ulrich

    2015-08-01

    Adsorption-desorption processes are ubiquitous in physics, chemistry, and biology. Models usually assume hard particles, but within the realm of soft matter physics the adsorbing particles are compressible. A minimal 1D model reveals that softness fundamentally changes the kinetics: Below the desorption time scale, a logarithmic increase of the particle density replaces the usual Rényi jamming plateau, and the subsequent relaxation to equilibrium can be nonmonotonic and much faster than for hard particles. These effects will impact the kinetics of self-assembly and reaction-diffusion processes.

  18. 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

  19. Adsorption kinetics of diatomic molecules.

    PubMed

    Burde, Jared T; Calbi, M Mercedes

    2014-05-01

    The adsorption dynamics of diatomic molecules on solid surfaces is examined by using a Kinetic Monte Carlo algorithm. Equilibration times at increasing loadings are obtained, and explained based on the elementary processes that lead to the formation of the adsorbed film. The ability of the molecules to change their orientation accelerates the overall uptake and leads to competitive kinetic behaviour between the different orientations. The dependence of the equilibration time on coverage follows the same decreasing trend obtained experimentally for ethane adsorption on closed-end carbon nanotube bundles. The exploration of molecule-molecule interaction effects on this trend provides relevant insights to understand the kinetic behaviour of other species, from simpler molecules to larger polyatomic molecules, adsorbing on surfaces with different binding strength. PMID:24654004

  20. Grinding kinetics and equilibrium states

    NASA Technical Reports Server (NTRS)

    Opoczky, L.; Farnady, F.

    1984-01-01

    The temporary and permanent equilibrium occurring during the initial stage of cement grinding does not indicate the end of comminution, but rather an increased energy consumption during grinding. The constant dynamic equilibrium occurs after a long grinding period indicating the end of comminution for a given particle size. Grinding equilibrium curves can be constructed to show the stages of comminution and agglomeration for certain particle sizes.

  1. Rapid-Equilibrium Enzyme Kinetics

    ERIC Educational Resources Information Center

    Alberty, Robert A.

    2008-01-01

    Rapid-equilibrium rate equations for enzyme-catalyzed reactions are especially useful because if experimental data can be fit by these simpler rate equations, the Michaelis constants can be interpreted as equilibrium constants. However, for some reactions it is necessary to use the more complicated steady-state rate equations. Thermodynamics is…

  2. Kinetics and isotherms of Neutral Red adsorption on peanut husk.

    PubMed

    Han, Runping; Han, Pan; Cai, Zhaohui; Zhao, Zhenhui; Tang, Mingsheng

    2008-01-01

    Adsorption of Neutral Red (NR) onto peanut husk in aqueous solutions was investigated at 295 K. Experiments were carried out as function of pH, adsorbent dosage, contact time, and initial concentration. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, and Toth isotherm models. The results indicated that the Toth and Langmuir models provided the best correlation of the experimental data. The adsorption capacity of peanut husk for the removal of NR was determined with the Langmuir and found to be 37.5 mg/g at 295 K. The adsorption kinetic data were modeled using the pseudo-first order, pseudo-second order, and intra-particle diffusion kinetic equations. It was seen that the pseudo-first order and pseudo-second order kinetic equations could describe the adsorption kinetics. The intraparticle diffusion model was also used to express the adsorption process at the two-step stage. It was implied that peanut husk may be suitable as adsorbent material for adsorption of NR from aqueous solutions. PMID:19143308

  3. 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

  4. Removal of mercury(II) ions in aqueous solution using the peel biomass of Pachira aquatica Aubl: kinetics and adsorption equilibrium studies.

    PubMed

    Santana, Andrea J; Dos Santos, Walter N L; Silva, Laiana O B; das Virgens, Cesário F

    2016-05-01

    Mercury is a highly toxic substance that is a health hazard to humans. This study aims to investigate powders obtained from the peel of the fruit of Pachira aquatica Aubl, in its in natura and/or acidified form, as an adsorbent for the removal of mercury ions in aqueous solution. The materials were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. The infrared spectra showed bands corresponding to the axial deformation of carbonyls from carboxylic acids, the most important functional group responsible for fixing the metal species to the adsorbent material. The thermograms displayed mass losses related to the decomposition of three major components, i.e., hemicellulose, cellulose, and lignin. The adsorption process was evaluated using cold-vapor atomic fluorescence spectrometry (CV AFS) and cold-vapor atomic absorption spectrometry (CV AAS). Three isotherm models were employed. The adsorption isotherm model, Langmuir-Freundlich, best represented the adsorption process, and the maximum adsorption capacity was predicted to be 0.71 and 0.58 mg g(-1) at 25 °C in nature and acidified, respectively. Adsorption efficiencies were further tested on real aqueous wastewater samples, and removal of Hg(II) was recorded as 69.6 % for biomass acidified and 76.3 % for biomass in nature. Results obtained from sorption experiments on real aqueous wastewater samples revealed that recovery of the target metal ions was very satisfactory. The pseudo-second-order model showed the best correlation to the experimental data. The current findings showed that the investigated materials are potential adsorbents for mercury(II) ion removal in aqueous solution, with acidified P. aquatica Aubl being the most efficient adsorbent. PMID:27084802

  5. Far-from-equilibrium kinetic processes

    NASA Astrophysics Data System (ADS)

    Rubí, J. Miguel; Pérez-Madrid, Agustin

    2015-12-01

    We analyze the kinetics of activated processes that take place under far-from-equilibrium conditions, when the system is subjected to external driving forces or gradients or at high values of affinities. We use mesoscopic non-equilibrium thermodynamics to show that when a force is applied, the reaction rate depends on the force. In the case of a chemical reaction at high affinity values, the reaction rate is no longer constant but depends on affinity, which implies that the law of mass action is no longer valid. This result is in good agreement with the kinetic theory of reacting gases, which uses a Chapman-Enskog expansion of the probability distribution.

  6. Adsorption kinetics of Rhodamine-B on used black tea leaves

    PubMed Central

    2012-01-01

    Rhodamine B (Rh-B) is one of the most common pollutants in the effluents of textile industries effluents in developing countries. This study was carried out to evaluate the applicability of used black tea leaves (UBTL) for the adsorptive removal of Rh-B from aqueous system by investigating the adsorption kinetics in batch process. The effects of concentration and temperature on adsorption kinetics were examined. First-, second- and pseudo-second order kinetic equations were used to investigate the adsorption mechanism. The adsorption of Rh-B on UBTL followed pseudo-second order kinetics. The equilibrium amount adsorbed and the equilibrium concentration were calculated from pseudo-second-order kinetic plots for different initial concentrations of Rh-B to construct the adsorption isotherm. The adsorption isotherm was well expressed by Langmuir equation. The maximum adsorption capacity of UBTL to Rh-B was found to be 53.2 mg/g at pH = 2.0. The equilibrium amount adsorbed, calculated from pseudo-second-order kinetic plots, increased with temperature increase. The positive value of enthalpy of adsorption, ΔHads = 31.22 kJ/mol, suggested that the adsorption of Rh-B on UBTL at pH = 2.0 is an endothermic process. PMID:23369452

  7. Adsorption Kinetics at Silica Gel/Ionic Liquid Solution Interface.

    PubMed

    Flieger, Jolanta; Tatarczak-Michalewska, Małgorzata; Groszek, Anna; Blicharska, Eliza; Kocjan, Ryszard

    2015-01-01

    A series of imidazolium and pyridinium ionic liquids with different anions (Cl(-), Br(-), BF₄(-), PF₆(-)) has been evaluated for their adsorption activity on silica gel. Quantification of the ionic liquids has been performed by the use of RP-HPLC with organic-aqueous eluents containing an acidic buffer and a chaotropic salt. Pseudo-second order kinetic models were applied to the experimental data in order to investigate the kinetics of the adsorption process. The experimental data showed good fitting with this model, confirmed by considerably high correlation coefficients. The adsorption kinetic parameters were determined and analyzed. The relative error between the calculated and experimental amount of ionic liquid adsorbed at equilibrium was within 7%. The effect of various factors such as initial ionic liquid concentration, temperature, kind of solvent, kind of ionic liquid anion and cation on adsorption efficiency were all examined in a lab-scale study. Consequently, silica gel showed better adsorptive characteristics for imidazolium-based ionic liquids with chaotropic anions from aqueous solutions in comparison to pyridinium ionic liquids. The adsorption was found to decrease with the addition of organic solvents (methanol, acetonitrile) but it was not sensitive to the change of temperature in the range of 5-40 °C. PMID:26690392

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

    PubMed

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

    2011-07-15

    The contribution of variable grain sizes to uranium adsorption/desorption was studied using a sediment from the US DOE Hanford site. The sediment was wet sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.053-0.2 mm), and clay/silt fraction (<0.053 mm). For each size fraction and their composite (sediment), batch and flow-cell experiments were performed to determine uranium adsorption isotherms and kinetic uranium adsorption and subsequent desorption. The results showed that uranium adsorption isotherms and adsorption/desorption kinetics were size specific, reflecting the effects of size-specific adsorption site concentration and kinetic rate constants. The larger-size fraction had a larger mass percentage in the sediment but with a smaller adsorption site concentration and generally a slower uranium adsorption/desorption rate. The same equilibrium surface complexation reaction and reaction constant could describe uranium adsorption isotherms for all size fractions and the composite after accounting for the effect of adsorption site concentration. Mass-weighted, linear additivity was observed for both uranium adsorption isotherms and adsorption/desorption kinetics in the composite. One important implication of this study is that grain-size distribution may be used to estimate uranium adsorption site and adsorption/desorption kinetic rates in heterogeneous sediments from a common location. PMID:21648458

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  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. Thermodynamics and Kinetics of Chemical Equilibrium in Solution.

    ERIC Educational Resources Information Center

    Leenson, I. A.

    1986-01-01

    Discusses theory of thermodynamics of the equilibrium in solution and dissociation-dimerization kinetics. Describes experimental procedure including determination of molar absorptivity and equilibrium constant, reaction enthalpy, and kinetics of the dissociation-dimerization reaction. (JM)

  13. Removal of water and iodine by solid sorbents: adsorption isotherms and kinetics

    SciTech Connect

    Lin, R.; Tavlarides, L.L.

    2013-07-01

    Tritium and iodine-129 are two major radioactive elements that are present in off-gases from spent fuel reprocessing plants. Adsorption by solid sorbents is the state-of-the-art technique for removal of these species from off-gases. Modeling and simulating adsorption processes require accurate adsorption equilibrium and kinetic data to permit reasonable estimates of process parameters. We have developed a continuous flow single-pellet adsorption system to gather accurate adsorption equilibrium and kinetic data for adsorption of water by molecular sieve 3A and for adsorption of iodine by silver exchanged mordenite. In this paper, the design of the water and iodine adsorption experimental systems are briefly described and results of water adsorption experiments are presented and discussed. Water uptake curves are fitted with the linear-driving force (LDF) model and the shrinking-core model to determine kinetic parameters. It is shown that the kinetics of water adsorption on zeolite 3A under current experimental conditions is controlled by both the external film resistance and the macro-pore diffusion and can be predicted by both the LDF model and the shrinking-core model with the former one performing slightly better. Preliminary results from iodine adsorption experiments will be presented in the conference.

  14. Adsorption Kinetics in Nanoscale Porous Coordination Polymers

    SciTech Connect

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

    2015-10-07

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

  15. Adsorption kinetics of silicic acid on akaganeite.

    PubMed

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

    2013-06-01

    As part of a series of studies on the interaction between ferric ions and silicic acid in the hydrosphere, the adsorption of silicic acid on akaganeite was investigated kinetically at various pH values. The adsorption of silicic acid increased with increasing pH over an initial pH range of 4-11.5. In the kinetic experiment, the Cl(-) was released from akaganeite much faster than silicic acid was adsorbed. From this result, we concluded that chloride ions bound on the surface of akaganeite are released and Fe-OH or Fe-O(-) sites are formed, which then acts as an adsorption site for silicic acid. The uptake mechanism of silicic acid by akaganeite is significantly different from that by schwertmannite, despite the presence of the same tunnel structure. PMID:23538050

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

    PubMed Central

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

    2015-01-01

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

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

    SciTech Connect

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

    2011-07-27

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

  18. KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

    SciTech Connect

    Yeh, G.T.; Iskra, G.A.; Szecsody, J.E.; Zachara, J.M.; Streile, G.P.

    1995-01-01

    This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength.

  19. Protein adsorption kinetics in different surface potentials

    NASA Astrophysics Data System (ADS)

    Quinn, A.; Mantz, H.; Jacobs, K.; Bellion, M.; Santen, L.

    2008-03-01

    We have studied the adsorption kinetics of the protein amylase at solid/liquid interfaces. Offering substrates with tailored properties, we are able to separate the impact of short- and long-range interactions. By means of a colloidal Monte Carlo approach including conformational changes of the adsorbed proteins induced by density fluctuations, we develop a scenario that is consistent with the experimentally observed three-step kinetics on specific substrates. Our observations show that not only the surface chemistry determines the properties of an adsorbed protein layer but also the van der Waals contributions of a composite substrate may lead to non-negligible effects.

  20. Modeling high adsorption capacity and kinetics of organic macromolecules on super-powdered activated carbon.

    PubMed

    Matsui, Yoshihiko; Ando, Naoya; Yoshida, Tomoaki; Kurotobi, Ryuji; Matsushita, Taku; Ohno, Koichi

    2011-02-01

    The capacity to adsorb natural organic matter (NOM) and polystyrene sulfonates (PSSs) on small particle-size activated carbon (super-powdered activated carbon, SPAC) is higher than that on larger particle-size activated carbon (powdered-activated carbon, PAC). Increased adsorption capacity is likely attributable to the larger external surface area because the NOM and PSS molecules do not completely penetrate the adsorbent particle; they preferentially adsorb near the outer surface of the particle. In this study, we propose a new isotherm equation, the Shell Adsorption Model (SAM), to explain the higher adsorption capacity on smaller adsorbent particles and to describe quantitatively adsorption isotherms of activated carbons of different particle sizes: PAC and SPAC. The SAM was verified with the experimental data of PSS adsorption kinetics as well as equilibrium. SAM successfully characterized PSS adsorption isotherm data for SPACs and PAC simultaneously with the same model parameters. When SAM was incorporated into an adsorption kinetic model, kinetic decay curves for PSSs adsorbing onto activated carbons of different particle sizes could be simultaneously described with a single kinetics parameter value. On the other hand, when SAM was not incorporated into such an adsorption kinetic model and instead isotherms were described by the Freundlich model, the kinetic decay curves were not well described. The success of the SAM further supports the adsorption mechanism of PSSs preferentially adsorbing near the outer surface of activated carbon particles. PMID:21172719

  1. 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.

  2. 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

  3. 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.

  4. Binary adsorption equilibrium of carbon dioxide and water vapor on activated alumina.

    PubMed

    Li, Gang; Xiao, Penny; Webley, Paul

    2009-09-15

    Adsorption equilibria of a CO2/H2O binary mixture on activated alumina F-200 were measured at several temperatures and over a wide range of concentrations from 4% to around 90% of the saturated water vapor pressure. In comparison with the single-component data, the loading of CO2 was not reduced in the presence of H2O, whereas at low relative humidity the adsorption of H2O was depressed. The binary system was described by a competitive/cooperative adsorption model where the readily adsorbed water layers acted as secondary sites for further CO2 adsorption via hydrogen bonding or hydration reaction. The combination of kinetic models, namely, a Langmuir isotherm for characterizing pure CO2 adsorption and a BET isotherm for H2O, was extended to derive a binary adsorption equilibrium model for the CO2/H2O mixture. Models based on the ideal adsorbed solution theory of Myers and Prausnitz failed to characterize the data over the whole composition range, and a large deviation of binary CO2/H2O equilibrium from ideal solution behavior was observed. The extended Langmuir-BET (LBET) isotherm, analogous to the extended Langmuir equation, drastically underestimated the CO2 loading. By incorporating the interactions between CO2 and H2O molecules on the adsorbent surface and taking into account the effect of nonideality, the realistic interactive LBET (R-LBET) model was found to be in very good agreement with the experimental data. The derived binary isosteric heat of adsorption showed that the heat was reduced by competitive adsorption but promoted by cooperative adsorption. PMID:19678623

  5. IMPACT OF OXYGEN MEDIATED OXIDATIVE COUPLING ON ADSORPTION KINETICS

    EPA Science Inventory

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

  6. Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

    ERIC Educational Resources Information Center

    Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.

    2011-01-01

    Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…

  7. 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

  8. Removal Rate of Organic Matter Using Natural Cellulose via Adsorption Isotherm and Kinetic Studies.

    PubMed

    Din, Mohd Fadhil Md; Ponraj, Mohanadoss; Low, Wen-Pei; Fulazzaky, Mohamad Ali; Iwao, Kenzo; Songip, Ahmad Rahman; Chelliapan, Shreeshivadasan; Ismail, Zulhilmi; Jamal, Mohamad Hidayat

    2016-02-01

    In this study, the removal of natural organic matter (NOM) using coconut fiber (CF) and palm oil fiber (POF) was investigated. Preliminary analysis was performed using a jar test for the selection of optimal medium before the fabricated column model experiment. The equilibrium studies on isotherms and kinetic models for NOM adsorption were analyzed using linearized correlation coefficient. Results showed that the equilibrium data were fitted to Langmuir isotherm model for both CF and POF. The most suitable adsorption model was the pseudo-first-order kinetic model for POF and pseudo-second-order kinetic model for CF. The adsorption capacities achieved by the CF and POF were 15.67 and 30.8 mg/g respectively. Based on this investigation, it can be concluded that the POF is the most suitable material for the removal of NOM in semi polluted river water. PMID:26803100

  9. 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.

  10. Kinetic model of water vapour adsorption by gluten-free starch

    NASA Astrophysics Data System (ADS)

    Ocieczek, Aneta; Kostek, Robert; Ruszkowska, Millena

    2015-01-01

    This study evaluated the kinetics of water vapour adsorption on the surface of starch molecules derived from wheat. The aim of the study was to determine an equation that would allow estimation of water content in tested material in any timepoint of the adsorption process aimed at settling a balance with the environment. An adsorption isotherm of water vapour on starch granules was drawn. The parameters of the Guggenheim, Anderson, and De Boer equation were determined by characterizing the tested product and adsorption process. The equation of kinetics of water vapour adsorption on the surface of starch was determined based on the Guggenheim, Anderson, and De Boer model describing the state of equilibrium and on the model of a first-order linear inert element describing the changes in water content over time.

  11. Kinetic study of aluminum adsorption by aluminosilicate clay minerals

    SciTech Connect

    Walker, W.J.; Cronan, C.S.; Patterson, H.H.

    1988-01-01

    The adsorption kinetics of Al/sup 3 +/ by montmorillonite, kaolinite, and vermiculite were investigated as a function of the initial Al concentration, the surface area of the clay, and H/sup +/ concentration, at 25/sup 0/, 18/sup 0/, and 10/sup 0/C. In order to minimize complicated side reactions the pH range was kept between 3.0 and 4.1. Results showed that the adsorption rate was first order with respect to both the initial Al concentration and the clay surface area. Changes in pH within this narrow range had virtually no effect on adsorption rate. This zero order reaction dependence suggested that the H/sup +/, compared to Al, has a weak affinity for the surface. The rates of adsorption decreased in the order of montmorillonite > kaolinite > vermiculite when compared on the basis of equal surface areas, but changed to kaolinite > montmorillonite > vermiculite when the clays were compared on an equal exchange capacity basis. The calculated apparent activation energies were < 32 kJ mol/sup -1/, indicating that over the temperature range of the study the adsorption process is only marginally temperature sensitive. The mechanism is governed by a simple electrostatic cation exchange involving outer sphere complexes between adsorbed Al and the clay surface. Vermiculite, may have a second reaction step governed by both electrostatic attraction and internal ion diffusion. Equilibrium constants for the formation of an adsorbed Al clay complex were also estimated and are 10/sup 5.34/, 10/sup 5.18/, and 10/sup 4.94/ for kaolinite, montmorillonite, and vermiculite, respectively, suggesting that these clays could play a significant role in controlling soil solutions Al concentrations.

  12. Equilibrium and kinetic mechanisms of woody biochar on aqueous glyphosate removal.

    PubMed

    Mayakaduwa, S S; Kumarathilaka, Prasanna; Herath, Indika; Ahmad, Mahtab; Al-Wabel, Mohammed; Ok, Yong Sik; Usman, Adel; Abduljabbar, Adel; Vithanage, Meththika

    2016-02-01

    We investigated the removal of aqueous glyphosate using woody (dendro) biochar obtained as a waste by product from bioenergy industry. Equilibrium isotherms and kinetics data were obtained by adsorption experiments. Glyphosate adsorption was strongly pH dependent occurring maximum in the pH range of 5-6. The protonated amino moiety of the glyphosate molecule at this pH may interact with π electron rich biochar surface via π-π electron donor-acceptor interactions. Isotherm data were best fitted to the Freundlich and Temkin models indicating multilayer sorption of glyphosate. The maximum adsorption capacity of dendro biochar for glyphosate was determined by the isotherm modeling to be as 44 mg/g. Adsorption seemed to be quite fast, reaching the equilibrium <1 h. Pseudo-second order model was found to be the most effective in describing kinetics whereas the rate limiting step possibly be chemical adsorption involving valence forces through sharing or exchanging electrons between the adsorbent and sorbate. The FTIR spectral analysis indicated the involvement of functional groups such as phenolic, amine, carboxylic and phosphate in adsorption. Hence, a heterogeneous chemisorption process between adsorbate molecules and functional groups on biochar surface can be suggested as the mechanisms involved in glyphosate removal. PMID:26340852

  13. Uranium removal from aqueous solution by coir pith: equilibrium and kinetic studies.

    PubMed

    Parab, Harshala; Joshi, Shreeram; Shenoy, Niyoti; Verma, Rakesh; Lali, Arvind; Sudersanan, M

    2005-07-01

    Basic aspects of uranium adsorption by coir pith have been investigated by batch equilibration. The influence of different experimental parameters such as final solution pH, adsorbent dosage, sorption time, temperature and various concentrations of uranium on uptake were evaluated. Maximum uranium adsorption was observed in the pH range 4.0-6.0. The Freundlich and Langmuir adsorption models were used for the mathematical description of the adsorption equilibrium. The equilibrium data fitted well to both the equilibrium models in the studied concentration range of uranium (200-800 mg/l) and temperatures (305-336 K). The coir pith exhibited the highest uptake capacity for uranium at 317 K, at the final solution pH value of 4.3 and at the initial uranium concentration of 800 mg/l. The kinetics of the adsorption process followed a second-order adsorption. The adsorbent used proved to be suitable for removal of uranium from aqueous solutions. 0.2 N HCl was effective in uranium desorption. The results indicated that the naturally abundant coir pith of otherwise nuisance value exhibited considerable potential for application in removal of uranium from aqueous solution. PMID:15734311

  14. Metal adsorption by agricultural biosorbents: Adsorption isotherm, kinetic and biosorbents chemical structures.

    PubMed

    Sadeek, Sadeek A; Negm, Nabel A; Hefni, Hassan H H; Wahab, Mostafa M Abdel

    2015-11-01

    Biosorption of Cu(II), Co(II) and Fe(III) ions from aqueous solutions by rice husk, palm leaf and water hyacinth was investigated as a function of initial pH, initial heavy metal ions concentration and treatment time. The adsorption process was examined by two adsorption isotherms: Langmuir and Freundlich isotherms. The experimental data of biosorption process were analyzed using pseudo-first order, pseudo-second order kinetic models. The equilibrium biosorption isotherms showed that the three studied biosorbents possess high affinity and sorption capacity for Cu(II), Co(II) and Fe(III) ions. Rice husk showed more efficiency than palm leaf and water hyacinth. Adsorption of Cu(II) and Co(II) was more efficient in alkaline medium (pH 9) than neutral medium due to the high solubility of metal ion complexes. The metal removal efficiency of each biosorbent was correlated to its chemical structure. DTA studies showed formation of metal complex between the biosorbents and the metal ions. The obtained results showed that the tested biosorbents are efficient and alternate low-cost biosorbent for removal of heavy metal ions from aqueous media. PMID:26282929

  15. Kinetic aspects of the adsorption of xyloglucan onto cellulose nanocrystals.

    PubMed

    Villares, Ana; Moreau, Céline; Dammak, Abir; Capron, Isabelle; Cathala, Bernard

    2015-08-28

    In this work, the adsorption of a neutral flexible polysaccharide, xyloglucan (XG), onto thin cellulose nanocrystal (CNC) surfaces has been investigated to get more insight into the CNC-XG association. Gold-coated quartz crystals were spin-coated with one layer of CNC, and XG adsorption was monitored in situ using a quartz crystal microbalance with dissipation (QCM-D). The adsorption of XG under flow at different concentrations did not result in the same surface concentration, which evidenced a kinetically controlled process. In an attempt to describe the binding of XG to CNCs, adsorption data were fitted to a kinetic model comprising a contribution from XG adsorption onto uncovered CNC surfaces and a contribution from XG adsorption after rearrangement. Kinetic studies evidenced the presence of two adsorption regimes as a function of XG concentration. For low XG concentrations, the kinetic constant for chain rearrangement is comparable to the kinetic constant for adsorption. This fact implies a rearrangement and alignment of XG molecules on CNCs. Differently, for higher XG concentrations, the kinetic constant related to the conformational rearrangement decreases, indicating that XG molecules have no time to laterally rearrange before new XG molecules adsorb. PMID:26179417

  16. 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.

  17. 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.

  18. Derivation of the Freundlich Adsorption Isotherm from Kinetics

    ERIC Educational Resources Information Center

    Skopp, Joseph

    2009-01-01

    The Freundlich adsorption isotherm is a useful description of adsorption phenomena. It is frequently presented as an empirical equation with little theoretical basis. In fact, a variety of derivations exist. Here a new derivation is presented using the concepts of fractal reaction kinetics. This derivation provides an alternative basis for…

  19. Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

    EPA Science Inventory

    Arsenate adsorption on amorphous (RuO2•1.1H2O) and crystalline (RuO2) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

  20. 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

  1. 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

  2. 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

  3. Diffusion barriers in the kinetics of water vapor adsorption/desorption on activated carbons

    SciTech Connect

    Harding, A.W.; Foley, N.J.; Thomas, K.M.; Norman, P.R.; Francis, D.C.

    1998-07-07

    The adsorption of water vapor on a highly microporous coconut-shell-derived carbon and a mesoporous wood-derived carbon was studied. These carbons were chosen as they had markedly different porous structures. The adsorption and desorption characteristics of water vapor on the activated carbons were investigated over the relative pressure range p/p{degree} = 0--0.9 for temperatures in the range 285--313 K in a static water vapor system. The adsorption isotherms were analyzed using the Dubinin-Serpinski equation, and this provided an assessment of the polarity of the carbons. The kinetics of water vapor adsorption and desorption were studied with different amounts of preadsorbed water for set changes in pressure relative to the saturated vapor pressure (p/p{degree}). The adsorption kinetics for each relative pressure step were compared and used to calculate the activation energies for the vapor pressure increments. The kinetic results are discussed in relation to their relative position on the equilibrium isotherm and the adsorption mechanism of water vapor on activated carbons.

  4. Equilibrium and Kinetics of Block Copolymers Micelles

    NASA Astrophysics Data System (ADS)

    Mysona, Joshua; Morse, David

    Both equilibrium properties of micelles, such as the critical micelle concentration (CMC), and dynamical properties such as the micelle lifetime are difficult to study in simulations because of the slow dynamics of the processes by which micelles are created and destroyed. We first discuss a method of precisely identifying the CMC in a simple model of block copolymer micelles in a homopolymer matrix, which makes use of thermodynamic integration to compute the free energy of formation. We then examine the free energy barriers to competing mechanisms for creating and destroying micelles, which could occur predominantly either by a step-wise process involving insertion and extraction of single molecules or by fission and fusion of entire micelles.

  5. Adsorption and decolorization kinetics of methyl orange by anaerobic sludge.

    PubMed

    Yu, Lei; Li, Wen-Wei; Lam, Michael Hon-Wah; Yu, Han-Qing

    2011-05-01

    Adsorption and decolorization kinetics of methyl orange (MO) by anaerobic sludge in anaerobic sequencing batch reactors were investigated. The anaerobic sludge was found to have a saturated adsorption capacity of 36 ± 1 mg g MLSS(-1) to MO. UV/visible spectrophotometer and high-performance liquid chromatography analytical results indicated that the MO adsorption and decolorization occurred simultaneously in this system. This process at various substrate concentrations could be well simulated using a modified two-stage model with apparent pseudo first-order kinetics. Furthermore, a noncompetitive inhibition kinetic model was also developed to describe the MO decolorization process at high NaCl concentrations, and an inhibition constant of 3.67 g NaCl l(-1) was estimated. This study offers an insight into the adsorption and decolorization processes of azo dyes by anaerobic sludge and provides a better understanding of the anaerobic dye decolorization mechanisms. PMID:21279343

  6. UV-induced photocatalytic degradation of aqueous acetaminophen: the role of adsorption and reaction kinetics.

    PubMed

    Basha, Shaik; Keane, David; Nolan, Kieran; Oelgemöller, Michael; Lawler, Jenny; Tobin, John M; Morrissey, Anne

    2015-02-01

    Nanostructured titania supported on activated carbon (AC), termed as integrated photocatalytic adsorbents (IPCAs), were prepared by ultrasonication and investigated for the photocatalytic degradation of acetaminophen (AMP), a common analgesic and antipyretic drug. The IPCAs showed high affinity towards AMP (in dark adsorption studies), with the amount adsorbed proportional to the TiO2 content; the highest adsorption was at 10 wt% TiO2. Equilibrium isotherm studies showed that the adsorption followed the Langmuir model, indicating the dependence of the reaction on an initial adsorption step, with maximum adsorption capacity of 28.4 mg/g for 10 % TiO2 IPCA. The effects of initial pH, catalyst amount and initial AMP concentration on the photocatalytic degradation rates were studied. Generally, the AMP photodegradation activity of the IPCAs was better than that of bare TiO2. Kinetic studies on the photocatalytic degradation of AMP under UV suggest that the degradation followed Langmuir-Hinshelwood (L-H) kinetics, with an adsorption rate constant (K) that was considerably higher than the photocatalytic rate constant (k r), indicating that the photocatalysis of AMP is the rate-determining step during the adsorption/photocatalysis process. PMID:25173973

  7. Biosorption of zinc from aqueous solution using Azadirachta indica bark: equilibrium and kinetic studies.

    PubMed

    King, P; Anuradha, K; Lahari, S Beena; Prasanna Kumar, Y; Prasad, V S R K

    2008-03-21

    The removal of zinc ions from aqueous solutions on the biomass of Azadirachta indica bark has been studied by using batch adsorption technique. The biosorption studies were determined as a function of contact time, pH, initial metal ion concentration, average biosorbent size and biosorbent dosage. The equilibrium metal uptake was increased and percentage biosorption was decreased with an increase in the initial concentration and particle size of biosorbent. The maximum zinc biosorption occurred at pH 6 and percentage biosorption increases with increase in the biosorbent dosage. Experimental data obtained were tested with the adsorption models like Langmuir, Freundlich and Redlich-Peterson isotherms. Biosorption isothermal data were well interpreted by Langmuir model with maximum biosorption capacity of 33.49mg/g of zinc ions on A. indica bark biomass and kinetic data were properly fitted with the pseudo-second-order kinetic model. PMID:17681426

  8. Kinetic studies of the liquid-phase adsorption of a reactive dye onto activated lignite

    SciTech Connect

    Petrolekas, P.D.; Maggenakis, G.

    2007-02-14

    The kinetics of batch adsorption of a commercial reactive dye onto activated lignite has been investigated at temperatures of 26, 40, and 55{sup o}C, using aqueous solutions with initial dye concentrations in the range of 15-60 mg/L. An empirical single parameter relationship of the adsorbent loading versus the square root of contact time was proposed, which was determined to provide a very good description of the batch adsorption transients up to equilibrium. The data were also examined by means of the Elovich equation. The effect of the temperature and the initial dye concentration on the adsorption kinetics was analyzed, and the results were discussed by considering that intraparticle diffusion is the dominant mechanism.

  9. Equilibrium and kinetic selectivity profiling on the human adenosine receptors.

    PubMed

    Guo, Dong; Dijksteel, Gabrielle S; van Duijl, Tirsa; Heezen, Maxime; Heitman, Laura H; IJzerman, Adriaan P

    2016-04-01

    Classical evaluation of target selectivity is usually undertaken by measuring the binding affinity of lead compounds against a number of potential targets under equilibrium conditions, without considering the kinetics of the ligand-receptor interaction. In the present study we propose a combined strategy including both equilibrium- and kinetics-based selectivity profiling. The adenosine receptor (AR) was chosen as a prototypical drug target. Six in-house AR antagonists were evaluated in a radioligand displacement assay for their affinity and in a competition association assay for their binding kinetics on three AR subtypes. One of the compounds with a promising kinetic selectivity profile was also examined in a [(35)S]-GTPγS binding assay for functional activity. We found that XAC and LUF5964 were kinetically more selective for the A1R and A3R, respectively, although they are non-selective in terms of their affinity. In comparison, LUF5967 displayed a strong equilibrium-based selectivity for the A1R over the A2AR, yet its kinetic selectivity thereon was less pronounced. In a GTPγS assay, LUF5964 exhibited insurmountable antagonism on the A3R while having a surmountable effect on the A1R, consistent with its kinetic selectivity profile. This study provides evidence that equilibrium and kinetic selectivity profiling can both be important in the early phases of the drug discovery process. Our proposed combinational strategy could be considered for future medicinal chemistry efforts and aid the design and discovery of different or even better leads for clinical applications. PMID:26930564

  10. Kafirin adsorption on ion-exchange resins: isotherm and kinetic studies.

    PubMed

    Kumar, Prashant; Lau, Pei Wen; Kale, Sandeep; Johnson, Stuart; Pareek, Vishnu; Utikar, Ranjeet; Lali, Arvind

    2014-08-22

    Kafirin is a natural, hydrophobic and celiac safe prolamin protein obtained from sorghum seeds. Today kafirin is found to be useful in designing delayed delivery systems and coatings of pharmaceuticals and nutraceuticals where its purity is important and this can be obtained by adsorptive chromatography. This study is the first scientific insight into the isotherm and kinetic studies of kafirin adsorption on anion- and cation-exchange resins for practical applications in preparative scale chromatography. Adsorption isotherms of kafirin were determined for five anion- and two cation-exchange resins in batch systems. Isotherm parameters such as maximum binding capacity and dissociation constant were determined from Langmuir isotherm, and adsorptive capacity and affinity constant from Freundlich isotherm. Langmuir isotherm was found to fit the adsorption equilibrium data well. Batch uptake kinetics for kafirin adsorption on these resins was also carried out and critical parameters including the diffusion coefficient, film mass transfer coefficient, and Biot number for film-pore diffusion model were calculated. Both the isotherm and the kinetic parameters were considered for selection of appropriate resin for kafirin purification. UNOsphere Q (78.26 mg/ml) and Toyopearl SP-650M (57.4 mg/ml) were found to offer better kafirin binding capacities and interaction strength with excellent uptake kinetics under moderate operating conditions. With these adsorbents, film diffusion resistance was found to be major governing factor for adsorption (Bi<10 and δ<1). Based on designer objective function, UNOsphere Q was found be best adsorbent for binding of kafirin. The data presented is valuable for designing large scale preparative adsorptive chromatographic kafirin purification systems. PMID:25022481

  11. Adsorption kinetics and isotherm of anionic dyes onto organo-bentonite from single and multisolute systems.

    PubMed

    Shen, Dazhong; Fan, Jianxin; Zhou, Weizhi; Gao, Baoyu; Yue, Qinyan; Kang, Qi

    2009-12-15

    The performances of polydiallydimethylammonium modified bentonite (PDADMA-bentonite) as an adsorbent to remove anionic dyes, namely Acid Scarlet GR (AS-GR), Acid Turquoise Blue 2G (ATB-2G) and Indigo Carmine (IC), were investigated in single, binary and ternary dye systems. In adsorption from single dye solutions with initial concentration of 100 micromol/L, the dosage of PDADMA-bentonite needed to remove 95% dye was 0.42, 0.68 and 0.75 g/L for AS-GR, ATB-2G and IC, respectively. The adsorption isotherms of the three dyes obeyed the Langmuir isotherm model with the equilibrium constants of 0.372, 0.629 and 4.31 L/micromol, the saturation adsorption amount of 176.3, 149.2 and 228.7 micromol/g for ATB-2G, IC and AS-GR, respectively. In adsorption from mixed dye solutions, the isotherm of each individual dye followed an expanded Langmuir isotherm model and the relationship between the total amount of dyes adsorbed and the total equilibrium dye concentration was interpreted well by Langmuir isotherm model. In the region of insufficient dosage of PDADMA-bentonite, the dye with a larger affinity was preferentially removed by adsorption. Desorption was observed in the kinetic curve of the dye with lower affinity on PDADMA-bentonite surface by the competitive adsorption. The kinetics in single dye solution and the total adsorption of dyes in binary and ternary dye systems nicely followed pseudo-second-order kinetic model. PMID:19631461

  12. Adsorption of metal ions onto Moroccan stevensite: kinetic and isotherm studies.

    PubMed

    Benhammou, A; Yaacoubi, A; Nibou, L; Tanouti, B

    2005-02-15

    The aim of this paper is to study the adsorption of the heavy metals (Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II)) from aqueous solutions by a natural Moroccan stevensite called locally rhassoul. We carried out, first, a mineralogical and physicochemical characterization of stevensite. The surface area is 134 m2/g and the cation exchange capacity (CEC) is 76.5 meq/100 g. The chemical formula of stevensite is Si3.78Al0.22Mg2.92Fe0.09Na0.08K0.08O10(OH)2.4H2O. Adsorption tests of Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II) in batch reactors were carried out at ambient temperature and at constant pH. Two simplified models including pseudo-first-order and pseudo-second- order were used to test the adsorption kinetics. The equilibrium time and adsorption rate of adsorption were determined. The increasing order of the adsorption rates follows the sequence Mn(II) > Pb(II) > Zn(II) > Cu(II) > Cd(II). The Dubinin-Radushkevich (D-R), Langmuir, and Redlich-Peterson (R-P) models were adopted to describe the adsorption isotherms. The maximal adsorption capacities at pH 4.0 determined from the D-R and Langmuir models vary in the following order: Cu(II) > Mn(II) > Cd(II) > Zn(II) > Pb(II). The equilibrium data fitted well with the three-parameter Redlich-Peterson model. The values of mean energy of adsorption show mainly an ion-exchange mechanism. Also, the influence of solution pH on the adsorption onto stevensite was studied in the pH range 1.5-7.0. PMID:15589536

  13. Adsorption Isotherms and Surface Reaction Kinetics

    ERIC Educational Resources Information Center

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

    1974-01-01

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

  14. 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

    -parameter 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.

  15. Adsorption kinetic process of thiol ligands on gold nanocrystals.

    PubMed

    Cheng, Hao; Yang, Lina; Jiang, Yong; Huang, Yuanyuan; Sun, Zhihu; Zhang, Jing; Hu, Tiandou; Pan, Zhiyun; Pan, Guoqiang; Yao, Tao; Bian, Qing; Wei, Shiqiang

    2013-12-01

    Understanding the kinetic mechanism during ligand adsorption on gold nanocrystals is important for designing and fine-tuning their properties and implications. Here, we report a kinetic study on the adsorption process of dodecanethiol ligands on Au nanocrystals of 3.3 nm by an in situ time-resolved X-ray absorption fine structure technique. A two-step process of dodecanethiol adsorption on Au NC surfaces is proposed based on the obtained ligand coverage, which shows a quick increase from 0 to 0.40 within the first 20 min, followed by a much slower increase to the limiting value of 0.94. In-depth analysis suggests that the first stage involves the quick adsorption of dodecanethiol to the corner and edge sites of Au NCs surfaces, leading to remarkable surface Au-Au bond length relaxation (from 2.79 to 2.81 Å) and pronounced gold-to-ligand charge transfer. The second step that corresponds to the much slower adsorption process to the surface facets could be described by the Langmuir kinetics equation with an adsorption rate constant of 0.0132 min(-1) and an initial coverage of 0.41, in good agreement with the initially preferable adsorption of thiols to the most favorable sites. PMID:24122096

  16. Equilibrium Binding and Steady-State Enzyme Kinetics.

    ERIC Educational Resources Information Center

    Dunford, H. Brian

    1984-01-01

    Points out that equilibrium binding and steady-state enzyme kinetics have a great deal in common and that related equations and error analysis can be cast in identical forms. Emphasizes that if one type of problem solution is taught, the other is also taught. Various methods of data analysis are evaluated. (JM)

  17. On the fractality of the Freundlich adsorption isotherm in equilibrium and non-equilibrium cases.

    PubMed

    Borys, Przemysław; Grzywna, Zbigniew J

    2016-07-27

    We investigate the relationship between the Freundlich adsorption exponent and the fractal dimension of the adsorption sites for quasi-monolayer adsorption, and of the adsorbed aggregate for a simple case of multilayer adsorption. We further check whether the Freundlich adsorption mechanism may contribute to anomalous diffusion in the transport through porous materials. PMID:27414951

  18. Spectral Quasi-Equilibrium Manifold for Chemical Kinetics.

    PubMed

    Kooshkbaghi, Mahdi; Frouzakis, Christos E; Boulouchos, Konstantinos; Karlin, Iliya V

    2016-05-26

    The Spectral Quasi-Equilibrium Manifold (SQEM) method is a model reduction technique for chemical kinetics based on entropy maximization under constraints built by the slowest eigenvectors at equilibrium. The method is revisited here and discussed and validated through the Michaelis-Menten kinetic scheme, and the quality of the reduction is related to the temporal evolution and the gap between eigenvalues. SQEM is then applied to detailed reaction mechanisms for the homogeneous combustion of hydrogen, syngas, and methane mixtures with air in adiabatic constant pressure reactors. The system states computed using SQEM are compared with those obtained by direct integration of the detailed mechanism, and good agreement between the reduced and the detailed descriptions is demonstrated. The SQEM reduced model of hydrogen/air combustion is also compared with another similar technique, the Rate-Controlled Constrained-Equilibrium (RCCE). For the same number of representative variables, SQEM is found to provide a more accurate description. PMID:27116566

  19. Colloidal particle adsorption at liquid interfaces: capillary driven dynamics and thermally activated kinetics.

    PubMed

    Rahmani, Amir M; Wang, Anna; Manoharan, Vinothan N; Colosqui, Carlos E

    2016-08-14

    The adsorption of single colloidal microparticles (0.5-1 μm radius) at a water-oil interface has been recently studied experimentally using digital holographic microscopy [Kaz et al., Nat. Mater., 2012, 11, 138-142]. An initially fast adsorption dynamics driven by capillary forces is followed by an unexpectedly slow relaxation to equilibrium that is logarithmic in time and can span hours or days. The slow relaxation kinetics has been attributed to the presence of surface "defects" with nanoscale dimensions (1-5 nm) that induce multiple metastable configurations of the contact line perimeter. A kinetic model considering thermally activated transitions between such metastable configurations has been proposed [Colosqui et al., Phys. Rev. Lett., 2013, 111, 028302] to predict both the relaxation rate and the crossover point to the slow logarithmic regime. However, the adsorption dynamics observed experimentally before the crossover point has remained unstudied. In this work, we propose a Langevin model that is able to describe the entire adsorption process of single colloidal particles by considering metastable states produced by surface defects and thermal motion of the particle and liquid interface. Invoking the fluctuation dissipation theorem, we introduce a drag term that considers significant dissipative forces induced by thermal fluctuations of the liquid interface. Langevin dynamics simulations based on the proposed adsorption model yield close agreement with experimental observations for different microparticles, capturing the crossover from (fast) capillary driven dynamics to (slow) thermally activated kinetics. PMID:27373956

  20. Removal of aluminium from aqueous solutions using PAN-based adsorbents: characterisation, kinetics, equilibrium and thermodynamic studies.

    PubMed

    Aly, Zaynab; Graulet, Adrien; Scales, Nicholas; Hanley, Tracey

    2014-03-01

    Economic adsorbents in bead form were fabricated and utilised for the adsorption of Al(3+) from aqueous solutions. Polyacrylonitrile (PAN) beads, PAN powder and the thermally treated PAN beads (250 °C/48 h/Ar and 600 °C/48 h/Ar-H2) were characterised using different techniques including Fourier transform infrared spectroscopy, X-ray diffraction, specific surface analysis (Brunauer-Emmett-Teller), thermogravimetric analysis as well as scanning electron microscopy. Effects of pH, contact time, kinetics and adsorption isotherms at different temperatures were investigated in batch mode experiments. Aluminium kinetic data best fit the Lagergren pseudo-second-order adsorption model indicating a one-step, surface-only, adsorption process with chemisorption being the rate limiting step. Equilibrium adsorption data followed a Langmuir adsorption model with fairly low monolayer adsorption capacities suitable for freshwater clean-up only. Various constants including thermodynamic constants were evaluated from the experimental results obtained at 20, 40 and 60 °C. Positive values of ΔH° indicated that the adsorption of Al(3+) onto all three adsorbents was endothermic with less energy input required for PAN powder compared to PAN beads and low-temperature thermally treated PAN. Negative ΔG° values indicated that the aluminium adsorption process was spontaneous for all adsorbents examined. PMID:24297464

  1. Retention of phosphorous ions on natural and engineered waste pumice: Characterization, equilibrium, competing ions, regeneration, kinetic, equilibrium and thermodynamic study

    NASA Astrophysics Data System (ADS)

    Karimaian, Kamal Aldin; Amrane, Abdeltif; Kazemian, Hossein; Panahi, Reza; Zarrabi, Mansur

    2013-11-01

    Natural and Mg2+ modified pumice were used for the removal of phosphorous. The adsorbents were characterized using XRF, XRD, SEM and FTIR instrumental techniques. In the optimal conditions, namely at equilibrium time (30 min), for a phosphorus concentration of 15 mg/L and pH 6, 69 and 97% phosphorus removals were achieved using 10 g/L of natural and modified pumice adsorbents, respectively. Maximum adsorption capacities were 11.88 and 17.71 mg/g by natural and modified pumice, respectively. Pseudo-second order kinetic model was the most relevant to describe the kinetic of phosphorus adsorption. External mass transfer coefficient decreased for increasing phosphorous concentration and film diffusion was found to be the rate-controlling step. Only a very low dissolution of the adsorbent was observed, leading to a low increase in conductivity and turbidity. Removal efficiency decreased for increasing ionic strength. It also decreased in the presence of competing ions; however modified pumice remained effective, since 67% of phosphorus was removed, versus only 17% for the natural pumice. The efficiency of the modified pumice was confirmed during the regeneration tests, since 96% regeneration yield was obtained after 510 min experiment, while only 22% was observed for the raw pumice.

  2. Kinetics of protein adsorption/desorption mediated by pH-responsive polymer layer

    NASA Astrophysics Data System (ADS)

    Su, Xiao-Hang; Lei, Qun-Li; Ren, Chun-Lai

    2015-11-01

    We propose a new way of regulating protein adsorption by using a pH-responsive polymer. According to the theoretical results obtained from the molecular theory and kinetic approaches, both thermodynamics and kinetics of protein adsorption are verified to be well controlled by the solution pH. The kinetics and the amount of adsorbed proteins at equilibrium are greatly increased when the solution environment changes from acid to neutral. The reason is that the increased pH promotes the dissociation of the weak polyelectrolyte, resulting in more charged monomers and more stretched chains. Thus the steric repulsion within the polymer layer is weakened, which effectively lowers the barrier felt by the protein during the process of adsorption. Interestingly, we also find that the kinetics of protein desorption is almost unchanged with the variation of pH. It is because although the barrier formed by the polymer layer changes along with the change of pH, the potential at contact with the surface varies equally. Our results may provide useful insights into controllable protein adsorption/desorption in practical applications. Project supported by the National Natural Science Foundation of China (Grant Nos. 21274062, 11474155, and 91027040).

  3. Application of a new bifunctionalized chitosan derivative with zwitterionic characteristics for the adsorption of Cu(2+), Co(2+), Ni(2+), and oxyanions of Cr(6+) from aqueous solutions: Kinetic and equilibrium aspects.

    PubMed

    de Almeida, Francine Tatiane Rezende; Ferreira, Bruno Christiano Silva; Moreira, Ana Luísa da Silva Lage; de Freitas, Rossimiriam Pereira; Gil, Laurent Frédéric; Gurgel, Leandro Vinícius Alves

    2016-03-15

    This study describes the synthesis of a new chitosan derivative (C2) with zwitterionic characteristics and its use for the removal of cationic species Cu(2+), Co(2+), and Ni(2+) and anionic species of Cr(6+) in a single aqueous solution. The new adsorbent was synthesized by quaternization of the amine group of chitosan and esterification of hydroxyl groups with EDTA dianhydride. These combined reactions gave both cationic and anionic characteristics to C2 with the release of quaternary ammonium groups and carboxylic groups. The capacity of C2 to adsorb Cu(2+), Co(2+), Ni(2+), and oxyanions of Cr(6+) was evaluated in a batch process with different contact times, pH values, and initial concentrations. Adsorption isotherms were best fitted to the Langmuir and Sips models. The maximum adsorption capacities (Q(max)) of C2 for adsorption of Cu(2+), Co(2+), Ni(2+), and Cr(6+) were 0.698, 1.125, 0.725, and 1.910 mmol/g, respectively. The Δ(ads)G° values were in the range from -20 to -28 kJ/mol. These values suggest a mixed mechanism controlling adsorption. Desorption studies using an aqueous solution consisting of 0.1 mol/L HNO3 were carried out. The reusability of the recovered C2 adsorbent after desorption was also evaluated. PMID:26748062

  4. Kinetic study of lead adsorption to composite biopolymer adsorbent

    SciTech Connect

    Seki, H.; Suzuki, A.

    1999-03-15

    A kinetic study of lead adsorption to composite biopolymer adsorbents was carried out. Spherical and membranous adsorbents containing two biopolymers, humic acid and alginic acid, were used for lead adsorption in dilute acidic solutions. The shrinking core model derived by M.G. Rao and A.K. Gupta was applied to describe the rate process of lead adsorption to spherical adsorbents (average radii of 0.12, 0.15, and 0.16 cm). Furthermore, the shrinking core model was modified and adapted for description of the rate process of lead adsorption to membranous adsorbent (average thickness of 0.0216 cm). The adsorption rate process for both the cases was well described and average apparent lead diffusion coefficients of about 6 {times} 10{sup {minus}6} and 7 {times} 10{sup {minus}6} cm{sup 2}/s were found for the spherical and membranous adsorbents, respectively.

  5. Kinetic Study of Lead Adsorption to Composite Biopolymer Adsorbent.

    PubMed

    Seki; Suzuki

    1999-03-15

    A kinetic study of lead adsorption to composite biopolymer adsorbents was carried out. Spherical and membranous adsorbents containing two biopolymers, humic acid and alginic acid, were used for lead adsorption in dilute acidic solutions. The shrinking core model derived by M. G. Rao and A. K. Gupta (Chem. Eng. J. 24, 181, 1982) was applied to describe the rate process of lead adsorption to spherical adsorbents (average radii of 0.12, 0.15, and 0.16 cm). Furthermore, the shrinking core model was modified and adapted for description of the rate process of lead adsorption to membranous adsorbent (average thickness of 0.0216 cm). The adsorption rate process for the both cases was well described and average apparent lead diffusion coefficients of about 6 x 10(-6) and 7 x 10(-6) cm2 s-1 were found for the spherical and membranous adsorbents, respectively. Copyright 1999 Academic Press. PMID:10049553

  6. On the relationships between Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, Equilibrium Chemistry Approximation kinetics and quadratic kinetics

    DOE PAGESBeta

    Tang, J. Y.

    2015-09-03

    The Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use which of the two are often ambiguous. Here I show that these two kinetics are special approximations to the Equilibrium Chemistry Approximation kinetics, which is the first order approximation to the quadratic kinetics that solves the equation of enzyme-substrate complex exactly for a single enzyme single substrate biogeochemical reaction with the law of mass action and the assumption of quasi-steady-state formore » the enzyme-substrate complex and that the product genesis from enzyme-substrate complex is much slower than the equilibration between enzyme-substrate complexes, substrates and enzymes. In particular, I showed that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in the Equilibrium Chemistry Approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln k2+ of the reaction velocity v with respect to the maximum product genesis rate k2+, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln k1+ of v with respect to the intrinsic substrate affinity k1+, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln [ E ]T of v with respect the total enzyme concentration [ E ]T and persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln [ S ]T of v with respect to the total substrate concentration [ S ]T. Meanwhile, the

  7. On the relationships between Michaelis-Menten kinetics, reverse Michaelis-Menten kinetics, Equilibrium Chemistry Approximation kinetics and quadratic kinetics

    NASA Astrophysics Data System (ADS)

    Tang, J. Y.

    2015-09-01

    The Michaelis-Menten kinetics and the reverse Michaelis-Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use which of the two are often ambiguous. Here I show that these two kinetics are special approximations to the Equilibrium Chemistry Approximation kinetics, which is the first order approximation to the quadratic kinetics that solves the equation of enzyme-substrate complex exactly for a single enzyme single substrate biogeochemical reaction with the law of mass action and the assumption of quasi-steady-state for the enzyme-substrate complex and that the product genesis from enzyme-substrate complex is much slower than the equilibration between enzyme-substrate complexes, substrates and enzymes. In particular, I showed that the derivation of the Michaelis-Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis-Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in the Equilibrium Chemistry Approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis-Menten kinetics was found to persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln k2+ of the reaction velocity v with respect to the maximum product genesis rate k2+, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln k1+ of v with respect to the intrinsic substrate affinity k1+, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln [ E ]T of v with respect the total enzyme concentration [ E ]T and persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln [ S ]T of v with respect to the total substrate concentration [ S ]T. Meanwhile

  8. 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.

  9. Pre-equilibrium approximation in chemical and photophysical kinetics

    NASA Astrophysics Data System (ADS)

    Rae, Margaret; Berberan-Santos, Mário N.

    2002-07-01

    For most mechanisms of chemical reactions and molecular photophysical processes the time evolution of the concentration of the intervening species cannot be obtained analytically. The pre-equilibrium approximation is one of several useful approximation methods that allow the derivation of explicit solutions and simplify numerical solutions. In this work, a general view of the pre-equilibrium approximation is presented, along with the respective analytical solution. It is also shown that the kinetic behavior of systems subject to pre-equilibration can be obtained by the application of perturbation theory. Several photophysical systems are discussed, including excimer formation, thermally activated delayed fluorescence, and external-heavy atom quenching of luminescence.

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

    USGS Publications Warehouse

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

    1993-01-01

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

  11. Adsorption kinetic and mechanistic studies for pharmaceutical spherical carbon adsorbents: comparison of a brand product and two generics.

    PubMed

    Abe, Hiroyuki; Morikawa, Risa; Otsuka, Makoto

    2013-03-01

    The kinetic and mechanistic profiles of three pharmaceutical spherical carbon adsorbents, Kremezin as the brand product and two generics (Merckmezin and spherical carbon adsorbent "Mylan"), were compared. Five non-ionic active pharmaceutical ingredients with molecular weights of 136.1-424.1 Da were used as adsorbates. The results of Boehm titration, the standard method to qualify acidic or basic functional groups on a carbon surface, suggested distinctly different quantitative characteristics of each functional group among the three adsorbents. But those differences do not affect the adsorption to non-ionic adsorbates. The amount of theophylline adsorbed at equilibrium and surface area well correlated, suggesting that adsorptive ability was defined by surface area. In the tested molecular weight range, the order in terms of adsorption kinetics was spherical carbon adsorbent "Mylan">Kremezin>Merkmezin. The adsorption profile in the equilibrium and kinetic experiments, and the lack of an effect of pH on adsorption quantity suggested that the mechanism of adsorption for non-ionic substances to be Langmuir type monolayer adsorption. Kremezin and spherical carbon adsorbent "Mylan" are more likely to adsorb co-administered drugs than Merckmezin. PMID:23261577

  12. Non-equilibrium thermodynamics analysis of transcriptional regulation kinetics

    NASA Astrophysics Data System (ADS)

    Hernández-Lemus, Enrique; Tovar, Hugo; Mejía, Carmen

    2014-12-01

    Gene expression in eukaryotic cells is an extremely complex and interesting phenomenon whose dynamics are controlled by a large number of subtle physicochemical processes commonly described by means of gene regulatory networks. Such networks consist in a series of coupled chemical reactions, conformational changes, and other biomolecular processes involving the interaction of the DNA molecule itself with a number of proteins usually called transcription factors as well as enzymes and other components. The kinetics behind the functioning of such gene regulatory networks are largely unknown, though its description in terms of non-equilibrium thermodynamics has been discussed recently. In this work we will derive general kinetic equations for a gene regulatory network from a non-equilibrium thermodynamical description and discuss its use in understanding the free energy constrains imposed in the network structure. We also will discuss explicit expressions for the kinetics of a simple model of gene regulation and show that the kinetic role of mRNA decay during the RNA synthesis stage (or transcription) is somehow limited due to the comparatively low values of decay rates. At the level discussed here, this implies a decoupling of the kinetics of mRNA synthesis and degradation a fact that may become quite useful when modeling gene regulatory networks from experimental data on whole genome gene expression.

  13. Equilibrium Kinetic Network of the Villin Headpiece in Implicit Solvent

    PubMed Central

    Du, Weina; Bolhuis, Peter G.

    2015-01-01

    We applied the single-replica multiple-state transition-interface sampling method to elucidate the equilibrium kinetic network of the 35-residue-fragment (HP-35) villin headpiece in implicit water at room temperature. Starting from the native Protein Data Bank structure, nine (meta)stable states of the system were identified, from which the kinetic network was built by sampling pathways between these states. Application of transition path theory allowed analysis of the (un)folding mechanism. The resulting (un)folding rates agree well with experiments. This work demonstrates that high (un)folding barriers can now be studied. PMID:25606685

  14. Bioaccumulation of PCBs by algae: Kinetics versus equilibrium

    SciTech Connect

    Swackhamer, D.L.; Skoglund, R.S. )

    1993-05-01

    The objectives of this study were to test the hypothesis that bioaccumulation of hydrophobic organic compounds (HOCs) by phytoplankton is correlated to the compound's octanol/water partition coefficient (K[sub ow]) in a predictive relationship in laboratory experiments, and to confirm these findings with field observations. In laboratory experiments the authors measured the uptake of 40 representative polychlorinated biphenyl (PCB) congeners over time under conditions that inhibited and allowed phytoplankton growth. Results indicated that the bioaccumulation process is consistent with partitioning from water into cell lipids but is slower than previously thought. The uptake of PCBs was slow relative to growth of phytoplankton, preventing the chemical from reaching thermodynamic equilibrium in algal cells under conditions promoting growth (nonwinter). Thus under non-winter field conditions, many PCB congeners never reach equilibrium concentrations. Food-chain models that assume equilibrium between HOCs and the primary trophic level could be inaccurate and may need to use a kinetic framework.

  15. Lateral interactions and non-equilibrium in surface kinetics

    NASA Astrophysics Data System (ADS)

    Menzel, Dietrich

    2016-08-01

    Work modelling reactions between surface species frequently use Langmuir kinetics, assuming that the layer is in internal equilibrium, and that the chemical potential of adsorbates corresponds to that of an ideal gas. Coverage dependences of reacting species and of site blocking are usually treated with simple power law coverage dependences (linear in the simplest case), neglecting that lateral interactions are strong in adsorbate and co-adsorbate layers which may influence kinetics considerably. My research group has in the past investigated many co-adsorbate systems and simple reactions in them. We have collected a number of examples where strong deviations from simple coverage dependences exist, in blocking, promoting, and selecting reactions. Interactions can range from those between next neighbors to larger distances, and can be quite complex. In addition, internal equilibrium in the layer as well as equilibrium distributions over product degrees of freedom can be violated. The latter effect leads to non-equipartition of energy over molecular degrees of freedom (for products) or non-equal response to those of reactants. While such behavior can usually be described by dynamic or kinetic models, the deeper reasons require detailed theoretical analysis. Here, a selection of such cases is reviewed to exemplify these points.

  16. Investigation of molecule-adsorption kinetics by a pulsed laser desorption technique

    NASA Astrophysics Data System (ADS)

    Varakin, V. N.; Lozovskii, A. D.; Panesh, A. M.; Simonov, A. P.

    1987-02-01

    The laser thermal desorption technique is used to measure the adsorption kinetics of SO2 and CO molecules on stainless steel with the aim of investigating the initial stage of oxidation of the steel by adsorbed CO molecules. Attention is given to the dependence of the rate of establishment of the equilibrium concentration of adsorbed molecules on SO2-gas pressure; CO adsorption kinetics on stainless steel at a gas pressure of 9 x 10 to the -8th torr; and the dependence of the concentration of adsorbed CO molecules on exposure in the gas at a pressure of 9 x 10 to the -8th torr under irradiation by laser pulses with repetition periods of 1-2, 2-4, 3-6, and 4-8 min.

  17. 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.

  18. Dye adsorption of cotton fabric grafted with PPI dendrimers: Isotherm and kinetic studies.

    PubMed

    Salimpour Abkenar, Samera; Malek, Reza Mohammad Ali; Mazaheri, Firouzmehr

    2015-11-01

    In this research, the cotton fabrics grafted with two generations of the poly(propylene imine) dendrimers were applied to adsorb textile dyes from aqueous solutions. Direct Red 80 (anionic dye), Disperse Yellow 42 (nonionic dye) and Basic Blue 9 (cationic dye) were selected as model dyes. The effect of various experimental parameters such as initial concentration of dyes, charge of dyes molecule, salt and pH was investigated on the adsorption process. Furthermore, kinetics and equilibrium of the adsorption process on the grafted samples were studied. It was found that maximum adsorption of anionic and disperse dyes took place at around pH 3, while cationic dye could be adsorbed at around pH 11. The Langmuir equation was able to describe the mechanism of dyes adsorption. In addition, the second-order equation was found to be fit with the kinetics data. Interestingly, it seems that the dye adsorption of the grafted fabrics is strongly pH dependent. PMID:26292774

  19. Low-cost magnetic adsorbent for As(III) removal from water: adsorption kinetics and isotherms.

    PubMed

    Kango, Sarita; Kumar, Rajesh

    2016-01-01

    Magnetite nanoparticles as adsorbent for arsenic (As) were coated on sand particles. The coated sand was used for the removal of highly toxic element 'As(III)' from drinking water. Here, batch experiments were performed with the variation of solution pH, adsorbent dose, contact time and initial arsenic concentration. The adsorbent showed significant removal efficiency around 99.6 % for As(III). Analysis of adsorption kinetics revealed that the adsorbent follows pseudo-second-order kinetics model showing R (2) = 0.999, whereas for pseudo-first-order kinetics model, the value of R (2) was 0.978. In the case of adsorption equilibrium, the data is well fitted with Langmuir adsorption isotherm model (R (2) > 0.99), indicating monolayer adsorption of As(III) on the surface of adsorbent. The existence of commonly present ions in water influences the removal efficiency of As(III) minutely in the following order PO4 (3-) > HCO3 (-) > Cl(-) > SO4 (2-). The obtained adsorbent can be used to overcome the problem of water filtration in rural areas. Moreover, as the nano-magnetite is coated on the sand, it avoids the problem of extraction of nanoparticles from treated water and can easily be removed by a simple filtration process. PMID:26711813

  20. Surfaces of Microparticles in Colloids: Structure and Molecular Adsorption Kinetics

    NASA Astrophysics Data System (ADS)

    Dai, Hai-Lung

    2002-03-01

    Surfaces of micron and sub-micron size particles in liquid solution are probed by second harmonic generation (SHG) facilitated with femtosecond laser pulses. The particles probed include inorganic objects such as carbon black and color pigments, polymeric species like polystyrene beads, and biological systems such as blood cells and ecoli. In the experiments, dye molecules are first adsorbed onto the particle surface to allow generation of second harmonics upon light irradiation. Competition for adsorption between these surface dye molecules and the molecules of interest in the solution is then monitored by the SHG signal to reveal the molecular adsorption kinetics and surface structure. Specifically, surfactant adsorption on polymer surfaces, the structure of carbon black surface, and protein adsorption on biological surfaces, monitored by this technique, will be discussed.

  1. 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

  2. Water adsorption kinetics and contact angles of pharmaceutical powders.

    PubMed

    Muster, Tim H; Prestidge, Clive A

    2005-04-01

    Water sorption kinetics and water contact angles have been characterized for a range of pharmaceutical powders: ambroxol hydrochloride, griseofulvin, N,n-octyl-D-gluconamide, paracetamol, sulfathiazole, and theophylline. The uptake of water by powder samples at saturated vapor pressure was modeled using a pseudo first-order kinetic relationship. Parameters from this model have been correlated with the concentration and reactivity of the active surface sites of the pharmaceutical powders and their contact angles. The study has shown that analysis of water adsorption kinetics can be a powerful technique for characterizing the surface chemistry and wettability of pharmaceutical powders, and is particularly sensitive to their surface modification through excipient adsorption: ethyl(hydroxyethyl)cellulose treatment of griseofulvin and butyryl chloride treatment of sulfathiazole are reported as case studies. PMID:15736196

  3. Defluoridation using biomimetically synthesized nano zirconium chitosan composite: kinetic and equilibrium studies.

    PubMed

    Prasad, Kumar Suranjit; Amin, Yesha; Selvaraj, Kaliaperumal

    2014-07-15

    The present study reports a novel approach for synthesis of Zr nanoparticles using aqueous extract of Aloe vera. Resulting nanoparticles were embedded into chitosan biopolymer and termed as CNZr composite. The composite was subjected to detailed adsorption studies for removal of fluoride from aqueous solution. The synthesized Zr nanoparticles showed UV-vis absorption peak at 420nm. TEM result showed the formation of polydispersed, nanoparticles ranging from 18nm to 42nm. SAED and XRD analysis suggested an fcc (face centered cubic) Zr crystallites. EDAX analysis suggested that Zr was an integral component of synthesized nanoparticles. FT-IR study indicated that functional group like NH, CO, CN and CC were involved in particle formation. The adsorption of fluoride on to CNZr composite worked well at pH 7.0, where ∼99% of fluoride was found to be adsorbed on adsorbent. Langmuir isotherm model best fitted the equilibrium data since it presented higher R(2) value than Freundlich model. In comparison to pseudo-first order kinetic model, the pseudo-second order model could explain adsorption kinetic behavior of F(-) onto CNZr composite satisfactorily with a good correlation coefficient. The present study revealed that CNZr composite may work as an effective tool for removal of fluoride from contaminated water. PMID:24887125

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

    PubMed

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

    2006-08-15

    The adsorption kinetics of phosphate on goethite has been studied by batch adsorption experiments and by in situ ATR-IR spectroscopy at different pH, initial phosphate concentrations and stirring rates. Batch adsorption results are very similar to those reported by several authors, and show a rather fast initial adsorption taking place in a few minutes followed by a slower process taking place in days or weeks. The adsorption kinetics could be also monitored by integrating the phosphate signals obtained in ATR-IR experiments, and a very good agreement between both techniques was found. At pH 4.5 two surface complexes, the bidentate nonprotonated (FeO)(2)PO(2) and the bidentate protonated (FeO)(2)(OH)PO complexes, are formed at the surface. There are small changes in the relative concentrations of these species as the reaction proceeds, and they seem to evolve in time rather independently. At pH 7.5 and 9 the dominating surface species is (FeO)(2)PO(2), which is accompanied by an extra unidentified species at low concentration. They also seem to evolve independently as the reaction proceeds. The results are consistent with a mechanism that involve a fast adsorption followed by a slow diffusion into pores, and are not consistent with surface precipitation of iron phosphate. PMID:16643942

  5. Novel tannin-based adsorbent in removing cationic dye (Methylene Blue) from aqueous solution. Kinetics and equilibrium studies.

    PubMed

    Sánchez-Martín, J; González-Velasco, M; Beltrán-Heredia, J; Gragera-Carvajal, J; Salguero-Fernández, J

    2010-02-15

    Natural tannin-based adsorbent has been prepared on the basis of the gelification of Quebracho bark extract. The resulting product, Quebracho Tannin Gel (QTG) was tested as cationic dye adsorbent with Methylene Blue (MB). Kinetics of adsorption process were studied out and a period of 15 days was determined for reaching equilibrium. The influences of pH and temperature were evaluated. As pH or temperature raise q capacity of QTG increases. Theoretical modelization of dye-QTG adsorption was carried out by multiparametric adjustment according to Langmuir's hypothesis. Values of the k(l1), k(l2) and activation energies were calculated. PMID:19782466

  6. 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

  7. 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

  8. 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.

  9. 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

  10. Equilibrium study of single-solute adsorption of anionic surfactants with polymeric XAD resins

    SciTech Connect

    Garcia-Delgado, R.A.; Cotoruelo-Minguez, L.M.; Rodriguez, J.J. )

    1992-06-01

    Equilibrium data for the adsorption of sodium lauryl sulfate (SLS) and sodium dodecylbenzene sulfonate (SDBS) from aqueous solutions by Amberlite XAD-4 and XAD-7 polymeric resins at temperatures in the 10-40C range have been obtained. The specific surface area of the resins plays a major role in adsorption, and thus the best results have been obtained with XAD-4 resin. A higher adsorption of SDBS over SLS was also observed. Several adsorption isotherm models have been used to fit the experimental data. The best results have been obtained with the Redlich-Peterson and Langmuir-Freundlich equations. Estimations of the isosteric heat of adsorption, free energy, and entropy of adsorption are also reported.

  11. Kinetics of Protein Adsorption at liquid/solid interfaces

    NASA Astrophysics Data System (ADS)

    Bellion, Markus; Santen, Ludger; Nagel, Armin; Mantz, Hubert; Quinn, Anthony; Jacobs, Karin

    2006-03-01

    Protein adsorption processes are of crucial importance in many biomedical processes. From a physical point of view these processes raise a number of challenging questions, e.g.: How does the surface influence the conformation of proteins at the surface? What are the characteristics of the protein film at the liquid/solid interface? In this work we investigate the adsorption kinetics of salivary proteins on different kinds of surfaces in a liquid environment. The adsorbed protein layers are analyzed by means of ellipsometry, plasmon resonance, and SPM. It turns out that the adsorbed amount of proteins is sensitive to the long ranged interactions of the solid surface. The experimental data are compared to extensive Monte Carlo simulation of a colloidal protein model. The Monte Carlo results strongly suggest that induced conformal changes lead to the experimentally observed three step kinetics of amylase.

  12. Parametric and adsorption kinetic studies of methylene blue removal from simulated textile water using durian (Durio zibethinus murray) skin.

    PubMed

    Anisuzzaman, S M; Joseph, Collin G; Krishnaiah, D; Bono, A; Ooi, L C

    2015-01-01

    In this study, durian (Durio zibethinus Murray) skin was examined for its ability to remove methylene blue (MB) dye from simulated textile wastewater. Adsorption equilibrium and kinetics of MB removal from aqueous solutions at different parametric conditions such as different initial concentrations (2-10 mg/L), biosorbent dosages (0.3-0.7 g) and pH solution (4-9) onto durian skin were studied using batch adsorption. The amount of MB adsorbed increased from 3.45 to 17.31 mg/g with the increase in initial concentration of MB dye; whereas biosorbent dosage increased from 1.08 to 2.47 mg/g. Maximum dye adsorption capacity of the durian skin was found to increase from 3.78 to 6.40 mg/g, with increasing solution pH. Equilibrium isotherm data were analyzed according to Langmuir and Freundlich isotherm models. The sorption equilibrium was best described by the Freundlich isotherm model with maximum adsorption capacity of 7.23 mg/g and this was due to the heterogeneous nature of the durian skin surface. Kinetic studies indicated that the sorption of MB dye tended to follow the pseudo second-order kinetic model with promising correlation of 0.9836 < R(2) < 0.9918. PMID:26360749

  13. Kinetic Batch Soil Adsorption Studies of 2, 4-dinitroanisole (DNAN)

    NASA Astrophysics Data System (ADS)

    Arthur, J.; Mark, N. W.; Taylor, S.; Brusseau, M. L.; Dontsova, K.

    2014-12-01

    Currently the explosive 2, 4, 6- trinitrotoluene (TNT) is used as a main ingredient in munitions; however the compound has failed to meet sensitivity requirements. The replacement compound being tested is 2, 4-dinitroanisole (DNAN). DNAN is less sensitive to shock, high temperatures, and has good detonation characteristics. However, DNAN is more soluble than TNT, which can influence transport and fate behavior and thus bioavailability and exposure potential. DNAN has been shown to have some human and environmental toxicity. The objective of this study was to investigate the environmental fate of DNAN in soil, with a specific focus on sorption processes. Batch experiments were conducted using 11 soils collected from military installations located across the United States. The soils were characterized for pH, specific surface area, electrical conductivity, cation exchange capacity, and organic carbon content. Adsorption kinetic data determined at room temperature were fitted using the first order kinetic equation. Adsorption isotherms were fitted with linear and Freundlich isotherm equations. The magnitudes of the linear adsorption coefficients ranged from 0.6 to 6 cm3/g. Results indicated that the adsorption of DNAN is strongly dependent on the amount of organic carbon present in the soil.

  14. Comparative evaluation of adsorption kinetics of diclofenac and isoproturon by activated carbon.

    PubMed

    Torrellas, Silvia A; Rodriguez, Araceli R; Escudero, Gabriel O; Martín, José María G; Rodriguez, Juan G

    2015-01-01

    Adsorption mechanism of diclofenac and isoproturon onto activated carbon has been proposed using Langmuir and Freundlich isotherms. Adsorption capacity and optimum adsorption isotherms were predicted by nonlinear regression method. Different kinetic equations, pseudo-first-order, pseudo-second-order, intraparticle diffusion model and Bangham kinetic model, were applied to study the adsorption kinetics of emerging contaminants on activated carbon in two aqueous matrices. PMID:26301850

  15. Adsorption Kinetics of Ionic Surfactants with Detailed Account for the Electrostatic Interactions

    PubMed

    Vlahovska; Danov; Mehreteab; Broze

    1997-08-01

    The problem of diffusion-controlled adsorption from a non-micellar solution of an ionic surfactant in the absence of added electrolyte is solved analytically for the case of small deviations from equilibrium. For that purpose the electro-diffusion equations of the transport of surfactant ions and counterions are combined with the Poisson-Boltzmann equation for the electrical field. The resulting set of equations is linearized and Laplace transform is applied. Analytical expression for the Laplace image of the adsorption is obtained in terms of elementary functions. Simple formulae for the short-time and long-time asymptotics of adsorption and surface tension relaxation are derived. To illustrate the effect of the electrostatic interactions we calculated the theoretical dependence of the characteristic relaxation time on the bulk surfactant concentration and surface potential for aqueous surfactant solutions in contact with various non-aqueous phases (air, heptane, decane, petroleum ether) and two surfactants: SDS and DTAB. The general trend is that the electrostatic effects decelerate the process of adsorption, as it could be expected. The derived exact analytical expressions quantifying these effects can be directly applied for the interpretation of experimental data for the kinetics of ionic surfactant adsorption. The reliability of our approach is verified through a comparison with other available theories. PMID:9268559

  16. 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

  17. Reversible Adsorption Kinetics of Near Surface Dimer Colloids.

    PubMed

    Salipante, Paul F; Hudson, Steven D

    2016-08-30

    We investigate the effect of shape on reversible adsorption kinetics using colloidal polystyrene dimers near a solid glass surface as a model system. The interaction between colloid and wall is tuned using electrostatic, depletion, and gravity forces to produce a double-well potential. The dwell time in each of the potential wells is measured from long duration particle trajectories. The height of each monomer relative to the glass surface is measured to a resolution of <20 nm by in-line holographic microscopy. The measured transition probability distributions are used in kinetic equations to describe the flux of particles to and from the surface. The dimers are compared to independent isolated monomers to determine the effects of shape on adsorption equilibria and kinetics. To elucidate these differences, we consider both mass and surface coverage and two definitions of surface coverage. The results show that dimers with single coverage produce slower adsorption, lower surface coverage, and higher mass coverage in comparison to those of monomers, while dimers with double coverage adsorb faster and result in higher surface coverage. PMID:27483023

  18. Equilibrium studies of copper ion adsorption onto palm kernel fibre.

    PubMed

    Ofomaja, Augustine E

    2010-07-01

    The equilibrium sorption of copper ions from aqueous solution using a new adsorbent, palm kernel fibre, has been studied. Palm kernel fibre is obtained in large amounts as a waste product of palm oil production. Batch equilibrium studies were carried out and system variables such as solution pH, sorbent dose, and sorption temperature were varied. The equilibrium sorption data was then analyzed using the Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherms. The fit of these isotherm models to the equilibrium sorption data was determined, using the linear coefficient of determination, r(2), and the non-linear Chi-square, chi(2) error analysis. The results revealed that sorption was pH dependent and increased with increasing solution pH above the pH(PZC) of the palm kernel fibre with an optimum dose of 10g/dm(3). The equilibrium data were found to fit the Langmuir isotherm model best, with a monolayer capacity of 3.17 x 10(-4)mol/g at 339K. The sorption equilibrium constant, K(a), increased with increasing temperature, indicating that bond strength between sorbate and sorbent increased with temperature and sorption was endothermic. This was confirmed by the increase in the values of the Temkin isotherm constant, B(1), with increasing temperature. The Dubinin-Radushkevich (D-R) isotherm parameter, free energy, E, was in the range of 15.7-16.7kJ/mol suggesting that the sorption mechanism was ion exchange. Desorption studies showed that a high percentage of the copper was desorbed from the adsorbent using acid solutions (HCl, HNO(3) and CH(3)COOH) and the desorption percentage increased with acid concentration. The thermodynamics of the copper ions/palm kernel fibre system indicate that the process is spontaneous and endothermic. PMID:20346574

  19. Adsorption dynamics of methyl violet onto granulated mesoporous carbon: Facile synthesis and adsorption kinetics.

    PubMed

    Kim, Yohan; Bae, Jiyeol; Park, Hosik; Suh, Jeong-Kwon; You, Young-Woo; Choi, Heechul

    2016-09-15

    A new and facile one-step synthesis method for preparing granulated mesoporous carbon (GMC) with three-dimensional spherical mesoporous symmetry is prepared to remove large molecular weight organic compounds in aqueous phase. GMC is synthesized in a single step using as-synthesized mesoporous carbon particles and organic binders through a simple and economical synthesis approach involving a simultaneous calcination and carbonization process. Characterization results obtained from SEM, XRD, as well as surface and porosity analysis indicate that the synthesized GMC has similar physical properties to those of the powdered mesoporous carbon and maintains the Brunauer-Emmett-Teller (BET) surface area and pore volume because the new synthesis method prevents the collapse of the pores during the granulation process. Batch adsorption experiments revealed GMC showed a substantial adsorption capacity (202.8 mg/g) for the removal of methyl violet as a target large molecular contaminant in aqueous phase. The mechanisms and dynamics modeling of GMC adsorption were also fully examined, which revealed that surface diffusion was rate limiting step on adsorption process of GMC. Adsorption kinetics of GMC enables 3 times faster than that of granular activated carbon in terms of surface diffusion coefficient. This is the first study, to the best of our knowledge, to synthesize GMC as an adsorbent for water purification by using facile granulation method and to investigate the adsorption kinetics and characteristics of GMC. This study introduces a new and simple method for the synthesis of GMC and reveals its adsorption characteristics for large molecular compounds in a water treatment. PMID:27262123

  20. Capillary equilibrium and sintering kinetics in dispersed media and catalysts

    NASA Astrophysics Data System (ADS)

    Delannay, Francis

    2016-06-01

    The evolution of an aggregate of particles embedded in a fluid phase, no matter whether a liquid, a vapor, or a mixture of both, is determined by the dependence of the equilibrium interface area on porosity volume fraction. In system with open porosity, this equilibrium can be analyzed using a model representing the particles as a collection of cones of revolution, the number of which is the average particle coordination number. The accuracy of the model has been assessed using in situ X-ray microtomography. The model makes possible the computation of the driving force for sintering, commonly called sintering stress. It allows the mapping of the domains of relative density, coordination number, and dihedral angle that bring about aggregate densification or expansion. The contribution of liquid/vapor interfaces is enlightened, as well as the dependence of the equilibrium fluid phase distribution on particle size. Applied to foams and emulsions, the model provides insight into the relationship between osmotic pressure and coordination. Interface-governed transport mechanisms are considered dominant in the macroscopic viscosity. Both sintering stress and viscosity parameters strongly depend on particle size. The capacity of modeling the simultaneous particle growth is thus essential. The analysis highlights the microstructural parameters and material properties needed for kinetics simulation.

  1. Role of electrostatic interactions in the adsorption kinetics of nanoparticles at fluid-fluid interfaces.

    PubMed

    Dugyala, Venkateshwar Rao; Muthukuru, Jyothi Sri; Mani, Ethayaraja; Basavaraj, Madivala G

    2016-02-21

    The adsorption of particles to the fluid-fluid interface is a key factor for the stabilization of fluid-fluid interfaces such as those found in emulsions, foams and bijels. However, for the formation of stable particle-laden interfaces, the particles must migrate to the interface from the bulk. Recent studies show that the adsorption of particles to the interface formed during emulsification is influenced by the surface charge of the particles. To further investigate this phenomenon, we study the effect of the surface charge of the particle on the adsorption kinetics of particles to the oil-water interface. By suspending a drop of aqueous dispersion of charge stabilized nanoparticles in decane, the adsorption dynamics of particles to the decane-water interface is studied using the dynamic surface tension measurements. When the particles are highly charged (low salt), a negligible change in the interface tension is observed indicating that almost no particles are adsorbed. These results show that the charged particles experience an energy barrier when they approach the interface. But when the particle surface charge is screened by the addition of monovalent salt, a significant reduction in surface tension is observed indicating the migration and adsorption of particles to the decane-water interface. We estimate the effective diffusivity of particles to the interface by analyzing the initial decay in the measured surface tension by considering particle laden drops containing different amounts of salt using the modified Ward and Tordai theory. This effective diffusivity is used to calculate the energy barrier for the adsorption of particles to the interface. The energy barrier from the analysis of dynamic surface tension data agrees well with the concept of image charge repulsion which inhibits the adsorption of highly charged particles to the interface. By considering various types of relevant interactions, we derive an analytical expression that qualitatively

  2. 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).

  3. Equilibrium, kinetic, and reactive transport models for plutonium

    NASA Astrophysics Data System (ADS)

    Schwantes, Jon Michael

    Equilibrium, kinetic, and reactive transport models for plutonium (Pu) have been developed to help meet environmental concerns posed by past war-related and present and future peacetime nuclear technologies. A thorough review of the literature identified several hurdles that needed to be overcome in order to develop capable predictive tools for Pu. These hurdles include: (1) missing or ill-defined chemical equilibrium and kinetic constants for environmentally important Pu species; (2) no adequate conceptual model describing the formation of Pu oxy/hydroxide colloids and solids; and (3) an inability of two-phase reactive transport models to adequately simulate Pu behavior in the presence of colloids. A computer program called INVRS K was developed that integrates the geochemical modeling software of PHREEQC with a nonlinear regression routine. This program provides a tool for estimating equilibrium and kinetic constants from experimental data. INVRS K was used to regress on binding constants for Pu sorbing onto various mineral and humic surfaces. These constants enhance the thermodynamic database for Pu and improve the capability of current predictive tools. Time and temperature studies of the Pu intrinsic colloid were also conducted and results of these studies were presented here. Formation constants for the fresh and aged Pu intrinsic colloid were regressed upon using INVRS K. From these results, it was possible to develop a cohesive diagenetic model that describes the formation of Pu oxy/hydroxide colloids and solids. This model provides for the first time a means of deciphering historically unexplained observations with respect to the Pu intrinsic colloid, as well as a basis for simulating the behavior within systems containing these solids. Discussion of the development and application of reactive transport models is also presented and includes: (1) the general application of a 1-D in flow, three-phase (i.e., dissolved, solid, and colloidal), reactive

  4. Adsorption and desorption kinetics of (60)Co and (137)Cs in fresh water rivers.

    PubMed

    Fiengo Pérez, Fabricio; Sweeck, Lieve; Bauwens, Willy; Van Hees, May; Elskens, Marc

    2015-11-01

    Radionuclides released in water systems--as well as heavy metals and organic toxicants--sorb to both the suspended solid particles and the bed sediments. Sorption is usually represented mathematically by the distribution coefficient. This approach implies equilibrium between phases and instantaneous fixation (release) of the pollutant onto (from) the surface of the soil particle. However, empirical evidence suggests that for some radionuclides the fixation is not achieved instantaneously and that the reversibility of the process can be slow. Here the adsorption/desorption kinetics of (60)Co and (137)Cs in fresh water environments were simulated experimentally and later on modelled mathematically, while the influence of the most relevant factors affecting the sorption were taken into account. The experimental results suggest that for adsorption and the desorption more than 24 h are needed to reach equilibrium, moreover, It was observed that the desorption rate constants for (60)Co and (137)Cs lie within ranges which are of two to three orders of magnitude lower than the adsorption rate constants. PMID:26218323

  5. 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

  6. Experimental and kinetic studies on methylene blue adsorption by coir pith carbon.

    PubMed

    Kavitha, D; Namasivayam, C

    2007-01-01

    Varying the parameters such as agitation time, dye concentration, adsorbent dose, pH and temperature carried out the potential feasibility of thermally activated coir pith carbon prepared from coconut husk for removal of methylene blue. Greater percentage of dye was removed with decrease in the initial concentration of dye and increase in amount of adsorbent used. Kinetic study showed that the adsorption of dye on coir pith carbon was a gradual process. Lagergren first-order, second-order, intra particle diffusion model and Bangham were used to fit the experimental data. Equilibrium isotherms were analysed by Langmuir, Freundlich, Dubnin-Radushkevich, and Tempkin isotherm. The adsorption capacity was found to be 5.87 mg/g by Langmuir isotherm for the particle size 250-500 microm. The equilibrium time was found to be 30 and 60 min for 10 and 20 mg/L and 100 min for 30, 40 mg/L dye concentrations, respectively. A maximum removal of 97% was obtained at natural pH 6.9 for an adsorbent dose of 100 mg/50 mL and 100% removal was obtained for an adsorbent dose of 600 mg/50 mL of 10 mg/L dye concentration. The pH effect and desorption studies suggest that chemisorption might be the major mode of the adsorption process. The change in entropy (DeltaS0) and heat of adsorption (DeltaH0) of coir pith carbon was estimated as 117.20 J/mol/K and 30.88 kJ/mol, respectively. The high negative value of change in Gibbs free energy indicates the feasible and spontaneous adsorption of methylene blue on coir pith carbon. PMID:16427273

  7. Adsorption and kinetic studies of seven different organic dyes onto magnetite nanoparticles loaded tea waste and removal of them from wastewater samples.

    PubMed

    Madrakian, Tayyebeh; Afkhami, Abbas; Ahmadi, Mazaher

    2012-12-01

    Adsorption of seven different organic dyes from aqueous solutions onto magnetite nanoparticles loaded tea waste (MNLTW) was studied. MNLTW was prepared via a simple method and was fully characterized. The properties of this magnetic adsorbent were characterized by scanning electron microscopy and X-ray diffraction. Adsorption characteristics of the MNLTW adsorbent was examined using Janus green, methylene blue, thionine, crystal violet, Congo red, neutral red and reactive blue 19 as adsorbates. Dyes adsorption process was thoroughly studied from both kinetic and equilibrium points of view for all adsorbents. The experimental isotherm data were analyzed using Langmuir, Freundlich, Sips, Redlich-Peterson, Brouers-Sotolongo and Temkin isotherms. The results from Langmuir isotherm indicated that the capacity of MNLTW for the adsorption of cationic dyes was higher than that for anionic dyes. The adsorption kinetics was tested for the pseudo-first order and pseudo-second order kinetic models at different experimental conditions. PMID:23058993

  8. Adsorption and kinetic studies of seven different organic dyes onto magnetite nanoparticles loaded tea waste and removal of them from wastewater samples

    NASA Astrophysics Data System (ADS)

    Madrakian, Tayyebeh; Afkhami, Abbas; Ahmadi, Mazaher

    2012-12-01

    Adsorption of seven different organic dyes from aqueous solutions onto magnetite nanoparticles loaded tea waste (MNLTW) was studied. MNLTW was prepared via a simple method and was fully characterized. The properties of this magnetic adsorbent were characterized by scanning electron microscopy and X-ray diffraction. Adsorption characteristics of the MNLTW adsorbent was examined using Janus green, methylene blue, thionine, crystal violet, Congo red, neutral red and reactive blue 19 as adsorbates. Dyes adsorption process was thoroughly studied from both kinetic and equilibrium points of view for all adsorbents. The experimental isotherm data were analyzed using Langmuir, Freundlich, Sips, Redlich-Peterson, Brouers-Sotolongo and Temkin isotherms. The results from Langmuir isotherm indicated that the capacity of MNLTW for the adsorption of cationic dyes was higher than that for anionic dyes. The adsorption kinetics was tested for the pseudo-first order and pseudo-second order kinetic models at different experimental conditions.

  9. An eco-friendly dyeing of woolen yarn by Terminalia chebula extract with evaluations of kinetic and adsorption characteristics

    PubMed Central

    Shabbir, Mohd; Rather, Luqman Jameel; Shahid-ul-Islam; Bukhari, Mohd Nadeem; Shahid, Mohd; Ali Khan, Mohd; Mohammad, Faqeer

    2016-01-01

    In the present study Terminalia chebula was used as an eco-friendly natural colorant for sustainable textile coloration of woolen yarn with primary emphasis on thermodynamic and kinetic adsorption aspects of dyeing processes. Polyphenols and ellagitannins are the main coloring components of the dye extract. Assessment of the effect of pH on dye adsorption showed an increase in adsorption capacity with decreasing pH. Effect of temperature on dye adsorption showed 80 °C as optimum temperature for wool dyeing with T. chebula dye extract. Two kinetic equations, namely pseudo first-order and pseudo second-order equations, were employed to investigate the adsorption rates. Pseudo second-order model provided the best fit (R2 = 0.9908) to the experimental data. The equilibrium adsorption data were fitted by Freundlich and Langmuir isotherm models. The adsorption behavior accorded well (R2 = 0.9937) with Langmuir isotherm model. Variety of eco-friendly and sustainable shades were developed in combination with small amount of metallic mordants and assessed in terms of colorimetric (CIEL∗a∗b∗ and K/S) properties measured using spectrophotometer under D65 illuminant (10° standard observer). The fastness properties of dyed woolen yarn against light, washing, dry and wet rubbing were also evaluated. PMID:27222752

  10. An eco-friendly dyeing of woolen yarn by Terminalia chebula extract with evaluations of kinetic and adsorption characteristics.

    PubMed

    Shabbir, Mohd; Rather, Luqman Jameel; Shahid-Ul-Islam; Bukhari, Mohd Nadeem; Shahid, Mohd; Ali Khan, Mohd; Mohammad, Faqeer

    2016-05-01

    In the present study Terminalia chebula was used as an eco-friendly natural colorant for sustainable textile coloration of woolen yarn with primary emphasis on thermodynamic and kinetic adsorption aspects of dyeing processes. Polyphenols and ellagitannins are the main coloring components of the dye extract. Assessment of the effect of pH on dye adsorption showed an increase in adsorption capacity with decreasing pH. Effect of temperature on dye adsorption showed 80 °C as optimum temperature for wool dyeing with T. chebula dye extract. Two kinetic equations, namely pseudo first-order and pseudo second-order equations, were employed to investigate the adsorption rates. Pseudo second-order model provided the best fit (R (2) = 0.9908) to the experimental data. The equilibrium adsorption data were fitted by Freundlich and Langmuir isotherm models. The adsorption behavior accorded well (R (2) = 0.9937) with Langmuir isotherm model. Variety of eco-friendly and sustainable shades were developed in combination with small amount of metallic mordants and assessed in terms of colorimetric (CIEL(∗) a (∗) b (∗) and K/S) properties measured using spectrophotometer under D65 illuminant (10° standard observer). The fastness properties of dyed woolen yarn against light, washing, dry and wet rubbing were also evaluated. PMID:27222752

  11. Biosorption of uranium by melanin: kinetic, equilibrium and thermodynamic studies.

    PubMed

    Saini, Amardeep Singh; Melo, Jose Savio

    2013-12-01

    Limitation of conventional techniques for the removal of heavy metals present at low concentrations, has led to the need for developing alternate technologies like biosorption. In the present study we describe the use of melanin pigment synthesized through green technology, for sorption of uranium from aqueous system. Biosynthesized melanin showed good uptake over a broad pH range. Removal of uranium was rapid and equilibrium was reached within 2h of contact. It was observed that the kinetic data fits well into Lagergren's pseudo-second order equation. A maximum loading capacity of 588.24 mg g(-1) was calculated from Langmuir plot. Thermodynamic studies performed revealed that sorption process was favorable. Binding of uranium on the surface of melanin was confirmed by FT-IR and energy dispersive spectroscopy (EDS). Thus, biosynthesized melanin can be efficiently used as a sorbent for removal of uranium from aqueous solution. PMID:24099972

  12. 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

  13. Reactive Gas transport in soil: Kinetics versus Local Equilibrium Approach

    NASA Astrophysics Data System (ADS)

    Geistlinger, Helmut; Jia, Ruijan

    2010-05-01

    Gas transport through the unsaturated soil zone was studied using an analytical solution of the gas transport model that is mathematically equivalent to the Two-Region model. The gas transport model includes diffusive and convective gas fluxes, interphase mass transfer between the gas and water phase, and biodegradation. The influence of non-equilibrium phenomena, spatially variable initial conditions, and transient boundary conditions are studied. The objective of this paper is to compare the kinetic approach for interphase mass transfer with the standard local equilibrium approach and to find conditions and time-scales under which the local equilibrium approach is justified. The time-scale of investigation was limited to the day-scale, because this is the relevant scale for understanding gas emission from the soil zone with transient water saturation. For the first time a generalized mass transfer coefficient is proposed that justifies the often used steady-state Thin-Film mass transfer coefficient for small and medium water-saturated aggregates of about 10 mm. The main conclusion from this study is that non-equilibrium mass transfer depends strongly on the temporal and small-scale spatial distribution of water within the unsaturated soil zone. For regions with low water saturation and small water-saturated aggregates (radius about 1 mm) the local equilibrium approach can be used as a first approximation for diffusive gas transport. For higher water saturation and medium radii of water-saturated aggregates (radius about 10 mm) and for convective gas transport, the non-equilibrium effect becomes more and more important if the hydraulic residence time and the Damköhler number decrease. Relative errors can range up to 100% and more. While for medium radii the local equilibrium approach describes the main features both of the spatial concentration profile and the time-dependence of the emission rate, it fails completely for larger aggregates (radius about 100 mm

  14. The influence of protein aggregation on adsorption kinetics

    NASA Astrophysics Data System (ADS)

    Rovner, Joel; Roberts, Christopher; Furst, Eric; Hudson, Steven

    2015-03-01

    When proteins adsorb to an air-water interface they lower the surface tension and may form an age-dependent viscoelastic film. Protein adsorption to surfaces is relevant to both commercial uses and biological function. The rate at which the surface tension decreases depends strongly on temperature, solution pH, and protein structure. These kinetics also depend on the degree to which the protein is aggregated in solution. Here we explore these differences using Chymotrypsinogen as a model protein whose degree of aggregation is adjusted through controlled heat treatment and measured by chromatography. To study these effects we have used a micropipette tensiometer to produce a spherical-cap bubble whose interfacial pressure was controlled - either steady or oscillating. Short heat treatment produced small soluble aggregates, and these adsorbed faster than the original protein monomer. Longer heat treatment produced somewhat larger soluble aggregates which adsorbed more slowly. These results point to complex interactions during protein adsorption.

  15. 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

  16. One-step fabricated Fe3O4@C core-shell composites for dye removal: Kinetics, equilibrium and thermodynamics

    NASA Astrophysics Data System (ADS)

    Qu, Lingling; Han, Tingting; Luo, Zhijun; Liu, Cancan; Mei, Yan; Zhu, Ting

    2015-03-01

    B-Fe3O4@C core-shell composites were synthesized via one-pot hydrothermal carbonization (HTC) process and used as an adsorbent for the removal of methylene blue (MB) from aqueous solution. By using sodium borate as the catalyst, the hydrothermal carbonization process of B-Fe3O4@C core-shell composites was optimized and a higher surface area was obtained. The adsorbent was characterized by XRD, Raman spectra, SEM, TEM and N2 adsorption/desorption isotherms. We studied the dye adsorption process at different conditions and analyzed the data by employing the Langmuir and Freundlich models, and the equilibrium data fitted well with both models. Kinetic analyses were conducted by using the Lagergren pseudo-first-order and pseudo-second-order model and the results showed that the adsorption process was more consistent with the pseudo-second-order kinetics. To better understand the dye adsorption process from the thermodynamics perspective, we also calculated ΔHο, ΔSο, ΔGο and Ea, the results suggesting that the MB adsorption process was physisorption endothermic process, and spontaneous at room temperature. The as-synthesized B-Fe3O4@C showing high magnetic sensitivity provides a facile and efficient way to recycle from aqueous solution.

  17. Effect of the adsorbate (Bromacil) equilibrium concentration in water on its adsorption on powdered activated carbon. Part 3: Competition with natural organic matter.

    PubMed

    Al Mardini, Fadi; Legube, Bernard

    2010-10-15

    This study (part 3) was carried out to investigate the effect of the natural organic matter (NOM) concentration on Bromacil (pesticide) adsorption on powdered activated carbon (PAC) in the same experimental conditions as in our previous studies (parts 1 and 2). Our previous findings showed that Bromacil adsorption in buffered pure water (pH 7.8) occurred at two types of site. In the presence of NOM (three kinds), we noted a significant reduction in Bromacil adsorption capacities due to the competitive effects exerted by NOM. Highly reactive sites (or pores) in PAC appeared to be blocked by NOM adsorption, as demonstrated by the application of a pseudo-single solute isotherm and of the simplified ideal adsorbed solution theory (IAST), regardless of the initial Bromacil and NOM concentrations. The competing effect of low-molecular weight NOM was found to be greater than the competing effect of high-molecular weight NOM. The pseudo-second order surface-reaction model fitted Bromacil adsorption particularly well, even in the presence of NOM. However, the adsorption-kinetic constant values were found to be independent of the aqueous equilibrium concentration of the target compound, contrary to that observed in pure water. The kinetic data thus confirmed that high reactivity PAC sites were blocked by NOM adsorption. A practical approach concluded this work. PMID:20619963

  18. Effective computer simulation of equilibrium adsorption with limited solubility

    NASA Astrophysics Data System (ADS)

    Zedek, Lukáš; Šembera, Jan

    2014-12-01

    Radioactive waste repositories are discussed to be built in compact granite rock massif somewhere in the Czech Republic. To support the decision-making, various computer simulations are performed. These simulations help to evaluate risks connected with potential isolation failures, followed by transport of released radionuclides in the groundwater. Transport of radionuclides is affected by many natural processes. In this paper we focus on two important processes: adsorption and limited solubility (surface precipitation) of radionuclides in groundwater. Presented approach is based on interpolation instead of time demanding solution of nonlinear equations arising from mathematical description of the problem. The effectiveness of the proposed approach consists in creation of an interpolation table of points lying on an isotherm and transformed to mass balance maintaining system of coordinates. This kind of table is used to project data from transport part of simulation on the isotherm. The interpolation table points are computed using free derivative, nonlinear equation solver which avoids some of numerical solution difficulties. Results achieved with the use of our approach are comparable to Newton-Raphson method achieved solutions, but the simulation times are shorter.

  19. Recyclable Mg-Al layered double hydroxides for fluoride removal: Kinetic and equilibrium studies.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2015-12-30

    Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg-Al LDH) and Cl(-) (Cl · Mg-Al LDH) were found to adsorb fluoride from aqueous solutions. Fluoride is removed by anion exchange in solution with NO3(-) and Cl(-) intercalated in the LDH interlayer. In both cases, the residual F concentration is lower than the effluent standards for F in Japan (8 mg/L). The rate-determining step in the removal of F using NO3 · Mg-Al and Cl · Mg-Al LDH is chemical adsorption involving F(-) anion exchange with intercalated NO3(-) and Cl(-) ions. The removal of F is described by pseudo-second-order reaction kinetics, with Langmuir-type adsorption. The values obtained for the maximum adsorption and the equilibrium adsorption constant are respectively 3.3 mmol g(-1) and 2.8 with NO3 · Mg-Al LDH, and 3.2 mmol g(-1) and 1.5 with Cl · Mg-Al LDH. The F in the F · Mg-Al LDH produced in these reactions was found to exchange with NO3(-) and Cl(-) ions in solution. The regenerated NO3 · Mg-Al and Cl · Mg-Al LDHs thus obtained can be used once more to capture aqueous F. This suggests that NO3 · Mg-Al and Cl · Mg-Al LDHs can be recycled and used repeatedly for F removal. PMID:26223022

  20. Development and application of a numerical model of kinetic and equilibrium microbiological and geochemical reactions (BIOKEMOD)

    NASA Astrophysics Data System (ADS)

    Salvage, Karen M.; Yeh, Gour-Tsyh

    1998-08-01

    This paper presents the conceptual and mathematical development of the numerical model titled BIOKEMOD, and verification simulations performed using the model. BIOKEMOD is a general computer model for simulation of geochemical and microbiological reactions in batch aqueous solutions. BIOKEMOD may be coupled with hydrologic transport codes for simulation of chemically and biologically reactive transport. The chemical systems simulated may include any mixture of kinetic and equilibrium reactions. The pH, pe, and ionic strength may be specified or simulated. Chemical processes included are aqueous complexation, adsorption, ion-exchange and precipitation/dissolution. Microbiological reactions address growth of biomass and degradation of chemicals by microbial metabolism of substrates, nutrients, and electron acceptors. Inhibition or facilitation of growth due to the presence of specific chemicals and a lag period for microbial acclimation to new substrates may be simulated if significant in the system of interest. Chemical reactions controlled by equilibrium are solved using the law of mass action relating the thermodynamic equilibrium constant to the activities of the products and reactants. Kinetic chemical reactions are solved using reaction rate equations based on collision theory. Microbiologically mediated reactions for substrate removal and biomass growth are assumed to follow Monod kinetics modified for the potentially limiting effects of substrate, nutrient, and electron acceptor availability. BIOKEMOD solves the ordinary differential and algebraic equations of mixed geochemical and biogeochemical reactions using the Newton-Raphson method with full matrix pivoting. Simulations may be either steady state or transient. Input to the program includes the stoichiometry and parameters describing the relevant chemical and microbiological reactions, initial conditions, and sources/sinks for each chemical species. Output includes the chemical and biomass concentrations

  1. 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

  2. Kinetics and equilibrium of solute diffusion into human hair.

    PubMed

    Wang, Liming; Chen, Longjian; Han, Lujia; Lian, Guoping

    2012-12-01

    The uptake kinetics of five molecules by hair has been measured and the effects of pH and physical chemical properties of molecules were investigated. A theoretical model is proposed to analyze the experimental data. The results indicate that the binding affinity of solute to hair, as characterized by hair-water partition coefficient, scales to the hydrophobicity of the solute and decreases dramatically as the pH increases to the dissociation constant. The effective diffusion coefficient of solute depended not only on the molecular size as most previous studies suggested, but also on the binding affinity as well as solute dissociation. It appears that the uptake of molecules by hair is due to both hydrophobic interaction and ionic charge interaction. Based on theoretical considerations of the cellular structure, composition and physical chemical properties of hair, quantitative-structure-property-relationships (QSPR) have been proposed to predict the hair-water partition coefficient (PC) and the effective diffusion coefficient (D (e)) of solute. The proposed QSPR models fit well with the experimental data. This paper could be taken as a reference for investigating the adsorption properties for polymeric materials, fibres, and biomaterials. PMID:22777125

  3. Kinetic and calorimetric study of the adsorption of dyes on mesoporous activated carbon prepared from coconut coir dust.

    PubMed

    Macedo, Jeremias de Souza; da Costa Júnior, Nivan Bezerra; Almeida, Luis Eduardo; Vieira, Eunice Fragoso da Silva; Cestari, Antonio Reinaldo; Gimenez, Iara de Fátima; Villarreal Carreño, Neftali Lênin; Barreto, Ledjane Silva

    2006-06-15

    Mesoporous activated carbon has been prepared from coconut coir dust as support for adsorption of some model dye molecules from aqueous solutions. The methylene blue (MB) and remazol yellow (RY) molecules were chosen for study of the adsorption capacity of cationic and anionic dyes onto prepared activated carbon. The adsorption kinetics was studied with the Lagergren first- and pseudo-second-order kinetic models as well as the intraparticle diffusion model. The results for both dyes suggested a multimechanism sorption process. The adsorption mechanisms in the systems dyes/AC follow pseudo-second-order kinetics with a significant contribution of intraparticle diffusion. The samples simultaneously present acidic and basic sites able to act as anchoring sites for basic and acidic dyes, respectively. Calorimetric studies reveal that dyes/AC interaction forces are correlated with the pH of the solution, which can be related to the charge distribution on the AC surface. These AC samples also exhibited very short equilibrium times for the adsorption of both dyes, which is an economically favorable requisite for the activated carbon described in this work, in addition to the local abundance of the raw material. PMID:16497318

  4. Adsorption-desorption kinetics of soft particles onto surfaces

    NASA Astrophysics Data System (ADS)

    Osberg, Brendan; Gerland, Ulrich

    A broad range of physical, chemical, and biological systems feature processes in which particles randomly adsorb on a substrate. Theoretical models usually assume ``hard'' (mutually impenetrable) particles, but in soft matter physics the adsorbing particles can be effectively compressible, implying ``soft'' interaction potentials. We recently studied the kinetics of such soft particles adsorbing onto one-dimensional substrates, identifying three novel phenomena: (i) a gradual density increase, or ''cramming'', replaces the usual jamming behavior of hard particles, (ii) a density overshoot, can occur (only for soft particles) on a time scale set by the desorption rate, and (iii) relaxation rates of soft particles increase with particle size (on a lattice), while hard particles show the opposite trend. The latter occurs since unjamming requires desorption and many-bodied reorganization to equilibrate -a process that is generally very slow. Here we extend this analysis to a two-dimensional substrate, focusing on the question of whether the adsorption-desorption kinetics of particles in two dimensions is similarly enriched by the introduction of soft interactions. Application to experiments, for example the adsorption of fibrinogen on two-dimensional surfaces, will be discussed.

  5. 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

  6. Equilibrium adsorption of hexahistidine on pH-responsive hydrogel nanofilms.

    PubMed

    Longo, Gabriel S; de la Cruz, Monica Olvera; Szleifer, Igal

    2014-12-23

    We present a molecular theory to study the adsorption of different species within pH-sensitive hydrogel nanofilms. The theoretical framework allows for a molecular-level description of all the components of the system, and it explicitly accounts for the acid-base equilibrium. We concentrate on the adsorption of hexahistidine, one of the most widely used tags in bio-related systems, particularly in chromatography of proteins. The adsorption of hexahistidine within a grafted polyacid hydrogel film shows a nonmonotonic dependence on the solution pH. Depending on the salt concentration, the density of the polymer network, and the bulk concentration of peptide, substantial adsorption is predicted in the intermediate pH range where both the network and the amino acids are charged. To enhance the electrostatic attractions, the acid-base equilibrium of adsorbed hexahistidine is shifted significantly, increasing the degree of charge of the residues as compared to the bulk solution. Such a shift depends critically on the conditions of the environment at the nanoscale. At the same time, the degree of dissociation of the network becomes that of the isolated acid group in a dilute solution, which means that the network is considerably more charged than when there is no adsorbate molecules. This work provides fundamental information on the physical chemistry behind the adsorption behavior and the response of the hydrogel film. This information can be useful in designing new materials for the purification or separation/immobilization of histidine-tagged proteins. PMID:25434993

  7. Mechanism of Cr(VI) adsorption by coir pith studied by ESR and adsorption kinetic.

    PubMed

    Suksabye, Parinda; Nakajima, Akira; Thiravetyan, Paitip; Baba, Yoshinari; Nakbanpote, Woranan

    2009-01-30

    The oxidation state of chromium in coir pith after Cr(VI) adsorption from aqueous solution was investigated using electron spin resonance (ESR). To elucidate the mechanism of chromium adsorption on coir pith, the adsorption studies of Cr(VI) onto lignin, alpha-cellulose and holocellulose extracted from coir pith were also studied. ESR signals of Cr(V) and Cr(III) were observed in coir pith adsorbed Cr(VI) at solution pH 2, while ESR spectra of lignin extracted from coir pith revealed only the Cr(III) signal. In addition, ESR signal of Cr(V) was observed in alpha-cellulose and holocellulose extracted from coir pith adsorbed Cr(VI). These results confirmed that lignin in coir pith reduced Cr(VI) to Cr(III) while alpha-cellulose and holocellulose extracted from coir pith reduced Cr(VI) to Cr(V). The Cr(V) signal exhibited in ESR of alpha-cellulose and holocellulose might be bound with glucose in cellulose part of coir pith. In addition, xylose which is main in pentosan part of coir pith, indicated that it is involved in form complex with Cr(V) on coir pith. The adsorption kinetic of Cr(VI) from aqueous solution on coir pith was also investigated and described well with pseudo second order model. ESR and desorption experiments confirmed that Cr(VI), Cr(V) and Cr(III), exist in coir pith after Cr(VI) adsorption. The desorption data indicated that the percentage of Cr(VI), Cr(V) and Cr(III) in coir pith were 15.63%, 12.89% and 71.48%, respectively. PMID:18513862

  8. 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

  9. 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

  10. 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

  11. Adsorption of heavy metal ions using hierarchical CaCO3-maltose meso/macroporous hybrid materials: adsorption isotherms and kinetic studies.

    PubMed

    Ma, Xiaoming; Li, Liping; Yang, Lin; Su, Caiyun; Wang, Kui; Yuan, Shibao; Zhou, Jianguo

    2012-03-30

    Highly ordered hierarchical calcium carbonate is an important phase and has technological interest in the development of functional materials. The work describes hierarchical CaCO(3)-maltose meso/macroporous hybrid materials were synthesized using a simple gas-diffusion method. The uniform hexagonal-shaped CaCO(3)-maltose hybrid materials are formed by the hierarchical assembly of nanoparticles. The pore structure analysis indicates that the sample possesses the macroporous structure of mesoporous framework. The distinguishing features of the hierarchical CaCO(3)-maltose materials in water treatment involve not only high removal capacities, but also decontamination of trace metal ions. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The maximum removal capacity of the CaCO(3)-maltose hybrid materials for Pb(2+), Cd(2+), Cu(2+), Co(2+), Mn(2+) and Ni(2+) ions was 3242.48, 487.80, 628.93, 393.70, 558.66 and 769.23 mg/g, respectively. Adsorption data were modeled using the pseudo-first-order, pseudo-second-order and intra-particle diffusion kinetics equations. The results indicate that pseudo-second-order kinetic equation and intra-particle diffusion model can better describe the adsorption kinetics. The adsorption and precipitation transformation mechanism can be considered due to hierarchical meso/macroporous structure, rich organic ligands of the CaCO(3)-maltose hybrid materials and the larger solubility product of CaCO(3). PMID:22326246

  12. Kinetic models for the adsorption of lead ions by steel slag.

    PubMed

    Liu, Sheng-Yu; Gao, Jin; Qu, Bin; Yang, Yi-Jin; Xin, Xin

    2010-08-01

    Batch experiments were carried out to investigate the kinetics of adsorption of lead ions by steel slag on the basis of the external diffusion, intraparticle diffusion and adsorption reaction model (pseudo-first-order, pseudo-second-order). The results showed that the controlling step for the adsorption kinetics changed with experimental parameters varied. When the particle size of steel slag was larger than 120 mesh, intraparticle diffusion of Pb(2+) was the controlling step; when the initial concentration of Pb(2+) was less than 150 mg L(-1) or the shaking rate was lower than 150 rpm, external diffusion of Pb(2+) was promoted. Contrary to the former experimental conditions, the adsorption reaction was the controlling step, and the adsorption followed second-order kinetics, with an adsorption rate constant of 13.26 g mg(-1) min(- 1). The adsorption isotherm of Pb(2+) with steel slag followed the Langmuir model, with a correlation coefficient of 0.99. PMID:19808736

  13. Biosorption of Cu(II) by immobilized microalgae using silica: kinetic, equilibrium, and thermodynamic study.

    PubMed

    Lee, Hongkyun; Shim, Eunjung; Yun, Hyun-Shik; Park, Young-Tae; Kim, Dohyeong; Ji, Min-Kyu; Kim, Chi-Kyung; Shin, Won-Sik; Choi, Jaeyoung

    2016-01-01

    Immobilized microalgae using silica (IMS) from Micractinium reisseri KGE33 was synthesized through a sol-gel reaction. Green algal waste biomass, the residue of M. reisseri KGE33 after oil extraction, was used as the biomaterial. The adsorption of Cu(II) on IMS was tested in batch experiments with varying algal doses, pH, contact times, initial Cu(II) concentrations, and temperatures. Three types of IMSs (IMS 14, 70, and 100) were synthesized according to different algal doses. The removal efficiency of Cu(II) in the aqueous phase was in the following order: IMS 14 (77.0%) < IMS 70 (83.3%) < IMS 100 (87.1%) at pH 5. The point of zero charge (PZC) value of IMS100 was 4.5, and the optimum pH for Cu(II) adsorption was 5. Equilibrium data were described using a Langmuir isotherm model. The Langmuir model maximum Cu(II) adsorption capacity (q m) increased with the algal dose in the following order: IMS 100 (1.710 mg g(-1)) > IMS 70 (1.548 mg g(-1)) > IMS 14 (1.282 mg g(-1)). The pseudo-second-order equation fitted the kinetics data well, and the value of the second-order rate constant increased with increasing algal dose. Gibbs free energies (ΔG°) were negative within the temperature range studied, which indicates that the adsorption process was spontaneous. The negative value of enthalpy (ΔH°) again indicates the exothermic nature of the adsorption process. In addition, SEM-energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS) analyses of the IMS surface reveal that the algal biomass on IMS is the main site for Cu(II) binding. This study shows that immobilized microalgae using silica, a synthesized biosorbent, can be used as a cost-effective sorbent for Cu(II) removal from the aqueous phase. PMID:25953610

  14. Atomistic simulations of surfactant adsorption kinetics at interfaces

    NASA Astrophysics Data System (ADS)

    Iskrenova, Eugeniya; Patnaik, Soumya

    2014-03-01

    Heat transfer control and enhancement is an important and challenging problem in a variety of industrial and technological applications including aircraft thermal management. The role of additives in nucleate boiling and phase change in general has long been recognized and studied experimentally and modeled theoretically but in-depth description and atomistic understanding of the multiscale processes involved are still needed for better prediction and control of the heat transfer efficiency. Surfactant additives have been experimentally observed to either enhance or inhibit the boiling heat transfer depending on the surfactant concentration and chemistry and, on a molecular level, their addition leads to dynamic surface tension and changes in interfacial and transfer properties, thus contributing to the complexity of the problem. We present our atomistic modeling study of the interfacial adsorption kinetics of aqueous surfactant (sodium dodecyl sulfate) systems at a range of concentrations at room and boiling temperatures. Classical molecular dynamics and Umbrella Sampling simulations were used to study the surfactant transport properties and estimate the adsorption and desorption rates at liquid-vacuum and liquid-solid interfaces. The authors gratefully acknowledge funding from AFOSR Thermal Science Program and the Air Force Research Laboratory DoD Supercomputing Resource Center for computing time and resources.

  15. Effect of humic acid on the adsorption/desorption behavior of glyphosate on goethite. Isotherms and kinetics.

    PubMed

    Arroyave, Jeison Manuel; Waiman, Carolina C; Zanini, Graciela P; Avena, Marcelo J

    2016-02-01

    The effects of humic acid (HA) on the adsorption/desorption of glyphosate (Gly) on goethite were investigated under pseudo equilibrium conditions by adsorption isotherms and under kinetic conditions by ATR-FTIR spectroscopy. Isotherms reveal that the attachment of Gly is almost completely inhibited by HA molecules. The opposite effect is not observed: HA adsorption is not affected by the presence of Gly. ATR-FTIR allowed the simultaneous detection of adsorbed HA and Gly during kinetic runs, revealing that HA at the surface decreases markedly the adsorption rate of Gly likely as a result of a decreased availability of sites for Gly adsorption and because of electrostatic repulsion. In addition, HA in solution increases the desorption rate of Gly. The rate law for Gly desorption could be determined giving important insights on the desorption mechanism. The herbicide is desorbed by two parallel processes: i) a direct detachment from the surface, which is first order in adsorbed Gly; and ii) a ligand exchange with HA molecules, which is first order in adsorbed Gly and first order in dissolved HA. Rate constants for both processes were quantified, leading to half-lives of 3.7 h for the first process, and 1.4 h for the second process in a 400 mg L(-1) HA solution. These data are important for modeling the dynamics of glyphosate in environmentally relevant systems, such as soils and surface waters. PMID:26657085

  16. 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

  17. Simulating adsorption of U(VI) under transient groundwater flow and hydrochemistry – Physical versus non-equilibrium model

    SciTech Connect

    Greskowiak, Janek; Hay, Michael B.; Prommer, Henning; Liu, Chongxuan; Post, Vincent; Ma, Rui; Davis, James A.; Zheng, Chunmiao; Zachara, John M.

    2011-08-03

    Coupled intra-grain diffusional mass-transfer and non-linear surface complexation processes play an important role for the transport behaviour of U(VI) in contaminated aquifers. Two alternative model approaches for simulating these coupled processes have been analysed and compared: (i) the physical non-equilibrium approach that explicitly accounts for aqueous speciation and instantaneous surface complexation reactions in the intra-grain regions and approximates the diffusive mass exchange between the immobile intra-grain pore water and the advective pore water as multi-rate 1st-order mass transfer and (ii) the chemical non-equilibrium approach that approximates the diffusion-limited intra-grain surface complexation reactions by a set of multiple 1st-order surface complexation reaction kinetics, thereby eliminating the explicit treatment of aqueous speciation in the intra grain pore water. Model comparison has been carried out for column and field scale scenarios, representing the highly transient hydrological and geochemical conditions in the U(VI)-contaminated aquifer at the Hanford 300A site, Washington, USA. It was found that the response of apparent U(VI) adsorption/desorption kinetic behaviour to hydrogeochemically induced changes in U(VI) sorption strength is more pronounced in the physical than in the chemical non-equilibrium model. The magnitude of the differences in model behaviour depends particularly on the degree of disequilibrium between the advective and immobile phase U(VI) concentrations. While a clear difference in U(VI) transport behaviour between the two models was noticeable for the column-scale scenarios, only minor differences were found for the Hanford 300A field scale scenarios, where the model-generated disequilibrium conditions were less pronounced as a result of high frequent groundwater flow reversals.

  18. Adsorption of cobalt ferrite nanoparticles within layer-by-layer films: a kinetic study carried out using quartz crystal microbalance.

    PubMed

    Alcantara, Gustavo B; Paterno, Leonardo G; Afonso, André S; Faria, Ronaldo C; Pereira-da-Silva, Marcelo A; Morais, Paulo C; Soler, Maria A G

    2011-12-28

    The paper reports on the successful use of the quartz crystal microbalance technique to assess accurate kinetics and equilibrium parameters regarding the investigation of in situ adsorption of nanosized cobalt ferrite particles (CoFe(2)O(4)--10.5 nm-diameter) onto two different surfaces. Firstly, a single layer of nanoparticles was deposited onto the surface provided by the gold-coated quartz resonator functionalized with sodium 3-mercapto propanesulfonate (3-MPS). Secondly, the layer-by-layer (LbL) technique was used to build multilayers in which the CoFe(2)O(4) nanoparticle-based layer alternates with the sodium sulfonated polystyrene (PSS) layer. The adsorption experiments were conducted by modulating the number of adsorbed CoFe(2)O(4)/PSS bilayers (n) and/or by changing the CoFe(2)O(4) nanoparticle concentration while suspended as a stable colloidal dispersion. Adsorption of CoFe(2)O(4) nanoparticles onto the 3-MPS-functionalized surface follows perfectly a first order kinetic process in a wide range (two orders of magnitude) of nanoparticle concentrations. These data were used to assess the equilibrium constant and the adsorption free energy. Alternatively, the Langmuir adsorption constant was obtained while analyzing the isotherm data at the equilibrium. Adsorption of CoFe(2)O(4) nanoparticles while growing multilayers of CoFe(2)O(4)/PSS was conducted using colloidal suspensions with CoFe(2)O(4) concentration in the range of 10(-8) to 10(-6) (moles of cobalt ferrite per litre) and for different numbers of cycles n = 1, 3, 5, and 10. We found the adsorption of CoFe(2)O(4) nanoparticles within the CoFe(2)O(4)/PSS bilayers perfectly following a first order kinetic process, with the characteristic rate constant growing with the increase of CoFe(2)O(4) nanoparticle concentration and decreasing with the rise of the number of LbL cycles (n). Additionally, atomic force microscopy was employed for assessing the LbL film roughness and thickness. We found the film

  19. 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

  20. Treatment of dairy wastewater by commercial activated carbon and bagasse fly ash: Parametric, kinetic and equilibrium modelling, disposal studies.

    PubMed

    Kushwaha, Jai Prakash; Srivastava, Vimal Chandra; Mall, Indra Deo

    2010-05-01

    Present study reports treatment of synthetic dairy wastewater (SDW) in terms of chemical oxygen demand (COD) removal by means of adsorption onto activated carbon-commercial grade (ACC) and bagasse fly ash (BFA). Optimum conditions for SDW treatment were found to be: initial pH approximately 4.8, adsorbent dose of 20g/l for ACC and 10g/l for BFA and contact time approximately 8h. Pseudo-second-order kinetic model was found to fit the kinetic data and Redlich-Peterson isotherm model was generally found to best represent the equilibrium data for SDW treatment by ACC and BFA. The change in entropy and enthalpy for SDW adsorption onto ACC and BFA were estimated as 125.85kJ/molK and 91.53kJ/mol; and 25.71kJ/molK and 17.26kJ/mol, respectively. The negative values of change in Gibbs free energy indicate the feasibility and spontaneous nature of the adsorptive treatment. PMID:20097555

  1. On the electron equilibrium distribution function in the kinetic theory of electron cyclotron maser

    NASA Astrophysics Data System (ADS)

    Shenggang, Liu

    1981-11-01

    The problems concerning the specification of electron equilibrium distribution function for the kinetic theory of ECRM are investigated in this paper. After detailed analysis of the published equilibium distribution functions, several conclusion have been achieved.

  2. Biosorption of lead (II) from water using heartwood charcoal of Areca catechu: equilibrium and kinetics studies

    NASA Astrophysics Data System (ADS)

    Haloi, Nabanita; Sarma, H. P.; Chakravarty, P.

    2013-09-01

    Present study was conducted to investigate the removal of Pb(II) from water by using heartwood charcoal of Areca catechu (HCAC). Batch experiments were conducted to determine the adsorption properties at different contact times (5-30 min), concentrations (0.1-10 mg/L), amounts of adsorbents (0.1-0.6 g), and in a range of pH 2-7. Most favorable biosorption condition was found at pH 5.0, 0.5 g biomass dosage and at 25 min equilibrium time. The experimental results were fitted to the Langmuir and Freundlich isotherm models; the Freundlich isotherm was found to well represent the measured sorption data implying HCAC has heterogeneous surface. Lagergren first-order and pseudo-second-order kinetic model were used to analyze the biosorption data; it was observed that the pseudo-second-order model best represented the relationship. Scanning electron microscopy image and energy dispersive X-ray analysis were also incorporated in support of the study. The result shows that HCAC has the potentiality to remove Pb(II) from water.

  3. Equilibrium and kinetic models for colloid release under transient solution chemistry conditions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We present continuum models to describe colloid release in the subsurface during transient physicochemical conditions. Our modeling approach relates the amount of colloid release to changes in the fraction of the solid surface area that contributes to retention. Equilibrium, kinetic, equilibrium and...

  4. Kinetic and equilibrium studies of the removal of ammonium ions from aqueous solution by rice husk ash-synthesized zeolite Y and powdered and granulated forms of mordenite.

    PubMed

    Yusof, Alias Mohd; Keat, Lee Kian; Ibrahim, Zaharah; Majid, Zaiton Abdul; Nizam, Nik Ahmad

    2010-02-15

    The removal of ammonium from aqueous solutions using zeolite NaY prepared from a local agricultural waste, rice husk ash waste was investigated and a naturally occurring zeolite mordenite in powdered and granulated forms was used as comparison. Zeolite NaY and mordenite were well characterized by powder X-ray diffraction (XRD), energy dispersive X-ray (EDX) analysis and the total cation exchange capacity (CEC). CEC of the zeolites were measured as 3.15, 1.46 and 1.34 meq g(-1) for zeolite Y, powdered mordenite and granular mordenite, respectively. Adsorption kinetics and equilibrium data for the removal of NH(4)(+) ions were examined by fitting the experimental data to various models. Kinetic studies showed that the adsorption followed a pseudo-second-order reaction. The equilibrium pattern fits well with the Langmuir isotherm compared to the other isotherms. The monolayer adsorption capacity for zeolite Y (42.37 mg/g) was found to be higher than that powdered mordenite (15.13 mg/g) and granular mordenite (14.56 mg/g). Thus, it can be concluded that the low cost and economical rice husk ash-synthesized zeolite NaY could be a better sorbent for ammonium removal due to its rapid adsorption rate and higher adsorption capacity compared to natural mordenite. PMID:19879040

  5. From Non-equilibrium to Equilibrium: Micellar Kinetics seen by Time-resolved Small-angle Scattering

    NASA Astrophysics Data System (ADS)

    Lund, Reidar

    The kinetic pathways of self-assembled nanostructures are not fully understood. Time-resolved small-angle X-ray/neutron scattering (TR-SAXS/SANS) is powerful technique1 that allows kinetics processes such as nucleation processes2,3 and morphological transitions4,5 to be followed with structural resolution over time scales starting from milliseconds. Neutrons offer the additional advantage of facile contrast variation through H/D substitution schemes, which also allow equilibrium processes such as molecular exchange and diffusion to be studied1 , 6 , 7. Here we will highlight the current capabilities of TR-SAS and show results on the kinetics of polymeric micelles. We will address how the understanding of kinetic pathways can be used control the nanostructure.

  6. Sorption kinetics and equilibrium uptake for water vapor in soft-contact-lens hydrogels.

    PubMed

    Weinmüller, C; Langel, C; Fornasiero, F; Radke, C J; Prausnitz, J M

    2006-05-01

    A gravimetric-sorption technique was used to obtain kinetic and equilibrium adsorption/desorption data for water vapor in four different soft-contact-lens (SCL) polymers at 35 degrees C. The SCL materials are a conventional hydrogel (polymacon) with a low water content at saturation (<50 wt %); two conventional hydrogels (hilafilcon A and alphafilcon A) with a high water content at saturation (>50 wt %); and a siloxane hydrogel (balafilcon A). Absorption and desorption equilibrium isotherms (water activity versus water weight fraction) overlap at high water contents, whereas significant hysteresis is observed at low water contents. The hysteresis loop is likely due to trapping of water in the polymer during the desorption process because of a rubber-to-glass transition of the SCL-film surfaces. Sorption data were interpreted using Flory-Rehner theory. The positive Zimm and Lundberg cluster function suggests that water tends to cluster in these SCL materials, except at very low water content. For polymacon and hilafilcon A, Fickian diffusion is observed for all activities for both water sorption and desorption. However, for alphafilcon A and balafilcon A, non-Fickian features appear at intermediate/low activities, in particular during water desorption, suggesting coupling of the diffusion process with polymer-matrix relaxation. The diffusion coefficient increases significantly with water concentration for polymacon and hilafilcon A (from approximately 0.3 x 10(-8) to 4.0 x 10(-8) cm2/s) because of augmented mixture free volume induced by water sorption, whereas a more complex composition dependence is observed for alphafilcon A and balafilcon A probably as consequence of a combined effect of polymer relaxation, plasticization, and water clustering. PMID:16392136

  7. Density functional theory of equilibrium random copolymers: application to surface adsorption of aggregating peptides

    NASA Astrophysics Data System (ADS)

    Wang, Haiqiang; Forsman, Jan; Woodward, Clifford E.

    2016-06-01

    We generalize a recently developed polymer density functional theory (PDFT) for polydisperse polymer fluids to the case of equilibrium random copolymers. We show that the generalization of the PDFT to these systems allows us to obtain a remarkable simplification compared to the monodispersed polymers. The theory is used to treat a model for protein aggregation into linear filaments in the presence of surfaces. Here we show that, for attractive surfaces, there is evidence of significant enhancement of protein aggregation. This behaviour is a consequence of a surface phase transition, which has been shown to occur with ideal equilibrium polymers in the presence of sufficiently attractive surfaces. For excluding monomers, this transition is suppressed, though an echo of the underlying ideal transition is present in the sudden change in the excess adsorption.

  8. Density functional theory of equilibrium random copolymers: application to surface adsorption of aggregating peptides.

    PubMed

    Wang, Haiqiang; Forsman, Jan; Woodward, Clifford E

    2016-06-22

    We generalize a recently developed polymer density functional theory (PDFT) for polydisperse polymer fluids to the case of equilibrium random copolymers. We show that the generalization of the PDFT to these systems allows us to obtain a remarkable simplification compared to the monodispersed polymers. The theory is used to treat a model for protein aggregation into linear filaments in the presence of surfaces. Here we show that, for attractive surfaces, there is evidence of significant enhancement of protein aggregation. This behaviour is a consequence of a surface phase transition, which has been shown to occur with ideal equilibrium polymers in the presence of sufficiently attractive surfaces. For excluding monomers, this transition is suppressed, though an echo of the underlying ideal transition is present in the sudden change in the excess adsorption. PMID:27115518

  9. Equilibrium and kinetic modeling of contaminant immobilization by activated carbon amended to sediments in the field.

    PubMed

    Rakowska, Magdalena I; Kupryianchyk, Darya; Koelmans, Albert A; Grotenhuis, Tim; Rijnaarts, Huub H M

    2014-12-15

    Addition of activated carbons (AC) to polluted sediments and soils is an attractive remediation technique aiming at reducing pore water concentrations of hydrophobic organic contaminants (HOCs). In this study, we present (pseudo-)equilibrium as well as kinetic parameters for sorption of a series of PAHs and PCBs to powdered and granular activated carbons (AC) after three different sediment treatments: sediment mixed with powdered AC (PAC), sediment mixed with granular AC (GAC), and addition of GAC followed by 2 d mixing and subsequent removal ('sediment stripping'). Remediation efficiency was assessed by quantifying fluxes of PAHs towards SPME passive samplers inserted in the sediment top layer, which showed that the efficiency decreased in the order of PAC > GAC stripping > GAC addition. Sorption was very strong to PAC, with Log KAC (L/kg) values up to 10.5. Log KAC values for GAC ranged from 6.3-7.1 and 4.8-6.2 for PAHs and PCBs, respectively. Log KAC values for GAC in the stripped sediment were 7.4-8.6 and 5.8-7.7 for PAH and PCB. Apparent first order adsorption rate constants for GAC (kGAC) in the stripping scenario were calculated with a first-order kinetic model and ranged from 1.6 × 10(-2) (PHE) to 1.7 × 10(-5) d(-1) (InP). Sorption affinity parameters did not change within 9 months post treatment, confirming the longer term effectiveness of AC in field applications for PAC and GAC. PMID:25262554

  10. On the relationships between the Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, equilibrium chemistry approximation kinetics, and quadratic kinetics

    DOE PAGESBeta

    Tang, J. Y.

    2015-12-01

    The Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use either of the two are often ambiguous. Here I show that these two kinetics are special approximations to the equilibrium chemistry approximation (ECA) kinetics, which is the first-order approximation to the quadratic kinetics that solves the equation of an enzyme–substrate complex exactly for a single-enzyme and single-substrate biogeochemical reaction with the law of mass action and the assumption of a quasi-steadymore » state for the enzyme–substrate complex and that the product genesis from enzyme–substrate complex is much slower than the equilibration between enzyme–substrate complexes, substrates, and enzymes. In particular, I show that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in deriving the equilibrium chemistry approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln k2+ of the reaction velocity v with respect to the maximum product genesis rate k2+, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln k1+ of v with respect to the intrinsic substrate affinity k1+, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln [E]T of v with respect the total enzyme concentration [E]T, and persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln [S]T of v with respect to the total substrate concentration

  11. On the relationships between the Michaelis-Menten kinetics, reverse Michaelis-Menten kinetics, equilibrium chemistry approximation kinetics, and quadratic kinetics

    NASA Astrophysics Data System (ADS)

    Tang, J. Y.

    2015-12-01

    The Michaelis-Menten kinetics and the reverse Michaelis-Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use either of the two are often ambiguous. Here I show that these two kinetics are special approximations to the equilibrium chemistry approximation (ECA) kinetics, which is the first-order approximation to the quadratic kinetics that solves the equation of an enzyme-substrate complex exactly for a single-enzyme and single-substrate biogeochemical reaction with the law of mass action and the assumption of a quasi-steady state for the enzyme-substrate complex and that the product genesis from enzyme-substrate complex is much slower than the equilibration between enzyme-substrate complexes, substrates, and enzymes. In particular, I show that the derivation of the Michaelis-Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis-Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in deriving the equilibrium chemistry approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis-Menten kinetics was found to persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln k2+ of the reaction velocity v with respect to the maximum product genesis rate k2+, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln k1+ of v with respect to the intrinsic substrate affinity k1+, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln [E]T of v with respect the total enzyme concentration [E]T, and persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln [S]T of v with respect to the total substrate concentration [S

  12. Adsorption kinetics of benzotriazole and its derivatives by nano Zn-Al-O.

    PubMed

    Xu, Bingbing; Qi, Fei; Wu, Fengchang; Xu, Qiujin; Chen, Zhonglin

    2014-09-01

    Benzotriazole and its derivatives are important industrial auxiliaries, which are serious pollution sources in the natural aquatic environment. Benzotriazole and its derivatives adsorption by a novel nano absorbent (nano Zn-Al-O binary metal oxide, named as ZAO) being explored as an effective water treatment method, was carried out in this study. Results showed that benzotriazole and its derivatives were all effectively adsorbed from water by ZAO. Removal efficiencies of benzotriazole, 5-methyl-benzotriazol and 5,6-dimethyl-benzotriazole with 5 g/L adsorbent dosage achieved 89%, 81% and 92%, respectively. The adsorption kinetics and isotherm models were used to express the adsorption process and discuss the adsorption mechanism. The adsorption kinetics well followed pseudo-second-order model, indicating that chemical adsorption dominated the adsorption. Adsorption isotherm was well expressed by Freundlich model. Structure characteristics of benzotriazole and its derivatives had great effect on their adsorption. Hydrogen-bond interaction was considered as the main mechanism for the surface adsorption. However, hydrophobic interactions played an important role in 5,6-dimethyl-benzotriazole adsorption due to its weak polarity. PMID:25924402

  13. Determinants of cation transport selectivity: Equilibrium binding and transport kinetics

    PubMed Central

    2015-01-01

    The crystal structures of channels and transporters reveal the chemical nature of ion-binding sites and, thereby, constrain mechanistic models for their transport processes. However, these structures, in and of themselves, do not reveal equilibrium selectivity or transport preferences, which can be discerned only from various functional assays. In this Review, I explore the relationship between cation transport protein structures, equilibrium binding measurements, and ion transport selectivity. The primary focus is on K+-selective channels and nonselective cation channels because they have been extensively studied both functionally and structurally, but the principles discussed are relevant to other transport proteins and molecules. PMID:26078056

  14. Removal of semivolatiles from soils by steam stripping. IV. Effects of adsorption/desorption kinetics

    SciTech Connect

    Rodriguez-Maroto, J.M.; Gomez-Lahoz, C.; Wilson, D.J.

    1995-07-01

    A mathematical model is developed for in-situ steam stripping of semivolatile organic compounds (SVOCs) in which the adsorption isotherm of the SVOCs on the soil is nonlinear and in which desorption kinetics may be rate limiting. Severe tailing, similar to that found with diffusion-limited steam stripping, is readily produced by the model, even under situations in which adsorption-desorption kinetics are rapid. The results also indicate that field experiments alone are not likely to be able to distinguish between limitations imposed on the rate of steam-stripping remediation by diffusion kinetics and those imposed by desorption kinetics.

  15. Studies of adsorption equilibria and kinetics in the systems: Aqueous solution of dyes-mesoporous carbons

    NASA Astrophysics Data System (ADS)

    Derylo-Marczewska, A.; Marczewski, A. W.; Winter, Sz.; Sternik, D.

    2010-06-01

    Two carbonaceous materials were synthesized by using the method of impregnation of mesoporous silicas obtained by applying the Pluronic copolymers as pore-creating agents. The isotherms of adsorption of methylene blue and methyl orange from aqueous solutions were measured by the static method. The profiles of adsorbate concentration change in time were obtained from the UV-vis spectra. The adsorption isotherms and kinetic dependence were discussed in the terms of theory of adsorption on heterogeneous surfaces.

  16. Kinetic Study of Adsorption Processes in Solution: An Undergraduate Physical Chemistry Experiment.

    ERIC Educational Resources Information Center

    Casado, Julio; And Others

    1985-01-01

    Background information, apparatus needed, procedures used, and results obtained are provided for a simple kinetic method for the monitoring of adsorption processes. The method, which involved adsorption of crystal violet onto activated carbon, is suitable for classroom and/or research purposes. (JN)

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

    PubMed

    Tripathi, Sumit; Tabor, Rico F

    2016-08-15

    The adsorption kinetics of many systems show apparent two-rate processes, where there appears to be resolved fast and slow adsorption steps. Such non-standard adsorption processes cannot be accounted for by conventional modeling methods, motivating new approaches. In this work, we present four different models that can account for two-rate adsorption and are based upon physically realistic processes - two adsorbing species, two surface sites having different energies, bilayer formation and molecular rearrangement modes. Each model is tested using a range of conditions, and the characteristic behavior is explored and compared. In these models, the effects of mass transport and bulk concentration are also accounted for, making them applicable in systems which are transport-limited or attachment-limited, or intermediate between the two. The applicability of these models is demonstrated by fitting exemplar experimental data for each of the four models, selecting the model on the basis of the known physical behavior of the adsorption kinetics. These models can be applied in a wide range of systems, from stagnant adsorption in large volume water treatment to highly dynamic flow conditions relevant to printing, coating and processing applications. PMID:27209397

  18. Combining an Optical Resonance Biosensor with Enzyme Activity Kinetics to Understand Protein Adsorption and Denaturation

    PubMed Central

    Wilson, Kerry A.; Finch, Craig A.; Anderson, Phillip; Vollmer, Frank; Hickman, James J.

    2014-01-01

    Understanding protein adsorption and resultant conformation changes on modified and unmodified silicon dioxide surfaces is a subject of keen interest in biosensors, microfluidic systems and for medical diagnostics. However, it has been proven difficult to investigate the kinetics of the adsorption process on these surfaces as well as understand the topic of the denaturation of proteins and its effect on enzyme activity. A highly sensitive optical whispering gallery mode (WGM) resonator was used to study a catalytic enzyme’s adsorption processes on different silane modified glass substrates (plain glass control, DETA, 13F, and SiPEG). The WGM sensor was able to obtain high resolution kinetic data of glucose oxidase (GO) adsorption with sensitivity of adsorption better than that possible with SPR. The kinetic data, in combination with a functional assay of the enzyme activity, was used to test hypotheses on adsorption mechanisms. By fitting numerical models to the WGM sensograms for protein adsorption, and by confirming numerical predictions of enzyme activity in a separate assay, we were able to identify mechanisms for GO adsorption on different alkylsilanes and infer information about the adsorption of protein on nanostructured surfaces. PMID:25453976

  19. 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

  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. [Characterization of Cr (VI) removal and total Cr equilibrium adsorption by sulfate reducing granular sludge in stimulant wastewater].

    PubMed

    Luo, Jun; Pang, Zhi-Hua; Hu, Yong-You; Zhong, Hai-Tao; Chen, Jian-Yu; Lin, Fang-Min

    2010-11-01

    Sulfate reducing granular sludge (SRGS) cultivated in small scale EGSB reactor was used for Cr (VI) removing. Characterization of Cr (VI) removal and total Cr equilibrium adsorption was studied, and the adsorption isotherm was fitted. Results showed that removal of Cr (VI) was in connection with the structure and chemical composition of SRGS and several environmental factors. The Cr (VI) removal rate increased with the dosage of granular sludge; the increasing of oscillation speed and temperature could enhance Cr (VI) removal and total Cr adsorption, but while the oscillation speed reached 150 r x min(-1) or the temperature came to 40 degrees C, the physical structure of granular sludge would be affected and the granular sludge discrete, and total Cr equilibrium adsorption decreased; lower pH value caused higher Cr (VI) removal rate, however the sulfate on the surface of granular sludge was affected by lower pH value easily and would translate into H2S, then total Cr adsorption rate decreased. Cr (VI) removal would be influenced by physical, chemical and biological factors, and the process included reduction and adsorption mainly. The maximum adsorption of total Cr by granular sludge was 6.84 mg x g(-1), and the total Cr adsorbing process fitted in with Langmuir adsorption isotherm. PMID:21250453

  2. Rare Earth Element - Humic Acid Interaction: Experimental Evidence for Kinetic and Equilibrium Fractionation in Aqueous Systems.

    NASA Astrophysics Data System (ADS)

    Sonke, J. E.; Salters, V. J.; Benedetti, M. F.

    2003-12-01

    Dissolved organic matter (DOM) is well known for it's strong binding capacity for trace metals. In order to better predict the role of DOM in the speciation and transport of trace metals in the environment we coupled capillary electrophoresis (CE), a molecular separation technique, to a Sector Field Inductively Coupled Plasma Mass Spectrometer (SF-ICP-MS). The combination of these two techniques allows for the study of non-labile metal speciation in aquatic samples. By separating Rare Earth Element (REE) complexes with EDTA and Humic Acid's (i.e. ligand competition) we have been able to determine conditional equilibrium binding constants (Kc) and kinetic rate constants for all 14 REE's with Humic (HA) and Fulvic Acids (FA) as a function of pH (6-9) and ionic strength (IS, 0.01-0.1 mol/L). Assuming a 1:1 binding mechanism, logKc values for REE-FA varied from 9.0 (La) to 10.5 (Lu) at pH 6, 0.1 mol/L IS, and 11.7 (La) to 14.6 (Lu) at pH 9, 0.1 mol/L IS. LogKc values for REE-HA were 10.6 (La) to 12.2 (Lu) at pH 6, 0.1 mol/L IS and 13.2 (La) to 16.5 (Lu) at pH 9, 0.1 mol/L IS. Slightly higher values for Kc were obtained at 0.01 mol/L IS. The general observations of stronger REE-HA binding compared to REE-FA, and stronger binding with increasing pH and decreasing IS correlate with our current understanding of metal-DOM interactions (1). Both Kc's as well as kinetic rate constants increase with increasing REE mass number (decreasing ionic radius); a reflection of the well-known lanthanide contraction. This is the first comprehensive metal binding dataset between REE and DOM, and the first experimental evidence for differential equilibrium and kinetic binding behavior between REE's and DOM. The 30-1000 fold increase in binding strength of heavy REE's with DOM provides for a an equilibrium fractionation mechanism that may explain features of the global geochemical REE cycle such as fractionation related to weathering, estuarine mixing, and REE scavenging in the deep ocean

  3. Dissociative adsorption of O2 on unreconstructed metal (100) surfaces: Pathways, energetics, and sticking kinetics

    SciTech Connect

    Liu, Da-Jiang; Evans, James W.

    2014-05-06

    An accurate description of oxygen dissociation pathways and kinetics for various local adlayer environments is key for an understanding not just of the coverage dependence of oxygen sticking, but also of reactive steady states in oxidation reactions. Density functional theory analysis for M(100) surfaces with M=Pd, Rh, and Ni, where O prefers the fourfold hollow adsorption site, does not support the traditional Brundle-Behm-Barker picture of dissociative adsorption onto second-nearest-neighbor hollow sites with an additional blocking constraint. Rather adsorption via neighboring vicinal bridge sites dominates, although other pathways can be active. The same conclusion also applies for M=Pt and Ir, where oxygen prefers the bridge adsorption site. Statistical mechanical analysis is performed based on kinetic Monte Carlo simulation of a multisite lattice-gas model consistent with our revised picture of adsorption. This analysis determines the coverage and temperature dependence of sticking for a realistic treatment of the oxygen adlayer structure.

  4. On the adsorption/photodegradation of amoxicillin in aqueous solutions by an integrated photocatalytic adsorbent (IPCA): experimental studies and kinetics analysis.

    PubMed

    Basha, Shaik; Barr, Colin; Keane, David; Nolan, Kieran; Morrissey, Anne; Oelgemöller, Michael; Tobin, John M

    2011-06-01

    Activated carbon-supported TiO(2) nanoparticles, termed integrated photocatalytic adsorbents (IPCAs), were prepared using an ultrasonic impregnation technique and investigated for the photocatalytic degradation of amoxicillin (AMO), a β-lactam antibiotic. The IPCAs had high adsorption affinity for AMO with the amount adsorbed proportional to the TiO(2) loading and the highest adsorption was at 10 wt% TiO(2) loading. A pseudo-second-order model was found to fit the experimental data and consistently predicted the amount of AMO adsorbed over the adsorption period. Equilibrium isotherm studies showed that the adsorption followed the Redlich-Peterson model with maximum adsorption capacity of 441.3 mg g(-1) for 10% IPCA, 23% higher than the pure activated carbon (AC). Kinetic studies on the photocatalytic degradation of AMO using non-linear regression analysis suggest that the degradation followed Langmuir-Hinshelwood (L-H) kinetics. The adsorption rate constant (K(ad)) was considerably higher than the photocatalytic rate constant (k(L-H)), indicating that the photocatalysis of AMO is the rate-determining step during the adsorption/photocatalysis process. The 10% IPCA exhibited excellent stability and reusability over four photodegradation cycles. PMID:21380442

  5. Gas absorption using a nanofluid solvent: kinetic and equilibrium study

    NASA Astrophysics Data System (ADS)

    Azizi, S.; Peyghambarzadeh, S. M.; Saremi, M.; Tahmasebi, H.

    2014-12-01

    An experimental study has been performed to explore gas absorption in a nanofluid solvent. Propane and propylene were separately absorbed in a non-aqueous based nanofluid composed of N-methyl 2-pyrolidone (NMP) + small amount of TiO2 nanoparticle. Absorption was performed at different initial pressures and nanoparticle concentrations. Results showed that the addition of small amount of nanoparticle enhances the rate of absorption. Nanofluid decreased the time needed to achieve equilibrium and increased the maximum amount of gas absorbed.

  6. Long-term adsorption kinetics of asphaltenes at the oil-water interface: a random sequential adsorption perspective.

    PubMed

    Pauchard, Vincent; Rane, Jayant P; Zarkar, Sharli; Couzis, Alexander; Banerjee, Sanjoy

    2014-07-22

    Previous studies indicated that asphaltenes adsorbed as monomers on oil-water interfaces and the early stage kinetics of the process was controlled by diffusion and hence dependent on oil viscosity. By measuring interfacial tension (IFT) as a function of surface coverage during droplet expansions in pendant drop experiments, it was also concluded that the IFT data could be interpreted with a Langmuir equation of state (EoS), which was independent of oil viscosity, time of adsorption, and bulk asphaltenes concentration. The surface excess coverage was calculated to be ∼0.3 nm(2)/molecule, which suggested adsorption in face-on configuration of asphaltenes monomers at the interface and average PAH core per molecule of about 6 for the asphaltenes investigated, consistent with the Yen-Mullins model. The current study focuses on the kinetics of asphaltenes adsorption at longer times and higher interfacial coverage. Long-term IFT data have been measured by the pendant drop method for different asphaltenes concentrations and for different bulk viscosities of the oil phase (0.5-28 cP). The data indicate that when coverage reaches 35-40%, the adsorption rates slow down considerably compared to the diffusion-controlled rates at the very early stages. The surface pressure increase rate (or IFT decrease rate) at these higher coverages is now independent of oil viscosity but dependent upon both surface pressure itself and asphaltene monomer concentration. The long-term asymptotic behavior of surface coverage is found to be consistent with the predictions from surface diffusion-mediated random sequential adsorption (RSA) theory which indicates a linear dependency of surface coverage on 1/√t and an asymptotic limit very close to 2D random close packing of polydispersed disks (85%). From these observations RSA theory parameters were extracted that enabled description of adsorption kinetics for the range of conditions above surface coverage of 35%. PMID:24946262

  7. Low-pressure equilibrium binary argon-methane gas mixture adsorption on exfoliated graphite: Experiments and simulations

    NASA Astrophysics Data System (ADS)

    Albesa, Alberto; Russell, Brice; Vicente, José Luis; Rafti, Matías

    2016-04-01

    Adsorption equilibrium measurements of pure methane, pure argon, and binary mixtures over exfoliated graphite were carried for different initial compositions, temperatures, and total pressures in the range of 0.1-1.5 Torr using the volumetric static method. Diagrams for gas and adsorbed phase compositions were constructed for the conditions explored, and isosteric heats of adsorption were calculated. Experimental results were compared with predictions obtained with Monte Carlo simulations and using the Ideal Adsorbed Solution Theory (IAST).

  8. 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

  9. Sodium dopants in helium clusters: Structure, equilibrium and submersion kinetics

    SciTech Connect

    Calvo, F.

    2015-12-31

    Alkali impurities bind to helium nanodroplets very differently depending on their size and charge state, large neutral or charged dopants being wetted by the droplet whereas small neutral impurities prefer to reside aside. Using various computational modeling tools such as quantum Monte Carlo and path-integral molecular dynamics simulations, we have revisited some aspects of the physical chemistry of helium droplets interacting with sodium impurities, including the onset of snowball formation in presence of many-body polarization forces, the transition from non-wetted to wetted behavior in larger sodium clusters, and the kinetics of submersion of small dopants after sudden ionization.

  10. Adsorption kinetic character of copper ions onto a modified chitosan transparent thin membrane from aqueous solution.

    PubMed

    Cheng, Zihong; Liu, Xiaoshuai; Han, Mei; Ma, Wei

    2010-10-15

    A modified chitosan transparent thin membrane (MCTTM) was prepared and used as the adsorbent to investigate the adsorption kinetics due to excellent capacity of removing copper ions in water solution. The structure and morphology of MCTTM were characterized by SEM analysis and FTIR analysis. External mass transfer, intra particle diffusion, and pseudo-first and pseudo-second order models were used to describe the adsorption process. The results obtained from the study illustrated that the adsorption process could be described by the pseudo-second order model, which indicated adsorption process was a chemical adsorption behavior of chelation ion exchange proved by the FTIR and adsorption free energy analysis. External mass transfer and intra particle diffusion processes were the rate-controlling steps. PMID:20634000

  11. Kinetic and isotherm studies of adsorption and biosorption processes in the removal of phenolic compounds from aqueous solutions: comparative study

    PubMed Central

    2013-01-01

    The phenolic compounds are known by their carcinogenicity and high toxicity as well as creating unpleasant taste and odor in water resources. The present study develops a cost-effective technology for the treatment of water contaminated with phenolic compounds, including Phenol (Ph), 2-chlorophenol (2-CP), and 4-chlorophenol (4-CP). So, two sorbents, rice bran ash (RBA) and biomass of brown algae, Cystoseiraindica, were used and results were compared with the commercially granular activated carbon (GAC). The phenolic compounds were determined using a high performance liquid chromatography (HPLC) under batch equilibrium conditions. The effects of contact time, pH, initial adsorbate concentration, and adsorbent dosages on the removal efficiency were studied. The adsorption data were simulated by isotherm and kinetic models. Results indicated that RBA and GAC had the lowest efficiency for the removal of 2-CP, while the order of removal efficiency for C. indica biomass was as follows: 2-CP > 4-CP > phenol. The efficiency of GAC was higher than those of other adsorbents for all of the phenolic compounds. Furthermore, the adsorption capacity of RBA was found to be higher than that of C. indica biomass. The optimal initial pH for the removal of phenol, 2-CP and 4-CP was determined to be 5, 7, and 7 for RBA, GAC, and algal biomass, respectively. Kinetic studies suggested that the pseudo-second order best fitted the kinetic data. PMID:24355013

  12. Adsorption isotherms and kinetics of methylene blue on a low-cost adsorbent recovered from a spent catalyst of vinyl acetate synthesis

    NASA Astrophysics Data System (ADS)

    Zhang, Zhengyong; Zhang, Zebiao; Fernández, Y.; Menéndez, J. A.; Niu, Hao; Peng, Jinhui; Zhang, Libo; Guo, Shenghui

    2010-02-01

    A regenerated activated carbon used as catalyst support in the synthesis of vinyl acetate has been tested as a low-cost adsorbent for the removal of dyes. After a thorough textural characterization of the regenerated activated carbon, its adsorption isotherms and kinetics were determined using methylene blue as model compound at different initial concentrations. Both Langmuir and Freundlich isotherm models were developed and then compared. It was found that the equilibrium data were best represented by the Langmuir isotherm model. The kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models, and it was found that the best fitting corresponded to the pseudo-second-order kinetic model. The results showed that this novel adsorbent had a high adsorption capacity, making it suitable for use in the treatment of methylene blue enriched wastewater.

  13. Influence of particle/solid surface zeta potential on particle adsorption kinetics.

    PubMed

    Savaji, Kunal V; Niitsoo, Olivia; Couzis, Alexander

    2014-10-01

    In this paper we attempt to understand monolayer formation of spherical particles on a solid surface immersed in a suspension and driven by electrostatic interaction force. The study focuses on the theoretical aspects of the particle adsorption and modeling work based on the random sequential adsorption (RSA) approach is done in order to describe the particle adsorption kinetics and the saturation coverage. The theoretical model is then compared with experimental data obtained under conditions similar to those of the modeling work. Studying the adsorption of polystyrene particles on a silicon wafer in an aqueous system was employed to experimentally validate the theoretical framework. It has been shown both theoretically and experimentally that the particle and solid surface zeta potential values do influence the adsorption kinetics but the effect is too negligible to be of any use in accelerating the kinetics. We have shown that the electrostatically driven particle adsorption is a transport limited process and the rate of transport is not a major function of the zeta potential values of the particle and the solid surface. The faster kinetics seen when the ionic concentration of the suspension is increased is because of the blocking effects and not due to faster approach of particles towards the solid surface. Finally, we have made an important addition to the existing models by incorporating the variation in the flux as a function of particle/solid surface zeta potentials, surface coverage and the randomized position of incidence of an incoming particle on the solid surface. PMID:24996026

  14. Effect of cation type, alkyl chain length, adsorbate size on adsorption kinetics and isotherms of bromide ionic liquids from aqueous solutions onto microporous fabric and granulated activated carbons.

    PubMed

    Hassan, Safia; Duclaux, Laurent; Lévêque, Jean-Marc; Reinert, Laurence; Farooq, Amjad; Yasin, Tariq

    2014-11-01

    The adsorption from aqueous solution of imidazolium, pyrrolidinium and pyridinium based bromide ionic liquids (ILs) having different alkyl chain lengths was investigated on two types of microporous activated carbons: a fabric and a granulated one, well characterized in terms of surface chemistry by "Boehm" titrations and pH of point of zero charge measurements and of porosity by N2 adsorption at 77 K and CO2 adsorption at 273 K. The influence of cation type, alkyl chain length and adsorbate size on the adsorption properties was analyzed by studying kinetics and isotherms of eight different ILs using conductivity measurements. Equilibrium studies were carried out at different temperatures in the range [25-55 °C]. The incorporation of ILs on the AC porosity was studied by N2 adsorption-desorption measurements at 77 K. The experimental adsorption isotherms data showed a good correlation with the Langmuir model. Thermodynamic studies indicated that the adsorption of ILs onto activated carbons was an exothermic process, and that the removal efficiency increased with increase in alkyl chain length, due to the increase in hydrophobicity of long chain ILs cations determined with the evolution of the calculated octanol-water constant (Kow). The negative values of free energies indicated that adsorption of ILs with long chain lengths having hydrophobic cations was more spontaneous at the investigated temperatures. PMID:24929502

  15. Kinetic studies on the adsorption of methylene blue onto vegetal fiber activated carbons

    NASA Astrophysics Data System (ADS)

    Cherifi, Hakima; Fatiha, Bentahar; Salah, Hanini

    2013-10-01

    The vegetable sponge of cylindrical loofa (CL), a natural product which grows in the north of Algeria, was used to prepare activated carbons. Two activated carbons, AC1 and AC2, by two physiochemical activation methods to be used for methylene blue removal from wastewater. The surface structure of AC1, AC2 and CL were analyzed by scanning electron microscopy. Adsorption isotherm of methylene blue onto the prepared activated carbons was determined by batch tests. The effects of various parameters such as contact time, initial concentration, pH, temperature, adsorbent dose and granulometry were investigated, at agitation rate 150 rpm. The results showed that the equilibrium uptake increased with increasing initial MB concentration. The maximum % removal of MB obtained was 99% at 50 °C for AC1 and 82% at 30 °C for AC2. The increase in initial pH in the ranges of 2-10 increases the yields removal of MB on AC2. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The latter provided the best correlation of the experimental data compared to the pseudo-first-order model.

  16. Study of the kinetics and the adsorption isotherm of cadmium(II) from aqueous solution using green algae (Ulva lactuca) biomass.

    PubMed

    Asnaoui, H; Laaziri, A; Khalis, M

    2015-01-01

    Batch experiments were conducted to study the adsorption of hazardous cadmium onto low-cost algae biomass in aqueous solution with respect to concentration of adsorbate, adsorbent dosage, contact time, solution pH and temperature. Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The activation energy of adsorption was also evaluated for the adsorption of cadmium onto Ulva lactuca biomass. Experimental data were tested in terms of biosorption kinetics using pseudo-first-order and pseudo-second-order kinetic models. The results showed that the biosorption processes of Cd(II) followed well pseudo-second-order kinetics. Langmuir and Freundlich models were applied to describe the biosorption isotherm of the metal ions by Ulva lactuca biomass. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The biosorption capacity of Ulva lactuca biomass for cadmium was found to be 3.02 mg/g at pH 5.60 min equilibrium time and 20 °C. The mean free energy which was calculated was 6.24 kJ/mol for Cd(II) biosorption, which shows that the adsorption is physical. The calculated thermodynamic parameters (ΔG0, ΔH0 and ΔS0) showed that the biosorption of Cd(II) onto Ulva lactuca biomass was feasible, spontaneous and exothermic under examined conditions. The results indicate that algae Ulva lactuca could be employed as a low-cost material for the removal of metal ions from aqueous solution. PMID:26524441

  17. 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

  18. Quantifying differences in the impact of variable chemistry on equilibrium uranium(VI) adsorption properties of aquifer sediments

    SciTech Connect

    Stoliker, Deborah L.; Kent, Douglas B.; Zachara, John M.

    2011-09-16

    Uranium adsorption-desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500-1000 hours although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A non-electrostatic surface complexation reaction, >SOH + UO22+ + 2CO32- = >SOUO2(CO3HCO3)2-, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logKc) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logKc values. Using this approach, logKc values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (<0.063 mm) of another could be demonstrated despite the fines requiring a different reaction stoichiometry. Estimates of logKc uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors.

  19. Quantifying differences in the impact of variable chemistry on equilibrium uranium(VI) adsorption properties of aquifer sediments

    USGS Publications Warehouse

    Stoliker, Deborah L.; Kent, Douglas B.; Zachara, John M.

    2011-01-01

    Uranium adsorption-desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500-1000 h although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A nonelectrostatic surface complexation reaction, >SOH + UO22+ + 2CO32- = >SOUO2(CO3HCO3)2-, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logKc) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logKc values. Using this approach, logKc values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (Kc uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors.

  20. Tested Demonstrations: Thermodynamic Changes, Kinetics, Equilibrium, and LeChatelier's Principle.

    ERIC Educational Resources Information Center

    Gilbert, George L., Ed.

    1984-01-01

    Procedures for demonstrating thermodynamic changes, kinetics and reaction mechanisms, equilibrium, and LeChatelier's principle are presented. The only materials needed for these demonstrations are beakers, water, assorted wooden blocks of varying thickness, assorted rubber tubing, and a sponge. The concepts illustrated in each demonstration are…

  1. 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

  2. DIRECT COMPARISON OF KINETIC AND LOCAL EQUILIBRIUM FORMULATIONS FOR SOLUTE TRANSPORT AFFECTED BY SURFACE REACTIONS.

    USGS Publications Warehouse

    Bahr, Jean M.; Rubin, Jacob

    1987-01-01

    Modeling transport of reacting solutes in porous media often requires a choice between models based on the local equilibrium assumption (LEA) and models involving reaction kinetics. Direct comparison of the mathematical formulations for these two types of transport models can aid in this choice. For cases of transport affected by surface reaction, such a comparison is made possible by a new derivation procedure. This procedure yields a kinetics-based formulation that is the sum of the LEA formulation and one or more kinetically influenced terms. The dimensionless form of the new kinetics-based formulation facilitates identification of critical parameter groupings which control the approach to transport behavior consistent with LEA model predictions. Results of numerical experiments demonstrate that criteria for LEA applicability can be expressed conveniently in terms of these parameter groupings. The derivation procedure is demonstrated for examples of surface reactions including first-order reversible sorption, Langmuir-type kinetics and binary, homovalent ion exchange.

  3. Adsorption and dissociation kinetics of alkanes on CaO(100)

    NASA Astrophysics Data System (ADS)

    Chakradhar, A.; Liu, Y.; Schmidt, J.; Kadossov, E.; Burghaus, U.

    2011-08-01

    The adsorption kinetics of ethane, butane, pentane, and hexane on CaO(100) have been studied by multi-mass thermal desorption (TDS) spectroscopy. The sample cleanliness was checked by Auger electron spectroscopy. A molecular and dissociative adsorption pathway was evident for the alkanes, except for ethane, which does not undergo bond activation. Two TDS peaks appeared when recording the parent mass, which are assigned to different adsorption sites/configurations of the molecularly adsorbed alkanes. Bond activation leads to desorption of hydrogen and several alkane fragments assigned to methane and ethylene formation. Only one TDS feature is seen in this case. Formation of carbon residuals was absent.

  4. Kinetics of tetracycline, oxytetracycline, and chlortetracycline adsorption and desorption on two acid soils.

    PubMed

    Fernández-Calviño, David; Bermúdez-Couso, Alipio; Arias-Estévez, Manuel; Nóvoa-Muñoz, Juan Carlos; Fernández-Sanjurjo, Maria J; Álvarez-Rodríguez, Esperanza; Núñez-Delgado, Avelino

    2015-01-01

    The purpose of this work was to quantify retention/release of tetracycline, oxytetracycline, and chlortetracycline on two soils, paying attention to sorption kinetics and to implications of the adsorption/desorption processes on transfer of these pollutants to the various environmental compartments. We used the stirred flow chamber (SFC) procedure to achieve this goal. All three antibiotics showed high affinity for both soils, with greater adsorption intensity for soil 1, the one with the highest organic matter and Al and Fe oxides contents. Desorption was always <15%, exhibiting strong hysteresis in the adsorption/desorption processes. Adsorption was adequately modeled using a pseudo first-order equation with just one type of adsorption sites, whereas desorption was better adjusted considering both fast and slow sorption sites. The adsorption maximum (qmax) followed the sequence tetracycline > oxytetracycline > chlortetracycline in soil 1, with similar values for the three antibiotics and the sequence tetracycline > chlortetracycline > oxytetracycline in soil 2. The desorption sequences were oxytetracycline > tetracycline > chlortetracycline in soil 1 and oxytetracycline > chlortetracycline > tetracycline in soil 2. In conclusion, the SFC technique has yielded new kinetic data regarding tetracycline, oxytetracycline, and chlortetracycline adsorption/desorption on soils, indicating that it can be used to shed further light on the retention and transport processes affecting antibiotics on soils and other media, thus increasing knowledge on the behavior and evolution of these pharmaceutical residues in the environment. PMID:25081007

  5. Kinetic limitations in measuring stabilities of metal complexes by competitive ligand exchange-adsorptive stripping voltammetry (CLE-AdSV).

    PubMed

    Van Leeuwen, Herman P; Town, Raewyn M

    2005-09-15

    The kinetic limitations of Competitive Ligand Exchange-Adsorptive Stripping Voltammetry, CLE-AdSV, for the determination of very stable metal complexes are explained in detail. For a given type of metal, from a certain lower limit of the complex stability constant, K, the usual simple equilibrium interpretation of CLE-AdSV measurements is not generally valid. By critical assessment of data for natural waters we show that in many cases the reported stability constants appearto derive from nonequilibrium conditions in the bulk sample and hence overestimate the real values. Fe(II) is a special case due to the particular kinetic features of hydroxide as a ligand. Our results call for validation of such data by analysis on the basis of the kinetics involved and/or by independent kinetic-free experimental approaches. Earlier speculations from CLE-AdSV results on very strong ligands and derived features such as the potential bioavailability of trace metals in natural waters require reconsideration. PMID:16201651

  6. 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

  7. 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

  8. The effect of adsorption kinetics on the rate of surfactant-enhanced spreading.

    PubMed

    Kovalchuk, N M; Matar, O K; Craster, R V; Miller, R; Starov, V M

    2016-01-28

    A comparison of the kinetics of spreading of aqueous solutions of two different surfactants on an identical substrate and their short time adsorption kinetics at the water/air interface has shown that the surfactant which adsorbs slower provides a higher spreading rate. This observation indicates that Marangoni flow should be an important part of the spreading mechanism enabling surfactant solutions to spread much faster than pure liquids with comparable viscosities and surface tensions. PMID:26610693

  9. Quantifying Differences in the Impact of Variable Chemistry on Equilibrium Uranium(VI) Adsorption Properties of Aquifer Sediments

    PubMed Central

    2011-01-01

    Uranium adsorption–desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500–1000 h although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A nonelectrostatic surface complexation reaction, >SOH + UO22+ + 2CO32- = >SOUO2(CO3HCO3)2–, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logKc) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logKc values. Using this approach, logKc values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (<0.063 mm) of another could be demonstrated despite the fines requiring a different reaction stoichiometry. Estimates of logKc uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors. PMID:21923109

  10. A breakthrough biosorbent in removing heavy metals: Equilibrium, kinetic, thermodynamic and mechanism analyses in a lab-scale study.

    PubMed

    Abdolali, Atefeh; Ngo, Huu Hao; Guo, Wenshan; Lu, Shaoyong; Chen, Shiao-Shing; Nguyen, Nguyen Cong; Zhang, Xinbo; Wang, Jie; Wu, Yun

    2016-01-15

    A breakthrough biosorbent namely multi-metal binding biosorbent (MMBB) made from a combination of tea wastes, maple leaves and mandarin peels, was prepared to evaluate their biosorptive potential for removal of Cd(II), Cu(II), Pb(II) and Zn(II) from multi-metal aqueous solutions. FTIR and SEM were conducted, before and after biosorption, to explore the intensity and position of the available functional groups and changes in adsorbent surface morphology. Carboxylic, hydroxyl and amine groups were found to be the principal functional groups for the sorption of metals. MMBB exhibited best performance at pH 5.5 with maximum sorption capacities of 31.73, 41.06, 76.25 and 26.63 mg/g for Cd(II), Cu(II), Pb(II) and Zn(II), respectively. Pseudo-first and pseudo-second-order models represented the kinetic experimental data in different initial metal concentrations very well. Among two-parameter adsorption isotherm models, the Langmuir equation gave a better fit of the equilibrium data. For Cu(II) and Zn(II), the Khan isotherm describes better biosorption conditions while for Cd(II) and Pb(II), the Sips model was found to provide the best correlation of the biosorption equilibrium data. The calculated thermodynamic parameters indicated feasible, spontaneous and exothermic biosorption process. Overall, this novel MMBB can effectively be utilized as an adsorbent to remove heavy metal ions from aqueous solutions. PMID:26544889

  11. Use of Mg-Al oxide for boron removal from an aqueous solution in rotation: Kinetics and equilibrium studies.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2016-01-01

    Mg-Al oxide prepared through the thermal treatment of [Formula: see text] intercalated Mg-Al layered double hydroxides (CO3·Mg-Al LDH) was found to remove boron (B) from an aqueous solution. B was removed by the rehydration of Mg-Al oxide accompanied by combination with [Formula: see text] . When using twice the stoichiometric quantity of Mg-Al oxide for Mg/Al = 4, the residual concentration of B dropped from 100 to 2.8 mg/L in 480 min, and for Mg/Al = 2, it decreased from 100 to 2.5 mg/L in 240 min. In both cases, the residual concentration of B was highlighted to be lower than the current Japanese effluent standards (10 mg/L). The removal of B can be explained by way of pseudo-first-order reaction kinetics. The apparent activation energy of 63.5 kJ mol(-1), calculated from the Arrhenius plot indicating that a chemical reaction dominates the removal of B by Mg-Al oxide (Mg/Al = 2). The adsorption of B acts upon a Langmuir-type phenomena. The maximum adsorption (qm) and equilibrium adsorption constants (KL) were 7.4 mmol g(-1) and 1.9 × 10(3), respectively, for Mg-Al oxide (Mg/Al = 2). [Formula: see text] in B(OH)4·Mg-Al LDH produced by the removal of B was observed to undergo anion exchange with [Formula: see text] in solution. Following regeneration, the Mg-Al oxide maintained the ability to remove B from an aqueous solution. This study has clarified the possibility of recycling Mg-Al oxide for B removal. PMID:26454072

  12. Equilibrium, kinetic and thermodynamic studies on the removal of U(VI) by low cost agricultural waste.

    PubMed

    Kausar, Abida; Bhatti, Haq Nawaz; MacKinnon, Gillian

    2013-11-01

    In this research, biosorption efficiency of different agro-wastes was evaluated with rice husk showing maximum biosorption capacity among the selected biosorbents. Optimization of native, SDS-treated and immobilized rice husk adsorption parameters including pH, biosorbent amount, contact time, initial U(VI) concentration and temperature for maximum U(VI) removal was investigated. Maximum biosorption capacity for native (29.56 mg g(-1)) and immobilized biomass (17.59 mg g(-1)) was observed at pH 4 while SDS-treated biomass showed maximum removal (28.08 mg g(-1)) at pH 5. The Langmuir sorption isotherm model correlated best with the U(IV) biosorption equilibrium data for the 10-100 mg L(-1) concentration range. The kinetics of the reaction followed pseudo-second order kinetic model. Thermodynamic parameters like free energy (ΔG(0)) and enthalpy (ΔH°) confirmed the spontaneous and exothermic nature of the process. Experiments to determine the regeneration capacity of the selected biosorbents and the effect of competing metal ions on biosorption capacity were also conducted. The biomass was characterized using scanning electron microscopy, surface area analysis, Fourier transformed infra-red spectroscopy and thermal gravimetric analysis. The study proved that rice husk has potential to treat uranium in wastewater. PMID:23787279

  13. 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

  14. Adsorption of selected pharmaceuticals and an endocrine disrupting compound by granular activated carbon. 1. Adsorption capacity and kinetics

    SciTech Connect

    Yu, Z.; Peldszus, S.; Huck, P.M.

    2009-03-01

    The adsorption of two representative PhACs (naproxen and carbamazepine) and one EDC (nonylphenol) were evaluated on two granular activated carbons (GAC) namely coal-based Calgon Filtrasorb 400 and coconut shell-based PICA CTIF TE. The primary objective was to investigate preloading effects by natural organic matter (NOM) on adsorption capacity and kinetics under conditions and concentrations (i.e., ng/L) relevant for drinking water treatment. Isotherms demonstrated that all compounds were significantly negatively impacted by NOM fouling. Adsorption capacity reduction was most severe for the acidic naproxen, followed by the neutral carbamazepine and then the more hydrophobic nonylphenol. The GAC with the wider pore size distribution had considerably greater NOM loading, resulting in lower adsorption capacity. Different patterns for the change in Freundlich KF and 1/n with time revealed different competitive mechanisms for the different compounds. Mass transport coefficients determined by short fixed-bed (SFB) tests with virgin and preloaded GAC demonstrated that film diffusion primarily controls mass transfer on virgin and preloaded carbon. Naproxen suffered the greatest deteriorative effect on kinetic parameters due to preloading, followed by carbamazepine, and then nonylphenol. A type of surface NOM/biofilm, which appeared to add an additional mass transfer resistance layer and thus reduce film diffusion, was observed. In addition, electrostatic interactions between NOM/biofilm and the investigated compounds are proposed to contribute to the reduction of film diffusion. A companion paper building on this work describes treatability studies in pilot-scale GAC adsorbers and the effectiveness of a selected fixed-bed model. 32 refs., 3 figs., 2 tabs.

  15. New treatment method for boron in aqueous solutions using Mg-Al layered double hydroxide: Kinetics and equilibrium studies.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2015-08-15

    Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg - Al LDHs) and with Cl(-) (Cl · Mg - Al LDHs) were found to take up boron from aqueous solutions. Boron was removed by anion exchange of B(OH)4(-) in solution with NO3(-) and Cl(-) intercalated in the interlayer of the LDH. Using three times the stoichiometric quantity of NO3 · Mg-Al LDH, the residual concentration of B decreased from 100 to 1.9 mg L(-1) in 120 min. Using five times the stoichiometric quantity of Cl · Mg - Al LDH, the residual concentration of B decreased from 100 to 5.6 mg L(-1) in 120 min. It must be emphasized that, in both cases, the residual concentration of B was less than the effluent standards in Japan (10 mg L(-1)). The rate-determining step of B removal by the NO3 · Mg - Al and Cl · Mg - Al LDHs was found to be chemical adsorption involving anion exchange of B(OH)4(-) with intercalated NO3(-) and Cl(-). The removal of B was well described by a pseudo second-order kinetic equation. The adsorption of B by NO3 · Mg - Al LDH and Cl · Mg - Al LDH followed a Langmuir-type adsorption. The values of the maximum adsorption and the equilibrium adsorption constant were 3.6 mmol g(-1) and 1.7, respectively, for NO3 · Mg - Al LDH, and 3.8 mmol g(-1) and 0.7, respectively, for Cl · Mg-Al LDH. The B(OH)4(-) in B(OH)4 · Mg - Al LDH produced by removal of B was found to undergo anion exchange with NO3(-) and Cl(-) in solution. The NO3 · Mg - Al and Cl · Mg - Al LDHs obtained after this regeneration treatment were able to remove B from aqueous solutions, indicating the possibility of recycling NO3 · Mg - Al and Cl · Mg - Al LDHs for B removal. PMID:25827268

  16. Kinetics of adsorption with granular, powdered, and fibrous activated carbon

    SciTech Connect

    Shmidt, J.L.; Pimenov, A.V.; Lieberman, A.I.; Cheh, H.Y.

    1997-08-01

    The properties of three different types of activated carbon, fibrous, powdered, and granular, were investigated theoretically and experimentally. The adsorption rate of the activated carbon fiber was found to be two orders of magnitude higher than that of the granular activated carbon, and one order of magnitude higher than that of the powdered activated carbon. Diffusion coefficients of methylene blue in the fibrous, powdered, and granular activated carbons were determined experimentally. A new method for estimating the meso- and macropore surface areas in these carbons was proposed.

  17. 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

  18. Kinetics and mechanisms of hydrogen sulfide adsorption by biochars.

    PubMed

    Shang, Guofeng; Shen, Guoqing; Liu, Liang; Chen, Qin; Xu, Zhiwei

    2013-04-01

    Three different biochars as cost-effective substitutes for activated carbon (AC) were tested for their hydrogen sulfide (H2S) adsorption ability. The biochars were produced from camphor (SC), bamboo (SB), and rice hull (SR) at 400°C by oxygen-limited pyrolysis. The surface area (SA), pH, and Fourier transform infrared spectras of the biochars and AC were compared. The maximum removal rates and the saturation constants were obtained using the Michaelis-Menten-type equation. The three biochars were found to be alkaline, and the SAs of the biochars were much smaller than that of the AC. The H2S breakthrough capacity was related to the local pH within the pore system of the biochar. The order observed in terms of both biochar and AC adsorption capacity was SR>SB>SC>AC. SR efficiently removed H2S within the inlet concentration range of 10-50 μL/L. Biochars derived from agricultural/forestry wastes are a promising H2S adsorbent with distinctive properties. PMID:23455220

  19. The effect of water temperature on the adsorption equilibrium of dissolved organic matter and atrazine on granular activated carbon

    SciTech Connect

    Bernd Schreiber; Viktor Schmalz; Thomas Brinkmann; Eckhard Worch

    2007-09-15

    The influence of water temperature on the adsorption of natural dissolved organic matter (DOM) on activated carbon has not been investigated intensively yet. In this study, batch experiments with granular activated carbon (GAC) F300, from bituminous coal, have been carried out at three temperatures (5, 20, 35{sup o} C) using a humic acid model water and different types of surface water (lake, river, canal). Furthermore, the adsorption of an anthropogenic contaminant, atrazine, was quantified in the absence and presence of DOM. The results indicate a significant influence of water temperature on the adsorption equilibrium of DOM and atrazine. Contrary to expectations, DOM and atrazine adsorption in surface water tends to be increased with increasing water temperature, whereas the extent of this effect is dependent on the type and concentration of DOM. Furthermore, the temperature effect on atrazine adsorption is controlled by competition of DOM and atrazine on adsorption sites. Some assumptions are proposed and discussed for explaining the temperature effects observed in the batch studies. 39 refs., 4 figs., 2 tabs.

  20. The effects of surface chemistry of mesoporous silica materials and solution pH on kinetics of molsidomine adsorption

    SciTech Connect

    Dolinina, E.S.; Parfenyuk, E.V.

    2014-01-15

    Adsorption kinetics of molsidomine on mesoporous silica material (UMS), the phenyl- (PhMS) and mercaptopropyl-functionalized (MMS) derivatives from solution with different pH and 298 K was studied. The adsorption kinetics was found to follow the pseudo-second-order kinetic model for all studied silica materials and pH. Effects of surface functional groups and pH on adsorption efficiency and kinetic adsorption parameters were investigated. At all studied pH, the highest molsidomine amount is adsorbed on PhMS due to π–π interactions and hydrogen bonding between surface groups of PhMS and molsidomine molecules. An increase of pH results in a decrease of the amounts of adsorbed molsidomine onto the silica materials. Furthermore, the highest adsorption rate kinetically evaluated using a pseudo-second-order model, is observed onto UMS and it strongly depends on pH. The mechanism of the adsorption process was determined from the intraparticle diffusion and Boyd kinetic film–diffusion models. The results showed that the molsidomine adsorption on the silica materials is controlled by film diffusion. Effect of pH on the diffusion parameters is discussed. - Graphical abstract: The kinetic study showed that the k{sub 2} value, the rate constant of pseudo-second order kinetic model, is the highest for molsidomine adsorption on UMS and strongly depends on pH because it is determined by availability and accessibility of the reaction sites of the adsorbents molsidomine binding. Display Omitted - Highlights: • The adsorption capacities of UMS, PhMS and MMS were dependent on the pH. • At all studied pH, the highest molsidomine amount is adsorbed on PhMS. • The highest adsorption rate, k{sub 2}, is observed onto UMS and strongly depends on pH. • Film diffusion was the likely rate-limiting step in the adsorption process.

  1. KINETIC THEORY OF EQUILIBRIUM AXISYMMETRIC COLLISIONLESS PLASMAS IN OFF-EQUATORIAL TORI AROUND COMPACT OBJECTS

    SciTech Connect

    Cremaschini, Claudio; Kovář, Jiří; Slaný, Petr; Stuchlík, Zdeněk; Karas, Vladimír

    2013-11-01

    The possible occurrence of equilibrium off-equatorial tori in the gravitational and electromagnetic fields of astrophysical compact objects has been recently proved based on non-ideal magnetohydrodynamic theory. These stationary structures can represent plausible candidates for the modeling of coronal plasmas expected to arise in association with accretion disks. However, accretion disk coronae are formed by a highly diluted environment, and so the fluid description may be inappropriate. The question is posed of whether similar off-equatorial solutions can also be determined in the case of collisionless plasmas for which treatment based on kinetic theory, rather than a fluid one, is demanded. In this paper the issue is addressed in the framework of the Vlasov-Maxwell description for non-relativistic, multi-species axisymmetric plasmas subject to an external dominant spherical gravitational and dipolar magnetic field. Equilibrium configurations are investigated and explicit solutions for the species kinetic distribution function are constructed, which are expressed in terms of generalized Maxwellian functions characterized by isotropic temperature and non-uniform fluid fields. The conditions for the existence of off-equatorial tori are investigated. It is proved that these levitating systems are admitted under general conditions when both gravitational and magnetic fields contribute to shaping the spatial profiles of equilibrium plasma fluid fields. Then, specifically, kinetic effects carried by the equilibrium solution are explicitly provided and identified here with diamagnetic energy-correction and electrostatic contributions. It is shown that these kinetic terms characterize the plasma equation of state by introducing non-vanishing deviations from the assumption of thermal pressure.

  2. 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.

  3. A model for the adsorption kinetics of CO2 on amine-impregnated mesoporous sorbents in the presence of water

    SciTech Connect

    Lee, A.; Mebane, D.; Fauth, D.; Miller, D.

    2011-01-01

    A simple model for the adsorption kinetics carbon dioxide onto an amine-impregnated mesoporous sorbent, NETL-32D, was developed. The model was developed based on the mechanistic pathways believed to be responsible for the uptake of CO2 by the sorbent, including interactions with H2O. The model consists of quasi-ideal expressions to describe the kinetics of three reactions responsible for the uptake of CO2 and H2O by the sorbent. The model was fitted to experimental data obtained from thermogravimetric analysis and found to be a reasonable representation of the observed equilibrium and kinetics. The model is able to predict the increased uptake due to the interaction between CO2 and H2O in the sorbent. The heat of reaction predicted by the model for the uptake of CO2 in dry conditions of -65 kJ/mol compares well to the value of -67 kJ/mol obtained via calorimetry for similar sorbents.

  4. Kinetic equilibrium for an asymmetric tangential layer with rotation of the magnetic fiel

    NASA Astrophysics Data System (ADS)

    Dorville, N.; Belmont, G.; Aunai, N.; Rezeau, L.

    2014-12-01

    Finding kinetic equilibria for tangential current layers is a key issue for the modeling of plasma phenomena such as magnetic reconnection, for which theoretical and numerical studies usually aim in starting from steady state current layers. The famous Harris equilibrium is known to be limited to symmetric layers surrounded by vacuum, with constant temperature, and constant ion and electron flow velocities, and with a current variation depending only on the density variation. It is clearly not suited for the modeling of ``magnetopause-like'' layers, which separate two plasmas of different densities and temperatures. In order to understand this kind of boundaries, Belmont et al (2012) presented a new asymmetric equilibrium which was validated in a hybrid simulation by Aunai et al (2013), and more recently in a fully kinetic simulation as well. For this equilibrium to be computed, the magnetic field had to stay coplanar inside the layer. We present here an important generalization, where the magnetic field rotates inside the layer (restricted to a 180° rotation hitherto). The tangential layers so obtained are thus closer to those encountered at the magnetopause. This will be necessary, in the future, for comparing directly the theoretical profiles with the experimental ones for the various physical parameters. As it was done previously, the equilibrium is tested with a hybrid simulation.

  5. Computational methods for multiphase equilibrium and kinetics calculations for geochemical and reactive transport applications

    NASA Astrophysics Data System (ADS)

    Leal, Allan; Saar, Martin

    2016-04-01

    Computational methods for geochemical and reactive transport modeling are essential for the understanding of many natural and industrial processes. Most of these processes involve several phases and components, and quite often requires chemical equilibrium and kinetics calculations. We present an overview of novel methods for multiphase equilibrium calculations, based on both the Gibbs energy minimization (GEM) approach and on the solution of the law of mass-action (LMA) equations. We also employ kinetics calculations, assuming partial equilibrium (e.g., fluid species in equilibrium while minerals are in disequilibrium) using automatic time stepping to improve simulation efficiency and robustness. These methods are developed specifically for applications that are computationally expensive, such as reactive transport simulations. We show how efficient the new methods are, compared to other algorithms, and how easy it is to use them for geochemical modeling via a simple script language. All methods are available in Reaktoro, a unified open-source framework for modeling chemically reactive systems, which we also briefly describe.

  6. An Equilibrium Model for the Combined Effect of Macromolecular Crowding and Surface Adsorption on the Formation of Linear Protein Fibrils

    PubMed Central

    Hoppe, Travis; Minton, Allen P.

    2015-01-01

    The formation of linear protein fibrils has previously been shown to be enhanced by volume exclusion or crowding in the presence of a high concentration of chemically inert protein or polymer, and by adsorption to membrane surfaces. An equilibrium mesoscopic model for the combined effect of both crowding and adsorption upon the fibrillation of a dilute tracer protein is presented. The model exhibits behavior that differs qualitatively from that observed in the presence of crowding or adsorption alone. The model predicts that in a crowded solution, at critical values of the volume fraction of crowder or intrinsic energy of the tracer-wall interaction, the tracer protein will undergo an extremely cooperative transition—approaching a step function—from existence as a slightly self-associated species in solution to existence as a highly self-associated and completely adsorbed species. Criteria for a valid experimental test of these predictions are presented. PMID:25692600

  7. Equilibrium and kinetics analysis of carbon dioxide capture using immobilized amine on a mesoporous silica

    SciTech Connect

    Monazam, E., Shadle, L., Pennline, H., Miller, D., Fauth, D., Hoffman, J., Gray, M.

    2012-01-01

    The equilibrium and conversion-time data on the absorption of carbon dioxide (CO{sub 2}) with amine-based solid sorbent were analyzed over the range of 303–373 K. Data on CO{sub 2} loading on amine based solid sorbent at these temperatures and CO{sub 2} partial pressure between 10 and 760 mm Hg obtained from volumetric adsorption apparatus were fitted to a simple equilibrium model to generate the different parameters (including equilibrium constant) in the model. Using these constants, a correlation was obtained to define equilibrium constant and maximum CO{sub 2} loading as a function of temperature. In this study, a shrinking core model (SCM) was applied to elucidate the relative importance of pore diffusion and surface chemical reaction in controlling the rate of reaction. Application of SCM to the data suggested a surface reaction-controlled mechanism for the temperature of up to 40°C and pore-diffusion mechanism at higher temperature.

  8. Equilibrium and Absorption Kinetics of Carbon Dioxide by solid Supported Amine Sorbent

    SciTech Connect

    Monazam, Esmail R.; Shadle, Lawrence J.; Siriwardane, Ranjani

    2011-11-01

    The equilibrium and conversion-time data on the absorption of carbon dioxide (CO{sub 2}) with amine-based solid sorbent were analyzed over the range of 303–373 K. Data on CO{sub 2} loading on amine based solid sorbent at these temperatures and CO{sub 2} partial pressure between 10 and 760 mm Hg obtained from volumetric adsorption apparatus were fitted to a simple equilibrium model to generate the different parameters (including equilibrium constant) in the model. Using these constants, a correlation was obtained to define equilibrium constant and maximum CO{sub 2} loading as a function of temperature. In this study, a shrinking core model (SCM) was applied to elucidate the relative importance of pore diffusion and surface chemical reaction in controlling the rate of reaction. Application of SCM to the data suggested a surface reaction-controlled mechanism for the temperature of up to 40°C and pore-diffusion mechanism at higher temperature.

  9. Adsorption kinetics of phosphate and arsenate on goethite. A comparative study.

    PubMed

    Luengo, Carina; Brigante, Maximiliano; Avena, Marcelo

    2007-07-15

    The adsorption kinetics of phosphate and arsenate on goethite is studied and compared. Batch adsorption experiments were performed at different adsorbate concentrations, pH, temperatures and stirring rates. For both oxoanions the adsorption rate increases by increasing adsorbate concentration, decreasing pH and increasing temperature. It does not change by changing stirring rate. The adsorption takes place in two processes: a fast one that takes place in less than 5 min and a slow one that takes place in several hours or more. The rate of the slow process does not depend directly on the concentration of phosphate or arsenate in solution, but depends linearly on the amount of phosphate or arsenate that was adsorbed during the fast process. Apparent activation energies and absence of stirring rate effects suggest that the slow process is controlled by diffusion into pores, although the evidence is not conclusive. The similarities in the adsorption kinetics of phosphate and arsenate are quantitatively shown by using a three-parameters equation that takes into account both the fast and the slow processes. These similarities are in line with the similar reactivity that phosphate and arsenate have in general and may be important for theoretical and experimental studies of the fate of these oxoanions in the environment. PMID:17448491

  10. New Direction in Hydrogeochemical Transport Modeling: Incorporating Multiple Kinetic and Equilibrium Reaction Pathways

    SciTech Connect

    Steefel, C.I.

    2000-02-02

    At least two distinct kinds of hydrogeochemical models have evolved historically for use in analyzing contaminant transport, but each has important limitations. One kind, focusing on organic contaminants, treats biodegradation reactions as parts of relatively simple kinetic reaction networks with no or limited coupling to aqueous and surface complexation and mineral dissolution/precipitation reactions. A second kind, evolving out of the speciation and reaction path codes, is capable of handling a comprehensive suite of multicomponent complexation (aqueous and surface) and mineral precipitation and dissolution reactions, but has not been able to treat reaction networks characterized by partial redox disequilibrium and multiple kinetic pathways. More recently, various investigators have begun to consider biodegradation reactions in the context of comprehensive equilibrium and kinetic reaction networks (e.g. Hunter et al. 1998, Mayer 1999). Here we explore two examples of multiple equilibrium and kinetic reaction pathways using the reactive transport code GIMRT98 (Steefel, in prep.): (1) a computational example involving the generation of acid mine drainage due to oxidation of pyrite, and (2) a computational/field example where the rates of chlorinated VOC degradation are linked to the rates of major redox processes occurring in organic-rich wetland sediments overlying a contaminated aerobic aquifer.

  11. 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.

  12. Modeling Adsorption Kinetics (Bio-remediation of Heavy Metal Contaminated Water)

    NASA Astrophysics Data System (ADS)

    McCarthy, Chris

    My talk will focus on modeling the kinetics of the adsorption and filtering process using differential equations, stochastic methods, and recursive functions. The models have been developed in support of our interdisciplinary lab group which is conducting research into bio-remediation of heavy metal contaminated water via filtration through biomass such as spent tea leaves. The spent tea leaves are available in large quantities as a result of the industrial production of tea beverages. The heavy metals bond with the surfaces of the tea leaves (adsorption). Funding: CUNY Collaborative Incentive Research Grant.

  13. Equilibrium and stability properties of detonation waves in the hydrodynamic limit of a kinetic model

    NASA Astrophysics Data System (ADS)

    Marques, Wilson, Jr.; Jacinta Soares, Ana; Pandolfi Bianchi, Miriam; Kremer, Gilberto M.

    2015-06-01

    A shock wave structure problem, like the one which can be formulated for the planar detonation wave, is analyzed here for a binary mixture of ideal gases undergoing the symmetric reaction {{A}1}+{{A}1}\\rightleftharpoons {{A}2}+{{A}2}. The problem is studied at the hydrodynamic Euler limit of a kinetic model of the reactive Boltzmann equation. The chemical rate law is deduced in this frame with a second-order reaction rate, in a chemical regime such that the gas flow is not far away from the chemical equilibrium. The caloric and the thermal equations of state for the specific internal energy and temperature are employed to close the system of balance laws. With respect to other approaches known in the kinetic literature for detonation problems with a reversible reaction, this paper aims to improve some aspects of the wave solution. Within the mathematical analysis of the detonation model, the equation of the equilibrium Hugoniot curve of the final states is explicitly derived for the first time and used to define the correct location of the equilibrium Chapman-Jouguet point in the Hugoniot diagram. The parametric space is widened to investigate the response of the detonation solution to the activation energy of the chemical reaction. Finally, the mathematical formulation of the linear stability problem is given for the wave detonation structure via a normal-mode approach, when bidimensional disturbances perturb the steady solution. The stability equations with their boundary conditions and the radiation condition of the considered model are explicitly derived for small transversal deviations of the shock wave location. The paper shows how a second-order chemical kinetics description, derived at the microscopic level, and an analytic deduction of the equilibrium Hugoniot curve, lead to an accurate picture of the steady detonation with reversible reaction, as well as to a proper bidimensional linear stability analysis.

  14. 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

  15. Equilibrium and Kinetic Models for Colloid Release Under Transient Solution Chemistry Conditions

    NASA Astrophysics Data System (ADS)

    Bradford, S. A.; Torkzaban, S.; Leij, F. J.; Simunek, J.

    2014-12-01

    Colloid retention and release is well known to depend on a wide variety of physical, chemical, and microbiological factors that may vary temporally in the subsurface environment. We present equilibrium, kinetic, combined equilibrium and kinetic, and two-site kinetic models of colloid release during transient physicochemical conditions. Our mathematical modeling approach relates colloid release under transient conditions to changes in the fraction of the solid surface area that contributes to retention. The developed models were subsequently applied to experimental colloid release datasets to investigate the influence of variations in ionic strength (IS), pH, cation exchange, colloid size, and water velocity on release. Various combinations of equilibrium and/or kinetic release models were needed to describe the experimental data depending on the transient conditions and colloid type. Release of E. coli D21g was promoted by a decrease in solution IS and an increase in pH, similar to expected trends for a reduction in the secondary minimum and nanoscale chemical heterogeneity, respectively. The retention and release of 20 nm carboxyl modified latex nanoparticles (NPs) were demonstrated to be more sensitive to the presence of Ca2+ than D21g. Specifically, retention of NPs was greater than D21g in the presence of 2 mM CaCl2 solution, and release of NPs only occurred after exchange of Ca2+ by Na+ and then a reduction in the solution IS. These findings highlight the limitations of conventional interaction energy calculations to describe colloid retention and release, and point to the need to consider Born repulsion and nanoscale heterogeneity. Temporal changes in the water velocity did not have a large influence on the release of D21g. This insensitivity was likely due to factors that reduce the applied hydrodynamic torque and/or increase the resisting adhesive torque. Collectively, experimental and modeling results indicate that episodic colloid transport in the

  16. Effect of Humic Acid on As Redox Transformation and Kinetic Adsorption onto Iron Oxide Based Adsorbent (IBA)

    PubMed Central

    Fakour, Hoda; Lin, Tsair-Fuh

    2014-01-01

    Due to the importance of adsorption kinetics and redox transformation of arsenic (As) during the adsorption process, the present study elucidated natural organic matter (NOM) effects on As adsorption-desorption kinetics and speciation transformation. The experimental procedures were conducted by examining interactions of arsenate and arsenite with different concentrations of humic acid (HA) as a model representative of NOM, in the presence of iron oxide based adsorbent (IBA), as a model solid surface in three environmentally relevant conditions, including the simultaneous adsorption of both As and HA onto IBA, HA adsorption onto As-presorbed IBA, and As adsorption onto HA-presorbed IBA. Experimental adsorption-desorption data were all fitted by original and modified Lagergren pseudo-first and -second order adsorption kinetic models, respectively. Weber’s intraparticle diffusion was also used to gain insight into the mechanisms and rate controlling steps, which the results suggested that intraparticle diffusion of As species onto IBA is the main rate-controlling step. Different concentrations of HA mediated the redox transformation of As species, with a higher oxidation ability than reduction. The overall results indicated the significant effect of organic matter on the adsorption kinetics and redox transformation of As species, and consequently, the fate, transport and mobility of As in different environmentally relevant conditions. PMID:25325357

  17. Application of novel, low-cost, laterite-based adsorbent for removal of lead from water: Equilibrium, kinetic and thermodynamic studies.

    PubMed

    Chatterjee, Somak; De, Sirshendu

    2016-01-01

    Contamination of groundwater by carcinogenic heavy metal, e.g., lead is an important issue and possibility of using a natural rock, laterite, is explored in this work to mitigate this problem. Treated laterite (TL- prepared using hydrochloric acid and sodium hydroxide) was successfully utilized for this purpose. The adsorbent was characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX), and Fourier Transform Infrared Spectroscopy (FTIR) to highlight its physical and chemical properties. Optimized equilibrium conditions were 1 g L(-1) adsorbent concentration, 0.26 mm size and a pH of 7 ± 0.2. Monolayer adsorption capacity of lead on treated laterite was 15 mg/g, 14.5 and 13 mg g(-1) at temperatures of 303 K, 313 K and 323 K, respectively. The adsorption was exothermic and physical in nature. At 303 K, value of effective diffusivity of (De) and mass transfer co-efficient (Kf) of lead onto TL were 6.5 × 10(-10) m(2)/s and 3.3 × 10(-4) m/s, respectively (solved from shrinking core model of adsorption kinetics). Magnesium and sulphate show highest interference effect on the adsorption of lead by TL. Efficacy of the adsorbent has been verified using real-life contaminated groundwater. Thus, this work demonstrates performance of a cost-effective media for lead removal. PMID:26646980

  18. Sorption of water alkalinity and hardness from high-strength wastewater on bifunctional activated carbon: process optimization, kinetics and equilibrium studies.

    PubMed

    Amosa, Mutiu K

    2016-08-01

    Sorption optimization and mechanism of hardness and alkalinity on bifunctional empty fruit bunch-based powdered activation carbon (PAC) were studied. The PAC possessed both high surface area and ion-exchange properties, and it was utilized in the treatment of biotreated palm oil mill effluent. Batch adsorption experiments designed with Design Expert(®) were conducted in correlating the singular and interactive effects of the three adsorption parameters: PAC dosage, agitation speed and contact time. The sorption trends of the two contaminants were sequentially assessed through a full factorial design with three factor interaction models and a central composite design with polynomial models of quadratic order. Analysis of variance revealed the significant factors on each design response with very high R(2) values indicating good agreement between model and experimental values. The optimum operating conditions of the two contaminants differed due to their different regions of operating interests, thus necessitating the utility of desirability factor to get consolidated optimum operation conditions. The equilibrium data for alkalinity and hardness sorption were better represented by the Langmuir isotherm, while the pseudo-second-order kinetic model described the adsorption rates and behavior better. It was concluded that chemisorption contributed majorly to the adsorption process. PMID:26752149

  19. 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

  20. Equilibrium Liquid Crystal Phase Diagrams and Detection of Kinetic Arrest in Cellulose Nanocrystal Suspensions

    NASA Astrophysics Data System (ADS)

    Honorato Rios, Camila; Kuhnhold, Anja; Bruckner, Johanna; Dannert, Rick; Schilling, Tanja; Lagerwall, Jan

    2016-05-01

    The cholesteric liquid crystal self-assembly of water-suspended cellulose nanocrystal (CNC) into a helical arrangement was observed already more than 20 years ago and the phenomenon was used to produce iridescent solid films by evaporating the solvent or via sol-gel processing. Yet it remains challenging to produce optically uniform films and to control the pitch reproducibly, reflecting the complexity of the three-stage drying process that is followed in preparing the films. An equilibrium liquid crystal phase formation stage is followed by a non-equilibrium kinetic arrest, which in turn is followed by structural collapse as the remaining solvent is evaporated. Here we focus on the first of these stages, combining a set of systematic rheology and polarizing optics experiments with computer simulations to establish a detailed phase diagram of aqueous CNC suspensions with two different values of the surface charge, up to the concentration where kinetic arrest sets in. We also study the effect of varying ionic strength of the solvent. Within the cholesteric phase regime, we measure the equilibrium helical pitch as a function of the same parameters. We report a hitherto unnoticed change in character of the isotropic-cholesteric transition at increasing ionic strength, with a continuous weakening of the first-order character up to the point where phase coexistence is difficult to detect macroscopically due to substantial critical fluctuations.

  1. Development, Construction, and Operation of a Multisample Volumetric Apparatus for the Study of Gas Adsorption Equilibrium

    ERIC Educational Resources Information Center

    Ribeiro, Rui P. P. L.; Silva, Ricardo J. S.; Esteves, Isabel A. A. C.; Mota, Jose´ P. B.

    2015-01-01

    The construction of a simple volumetric adsorption apparatus is highlighted. The setup is inexpensive and provides a clear demonstration of gas phase adsorption concepts. The topic is suitable for undergraduate chemistry and chemical engineering students. Moreover, this unit can also provide quantitative data that can be used by young researchers…

  2. Equilibrium and Kinetic Studies of Cd2+ Biosorption by the Brown Algae Sargassum fusiforme

    PubMed Central

    Zou, Hui-Xi; Li, Nan; Wang, Li-Hua; Yu, Ping; Yan, Xiu-Feng

    2014-01-01

    A fundamental investigation of the biosorption of Cd2+ from aqueous solution by the edible seaweed Sargassum fusiforme was performed under batch conditions. The influences of experimental parameters, such as the initial pH, sorption time, temperature, and initial Cd2+ concentration, on Cd2+ uptake by S. fusiforme were evaluated. The results indicated that the biosorption of Cd2+ depended on the initial Cd2+ concentration, as well as the pH. The uptake of Cd2+ could be described by the Langmuir isotherm model, and both the Langmuir biosorption equilibrium constant and the maximum biosorption capacity of the monolayer decreased with increasing temperature, thereby confirming the exothermic character of the sorption process. The biosorption kinetics follows the pseudo-second-order kinetic model, and intraparticle diffusion is the sole rate-limiting step for the entire biosorption period. These fundamental equilibrium and kinetic results can support further studies to the removal of cadmium from S. fusiforme harvested from cadmium-polluted waters. PMID:24736449

  3. 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

  4. Adsorption and removal kinetics of phosphonate from water using natural adsorbents.

    PubMed

    Kumar, R Anil; Velayudhan, K T; Ramachandran, V; Bhai, R Susheela; Unnikrishnan, G; Vasu, K

    2010-01-01

    The removal of phosphonate from water was studied using some natural adsorbents. Potassium phosphonate is a fungicide used for the control of Phytophthora capsici, which is prevalent in black pepper (Piper nigrum L.). Batch adsorption kinetic experiments were conducted on the adsorption of phosphonate onto the adsorbents. The concentration of phosphonate was measured on a high-performance liquid chromatograph fitted with a conductivity detector. The percentage removal of phosphonate by powdered laterite stone (PLS) from water was 40.4%, within a residence time of 15 minutes. The mechanisms of the rate of adsorption were analyzed and compared using the pseudo-second-order, Elovich, and intraparticle diffusion models. The experimental data was found to correlate well with the pseudo-second-order kinetic model, indicating adsorption as a chemisorption process. A possible reaction in the phosphonate-PLS system also has been proposed. The PLS can be used as a low-cost natural adsorbent for phosphonate removal from water. PMID:20112539

  5. Kinetics of the water adsorption driven structural transformationof ZnS nanoparticles

    SciTech Connect

    Goodell, C.M.; Gilbert, B.; Weigand, S.J.; Banfield, J.F.

    2007-08-01

    Nanoparticles of certain materials can respond structurally to changes in their surface environments. We have previously shown that methanol, water adsorption, and aggregation-disaggregation can change the structure of 3 nm diameter zinc sulfide (ZnS). However, in prior observations of water-driven structure change, aggregation may also have taken place. Therefore, we investigated the structural consequences of water adsorption alone on anhydrous nanoparticles that were dried to minimize changes in aggregation. Using simultaneously collected small- and wide-angle x-ray scattering (SAXS/WAXS) data, we show that water vapor adsorption alone drives a structural transformation in ZnS nanoparticles in the temperature range 22-40 C. The transition kinetics are strongly temperature dependent, with an activation energy of 58.1 {+-} 9.8 kJ/mol, consistent with atom displacement rather than bond breaking. At 50 C, aggregate restructuring occurred, increasing the transition kinetics beyond the rate expected for water adsorption alone. The observation of isosbestic points in the WAXS data suggests that the particles do not transform continuously between the initial and final structural state but rather undergo an abrupt change from a less ordered to a more ordered state.

  6. Effect of humidity on the adsorption kinetics of lung surfactant at air-water interfaces.

    PubMed

    Zuo, Yi Y; Gitiafroz, Roya; Acosta, Edgar; Policova, Zdenka; Cox, Peter N; Hair, Michael L; Neumann, A Wilhelm

    2005-11-01

    The in vitro adsorption kinetics of lung surfactant at air-water interfaces is affected by both the composition of the surfactant preparations and the conditions under which the assessment is conducted. Relevant experimental conditions are surfactant concentration, temperature, subphase pH, electrolyte concentration, humidity, and gas composition of the atmosphere exposed to the interface. The effect of humidity on the adsorption kinetics of a therapeutic lung surfactant preparation, bovine lipid extract surfactant (BLES), was studied by measuring the dynamic surface tension (DST). Axisymmetric drop shape analysis (ADSA) was used in conjunction with three different experimental methodologies, i.e., captive bubble (CB), pendant drop (PD), and constrained sessile drop (CSD), to measure the DST. The experimental results obtained from these three methodologies show that for 100% relative humidity (RH) at 37 degrees C the rate of adsorption of BLES at an air-water interface is substantially slower than for low humidity. It is also found that there is a difference in the rate of surface tension decrease measured from the PD and CB/CSD methods. These experimental results agree well with an adsorption model that considers the combined effects of entropic force, electrostatic interaction, and gravity. These findings have implications for the development and evaluation of new formulations for surfactant replacement therapy. PMID:16262325

  7. The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

    PubMed

    Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

    2016-07-27

    An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting. PMID:27147197

  8. Kinetics of protein adsorption on gold nanoparticle with variable protein structure and nanoparticle size.

    PubMed

    Khan, S; Gupta, A; Verma, N C; Nandi, C K

    2015-10-28

    The spontaneous protein adsorption on nanomaterial surfaces and the formation of a protein corona around nanoparticles are poorly understood physical phenomena, with high biological relevance. The complexity arises mainly due to the poor knowledge of the structural orientation of the adsorbed proteins onto the nanoparticle surface and difficulties in correlating the protein nanoparticle interaction to the protein corona in real time scale. Here, we provide quantitative insights into the kinetics, number, and binding orientation of a few common blood proteins when they interact with citrate and cetyltriethylammoniumbromide stabilized spherical gold nanoparticles with variable sizes. The kinetics of the protein adsorption was studied experimentally by monitoring the change in hydrodynamic diameter and zeta potential of the nanoparticle-protein complex. To understand the competitive binding of human serum albumin and hemoglobin, time dependent fluorescence quenching was studied using dual fluorophore tags. We have performed molecular docking of three different proteins--human serum albumin, bovine serum albumin, and hemoglobin--on different nanoparticle surfaces to elucidate the possible structural orientation of the adsorbed protein. Our data show that the growth kinetics of a protein corona is exclusively dependent on both protein structure and surface chemistry of the nanoparticles. The study quantitatively suggests that a general physical law of protein adsorption is unlikely to exist as the interaction is unique and specific for a given pair. PMID:26520545

  9. Adsorption kinetics of plasma proteins on ultrasmall superparamagnetic iron oxide (USPIO) nanoparticles.

    PubMed

    Jansch, M; Stumpf, P; Graf, C; Rühl, E; Müller, R H

    2012-05-30

    In this study the kinetics of plasma protein adsorption onto ultrasmall superparamagnetic iron oxide (USPIO) particles have been analyzed and compared to previously published kinetic studies on polystyrene particles (PS particles), oil-in-water nanoemulsions and solid lipid nanoparticles (SLNs). SPIO and USPIO nanoparticles are commonly used as magnetic resonance imaging (MRI) enhancers for tumor imaging as well as in drug delivery applications. Two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) has been used to determine the plasma protein adsorption onto the citrate/triethylene glycol-stabilized iron oxide surface. The results indicate that the existence of a Vroman effect, a displacement of previously adsorbed abundant proteins, such as albumin or fibrinogen, respectively, on USPIO particles has to be denied. Previously, identical findings have been reported for oil-in-water nanoemulsions. Furthermore, the protein adsorption kinetics differs dramatically from that of other solid drug delivery systems (PS, SLN). More relevant for the in vivo fate of long circulating particles is the protein corona after several minutes or even hours. Interestingly, the patterns received after an incubation time of 0.5 min to 240 min are found to be qualitatively and quantitatively similar. This leads to the assumption of a long-lived ("hard") protein corona around the iron oxide nanoparticles. PMID:22342465

  10. Kinetics of protein adsorption on gold nanoparticle with variable protein structure and nanoparticle size

    NASA Astrophysics Data System (ADS)

    Khan, S.; Gupta, A.; Verma, N. C.; Nandi, C. K.

    2015-10-01

    The spontaneous protein adsorption on nanomaterial surfaces and the formation of a protein corona around nanoparticles are poorly understood physical phenomena, with high biological relevance. The complexity arises mainly due to the poor knowledge of the structural orientation of the adsorbed proteins onto the nanoparticle surface and difficulties in correlating the protein nanoparticle interaction to the protein corona in real time scale. Here, we provide quantitative insights into the kinetics, number, and binding orientation of a few common blood proteins when they interact with citrate and cetyltriethylammoniumbromide stabilized spherical gold nanoparticles with variable sizes. The kinetics of the protein adsorption was studied experimentally by monitoring the change in hydrodynamic diameter and zeta potential of the nanoparticle-protein complex. To understand the competitive binding of human serum albumin and hemoglobin, time dependent fluorescence quenching was studied using dual fluorophore tags. We have performed molecular docking of three different proteins—human serum albumin, bovine serum albumin, and hemoglobin—on different nanoparticle surfaces to elucidate the possible structural orientation of the adsorbed protein. Our data show that the growth kinetics of a protein corona is exclusively dependent on both protein structure and surface chemistry of the nanoparticles. The study quantitatively suggests that a general physical law of protein adsorption is unlikely to exist as the interaction is unique and specific for a given pair.

  11. A kinetic and equilibrium analysis of silicon carbide chemical vapor deposition on monofilaments

    NASA Technical Reports Server (NTRS)

    Gokoglu, S. A.; Kuczmarski, M. A.

    1993-01-01

    Chemical kinetics of atmospheric pressure silicon carbide (SiC) chemical vapor deposition (CVD) from dilute silane and propane source gases in hydrogen is numerically analyzed in a cylindrical upflow reactor designed for CVD on monofilaments. The chemical composition of the SiC deposit is assessed both from the calculated total fluxes of carbon and silicon and from chemical equilibrium considerations for the prevailing temperatures and species concentrations at and along the filament surface. The effects of gas and surface chemistry on the evolution of major gas phase species are considered in the analysis.

  12. 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.

  13. Kinetics of Adsorption of Cationic Surfactants at Silica-Water Interface.

    PubMed

    Biswas; Chattoraj

    1998-09-01

    The kinetics of adsorption of cationic surfactants (CTAB, MTAB and DTAB) at silica surface has been studied at various values of bulk surfactant concentration (Ct2), pH, ionic strength, and temperature and in presence of different electrolytes and urea. The adsorption process has been found to follow a two-step first-order kinetic rate equation with two different rate constants k1 and k2. From the variation of k1 and k2 with temperature, values of energies of activation Ea1 and Ea2 for both the kinetic steps have been evaluated. The corresponding values of enthalpies of activation (DeltaH1# and DeltaH2#), entropies of activation (DeltaS1# and DeltaS2#) have been evaluated using Eyring's equation for absolute reaction rate. It has been found that for both the kinetic steps, DeltaH1# < TavDeltaS1# and DeltaH2# < TavDeltaS2#, which means that activation reaction is largely entropy controlled. Again, for both kinetic steps, DeltaH# varies linearly with TavDeltaS#, and DeltaG1# and DeltaG2# vary between 70 and 88 kJ/mole of surfactant, respectively. Thus there is a entropy-enthalpy compensation effect in the adsorption process. Copyright 1998 Academic Press. PMID:9710495

  14. Synthesis of a novel magnetic zeolite nanocomposite for removal of Cs+ and Sr2+ from aqueous solution: kinetic, equilibrium, and thermodynamic studies.

    PubMed

    Faghihian, Hossein; Moayed, Mohammad; Firooz, Alireza; Iravani, Mozhgan

    2013-03-01

    In this study, a novel magnetic zeolite nanocomposite (MZNC) was prepared by nanozeolite A and iron oxide. Nanocrystalline zeolite A was synthesized, and then, iron oxide nanocrystals were prepared in the presence of nanozeolite. The prepared nanocomposite was characterized by XRD, XRF, FT-IR, DTG, VSM, and TEM methods. The applicability of the synthesized nanocomposite for removal of Cs(+) and Sr(2+) from aqueous solutions was assessed, and the effective parameters such as initial concentration, initial pH, contact time, and temperature on the sorption process were studied and optimized. The composite was able to remove 95.2% and 81.4% of Sr(+2) and Cs(+1) from 0.01 N aqueous solutions, respectively. The kinetic studies showed that the process was quite rapid, and 90% of equilibrium capacity was achieved within 30 min. Experimental kinetic data were found to be well fitted with pseudo-second-order kinetic model with rate constant of 0.2845 and 0.2722 g mmol(-1) min(-1) for Cs(+) and Sr(2+), respectively. The Langmuir, Freundlich, and D-R isotherm models were used to describe the equilibrium data. The saturation magnetization of nanocomposite was measured as 19.50 emu g(-1), which facilitated magnetic separation of the sample after adsorption process. PMID:23266030

  15. Kinetics and equilibrium of the sorption of bisphenol A by carbon nanotubes from wastewater.

    PubMed

    Bohdziewicz, J; Kamińska, G

    2013-01-01

    The aim of this study was to determine the sorption potential of carbon nanotubes (CNTs) to bisphenol A (BPA) contained in synthetic wastewater whose composition corresponds to biologically treated effluents. These nanotubes differed in their outer diameter, the number of graphene layers and the presence of modifying functional groups. Based on the nitrogen adsorption-desorption isotherms, mensuration of the specific surface area and pore size distribution was undertaken. The porous structure of the CNTs was bidispersive; the majority consisted of micropores, there was an average fraction of mesopores, and macropores did not occur. On the basis of common kinetics models (pseudo-first-order and pseudo-second-order models), a trial of modelling the kinetics of BPA sorption onto nanotubes was undertaken. The experimental data were well fitted only to the pseudo-second-order models. The kinetics study indicated that adsorption of BPA on CNTs proceeded very fast, with the majority of the adsorbate being adsorbed in the first few seconds. The sorption capacity of nanotubes to BPA was the highest for single-walled CNTs. A decrease in the sorption potential of the nanotubes for higher pH values occurred as a result of the deprotonation of the BPA and formation of bisphenolate anions, consequently leading to a decrease of π-π (hydrophobic) interaction and enhancing electrostatic repulsion. Overall, these results unequivocally confirm the ideal performance and potential of nanotubes for removal of micropollutants from synthetic wastewater. Replicating the conditions occurring in real wastewater allows us to expect a high sorption of BPA in real competitive sorption systems. PMID:24056428

  16. The Universal Statistical Distributions of the Affinity, Equilibrium Constants, Kinetics and Specificity in Biomolecular Recognition

    PubMed Central

    Zheng, Xiliang; Wang, Jin

    2015-01-01

    We uncovered the universal statistical laws for the biomolecular recognition/binding process. We quantified the statistical energy landscapes for binding, from which we can characterize the distributions of the binding free energy (affinity), the equilibrium constants, the kinetics and the specificity by exploring the different ligands binding with a particular receptor. The results of the analytical studies are confirmed by the microscopic flexible docking simulations. The distribution of binding affinity is Gaussian around the mean and becomes exponential near the tail. The equilibrium constants of the binding follow a log-normal distribution around the mean and a power law distribution in the tail. The intrinsic specificity for biomolecular recognition measures the degree of discrimination of native versus non-native binding and the optimization of which becomes the maximization of the ratio of the free energy gap between the native state and the average of non-native states versus the roughness measured by the variance of the free energy landscape around its mean. The intrinsic specificity obeys a Gaussian distribution near the mean and an exponential distribution near the tail. Furthermore, the kinetics of binding follows a log-normal distribution near the mean and a power law distribution at the tail. Our study provides new insights into the statistical nature of thermodynamics, kinetics and function from different ligands binding with a specific receptor or equivalently specific ligand binding with different receptors. The elucidation of distributions of the kinetics and free energy has guiding roles in studying biomolecular recognition and function through small-molecule evolution and chemical genetics. PMID:25885453

  17. The universal statistical distributions of the affinity, equilibrium constants, kinetics and specificity in biomolecular recognition.

    PubMed

    Zheng, Xiliang; Wang, Jin

    2015-04-01

    We uncovered the universal statistical laws for the biomolecular recognition/binding process. We quantified the statistical energy landscapes for binding, from which we can characterize the distributions of the binding free energy (affinity), the equilibrium constants, the kinetics and the specificity by exploring the different ligands binding with a particular receptor. The results of the analytical studies are confirmed by the microscopic flexible docking simulations. The distribution of binding affinity is Gaussian around the mean and becomes exponential near the tail. The equilibrium constants of the binding follow a log-normal distribution around the mean and a power law distribution in the tail. The intrinsic specificity for biomolecular recognition measures the degree of discrimination of native versus non-native binding and the optimization of which becomes the maximization of the ratio of the free energy gap between the native state and the average of non-native states versus the roughness measured by the variance of the free energy landscape around its mean. The intrinsic specificity obeys a Gaussian distribution near the mean and an exponential distribution near the tail. Furthermore, the kinetics of binding follows a log-normal distribution near the mean and a power law distribution at the tail. Our study provides new insights into the statistical nature of thermodynamics, kinetics and function from different ligands binding with a specific receptor or equivalently specific ligand binding with different receptors. The elucidation of distributions of the kinetics and free energy has guiding roles in studying biomolecular recognition and function through small-molecule evolution and chemical genetics. PMID:25885453

  18. Biosorption of methylene blue by de-oiled algal biomass: equilibrium, kinetics and artificial neural network modelling.

    PubMed

    Maurya, Rahulkumar; Ghosh, Tonmoy; Paliwal, Chetan; Shrivastav, Anupama; Chokshi, Kaumeel; Pancha, Imran; Ghosh, Arup; Mishra, Sandhya

    2014-01-01

    The main objective of the present study is to effectively utilize the de-oiled algal biomass (DAB) to minimize the waste streams from algal biofuel by using it as an adsorbent. Methylene blue (MB) was used as a sorbate for evaluating the potential of DAB as a biosorbent. The DAB was characterized by SEM, FTIR, pHPZC, particle size, pore volume and pore diameter to understand the biosorption mechanism. The equilibrium studies were carried out by variation in different parameters, i.e., pH (2-9), temperature (293.16-323.16 K), biosorbent dosage (1-10 g L(-1)), contact time (0-1,440 min), agitation speed (0-150 rpm) and dye concentration (25-2,500 mg L(-1)). MB removal was greater than 90% in both acidic and basic pH. The optimum result of MB removal was found at 5-7 g L(-1) DAB concentration. DAB removes 86% dye in 5 minutes under static conditions and nearly 100% in 24 hours when agitated at 150 rpm. The highest adsorption capacity was found 139.11 mg g(-1) at 2,000 mg L(-1) initial MB concentration. The process attained equilibrium in 24 hours. It is an endothermic process whose spontaneity increases with temperature. MB biosorption by DAB follows pseudo-second order kinetics. Artificial neural network (ANN) model also validates the experimental dye removal efficiency (R2 = 0.97) corresponding with theoretically predicted values. Sensitivity analysis suggests that temperature and agitation speed affect the process most with 23.62% and 21.08% influence on MB biosorption, respectively. Dye adsorption capacity of DAB in fixed bed column was 107.57 mg g(-1) in preliminary study while it went up to 139.11 mg g(-1) in batch studies. The probable mechanism for biosorption in this study is chemisorptions via surface active charges in the initial phase followed by physical sorption by occupying pores of DAB. PMID:25310576

  19. Biosorption of Methylene Blue by De-Oiled Algal Biomass: Equilibrium, Kinetics and Artificial Neural Network Modelling

    PubMed Central

    Maurya, Rahulkumar; Ghosh, Tonmoy; Paliwal, Chetan; Shrivastav, Anupama; Chokshi, Kaumeel; Pancha, Imran; Ghosh, Arup; Mishra, Sandhya

    2014-01-01

    The main objective of the present study is to effectively utilize the de-oiled algal biomass (DAB) to minimize the waste streams from algal biofuel by using it as an adsorbent. Methylene blue (MB) was used as a sorbate for evaluating the potential of DAB as a biosorbent. The DAB was characterized by SEM, FTIR, pHPZC, particle size, pore volume and pore diameter to understand the biosorption mechanism. The equilibrium studies were carried out by variation in different parameters, i.e., pH (2–9), temperature (293.16–323.16 K), biosorbent dosage (1–10 g L−1), contact time (0–1,440 min), agitation speed (0–150 rpm) and dye concentration (25–2,500 mg L−1). MB removal was greater than 90% in both acidic and basic pH. The optimum result of MB removal was found at 5–7 g L−1 DAB concentration. DAB removes 86% dye in 5 minutes under static conditions and nearly 100% in 24 hours when agitated at 150 rpm. The highest adsorption capacity was found 139.11 mg g−1 at 2,000 mg L−1 initial MB concentration. The process attained equilibrium in 24 hours. It is an endothermic process whose spontaneity increases with temperature. MB biosorption by DAB follows pseudo-second order kinetics. Artificial neural network (ANN) model also validates the experimental dye removal efficiency (R2 = 0.97) corresponding with theoretically predicted values. Sensitivity analysis suggests that temperature and agitation speed affect the process most with 23.62% and 21.08% influence on MB biosorption, respectively. Dye adsorption capacity of DAB in fixed bed column was 107.57 mg g−1 in preliminary study while it went up to 139.11 mg g−1 in batch studies. The probable mechanism for biosorption in this study is chemisorptions via surface active charges in the initial phase followed by physical sorption by occupying pores of DAB. PMID:25310576

  20. Adsorption equilibrium of organic vapors on single-walled carbon nanotubes

    USGS Publications Warehouse

    Agnihotri, S.; Rood, M.J.; Rostam-Abadi, M.

    2005-01-01

    Gravimetric techniques were employed to determine the adsorption capacities of commercially available purified electric arc and HiPco single-walled carbon nanotubes (SWNTs) for organic compounds (toluene, methyl ethyl ketone (MEK), hexane and cyclohexane) at relative pressures, p/p0, ranging from 1 ?? 10-4 to 0.95 and at isothermal conditions of 25, 37 and 50 ??C. The isotherms displayed both type I and type II characteristics. Adsorption isotherm modeling showed that SWNTs are heterogeneous adsorbents, and the Freundlich equation best describes the interaction between organic molecules and SWNTs. The heats of adsorption were 1-4 times the heats of vaporization, which is typical for physical adsorption of organic vapors on porous carbons. ?? 2005 Elsevier Ltd. All rights reserved.

  1. 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

  2. Equilibrium and kinetics of color removal from dye solutions with bentonite and polyaluminum hydroxide.

    PubMed

    Kacha, S; Derriche, Z; Elmaleh, S

    2003-01-01

    Wastewater from the textile industry contains soluble dyes that are toxic and particularly difficult to remove. A promising low-cost treatment, however, is use of polyaluminum hydroxide associated with bentonite. At suitable conditions, this process is able to efficiently remove color from solutions containing mixtures of soluble acid azo dyes and produce easily settleable sludge. The removal mechanism, which is believed to involve adsorption or precipitation and weak pH variations, is not well understood. With the overall reaction being second order, two elementary first-order reactions could be assumed. The equilibrium removal is a decreasing function of the temperature. However, this effect is weak and decreases when the dye concentration increases. At usual values of concentration in textile wastewater, this effect can be neglected. The resulting solid compound is particularly resistant to mechanical stress. Moreover, color was significantly released at pH greater than 8. Sodium ions have no influence on the compound stability, which reinforces the assumption of the involvement of an adsorption process. PMID:12683459

  3. 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

  4. APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems

    SciTech Connect

    Nguyen, H.D.

    1991-11-01

    Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a ``glass like`` material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.

  5. APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems

    SciTech Connect

    Nguyen, H.D.

    1991-11-01

    Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a glass like'' material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.

  6. Metal-anion sorption by chitosan beads: Equilibrium and kinetic studies

    SciTech Connect

    Guibal, E.; Milot, C.; Tobin, J.M.

    1998-04-01

    Chitosan is a well-known biopolymer, whose high nitrogen content confers remarkable ability for the sorption of metal ions from dilute effluents. However, its sorption performance in both equilibrium and kinetic terms is controlled by diffusion processes. Gel bead formation allows an expansion of the polymer network, which improves access to the internal sorption sites and enhances diffusion mechanisms. Molybdate and vanadate recovery using glutaraldehyde cross-linked chitosan beads reaches uptake capacities as high as 7--8 mmol/g, depending on the pH. The optimum pH (3--3.5) corresponded to the predominance range of hydrolyzed polynuclear metal forms and optimum electrostatic attraction. While for beads, particle size does not influence equilibrium, for flakes, increasing sorbent radius significantly decreases uptake capacities to 1.5 mmol/g. Sorption kinetics are mainly controlled by intraparticle diffusion for beads, while for flakes the controlling mechanisms are both external and intraparticle diffusion. The gel conditioning increases the intraparticle diffusivity by 3 orders of magnitude: intraparticle diffusivities range between 10{sup {minus}13} and 10{sup {minus}10} m{sup 2}/min, depending on the sorbent size and the conditioning.

  7. An improved equilibrium-kinetics speciation algorithm for redox reactions in variably saturated subsurface flow systems

    NASA Astrophysics Data System (ADS)

    Xu, Tianfu; Pruess, Karsten; Brimhall, George

    1999-07-01

    Reactive chemical transport occurs in a variety of geochemical environments, and over a broad range of space and time scales. Efficiency of the chemical speciation and water-rock-gas interaction calculations is important for modeling field-scale multidimensional reactive transport problems. An improved efficient model, REACT, for simulating water-rock-gas interaction under equilibrium and kinetic conditions, has been developed. In this model, equilibrium and kinetic reactions are solved simultaneously by Newton-Raphson iteration. The REACT speciation model was coupled with the multidimensional nonisothermal multiphase flow and mass transport code TOUGH2, resulting in the general purpose reactive chemical transport simulator TOUGHREACT. An application to supergene copper enrichment of a typical copper protore that includes the sulfide minerals pyrite (FeS 2) and chalcopyrite (CuFeS 2) is presented. The efficiency and convergence of the present model is demonstrated from this numerically difficult application that involves very large variations in the concentrations of oxygen, and sulfide and sulfate species. TOUGHREACT provides a detailed description of water-rock-gas interactions during fully transient, multiphase, nonisothermal flow and transport in hydrologically and geochemically heterogeneous media. The code is helpful for assessment of acid mine drainage remediation, geothermal convection, waste disposal, contaminant transport and water quality.

  8. Biosorption of Malachite Green from aqueous solutions onto aerobic granules: kinetic and equilibrium studies.

    PubMed

    Sun, Xue-Fei; Wang, Shu-Guang; Liu, Xian-Wei; Gong, Wen-Xin; Bao, Nan; Gao, Bao-Yu; Zhang, Hua-Yong

    2008-06-01

    Batch experiments were conducted to study the biosorption characteristics of a cationic dye, Malachite Green (MG), onto aerobic granules. Effects of pH, aerobic granule dosage, contact time and solution temperature on MG biosorption by aerobic granules were evaluated. Simultaneity the thermodynamic analysis was also performed. The results showed that alkaline pH was favorable for the biosorption of MG and chemisorption seemed to play a major role in the biosorption process. Kinetic studies indicate that MG biosorption on aerobic granules in the system follows the pseudo-second order kinetics. The equilibrium time was 60 min for both 50 and 60 mg/L and 120 min for both 70 and 80 mg/L MG concentrations, respectively. Moreover, the experimental equilibrium data have been analyzed using the linearized forms of Langmuir, Freundlich, and Redlich-Peterson isotherms and the Langmuir isotherm was found to provide the best theoretical correlation of the experimental data for the biosorption of MG. The monolayer biosorption (saturation) capacities were determined to be 56.8 mg of MG per gram of aerobic granules at 30 degrees C. Thermodynamic analysis show that biosorption follows an endothermic path of the positive value of Delta H( composite function) and spontaneous with negative value of Delta G( composite function). PMID:17855080

  9. Equilibrium and kinetic models for colloid release under transient solution chemistry conditions.

    PubMed

    Bradford, Scott A; Torkzaban, Saeed; Leij, Feike; Simunek, Jiri

    2015-10-01

    We present continuum models to describe colloid release in the subsurface during transient physicochemical conditions. Our modeling approach relates the amount of colloid release to changes in the fraction of the solid surface area that contributes to retention. Equilibrium, kinetic, equilibrium and kinetic, and two-site kinetic models were developed to describe various rates of colloid release. These models were subsequently applied to experimental colloid release datasets to investigate the influence of variations in ionic strength (IS), pH, cation exchange, colloid size, and water velocity on release. Various combinations of equilibrium and/or kinetic release models were needed to describe the experimental data depending on the transient conditions and colloid type. Release of Escherichia coli D21g was promoted by a decrease in solution IS and an increase in pH, similar to expected trends for a reduction in the secondary minimum and nanoscale chemical heterogeneity. The retention and release of 20nm carboxyl modified latex nanoparticles (NPs) were demonstrated to be more sensitive to the presence of Ca(2+) than D21g. Specifically, retention of NPs was greater than D21g in the presence of 2mM CaCl2 solution, and release of NPs only occurred after exchange of Ca(2+) by Na(+) and then a reduction in the solution IS. These findings highlight the limitations of conventional interaction energy calculations to describe colloid retention and release, and point to the need to consider other interactions (e.g., Born, steric, and/or hydration forces) and/or nanoscale heterogeneity. Temporal changes in the water velocity did not have a large influence on the release of D21g for the examined conditions. This insensitivity was likely due to factors that reduce the applied hydrodynamic torque and/or increase the resisting adhesive torque; e.g., macroscopic roughness and grain-grain contacts. Our analysis and models improve our understanding and ability to describe the amounts

  10. Molecular kinetic theory of strongly nonequilibrium processes of mass, momentum, and energy transfer: Local equilibrium criteria

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.

    2015-09-01

    Consequences of the complete system of transfer equations of the properties (momentum, energy, and mass) of particles and their pairs are considered under local equilibrium conditions with regard to the Bogoliubov hierarchy of relaxation times between the first and second distribution functions (DFs) and distinctions in the characteristic relaxation times of particle momentum, energy, and mass. It is found that even under the local equilibrium condition in the Bogoliubov hierarchy of relaxation times between the first and second DFs, pair correlations are maintained between all dynamic variables (velocity, temperature, and density) whose values are proportional to the gradients of transferable properties. A criterion is introduced requiring there be no local equilibrium condition upon reaching the critical value at which the description of the transfer process becomes incorrect in classical nonequilibrium thermodynamics. External forces are considered in the equations for strongly nonequilibrium processes. Along with allowing for intermolecular potentials, it becomes possible to discuss the concept of passive forces (introduced in thermodynamics by Gibbs) from the standpoint of the kinetic theory. It is shown that use of this concept does not reflect modern representations of real processes.

  11. Flux line non-equilibrium relaxation kinetics following current quenches in disordered type-II superconductors

    NASA Astrophysics Data System (ADS)

    Chaturvedi, Harshwardhan; Assi, Hiba; Dobramysl, Ulrich; Pleimling, Michel; Täuber, Uwe

    We investigate the relaxation dynamics of magnetic vortex lines in disordered type-II superconductors following rapid changes in the external driving current by means of Langevin molecular dynamics simulations for an elastic line model. A system of driven interacting flux lines in a sample with randomly distributed point pinning centers is initially relaxed to a moving non-equilibrium steady state. The current is then instantaneously decreased, such that the final stationary state resides either still in the moving regime, or in the pinned Bragg glass phase. The ensuing non-equilibrium relaxation kinetics of the vortices is studied in detail by measuring the mean flux line gyration radius and the two-time transverse height autocorrelation function. The latter allows us to investigate the physical aging properties for quenches from the moving into the glassy phase, and to compare with non-equilibrium relaxation features obtained with different initial configurations. Research supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-FG02-09ER46613.

  12. Mechanism of highly efficient adsorption of 2-chlorophenol onto ultrasonic graphene materials: Comparison and equilibrium.

    PubMed

    Soltani, Tayyebeh; Lee, Byeong-Kyu

    2016-11-01

    The deficiencies of the recently reported improved Hummers method for the synthesis of graphene oxide (GO), such as high reaction temperature (60°C) and long reaction time (10h), were successfully solved using a low-intensity ultrasonic bath for 30min at 40°C. Furthermore, compared to its conventional synthesis counterpart, a facile and fast, one-step ultrasonic method that excluded hydrazine hydrate was developed to synthesize reduced GO (rGO) from graphite (10min, 50°C) in the presence of hydrazine hydrate (rGO-C, 12h, 90°C). The adsorption characteristics of 2-chlorophenol (2-CP) from an aqueous solution were investigated using rGOs and GOs prepared by ultrasonic (rGO-Us/GO-Us) and conventional (rGO-C/GO-C) methods. Whereas 2-CP was completely removed with rGO-Us after 50min, only 40% of 2-CP was eliminated with rGO-C. The maximum adsorption capacity of 2-CP calculated by the Langmuir model onto rGO-Us (208.67mg/g) was much higher than that onto GO-Us (134.49mg/g). In addition, the ultrasonic graphene adsorption capacities were much higher than the corresponding values of rGO-C (49.9mg/g) and GO-C (32.06mg/g). The enhanced adsorption for rGO-Us and GO-Us is attributed to their greater surface areas, excellent oxygenated groups for GO-Us and superior π-electron-rich matrix for rGO-Us, compared to other adsorbents. The adsorption of 2-CP on the rGO materials increased with increasing solution pH to a maximum around its pKa (pKa=8.85), while the adsorption for the GO materials increased with decreasing solution pH. The adsorption mechanism proceeded via hydrogen bonding in neutral and acidic media, but via π-π electron donor-accepter (EDA) interactions between 2-CP and graphene materials in basic medium. The FTIR spectrum of GO-Us after adsorption indicates that the position and intensity of many peaks of GO-Us were affected due to the adsorption of different 2-CP groups at different pHs. PMID:27474817

  13. A comparative examination of the adsorption mechanism of an anionic textile dye (RBY 3GL) onto the powdered activated carbon (PAC) using various the isotherm models and kinetics equations with linear and non-linear methods

    NASA Astrophysics Data System (ADS)

    Açıkyıldız, Metin; Gürses, Ahmet; Güneş, Kübra; Yalvaç, Duygu

    2015-11-01

    The present study was designed to compare the linear and non-linear methods used to check the compliance of the experimental data corresponding to the isotherm models (Langmuir, Freundlich, and Redlich-Peterson) and kinetics equations (pseudo-first order and pseudo-second order). In this context, adsorption experiments were carried out to remove an anionic dye, Remazol Brillant Yellow 3GL (RBY), from its aqueous solutions using a commercial activated carbon as a sorbent. The effects of contact time, initial RBY concentration, and temperature onto adsorbed amount were investigated. The amount of dye adsorbed increased with increased adsorption time and the adsorption equilibrium was attained after 240 min. The amount of dye adsorbed enhanced with increased temperature, suggesting that the adsorption process is endothermic. The experimental data was analyzed using the Langmuir, Freundlich, and Redlich-Peterson isotherm equations in order to predict adsorption isotherm. It was determined that the isotherm data were fitted to the Langmuir and Redlich-Peterson isotherms. The adsorption process was also found to follow a pseudo second-order kinetic model. According to the kinetic and isotherm data, it was found that the determination coefficients obtained from linear method were higher than those obtained from non-linear method.

  14. Modeling of arsenic adsorption kinetics of synthetic and contaminated groundwater on natural laterite.

    PubMed

    Maiti, Abhijit; Sharma, Himanshu; Basu, Jayanta Kumar; De, Sirshendu

    2009-12-30

    A simple shrinking core model is applied to predict the adsorption kinetics of arsenite and arsenate species onto natural laterite (NL) in a stirred tank adsorber. The proposed model is a two-resistance model, in which two unknown parameters, external mass transfer coefficient (K(f)) and pore diffusion coefficient (D(e)) are estimated by comparing the simulation concentration profile with the experimental data using a nonlinear optimization technique. The model is applied under various operating conditions, e.g., initial arsenic concentration, NL dose, NL particle size, temperature, stirring speed, etc. Estimated values of D(e) and K(f) are found to be in the range of 2.2-2.6 x 10(-11)m(2)/s and 1.0-1.4 x 10(-6)m/s at 305K for different operating conditions, respectively. D(e) and K(f) values are found to be increasing with temperature and stirrer speed, respectively. Calculated values of Biot numbers indicate that both external mass transfer and pore diffusion are important during the adsorption. The model is also applied satisfactorily to predict the arsenic adsorption kinetics of arsenic contaminated groundwater-NL system and can be used to scale up. PMID:19717233

  15. Adsorption-uptake-metabolism kinetic model on the removal of BDE-47 by a Chlorella isolate.

    PubMed

    Deng, Dan; Tam, Nora F Y

    2016-05-01

    Polybrominated diphenyl ethers (PBDEs) are persistent and toxic organic pollutants, causing hazardous to ecosystems and human health but are difficult to remove from contaminated environments. The mechanism and kinetics of a Chlorella isolate to remove BDE-47 were investigated. This species isolated from the influent of wastewater treatment plants in Hong Kong was PBDE tolerant. More than 80% of BDE-47 was removed in short- and long-term experiments lasting 1 h and 7 days, respectively. The dominant removal process was adsorption on cell surfaces, with 73% of the spiked BDE-47 removed within five minutes of exposure. As the exposure prolonged, the adsorption became saturated. BDE-47 on cell surfaces was then gradually taken up into cells. At the end of the 7-day exposure, 17% of the spiked BDE-47 was within cells, while 27% was metabolized. Four metabolites, including BDE-28, 6-OH- and 5-OH-BDE-47, and 6-MeO-BDE-47, were produced from the debromination, hydroxylation and methoxylation of BDE-47. The removal kinetics of BDE-47 by freshwater microalgae could be explained by the multi-compartmental adsorption-uptake-metabolism model developed in this study. PMID:26854698

  16. Arsenate adsorption and desorption kinetics on a Fe(III)-modified montmorillonite.

    PubMed

    Luengo, Carina; Puccia, Virginia; Avena, Marcelo

    2011-02-28

    The adsorption-desorption kinetics of arsenate on a Fe(III)-modified montmorillonite (Fe-M) was studied at different arsenate concentrations, pH and stirring rates. The synthesized solid was a porous sample with Fe(III) present as a mix of monomeric and polymeric Fe(III) species in the interlayer and on the external surface. Adsorption took place in a two-step mechanism, with an initial fast binding of arsenate to Fe(III) species at the external surface (half-lives of 1 min or shorter) followed by a slower binding to less accessible Fe(III) species in pores and the interlayer (half-lives of around 1 h). Desorption kinetics also reflected the presence of externally and internally adsorbed arsenate. At pH 6 the maximum adsorbed arsenate was 52 μmol/g, a value that is low as compared to adsorption on ferrihydrite (700 μmol/g) and goethite (192-220 μmol/g). However, since the Fe(III) content of Fe-M is much lower than that of ferrihydrite and goethite, Fe(III) species in Fe-M are more efficient in binding arsenate than in ferrihydrite or goethite (one As atom is attached every 8.95 iron atoms). This high binding efficiency indicates that Fe(III) species are well spread on montmorillonite, forming small oligomeric species or surface clusters containing just a few iron atoms. PMID:21242027

  17. Chemistry of inorganic arsenic in soils: kinetics of arsenic adsorption-desorption.

    PubMed

    Smith, E; Naidu, R

    2009-04-01

    The influence of ionic strength, index cations and competing anions on arsenate (As(V)) adsorption-desorption kinetics was studied in an Alfisol soil. A flow-through reactor system similar to that developed by Carski and Sparks (Soil Sci Soc Am J 49:1114-1116, 1985) was constructed for the experiments. Arsenate adsorption kinetics for all the treatments were initially fast with 58-91% of As(V) adsorbed in the first 15 min. Beyond 15 min, As(V) adsorption continued at a slower rate for the observation period of the experiments. Changes in the solution composition had differing effects on the cumulative amount of As(V) adsorbed by the soil. Ionic strength and different index cations had little effect on the amount of As(V) adsorbed, while the presence of phosphate decreased the amount of As(V) adsorbed from 169 to 89 and 177 to 115 g As(V) microg(-1) in 0.03 M sodium nitrate and 0.01 M calcium nitrate, respectively. Considerably less As(V) was desorbed than was adsorbed, with only between 2 to 17% of the adsorbed As(V) desorbed. The presence of phosphate increased the amount of As(V) desorbed by 17%, but other changes in the solution ionic strength or index cation had little effect on the amount of As(V) desorbed. PMID:19101807

  18. The association-dissociation behavior of the ApoE proteins: kinetic and equilibrium studies

    PubMed Central

    Garai, Kanchan; Frieden, Carl

    2010-01-01

    The apolipoprotein E family consists of three major protein isoforms: apolipoprotein E4 (ApoE4), ApoE3 and ApoE2. The isoforms, which contain 299 residues, differ only by single amino acid changes but of the three only ApoE4 is a risk factor for Alzheimer’s Disease. At μM concentrations lipid-free ApoE exists predominantly as tetramers. In more dilute solutions, lower molecular weight species predominate. Using Fluorescence Correlation Spectroscopy (FCS), intermolecular Fluorescence Resonance Energy Transfer (FRET) and sedimentation methods we find that the association-dissociation reaction of ApoE can be modeled with a monomer-dimer-tetramer process. Equilibrium constants have been determined from the sedimentation data while the individual rate constants for association and dissociation are determined by measuring the kinetics of dissociation of ApoE and are in agreement with the equilibrium constants. Dissociation kinetics as measured by intermolecular FRET show two phases reflecting the dissociation of tetramer to dimer and of dimer to monomer with dissociation from tetramer to dimer being more rapid than the dimer to monomer dissociation. The rate constants differ for the different ApoE isoforms showing that the association-dissociation process is isoforms specific. Strikingly, the association rate constants are almost two orders of magnitude slower than expected for a diffusion controlled process. Dissociation kinetics were also monitored by tryptophan fluorescence in presence of acrylamide and the data found to be consistent with the monomer-dimer-tetramer model. The approach combining multiple methods establishes the reaction scheme of ApoE self-association. PMID:20923231

  19. Relation of organic contaminant equilibrium sorption and kinetic uptake in plants

    USGS Publications Warehouse

    Li, H.; Sheng, G.; Chiou, C.T.; Xu, O.

    2005-01-01

    Plant uptake is one of the environmental processes that influence contaminant fate. Understanding the magnitude and rate of plant uptake is critical to assessing potential crop contamination and the development of phytoremediation technologies. We determined (1) the partition-dominated equilibrium sorption of lindane (LDN) and hexachlorobenzene (HCB) by roots and shoots of wheat seedlings, (2) the kinetic uptake of LDN and HCB by roots and shoots of wheat seedlings, (3) the kinetic uptake of HCB, tetrachloroethylene (PCE), and trichloroethylene (TCE) by roots and shoots of ryegrass seedlings, and (4) the lipid, carbohydrate, and water contents of the plants. Although the determined sorption and the plant composition together suggest the predominant role of plant lipids for the sorption of LDN and HCB, the predicted partition with lipids of LDN and HCB using the octanol-water partition coefficients is notably lower than the measured sorption, due presumably to underestimation of the plant lipid contents and to the fact that octanol is less effective as a partition medium than plant lipids. The equilibrium sorption or the estimated partition can be viewed as the kinetic uptake limits. The uptakes of LDN, PCE, and TCE from water at fixed concentrations increased with exposure time in approach to steady states. The uptake of HCB did not reach a plateau within the tested time because of its exceptionally high partition coefficient. In all of the cases, the observed uptakes were lower than their respective limits, due presumably to contaminant dissipation in and limited water transpiration by the plants. ?? 2005 American Chemical Society.

  20. Calcium-mediated DNA adsorption to yeast cells and kinetics of cell transformation by electroporation.

    PubMed Central

    Neumann, E; Kakorin, S; Tsoneva, I; Nikolova, B; Tomov, T

    1996-01-01

    Detailed kinetic data suggest that the direct transfer of plasmid DNA (YEp 351, 5.6 kbp, supercoiled, Mr approximately 3.5 x 10(6)) by membrane electroporation of yeast cells (Saccharomyces cerevisiae, strain AH 215) is mainly due to electrodiffusive processes. The rate-limiting step for the cell transformation, however, is a bimolecular DNA-binding interaction in the cell interior. Both the adsorption of DNA, directly measured with [32P]dCTP DNA, and the number of transformants are collinearly enhanced with increasing total concentrations [Dt] and [Cat] of DNA and of calcium, respectively. At [Cat] = 1 mM, the half-saturation or equilibrium constant is KD = 15 +/- 1 nM at 293 K (20 degrees C). The optimal transformation frequency is TFopt = 4.1 +/- 0.4 X 10(-5) if a single exponential pulse of initial field strength E0 = 4 kV cm-1 and decay time constant tauE = 45 ms is applied at [Dt] = 2.7 nM and 10(8) cells in 0.1 ml. The dependence of TF on [Cat] yields the equilibrium constants KCazero = 1.8 +/- 0.2 mM (in the absence of DNA) and K'Ca (at 2.7 nM DNA), comparable with and derived from electrophoresis data. In yeast cells, too, the appearance of a DNA molecule in its whole length in the cell interior is clearly an after-field event. At Eo = 4.0 kV cm-1 and T = 293 K, the flow coefficient of DNA through the porous membrane patches is Kto = 7.0 +/- 0.7 x 10(3)S-1 and the electrodiffusion of DNA is approximately 10 times more effective than simple diffusion: D/D0 approximately 10.3. The mean radius of these pores is rp = 0.39 +/- 0.05 nm, and the mean number of pores per cell (of size ø approximately 5.5 microns) is Np = 2.2 +/- 0.2 x 10(4). The maximal membrane area that is involved in the electrodiffusive penetration of adsorbed DNA into the outer surface of the electroporated cell membrane patches is only 0.023% of the total cell surface. The surface penetration is followed either by additional electrodiffusive or by passive (after-field) diffusive

  1. Kinetic and isotherms studies of phosphorus adsorption onto natural riparian wetland sediments: linear and non-linear methods.

    PubMed

    Zhang, Liang; Du, Chao; Du, Yun; Xu, Meng; Chen, Shijian; Liu, Hongbin

    2015-06-01

    Riparian wetlands provide critical functions for the improvement of surface water quality and storage of nutrients. Correspondingly, investigation of the adsorption characteristic and capacity of nutrients onto its sediments is benefit for utilizing and protecting the ecosystem services provided by riparian areas. The Langmuir and Freundlich isotherms and pseudo-second-order kinetic model were applied by using both linear least-squares and trial-and-error non-linear regression methods based on the batch experiments data. The results indicated that the transformations of non-linear isotherms to linear forms would affect the determination process significantly, but the non-linear regression method could prevent such errors. Non-linear Langmuir and Freundlich isotherms both fitted well with the phosphorus adsorption process (r (2) > 0.94). Moreover, the influences of temperature and ionic strength on the adsorption of phosphorus onto natural riparian wetland sediments were also studied. Higher temperatures were suitable for phosphorus uptake from aqueous solution using the present riparian wetland sediments. The adsorption capacity increased with the enhancement of ionic strength in agreement with the formation of inner-sphere complexes. The quick adsorption of phosphorus by the sediments mainly occurred within 10 min. The adsorption kinetic was well-fitted by pseudo-second-order kinetic model (r (2) > 0.99). The scanning electron microscopy (SEM) and Fourier transformation infrared (FT-IR) spectra analyses before and after phosphorus adsorption revealed the main adsorption mechanisms in the present system. PMID:26017810

  2. Nanoalginate based biosorbent for the removal of lead ions from aqueous solutions: Equilibrium and kinetic studies.

    PubMed

    Geetha, P; Latha, M S; Pillai, Saumya S; Koshy, Mathew

    2015-12-01

    Population explosion, depletion of water resources and prolonged droughts and floods due to climatic change lead to scarcity of pure and hygienic drinking water in most of the developing countries. Recently nanomaterials attained considerable attention as biosorbent for water purification purpose. However difficulties in removing polymeric surfactants and organic solvents used for nanoproduction and instability of the generated nanoparticles limit the scope of this approach in water cleanup. Here, we describe a novel green method for synthesizing polysaccharide nanoparticles in aqueous medium using honey as the capping agent. The highly stable alginate nanoparticles, characterized by various microscopic and spectroscopic techniques, exhibited a maximum uptake capacity of 333 mg g (-1)of Pb(II) ions from aqueous solution. The effect of various parameters such as initial metal concentration, pH, contact time, temperature and adsorbent dose on sorption process was investigated in batch mode technique. The maximum removal percentage was 94.81 at 45 °C and at pH 4.5 in 60 min contact time. The biosorption followed Freundlich model indicating multilayer adsorption and pseudo second order kinetics. The mechanism involves both surface adsorption and pore diffusion. The positive values of ΔH°, ∆S° and the negative value of ΔG°, confirmed the endothermic nature, randomness and spontaneity of biosorption process. PMID:26164724

  3. Sorption of methylene blue on treated agricultural adsorbents: equilibrium and kinetic studies

    NASA Astrophysics Data System (ADS)

    Tiwari, D. P.; Singh, S. K.; Sharma, Neetu

    2015-03-01

    Agricultural adsorbents are reported to have a remarkable performance for adsorption of dyes. In the present study, formaldehyde and sulphuric acid treated two agricultural adsorbents; potato peel and neem bark are used to adsorb methylene blue. On the whole, the acid-treated adsorbents are investigated to have high sorption efficiency compared to HCHO treated adsorbents. The percentage removal efficiency of H2SO4 treated potato peel (APP) increases considerably high from 75 to 100 % with increase in adsorbent dose, whereas the removal efficiency of H2SO4 treated neem bark (ANB) is found to be 98 % after adding the first dose only. The monolayer sorption behaviour of HCHO treated potato peel (PP) and APP is well defined by Langmuir, whereas the chemisorptions behaviour of HCHO treated neem bark (NB) and ANB is suggested by Temkin's isotherm model. The maximum adsorption capacity measured is highest in ANB followed by NB, PP and APP with the values of 1000, 90, 47.62 and 40.0 mg/g, respectively. The pseudo-second-order kinetic model fitted well with the observed data of all the four adsorbents. The results obtained reveal that NB and ANB both are good adsorbents compared to PP and APP.

  4. Kinetics, equilibrium and mechanism of Cd2+ removal from aqueous solution by mungbean husk.

    PubMed

    Saeed, Asma; Iqbal, Muhammad; Höll, Wolfgang H

    2009-09-15

    Mungbean husk (mbh), an agrowaste material, was investigated as a new sorbent for the removal of Cd(2+) from aqueous solution. The maximum removal of Cd(2+) was found to be 35.41 mg g(-1) at pH 5.0, 500 mg l(-1) initial Cd(2+) concentration and 5 g l(-1) sorbent dosage. Sorption kinetics and equilibria followed pseudo-second order and Langmuir isotherm equations. The mechanism of Cd(2+) adsorption on mbh was investigated by DRIFT spectroscopy, SEM-EDX analysis, and by monitoring the release of alkali and alkaline earth metal cations (Ca(2+), Mg(2+), K(+) and Na(+)) during the uptake of Cd(2+). DRIFT spectra of mbh showed the presence of amino, carboxyl, carbonyl and hydroxyl as the major functional groups involved in the sorption of Cd(2+). The sum of Ca(2+), Mg(2+), Na(+) and K(+) released from mbh with the quantitatively equivalent uptake of Cd(2+) indicated that the main mechanism of Cd(2+) adsorption was ion exchange. EDX analysis data supported the hypothesis of the involvement of ion exchange, as alkali and alkaline earth metal cations were noted to disappear in EDX spectrum of mbh after the uptake of Cd(2+). No significant loss in Cd(2+) sorption capacity of regenerated mbh was noted during reuse for five successive sorption-desorption cycles. PMID:19386413

  5. Adsorption kinetics of surfactant mixtures from micellar solutions as studied by maximum bubble pressure technique.

    PubMed

    Frese, Ch; Ruppert, S; Sugár, M; Schmidt-Lewerkühne, H; Wittern, K P; Fainerman, V B; Eggers, R; Miller, R

    2003-11-15

    The adsorption kinetics of micellar solutions of anionic/cationic SDS/DATB mixtures with mixing ratios of 10/1 and 10/2, respectively, are studied experimentally by means of the maximum bubble pressure method. For long adsorption times the adsorption of the highly surface-active anionic/cationic complex leads to a decrease of dynamic surface tension in comparison to the single SDS system. However, the situation is the reverse for short adsorption times where the dynamic surface tension is increased by addition of the cationic surfactant, although the overall concentration is increased. This unexpected behavior is explained by partial solubilization of free SDS molecules into micelles formed by SDS/DTAB complexes. With increasing overall concentration, when eventually the CMC of SDS is reached, the anionic/cationic complex itself is solubilized by SDS micelles. Finally, no complex micelles, which for their part can solubilize an excess of SDS molecules, are present. Hence, the dynamic properties of the solution are no longer influenced by the depletion of SDS molecules and the mixture tends to behave like a pure SDS solution. PMID:14583225

  6. Adsorption of malachite green by polyaniline-nickel ferrite magnetic nanocomposite: an isotherm and kinetic study

    NASA Astrophysics Data System (ADS)

    Patil, Manohar R.; Shrivastava, V. S.

    2014-11-01

    This work deals with the development of an efficient method for the removal of a MG (malachite green) dye from aqueous solution using polyaniline (PANI)-Nickel ferrite (NiFe2O4) magnetic nanocomposite. It is successfully synthesised in situ through self polymerisation of monomer aniline. Adsorptive removal studies are carried out for water soluble MG dye using PANI-Nickel ferrite magnetic nanocomposite in aqueous solution. Different parameters like dose of adsorbent, contact time, different initial conc., and pH have been studied to optimise reaction condition. It is concluded that adsorptive removal by PANI-Nickel ferrite magnetic nanocomposite is an efficient method for removing a MG dye from aqueous solution than work done before. The optimum conditions for the removal of the dye are initial concentration 30 mg l-1, adsorbent dose 5gm l-1 and pH 7. The adsorption capacity is found 4.09 mg g-1 at optimum condition 30 mg l-1. The adsorption followed pseudo-second-order kinetics. The experimental isotherm is found to fit with Langmuir equation. The prepared adsorbent is characterised by techniques SEM, EDS, XRD and VSM.

  7. Kinetics of CO adsorption on epitaxial (111)Cu on (111)Pd thin films

    SciTech Connect

    Oral, B.; Kothari, R.; Vook, R.W.

    1989-05-01

    CO adsorption has been studied on (111)Cu/Pd thin-film surfaces grown epitaxially on mica in UHV of base pressure 5 x 10/sup -11/ Torr. Auger electron spectroscopy investigations of the growth of Cu on (111)Pd films showed that layer growth occurred. The Kelvin probe, work function method was used to monitor the CO adsorption at 298 K as a function of Cu overlayer thickness. It was found that very thin Cu overlayers had a drastic effect on saturation CO coverage: one monolayer of copper reduced the saturation CO coverage by /similar to/95%. For the pure (111)Pd thin-film surface, the data showed that the rate of CO adsorption changes when the CO fractional coverage approaches /similar to/0.4. This result is most likely due to the previously reported change in CO superlattice structure that occurs with increasing coverage. The kinetic adsorption data for various bilayers were interpreted in terms of a first-order Kisliuk mobile precursor model.

  8. TICKET-UWM: a coupled kinetic, equilibrium, and transport screening model for metals in lakes.

    PubMed

    Farley, Kevin J; Carbonaro, Richard F; Fanelli, Christopher J; Costanzo, Robert; Rader, Kevin J; Di Toro, Dominic M

    2011-06-01

    The tableau input coupled kinetic equilibrium transport-unit world model (TICKET-UWM) has been developed as a screening model for assessing potential environmental risks associated with the release of metals into lakes. The model is based on a fully implicit, one-step solution algorithm that allows for simultaneous consideration of dissolved and particulate phase transport; metal complexation to organic matter and inorganic ligands; precipitation of metal hydroxides, carbonates, and sulfides; competitive interactions of metals and major cations with biotic ligands; a simplified description of biogeochemical cycling of organic carbon and sulfur; and dissolution kinetics for metal powders, massives, and other solid forms. Application of TICKET-UWM to a generalized lake in the Sudbury area of the Canadian Shield is presented to demonstrate the overall cycling of metals in lakes and the nonlinear effects of chemical speciation on metal responses. In addition, the model is used to calculate critical loads for metals, with acute toxicity of Daphnia magna as the final endpoint. Model results show that the critical loads for Cu, Ni, Pb, and Zn varied from 2.5 to 39.0 g metal/m(2) -year and were found to be one or more orders of magnitude higher than comparable loads for pesticides (lindane, 4,4'-DDT) and several polyaromatic hydrocarbon (PAH) compounds. In sensitivity calculations, critical metal-loading rates were found to vary significantly as a function of the hydraulic detention time, water hardness, and metal dissolution kinetic rates. PMID:21381089

  9. 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

  10. Dynamic behaviour of Cd2+ adsorption in equilibrium batch studies by CaCO3(-)-rich Corbicula fluminea shell.

    PubMed

    Ismail, Farhah Amalya; Aris, Ahmad Zaharin; Latif, Puziah Abdul

    2014-01-01

    This work presents the structural and adsorption properties of the CaCO3(-)-rich Corbicula fluminea shell as a natural and economic adsorbent to remove Cd ions from aqueous solutions under batch studies. Experiments were conducted with different contact times, various initial concentrations, initial solution pH and serial biosorbent dosage to examine the dynamic characterization of the adsorption and its influence on Cd uptake capacity. The characterization of the C. fluminea shell using SEM/EDX revealed that the adsorbent surface is mostly impregnated by small particles of potentially calcium salts. The dominant Cd adsorption mechanism is strongly pH and concentration dependent. A maximum Cd removal efficiency of 96.20% was obtained at pH 7 while the optimum adsorbent dosage was observed as 5 g/L. The Langmuir isotherm was discovered to be more suitable to represent the experimental equilibrium isotherm results with higher correlation coefficients (R(2) > 0.98) than Freundlich (R(2) < 0.97).The correlation coefficient values (p < 0.01) indicated the superiority of the Langmuir isotherm over the Freundlich isotherm. PMID:23771443

  11. Adsorption of heavy metal cations by Na-clinoptilolite: equilibrium and selectivity studies.

    PubMed

    Mihaly-Cozmuta, L; Mihaly-Cozmuta, A; Peter, A; Nicula, C; Tutu, H; Silipas, Dan; Indrea, Emil

    2014-05-01

    This paper summarizes the conclusions of experiments conducted on the adsorption of Cd(2+), Co(2+), Cu(2+), Mn(2+), Ni(2+), Pb(2+) and Zn(2+) onto zeolite. The focus of the experiments was to establish the influence of the initial pH of the contact solution as well as the selectivity of zeolite on the efficiency of the adsorption process. To this end, experimental adsorption isotherms were established for the pH values ranging from 1 to 4 by using the Na-form of clinoptilolite (particle size range 0.5-1 mm) as an adsorbent. Langmuir, Freundlich and Dubinin-Raduschkevich isotherm models were used to validate the experimental data and the Gibbs free energy was calculated based on the distribution coefficient. From the Langmuir model, correlations between the maximum adsorption capacity and selected physical-chemical parameters of the cations studied were established. The results of the experiments suggest that the selectivity of zeolite is strongly influenced by the pH of the contact solution, dehydration energy of cations, diffusion coefficient and the pH at which the precipitation of hydroxides occurs. PMID:24603029

  12. Process development for removal and recovery of cadmium from wastewater by a low-cost adsorbent: Adsorption rates and equilibrium studies

    SciTech Connect

    Periasamy, K.; Namasivayam, C. . Dept. of Environmental Sciences)

    1994-02-01

    Activated carbon prepared from peanut hulls (PHC), an agricultural waste by-product, has been used for the adsorption of Cd(II) from synthetic wastewater. The adsorption data fit better with the Freundlich adsorption isotherm. The applicability of the Lagergren kinetic model has also been investigated. An almost quantitative removal of 20 mg/L Cd(II) by 0.7 g of PHC/L of aqueous solution was observed in the pH range 3.5--9.5. A comparative study with a commercial granular activated carbon (CAC) showed that the adsorption capacity (K[sub f]) of PHC was 31 times larger than that of CAC.

  13. Equilibrium study of selected divalent d-electron metals adsorption on A-type zeolite.

    PubMed

    Majdan, Marek; Pikus, Stanisław; Kowalska-Ternes, Monika; Głdysz-Płaska, Agnieszka; Staszczuk, Piotr; Fuks, Leon; Skrzypek, Henryk

    2003-06-15

    The objective of the presented study was to investigate the adsorption of Cu, Co, Mn, Zn, Cd and Mn on A-type zeolite. The isotherms for adsorption of metals from their nitrates were registered. The following adsorption constants K of metals were found: 162,890, 124,260, 69,025, 16,035, 10,254, and 151 [M(-1)] for Cu, Co, Mn, Zn, Cd, and Ni, respectively, for the concentration range 10(-4)-10(-3) M. On the other hand, the investigation of pH influence on the distribution constants of metals showed that the adsorption of metals proceeds essentially through an ion-exchange process, surface hydrolysis, and surface complexation. The supplementary results from DRIFT, scanning electron microscopy, and X-ray diffraction methods confirmed the presumption about the possible connection between the electronic structure of divalent ions and their adsorption behavior, showing that ions with d5 and d10 configurations such as Mn2+, Zn2+, Cd2+, with much weaker hydrolytic properties than Cu2+ and Ni2+, strongly interact with the zeolite framework and therefore their affinity to the zeolite phase is much stronger when compared with that of the Ni2+ ion, but at the same time not as strong as the affinity of the Cu2+ ion, the latter forming a new phase during the interaction with zeolite framework. For Zn2+, during inspection of the correlation between the proton concentration H/Al and zinc concentration Zn/Al on the zeolite surface, the formation of the surface complex [triple bond]S-OZn(OH) was proposed. A correlation between the heterogeneity of proton concentrations H/Al on Me-zeolite surfaces and the hydrolysis constants pKh of Me2+ ions was found. PMID:16256612

  14. Species of dissolved Cu and Ni and their adsorption kinetics in turbid riverwater

    NASA Astrophysics Data System (ADS)

    Herzl, V. M. C.; Millward, G. E.; Wollast, R.; Achterberg, E. P.

    2003-01-01

    Time-dependent sorption experiments have been carried out under controlled laboratory conditions, using filtered river water and particles from the turbidity maximum zone (TMZ) of the Tamar Estuary (UK). Adsorptive cathodic stripping voltammetry (ACSV) was used to determine ACSV labile and total dissolved Cu and Ni, without prior sample handling and/or pre-concentration. The ACSV metal lability is theoretically defined and is dependent upon the α-coefficient ( αMAL) of the added ACSV ligand. The fraction of labile dissolved Cu in the river water was in the range 28-41% of the total, while labile Ni was 80-90% of the total dissolved Ni. After 24 h incubation with the particles, the concentration of total dissolved Cu was reduced to half the original value and involved the removal of 40% of labile Cu and 70% of the non-labile Cu. Removal of total dissolved Ni after 24 h ranged from 40 to 60% and the uptake kinetics were dominated by adsorption of labile Ni. The kinetics of adsorption for the different chemical forms of Cu and Ni were interpreted by assuming a first-order reversible reaction between the dissolved components and the particulate phase. The chemical response time for the removal of labile Cu was 1.1 and 0.5 h for non-labile Cu. The chemical response time for labile Ni was in a range from 0.7 to 0.3 h. The results are interpreted in terms of the role played by chemical kinetics in determining the phase transport of metals in the reactive zones of estuaries.

  15. Comparing equilibrium and kinetic protein unfolding using time-resolved electrospray-coupled ion mobility mass spectrometry.

    PubMed

    Liuni, Peter; Deng, Bin; Wilson, Derek J

    2015-10-21

    Protein unfolding intermediates are thought to play a critical role in conformational pathogenesis, acting as a 'gateway' to inactivation or pathogenic aggregation. Unfolding intermediates have long been studied either by populating partially-folded species at equilibrium using incresingly denaturing conditions, or by transiently populating 'kinetic' intermediates under fully denaturing conditions using a time-resolved approach (e.g. stopped-flow fluorescence). However, it is not clear that the folding intermediates populated under equilibrium conditions are comparable to intermediates transiently populated in kinetic experiments. In this work, we combine time-resolved electrospray (TRESI) with travelling wave Ion Mobility Spectrometry (IMS) for the first time to directly compare equilibrium and kinetic unfolding intermediates of cytochrome c. Our results show a high degree of correlation between all species populated under these substantially different regimes. PMID:26115375

  16. Dimension reduction of non-equilibrium plasma kinetic models using principal component analysis

    NASA Astrophysics Data System (ADS)

    Peerenboom, Kim; Parente, Alessandro; Kozák, Tomáš; Bogaerts, Annemie; Degrez, Gérard

    2015-04-01

    The chemical complexity of non-equilibrium plasmas poses a challenge for plasma modeling because of the computational load. This paper presents a dimension reduction method for such chemically complex plasmas based on principal component analysis (PCA). PCA is used to identify a low-dimensional manifold in chemical state space that is described by a small number of parameters: the principal components. Reduction is obtained since continuity equations only need to be solved for these principal components and not for all the species. Application of the presented method to a CO2 plasma model including state-to-state vibrational kinetics of CO2 and CO demonstrates the potential of the PCA method for dimension reduction. A manifold described by only two principal components is able to predict the CO2 to CO conversion at varying ionization degrees very accurately.

  17. Three model space experiments on chemical reactions. [Gibbs adsorption, equilibrium shift and electrodeposition

    NASA Technical Reports Server (NTRS)

    Grodzka, P.; Facemire, B.

    1977-01-01

    Three investigations conducted aboard Skylab IV and Apollo-Soyuz involved phenomena that are of interest to the biochemistry community. The formaldehyde clock reaction and the equilibrium shift reaction experiments conducted aboard Apollo Soyuz demonstrate the effect of low-g foams or air/liquid dispersions on reaction rate and chemical equilibrium. The electrodeposition reaction experiment conducted aboard Skylab IV demonstrate the effect of a low-g environment on an electrochemical displacement reaction. The implications of the three space experiments for various applications are considered.

  18. Folding mechanism of reduced cytochrome c: Equilibrium and kinetic properties in the presence of carbon monoxide

    PubMed Central

    Latypov, Ramil F.; Maki, Kosuke; Cheng, Hong; Luck, Stanley D.; Roder, Heinrich

    2008-01-01

    Despite close structural similarity, the ferric and ferrous forms of cytochrome c (cyt c) differ greatly in terms of their ligand binding properties, stability, folding and dynamics. The reduced heme iron binds diatomic ligands such as CO only under destabilizing conditions that promote weakening or disruption of the native methionine-iron linkage. This makes CO a useful conformational probe for detecting partially structured states that cannot be observed in the absence of endogenous ligands. Heme absorbance, circular dichroism and NMR were used to characterize the denaturant-induced unfolding equilibrium of Fe2+ cyt c in the presence and absence of CO. In addition to the native state (N), which does not bind CO, and the unfolded CO-complex (U-CO), a structurally distinct CO-bound form (M-CO) accumulates to high levels (~75% of the population) at intermediate guanidine hydrochloride concentrations. Comparison of the unfolding transition for different conformational probes reveals that M-CO is a compact state containing a native-like helical core and regions of local disorder in the segment containing the native Met80 ligand and adjacent loops. Kinetic measurements of CO binding and dissociation under native, partially denaturing and fully unfolded conditions indicate that a state, M, that is structurally analogous to M-CO is populated even in the absence of CO. The binding energy of the CO ligand lowers the free energy of this high-energy state to such an extent that it accumulates even under mildly denaturing equilibrium conditions. The thermodynamic and kinetic parameters obtained in this study provide a fully self-consistent description of the linked unfolding/CO-binding equilibria of reduced cyt c. PMID:18761351

  19. Shape transition of endotaxial islands growth from kinetically constrained to equilibrium regimes

    SciTech Connect

    Li, Zhi-Peng; Tok, Engsoon; Foo, Yonglim

    2013-09-01

    Graphical abstract: - Highlights: • All Fe{sub 13}Ge{sub 8} islands will grow into Ge(0 0 1) substrate at temperatures from 350 to 675 °C. • Shape transition occurred from kinetically constrained to equilibrium regime. • All endotaxial islands can be clarified into two types. • The mechanisms of endotaxial growth and shape transition have been rationalized. - Abstract: A comprehensive study of Fe grown on Ge(0 0 1) substrates has been conducted at elevated temperatures, ranging from 350 to 675 °C. All iron germinide islands, with the same Fe{sub 13}Ge{sub 8} phase, grow into the Ge substrate with the same epitaxial relationship. Shape transition occurs from small square islands (low temperatures), to elongated orthogonal islands or orthogonal nanowires (intermediate temperatures), and then finally to large square orthogonal islands (high temperatures). According to both transmission electron microscopy (TEM) and atomic force microscopy (AFM) investigations, all islands can be defined as either type-I or type-II. Type-I islands usually form at kinetically constrained growth regimes, like truncated pyramids. Type-II islands usually appear at equilibrium growth regimes forming a dome-like shape. Based on a simple semi-quantitative model, type-II islands have a lower total energy per volume than type-I, which is considered as the dominant mechanism for this type of shape transition. Moreover, this study not only elucidates details of endotaxial growth in the Fe–Ge system, but also suggests the possibility of controlled fabrication of temperature-dependent nanostructures, especially in materials with dissimilar crystal structures.

  20. Protein loading into porous CaCO3 microspheres: adsorption equilibrium and bioactivity retention.

    PubMed

    Balabushevich, N G; Lopez de Guerenu, A V; Feoktistova, N A; Volodkin, D

    2015-01-28

    Formulation of proteins into particulate form is a principal strategy to achieve controlled and targeted delivery, as well as to protect fragile protein molecules. Control over size, mechanical properties, and surface area (porosity) of particulate proteins has been successfully achieved by hard templating under mild conditions using porous CaCO3 microspheres. A crucial step in this approach, which determines protein content, is the loading of proteins into the CaCO3 microspheres. In this study, the adsorption of different proteins into the microspheres has been investigated. Proteins differing in characteristics such as molecular weight and charge have been employed: catalase (Cat), insulin (Ins), aprotinin (Apr), and protamine (Pro). Thermodynamics of adsorption equilibria have been studied, together with quantitative and qualitative analysis of protein loading and distribution in the microspheres. Protein interaction with the CaCO3 microspheres is not limited by the diffusion of protein molecules (protein dimensions are significantly smaller than microsphere pores) but is determined by the protein affinity for the microsphere surface. Cat and Ins bind much more strongly to the microspheres than Apr and Pro, which can be explained by electrostatic attractive forces. Protein binding/release and protein biological activity have been investigated as a function of pH. It is shown that pH variation during the adsorption process plays a principal role and defines not only the amount of protein adsorbed/released but also protein biological activity. Protein adsorption and microsphere elimination (by EDTA) do not affect protein bioactivity. In addition to applications for protein particle/capsule formulations, the findings of this study might help in understanding protein interactions with carbonate minerals such as calcium carbonate, which is used as a natural material for multiple applications. PMID:25493351

  1. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    SciTech Connect

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly; Kim, Young Jin; Jardine, Philip M; Watson, David B

    2007-01-01

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  2. Kinetic, Equilibrium and thermodynamic studies on the biosorption of Cd(II) from aqueous solutions by the leaf biomass of Calotropis procera - 'Sodom apple'

    NASA Astrophysics Data System (ADS)

    Chukwudumebi Overah, Loretta; Babalola, Oyebamiji.; Babarinde, Adesola; Oninla, Vincent; Olatunde, Abimbola

    2013-04-01

    The kinetics, equilibrium and thermodynamics of the biosorption of Cd (II) from aqueous solution by the leaf biomass of Calotropis procera popularly known in western Nigeria as 'bom bom' and generally known as Sodom apple were investigated at different experimental conditions. Optimum conditions of pH,contact time, biomass dosage, initial metal ion concentration and temperature were determined to be 5, 60 minutes, 110 mg, 0.3 mM and 27°C respectively. The maximum biosorption capacity was found to be 8.91 mg/g. The kinetic studies indicated that the biosorption process of the metal ion followed the pseudo-second-order and intra-particle diffusion models with an R-square value of 0.998 and 0.985 respectively. Equilibrium studies showed that the biosorption of Cd (II) is well represented by both Freundlich and Langmuir isotherms but the Langmuir model gave a better fit with an R-square value of 0.979,Langmuir constant, bm of 0.0080 and monolayer adsorption capacity, μm of 123.46. The calculated thermodynamic parameters (ΔG° -4.846 kJmol-1, ΔH° 10.60 kJmol-1 and ΔS° 0.052 kJK-1mol-1) showed that the biosorption of Cd (II)is feasible, spontaneous, endothermic and highly disordered in nature under the experimental conditions. Thesefindings indicate that the leaf of Calotropis procera could be employed in the removal of Cd (II) from industrial effluents. Key words: Calotropis procera, Cadmium, Adsorption isotherm.

  3. Equilibrium and Kinetics of Sin Nombre Hantavirus Binding at DAF/CD55 Functionalized Bead Surfaces

    PubMed Central

    Buranda, Tione; Swanson, Scarlett; Bondu, Virginie; Schaefer, Leah; Maclean, James; Mo, Zhenzhen; Wycoff, Keith; Belle, Archana; Hjelle, Brian

    2014-01-01

    Decay accelerating factor (DAF/CD55) is targeted by many pathogens for cell entry. It has been implicated as a co-receptor for hantaviruses. To examine the binding of hantaviruses to DAF, we describe the use of Protein G beads for binding human IgG Fc domain-functionalized DAF ((DAF)2-Fc). When mixed with Protein G beads the resulting DAF beads can be used as a generalizable platform for measuring kinetic and equilibrium binding constants of DAF binding targets. The hantavirus interaction has high affinity (24–30 nM; kon ~ 105 M−1s−1, koff ~ 0.0045 s−1). The bivalent (DAF)2-Fc/SNV data agree with hantavirus binding to DAF expressed on Tanoue B cells (Kd = 14.0 nM). Monovalent affinity interaction between SNV and recombinant DAF of 58.0 nM is determined from competition binding. This study serves a dual purpose of presenting a convenient and quantitative approach of measuring binding affinities between DAF and the many cognate viral and bacterial ligands and providing new data on the binding constant of DAF and Sin Nombre hantavirus. Knowledge of the equilibrium binding constant allows for the determination of the relative fractions of bound and free virus particles in cell entry assays. This is important for drug discovery assays for cell entry inhibitors. PMID:24618810

  4. Modelling Coral Biomineralization: Mixed Kinetic/Equilibrium Trace Element Coprecipitation Models Reveal new Complexity

    NASA Astrophysics Data System (ADS)

    Sinclair, D. J.; Risk, M.

    2004-12-01

    A mixed kinetic/equilibrium steady state model of trace-element co-precipitation in coral skeleton is presented, and tested against high spatial resolution observations of coral trace-element composition made previously by LA-ICP-MS. The model is implemented in PHREEQC, and simulates physicochemical precipitation from a small pocket of seawater which is isolated by the coral, and modified by enzyme exchange of 2 H+ for Ca2+. The model assumes that all aqueous trace-element species in the calcifying fluid are in full equilibrium and that selected trace element species compete kinetically for precipitation with the major aqueous species (Ca2+ for cation substituents and CO32- for anion substituents). No equilibrium is assumed for the CaCO3 skeleton. Carbon is supplied to the system by diffusion of CO2 into the high-pH calcifying fluid, and trace elements are continuously replenished through the addition of fresh seawater. The rate at which the coral operates the enzyme pump, and the rate at which it replenishes the seawater component are independent variables, and the steady state trace-element composition of the skeleton/calcifying fluid are evaluated over a 2D grid of variables spanning realistic rates of pumping and seawater influx. It is assumed that variations in the trace element composition of the coral skeleton are the result of shifts in the steady-state caused by changes to these variables. The results indicate an unexpected complexity in the response of the trace elements. First order predictions suggest that increasing the rate of calcification by increasing the enzyme pumping should result in a mutual dilution of most trace element species by pumped Ca2+ and diffused CO2. However, for high rates of pumping and low seawater replenishment, the model predicts a change in the trace-element response of the system as high CO32- concentrations drive calcification and deplete Ca2+. This added complexity makes rationalizing observations with models more difficult.

  5. Amaranth proteins foaming properties: adsorption kinetics and foam formation--part 1.

    PubMed

    Bolontrade, Agustín J; Scilingo, Adriana A; Añón, María C

    2013-05-01

    This work has focused on the study of the relationships between the structural changes in proteins of amaranth under different conditions of pH and ionic strength and the ability to form foam, also taking into consideration the kinetics of adsorption of proteins at the interface. Results showed that treatment at pH 2.0 significantly improves the foaming properties of amaranth proteins. The structural studies performed indicate that amaranth proteins at acidic pH are denatured, dissociated and undergo partial hydrolysis due to the existence of an endoprotease. They also present a lower content of β-sheet and random coil secondary structures. Diffusion-adsorption studies of proteins at the air:water interface allowed to determine that the acidic pH favors adsorption thereof (higher values of kdiff and ka) and reduces the need for a rearrangement (higher values of γr). The interfacial behavior of amaranth proteins is a direct consequence of the structural changes they undergo at acidic pH, changes that also were reflected on the increased foaming capacity (higher vo) thus forming more dense and homogeneous foams. The behavior of the soluble proteins as surfactants was not altered by the presence of protein aggregates and insoluble proteins. PMID:23384694

  6. Study of intradrystalline diffusion in zeolites communication 3. Kinetics of adsorption of trans-2-butene by NaA and NaMgA zeolites

    SciTech Connect

    Broddak, R.; Dubinin, M.M.; Falko, L.A.; Gorlov, V.A.; Kuhlmann, B.; Scholner, E.; Voloshchuk, A.M.

    1985-09-10

    This article studies the kinetics of adsorption of trans-2-butene by NaA zeolite with a varying crystal size, microcrystalline granulated NaA zeolite using granules of different sizes, and microcrystalline powdered Na/sub 8/Mg/sub 2/A zeolite. It is shown that the rate of adsorption is determined by the intracrystalline diffusion and that the effect of transfer in the transport pores and the final rate of dissipation of the heat of adsorption can be neglected. In adsorption of trans-2-butene by Na/sub 8/Mg/sub 2/A zeolite with a stepwise change in the pressure of the adsorbate, the kinetic curves are satisfactorily described by an internal diffusion equation for the kinetics of isothermal adsorption. The kinetics of adsorption were studied at 303 degrees K from the one-component vapor phase on a vacuum adsorption setup using quartz spring balance.

  7. 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

  8. CO2 adsorption using TiO2 composite polymeric membranes: A kinetic study.

    PubMed

    Hafeez, Sarah; Fan, X; Hussain, Arshad; Martín, C F

    2015-09-01

    CO2 is the main greenhouse gas which causes global climatic changes on larger scale. Many techniques have been utilised to capture CO2. Membrane gas separation is a fast growing CO2 capture technique, particularly gas separation by composite membranes. The separation of CO2 by a membrane is not just a process to physically sieve out of CO2 through the controlled membrane pore size. It mainly depends upon diffusion and solubility of gases, particularly for composite dense membranes. The blended components in composite membranes have a high capability to adsorb CO2. The adsorption kinetics of the gases may directly affect diffusion and solubility. In this study, we have investigated the adsorption behaviour of CO2 in pure and composite membranes to explore the complete understanding of diffusion and solubility of CO2 through membranes. Pure cellulose acetate (CA) and cellulose acetate-titania nanoparticle (CA-TiO2) composite membranes were fabricated and characterised using SEM and FTIR analysis. The results indicated that the blended CA-TiO2 membrane adsorbed more quantity of CO2 gas as compared to pure CA membrane. The high CO2 adsorption capacity may enhance the diffusion and solubility of CO2 in the CA-TiO2 composite membrane, which results in a better CO2 separation. The experimental data was modelled by Pseudo first-order, pseudo second order and intra particle diffusion models. According to correlation factor R(2), the Pseudo second order model was fitted well with experimental data. The intra particle diffusion model revealed that adsorption in dense membranes was not solely consisting of intra particle diffusion. PMID:26354705

  9. Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface

    USGS Publications Warehouse

    Power, L.E.; Arai, Y.; Sparks, D.L.

    2005-01-01

    Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (??-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L-1; pH 4.5 and 6.0; I = 0.01 M NaCl). Divalent Zn adsorption on synthetic ??-MnO 2 in the absence of As(III) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 ??M. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the ??-MnO 2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.

  10. A Unified Kinetics and Equilibrium Experiment: Rate Law, Activation Energy, and Equilibrium Constant for the Dissociation of Ferroin

    ERIC Educational Resources Information Center

    Sattar, Simeen

    2011-01-01

    Tris(1,10-phenanthroline)iron(II) is the basis of a suite of four experiments spanning 5 weeks. Students determine the rate law, activation energy, and equilibrium constant for the dissociation of the complex ion in acid solution and base dissociation constant for phenanthroline. The focus on one chemical system simplifies a daunting set of…

  11. Kinetic modeling of liquid-phase adsorption of Congo red dye using guava leaf-based activated carbon

    NASA Astrophysics Data System (ADS)

    Ojedokun, Adedamola Titi; Bello, Olugbenga Solomon

    2016-02-01

    Guava leaf, a waste material, was treated and activated to prepare adsorbent. The adsorbent was characterized using Scanning Electron Microscopy (SEM), Fourier Transform Infra Red (FTIR) and Energy-Dispersive X-ray (EDX) techniques. The carbonaceous adsorbent prepared from guava leaf had appreciable carbon content (86.84 %). The adsorption of Congo red dye onto guava leaf-based activated carbon (GLAC) was studied in this research. Experimental data were analyzed by four different model equations: Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms and it was found to fit Freundlich equation most. Adsorption rate constants were determined using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion model equations. The results clearly showed that the adsorption of CR dye onto GLAC followed pseudo-second-order kinetic model. Intraparticle diffusion was involved in the adsorption process. The mean energy of adsorption calculated from D-R isotherm confirmed the involvement of physical adsorption. Thermodynamic parameters were obtained and it was found that the adsorption of CR dye onto GLAC was an exothermic and spontaneous process at the temperatures under investigation. The maximum adsorption of CR dye by GLAC was found to be 47.62 mg/g. The study shows that GLAC is an effective adsorbent for the adsorption of CR dye from aqueous solution.

  12. 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

  13. Dynamic, equilibrium and human studies of adsorption of 201Tl by Prussian blue.

    PubMed

    Bhardwaj, Nidhi; Bhatnagar, Aseem; Pathak, D P; Singh, A K

    2006-03-01

    Prussian blue is the recommended but infrequently required antidote for radiocesium and thallium chemical poisoning. Conceivably, its most frequent application will be the decontamination of radiothallium (thallous chloride) from human body following myocardial scintigraphy. Dosage schedule and physicochemical parameters of interaction with radiothallium, however, need to be defined, as the known data is inadequate on this account. The objective of the present study is to create physiologically relevant and mathematically rigorous data on interaction of Prussian blue with Tl, to estimate dosage schedule of Prussian blue suitable for myocardial scintigraphy, and to perform preliminary human studies to evaluate the efficacy of the antidote in reducing the considerable radiation burden imparted by this radiotracer. Adsorption efficacy of Prussian blue for radiothallium was found to be more than 95% at basic (intestinal) pH even at low concentrations and in presence of the physiological cations, potassium and sodium. Isotherm analysis and derivations using Langmuir, Bajpai, Lagergreen, and Freundlich equations suggest a favorable adsorption of Tl on Prussian blue with qmax being 5,000 MBq g. Based on these findings and clinical considerations, particularly preferential gall bladder excretion and enterohepatic recycling of radioactive thallous chloride, a dose of 100 mg Prussian blue with every major meal for 3 days was considered adequate for the purpose. Our experience with the first two patients (serving as their own self-controls) suggests that Prussian blue therapy is a safe and effective method to significantly reduce radiation burden imparted by thallium myocardial scintigraphy. PMID:16505622

  14. Evaporation kinetics of laser heated silica in reactive and inert gases based on near-equilibrium dynamics.

    PubMed

    Elhadj, Selim; Matthews, Manyalibo J; Yang, Steven T; Cooke, Diane J

    2012-01-16

    Evaporation kinetics of fused silica were measured up to ≈3000K using CO(2) laser heating, while solid-gas phase chemistry of silica was assessed with hydrogen, air, and nitrogen. Enhanced evaporation in hydrogen was attributed to an additional reduction pathway, while oxidizing conditions pushed the reaction backwards. The observed mass transport limitations supported use of a near-equilibrium analysis for interpreting kinetic data. A semi-empirical model of the evaporation kinetics is derived that accounts for heating, gas chemistry and transport properties. The approach described should have application to materials laser processing, and in applications requiring knowledge of thermal decomposition chemistry under extreme temperatures. PMID:22274500

  15. 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.

  16. Kinetic Interpretation of Water Vapor Adsorption-Desorption Behavior of a Desiccant Rotor Showing S-shaped Adsorption Isotherm

    NASA Astrophysics Data System (ADS)

    Okamoto, Kumiko; Oshima, Kazunori; Takewaki, Takahiko; Kodama, Akio

    Adsorption / desorption behavior of water vapor in a desiccant rotor containing an iron aluminophosphate type zeolite FAM-Z01 (Functional Adsorbent Material Zeolite 01) was experimentally investigated for humidity swing. This rotor exhibited an S-shaped adsorption isotherm with its temperature dependence. Humidity swing, using a small piece of the rotor, could be usefully applied to interpret adsorption / desorption mechanisms by observing their rates. The most significant finding was that the adsorption / desorption rates in humidity swing could be described by the amount of adsorption, temperature and amplitude of the humidity swing, not by cycle time. Also, using the liner driving force (LDF) model, the overall mass transfer coefficient changed with the elapse of time or with the amount of adsorbed water. This implied that the LDF model, considering constant value of the overall mass transfer coefficient, was probably unable to explain the water adsorption / desorption behavior of FAM-Z01 desiccant rotor.

  17. Non-equilibrium passive sampling of hydrophobic organic contaminants in sediment pore-water: PCB exchange kinetics.

    PubMed

    Choi, Yongju; Wu, Yanwen; Luthy, Richard G; Kang, Seju

    2016-11-15

    This study investigates the isotropic exchange kinetics of PCBs for polyethylene (PE) passive samplers in quiescent sediment and develops a novel non-equilibrium passive sampling method using PE with multiple thicknesses. The release and uptake kinetics of PCBs in quiescent sediment are reproduced by a 1-D diffusion model using sediment diffusion parameters fitted with the data from actual measurements. From the sediment diffusion parameters observed for uptake and release kinetics, it is seen that the uptake kinetics are distinctly slower than the release kinetics, most likely because of the sorption-desorption hysteresis of PCBs in the study sediment. Despite the presence of the anisotropic PCB exchange kinetics, a performance reference compound (PRC)-based method, which is grounded on the assumption of isotropic exchange kinetics, estimated the freely dissolved aqueous concentrations (Cfree) of PCBs in sediment pore-water with less than a factor of two error for the study sediment. The novel method developed in this study using PE with multiple thicknesses also gives reasonable estimates of Cfree, demonstrating its potential as another option for non-equilibrium passive sampling for hydrophobic organic contaminants in sediment pore-water. PMID:27472074

  18. Adsorption of geosmin and 2-methylisoborneol onto powdered activated carbon at non-equilibrium conditions: influence of NOM and process modelling.

    PubMed

    Zoschke, Kristin; Engel, Christina; Börnick, Hilmar; Worch, Eckhard

    2011-10-01

    The adsorption of the taste and odour (T&O) compounds geosmin and 2-methylisoborneol (2-MIB) onto powdered activated carbon (PAC) has been studied under conditions which are typical for a drinking water treatment plant that uses reservoir water for drinking water production. The reservoir water as well as the pre-treated water (after flocculation) contains NOM that competes with the trace compounds for the adsorption sites on the carbon surface. Although the DOC concentrations in the reservoir water and in the pre-treated water were different, no differences in the competitive adsorption could be seen. By using two special characterisation methods for NOM (adsorption analysis, LC/OCD) it could be proved that flocculation removes only NOM fractions which are irrelevant for competitive adsorption. Different model approaches were applied to describe the competitive adsorption of the T&O compounds and NOM, the tracer model, the equivalent background compound model, and the simplified equivalent background compound model. All these models are equilibrium models but in practice the contact time in flow-through reactors is typically shorter than the time needed to establish the adsorption equilibrium. In this paper it is demonstrated that the established model approaches can be used to describe competitive adsorption of T&O compounds and NOM also under non-equilibrium conditions. The results of the model applications showed that in particular the simplified equivalent background compound model is a useful tool to determine the PAC dosage required to reduce the T&O compounds below the threshold concentration. PMID:21752419

  19. Label-Free Kinetics: Exploiting Functional Hemi-Equilibrium to Derive Rate Constants for Muscarinic Receptor Antagonists.

    PubMed

    Riddy, Darren M; Valant, Celine; Rueda, Patricia; Charman, William N; Sexton, Patrick M; Summers, Roger J; Christopoulos, Arthur; Langmead, Christopher J

    2015-10-01

    Drug receptor kinetics is as a key component in drug discovery, development, and efficacy; however, determining kinetic parameters has historically required direct radiolabeling or competition with a labeled tracer. Here we present a simple approach to determining the kinetics of competitive antagonists of G protein-coupled receptors by exploiting the phenomenon of hemi-equilibrium, the state of partial re-equilibration of agonist, antagonist, and receptor in some functional assays. Using functional [Ca(2+)]i-flux and extracellular kinases 1 and 2 phosphorylation assays that have short incubation times and therefore are prone to hemi-equilibrium "behaviors," we investigated a wide range of structurally and physicochemically distinct muscarinic acetylcholine receptor antagonists. Using a combined operational and hemi-equilibrium model of antagonism to both simulate and analyze data, we derived estimates of association and dissociation rates for the test set of antagonists, identifying both rapidly dissociating (4-DAMP, himbacine) and slowly dissociating (tiotropium, glycopyrrolate) ligands. The results demonstrate the importance of assay incubation time and the degree of receptor reserve in applying the analytical model. There was an excellent correlation between estimates of antagonist pK(B), k(on), and k(off) from functional assays and those determined by competition kinetics using whole-cell [(3)H]N-methylscopolamine binding, validating this approach as a rapid and simple method to functionally profile receptor kinetics of competitive antagonists in the absence of a labeled tracer. PMID:26243731

  20. Adsorption isotherms and kinetics of activated carbons produced from coals of different ranks.

    PubMed

    Purevsuren, B; Lin, Chin-Jung; Davaajav, Y; Ariunaa, A; Batbileg, S; Avid, B; Jargalmaa, S; Huang, Yu; Liou, Sofia Ya-Hsuan

    2015-01-01

    Activated carbons (ACs) from six coals, ranging from low-rank lignite brown coal to high-rank stone coal, were utilized as adsorbents to remove basic methylene blue (MB) from an aqueous solution. The surface properties of the obtained ACs were characterized via thermal analysis, N2 isothermal sorption, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Boehm titration. As coal rank decreased, an increase in the heterogeneity of the pore structures and abundance of oxygen-containing functional groups increased MB coverage on its surface. The equilibrium data fitted well with the Langmuir model, and adsorption capacity of MB ranged from 51.8 to 344.8 mg g⁻¹. Good correlation coefficients were obtained using the intra-particle diffusion model, indicating that the adsorption of MB onto ACs is diffusion controlled. The values of the effective diffusion coefficient ranged from 0.61 × 10⁻¹⁰ to 7.1 × 10⁻¹⁰ m² s⁻¹, indicating that ACs from lower-rank coals have higher effective diffusivities. Among all the ACs obtained from selected coals, the AC from low-rank lignite brown coal was the most effective in removing MB from an aqueous solution. PMID:25909729

  1. 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

  2. Effect of the porous structure of activated carbon on the adsorption kinetics of gold(I) cyanide complex

    NASA Astrophysics Data System (ADS)

    Ibragimova, P. I.; Grebennikov, S. F.; Gur'yanov, V. V.; Fedyukevich, V. A.; Vorob'ev-Desyatovskii, N. V.

    2014-06-01

    The effect the porous structure of activated carbons obtained from furfural and coconut shells has on the kinetics of [Au(CN)2]- ion adsorption is studied. Effective diffusion coefficients for [Au(CN)2]- anions in transport and adsorbing pores and mass transfer coefficients in a transport system of the pores and in microporous zones are calculated using the statistical moments of the kinetic curve.

  3. Removal of phenol from aqueous solutions by adsorption.

    PubMed

    Roostaei, Nadia; Tezel, F Handan

    2004-02-01

    Experiments have been conducted to examine the liquid-phase adsorption of phenol from water by silica gel, HiSiv 3000, activated alumina, activated carbon, Filtrasorb-400, and HiSiv 1000. Experiments were carried out for the analysis of adsorption equilibrium capacities and kinetics. The adsorption isotherm model of the Langmuir-Freundlich type was the best to describe adsorption equilibrium data for phenol for the adsorbents studied. Results of kinetic experiments indicated that HiSiv 1000 had the highest rate of adsorption among the adsorbents studied and therefore more detailed studies were carried out with this adsorbent. The influence of particle size, temperature, and thermal regeneration on adsorption of phenol by HiSiv 1000 was evaluated. From particle size experiments it appeared that adsorption capacity of HiSiv 1000 did not change by changing the particle size, but the rate of adsorption decreased considerably by increasing the particle size. The effect of temperature on adsorption was studied by determining equilibrium isotherms for HiSiv 1000 at 25, 40, and 55 degrees C. The results showed that adsorption capacity decreased with increasing temperature. Thermal regeneration of HiSiv 1000 was performed at 360 degrees C. It was observed that adsorption capacity of HiSiv 1000 did not change after 14 regeneration cycles. Equilibrium experiments showed that the adsorption capacities of activated carbon and Filtrasorb-400 were several times higher than that of HiSiv 1000. PMID:15160741

  4. Biosorption of arsenic from groundwater using Vallisneria gigantea plants. Kinetics, equilibrium and photophysical considerations.

    PubMed

    Iriel, Analia; Lagorio, M Gabriela; Fernández Cirelli, Alicia

    2015-11-01

    Arsenic (V) uptake from groundwater by using Vallisneria gigantea plants was studied using batch experiments. Reflectance and fluorescence of intact plants were investigated and changes in photophysical properties following arsenic absorption were reported. Good correlations have been found between arsenic concentration in groundwater and parameters derived from reflectance and fluorescence measurements. This system reached its equilibrium after seven days when the removal quantities were strongly dependent on the initial arsenic concentration. Interestingly, Vallisneria plants were able to accumulate from 100 to 600 mg As kg(-1) in roots and fronds although the translocation factors were low (0.6-1.6). Kinetic data for biosorption process followed a first-order law. At low arsenic concentrations the uptake in plants was governed by diffusion aspects. Langmuir, Freundlich and Dubinin-Radushkevich models were applied and results demonstrated that arsenic uptake was better described by the Langmuir model. As a final remark we concluded that a plant of this species should be able to remove 1mg As per week. PMID:26143400

  5. Modeling of methane and ethane hydrate formation kinetics based on non-equilibrium thermodynamics

    NASA Astrophysics Data System (ADS)

    Mottahedin, Mona; Varaminian, Farshad; Mafakheri, Kaveh

    2011-05-01

    In this study, experimental data of the kinetics of methane and ethane hydrate formation at constant volume were collected. The experiments were carried out in a batch reactor at different temperatures and pressures. The property of chemical affinity was used in the modeling of hydrate formation rate in a constant volume process. In this model a macroscopic driving force was defined which only needed the initial (experimental condition, temperature, and pressure) and final conditions (equilibrium conditions); thus, this model did not have the limitations of microscopic models, such as heat and mass transfer coefficients or population of particles, which may differ for each experiment. The experiments were carried out at temperatures 273, 274, 275.5, and 276 K for methane and 272, 273, 274, and 275 K for ethane with different initial pressures. The parameters of the model, Ar and tK , were obtained for each experiment, and the results show that the parameter of for each gas has a constant value. Subsequently, parameters of the model were used to predict experimental data and the variation of pressures with time. The results indicated that this model can well predict constant volume experimental data for crystals I hydrate former.

  6. Liquid phase adsorptions of Rhodamine B dye onto raw and chitosan supported mesoporous adsorbents: isotherms and kinetics studies

    NASA Astrophysics Data System (ADS)

    Inyinbor, A. A.; Adekola, F. A.; Olatunji, G. A.

    2016-04-01

    Irvingia gabonensis endocarp waste was charred (DNc) and subsequently coated with chitosan (CCDNc). Physicochemical characteristics of the two adsorbents were established, while Fourier transform infrared (FTIR), Scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) surface area methods were further employed for characterization. Efficiencies of the prepared adsorbents in the uptake of Rhodamine B (RhB) from aqueous effluent were investigated and adsorption data were tested using four isotherms and four kinetics models. The BET surface areas of the prepared adsorbent were 0.0092 and 4.99 m2/g for DNc and CCDNc, respectively, and maximum adsorption was recorded at pH between 3 and 4, respectively. While monolayer adsorption dominates the uptake of RhB onto DNc, uptake of RhB onto CCDNc was onto heterogeneous surface. The maximum monolayer adsorption capacities (q max) obtained from the Langmuir equation are 52.90 and 217.39 mg/g for DNc and CCDNc, respectively. Pseudo second order and Elovich kinetic models well described the kinetics of the two adsorption processes. The mean sorption energy (E) calculated from the D-R model and desorption efficiencies suggests that while the uptake of RhB onto DNc was physical in nature, for RhB-CCDNc system chemisorption dominates.

  7. 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

  8. A two-dimensional adsorption kinetic model for thermal hysteresis activity in antifreeze proteins.

    PubMed

    Li, Q Z; Yeh, Y; Liu, J J; Feeney, R E; Krishnan, V V

    2006-05-28

    Antifreeze proteins (AFPs) and antifreeze glycoproteins (AFGPs), collectively abbreviated as AF(G)Ps, are synthesized by various organisms to enable their cells to survive in subzero environments. Although the AF(G)Ps are markedly diverse in structure, they all function by adsorbing to the surface of embryonic ice crystals to inhibit their growth. This adsorption results in a freezing temperature depression without an appreciable change in the melting temperature. The difference between the melting and freezing temperatures, termed thermal hysteresis (TH), is used to detect and quantify the antifreeze activity. Insights from crystallographic structures of a number of AFPs have led to a good understanding of the ice-protein interaction features. Computational studies have focused either on verifying a specific model of AFP-ice interaction or on understanding the protein-induced changes in the ice crystal morphology. In order to explain the origin of TH, we propose a novel two-dimensional adsorption kinetic model between AFPs and ice crystal surfaces. The validity of the model has been demonstrated by reproducing the TH curve on two different beta-helical AFPs upon increasing the protein concentration. In particular, this model is able to accommodate the change in the TH behavior observed experimentally when the size of the AFPs is increased systematically. Our results suggest that in addition to the specificity of the AFPs for the ice, the coverage of the AFPs on the ice surface is an equally necessary condition for their TH activity. PMID:16774359

  9. CO{sub 2} adsorption: Experimental investigation with kinetics verification and CFD reactor model validation

    SciTech Connect

    Breault, Ronald W,; Huckaby, Ernest D.; Shadle, Lawrence J; Spenik, James L.

    2013-01-01

    The National Energy Technology Laboratory is investigating a new process for CO{sub 2} capture from large sources such as utility power generation facilities as an alternative to liquid amine based absorption processes. Many, but not all of these advanced dry processes are based upon sorbents composed of supported polyamines. In this analysis, experiments have been conducted in a small facility at different temperatures and compared to CFD reactor predictions using kinetics obtained from TGA tests. This particular investigation compares the predicted performance and the experimental performance of one of these new class of sorbents in a fluidized bed reactor. In the experiment, the sorbent absorbs CO{sub 2} from simulated flue gas in a riser reactor, separates the carbonated particles from the de-carbonated flue gas in a cyclone and then regenerates the sorbent, creating a concentrated stream of pure CO{sub 2} for sequestration. In this work, experimental measurements of adsorption are compared to predictions from a 3-dimensional non-isothermal reacting multiphase flow model. The effects of the gas flow rate and reactor temperature are explored. It is shown that the time duration for CO{sub 2} adsorption decreased for an increase in the gas flow. The details of the experimental facility and the model as well as the comparative analysis between the data and the simulation results are discussed.

  10. Adsorption kinetics of random copolymers with tunable monomer sequences onto flat surfaces

    NASA Astrophysics Data System (ADS)

    Jhon, Young; Semler, James; Szleifer, Igal; Genzer, Jan

    2007-03-01

    We report on the adsorption kinetics of heteropolymers with adjustable monomer sequences (HAMS) on flat substrates. Poly(styrene-co-4-bromostyrene) (PBrxS) HAMS, where x denotes the mole fraction of 4-bromostyrene (4-BrS), have been prepared by brominating parent polystyrene chains. By adjusting the solvent quality during the bromination reaction a series of PBrxS HAMS has been prepared that posses random (good solvent) or random-blocky (poor solvent) distribution of 4-BrS units. We studied the adsorption of PBrxS HAMS from various solvents onto flat silica surfaces, where the 4-BrS units possess strong affinity towards silica while the interaction between styrene and the surface is nearly athermal. For a given solvent, the amount of PBrxS HAMS adsorbed onto the surface increases with increasing the 4-BrS content and the blockiness in the monomer distribution. Concurrently, the amount of PBrxS HAMS on the substrate also increases with decreasing the quality of the solvent from which the copolymer is adsorbed.

  11. Kinetic-MHD hybrid equilibrium model using a Monte-Carlo calculation of runaway electron distribution function

    NASA Astrophysics Data System (ADS)

    Matsuyama, Akinobu; Aiba, Nobuyuki; Yagi, Masatoshi

    2015-11-01

    An axisymmetric MHD equilibrium model is studied to allow the inclusion of both beam inertia and energy spectrum for runaway electron beam. Following kinetic-MHD hybrid approach, we evaluate the RE beam current from the integrals of the RE distribution function. The distribution function is here evaluated by a relativistic guiding-center trace code ETC-Rel, where we have implemented the effects of collisions, radiations, and exponential growth into the code. Because to directly treat the Dreicer mechanism in particle simulations is time consuming, the primary RE source is modeled by a Monte-Carlo weighing scheme taking into account the instantaneous generation rate. This paper applies ETC-Rel to the parametric study of the MHD equilibrium with different RE beam parameters. Kinetic effects on the MHD equilibrium appears, e.g., as enhanced Shafranov shifts due to the inertia of highly relativistic electrons. A kinetic modification to the equilibrium becomes significant if the contribution of the beam inertia - being increased with the total electron mass of multi-MeV RE populations - becomes large enough to affect the radial force balance. This work was supported in part by MEXT KAKENHI Grant No. 23561009 and 26820404.

  12. Comparison of Kinetic and Equilibrium Reaction Models inSimulating the Behavior of Gas Hydrates in Porous Media

    SciTech Connect

    Kowalsky, Michael B.; Moridis, George J.

    2006-05-12

    In this study we compare the use of kinetic and equilibrium reaction models in the simulation of gas (methane) hydrates in porous media. Our objective is to evaluate through numerical simulation the importance of employing kinetic versus equilibrium reaction models for predicting the response of hydrate-bearing systems to external stimuli, such as changes in pressure and temperature. Specifically, we (1) analyze and compare the responses simulated using both reaction models for production in various geological settings and for the case of depressurization in a core during extraction; and (2) examine the sensitivity to factors such as initial hydrate saturation, hydrate reaction surface area, and numerical discretization. We find that for systems undergoing thermal stimulation and depressurization, the calculated responses for both reaction models are remarkably similar, though some differences are observed at early times. Given these observations, and since the computational demands for the kinetic reaction model far exceed those for the equilibrium reaction model, the use of the equilibrium reaction model often appears to be justified and preferred for simulating the behavior of gas hydrates.

  13. Reconciling kinetic and equilibrium observations of iron(III) solubility in aqueous solutions with a polymer-based model

    NASA Astrophysics Data System (ADS)

    Rose, Andrew L.; David Waite, T.

    2007-12-01

    Due to hydrolysis reactions, iron(III) forms oxyhydroxide precipitates in natural waters that minimise its availability to living organisms. Thermodynamic studies have established equilibrium concentrations of dissolved iron at various pH values, however these studies offer no insight into the kinetics of iron(III) polymerisation and subsequent precipitation. In recent work, the kinetics of iron(III) precipitation and dissolution of the precipitate have been investigated, but there are apparent discrepancies between the equilibrium solubility of iron(III) calculated from the kinetic parameters and its solubility measured by separation of the solid and dissolved phases at equilibrium. In this work, we reconcile kinetic and thermodynamic measurements using a polymer-based mechanistic model of the processes responsible for iron(III) precipitation in aqueous solutions based on a variety of previously published experimental data. This model is used to explain the existence of a solubility limit, including the effect of precipitate ageing on its solubility. We suggest that the model provides a unified approach for examining aqueous systems containing dissolved, solid-phase and surface species.

  14. Cempedak durian as a potential biosorbent for the removal of Brilliant Green dye from aqueous solution: equilibrium, thermodynamics and kinetics studies.

    PubMed

    Dahri, Muhammad Khairud; Lim, Linda B L; Mei, Chan Chin

    2015-08-01

    Cempedak durian peel (CDP) was used to remove Brilliant Green (BG) dye from aqueous solution. The adsorption of BG onto CDP was studied as functions of contact time, pH, temperature, ionic strength and initial concentration. In order to understand the adsorption process and its mechanisms, adsorption isotherm and kinetics models were used. The experiments were done under optimized 2-h contact time and ambient pH. Adsorption study showed that the Langmuir model best fitted with experimental data, and the maximum adsorption capacity was determined as 0.203 mmol g(-1) (97.995 mg g(-1)). Adsorption kinetics followed the pseudo 2nd order model, and intraparticle diffusion is involved but not as the rate-limiting step while Boyd model suggests that film diffusion might be in control of the adsorption process. Fourier transform infrared (FTIR) analysis showed that OH, C=O, C=C and NH functional groups might be involved in the adsorption of BG onto CDP. Thermodynamic study suggested that the adsorption of BG onto CDP is endothermic with ΔH (o) value of 12 kJ mol(-1) and adsorption is feasible. Regeneration of CDP's ability to remove BG was also studied using three different washing solutions. NaOH (0.1 M) was not only sufficient to be used to regenerate CDP's ability to remove BG but also improved its adsorption capability. PMID:26231977

  15. Silica coated magnetic particles using microwave synthesis for removal of dyes from natural water samples: Synthesis, characterization, equilibrium, isotherm and kinetics studies

    NASA Astrophysics Data System (ADS)

    Ahmed, Salwa A.; Soliman, Ezzat M.

    2013-11-01

    Monitoring pollutants in water samples is a challenge to analysts. So, the removal of Napthol blue black (NBB) and Erichrome blue black R (EBBR) from aqueous solutions was investigated using magnetic chelated silica particles. Magnetic solids are widely used in detection and analytical systems because of the performance advantages they offer compared to similar solids that lack magnetic properties. In this context, a fast, simple and clean method for modification of magnetic particles (Fe3O4) with silica gel was developed using microwave technique to introduce silica gel coated magnetic particles (SG-MPs) sorbent. The magnetic sorbent was characterized by the FT-IR, X-ray diffraction (XRD), and scan electron microscope (SEM) analyses. The effects of pH, time, weight of sorbent and initial concentration of dye were evaluated. It was interesting to find from results that SG-MPs exhibits high percentage extraction of the studied dyes (100% for NBB and 98.75% for EBBR) from aqueous solutions. The Freundlich isotherm with r2 = 0.973 and 0.962 and Langmuir isotherms with r2 = 0.993 and 0.988 for NBB and EBBR, respectively were used to describe adsorption equilibrium. Also, adsorption kinetic experiments have been carried out and the data have been well fitted by a pseudo-second-order equation r2 = 1.0 for NBB and 0.999 for EBBR. The prepared sorbent with rapid adsorption rate and separation convenience was applied for removal of NBB and EBBR pollutants from natural water samples with good precision (RSD% = 0.05-0.3%).

  16. 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

  17. Cr(VI) sorption by free and immobilised chromate-reducing bacterial cells in PVA-alginate matrix: equilibrium isotherms and kinetic studies.

    PubMed

    Rawat, Monica; Rawat, A P; Giri, Krishna; Rai, J P N

    2013-08-01

    Chromate-resistant bacterial strain isolated from the soil of tannery was studied for Cr(VI) bioaccumulation in free and immobilised cells to evaluate its applicability in chromium removal from aqueous solution. Based on the comparative analysis of the 16S rRNA gene, and phenotypic and biochemical characterization, this strain was identified as Paenibacillus xylanilyticus MR12. Mechanism of Cr adsorption was also ascertained by chemical modifications of the bacterial biomass followed by Fourier transform infrared spectroscopy analysis of the cell wall constituents. The equilibrium biosorption analysed using isotherms (Langmuir, Freundlich and Dubinin-Redushkevich) and kinetics models (pseudo-first-order, second-order and Weber-Morris) revealed that the Langmuir model best correlated to experimental data, and Weber-Morris equation well described Cr(VI) biosorption kinetics. Polyvinyl alcohol alginate immobilised cells had the highest Cr(VI) removal efficiency than that of free cells and could also be reused four times for Cr(VI) removal. Complete reduction of chromate in simulated effluent containing Cu(2+), Mg(2+), Mn(2+) and Zn(2+) by immobilised cells, demonstrated potential applications of a novel immobilised bacterial strain MR12, as a vital bioresource in Cr(VI) bioremediation technology. PMID:23361177

  18. Influence of adsorption kinetics on stress evolution in magnetron-sputtered SiO2 and SiNx films

    NASA Astrophysics Data System (ADS)

    Li, Jingping; Fang, Ming; He, Hongbo; Shao, Jianda; Li, Zhaoyang

    2013-07-01

    An in situ multi-beam optical sensor system was used to monitor and analyze the force per unit width (F/w) and stress evolution during several stages in magnetron-sputtered SiO2 and SiNx films. Stress was observed to relieve quickly after interrupt and recover rapidly after growth resumption in both films. Stress relief was reversible in SiO2 film but partial reversible in SiNx film. Stress relief results from both physical and chemical adsorption. Stress recovery is caused by physical desorption. And chemical adsorption results in an irreversible stress relief component. No chemical adsorption occurs in SiO2 film because of the stable chemical structure. The relationship between adsorption kinetics and films' mechanical behavior is revealed.

  19. Simultaneous removal of potent cyanotoxins from water using magnetophoretic nanoparticle of polypyrrole: adsorption kinetic and isotherm study.

    PubMed

    Hena, S; Rozi, R; Tabassum, S; Huda, A

    2016-08-01

    Cyanotoxins, microcystins and cylindrospermopsin, are potent toxins produced by cyanobacteria in potable water supplies. This study investigated the removal of cyanotoxins from aqueous media by magnetophoretic nanoparticle of polypyrrole adsorbent. The adsorption process was pH dependent with maximum adsorption occurring at pH 7 for microcystin-LA, LR, and YR and at pH 9 for microcystin-RR and cylindrospermopsin (CYN). Kinetic studies and adsorption isotherms reflected better fit for pseudo-second-order rate and Langmuir isotherm model, respectively. Thermodynamic calculations showed that the cyanotoxin adsorption process is endothermic and spontaneous in nature. The regenerated adsorbent can be successfully reused without appreciable loss of its original capacity. PMID:27072032

  20. Lead removal kinetics from synthetic effluents using Algerian pine, beech and fir sawdust's: optimization and adsorption mechanism

    NASA Astrophysics Data System (ADS)

    Nordine, N.; El Bahri, Z.; Sehil, H.; Fertout, R. I.; Rais, Z.; Bengharez, Z.

    2014-10-01

    The present paper exposes the lead adsorption from synthetic effluents using natural and available materials. Pine, beech and fir sawdust's were used and compared for their lead adsorption ability. To optimize the sorption phenomenon, some process parameters were studied namely temperature, pH, contact time, initial Pb(II) concentration, sawdust's dosage and granulometry, stirring speed and medium salinity. The materials were characterized by FTIR spectroscopy, X-ray diffraction and fluorescence. The results demonstrated that the pine sawdust gave the best level for lead adsorption (15.5 mg/g) in the following conditions and at 23 ± 2 °C of temperature : pH 5.45 ± 0.05, 100 mg/L of initial Pb(II) concentration and 10 g (per liter of solution) of pine sawdust composed from granules with mean diameter lower than 500 µm. As well, the adsorption kinetics seem to satisfy to Langmuir isotherm model.

  1. Three-stage multilayer formation kinetics during adsorption of an anionic fluorinated surfactant onto germanium. 1. Concentration effect.

    PubMed

    Xing, Rong; Rankin, Stephen E

    2006-01-12

    The adsorption of tetraethylammonium perfluorooctylsulfonate (TEA-FOS) from aqueous solution onto hydroxylated germanium is studied using in situ polarized attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The adsorption is monitored at a series of bulk solution concentrations spanning from well below to above the critical micelle concentration (CMC; 1.0 mM). The kinetics of adsorption is followed by monitoring the intensity of the fluorocarbon bands. The orientation of the fluorocarbon director with respect to the germanium surface is determined by circular dichroism measurements of CF2 stretching bands. At bulk concentrations ranging from 10% of the CMC to at least 500% of the CMC, the adsorption occurs in an unusual sequence of three stages. Initially, rapid adsorption occurs within 200 min, leading to coverage of a monolayer or less. A long period of slow adsorption follows, during which we hypothesize that surfactant molecules form clusters, some of which serve as nuclei for multilayer growth. This stage concludes suddenly with an acceleration in the rate of adsorption, which eventually leads to multilayer formation. Because this is an anionic surfactant adsorbing onto a negatively charged surface at pH 6, the tetraethylammonium ions must mediate the interactions between the surfactant headgroups and the surface. The dichroism measurements show that TEA-FOS is initially oriented randomly or somewhat parallel to the surface, but over time adopts an orientation somewhat normal to the surface. This behavior is consistent with initial adsorption at isolated sites, followed by aggregation into isotropic admicelles, and finally growth into flattened admicelles. The sudden onset of accelerated adsorption can be explained either by autoaccelerating adsorption or nucleation and growth of a hydrophobic multilayer structure. PMID:16471536

  2. Kinetics and equilibrium studies on Mg-Al oxide for removal of fluoride in aqueous solution and its use in recycling.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2015-06-01

    Mg-Al oxide obtained by the thermal decomposition of Mg-Al layered double hydroxide (LDH) intercalated with CO3(2-) (CO3·Mg-Al LDH) was found to take up fluoride from aqueous solution. Fluoride was removed by rehydration of Mg-Al oxide accompanied by combination with F(-). Using five times the stoichiometric quantity of Mg-Al oxide, the residual concentration of F was decreased from 100 to 6.3 mg/L in 480 min, which was below the effluent standard in Japan (8 mg/L). Removal of F(-) can be represented by pseudo-second-order reaction kinetics. The apparent rate constants at 10 °C, 30 °C, and 60 °C were 2.3 × 10(-3), 2.2 × 10(-2), and 2.5 × 10(-1) g mmol(-1) min(-1), respectively. The apparent activation energy was 73.3 kJ mol(-1). The rate-determining step for F removal by Mg-Al oxide was consistent with chemical adsorption involving intercalation of F(-) into the reconstructed Mg-Al LDH due to electrostatic attraction. The adsorption of F by Mg-Al oxide follows a Langmuir-type adsorption. The values of the maximum adsorption and the equilibrium adsorption constant were 3.0 mmol g(-1) and 1.1 × 10(3), respectively, for Mg-Al oxide. The F(-) in the F·Mg-Al LDH thus produced was found to be anion-exchanged with CO3(2-) in solution. The Mg-Al oxide after regeneration treatment had excellent properties for removal of F in aqueous solution. In conclusion, the results of this study indicated that Mg-Al oxide has potential for use in recycling to remove F in aqueous solution. PMID:25867103

  3. A Kinetic Ladle Furnace Process Simulation Model: Effective Equilibrium Reaction Zone Model Using FactSage Macro Processing

    NASA Astrophysics Data System (ADS)

    Van Ende, Marie-Aline; Jung, In-Ho

    2016-05-01

    The ladle furnace (LF) is widely used in the secondary steelmaking process in particular for the de-sulfurization, alloying, and reheating of liquid steel prior to the casting process. The Effective Equilibrium Reaction Zone model using the FactSage macro processing code was applied to develop a kinetic LF process model. The slag/metal interactions, flux additions to slag, various metallic additions to steel, and arcing in the LF process were taken into account to describe the variations of chemistry and temperature of steel and slag. The LF operation data for several steel grades from different plants were accurately described using the present kinetic model.

  4. 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

  5. Kinetics, equilibrium, and mechanisms of sorption and desorption of 17α-ethinyl estradiol in two natural soils and their organic fractions.

    PubMed

    Li, Jianzhong; Fu, Jing; Xiang, Xi; Wu, Miaomiao; Liu, Xiang

    2013-05-01

    A study was conducted on the kinetics, equilibrium, and mechanisms of sorption and desorption of 17α-ethinyl estradiol (EE2) in six sorbents, which were two natural soils (Bulk1 and Bulk2) and their fractions obtained by alkaline extraction, namely, humic acids (HA1 and HA2), and mineral-bond humins (MHU1 and MHU2). These sorbents, characterized by total organic carbon (TOC), black carbon (BC), gas adsorption and Fourier transform infrared spectra, were shown to be porous solids containing aromatic (hard carbon) and aliphatic carbon (soft carbon). The two-compartment first-order model fitted the kinetics of sorption very well (R(2)>0.990). The fast and slow sorption rate constants ranged from 1.110 h(-1) and 0.026 h(-1) to 2.063 h(-1) and 0.067 h(-1), respectively. The slow sorption was attributed to the diffusion of EE2 in micropores rather than organic matter. The Freundlich model fitted the equilibrium of sorption and desorption very well. The nonlinearity of sorption took the order MHU>bulk soil>HA and was positively related to BC/TOC (p<0.01). The hysteresis in MHU2 with higher BC/TOC was stronger than that in Bulk2 with lower BC/TOC, but a contrary observation was found in MHU1 and Bulk1. This contradictory phenomenon could be attributed to the location difference of hard carbon which greatly affected the desorption process. These findings could give an insight into the sorption mechanisms and promote an accurate model for the transport, fate and risk assessment of EE2 in the environment. PMID:23542434

  6. 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

  7. Mobility of pharmaceutical compounds in the terrestrial environment: Adsorption kinetics of the macrocyclic lactone eprinomectin in soils.

    PubMed

    Vassilis, Litskas D; George, Batzias C; Charalampos, Paraskevas G; Athina, Pavlatou-Ve; Xanthippos, Karamanlis N

    2016-02-01

    Avermectins, such as eprinomectin (EPM), are antiparasitic drugs widely and globally used. There is undisputed evidence that they could be a threat for the terrestrial ecosystem. Despite their global use, data for avermectins behaviour and fate in soils are scarce. The objectives of this research were to conduct adsorption experiments in the soil to determine kinetics and isotherms as well as to explore the EPM adsorption mechanism. Accordingly, various models were employed to study the adsorption behaviour and kinetics as well as the adsorption mechanism of EPM in soils. The results showed that the degree of EPM adsorption to soils is determined by the soils' physicochemical properties and the EPM initial concentration. It is possible that dissolved EPM concentration will be higher in soils that contain low amounts of clay minerals and organic matter, resulting in higher toxicity risk for the soil biota and shallow groundwater aquifers contamination. The results of this study are crucial for impact assessment of EPM and in the design of environmental fate or ecotoxicological studies. PMID:26469933

  8. The equilibrium assumption is valid for the kinetic treatment of most time-dependent protein-modification reactions.

    PubMed Central

    Brocklehurst, K

    1979-01-01

    To facilitate mechanistic interpretation of the kinetics of time-dependent inhibition of enzymes and of similar protein modification reactions, it is important to know when the equilibrium assumption may be applied to the model: formula: (see text). The conventional criterion of quasi-equilibrium, k + 2 less than k-1, is not always easy to assess, particularly when k + 2 cannot be separately determined. It is demonstrated that the condition k + 2 less than k-1 is necessarily true, however, when the value of the apparent second-order rate constant for the modification reaction is much smaller than the value of k + 1. Since k + 1 is commonly at least 10(7)M-1.S-1 for substrates, it is probable that the equilibrium assumption may be properly applied to most irreversible inhibitions and modification reactions. PMID:518556

  9. An experimental study of trace element partitioning between olivine, orthopyroxene and melt in chondrules - Equilibrium values and kinetic effects

    NASA Technical Reports Server (NTRS)

    Kennedy, A. K.; Lofgren, G. E.; Wasserburg, G. J.

    1993-01-01

    Mineral/melt partition coefficients were measured using an ion microprobe for 32 elements in orthopyroxene and olivine in equilibrium and dynamic crystallization experiments on compositions corresponding to chondrules. The mineral/melt partition coefficients calculated from the measured concentrations for both olivine and orthopyroxene show very little change between equilibrium experiments and dynamic experiments with cooling rates of up to 100 C/h. The results provide a self-consistent set of partition coefficients that can be used in thermodynamic models of equilibrium and kinetic partitioning between olivine, orthopyroxene, and melt. These data can be used in models of partial melting and crystal fractionation in olivine- and orthopyroxene-rich systems, such as chondrules. The results may also be applicable to mantle peridotites, komatiitic and picritic lavas, and ultramafic intrusions.

  10. Chromium Biosorption from Cr(VI) Aqueous Solutions by Cupressus lusitanica Bark: Kinetics, Equilibrium and Thermodynamic Studies

    PubMed Central

    Netzahuatl-Muñoz, Alma Rosa; Cristiani-Urbina, María del Carmen; Cristiani-Urbina, Eliseo

    2015-01-01

    The present study investigated the kinetics, equilibrium and thermodynamics of chromium (Cr) ion biosorption from Cr(VI) aqueous solutions by Cupressus lusitanica bark (CLB). CLB total Cr biosorption capacity strongly depended on operating variables such as initial Cr(VI) concentration and contact time: as these variables rose, total Cr biosorption capacity increased significantly. Total Cr biosorption rate also increased with rising solution temperature. The pseudo-second-order model described the total Cr biosorption kinetic data best. Langmuir´s model fitted the experimental equilibrium biosorption data of total Cr best and predicted a maximum total Cr biosorption capacity of 305.4 mg g-1. Total Cr biosorption by CLB is an endothermic and non-spontaneous process as indicated by the thermodynamic parameters. Results from the present kinetic, equilibrium and thermodynamic studies suggest that CLB biosorbs Cr ions from Cr(VI) aqueous solutions predominantly by a chemical sorption phenomenon. Low cost, availability, renewable nature, and effective total Cr biosorption make CLB a highly attractive and efficient method to remediate Cr(VI)-contaminated water and wastewater. PMID:26352933

  11. Chromium Biosorption from Cr(VI) Aqueous Solutions by Cupressus lusitanica Bark: Kinetics, Equilibrium and Thermodynamic Studies.

    PubMed

    Netzahuatl-Muñoz, Alma Rosa; Cristiani-Urbina, María del Carmen; Cristiani-Urbina, Eliseo

    2015-01-01

    The present study investigated the kinetics, equilibrium and thermodynamics of chromium (Cr) ion biosorption from Cr(VI) aqueous solutions by Cupressus lusitanica bark (CLB). CLB total Cr biosorption capacity strongly depended on operating variables such as initial Cr(VI) concentration and contact time: as these variables rose, total Cr biosorption capacity increased significantly. Total Cr biosorption rate also increased with rising solution temperature. The pseudo-second-order model described the total Cr biosorption kinetic data best. Langmuir´s model fitted the experimental equilibrium biosorption data of total Cr best and predicted a maximum total Cr biosorption capacity of 305.4 mg g(-1). Total Cr biosorption by CLB is an endothermic and non-spontaneous process as indicated by the thermodynamic parameters. Results from the present kinetic, equilibrium and thermodynamic studies suggest that CLB biosorbs Cr ions from Cr(VI) aqueous solutions predominantly by a chemical sorption phenomenon. Low cost, availability, renewable nature, and effective total Cr biosorption make CLB a highly attractive and efficient method to remediate Cr(VI)-contaminated water and wastewater. PMID:26352933

  12. Hybrid materials from agro-waste and nanoparticles: implications on the kinetics of the adsorption of inorganic pollutants.

    PubMed

    Omorogie, Martins O; Babalola, Jonathan O; Unuabonah, Emmanuel I; Gong, Jian R

    2014-01-01

    This study is a first-hand report of the immobilization of Nauclea diderrichii seed waste biomass (ND) (an agro-waste) with eco-friendly mesoporous silica (MS) and graphene oxide-MS (GO + MS) nanoparticles, producing two new hybrid materials namely: MND adsorbent for agro-waste modified with MS and GND adsorbent for agro-waste modified with GO + MS nanoparticles showed improved surface area, pore size and pore volume over those of the agro-waste. The abstractive potential of the new hybrid materials was explored for uptake of Cr(III) and Pb(II) ions. Analysis of experimental data from these new hybrid materials showed increased initial sorption rate of Cr(III) and Pb(II) ions uptake. The amounts of Cr(III) and Pb(II) ions adsorbed by MND and GND adsorbents were greater than those of ND. Modification of N. diderrichii seed waste significantly improved its rate of adsorption and diffusion coefficient for Cr(III) and Pb(II) more than its adsorption capacity. The rate of adsorption of the heavy metal ions was higher with GO + MS nanoparticles than for other adsorbents. Kinetic data were found to fit well the pseudo-second-order and the diffusion-chemisorption kinetic models suggesting that the adsorption of Cr(III) and Pb(II) onto these adsorbents is mainly through chemisorption mechanism. Analysis of kinetic data with the homogeneous particle diffusion kinetic model suggests that particle diffusion (diffusion of ions through the adsorbent) is the rate-limiting step for the adsorption process. PMID:24645440

  13. Lysozyme adsorption in pH-responsive hydrogel thin-films: the non-trivial role of acid-base equilibrium.

    PubMed

    Narambuena, Claudio F; Longo, Gabriel S; Szleifer, Igal

    2015-09-01

    We develop and apply a molecular theory to study the adsorption of lysozyme on weak polyacid hydrogel films. The theory explicitly accounts for the conformation of the network, the structure of the proteins, the size and shape of all the molecular species, their interactions as well as the chemical equilibrium of each titratable unit of both the protein and the polymer network. The driving forces for adsorption are the electrostatic attractions between the negatively charged network and the positively charged protein. The adsorption is a non-monotonic function of the solution pH, with a maximum in the region between pH 8 and 9 depending on the salt concentration of the solution. The non-monotonic adsorption is the result of increasing negative charge of the network with pH, while the positive charge of the protein decreases. At low pH the network is roughly electroneutral, while at sufficiently high pH the protein is negatively charged. Upon adsorption, the acid-base equilibrium of the different amino acids of the protein shifts in a nontrivial fashion that depends critically on the particular kind of residue and solution composition. Thus, the proteins regulate their charge and enhance adsorption under a wide range of conditions. In particular, adsorption is predicted above the protein isoelectric point where both the solution lysozyme and the polymer network are negatively charged. This behavior occurs because the pH in the interior of the gel is significantly lower than that in the bulk solution and it is also regulated by the adsorption of the protein in order to optimize protein-gel interactions. Under high pH conditions we predict that the protein changes its charge from negative in the solution to positive within the gel. The change occurs within a few nanometers at the interface of the hydrogel film. Our predictions show the non-trivial interplay between acid-base equilibrium, physical interactions and molecular organization under nanoconfined conditions

  14. Modeling arsenic(III) adsorption and heterogeneous oxidation kinetics in soils

    SciTech Connect

    Manning, B.A.; Suarez, D.L.

    2000-02-01

    Arsenite [As(III)] is a soluble and toxic species of arsenic that can be introduced into soil by geothermal waters, mining activities, irrigation practices, and disposal of industrial wastes. The authors determined the rates of As(III) adsorption, and subsequent oxidation to arsenate [As(V)] in aerobic soil-water suspensions using four California soils. The rate of As(III) adsorption on the soils was closely dependent on soil properties that reflect the reactivity of mineral surfaces including citrate-dithionite (CD) extractable metals, soil texture, specific surface area, and pH. Heterogeneous oxidation of As(III) to As(V) was observed in all soils studied. The recovery of As(V) from As(III)-treated soils was dependent on levels of oxalate-extractable Mn and soil texture. After derivation of rate equations to describe the changes in soluble and recoverable As(III) and As(V) in soil suspensions, soil property measurements were used to normalize the empirically derived rate constants for three soils. The fourth soil, which had substantially different soil properties from the other three soils, was used to independently test the derived soil property-normalized model. The soil property-normalized consecutive reaction model gave a satisfactory description of the trends seen in the experimental data for all four soils. Understanding the effects of soil properties on the kinetics of chemical reactions of As(III) and As(V) in soils will be essential to development of quantitative models for predicting the mobility of As in the field.

  15. CO2 adsorption on diatomaceous earth modified with cetyltrimethylammonium bromide and functionalized with tetraethylenepentamine: Optimization and kinetics.

    PubMed

    Pornaroonthama, Phuwadej; Thouchprasitchai, Nutthavich; Pongstabodee, Sangobtip

    2015-07-01

    The carbon dioxide (CO2) adsorbent diatomaceous earth (DE) was modified with cetyltrimethylammonium bromide (CTAB) and functionalized with varying levels of tetraethylenepentamine (TEPA). The CO2 absorption at atmospheric pressure was optimized by varying the TEPA-loading level (0-40% (w/w)), operating temperature (40-80 °C) and water vapor concentration (0-16% (v/v)) in a 10% (v/v) CO2 feed stream in helium balance using a full 2(3) factorial design. The TEPA/CTAB-DE adsorbents were characterized by X-ray diffractometry, Fourier transform infrared spectrometry and thermogravimetric analyses. The CO2 adsorption capacity increased as each of these three factors increased. The TEPA loading level-water concentration interaction had a positive influence on the CO2 adsorption while the operating temperature-water concentration interaction was antagonistic. The optimal condition for CO2 adsorption on 40%TEPA/CTAB-DE, evaluated via a factorial design response surface method (RSM), was a temperature of 58-68 °C and a water vapor concentration of 9.5-14% (v/v), with a maximum CO2 adsorption capacity of 149.4 mg g(-1) at 63.5 °C and 12% (v/v) water vapor concentration in the feed. Validation and sensitivity tests revealed that the estimated CO2 adsorption capacity was within ±4% of the experimental values, suggesting that the RSM model was satisfied and acceptable. From three kinetic models (pseudo-first-order, pseudo-second-order model and Avrami's equation), assessed using an error function (Err) and the coefficient of determination (R(2)), Avrami's equation was the most appropriate to describe the kinetics of CO2 adsorption on the 40%TEPA/CTAB-DE adsorbent and suggested that more than one reaction pathway occurred in the CO2 adsorption. PMID:25910973

  16. Biosorptive uptake of ibuprofen by steam activated biochar derived from mung bean husk: Equilibrium, kinetics, thermodynamics, modeling and eco-toxicological studies.

    PubMed

    Mondal, Sandip; Bobde, Kiran; Aikat, Kaustav; Halder, Gopinath

    2016-11-01

    The present study explores the use of steam activated mung bean husk biochar (SA-MBHB) as a potential sorbent for the removal of non-steroidal and anti-inflammatory drug ibuprofen from aqueous solution. SA-MBHB was characterized by SEM, FTIR, BET, TGA, point of zero charge (pHPZC) and UV-Vis spectrophotometer. The relation between removal percentages of ibuprofen and parameters such as adsorbent dose (0.05 g-250 g), contact time (5 min-210 min), pH (2-10), speed of agitation (40-280 rpm), temperature (293-308 K) and initial ibuprofen concentration (5-100 ppm) was investigated and optimized by a series of batch sorption experiments. The optimized conditions achieved were: adsorbent dose 0.1 g/L, agitation speed 200 rpm, pH 2, initial ibuprofen concentration 20 mg L(-1), equilibrium time 120 min and temperature 20 °C for more than 99% adsorptive removal of ibuprofen. The equilibrium adsorption data were well fitted into the Langmuir isotherm model while kinetic data suggested the removal process to follow pseudo second order reaction. The adsorption phenomena were optimized and simulated by using response surface methodology (RSM) and artificial neural network (ANN). Effect of process variables viz. dose, agitation speed and pH on the sorbed amount of IBP was studied through a 2(3) full factorial central composite design (CCD). The comparative analysis was done for ibuprofen removal by constructing ANN model training using same experimental matrix of CCD. The growth of Scenedesmus abundans was also observed to be affected by the IBP solution whereas the biochar treated with IBP solution did not significantly affect the growth of the Scenedesmus abundans. The results revealed that SA-MBHB could be a cost-effective, efficient and non-hazardous adsorbent for the removal of ibuprofen from aqueous solution. PMID:27544645

  17. Kinetic Adsorption Profile and Conformation Evolution at the DNA-Gold Nanoparticle Interface Probed by Dynamic Light Scattering

    PubMed Central

    2015-01-01

    The kinetic adsorption profile at the DNA–gold nanoparticle (AuNP) interface is probed by following the binding and organization of thiolated linear DNA and aptamers of varying chain lengths (15, 30, 44, and 51 mer) to the surface of AuNPs (13.0 ± 1.0 nm diameter). A systematic investigation utilizing dynamic light scattering has been performed to directly measure the changes in particle size during the course of a typical aging-salting thiolated DNA/AuNP preparation procedure. We discuss the effect of DNA chain length, composition, salt concentration, and secondary structure on the kinetics and conformation at the DNA–AuNP interface. The adsorption kinetics are chain-length dependent, composition independent, and not diffusion rate limited for the conditions we report here. The kinetic data support a mechanism of stepwise adsorption of thiols to the surface of AuNPs and reorganization of the thiols at the interface. Very interestingly, the kinetic increases of the particle sizes are modeled accurately by the pseudo-second-order rate model, suggesting that DNA could possess the statistically well-defined conformational evolution. Together with other experimental evidence, we propose a dynamic inner-layer and outer-tail (DILOT) model to describe the evolution of the DNA conformation after the initial adsorption of a single oligonucleotide layer. According to this model, the length of the tails that extend from the surface of AuNPs, capable for hybridization or molecular recognition, can be conveniently calculated. Considering the wide applications of DNA/AuNPs, the results should have important implications in sensing and DNA-directed nanoparticle assembly. PMID:25222203

  18. 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

  19. From Alfvén waves to kinetic Alfvén waves in an inhomogeneous equilibrium structure

    NASA Astrophysics Data System (ADS)

    Pucci, Francesco; Vasconez, Christian L.; Pezzi, Oreste; Servidio, Sergio; Valentini, Francesco; Matthaeus, William H.; Malara, Francesco

    2016-04-01

    Kinetic Alfvén waves are believed to primary form fluctuations in a hydromagnetic turbulence at scales of the order of the ion inertial length. We study a model where an initial Alfvén wave propagates inside an equilibrium structure which is inhomogeneous in the direction perpendicular to the equilibrium magnetic field. In a previous paper [1] this situation has been considered in a particular configuration where the initial wavevector is parallel to the magnetic field and the wave is polarized perpendicular to the inhomogeneity direction. Here, we consider other configurations, with a different polarization and possible initial oblique propagation. We employ numerical simulations, using both a Hall-Magnetohydrodynamics and a Hybrid Vlasov-Maxwell model. Results show that in all the considered cases the time evolution leads to the formation of Kinetic Alfvén waves within the inhomogeneity regions, which are identified by a comparison with analytical linear theory results. Then, in this context the formation of Kinetic Alfvén waves seems to be a general phenomenon which could be also extended to more complex situations, like turbulence. Kinetic simulations show that Kinetic Alfvén waves modify the ion distribution function, generating temperature anisotropy of both parallel and perpendicular to the local magnetic field as well as particle beams aligned along the local magnetic field. These results could be relevant both in the solar corona and in large-scale structures of the solar wind, where Alfvénic fluctuations are present along with large-scale inhomogeneities. [1] C. Vasconez et al., Kinetic Alfvén waves generation by large-scale phase-mixing, The Astrophysical Journal 815.1, 7 (2015).

  20. Kinetics and equilibrium of cadmium complexation with heterogeneous complexants: A stopped-flow study at Na-illite

    SciTech Connect

    Pohlmeier, A.; Ruetzel, H.

    1996-07-15

    Rapid kinetics and equilibrium of the ion exchange of Na{sup +} by Cd{sup 2+} at illite are studied by the stopped-flow technique and DPASV, respectively, as an example for reactions at heterogeneous surfaces. For the first time both kinetics and equilibrium are analyzed for the same system by kinetic- and affinity-spectra, taking into consideration the heterogeneity of binding sites. It is possible to calculate model independent kinetic spectra by means of the CONTIN program; the isotherm is evaluated by Sips` distribution function. Monomodal distribution functions are found, characterized by mean values and half widths at half height in the range between 0.2 and 0.3 log (k/s{sup {minus}1}) for the kinetics and 0.16 log (K/L/mol) for the affinity. From both analyses the mean ion exchange coefficient is determined as 2.2 {+-} 0.4 mol/liter and 1.5 {+-} 0.4 mol/liter, respectively. The kinetics are rapid; only one process is observed that is assigned to the binding of Cd{sup 2+} at the outer surface. The high activation-enthalpy of 35 kJ/mol proves that the exchange reaction of 2 Na{sup +} by cd{sup 2+} at the binding site is the rate-determining step and not the diffusion to the surface. The large negative activation-entropy of {minus}105 J/mol K indicates that this rate-determining step is of associative nature.

  1. Adsorption kinetics of asphaltenes at the oil-water interface and nanoaggregation in the bulk.

    PubMed

    Rane, Jayant P; Harbottle, David; Pauchard, Vincent; Couzis, Alexander; Banerjee, Sanjoy

    2012-07-01

    Asphaltenes constitute high molecular weight constituents of crude oils that are insoluble in n-heptane and soluble in toluene. They contribute to the stabilization of the water-in-oil emulsions formed during crude oil recovery and hinder drop-drop coalescence. As a result, asphaltenes unfavorably impact water-oil separation processes and consequently oil production rates. In view of this there is a need to better understand the physicochemical effects of asphaltenes at water-oil interfaces. This study elucidates aspects of these effects based on new data on the interfacial tension in such systems from pendant drop experiments, supported by results from nuclear magnetic resonance (NMR) and dynamic light scattering (DLS) studies. The pendant drop experiments using different asphaltene concentrations (mass fractions) and solvent viscosities indicate that the interfacial tension reduction kinetics at short times are controlled by bulk diffusion of the fraction of asphaltenes present as monomer. At low mass fractions much of the asphaltenes appear to be present as monomers, but at mass fractions greater than about 80 ppm they appear to aggregate into larger structures, a finding consistent with the NMR and DLS results. At longer times interfacial tension reduction kinetics are slower and no longer diffusion controlled. To investigate the controlling mechanisms at this later stage the pendant drop experiment was made to function in a fashion similar to a Langmuir trough with interfacial tension being measured during expansion of a droplet aged in various conditions. The interfacial tension was observed to depend on surface coverage and not on time. All observations indicate the later stage transition is to an adsorption barrier-controlled regime rather than to a conformational relaxation regime. PMID:22680071

  2. Peculiar mechanism of solubilization of a sparingly water soluble drug into polymeric micelles. Kinetic and equilibrium studies.

    PubMed

    Turco Liveri, Maria Liria; Licciardi, Mariano; Sciascia, Luciana; Giammona, Gaetano; Cavallaro, Gennara

    2012-04-26

    Complementary kinetic and equilibrium studies on the solubilization process of the sparingly water soluble tamoxifen (TAM) drug in polymeric aqueous solutions have been performed by using the spectrophotometric method. In particular, the amphiphilic copolymers obtained by derivatization of polymeric chain of poly(N-2-hydroxyethyl)-dl-aspartamide, PHEA, with poly(ethylene glycol)s, PEG (2000 or 5000 Da), and/or hexadecylamine chain, C16, namely PHEA-PEG2000-C16, PHEA-PEG5000-C16, PHEA-C16, have been employed. Preliminary to the kinetic and equilibrium data quantitative treatment, the molar absorption coefficient of TAM in polymeric micelle aqueous solution has been determined. By these studies the solubization sites of TAM into the polymeric micelles have been determined and the solubilization mechanism has been elucidated through a nonconventional approach by considering the TAM partitioned between three pseudophases, i.e., the aqueous pseudophase, the hydrophilic corona, and the hydrophobic core. The simultaneous solution of the rate laws associated with each step of the proposed mechanism allowed the calculation of the rate constants associated with the involved processes, the values of which are independent of both the copolymer concentration and nature, with the exception of the rate of the TAM transfer from the corona to the core. This has been attributed to the steric barrier, represented by the corona, which hampers the solubilization into the core. The binding constant values of the TAM to the hydrophilic corona of the polymeric micelles, calculated through the quantitative analysis of the equilibrium data, depend on the thickness of the hydrophilic headgroup, while those of the hydrophobic core are almost independent of the copolymer type. Further confirmation to the proposed solubilization mechanism has been provided by performing the kinetic and equilibrium measurements in the presence of PHEA-PEG2000 and PHEA-PEG5000 copolymers. PMID:22462632

  3. Investigation of adsorption kinetics and isotherm of cellulase and B-Glucosidase on lignocellulosic substrates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Clear understanding of enzyme adsorption during enzymatic hydrolysis of lignocellulosic biomass is essential to enhance the cost-efficiency of hydrolysis. However, conclusions from literatures often contradicted each other because enzyme adsorption is enzyme, biomass/pretreatment and experimental co...

  4. Adsorption of emulsified oil from metalworking fluid on activated bleaching earth-chitosan-SDS composites: Optimization, kinetics, isotherms.

    PubMed

    Naowanat, Nitiya; Thouchprasitchai, Nutthavich; Pongstabodee, Sangobtip

    2016-03-15

    The adsorption of emulsified oil from metalworking fluid (MWF) on activated bleaching earth (BE)-chitosan-sodium dodecyl sulfate (SDS) composites (BE/MCS) was investigated under a statistical design of experiments at a 95% confidence interval to identify the critical factors and to optimize the adsorption capacity. The BE/MCS adsorbents were characterized by means of X-ray diffraction, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller adsorption/desorption isotherms, contact angle analysis (sessile drop technique) and their zeta potential. From the results of a full 2(5) factorial design with three center points, the adsorbent weight and initial pH of the MWF had a significant antagonistic effect on the adsorption capacity while the initial MWF concentration and BE:chitosan:SDS weight ratio had a synergistic influence. Temperature factor has no discernible effect on the capacity. From the FCCC-RSM design, the optimal capacity range of 2840-2922.5 mg g(-1) was achieved at sorbent weight of 1.6-1.9 g, pH of 5.5-6.5, initial MWF concentration of 52-55 g l(-1) and BE:chitosan:SDS (w/w/w) ratio of 4.7:1:1-6.2:1:1. To test the validation and sensitivity of RSM model, the results showed that the estimated adsorption capacity was close to the experimental capacity within an error range of ±3%, suggesting that the RSM model was acceptable and satisfied. From three kinetics models (pseudo-first-order, pseudo-second-order model and Avrami's equation) and two adsorption isotherms (Langmuir model and Freundlich model), assessed using an error function (Err) and the coefficient of determination (R(2)), Avrami's equation and Freundlich isotherm model provided a good fitting for the data, suggesting the presence of more than one reaction pathway in the MWF adsorption process and the heterogeneous surface adsorption of the BC/ABE-5.5 composite. PMID:26731309

  5. A simple simulation of adsorption equilibrium of Pb(II) on Andosols in the presence of dissolved humic substances for monitoring soil contamination.

    PubMed

    Liu, Yuyu; Kobayashi, Takeshi; Takahashi, Yukari; Kameya, Takashi; Urano, Kohei

    2013-01-01

    The adsorption equilibrium of Pb(II) on Andosols was investigated and described quantitatively in order to develop a simple method for the rapid monitoring of heavy metals in soils. The effect of solution pH on adsorption isotherms was investigated experimentally and in simulations. At pH 7, the considerable desorption of Pb(II) due to the extensive dissolution of humic substances (HS) from soils into aqueous phases is known to be an obstacle to carrying out simulations. In batch experiments, the total organic carbon (TOC) of the aqueous phases was shown to be enhanced by the addition of pre-extracted HS to soil suspensions. By combining the ion-exchange and Freundlich models, the adsorption equilibriums of free Pb(2+) ions and Pb(2+)-HS were simulated and were shown to be in good agreement with the experimental results. By estimating the concentrations and adsorption amounts of Pb(2+) and Pb(2+)-HS from measured CPb and TOC, it is possible to accurately simulate the soil contamination status even in in the presence of dissolved HS in the water in the solid-liquid extraction samples. PMID:23947708

  6. Protein adsorption onto nanoparticles induces conformational changes: Particle size dependency, kinetics, and mechanisms

    PubMed Central

    Satzer, Peter; Svec, Frantisek; Sekot, Gerhard

    2015-01-01

    The use of nanomaterials in bioapplications demands a detailed understanding of protein–nanoparticle interactions. Proteins can undergo conformational changes while adsorbing onto nanoparticles, but studies on the impact of particle size on conformational changes are scarce. We have shown that conformational changes happening upon adsorption of myoglobin and BSA are dependent on the size of the nanoparticle they are adsorbing to. Out of eight initially investigated model proteins, two (BSA and myoglobin) showed conformational changes, and in both cases this conformational change was dependent on the size of the nanoparticle. Nanoparticle sizes ranged from 30 to 1000 nm and, in contrast to previous studies, we attempted to use a continuous progression of sizes in the range found in live viruses, which is an interesting size of nanoparticles for the potential use as drug delivery vehicles. Conformational changes were only visible for particles of 200 nm and bigger. Using an optimized circular dichroism protocol allowed us to follow this conformational change with regard to the nanoparticle size and, thanks to the excellent temporal resolution also in time. We uncovered significant differences between the unfolding kinetics of myoglobin and BSA. In this study, we also evaluated the plausibility of commonly used explanations for the phenomenon of nanoparticle size‐dependent conformational change. Currently proposed mechanisms are mostly based on studies done with relatively small particles, and fall short in explaining the behavior seen in our studies.

  7. Kinetics of the adsorption of radionuclides on tuff from Yucca Mountain

    SciTech Connect

    Rundberg, R.S.

    1984-12-31

    The sorption of simple cations in tuff is dominated by adsorption on aluminosilicates that have charged surfaces, such as zeolites and clays. The most significant sorbing minerals present in Nevada tuff are clinoptilolite, heulandite, mordenite, and montmorillonite. The kinetics of sorption on tuffs containing the minerals clinoptilolite and montmorillonite has been determined by studying the uptake of strontium, cesium, and barium on thin tuff wafers. The rate constants for uptake of these elements on tuff are consistent with a model of sorption that is diffusion limited but where diffusion occurs in two stages. First the cations diffuse into the rock through the water-filled pore space. Next, the cations must diffuse into the much narrower channels within the aluminosilicate crystals. After they are within the zeolite framework or between the clay planes, the cations may rapidly sorb on the negatively charged surfaces. The actinide elements have a time constant for the apparent sorption that is inconsistent with this model and may have a radically different mechanism of removal from solution. 12 references, 4 tables.

  8. Control of Uniform and Interconnected Macroporous Structure in PolyHIPE for Enhanced CO2 Adsorption/Desorption Kinetics.

    PubMed

    Wang, Quanyong; Liu, Yao; Chen, Jian; Du, Zhongjie; Mi, Jianguo

    2016-07-19

    The highly uniform and interconnected macroporous polymer materials were prepared within the high internal phase hydrosol-in-oil emulsions (HIPEs). Impregnated with polyethylenimine (PEI), the polyHIPEs were then employed as solid adsorbents for CO2 capture. Thermodynamic and kinetic capture-and-release tests were performed with pure CO2, 10% CO2/N2, and moist CO2, respectively. It has shown that the polyHIPE with suitable surface area and PEI impregnation exhibits high CO2 adsorption capacity, remarkable CO2/N2 selectivity, excellent adsorption/desorption kinetics, enhanced efficiency in the presence of water, and admirable stability in capture and release cycles. The results demonstrate the superior comprehensive performance of the present PEI-impregnated polyHIPE for CO2 capture from the postcombustion flue gas. PMID:27322734

  9. Whispering Gallery Mode Biosensor Quantification of Fibronectin Adsorption Kinetics onto Alkylsilane Monolayers and Interpretation of Resultant Cellular Response

    PubMed Central

    Wilson, Kerry A.; Finch, Craig A.; Anderson, Phillip; Vollmer, Frank; Hickman, James J.

    2011-01-01

    A Whispering Gallery Mode (WGM) biosensor was constructed to measure the adsorption of protein onto alkysilane self-assembled monolayers (SAMs) at solution concentrations unattainable with other techniques. The high sensitivity was provided by a WGM resonance excited in a silica microsphere that was functionalized with alkylsilane SAMs and integrated in a microfluidic flow cell under laminar flow conditions. It was found that FN adsorbed at biologically relevant surface densities, however, the adsorption kinetics and concentration dependent saturation values varied significantly from work published utilizing alkanethiol SAMs. Mathematical models were applied to the experimental results to interpret the observed kinetics of FN adsorption. Embryonic hippocampal neurons and skeletal myoblasts were cultured on the modified surfaces, and a live-dead assay was used to determine the viability of the FN surfaces for cell culture, and major differences were noted in the biological response to the different SAMs. The high sensitivity and simplicity of the WGM biosensor, combined with its ability to quantify the adsorption of any dilute protein in a label-free assay, establishes the importance of this technology for the study of surface accretion and its effect on cellular function, which can affect biomaterials for both in vivo and in vitro applications. PMID:21983134

  10. 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.

  11. Effects of the buffering capacity of the soil on the mobilization of heavy metals. Equilibrium and kinetics.

    PubMed

    Villen-Guzman, Maria; Paz-Garcia, Juan M; Amaya-Santos, Gema; Rodriguez-Maroto, Jose M; Vereda-Alonso, Carlos; Gomez-Lahoz, Cesar

    2015-07-01

    Understanding the possible pH-buffering processes is of maximum importance for risk assessment and remediation feasibility studies of heavy-metal contaminated soils. This paper presents the results about the effect of the buffering capacity of a polluted soil, rich in carbonates, on the pH and on the leaching evolution of its main contaminant (lead) when a weak acid (acetic acid) or a strong one (nitric acid) are slowly added. In both cases, the behavior of lead dissolution could be predicted using available (scientifically verified freeware) models assuming equilibrium between the solid and the aqueous phase. However, the experimental results indicate that the dissolution of calcium and magnesium carbonates is kinetically controlled. These kinetic limitations affect the overall behavior, and should be considered to understand also the response of the metals under local equilibrium. The well-known BCR sequential extraction procedure was used before- and after-treatment, to fractionate the lead concentration in the soil according to its mobility. The BCR results were also in agreement with the predictions of the equilibrium model. This agreement allows new insights about the information that could be derived from the BCR fractionation analysis. PMID:25781866

  12. Kinetic and Conformational Insights of Protein Adsorption onto Montmorillonite Revealed Using in Situ ATR-FTIR/2D-COS.

    PubMed

    Schmidt, Michael P; Martínez, Carmen Enid

    2016-08-01

    Protein adsorption onto clay minerals is a process with wide-ranging impacts on the environmental cycling of nutrients and contaminants. This process is influenced by kinetic and conformational factors that are often challenging to probe in situ. This study represents an in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic investigation of the adsorption of a model protein (bovine serum albumin (BSA)) onto a clay mineral (montmorillonite) at four concentrations (1.50, 3.75, 7.50, and 15.0 μM) under environmentally relevant conditions. At all concentrations probed, FTIR spectra show that BSA readily adsorbs onto montmorillonite. Adsorption kinetics follow an Elovich model, suggesting that primary limitations on adsorption rates are surface-related heterogeneous energetic restrictions associated with protein rearrangement and lateral protein-protein interaction. BSA adsorption onto montmorillonite fits the Langmuir model, yielding K = 5.97 × 10(5) M(-1). Deconvolution and curve fitting of the amide I band at the end of the adsorption process (∼120 min) shows a large extent of BSA unfolding upon adsorption at 1.50 μM, with extended chains and turns increasing at the expense of α-helices. At higher concentrations/surface coverages, BSA unfolding is less pronounced and a more compact structure is assumed. Two-dimensional correlation spectroscopic (2D-COS) analysis reveals three different pathways corresponding to adsorbed conformations. At 1.50 μM, adsorption increases extended chains, followed by a loss in α-helices and a subsequent increase in turns. At 3.75 μM, extended chains decrease and then aggregated strands increase and side chains decrease, followed by a decrease in turns. With 7.50 and 15.0 μM BSA, the loss of side-chain vibrations is followed by an increase in aggregated strands and a subsequent decrease in turns and extended chains. Overall, the BSA concentration and resultant surface coverage have a profound

  13. From Alfvén waves to kinetic Alfvén waves in an inhomogeneous equilibrium structure

    NASA Astrophysics Data System (ADS)

    Pucci, F.; Vásconez, C. L.; Pezzi, O.; Servidio, S.; Valentini, F.; Matthaeus, W. H.; Malara, F.

    2016-02-01

    Kinetic Alfvén waves are believed to primary form fluctuations in a hydromagnetic turbulence at scales of the order of the ion inertial length. We study a model where an initial Alfvén wave propagates inside an equilibrium structure which is inhomogeneous in the direction perpendicular to the equilibrium magnetic field. In a previous paper this situation has been considered in a particular configuration where the initial wave vector is parallel to the magnetic field and the wave is polarized perpendicular to the inhomogeneity direction. Here we consider other configurations, with a different polarization and possible initial oblique propagation. We employ numerical simulations, using both a Hall-magnetohydrodynamics and a Hybrid Vlasov-Maxwell model. Results show that in all the considered cases the time evolution leads to the formation of kinetic Alfvén waves within the inhomogeneity regions, which are identified by a comparison with analytical linear theory results. Then, in this context the formation of kinetic Alfvén waves seems to be a general phenomenon which could be also extended to more complex situations, like turbulence. Kinetic simulations show that kinetic Alfvén waves modify the ion distribution function, generating temperature anisotropy of both parallel and perpendicular to the local magnetic field as well as particle beams aligned along the local magnetic field. These results could be relevant both in the solar corona and in large-scale structures of the solar wind, where Alfvénic fluctuations are present along with large-scale inhomogeneities.

  14. Kinetics and Equilibrium Sorption Models: Fitting Plutonium, Strontium, Uranium and Neptunium Loading on Monosodium Titanate (MST)

    SciTech Connect

    Fondeur, F

    2006-03-08

    The Dubinin-Astashov (DA) isotherm parameters for U, Pu, Sr and Np have been updated to include additional data obtained since the original derivation. The DA isotherms were modified to include a kinetic function derived by Rahn to describe sorbate loading from the beginning of sorption up to steady state. The final functions describe both kinetic and thermodynamic sorption.

  15. Gas-kinetic theory and Boltzmann equation of share price within an equilibrium market hypothesis and ad hoc strategy

    NASA Astrophysics Data System (ADS)

    Ausloos, M.

    2000-09-01

    Recent observations have indicated that the traditional equilibrium market hypothesis (EMH; also known as Efficient Market Hypothesis) is unrealistic. It is shown here that it is the analog of a Boltzmann equation in physics, thus having some bad properties of mean-field approximations like a Gaussian distribution of price fluctuations. A kinetic theory for prices can be simply derived, considering in a first approach that market actors have all identical relaxation times, and solved within a Chapman-Enskog like formalism. In closing the set of equations, (i) an equation of state with a pressure and (ii) the equilibrium (isothermal) equation for the price (taken as the order parameter) of a stock as a function of the volume of money available are obtained.

  16. 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.

  17. Kinetic and equilibrium analyses of [(123)I]epidepride binding to striatal and extrastriatal dopamine D(2) receptors.

    PubMed

    Fujita, M; Seibyl, J P; Verhoeff, N P; Ichise, M; Baldwin, R M; Zoghbi, S S; Burger, C; Staley, J K; Rajeevan, N; Charney, D S; Innis, R B

    1999-12-15

    Quantitative SPECT measures of dopamine D(2) like receptors with [(123)I]epidepride is complicated by its high affinity and lipophilic metabolites. The purpose of this study was to use both parent (P) and lipophilic metabolites (M) as input functions in a kinetic paradigm and in comparison to the results of equilibrium studies. Kinetic studies on eleven healthy human subjects, ages 32+/- 10 were performed following i.v. injection of approximately 370 MBq of [(123)I]epidepride. Images were acquired for 13.5+/-1.0 hours. Equilibrium studies were done on seven of eleven subjects with a bolus injection of approximately 140 MBq, bolus/infusion ratio of 10 hours, and infusion for 30-32 hours. High (striatum) and low (temporal cortex) density regions were studied. Two (P and M) and one (P) input function models were applied in the kinetic studies. In receptor-rich regions, the distribution volumes in nondisplaceable compartments were fixed to those in cerebellum. In addition, in the two input function model, K(1)(P)/K(1)(M) was fixed to the values in the cerebellum. The one input function model provided V'(3) values (=f(1)*B'(max)/K(D)) which were consistent with those obtained in equilibrium studies in both receptor-rich regions, while the two input function model provided consistent values only in striatum. Poor identifiability of the rate constants of metabolites seemed to be the source of errors in the two input function model. These results suggest that correct V'(3) values can be obtained with the one input function model both in high- and low-density regions. PMID:10529723

  18. [Effect of SO2 volume fraction in flue gas on the adsorption behaviors adsorbed by ZL50 activated carbon and kinetic analysis].

    PubMed

    Gao, Ji-xian; Wang, Tie-feng; Wang, Jin-fu

    2010-05-01

    The influence of SO2 dynamic adsorption behaviors using ZL50 activated carbon for flue gas desulphurization and denitrification under different SO2 volume fraction was investigated experimentally, and the kinetic analysis was conducted by kinetic models. With the increase of SO2 volume fraction in flue gas, the SO2 removal ratio and the activity ratio of ZL50 activated carbon decreased, respectively, and SO2 adsorption rate and capacity increased correspondingly. The calculated results indicate that Bangham model has the best prediction effect, the chemisorption processes of SO2 was significantly affected by catalytic oxidative reaction. The adsorption rate constant of Lagergren's pseudo first order model increased with the increase of inlet SO, volume fraction, which indicated that catalytic oxidative reaction of SO2 adsorbed by ZL50 activated carbon may be the rate controlling step in earlier adsorption stage. The Lagergren's and Bangham's initial adsorption rate were deduced and defined, respectively. The Ho's and Elovich's initial adsorption rate were also deduced in this paper. The Bangham's initial adsorption rate values were defined in good agreement with those of experiments. The defined Bangham's adsorptive reaction kinetic model can describe the SO2 dynamic adsorption rate well. The studied results indicated that the SO2 partial order of initial reaction rate was one or adjacent to one, while the O2 and water vapor partial order of initial reaction rate were constants ranging from 0.15-0.20 and 0.45-0.50, respectively. PMID:20623845

  19. Chemical kinetics and relaxation of non-equilibrium air plasma generated by energetic photon and electron beams

    NASA Astrophysics Data System (ADS)

    Maulois, Melissa; Ribière, Maxime; Eichwald, Olivier; Yousfi, Mohammed; Azaïs, Bruno

    2016-04-01

    The comprehension of electromagnetic perturbations of electronic devices, due to air plasma-induced electromagnetic field, requires a thorough study on air plasma. In the aim to understand the phenomena at the origin of the formation of non-equilibrium air plasma, we simulate, using a volume average chemical kinetics model (0D model), the time evolution of a non-equilibrium air plasma generated by an energetic X-ray flash. The simulation is undertaken in synthetic air (80% N2 and 20% O2) at ambient temperature and atmospheric pressure. When the X-ray flash crosses the gas, non-relativistic Compton electrons (low energy) and a relativistic Compton electron beam (high energy) are simultaneously generated and interact with the gas. The considered chemical kinetics scheme involves 26 influent species (electrons, positive ions, negative ions, and neutral atoms and molecules in their ground or metastable excited states) reacting following 164 selected reactions. The kinetics model describing the plasma chemistry was coupled to the conservation equation of the electron mean energy, in order to calculate at each time step of the non-equilibrium plasma evolution, the coefficients of reactions involving electrons while the energy of the heavy species (positive and negative ions and neutral atoms and molecules) is assumed remaining close to ambient temperature. It has been shown that it is the relativistic Compton electron beam directly created by the X-ray flash which is mainly responsible for the non-equilibrium plasma formation. Indeed, the low energy electrons (i.e., the non-relativistic ones) directly ejected from molecules by Compton collisions contribute to less than 1% on the creation of electrons in the plasma. In our simulation conditions, a non-equilibrium plasma with a low electron mean energy close to 1 eV and a concentration of charged species close to 1013 cm-3 is formed a few nanoseconds after the peak of X-ray flash intensity. 200 ns after the flash

  20. Illite spatial distribution controls Cr(VI) adsorption capacity and kinetics

    NASA Astrophysics Data System (ADS)

    WANG, L.; Li, L.

    2013-12-01

    In the natural surbsurface, clays typically are the major sorbing minerals for contaminants. Clays are known to distribute unevenly with low permeability 'clay' zones, which can have significant impacts on the sorption of contaminants. In this work, the effects of illite spatial distribution on Cr(VI) adsorption was examined using column experiments and reactive transport modeling. Three columns were set up with the same volume fraction of illite (10%). The Mixed column has illite evenly distributed within a quartz matrix; the Flow-transverse column has illite distributed in one horizontal zone in the direction that is perpendicular to the main flow; the Flow-parallel column has illite distributed in one cylindrical zone in the direction parallel to the main flow direction. Cr(VI) adsorption experiments were carried out under flow velocities of 0.58, 2.93, and 14.67 m/day. Two-dimensional reactive transport modeling was used to understand the role of illite distribution in determining Cr(VI) sorption capacity and kinetics. The result showed that illite spatial distribution strongly influence Cr(VI) sorption, the extent of which depend on the flow conditions . The Cr(VI) sorption kinectics was influenced by the permeability contrast and the preferential flow paths were taken place in high permeability zones. Under the flow rate of 0.58 m/day, the Cr(VI) adsorption in the Mixed and Flow-transverse columns was very similar, showing similar breakthrough time and sorption capacity. In contrast, an early breakthrough and an extended of Cr(VI) occured in the Flow-parallel column. The 2D reactive transport model showed that the inlet fluids flow through the quartz zone and bypass the lower permeability illite zone. Cr(VI) was first adsorbed on the illite-quartz interface early on and gradually diffuse into the illite zone over time. At the flow velocity of 2.93 m/day, the difference among the three columns was similar to the difference at the flow rate of 0.58 m/day. At

  1. HYDROBIOGEOCHEM: A coupled model of HYDROlogic transport and mixed BIOGEOCHEMical kinetic/equilibrium reactions in saturated-unsaturated media

    SciTech Connect

    Yeh, G.T.; Salvage, K.M.; Gwo, J.P.; Zachara, J.M.; Szecsody, J.E.

    1998-07-01

    The computer program HYDROBIOGEOCHEM is a coupled model of HYDROlogic transport and BIOGEOCHEMical kinetic and/or equilibrium reactions in saturated/unsaturated media. HYDROBIOGEOCHEM iteratively solves the two-dimensional transport equations and the ordinary differential and algebraic equations of mixed biogeochemical reactions. The transport equations are solved for all aqueous chemical components and kinetically controlled aqueous species. HYDROBIOGEOCHEM is designed for generic application to reactive transport problems affected by both microbiological and geochemical reactions in subsurface media. Input to the program includes the geometry of the system, the spatial distribution of finite elements and nodes, the properties of the media, the potential chemical and microbial reactions, and the initial and boundary conditions. Output includes the spatial distribution of chemical and microbial concentrations as a function of time and space, and the chemical speciation at user-specified nodes.

  2. On the Kinetics of Adsorption and Two-Dimensional Self-Assembly of Annexin A5 on Supported Lipid Bilayers

    PubMed Central

    Richter, Ralf P.; Lai Kee Him, Joséphine; Tessier, Béatrice; Tessier, Céline; Brisson, Alain R.

    2005-01-01

    Annexin A5 is a protein that binds to membranes containing negatively charged phospholipids in a calcium-dependent manner. We previously found that annexin A5 self-assembles into two-dimensional (2D) crystals on supported lipid bilayers (SLBs) formed on mica while a monolayer of disordered trimers is formed on SLBs on silica. Here, we investigated in detail and correlated the adsorption kinetics of annexin A5 on SLBs, supported on silica and on mica, with the protein's 2D self-assembly behavior. For this study, quartz crystal microbalance with dissipation monitoring and ellipsometry were combined with atomic force microscopy. We find, in agreement with previous studies, that the adsorption behavior is strongly dependent on the concentration of dioleoylphosphatidylserine (DOPS) in the SLB and the calcium concentration in solution. The adsorption kinetics of annexin A5 are similar on silica-SLBs and on mica-SLBs, when taking into account the difference in accessible DOPS between silica-SLBs and mica-SLBs. In contrast, 2D crystals of annexin A5 form readily on mica-SLBs, even at low protein coverage (≤10%), whereas they are not found on silica-SLBs, except in a narrow range close to maximal coverage. These results enable us to construct the phase diagram for the membrane binding and the states of 2D organization of annexin A5. The protein binds to the membrane in two different fractions, one reversible and the other irreversible, at a given calcium concentration. The adsorption is determined by the interaction of protein monomers with the membrane. We propose that the local membrane environment, as defined by the presence of DOPS, DOPC, and calcium ions, controls the adsorption and reversibility of protein binding. PMID:16085777

  3. On the kinetics of adsorption and two-dimensional self-assembly of annexin A5 on supported lipid bilayers.

    PubMed

    Richter, Ralf P; Him, Joséphine Lai Kee; Tessier, Béatrice; Tessier, Céline; Brisson, Alain R

    2005-11-01

    Annexin A5 is a protein that binds to membranes containing negatively charged phospholipids in a calcium-dependent manner. We previously found that annexin A5 self-assembles into two-dimensional (2D) crystals on supported lipid bilayers (SLBs) formed on mica while a monolayer of disordered trimers is formed on SLBs on silica. Here, we investigated in detail and correlated the adsorption kinetics of annexin A5 on SLBs, supported on silica and on mica, with the protein's 2D self-assembly behavior. For this study, quartz crystal microbalance with dissipation monitoring and ellipsometry were combined with atomic force microscopy. We find, in agreement with previous studies, that the adsorption behavior is strongly dependent on the concentration of dioleoylphosphatidylserine (DOPS) in the SLB and the calcium concentration in solution. The adsorption kinetics of annexin A5 are similar on silica-SLBs and on mica-SLBs, when taking into account the difference in accessible DOPS between silica-SLBs and mica-SLBs. In contrast, 2D crystals of annexin A5 form readily on mica-SLBs, even at low protein coverage (< or =10%), whereas they are not found on silica-SLBs, except in a narrow range close to maximal coverage. These results enable us to construct the phase diagram for the membrane binding and the states of 2D organization of annexin A5. The protein binds to the membrane in two different fractions, one reversible and the other irreversible, at a given calcium concentration. The adsorption is determined by the interaction of protein monomers with the membrane. We propose that the local membrane environment, as defined by the presence of DOPS, DOPC, and calcium ions, controls the adsorption and reversibility of protein binding. PMID:16085777

  4. Evidence for a Shared Mechanism in the Formation of Urea-Induced Kinetic and Equilibrium Intermediates of Horse Apomyoglobin from Ultrarapid Mixing Experiments

    PubMed Central

    Mizukami, Takuya; Abe, Yukiko; Maki, Kosuke

    2015-01-01

    In this study, the equivalence of the kinetic mechanisms of the formation of urea-induced kinetic folding intermediates and non-native equilibrium states was investigated in apomyoglobin. Despite having similar structural properties, equilibrium and kinetic intermediates accumulate under different conditions and via different mechanisms, and it remains unknown whether their formation involves shared or distinct kinetic mechanisms. To investigate the potential mechanisms of formation, the refolding and unfolding kinetics of horse apomyoglobin were measured by continuous- and stopped-flow fluorescence over a time range from approximately 100 μs to 10 s, along with equilibrium unfolding transitions, as a function of urea concentration at pH 6.0 and 8°C. The formation of a kinetic intermediate was observed over a wider range of urea concentrations (0–2.2 M) than the formation of the native state (0–1.6 M). Additionally, the kinetic intermediate remained populated as the predominant equilibrium state under conditions where the native and unfolded states were unstable (at ~0.7–2 M urea). A continuous shift from the kinetic to the equilibrium intermediate was observed as urea concentrations increased from 0 M to ~2 M, which indicates that these states share a common kinetic folding mechanism. This finding supports the conclusion that these intermediates are equivalent. Our results in turn suggest that the regions of the protein that resist denaturant perturbations form during the earlier stages of folding, which further supports the structural equivalence of transient and equilibrium intermediates. An additional folding intermediate accumulated within ~140 μs of refolding and an unfolding intermediate accumulated in <1 ms of unfolding. Finally, by using quantitative modeling, we showed that a five-state sequential scheme appropriately describes the folding mechanism of horse apomyoglobin. PMID:26244984

  5. An upwind, kinetic flux-vector splitting method for flows in chemical and thermal non-equilibrium

    NASA Technical Reports Server (NTRS)

    Eppard, W. M.; Grossman, B.

    1993-01-01

    We have developed new upwind kinetic difference schemes for flows with non-equilibrium thermodynamics and chemistry. These schemes are derived from the Boltzmann equation with the resulting Euler schemes developed as moments of the discretized Boltzmann scheme with a locally Maxwellian velocity distribution. Splitting the velocity distribution at the Boltzmann level is seen to result in a flux-split Euler scheme and is called Kinetic Flux Vector Splitting (KFVS). Extensions to flows with finite-rate chemistry and vibrational relaxation is accomplished utilizing nonequilibrium kinetic theory. Computational examples are presented comparing KFVS with the schemes of Van Leer and Roe for a quasi-one-dimensional flow through a supersonic diffuser, inviscid flow through two-dimensional inlet, and viscous flow over a cone at zero angle-of-attack. Calculations are also shown for the transonic flow over a bump in a channel and the transonic flow over an NACA 0012 airfoil. The results show that even though the KFVS scheme is a Riemann solver at the kinetic level, its behavior at the Euler level is more similar to the existing flux-vector splitting algorithms than to the flux-difference splitting scheme of Roe.

  6. Kinetics of re-equilibrium of oppositely charged hydrogel-surfactant system and its application in controlled release.

    PubMed

    Wang, Wei; Sande, Sv Arne

    2013-06-01

    We report a study of re-equilibrium kinetics of an oppositely charged hydrogel-surfactant system (cationically modified hydroxyethyl cellulose (cat-HEC) and sodium dodecyl sulfate (SDS)) and an application of the formulation for delivery of a water-insoluble molecule. Hydrogels have been applied for long-term delivery of water-soluble drugs due to their controlled-release property. However, the release mechanism of drugs solubilized by surfactants has not been clear. In the present study, SDS was used to solubilize a hydrophobic model drug, and thereafter, by electrostatic interaction between cat-HEC and SDS, the solubilized model drug was loaded into two types of cat-HEC hydrogels with different charge density. We found that the charge density of the polymers had a crucial effect on the loading capacity, without affecting the re-equilibrium kinetics. By an elaborate design of the experiments, the release profiles were fitted with one-dimensional Fickian law where we found the diffusivity of the drug to be constant and comparable to free micelles over a wide region of surfactant concentrations. The observed long-term controlled diffusion is discussed from a thermodynamic point of view. PMID:23679106

  7. Insights into the equilibrium, kinetic and thermodynamics of nickel removal by environmental friendly Lansium domesticum peel biosorbent.

    PubMed

    Lam, Yun Fung; Lee, Lai Yee; Chua, Song Jun; Lim, Siew Shee; Gan, Suyin

    2016-05-01

    Lansium domesticum peel (LDP), a waste material generated from the fruit consumption, was evaluated as a biosorbent for nickel removal from aqueous media. The effects of dosage, contact time, initial pH, initial concentration and temperature on the biosorption process were investigated in batch experiments. Equilibrium data were fitted by the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models using nonlinear regression method with the best-fit model evaluated based on coefficient of determination (R(2)) and Chi-square (χ(2)). The best-fit isotherm was found to be the Langmuir model exhibiting R(2) very close to unity (0.997-0.999), smallest χ(2) (0.0138-0.0562) and largest biosorption capacity (10.1mg/g) at 30°C. Kinetic studies showed that the initial nickel removal was rapid with the equilibrium state established within 30min. Pseudo-second-order model was the best-fit kinetic model indicating the chemisorption nature of the biosorption process. Further data analysis by the intraparticle diffusion model revealed the involvement of several rate-controlling steps such as boundary layer and intraparticle diffusion. Thermodynamically, the process was exothermic, spontaneous and feasible. Regeneration studies indicated that LDP biosorbent could be regenerated using hydrochloric acid solution with up to 85% efficiency. The present investigation proved that LDP having no economic value can be used as an alternative eco-friendly biosorbent for remediation of nickel contaminated water. PMID:26802563

  8. 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.

  9. The mechanism of inward rectification in Kir channels: A novel kinetic model with non-equilibrium thermodynamics approach.

    PubMed

    Hsieh, Chi-Pan; Chiang, Cheng-Chin; Huang, Chiung-Wei

    2016-05-01

    The mechanisms of the strong inward rectification in inward rectifier K(+) (Kir) channels are controversial because the drop in electrical potential due to the movement of the blocker and coupling ions is insufficient to explain the steep voltage-dependent block near the equilibrium potential. Here, we study the "driving force"-dependent block in Kir channels with a novel approach incorporating concepts from the non-equilibrium thermodynamics of small systems, and computer kinetic simulations based on the experimental data of internal Ba(2+) block on Kir2.1 channels. The steep exponential increase in the apparent binding rate near the equilibrium potential is explained, when the encounter frequency is construed as the likelihood of transfer events down or against the electrochemical potential gradient. The exponent of flux ratio, nf=2.62, implies that the blockage of the internal blocker may be coupled with the outward transport of 2 to 3K(+) ions. The flux-coupled block in the single-file multi-ion pore can be demonstrated by the concentration gradient alone, as well as when the driving force is the electrochemical potential difference across the membrane. PMID:26945551

  10. Landscape and Flux Framework for Non-Equilibrium Networks: Kinetic Paths and Rate Dynamics

    NASA Astrophysics Data System (ADS)

    Wang, Jin

    2012-02-01

    We developed a general framework to quantify three key ingredients for dynamics of nonequilibrium systems through path integrals in length space. First, we identify dominant kinetic paths as the ones with optimal weights, leading to effective reduction of dimensionality or degrees of freedom from exponential to polynomial so large systems can be treated. Second, we uncover the underlying nonequilibrium potential landscapes from the explorations of the state space through kinetic paths. We apply our framework to a specific example of nonequilibrium network system: lambda phage genetic switch. Two distinct basins of attractions emerge. The dominant kinetic paths from one basin to another are irreversible and do not follow the usual steepest descent or gradient path along the landscape. It reflects the fact that the dynamics of nonequilibrium systems is not just determined by potential gradient but also the residual curl flux force, suggesting experiments to test theoretical predictions. Third, we have calculated dynamic transition time scales from one basin to another critical for stability of the system through instantons. Theoretical predictions are in good agreements with wild type and mutant experiments.We further uncover the correlations between the kinetic transition time scales and the underlying landscape topography: the barrier heights along the dominant paths. We found that both the dominant paths and the landscape are relatively robust against the influences of external environmental perturbations and the system tends to dissipate less with less fluctuations. Our theoretical framework is general and can be applied to other nonequilibrium systems.

  11. Kinetic and Mechanistic Studies of the Deuterium Exchange in Classical Keto-Enol Tautomeric Equilibrium Reactions

    ERIC Educational Resources Information Center

    Nichols, Michael A.; Waner, Mark J.

    2010-01-01

    An extension of the classic keto-enol tautomerization of beta-dicarbonyl compounds into a kinetic analysis of deuterium exchange is presented. It is shown that acetylacetone and ethyl acetoacetate undergo nearly complete deuterium exchange of the alpha-methylene carbon when dissolved in methanol-d[subscript 4]. The extent of deuteration may be…

  12. Nonlinear optical property of hemicyanine self-assembled monolayers on gold and its adsorption kinetics probed by optical second-harmonic generation and surface plasmon resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Naraoka, Ryo; Kaise, Go; Kajikawa, Kotaro; Okawa, Haruki; Ikezawa, Hiroki; Hashimoto, Kazuhiko

    2002-08-01

    We have prepared the organosulfur self-assembled monolayer (SAM) containing hemicyanine on gold. It shows a large second-order nonlinear optical susceptibility χzzz=58 pm/V. The adsorption kinetics of the SAM on gold was also probed by the in situ real time measurements of second-harmonic generation (SHG) and surface plasmon resonance (SPR) spectroscopy. While the SHG kinetics was saturated immediately after the immersion of the gold substrate in the solution, the SPR kinetics showed additional slow adsorption for more than 20 000 s. This means that rapid formation of the well-ordered hemicyanine SAM is followed by gradual physisorption where the molecules are disordered.

  13. Calculation of the acid-base equilibrium constants at the alumina/electrolyte interface from the ph dependence of the adsorption of singly charged ions (Na+, Cl-)

    NASA Astrophysics Data System (ADS)

    Gololobova, E. G.; Gorichev, I. G.; Lainer, Yu. A.; Skvortsova, I. V.

    2011-05-01

    A procedure was proposed for the calculation of the acid-base equilibrium constants at an alumina/electrolyte interface from experimental data on the adsorption of singly charged ions (Na+, Cl-) at various pH values. The calculated constants (p K {1/0}= 4.1, p K {2/0}= 11.9, p K {3/0}= 8.3, and p K {4/0}= 7.7) are shown to agree with the values obtained from an experimental pH dependence of the electrokinetic potential and the results of potentiometric titration of Al2O3 suspensions.

  14. 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.

  15. Determination of equilibrium constants for the reaction between acetone and HO2 using infrared kinetic spectroscopy.

    PubMed

    Grieman, Fred J; Noell, Aaron C; Davis-Van Atta, Casey; Okumura, Mitchio; Sander, Stanley P

    2011-09-29

    The reaction between the hydroperoxy radical, HO(2), and acetone may play an important role in acetone removal and the budget of HO(x) radicals in the upper troposphere. We measured the equilibrium constants of this reaction over the temperature range of 215-272 K at an overall pressure of 100 Torr using a flow tube apparatus and laser flash photolysis to produce HO(2). The HO(2) concentration was monitored as a function of time by near-IR diode laser wavelength modulation spectroscopy. The resulting [HO(2)] decay curves in the presence of acetone are characterized by an immediate decrease in initial [HO(2)] followed by subsequent decay. These curves are interpreted as a rapid (<100 μs) equilibrium reaction between acetone and the HO(2) radical that occurs on time scales faster than the time resolution of the apparatus, followed by subsequent reactions. This separation of time scales between the initial equilibrium and ensuing reactions enabled the determination of the equilibrium constant with values ranging from 4.0 × 10(-16) to 7.7 × 10(-18) cm(3) molecule(-1) for T = 215-272 K. Thermodynamic parameters for the reaction determined from a second-law fit of our van't Hoff plot were Δ(r)H°(245) = -35.4 ± 2.0 kJ mol(-1) and Δ(r)S°(245) = -88.2 ± 8.5 J mol(-1) K(-1). Recent ab initio calculations predict that the reaction proceeds through a prereactive hydrogen-bonded molecular complex (HO(2)-acetone) with subsequent isomerization to a hydroxy-peroxy radical, 2-hydroxyisopropylperoxy (2-HIPP). The calculations differ greatly in the energetics of the complex and the peroxy radical, as well as the transition state for isomerization, leading to significant differences in their predictions of the extent of this reaction at tropospheric temperatures. The current results are consistent with equilibrium formation of the hydrogen-bonded molecular complex on a short time scale (100 μs). Formation of the hydrogen-bonded complex will have a negligible impact on the

  16. Equilibrium and kinetic Si isotope fractionation factors and their implications on Si isotope distributions in the Earth's surface environments

    NASA Astrophysics Data System (ADS)

    Tang, M.; Zhang, S.; Liu, Y.

    2015-12-01

    Several important equilibrium Si isotope fractionation factors among minerals, organic molecules and the H4SiO4 solution are complemented to facilitate explanation of distributions of Si isotope in the Earth's surface environments. The results reveal that heavy Si isotopes will be significantly enriched in the secondary silicate minerals in comparison to aqueous H4SiO4. On the contrary, quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution. The extent of 28Si-enrichment in hyper-coordinated organosilicon complexes is found the largest. In addition, the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer is calculated and the result supports previous statement that highly 28Si-enrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations. With equilibrium Si isotope fractionation factors provided here, Si isotope distributions in many surface systems of the Earth can be explained. For example, the change of bulk soil δ30Si can be predicted as a concave pattern with respect to weathering degree, with the minimum value where allophane completely dissolves and the total amount of sesqui-oxides and poorly crystalline minerals reaches its maximum. When well-crystallized clays start to precipitate from pore solutions under equilibrium conditions, the bulk soil δ30Si will increase again and reach a constant value. Similarly, the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain δ30Si variations in the ground water profile. Equilibrium Si isotope fractionations among quadra-coordinated organosilicon complexes and the H4SiO4 solution may also shed the light on the Si isotope distributions in Si-accumulating plants.

  17. The kinetics of the bimolecular A+B --> 0 reaction in condensed matter: Effects of non-equilibrium charge screening

    NASA Astrophysics Data System (ADS)

    Kuzovkov, V. N.; Kotomin, E. A.; von Niessen, W.

    1996-12-01

    The kinetics of the bimolecular A+B→0 reaction between charged reactants is studied in two dimensions, i.e., on a surface. The theory is based on the Kirkwood superposition approximation for three-particle densities and the self-consistent treatment of the electrostatic interactions defined by the non-uniform spatial distribution of similar and dissimilar reactants. Special attention is paid to pattern formation and many-particle effects arising from reaction-induced formation of loose domains containing similar reactants only. It is shown that the critical exponent α characterizing the algebraic concentration decay law, n(t)∝t-α, differs strongly between symmetric (DA=DB) and asymmetric (DA=0) reactant mobilities. This effect is abnormal from the point of view of standard chemical kinetics. It arises directly from the specific spatial distribution in the system as in ``raisins A in a dough B.'' At long reaction times the asymptotics of the interaction potentials is of non-equilibrium type at large relative distances. The accumulation kinetics in the presence of a permanent source is studied. Results of the microscopic formalism are compared with a previous mesoscopic theory.

  18. Insight into biosorption equilibrium, kinetics and thermodynamics of crystal violet onto Ananas comosus (pineapple) leaf powder

    NASA Astrophysics Data System (ADS)

    Chakraborty, Sagnik; Chowdhury, Shamik; Saha, Papita Das

    2012-06-01

    Biosorption performance of pineapple leaf powder (PLP) for removal of crystal violet (CV) from its aqueous solutions was investigated. To this end, the influence of operational parameters such as pH, biosorbent dose, initial dye concentration and temperature were studied employing a batch experimental setup. The biosorption process followed the Langmuir isotherm model with high correlation coefficients ( R 2 > 0.99) at different temperatures. The maximum monolayer biosorption capacity was found to be 78.22 mg g-1 at 293 K. The kinetic data conformed to the pseudo-second-order kinetic model. The activation energy of the system was calculated as 58.96 kJ mol- 1 , indicating chemisorption nature of the ongoing biosorption process. A thermodynamic study showed spontaneous and exothermic nature of the biosorption process. Owing to its low cost and high dye uptake capacity, PLP has potential for application as biosorbent for removal of CV from aqueous solutions.

  19. Sampling the equilibrium kinetic network of Trp-cage in explicit solvent

    NASA Astrophysics Data System (ADS)

    Du, Weina; Bolhuis, Peter G.

    2014-05-01

    We employed the single replica multiple state transition interface sampling (MSTIS) approach to sample the kinetic (un)folding network of Trp-cage mini-protein in explicit water. Cluster analysis yielded 14 important metastable states in the network. The MSTIS simulation thus resulted in a full 14 × 14 rate matrix. Analysis of the kinetic rate matrix indicates the presence of a near native intermediate state characterized by a fully formed alpha helix, a slightly disordered proline tail, a broken salt-bridge, and a rotated arginine residue. This intermediate was also found in recent IR experiments. Moreover, the predicted rate constants and timescales are in agreement with previous experiments and simulations.

  20. A Photochemical Reactor for the Study of Kinetics and Adsorption Phenomena

    ERIC Educational Resources Information Center

    Poce-Fatou, J. A.; Gil, M. L. A.; Alcantara, R.; Botella, C.; Martin, J.

    2004-01-01

    The interaction between light and matter is examined with the help of a photochemical experiment. This experiment is useful for the investigation of heterogeneous catalysis, semiconductor properties and adsorption phenomena.

  1. Adsorption of gases and vapors on nanoporous Ni2(4,4'-Bipyridine)3(NO3)4 metal-organic framework materials templated with methanol and ethanol: structural effects in adsorption kinetics.

    PubMed

    Fletcher, Ashleigh J; Cussen, Edmund J; Bradshaw, Darren; Rosseinsky, Matthew J; Thomas, K Mark

    2004-08-11

    Desolvation of Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2CH(3)OH and Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2C(2)H(5)OH give flexible metal-organic porous structures M and E, respectively, which have the same stoichiometry, but subtly different structures. This study combines measurements of the thermodynamics and kinetics of carbon dioxide, methanol, and ethanol sorption on adsorbents M and E over a range of temperatures with adsorbent structural characterization at different adsorbate (guest) loadings. The adsorption kinetics for methanol and ethanol adsorption on porous structure E obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. The corresponding adsorption kinetics for porous structure M follow a double exponential (DE) model, which is consistent with two different barriers for diffusion through the windows and along the pores in the structure. The former is a high-energy barrier due to the opening of the windows in the structure, required to allow adsorption to occur, while the latter is a lower-energy barrier for diffusion in the pore cavities. X-ray diffraction studies at various methanol and ethanol loadings showed that the host porous structures E and M underwent different scissoring motions, leading to an increase in unit cell volume with the space group remaining unchanged during adsorption. The results are discussed in terms of reversible adsorbate/adsorbent (host/guest) structural changes and the adsorption mechanism involving hydrogen-bonding interactions with specific surface sites for methanol and ethanol adsorption in relation to pore size and extent of filling. This paper contains the first evidence for individual kinetic barriers to diffusion through windows and pore cavities in flexible porous coordination polymer frameworks. PMID:15291578

  2. Equilibrium and Kinetic Studies of Phosphate Removal from Solution onto a Hydrothermally Modified Oyster Shell Material

    PubMed Central

    Chen, Jie; Cai, Yun; Clark, Malcolm; Yu, Yan

    2013-01-01

    Phosphate removal to a hydrothermally modified fumed silica and pulverized oyster shell material for use in wastewater treatments were made. Sorption data modeling (pH’s 3–11, P concentrations of 3, 5, 10, 15, 20, & 25 mg/L, and at an ambient temperature of 23°C) indicate that an optimal removal of P occurs at pH 11. Three kinetic models were also applied (a pseudo-first-order Lagergren kinetic model, a pseudo-second-order (PSO) kinetic and Elovich) and indicate that a PSO model best describes P-removal. In addition, an application of the Weber and Morris intra-particle diffusion model indicates that external mass transfer and intra-particle diffusion were both involved in the rate-determining step. Langmuir, Freundlich modeling of the sorption data also indicate that the heterogeneous Freundlich sorption site model best describes the data although Langmuir data also fit with data tailing suggesting data are not linear. The data collected indicates that the hydrothermally modified fumed silica and pulverized oyster shell material is suitable for use in wastewater treatment, with P-removal to the solids being preferential and spontaneous. PMID:23565207

  3. Dynamic surface tension and adsorption kinetics of a siloxane dicephalic surfactant

    NASA Astrophysics Data System (ADS)

    Zhang, Dianlong; Qu, Wenshan; Li, Zhe

    2015-02-01

    The dynamic surface tension (DST) of a siloxane dicephalic surfactant was measured by using the maximum bubble pressure method. By using the classical Ward and Tordai equation, the diffusion coefficient for each bulk surfactant concentration was calculated. The results show that at the initial adsorption stage and at the end of the adsorption process, the dynamic surface tension data were all consistent with this diffusion-controlled mechanism. Their diffusion coefficient was slightly lower than that for conventional hydrocarbon surfactants.

  4. On the equivalence between specific adsorption and kinetic equation descriptions of the admittance response in electrolytic cells.

    PubMed

    Evangelista, Luiz Roberto; Lenzi, Ervin Kaminski; Barbero, Giovanni; Macdonald, James Ross

    2013-03-21

    The response of an electrolytic cell, in the shape of a slab, is analyzed in the framework of the Poisson-Nernst-Planck model in the limit of full dissociation. Two different types of boundary conditions on the electrodes are compared. One type describes the exchange of charges between the volume and the external circuit, in the form originally proposed by Chang and Jaffé and later extended to include specific adsorption, where the surface current density is proportional to the variation of the surface bulk density of ions with respect to the value of equilibrium. The other one describes the surface adsorption, in the limit of Langmuir. We show that in the simple case where the ions dissolved in the insulating liquid are identical in all the aspects, except for the sign of the charge, the two models are equivalent only if the phenomenological parameter entering the boundary condition of the Chang-Jaffé model, κ, is frequency dependent, and related to the adsorption coefficient, k(a), in the form κ = iωτ/(1 + iωτ)k(a), where τ is the desorption time and ω the circular frequency of the applied voltage, as proposed long ago by Macdonald. PMID:23534648

  5. Equilibrium and kinetic studies for the biosorption system of copper(II) ion from aqueous solution using Tectona grandis L.f. leaves powder.

    PubMed

    Prasanna Kumar, Y; King, P; Prasad, V S R K

    2006-09-21

    The biosorption of copper(II) ions from aqueous solution by Tectona grandis L.f. was studied in a batch adsorption system as a function of pH, metal ion concentration, adsorbent concentration and adsorbent size. The biosorption capacities and rates of copper(II) ions onto T. grandis L.f. were evaluated. The Langmuir, Freundlich, Redlich-Peterson and Temkin adsorption models were applied to describe the isotherms and isotherm constants. Biosorption isothermal data could be well interpreted by the Langmuir model with maximum adsorption capacity of 15.43 mg/g of copper(II) ion on T. grandis L.f. leaves powder. The kinetic experimental data properly correlated with the second-order kinetic model. Various thermodynamic parameters such as deltaG(o), deltaH(o), and deltaS(o) were calculated indicating that this system was a spontaneous and exothermic process. PMID:16704905

  6. Adsorption of chlorophenols on granular activated carbon

    SciTech Connect

    Yang, M.

    1993-12-31

    Studies were undertaken of the adsorption of chlorinated phenols from aqueous solution on granular activated carbon (Filtrasorb-400, 30 x 40 mesh). Single-component equilibrium adsorption data on the eight compounds in two concentration ranges at pH 7.0 fit the Langmuir equation better than the Freundlich equation. The adsorptive capacities at pH 7.0 increase from pentachlorophenol to trichlorophenols and are fairly constant from trichlorophenols to monochlorophenols. The adsorption process was found to be exothermic for pentachlorophenol and 2,4,6-trichlorophenol, and endothermic for 2,4-dichlorophenol and 4-chlorophenol. Equilibrium measurements were also conducted for 2,4,5-trichlorophenol, 2,4-dichlorophenol, and 4-chlorophenol over a wide pH range. A surface complexation model was proposed to describe the effect of pH on adsorption equilibria of chlorophenols on activated carbon. The simulations of the model are in excellent agreement with the experimental data. Batch kinetics studies were conducted of the adsorption of chlorinated phenols on granular activated carbon. The results show that the surface reaction model best describes both the short-term and long-term kinetics, while the external film diffusion model describes the short-term kinetics data very well and the linear-driving-force approximation improved its performance for the long-term kinetics. Multicomponent adsorption equilibria of chlorophenols on granular activated carbon was investigated in the micromolar equilibrium concentration range. The Langmuir competitive and Ideal Adsorbed Solution (IAS) models were tested for their performance on the three binary systems of pentachlorophenol/2,4,6-trichlorophenol, 2,4,6-trichlorophenol/2,4-dichlorophenol, and 2,4-dichlorophenol/4-chlorophenol, and the tertiary system of 2,4,6-trichlorophenol/2,4-dichlorophenol/4-chlorophenol, and found to fail to predict the two-component adsorption equilibria of the former two binary systems and the tertiary system.

  7. Graphical representation for isothermal kinetics of non-equilibrium grain-boundary segregation

    SciTech Connect

    Wang Kai; Xu Tingdong; Song Shenhua; Shao Chong

    2011-06-15

    A model of non-equilibrium grain-boundary segregation of solute is expressed with graphs for the isothermal aging at various temperatures after quenching from a solution temperature. It is found from the graphical representations that when the samples are aged for a certain time at various temperatures there is a maximum value in the segregation concentration at a certain temperature. The aging time is equal or close to the critical time of non-equilibrium segregation corresponding to this temperature. This finding is experimentally confirmed with sulfur in an Ni-base superalloy with the aid of Auger electron spectroscopy. As an application of the new finding, a mechanism for intermediate temperature embrittlement of alloys is suggested and identified experimentally with tension tests of the superalloy. - Research Highlights: {yields} A peak of solute segregation emerges at a temperature when aging for a certain time at various temperatures after quenching. {yields} The aging time is equal or close to the critical time of segregation at this temperature. {yields} This finding is experimentally confirmed in an Ni-Cr-Fe superalloy. {yields} A mechanism for intermediate temperature embrittlement of alloys is proposed.

  8. Supercritical CO2 extraction of oilseeds: review of kinetic and equilibrium models.

    PubMed

    del Valle, José M; de la Fuente, Juan C

    2006-01-01

    Mass transfer models on supercritical carbon dioxide (SC-CO2) extraction of vegetable oils are reviewed, that may facilitate the scale-up of laboratory data for industrial design purposes. Reviewed mechanisms of oil transport within the solid matrix include the desorption from the solid, the formation of a shrinking core of condensed oil in a non-adsorbing porous matrix, and diffusion in a homogenous medium. Analyzed simplificat ions of a general mass transfer model include external control of mass transfer rates, internal control of mass transfer rates, consideration of a linear driving force, and steady state approximations, among others. More complex two-stage models, and critical comparisons of some of the proposed models are also included. Trends for the external mass transfer coefficient and effective diffusivity in the solid matrix from studies on SC-CO2 extraction of oil from vegetable substrates are thoroughly discussed and contrasted with those obtained using simpler model systems. The possible effect of the axial dispersion on the rate of extraction is also discussed. Finally, the high-pressure vegetable oil-CO2 phase equilibrium is discussed in connection with its influence on the mass transfer process. Special emphasis is given to the role of the solid matrix on high-pressure phase equilibrium. PMID:16431407

  9. Structure regulation of silica nanotubes and their adsorption behaviors for heavy metal ions: pH effect, kinetics, isotherms and mechanism.

    PubMed

    Wang, Pan; Du, Mingliang; Zhu, Han; Bao, Shiyong; Yang, Tingting; Zou, Meiling

    2015-04-01

    Silica nanotubes (SNTs) with controlled nanotubular structure were synthesized via an electrospinning and calcination process. In this regard, SNTs were found to be ideal adsorbents for Pb(II) removal with a higher adsorption capacity, and surface modification of the SNTs by sym-diphenylcarbazide (SD-SNTs) markedly enhanced the adsorption ability due to the chelating interaction between imino groups and Pb(II). The pH effect, kinetics, isotherms and adsorption mechanism of SNTs and SD-SNTs on Pb(II) adsorption were investigated and discussed detailedly. The adsorption capacity for Pb(II) removal was found to be significantly improved with the decrease of pH value. The Langmuir adsorption model agreed well with the experimental data. As for kinetic study, the adsorption onto SNTs and SD-SNTs could be fitted to pseudo-first-order and pseudo-second-order model, respectively. In addition, the as-prepared SNTs and SD-SNTs also exhibit high adsorption ability for Cd(II) and Co(II). The experimental results demonstrate that the SNTs and SD-SNTs are potential adsorbents and can be used effectively for the treatment of heavy-metal-ions-containing wastewater. PMID:25615696

  10. Kinetic and equilibrium studies of porphyrin interactions with unilamellar lipidic vesicles.

    PubMed

    Kuzelová, K; Brault, D

    1994-08-16

    The interaction of deuteroporphyrin with dimyristoylphosphatidylcholine unilamellar vesicles of various sizes (ranging from 38 to 222 nm) has been studied using a stopped flow with fluorescence detection. Beside the kinetics of porphyrin incorporation into vesicles, the transfer of porphyrin from vesicles to human serum albumin has been investigated both experimentally and theoretically. The effects of both vesicle and albumin concentrations indicate that the transfer proceeds through the aqueous phase. It is governed by the rate of incorporation of porphyrin into the outer vesicle hemileaflet (kon), by the exit to the bulk aqueous medium (koff), and by the association (kas) and dissociation (kdis) constants relative to albumin. In both systems studied, a slower transbilayer flip-flop accounts for the biphasic character of the kinetics. This model is strongly supported by the effects of vesicle size, temperature, and cholesterol. The dependence of kon on the vesicle size indicates that the incorporation is diffusion controlled. The constant koff is found to be closely coupled to the phase state of the bilayer. The transbilayer flip-flop rate constant is approximately the same in both directions (approximately 0.4 s-1 at 32 degrees C and pH 7.4). It is strongly affected by the presence of cholesterol in vesicles and by the temperature, with a sharp enhancement around the phase transition. With the exception of very small vesicles obtained by sonication, no influence of the vesicle size on the flip-flop rate was observed. An accelerating effect of tetrahydrofuran, used to improve the solubility of porphyrin, has been noted. Steady-state measurements and kinetics results were in excellent agreement. The interest of systems involving albumin as a scavenger to extract important rate constants, is emphasized. PMID:8068619

  11. Equilibrium and kinetic studies on biosorption of Pb(II) by common edible macrofungi: a comparative study.

    PubMed

    Jiang, Yuan; Hao, Ruixia; Yang, Shiqin

    2016-04-01

    In this work, we studied the natural bioaccumulation and biosorption of Pb(II) in several common edible macrofungi. The macrofungi include the following species: Lentinus edodes, Pleurotus eryngii, Flammulina velutipes, Hypsizygus marmoreus, and Agrocybe cylindracea. The present analysis of Pb(II) revealed distinct capabilities of metal accumulation among individual species. Moreover, the natural concentrations of lead did not reach a health risk level when cultivated in uncontaminated soil. In the biosorption experiment by edible macrofungi, we found that the equilibrium data of living sporocarp (P. eryngii and H. marmoreus) and the homogenate of L. edodes and F. velutipes fit the Freundlich model well. Other data samples exhibited a better fit to the Langmuir model. The edible macrofungi showed a higher lead removal capacity than did other biosorbents. Furthermore, the pseudo-second-order kinetics model exhibited the best fit to the biosorption processes. The effectiveness of edible macrofungi as biosorbents for Pb(II) was confirmed. PMID:26928439

  12. Kinetic equilibrium of space charge dominated beams in a misaligned quadrupole focusing channel

    SciTech Connect

    Goswami, A.; Sing Babu, P.; Pandit, V. S.

    2013-07-15

    The dynamics of intense beam propagation through the misaligned quadrupole focusing channel has been studied in a self-consistent manner using nonlinear Vlasov-Maxwell equations. The equations of motion of the beam centroid have been developed and found to be independent of any specific beam distribution. A Vlasov equilibrium distribution and beam envelope equations have been obtained, which provide us a theoretical tool to investigate the dynamics of intense beam propagating in a misaligned quadrupole focusing channel. It is shown that the displaced quadrupoles only cause the centroid of the beam to wander off axis. The beam envelope around the centroid obeys the familiar Kapchinskij-Vladimirskij envelope equation that is independent of the centroid motion. However, the rotation of the quadrupole about its optical axis affects the beam envelope and causes an increase in the projected emittances in the two transverse planes due to the inter-plane coupling.

  13. Engineering Signaling Aptamers That Rely on Kinetic Rather Than Equilibrium Competition.

    PubMed

    Du, Yan; Zhen, Shu Jun; Li, Bingling; Byrom, Michelle; Jiang, Yu Sherry; Ellington, Andrew D

    2016-02-16

    During the past decade, aptasensors have largely been designed on the basis of the notion that ligand-modulated equilibration between aptamer conformations could be exploited for sensing. One implementation of this strategy has been to denature the aptamer with an antisense oligonucleotide, wait for dissociation of the antisense oligonucleotide, and stabilize the folded, signaling conformer with a ligand. However, there is a large kinetic barrier associated with releasing the oligonucleotide from the aptamer to again obtain an active, binding conformation. If the length of the antisense oligonucleotide is decreased to make dissociation from the aptamer more favorable, higher background signals are observed. To improve the general methodology for developing aptasensors, we have developed a novel and robust strategy for aptasensor design in which an oligonucleotide kinetically competes with the ligand for binding rather than having to be released from a stable duplex. While the oligonucleotide can induce conformational change, it initially chooses between the aptamer and a molecular beacon (MB), a process that does not require a lengthy pre-equilibration. Using an anti-ricin aptamer as a starting point, we developed a "competitive" aptasensor with a measured limit of detection (LOD) of 30 nM with an optical readout and as low as 3 nM for ricin toxin A-chain (RTA) detection on an electrochemical platform. PMID:26750592

  14. Equilibrium and kinetic studies on reversible and irreversible denaturation of micrococcal nuclease.

    PubMed

    Nohara, D; Yamada, T; Watanabe, A; Sakai, T

    1994-07-01

    The effect of pH and temperature on the thermal denaturation of micrococcal nuclease were investigated. The ranges employed were between pH3.30 and pH9.70 and between 10 degrees C and 85 degrees C, respectively. The reversible denaturation involved in the whole process was clearly discriminated from the irreversible one. The former took place with a large enthalpy change of 384 kJ mol(-1) at pH 9.70, where the enzyme exhibited it s maximum activity. The latter probably led to aggregation because the successive long incubation after complete deactivation caused precipitation. A reasonable scheme explaining the process involving both denaturations was proposed and the kinetic on the irreversible deactivation was performed. It was revealed that the irreversible deactivation involved two types of reactions whose activation energies were relatively small: 22.2 kJ mol(-1) and 18.8 kJ mol(-1). The presence of sucrose suppressed the reversible denaturation without significant influence on enthalpy change, whereas it affected little the irreversible deactivation kinetically. The effects of pH change and addition of sucrose on the denaturation were discussed thermodynamically, especially in terms of the entropy change. PMID:18618743

  15. Stabilizing and destabilizing protein surfactant-based foams in the presence of a chemical surfactant: Effect of adsorption kinetics.

    PubMed

    Li, Huazhen; Le Brun, Anton P; Agyei, Dominic; Shen, Wei; Middelberg, Anton P J; He, Lizhong

    2016-01-15

    Stimuli-responsive protein surfactants promise alternative foaming materials that can be made from renewable sources. However, the cost of protein surfactants is still higher than their chemical counterparts. In order to reduce the required amount of protein surfactant for foaming, we investigated the foaming and adsorption properties of the protein surfactant, DAMP4, with addition of low concentrations of the chemical surfactant sodium dodecylsulfate (SDS). The results show that the small addition of SDS can enhance foaming functions of DAMP4 at a lowered protein concentration. Dynamic surface tension measurements suggest that there is a synergy between DAMP4 and SDS which enhances adsorption kinetics of DAMP4 at the initial stage of adsorption (first 60s), which in turn stabilizes protein foams. Further interfacial properties were revealed by X-ray reflectometry measurements, showing that there is a re-arrangement of adsorbed protein-surfactant layer over a long period of 1h. Importantly, the foaming switchability of DAMP4 by metal ions is not affected by the presence of SDS, and foams can be switched off by the addition of zinc ions at permissive pH. This work provides fundamental knowledge to guide formulation using a mixture of protein and chemical surfactants towards a high performance of foaming at a low cost. PMID:26433478

  16. Kinetics of adsorptive removal of DEClP and GB on impregnated Al2O3 nanoparticles.

    PubMed

    Saxena, Amit; Srivastava, Avanish K; Singh, Beer; Gupta, Arvind K; Suryanarayana, Malladi V S; Pandey, Pratibha

    2010-03-15

    Nanoparticles of AP-Al(2)O(3) (aero-gel produced alumina) have been produced by an alkoxide based synthesis involving aluminum powder, methanol, toluene and water. Thus produced alumina nanoparticles were characterized and the data indicated the formation of nanoparticles of alumina in the size range of 2-30 nm with high surface area (375 m(2)/g). Thereafter, these nanoparticles were impregnated with reactive chemicals. Adsorptive removal kinetics for DEClP (diethylchlorophosphate) and GB (isopropylmethylphosphonofluoridate, sarin) was monitored by GC-FID (gas chromatograph coupled with flame ionization detector) technique and found to be following pseudo first order reaction kinetics. Among impregnated AP-Al(2)O(3) nanoparticles based sorbent systems AP-Al(2)O(3) impregnated with 9-molybdo-3-vanadophosphoric acid (10%, w/w) was found to be the most reactive with least half-life values of 7 and 30 min for the removal of DEClP and GB, respectively, whereas unimpregnated AP-Al(2)O(3) nanoparticles showed the best adsorption potential among all studied systems. In addition to this, hydrolysis reaction {identified using GC/MS (gas chromatograph coupled with mass spectrometer) technique} was found to be the route of degradation of DEClP and GB on impregnated alumina nanoparticles. PMID:19926215

  17. Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction.

    PubMed

    Xue, Dong-Xu; Belmabkhout, Youssef; Shekhah, Osama; Jiang, Hao; Adil, Karim; Cairns, Amy J; Eddaoudi, Mohamed

    2015-04-22

    Reticular chemistry approach was successfully employed to deliberately construct new rare-earth (RE, i.e., Eu(3+), Tb(3+), and Y(3+)) fcu metal-organic frameworks (MOFs) with restricted window apertures. Controlled and selective access to the resultant contracted fcu-MOF pores permits the achievement of the requisite sorbate cutoff, ideal for selective adsorption kinetics based separation and/or molecular sieving of gases and vapors. Predetermined reaction conditions that permitted the formation in situ of the 12-connected RE hexanuclear molecular building block (MBB) and the establishment of the first RE-fcu-MOF platform, especially in the presence of 2-fluorobenzoic acid (2-FBA) as a modulator and a structure directing agent, were used to synthesize isostructural RE-1,4-NDC-fcu-MOFs based on a relatively bulkier 2-connected bridging ligand, namely 1,4-naphthalenedicarboxylate (1,4-NDC). The subsequent RE-1,4-NDC-fcu-MOF structural features, contracted windows/pores and high concentration of open metal sites combined with exceptional hydrothermal and chemical stabilities, yielded notable gas/solvent separation properties, driven mostly by adsorption kinetics as exemplified in this work for n-butane/methane, butanol/methanol, and butanol/water pair systems. PMID:25825923

  18. 2,4-D adsorption to biochars: effect of preparation conditions on equilibrium adsorption capacity and comparison with commercial activated carbon literature data.

    PubMed

    Kearns, J P; Wellborn, L S; Summers, R S; Knappe, D R U

    2014-10-01

    Batch isotherm experiments were conducted with chars to study adsorption of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Chars generated from corncobs, bamboo and wood chips in a laboratory pyrolyzer at 400-700 °C were compared with traditional kiln charcoals collected from villages in S/SE Asia and with activated carbons (ACs). 2,4-D uptake by laboratory chars obtained from bamboo and wood chips after 14 h of pyrolysis at 700 °C, from wood chips after 96 h of pyrolysis at 600 °C, and one of the field-collected chars (basudha) was comparable to ACs. H:C and O:C ratios declined with pyrolysis temperature and duration while surface area increased to >500 m(2)/g. Increasing pyrolysis intensity by increasing temperature and/or duration of heating was found to positively influence adsorption capacity yield (mg(2,4-D/g(feedstock))) over the range of conditions studied. Economic analysis showed that high temperature chars can be a cost-effective alternative to ACs for water treatment applications. PMID:24934321

  19. Evidence for nascent equilibrium nuclei as progenitors of anomalous transformation kinetics in a Pu-Ga alloy

    SciTech Connect

    Jeffries, J R; Blobaum, K M; Wall, M A; Schwartz, A J

    2009-05-27

    By alloying Pu with Ga, the face-centered-cubic {delta} phase can be retained down to room temperature in a metastable configuration, which ultimately yields to chemical driving forces by undergoing the {delta} {yields} {alpha}' isothermal martensitic transformation below M{sub s} {approx} = -100 C. This transformation is found to exhibit anomalous transformation kinetics, the nature of which has remained elusive for over 30 years. Recently, a 'conditioning' treatment - an isothermal hold above M{sub s} - has been shown to dramatically affect the amount of {alpha}' phase formed during the transformation. Herein, we report evidence that the conditioning treatment induces the lower-C of the double-C curve, and we furthermore implicate the classical nucleation of equilibrium phases within the conditioning range as the underlying mechanism behind conditioning in Pu-Ga alloys. This mechanism should not be rigorously exclusive to plutonium alloys as it arises from the proximity between the retained metastable phase and the low-energy equilibrium phases.

  20. Kinetic studies of competitive adsorption processes related to automobile catalytic converters

    SciTech Connect

    Zaera, F.; Paffett, M.T.

    1998-12-31

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The goal of this project was to study the microscopic details for the adsorption of CO, NO, and O{sub 2} on transition metal surfaces under conditions resembling those present in automobile catalytic converters. Initial sticking coefficients were measured as a function of temperature on transition metal single crystals by using a method originally developed by King and Wells. These measurements were performed under conditions emulating those typical of competitive adsorption, namely, where the substrate is exposed to a mixture of two or more gases simultaneously, or where one molecule is adsorbed on the surface prior to exposure to the second gas. The experimental results were then analyzed by using Monte Carlo computer simulation algorithm in an attempt to better understand the relevant aspects of the adsorption process.

  1. 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.

  2. Engineering a lignocellulosic biosorbent--coir pith for removal of cesium from aqueous solutions: equilibrium and kinetic studies.

    PubMed

    Parab, Harshala; Sudersanan, M

    2010-02-01

    A novel method of engineering lignocellulosic biosorbent- coir pith (CP) by incorporation of nickel hexacyanoferrate (NiHCF), also referred to as Prussian blue analogue (PBA) inside its porous matrix is reported. Structural characterization confirmed the successful synthesis of NiHCF in the coir pith matrix. Sorption capacity of coir pith (CP) before and after loading of NiHCF was investigated for cesium (Cs) in batch equilibrium studies. Kinetic studies showed that the sorption process was rapid and saturation was attained within 30 min. The applicability of non linear Langmuir, Freundlich and Redlich Peterson isotherms was examined for the experimental data. The present studies revealed that there was nearly 100% increase in the sorption capacity of CP after its surface modification with NiHCF. Owing to its low cost, fast sorption kinetics and high uptake capacity, coir pith loaded with NiHCF (CP-NiHCF) seems to be one of the most promising biosorbents for recovery of cesium from liquid nuclear wastes. PMID:19819515

  3. Reaction of plutonium with water kinetic and equilibrium behavior of binary and ternary phases in the Pu + O + H system

    SciTech Connect

    Haschke, J.M.; Hodges, A.E. III; Bixby, G.E.; Lucas, R.L.

    1983-02-03

    The kinetic and equilibrium behavior of the Pu + O + H system has been studied by measuring the production of hydrogen gas formed by a sequence of hydrolysis reactions. The kinetic dependence of the Pu + H/sub 2/O reaction on salt concentration and temperature has been defined. The metal is quantitatively converted to a fine black powder which has been identified as plutonium monoxide monohydride, PuOH. Other hydrolysis products formed in aqueous media include a second oxide hydride, Pu/sub 7/O/sub 9/H/sub 3/, and the oxides Pu/sub 2/O/sub 3/, Pu/sub 7/O/sub 12/, Pu/sub 9/O/sub 16/, Pu/sub 10/O/sub 18/, Pu/sub 12/O/sub 22/, and PuO/sub 2/. Thermal decomposition products of PuOH include Pu/sub 2/O/sub 2/H and PuO. A tentative phase diagram for Pu + O + H is presented and structural relationships of the oxide hydrides and oxides are discussed. 10 figures, 5 tables.

  4. Equilibrium and kinetic studies on the interaction of tetracyclines with calcium and magnesium.

    PubMed

    Martin, S R

    1979-11-01

    The interaction of Ca2+ and Mg2+ with three Tetracycline antibiotics (tetracycline, chlorotetracycline, and oxytetracycline) has been investigated. Spectrophotometric measurements have been used to determine the apparent association constant for this interaction as a function of pH. It is shown that the results are consistent with a model in which the metal ion can form complexes with both the fully-deprotonated and mono-protonated forms of the Tetracycline. The temperature-jump relaxation method has been used to measure the kinetics of formation of the complexes of Mg2+ with the Tetracyclines. The results are compared with those of previous studies of Mg2+ complex formation reactions and it is shown that the data is consistent with the normal dissociative model. A possible role for metal ion chelation in the mechanism of antibacterial action of the Tetracyclines is discussed. PMID:16997226

  5. Accumulation kinetics and equilibrium partitioning coefficients for semivolatile organic pollutants in forest litter.

    PubMed

    Nizzetto, Luca; Liu, Xiang; Zhang, Gan; Komprdova, Klara; Komprda, Jiri

    2014-01-01

    Soils are important stores of environmentally cycling semivolatile organic contaminants (SVOCs) and represent relevant atmospheric secondary sources whenever environmental conditions favor re-emission. The exchange between air and soil is controlled by resistances posed by interfacial matrices such as the ubiquitously distributed vegetation litter. For the first time, this study focused on the experimental characterization of accumulation parameters for SVOCs in litter under real field conditions. The logarithm of the litter-air equilibrium partitioning coefficient ranged 6.8-8.9 and had a similar dependence on logKOA as that of plant foliage and soil data. Uptake and release rates were also KOA dependent with values (relevant for real environmental conditions) ranging 30,000-150,000 d(-1) and 0.0004-0.0134 d(-1), respectively. The overall mass transfer coefficient v controlling litter-air exchange (0.03-1.4 cm s(-1)) was consistent with previously reported data of v for foliage in forest canopies after normalization on leaf area index. Obtained data suggest that litter holds the potential for influencing atmospheric fugacity in proximity to soil, likely affecting overall exchange of SVOCs between the soil reservoir and the atmosphere. PMID:24320106

  6. Preparation of modified semi-coke by microwave heating and adsorption kinetics of methylene blue.

    PubMed

    Wang, Xin; Peng, Jin-Hui; Duan, Xin-Hui; Srinivasakannan, Chandrasekar

    2013-01-01

    Preparation of modified semi-coke has been achieved, using phosphoric acid as the modifying agent, by microwave heating from virgin semi-coke. Process optimization using a Central Composite Design (CCD) design of Response Surface Methodology (RSM) technique for the preparation of modifies semi-coke is presented in this paper. The optimum conditions for producing modified semi-coke were: concentration of phosphoric acid 2.04, heating time 20 minutes and temperature 587 degrees C, with the optimum iodine of 862 mg/g and yield of 47.48%. The textural characteristics of modified semi-coke were analyzed using scanning electron microscopy (SEM) and nitrogen adsorption isotherm. The BET surface area of modified semi-coke was estimated to be 989.60 m2/g, with the pore volume of 0.74 cm3/g and a pore diameter of 3.009 nm, with micro-pore volume contributing to 62.44%. The Methylene Blue monolayer adsorption capacity was found to be mg/g at K. The adsorption capacity of the modified semi-coke highlights its suitability for liquid phase adsorption application with a potential usage in waste water treatment. PMID:24779145

  7. Kinetic and equilibrium study on formic acid decomposition in relation to the water-gas-shift reaction.

    PubMed

    Yasaka, Yoshiro; Yoshida, Ken; Wakai, Chihiro; Matubayasi, Nobuyuki; Nakahara, Masaru

    2006-09-28

    Kinetics and equilibrium are studied on the hydrothermal decarbonylation and decarboxylation of formic acid, the intermediate of the water-gas-shift (WGS) reaction, in hot water at temperatures of 170-330 degrees C, to understand and control the hydrothermal WGS reaction. (1)H and (13)C NMR spectroscopy is applied to analyze as a function of time the quenched reaction mixtures in both the liquid and gas phases. Only the decarbonylation is catalyzed by HCl, and the reaction is first-order with respect to both [H(+)] and [HCOOH]. Consequently, the reaction without HCl is first and a half (1.5) order due to the unsuppressed ionization of formic acid. The HCl-accelerated decarbonylation path can thus be separated in time from the decarboxylation. The rate and equilibrium constants for the decarbonylation are determined separately by using the Henry constant (gas solubility data) for carbon monoxide in hot water. The rate constant for the decarbonylation is 1.5 x 10(-5), 2.0 x 10(-4), 3.7 x 10(-3), and 6.3 x 10(-2) mol(-1) kg s(-1), respectively, at 170, 200, 240, and 280 degrees C on the liquid branch of the saturation curve. The Arrhenius plot of the decarbonylation is linear and gives the activation energy as 146 +/- 3 kJ mol(-1). The equilibrium constant K(CO) = [CO]/[HCOOH] is 0.15, 0.33, 0.80, and 4.2, respectively, at 170, 200, 240, and 280 degrees C. The van't Hoff plot results in the enthalpy change of DeltaH = 58 +/- 6 kJ mol(-1). The decarboxylation rate is also measured at 240-330 degrees C in both acidic and basic conditions. The rate is weakly dependent on the solution pH and is of the order of 10(-4) mol kg(-1) s(-1) at 330 degrees C. Furthermore, the equilibrium constant K(CO2) = [CO(2)][H(2)]/[HCOOH] is estimated to be 1.0 x10(2) mol kg(-1) at 330 degrees C. PMID:16986841

  8. Kinetics and Mechanisms of Phosphorus Adsorption in Soils from Diverse Ecological Zones in the Source Area of a Drinking-Water Reservoir.

    PubMed

    Zhang, Liang; Loáiciga, Hugo A; Xu, Meng; Du, Chao; Du, Yun

    2015-11-01

    On-site soils are increasingly used in the treatment and restoration of ecosystems to harmonize with the local landscape and minimize costs. Eight natural soils from diverse ecological zones in the source area of a drinking-water reservoir in central China are used as adsorbents for the uptake of phosphorus from aqueous solutions. The X-ray fluorescence (XRF) spectrometric and BET (Brunauer-Emmett-Teller) tests and the Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) spectral analyses are carried out to investigate the soils' chemical properties and their potential changes with adsorbed phosphorous from aqueous solutions. The intra-particle diffusion, pseudo-first-order, and pseudo-second-order kinetic models describe the adsorption kinetic processes. Our results indicate that the adsorption processes of phosphorus in soils occurred in three stages and that the rate-controlling steps are not solely dependent on intra-particle diffusion. A quantitative comparison of two kinetics models based on their linear and non-linear representations, and using the chi-square (χ2) test and the coefficient of determination (r2), indicates that the adsorptive properties of the soils are best described by the non-linear pseudo-second-order kinetic model. The adsorption characteristics of aqueous phosphorous are determined along with the essential kinetic parameters. PMID:26569278

  9. Kinetics and Mechanisms of Phosphorus Adsorption in Soils from Diverse Ecological Zones in the Source Area of a Drinking-Water Reservoir

    PubMed Central

    Zhang, Liang; Loáiciga, Hugo A.; Xu, Meng; Du, Chao; Du, Yun

    2015-01-01

    On-site soils are increasingly used in the treatment and restoration of ecosystems to harmonize with the local landscape and minimize costs. Eight natural soils from diverse ecological zones in the source area of a drinking-water reservoir in central China are used as adsorbents for the uptake of phosphorus from aqueous solutions. The X-ray fluorescence (XRF) spectrometric and BET (Brunauer-Emmett-Teller) tests and the Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) spectral analyses are carried out to investigate the soils’ chemical properties and their potential changes with adsorbed phosphorous from aqueous solutions. The intra-particle diffusion, pseudo-first-order, and pseudo-second-order kinetic models describe the adsorption kinetic processes. Our results indicate that the adsorption processes of phosphorus in soils occurred in three stages and that the rate-controlling steps are not solely dependent on intra-particle diffusion. A quantitative comparison of two kinetics models based on their linear and non-linear representations, and using the chi-square (χ2) test and the coefficient of determination (r2), indicates that the adsorptive properties of the soils are best described by the non-linear pseudo-second-order kinetic model. The adsorption characteristics of aqueous phosphorous are determined along with the essential kinetic parameters. PMID:26569278

  10. Experimental study of the removal of copper ions using hydrogels of xanthan, 2-acrylamido-2-methyl-1-propane sulfonic acid, montmorillonite: Kinetic and equilibrium study.

    PubMed

    Aflaki Jalali, Marzieh; Dadvand Koohi, Ahmad; Sheykhan, Mehdi

    2016-05-20

    In this paper, removal of copper ions from aqueous solution using novel xanthan gum (XG) hydrogel, xanthan gum-graft-2-acrylamido-2-methyl-1-propane sulfonic acid (XG-g-P(AMPS)) hydrogel and xanthan gum-graft-2-acrylamido-2-methyl-1-propane sulfonic acid/montmorillonite (XG-g-P(AMPS)/MMT) hydrogel composite were studied. The structure and morphologies of the xanthan-based hydrogels were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM). Adsorbents comprised a porous crosslink structure with side chains that carried carboxyl, hydroxyl and sulfonate. Maximum adsorption was observed in the pH=5.2, initial concentrations of Cu(2+)=321.8 mg/L, Temperature=45 °C, contact time=5 h with 0.2 g/50 mL of the hydrogels. Adsorption process was found to follow Langmuir isotherm model with maximum adsorption capacity of 24.57, 39.06 and 29.49 mg/g for the XG, XG-g-P(AMPS) and XG-g-P(AMPS)/MMT, respectively. Adsorption kinetics data fitted well with pseudo second order model. The negative ΔG° values and the positive ΔS° confirmed that the adsorption was a spontaneous process. The positive ΔH° values suggested that the adsorption was endothermic in nature. PMID:26917382

  11. Equilibrium and Kinetics of DNA Overstretching Modeled with a Quartic Energy Landscape

    PubMed Central

    Argudo, David; Purohit, Prashant K.

    2014-01-01

    It is well known that the dsDNA molecule undergoes a phase transition from B-DNA into an overstretched state at high forces. For some time, the structure of the overstretched state remained unknown and highly debated, but recent advances in experimental techniques have presented evidence of more than one possible phase (or even a mixed phase) depending on ionic conditions, temperature, and basepair sequence. Here, we present a theoretical model to study the overstretching transition with the possibility that the overstretched state is a mixture of two phases: a structure with portions of inner strand separation (melted or M-DNA), and an extended phase that retains the basepair structure (S-DNA). We model the double-stranded DNA as a chain composed of n segments of length l, where the transition is studied by means of a Landau quartic potential with statistical fluctuations. The length l is a measure of cooperativity of the transition and is key to characterizing the overstretched phase. By analyzing the different values of l corresponding to a wide spectrum of experiments, we find that for a range of temperatures and ionic conditions, the overstretched form is likely to be a mix of M-DNA and S-DNA. For a transition close to a pure S-DNA state, where the change in extension is close to 1.7 times the original B-DNA length, we find l ≈ 25 basepairs regardless of temperature and ionic concentration. Our model is fully analytical, yet it accurately reproduces the force-extension curves, as well as the transient kinetic behavior, seen in DNA overstretching experiments. PMID:25418100

  12. The Monte Carlo Integration Computer as an Instructional Model for the Simulation of Equilibrium and Kinetic Chemical Processes: The Development and Evaluation of a Teaching Aid.

    ERIC Educational Resources Information Center

    Wood, Dean Arthur

    A special purpose digital computer which utilizes the Monte Carlo integration method of obtaining simulations of chemical processes was developed and constructed. The computer, designated as the Monte Carlo Integration Computer (MCIC), was designed as an instructional model for the illustration of kinetic and equilibrium processes, and was…

  13. 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

  14. RESORCINOL-FORMALDEHYDE ADSORPTION OF CESIUM (Cs+) FROM HANFORD WASTE SOLUTIONS-PART I: BATCH EQUILIBRIUM STUDY

    SciTech Connect

    HASSAN, NEGUIBM

    2004-03-30

    Batch equilibrium measurements were conducted with a granular Resorcinol-Formaldehyde (RF) resin to determine the distribution coefficients (Kds) for cesium. In the tests, Hanford Site actual waste sample containing radioactive cesium and a pretreated waste sample that was spiked with non-radioactive cesium were used. Initial concentrations of non-radioactive cesium in the waste sample were varied to generate an equilibrium isotherm for cesium. Two additional tests were conducted using a liquid to solid phase ratio of 10 and a contact time of 120 hours. The measured distribution coefficient (Kd) for radioactive cesium (137Cs) was 948 mL/g; the Kd for non-radioactive cesium (133Cs) was 1039 mL/g. The Kd for non-radioactive cesium decreased from 1039 to 691 mL/g as the initial cesium concentration increased. Very little change of the Kd was observed at initial cesium concentrations above 64 mg/mL. The maximum sorption capacity for cesium on granular RF resin was 1.17 mmole/g dry resin. T his value was calculated from the fit of the equilibrium isotherm data to the Dubinin-Radushkevich equation. Previously, a total capacity of 2.84 mmole/g was calculated by Bibler and Wallace for air-dried RF resin.

  15. Adsorption kinetics of surfactants at liquid-solid and liquid-vapor interfaces from atomic-scale simulations

    NASA Astrophysics Data System (ADS)

    Iskrenova, Eugeniya K.; Patnaik, Soumya S.

    2012-02-01

    Nucleate pool boiling of pure liquid is a complex process involving different size- and time-scale phenomena. The appearance of the first nanobubble in the liquid at the bottom of a hot pan, the detachment of the bubble from the solid surface, its subsequent coalescence with other bubbles, all represent complex multiscale phenomena. Surfactants added to water increase the complexity of the process by contributing to the dynamic surface tension at the liquid-vapor and liquid-solid interfaces and thus affecting the heat and mass transfer at those interfaces. We apply molecular dynamics simulations to study the adsorption kinetics of anionic, cationic, and non-ionic surfactants at liquid/solid and liquid/vapor interfaces. The all-atom vs. united-atom approaches for the solid and surfactants are surveyed in view of their applicability at near boiling temperatures and a range of model water potentials is assessed for reproducing the thermal properties of water at boiling conditions.

  16. Conformation, Orientation, and Adsorption Kinetics of Dermaseptin B2 onto Synthetic Supports at Aqueous/Solid Interface

    PubMed Central

    Noinville, S.; Bruston, F.; El Amri, C.; Baron, D.; Nicolas, P.

    2003-01-01

    The antimicrobial activity of cationic amphipathic peptides is due mainly to the adsorption of peptides onto target membranes, which can be modulated by such physicochemical parameters as charge and hydrophobicity. We investigated the structure of dermaseptin B2 (Drs B2) at the aqueous/synthetic solid support interface and its adsorption kinetics using attenuated total reflection Fourier transform infrared spectroscopy and surface plasmon resonance. We determined the conformation and affinity of Drs B2 adsorbed onto negatively charged (silica or dextran) and hydrophobic supports. Synthetic supports of differing hydrophobicity were obtained by modifying silica or gold with ω-functionalized alkylsilanes (bromo, vinyl, phenyl, methyl) or alkylthiols. The peptide molecules adsorbed onto negatively charged supports mostly had a β-type conformation. In contrast, a monolayer of Drs B2, mainly in the α-helical conformation, was adsorbed irreversibly onto the hydrophobic synthetic supports. The conformational changes during formation of the adsorbed monolayer were monitored by two-dimensional Fourier transform infrared spectroscopy correlation; they showed the influence of peptide-peptide interactions on α-helix folding on the most hydrophobic support. The orientation of the α-helical Drs B2 with respect to the hydrophobic support was determined by polarized attenuated total reflection; it was around 15 ± 5°. This orientation was confirmed and illustrated by a molecular dynamics study. These combined data demonstrate that specific chemical environments influence the structure of Drs B2, which could explain the many functions of antimicrobial peptides. PMID:12885663

  17. Adsorptive removal and kinetics of methylene blue from aqueous solution using NiO/MCM-41 composite

    NASA Astrophysics Data System (ADS)

    Xiao, Xuechun; Zhang, Fei; Feng, Zhipeng; Deng, Shaojuan; Wang, Yude

    2015-01-01

    Highly ordered mesoporous material MCM-41 was synthesized from tetraethylorthosilicate (TEOS) as Si source and cetyltrimethylammonium bromide (CTAB) as template. Well-dispersed NiO nanoparticles were introduced into the highly ordered mesoporous MCM-41 by chemical precipitation method to prepare the highly ordered mesoporous NiO/MCM-41 composite. X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and high-resolution TEM (HRTEM), and nitrogen adsorption-desorption measurement were used to examine the morphology and the microstructure of the obtained composite. The morphological study clearly revealed that the synthesized NiO/MCM-41 composite has a highly ordered mesoporous structure with a specific surface area of 435.9 m2 g-1. A possible formation mechanism is preliminary proposed for the formation of the nanostructure. The adsorption performance of NiO/MCM-41 composite as an adsorbent was further demonstrated in the removal azo dyes of methyl orange (MO), Congo red (CR), methylene blue (MB) and rhodaming B (RB) under visible light irradiation and dark, respectively. The kinetics and mechanism of removal methylene blue were studied. The results show that NiO/MCM-41 composite has a good removal capacity for organic pollutant MB from the wastewater under the room temperature. Compared with MCM-41 and NiO nanoparticles, 54.2% and 100% higher removal rate were obtained by the NiO/MCM-41 composite.

  18. Adsorption and photodegradation kinetics of herbicide 2,4,5-trichlorophenoxyacetic acid with MgFeTi layered double hydroxides.

    PubMed

    Nguyen, Thi Kim Phuong; Beak, Min-wook; Huy, Bui The; Lee, Yong-Ill

    2016-03-01

    The calcined layered double hydroxides (cLDHs) Ti-doped and undoped MgFe for this study were prepared by co-precipitation method followed by calcination at 500 °C. The as-prepared samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer Emmett Teller (BET) and UV-Vis diffuse reflectance spectrum (DRS) techniques and tested for adsorption and photodegradation (including photocatalytic and photo-Fenton-like) of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous solutions under visible light irradiation. In the range of studied operating conditions, the as-prepared samples exhibited excellent photo-Fenton-like activity, leading to more than 80-95% degradation of 2,4,5-T at initial concentration of 100 mg L(-1) with 4 g calcined LDHs per liter, was accomplished in 360 min, while 2,4,5-T half-life time was as short as 99-182 min. The kinetics of adsorption and photodegradation of 2,4,5-T were also discussed. These results offered a green, low cost and high efficiency photocatalyst for environmental remediation. PMID:26706931

  19. Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on TiO2(110)

    SciTech Connect

    Smith, R. Scott; Li, Zhenjun; Chen, Long; Dohnalek, Zdenek; Kay, Bruce D.

    2014-07-17

    The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (BBO), Ti, and oxygen vacancies (VO) sites in order of increasing peak temperature. Analysis of the saturated monolayer peak for both species reveals that the corresponding adsorption energies on all sites are greater for H2O and for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupy the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K. Further analysis shows that a ratio of 4 H2O to 3 CO2 molecules is needed to displace CO2 from the TiO2(110) surface.

  20. Effect of the adsorbate kinetic diameter on the accuracy of the Dubinin-Radushkevich equation for modeling adsorption of organic vapors on activated carbon.

    PubMed

    Jahandar Lashaki, Masoud; Fayaz, Mohammadreza; Niknaddaf, Saeid; Hashisho, Zaher

    2012-11-30

    This paper investigates the effect of the kinetic diameter (KD) of the reference adsorbate on the accuracy of the Dubinin-Radushkevich (D-R) equation for predicting the adsorption isotherms of organic vapors on microporous activated carbon. Adsorption isotherms for 13 organic compounds on microporous beaded activated carbon were experimentally measured, and predicted using the D-R model and affinity coefficients. The affinity coefficients calculated based on molar volumes, molecular polarizabilities, and molecular parachors were used to predict the isotherms based on four reference compounds (4.3≤KD≤6.8 Å). The results show that the affinity coefficients are independent of the calculation method if the reference and test adsorbates are from the same organic group. Choosing a reference adsorbate with a KD similar to that of the test adsorbate results in better prediction of the adsorption isotherm. The relative error between the predicted and the measured adsorption isotherms increases as the absolute difference in the kinetic diameters of the reference and test adsorbates increases. Finally, the proposed hypothesis was used to explain reports of inconsistent findings among published articles. The results from this study are important because they allow a more accurate prediction of adsorption capacities of adsorbents which allow for better design of adsorption systems. PMID:23044198

  1. Antarctic seawater temperature evaluation based on stable isotope measurements on Adamussium colbecki shells: kinetic effects vs. isotopic equilibrium

    NASA Astrophysics Data System (ADS)

    Trevisiol, A.; Bergamasco, A.; Montagna, P.; Sprovieri, M.; Taviani, M.

    2013-10-01

    A year-long controlled growth experiment of 60 specimens of the Antarctic bivalve Adamussium colbecki was conducted in Terra Nova Bay (Ross Sea) to evaluate its reliability as a suitable archive of water mass properties. Nine shells were sub-sampled for stable oxygen and carbon isotope analysis to study the inter and intra specimen variations. Slow-growing A. colbecki precipitate their calcitic shells close to the expected oxygen and carbon isotopic equilibrium, whereas the fast-growing individuals are strongly influenced by biogenetic and kinetic effects. The equation of Kim and O'Neil (1997) is considered a fair approximation for the δ18O-temperature relationship in slow-growing individuals. The reconstructed temperature is closer to the mean experimental summer temperature than the annual one. This fact is interpreted as reflecting a possible winter decrease of shell growth, the salinity variation and the corrections for negative temperature on calibrating the δ18O-temperature relationship. Our results support the hypothesis that A. colbecki might represent a good archive for encoding Antarctic Shelf water summer temperature information. Further improvements in adopting A. colbecki as a paleotemperature archive will require the evaluation of the seasonal variability in shell growth rate through culturing slow-growing A. colbecki individuals at near-freezing temperatures to calibrate a species-specific δ18O-temperature equation.

  2. Uptake of gaseous formaldehyde by soil surfaces: a combination of adsorption/desorption equilibrium and chemical reactions

    NASA Astrophysics Data System (ADS)

    Li, Guo; Su, Hang; Li, Xin; Kuhn, Uwe; Meusel, Hannah; Hoffmann, Thorsten; Ammann, Markus; Pöschl, Ulrich; Shao, Min; Cheng, Yafang

    2016-08-01

    Gaseous formaldehyde (HCHO) is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs). Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of ˜ 10 to 40 ppbv. For the determination of uptake coefficients (γ), we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity = 0 %), an initial γ of (1.1 ± 0.05) × 10-4 is determined, which gradually drops to (5.5 ± 0.4) × 10-5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partia