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1.
《分离科学与技术》2012,47(4):705-722
Abstract

The sorption behavior of 3.18×10?6 mol l?1 solution of Tm(III) metal ions onto 7.25 mg l?1 of 1‐(2‐pyridylazo)‐2‐naphthol (PAN) loaded polyurethane foam (PUF) has been investigated at different temperatures i.e. 303 K, 313 K, and 323 K. The maximum equilibration time of sorption was 30 minutes from pH 7.5 buffer solution at all temperatures. The various rate parameters of adsorption process have been investigated. The diffusional activation energy (ΔEads) and activation entropy (ΔSads) of the system were found to be 22.1±2.6 kJ mol?1 and 52.7±6.2 J mol?1 K?1, respectively. The thermodynamic parameters such as enthalpy (ΔH), entropy (ΔS), and Gibbs free energy (ΔG) were calculated and interpreted. The positive value of ΔH and negative value of ΔG indicate that sorption is endothermic and spontaneous in nature, respectively. The adsorption isotherms such as Freundlich, Langmuir, and Dubinin–Radushkevich isotherm were tested experimentally at different temperatures. The changes in adsorption isotherm constants were discussed. The binding energy constant (b) of Langmuir isotherm increases with temperature. The differential heat of adsorption (ΔHdiff), entropy of adsorption (ΔSdiff) and adsorption free energy (ΔGads) at 313 K were determined and found to be 38±2 kJ mol?1, 249±3 J mol?1 K?1 and –40.1±1.1 kJ mol?1, respectively. The stability of sorbed complex and mechanism involved in adsorption process has been discussed using different thermodynamic parameters and sorption free energy.  相似文献   

2.
《分离科学与技术》2012,47(16):2738-2748
ABSTRACT

The present study is aimed to optimized diluent type, tri-n-butyl phosphate (TBP) composition and temperature for the reactive extraction of p-nitro phenol (PNP) in two different PNP concentration ranges [(0.00036–0.00646) kmol·m?3 and (0.00646–0.01437) kmol·m?3] as found in industrial effluents. 1-Octanol is investigated as the best diluent with TBP based on COSMO-RS theory. Equilibrium study based on mass action law is performed to find the insights of extraction mechanisms, equilibrium constant (K = 295.12 k·mol?1) and stoichiometry (m:n = 1:1) as also confirmed by FTIR. Thermodynamic parameters, enthalpy (ΔH°), and entropy (ΔS°) are determined 27.51 K J mol?1 and ?50.21 J mol?1 K?1, respectively.  相似文献   

3.
《分离科学与技术》2012,47(5):1239-1259
Abstract

The present study aims to evaluate the influence of various experimental parameters viz. initial pH (pH 0), adsorbent dose, contact time, initial concentration and temperature on the adsorptive removal of furfural from aqueous solution by commercial grade activated carbon (ACC). Optimum conditions for furfural removal were found to be pH 0 ≈ 5.9, adsorbent dose ≈ 10 g/l of solution and equilibrium time ≈ 6.0 h. The adsorption followed pseudo‐second‐order kinetics. The effective diffusion coefficient of furfural was of the order of 10?13 m2/s. Furfural adsorption onto ACC was found to be best represented by the Redlich‐Peterson isotherm. A decrease in the temperature of the operation favorably influenced the adsorption of furfural onto ACC. The positive values of the change in entropy (ΔS 0); and the negatived value of heat of adsorption (ΔH 0) and change in Gibbs free energy (ΔG 0) indicated feasible, exothermic, and spontaneous nature of furfural adsorption onto ACC.  相似文献   

4.
The dielectric techniques used to investigate the relaxation behavior of poly (vinyl chloride-co-vinyl acetate-co-2-hydroxypropyl acrylate) (PVVH), poly (acrylonitrile-butadiene-styrene) (ABS), and its polyblends include broadband AC dielectric relaxation spectroscopy (DRS) in the frequency range from 10?2 to 105 Hz, and thermally stimulated depolarization current (TSDC) technique in the temperature range from 300 K to 413 K. It was observed that PVVH is characterized by a dipolar relaxation peak around 347 K and a space charge peak in the temperature range 353–383 K, whereas pure ABS is characterized by a dipolar relaxation peak at 389 K. On the other hand, polyblend samples are found to be characterized by two different relaxation peaks at 359 K and 387 K, respectively. The dielectric properties of pure materials and their polyblend are investigated. All samples are characterized by high dielectric constant (ε′) at very low and high temperature. The dielectric loss shows a single peak for pure materials, whereas polyblends show a broad peak at low frequency which could be attributed to the Maxwell-interfacial polarization (MWS) and another peak at high frequency which could be attributed to the dipolar relaxation. The temperature dependence of AC conductivity was investigated for all samples. The values of the exponent n suggest that the hopping mechanism dominates at lower temperatures.  相似文献   

5.
Abstract

The rate of uptake of alkaline earth metals, copper, and lead have been investigated by a chelating ion exchange resin containing iminodiacetic acid as ligand attached to the copolymer of styrene and divinyl benzene of macroporous matrix structure. It binds alkaline earth metals, Cu, and Pb by the formation of chelate complexes with the carboxylate group of this resin. The experiments discussed in this work have allowed to establish the paramount importance of the presence of this chelating group in obtaining practically useful rates of metal ion uptake. The kinetic parameters like diffusion coefficient (D o), activation energies (ΔE a) and entropy of activation have been evaluated under the conditions favoring a particle diffusion control mechanism and the study followed the three models i.e., Nernst Planck, B t technique and Ash model. K d values in demineralised water (DMW) were found in the order Cu2+ > Pb2+ > Mg2+ > Sr2+ > Ba2+ > Ca2+.  相似文献   

6.
Herein, in order to design the formulation of fluoropolymer bonded explosives, common fluoropolymers were selected and added to the high energy density compound hexanitrohexaazaisowurtzitane (ε-CL-20). Molecular dynamics simulations were carried out on fluoropolymers (F2603, F2311, F2314, F2426, and PTFE) and fluoropolymers bonded ε-CL-20. Glass transition temperature (Tg) of fluoropolymers were calculated. Besides, the mechanical properties and physical compatibilities of ε-CL-20 based polymer bonded explosives were predicted. The calculated results show that the order of Tg of fluoropolymers is: PTFE > F2314 > F2311 > F2462 ≈ F2603 and Tg of F2603 increases as the degree of polymerization increases. The binding energy for fluoropolymers with ε-CL-20 is in the following order: ε-CL-20/F2462 > ε-CL-20/F2603 > ε-CL-20/F2314 > ε-CL-20/F2311. All fluoropolymers interact with ε-CL-20 mainly in vdW force. The order of tensile modulues is: ε-CL-20 > ε-CL-20/F2314 > ε-CL-20/F2311 > ε-CL-20/F2462 > ε-CL-20/F2603, the orders of Poisson’s ration (γ) and the quotient bulk modulus (K)/shear modulus (G) are opposite.  相似文献   

7.
《分离科学与技术》2012,47(3):370-379
This study uses a waste iron oxide material (BT3), which is a by-product of the fluidized-bed Fenton reaction (FBR–Fenton), for the treatment of a fluoride (F?) solution. The purpose of this study is to investigate a low-cost sorbent as a replacement for the current costly methods of removing fluoride from wastewater. X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) are used to characterize the BT3. Contact time, F? concentration (from 0.75 to 6 mmol L?1), and temperature (from 303 to 323 K) are used as operation parameters to treat the fluoride. The highest F? adsorption capacity of the BT3 adsorbent was determined to be 1.17 mmol g?1 (22.2 mg g?1) for a 6 mmol L?1 initial F? concentration at pH 3.9 ± 0.2 and 303 ± 1 K. Adsorption data were well described by the Langmuir model, and the thermodynamic constants of the adsorption process, ΔG°, ΔH°, and ΔS°, were evaluated as ?1.63 kJ mol?1 (at 303 K), ?1.75 kJ mol?1, and ?52.4 J mol?1 K?1, respectively. Additionally, a pseudo-second-order rate model was adopted to describe the kinetics of adsorption. BT3 could be regenerated with NaOH, and the regeneration efficiency reached 95.1% when the concentration of NaOH was 0.05 mol L?1.  相似文献   

8.
《分离科学与技术》2012,47(14):2240-2251
ABSTRACT

The present investigation represents the synthesis of new p-sulphonatocalix[8]arene-based silica resin, p-SC8SR (5) and its application for the enhanced removal of methylene blue (MB) dye from contaminated water. The new p-SC8SR (5) resin was characterized by FT-IR, SEM, and EDX spectroscopy. The adsorption of MB on p-SC8SR (5) was investigated systematically by evaluating the effects of adsorbent dosage, initial pH, contact time, dye concentration, and ionic strength. Excellent adsorption (94%) of MB on p-SC8SR (5) was achieved at pH 9.5, contact time 10 min by using 0.2 mol L?1 ionic strength and 2 × 10?5 M initial MB dye concentration. Kinetic behavior of MB dye adsorption process on the newly synthesized p-SC8SR (5) adsorbent follows the pseudo-second-order rate model (R2 = 0.998 and 0.999 for 2 × 10?5 M and 1 × 10?4 M, respectively). Adsorption isotherms were fitted well by the Freundlich model with excellent value of coefficient of determination (R2) = 0.995 which demonstrated that the adsorption of MB follows multilayer mechanism. Wastewater samples contaminated with MB were used to assess efficiency of the p-SC8SR (5) adsorbent. Results indicated that newly synthesized p-SC8SR (5) was found to be efficient adsorbent. During the removal process, the role of different functional groups’ cyclic structure was scrutinized and found that the ionic property as well as π–π interaction of host molecules played imperative role in the extent of adsorption.  相似文献   

9.
ABSTRACT

NMR( Nuclear Magnetic Resonance ) measurements were car ried out to study the molecular movement of CMPO and La(III)(NO3) 3? CMPO complex and the ligand-exchange reaction for Eu(III) and Gd(III)-CMPO systems. From the 13C relaxation time measurement of La(NO3) 3 3CMPO it was found that the T1 value for the isobutyl CH and CH2 carbons and the carbonyl carbon became considerably shorter on complexation, indicating that the carbonyl group participates in the bonding between CMPO and La3+ ion as well as the phosphoryl group. The numbers of CMPO molecules coordinated to Eu3+ and Gd3+ ions in CDCl3 solution were estimated to be 3 and 2, respectively, in the presence of excess CMPO. The activation parameters for the ligand-exchange reaction were evaluated to be ΔH* = 37.8±1.9[kJ/mol],ΔS* = -59.9±6.5[J/molk? K] and ΔH* = 41.3±1.6[kJ/mol], ΔS* = -44.1±5.3[J/mol-K] for Eu(III)-CMPO and Gd(III)-CMPO systems, respectively. The independence of the exchange rate constants on the concentration of CMPO indicates that these ligand-exchange reactions seem to proceed through either a dissociative ( D ) mechanism or an interchange dissociative ( Id ) mechanism characterized by a stability constant of outer-sphere complex( KQ ) ≥ 100.  相似文献   

10.
ABSTRACT

Virgin polysiloxane and aluminum oxide nanopowder (10%–50%) reinforced polysiloxane composite films were prepared and its thermal, optical, surface properties were investigated. Polysiloxane/aluminum oxide (Al2O3) (50%–50%) composite film sample exhibit high thermal conductivity (k – 0.26 W/mK) and UV absorption, decreased junction temperature (ΔTJ = 25.69°C at 700 mA) and thermal resistance (?Rth-tot = 12.41 K/W at 700 mA) compared to virgin polysiloxane film. Overall, the prepared composites can be used as an alternate elastomer thermal pad for efficient thermal management as well as UV blocking encapsulant for future UV-free LED application development.  相似文献   

11.
Here we investigate isotope effects on the catalytic methanol synthesis reaction and the reactivity of copper-bound formate species in CO2–H2 atmospheres on Cu/SiO2 catalysts by simultaneous IR and MS measurements, both steady-state and transient. Studies of isotopic variants (H/D, 12C/13C) reveal that bidentate formate dominates the copper surface at steady state. The steady-state formate coverages of HCOO (in 6 bar 3:1 H2:CO2) and DCOO (in D2:CO2) are similar and the steady-state formate coverages in both systems decrease by ~80% from 350 K to 550 K. Over the temperature range 413 K–553 K, the steady-state methanol synthesis rate shows a weak H/D isotope effect (1.05 ± 0.05) with somewhat higher activation energies in H2:CO2 (79 kJ/mole) than D2:CO2 (71 kJ/mole) over the range 473 K–553 K. The reverse water gas shift (RWGS) rates are higher than methanol synthesis and also shows a weak positive H/D isotope effect with higher activation energy for H2/CO2 than D2/CO2 (108 vs. and 102 kJ/mole) The reactivity of the resulting formate species in 6 bar H2, 6 bar D2 and 6 bar Ar is strongly dominated by decomposition back to CO2 and H2. H2 and D2 exposure compared to Ar do not enhance the formate decomposition rate. The decomposition profiles on the supported catalyst deviate from first order decay, indicating distributed surface reactivity. The average decomposition rates are similar to values previously reported on single crystals. The average activation energies for formate decomposition are 90 ± 17 kJ/mole for HCOO and 119 ± 11 kJ/mole for DCOO. By contrast to the catalytic reaction rates, the formate decomposition rate shows a strong H/D kinetic isotope effect (H/D ~8 at 413 K), similar to previously observed values on Cu(110).  相似文献   

12.
The present study deals with the sorptive removal of furfural from aqueous solution by carbon-rich bagasse fly ash (BFA). Batch studies were performed to evaluate the influence of various experimental parameters, namely, initial pH (p H 0), adsorbent dose, contact time, initial concentration, and temperature on the removal of furfural. Optimum conditions for furfural removal were found to be p H 0 ≈ 5.5, adsorbent dose ≈4 g/L of solution, and equilibrium time ≈4 h. The adsorption followed pseudo-second-order kinetics. The effective diffusion coefficient of furfural is of the order of 10?13 m2/s. Equilibrium adsorption data on BFA was analyzed by Freundlich, Langmuir, Dubnin-Radushkevich, Redlich-Peterson, and Temkin isotherm equations using regression and error analysis. The Redlich-Peterson isotherm was found to best represent the data for furfural adsorption onto BFA. Adsorption of furfural on BFA is favorably influenced by a decrease in the temperature of the operation. Values of the change in entropy (ΔS 0) and heat of adsorption (ΔH 0) for furfural adsorption on BFA were negative. The high negative value of change in Gibbs free energy (ΔG 0) indicates the feasible and spontaneous adsorption of furfural on BFA.  相似文献   

13.
《分离科学与技术》2012,47(6):1382-1403
Abstract

Experimental investigations are carried out to adsorb toxic crystal violet dye from aqueous medium using kaolin as an adsorbent. Characterization of kaolin is done by measuring

  1. particle size distribution using particle size analyzer,

  2. BET surface area using BET surface analyzer,

  3. structural analysis using X ray diffractometer, and

  4. microscopic analysis using scanning electron microscope.

The effects of initial dye concentration, contact time, kaolin dose, stirring speed, pH, and temperature are studied for the adsorption of crystal violet in batch mode. Adsorption experiments indicate that the extent of adsorption is strongly dependent on the pH of the solution. Free energy of adsorption (ΔG o ), enthalpy (ΔH o ), and entropy (ΔS o ) changes are calculated to know the nature of adsorption. The calculated values of ΔG o are ?4.11 and ?4.48 kJ/mol at 295 K and 323 K, respectively, for 20 mg/L of dye concentration, which indicates that the adsorption process is spontaneous. The estimated values of ΔH o and ΔS o show the negative and positive sign, respectively, which indicate that the adsorption process is exothermic and the dye molecules are organized on the kaolin surface in more random fashion than in solution. The adsorption kinetic has been described by pseudo first order, pseudo second order and intra‐particle diffusion models. It is observed that the rate of dye adsorption follows pseudo second order model for the dye concentration range studied in the present case. Standard adsorption isotherms are used to fit the experimental equilibrium data. It is found that the adsorption of crystal violet on kaolin follows the Langmuir adsorption isotherm.  相似文献   

14.
《分离科学与技术》2012,47(11-12):1971-1983
Abstract

Ion-exchange displacement chromatography of calcium has been carried out successfully for the purpose of observing calcium isotope fractionation effects. Small but definite accumulation of the heavier isotopes has been observed at the front parts of the calcium adsorption bands, which means they are preferentially fractionated into the solution phase. The average values of the single-stage separation factor minus one per unit mass difference between isotopes (ε/Δ M) have been 2.0 × 10?5 for the calcium chloride system, 5.2 × 10?5 for the calcium lactate system, and 2.3 × 10?5 for the calcium acetate system at 25°C. The reduced partition function ratios of the calcium species involved in the present study have been estimated by using separation factor data and available data on calcium hydration under appropriate assumptions. The reduced partition function ratios of the complex species have been found to be larger than that of the simple hydrated calcium ion, which is a cause of the experimental results that the separation factor values of the calcium lactate and acetate systems are larger than that of the calcium chloride system. It has also been found that, for the alkali and alkaline earth metals, the magnitude of isotope effect per unit mass difference between isotopes accompanying pure ion exchange is nearly inversely proportional to the square of the atomic mass.  相似文献   

15.
《分离科学与技术》2012,47(11):1699-1708
Hydroxy terminated polybutadiene (HTPB)-based polyurethaneurea membranes with and without cross-linkage were synthesized and first used as membrane material to separate p-/o-xylene mixtures by pervaporation. Compared with HTPB-PU (without cross-linkage) membranes, HTPB-DVB-PU (cross-linked HTPB-PU with divinyl benzene) membranes demonstrated a lower degree of swelling in xylene isomer solutions and noticeable improved separation factor of p-/o-xylene. On the other hand, the amount of p-xylene adsorbed in HTPB-DVB-PU membranes increased significantly rather than that of o-xylene. While the separation factor of p-/o-xylene increased but the total flux decreased with increasing DVB content, which can be ascribed to the improved chemical structure and more homogeneous chain structures of the HTPB-DVB-PU membranes. The p-xylene normalized permeation rate and separation factor of p-/o-xylene of HTPB-DVB-PU membrane reached 2.70 kgµm/m2h and 2.23, respectively, at a feed concentration of 10 wt% p-xylene at 30°C.  相似文献   

16.
The objective of this study was to optimize the wall material concentration and the oil load on the encapsulation of Gac oil using spray drying by response surface methodology. Results showed that the quadratic polynomial model was sufficient to describe and predict encapsulation efficiencies in terms of oil, β-carotene, lycopene, peroxide value (PV), moisture content (MC), and total color difference (Δ E) with R 2 values of 0.96, 0.95, 0.86, 0.89, 0.88, and 0.87, respectively. Under optimum conditions (wall concentration of 29.5 % and oil load of 0.2), the encapsulation efficiencies for oil, β-carotene, lycopene, PV, MC, and Δ E were predicted and confirmed as 92 %, 80 %, 74 %, 3.91 meq/kg, 4.14 % and 12.38, respectively. The physical properties of the encapsulated oil powders obtained by different formulations were also determined. It was concluded that the protein-polysaccharide matrix as the wall material was effectively used for spray-drying encapsulation of Gac oil.  相似文献   

17.
《分离科学与技术》2012,47(10):1456-1462
The biosorption behavior of lanthanum and cerium ions from aqueous solution by leaf powder of Pinus brutia was separately studied in a batch system as a function of initial pH, contact time, initial metal ion concentration, temperature, and adsorbent amount. The uptake of lanthanum and cerium was increased when the initial pH of the solution was increased. Thermodynamic parameters such as standard enthalpy (ΔH°), entropy (ΔS°) and free energy (ΔG°) were calculated and the results indicated that biosorption was endothermic and spontaneous in nature. The biosorption of lanthanum and cerium on powdered leaf of Pinus brutia was investigated by the Freundlich, Langmuir, and D-R isotherms. The results show that lanthanum and cerium adsorption can be explained by the Langmuir isotherm model and monolayer capacity was found as 22.94 mg g?1 for lanthanum and 17.24 mg g?1 for cerium. Desorption of lanthanum and cerium was studied using 0.5 M HNO3 solution. The results suggested that powdered leaf of Pinus brutia may find promising applications for the recovery of lanthanum and cerium from aqueous effluents.  相似文献   

18.
Solvent extraction and separation of rare earths (REs: La ~ Lu, plus Y and Sc) by a novel synthesized extractant, (2-ethylhexylamino)methyl phosphonic acid mono-2-ethylhexyl ester (HEHAMP, abbreviated as H2A2), were investigated in chloride medium. The favorable separation factors (SFs) between adjacent heavy REs suggested that HEHAMP has a better separation performance than P507. The extracted complex of trivalent REs was determined to be REClH2A4 by the slope analysis method. Thermodynamic parameters (ΔH, ΔG, and ΔS) of Lu were calculated as 7.47 kJ mol?1, ?6.05 kJ mol?1, and 45.4 J mol?1 K?1 at 298.15 K, respectively, which indicate that the extraction reaction of Lu is an endothermic process. The loading capacity of 30% (v/v) HEHAMP toward Lu(III), Yb(III), and Y(III) was about 15.17 g Lu2O3/L, 14.46 g Yb2O3/L, and 12.64 g Y2O3/L, respectively. HCl is the most efficient stripping acid, and 92% of the loaded Yb(III) can be stripped by one-stage stripping with 2 mol/L HCl.  相似文献   

19.
Yougui Chen 《Drying Technology》2013,31(10):1114-1123
The effect of temperature on blueberry drying rate, shrinkage, and color changes was evaluated from drying experiments for both high bush (Vaccinium corymbosum L.) and wild (Vaccinium angustifolium) blueberries. Drying temperature significantly affected texture and color of both varieties. Temperatures above 55°C caused a significant color change (ΔE > 25) within 30 min of the beginning of drying, followed by a significant drop in density from 1.02 to 0.38 g/cm3. In contrast, drying at temperatures below 50°C resulted in nonsignificant color changes and an eventual density increase to 1.26 g/cm3. It follows that blueberry color could be used as an early stage indicator of quality degradation in the process of drying.  相似文献   

20.
ABSTRACT

Gadolinium isotopes were fractionated in a liquid-liquid extraction system using dicyclohexano-18-crown-6. The isotope enrichment factors showed breakdowns of the conventional Bigeleisen-Mayer approximation for every condition of the initial phases; the concentrations of gadolinium and hydrochloric acid and the type of organic solvents. The nuclear mass effect and the field shift effect were estimated by use of the isotope pairs 152Gd-160Gd and 154Gd-160Gd. Since both isotopes, 152Gd and 154Gd, have the unique characteristics of the nuclear charge radii, <r2>'s, the unusual isotope effects due to the field shifts took place, while the mass effects of the other isotopes canceled the field shift effects. The maximum isotope effect was observed to be ε160,152 =0·0252 ± 0·0024 whose initial aqueous phase was 0·023 M GdCl3 in 12 M HC1, and its organic phase was 0·2 M DC18C6 in chloroform: this was 0·00315 ± 0·00030 in terms of the enrichment factor for unit mass.  相似文献   

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