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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(4):472-485
Fluoride removal with varying different parameters at 303 ± 1.6 K and pH 6.5 ± 0.2 was investigated by hydrous iron(III)-chromium(III) bimetal oxide. The kinetic and equilibrium data fitted with the pseudo-second order and Langmuir isotherm equations very well (R2 = 0.99?1.00), respectively. The Langmuir capacity (θ) and free energy (EDR) of adsorption evaluated were 16.34 (±0.50) mg·g?1 and 15.81 kJ·mol?1, respectively. The estimated thermodynamic parameters viz. ΔH0, ΔG0, and ΔS0 indicated that the reaction was endothermic but spontaneous for entropy increase. The small-scale column filtration of high fluoride (C0 = 7.37 mg·L?1) water gave encouraging results.  相似文献   

3.
《分离科学与技术》2012,47(5):735-743
This paper is mainly about extending research on application and comparison of preparative high-speed countercurrent chromatography (HSCCC) and preparative high performance liquid chromatography (HPLC) in chiral separations. Preparative enantioseparations of α-cyclopentylmandelic acid and α-methylmandelic acid by HSCCC and HPLC were compared using hydroxypropy-β-cyclodextrin (HP-β-CD) and sulfobutyl ether-β-cyclodextrin (SBE-β-CD) as the chiral mobile phase additives. In preparative HPLC the enantioseparation was achieved on the ODS C18 reverse phase column with the mobile phase composed of a mixture of acetonitrile and 0.10 mol L?1 phosphate buffer at pH 2.68 containing 20 mmol L?1 HP-β-CD for α-cyclopentylmandelic acid and 20 mmol L?1 SBE-β-CD for α-methylmandelic acid. The maximum sample size for α-cyclopentylmandelic acid and α-methylmandelic acid was only about 10 mg and 5 mg, respectively. In preparative HSCCC the enantioseparations of these two racemates were performed with the two-phase solvent system composed of n-hexane-methyl tert.-butyl ether-0.1 molL?1 phosphate buffer solution at pH 2.67 containing 0.1 mol L?1 HP-β-CD for α-cyclopentylmandelic acid (8.5:1.5:10, v/v/v) and 0.1 mol L?1 SBE-β-CD for α-methylmandelic acid (3:7:10, v/v/v). Under the optimum separation conditions, totally 250 mg of racemic α-cyclopentylmandelic acid could be completely enantioseparated by HSCCC with HP-β-CD as a chiral mobile phase additive in a single run, yielding 114-116 mg of enantiomers with 98-99% purity and 89-92% recovery. But, no complete enantioseparation of α-methylmandelic acid was achieved by preparative HSCCC with either of the chiral selectors due to their limited enantioselectivity. In this paper, preparative enantioseparation by HSCCC and HPLC was compared from various aspects.  相似文献   

4.
《分离科学与技术》2012,47(16):3832-3853
Abstract

This paper presents a two-stage membrane filtration process for extracting and separating α-Lactalbumin (α-La) and β-Lactoglobulin (β-Lg), from UHT skim milk, using dynamic filtration. The 1st stage separates casein micelles in retentate from whey proteins in the permeate with rotating 0.2 µm pores ceramic membrane disks. Casein micelles rejection was excellent, while α-La and β-Lg transmissions remained between 80 and 90%. The permeate flux at 40°C ranged from 105 to 40 Lh?1m?2 at a volume reduction ratio of VRR = 4. The 2nd stage consisted of ultrafiltration of the previous permeate with a metal disk rotating at 2000 rpm near a fixed 50 kDa PES membrane, in order to concentrate β-Lg in retentate, while collecting α-La in the permeate. The flux dropped from 270 Lh?1m?2 at VRR = 1, and remained nearly constant at 200 Lh?1m?2 until a VRR of 3.3. α-La transmission increased with VRR to reach 23% at VRR = 3.3, while β-Lg transmission decayed at increasing VRR to 3%, to give a maximum selectivity of 8.  相似文献   

5.
Single-layer solar drying experiments were conducted for Mexican tea leaves (Chenopodium ambrosioides) grown in Marrakech. An indirect forced convection solar dryer was used in drying the Mexican tea leaves at different conditions such as ambient air temperature (21° to 35°C), drying air temperature (45° to 60°C) with relative humidity (29 to 53%), airflow rate (0.0277 to 0.0556 m 3/s), and solar radiation (150–920 W/m2). The experimental drying curves showed only a falling rate period. In order to select the suitable form of drying curves, 14 mathematical models were applied to the experimental data and compared according to their statistical parameters. The main factor in controlling the drying rate was found to be the temperature. The drying rate equation was determined empirically from the characteristic drying curve. The diffusion coefficient of the Chenopodium ambrosioides leaves was estimated and varied between 1.0209 × 10?9 and 1.0440 × 10?8 m 2·s?1.The activation energy was found to be 89.1486 kJ·mol?1.  相似文献   

6.
《分离科学与技术》2012,47(8):1190-1201
A precise and selective method has been developed for extraction spectrophotometric determination of osmium(IV) and ruthenium(III) using o-methoxyphenyl thiourea (OMePT) as a chromogenic ligand. The basis of the proposed methods are osmium(IV)-OMePT complex was formed in 0.8 mol L?1 at room temperature while ruthenium(III)-OMePT complex was formed in 3.4 mol L?1 aqueous hydrochloric acid media after 5.0 min heating in boiling water bath. The osmium(IV)-OMePT and ruthenium(III)-OMePT complex were measured at 518 and 640 nm against the reagent blank, respectively. Complexes were also extracted in 10 mL chloroform and showed comparable absorbance values. Beer’s law was obeyed up to 110.0 μg mL?1 for osmium(IV)-OMePT complex and up to 50.0 μg mL?1 for ruthenium(III)-OMePT complex. Molar absorptivity and Sandell’s sensitivity of osmium(IV)-OMePT and ruthenium(III)-OMePT complexes were 2.12 × 103 L mol?1 cm?1, 0.089 μg cm?2 and 2.34 × 103 L mol?1 cm?1, 0.043 μg cm?2, respectively. The stoichiometry of osmium(IV)-OMePT and ruthenium(III)-OMePT complex was 1:1 and 1:2, respectively. Stability of osmium(IV)-OMePT complex was > 8 days and that of ruthenium(III)-OMePT complex was > 48 h. The proposed method was successfully applied for determination of osmium(IV) and ruthenium(III) from synthetic mixtures corresponding to platinum-osmium alloy and fissium alloy, respectively. The method was successfully applied for sequential separation of osmium(IV), ruthenium(III), and platinum(IV).  相似文献   

7.
The reaction rate of enolization of p-chloroacetophenone has been studied in the presence of amino acids, namely, β-alanine, DL-alanine, L-alanine, and glycine. Maximum reaction rate was observed in the case of β-alanine at 22M concentration. The effects of parameters such as effect of ketone concentration, effect of dielectric constant, effect of catalysts, etc., have been found to exert a significant effect on the reaction rate. The effect of temperature was studied in the range of 313–328?K, and several thermodynamic parameters such as entropy (ΔS), enthalpy (ΔH), energy of activation (ΔEa), and Gibbs free energy (ΔF) were found to be ?10.32?e.u., 17.87?cal?mol?1, 19.24?kcal?mol?1, and 21.20?cal?mol?1, respectively. The reaction rate increased from 1.9 to 5.8?min?1 on increasing the percentage of dimethylformamide from 10 to 50% (v/v).  相似文献   

8.
Kinetic analysis of the Li|Li+ interphase in an electrolyte based on N-metyl-N-propylpyrrolidinium bis(trifluoromethanesulfon)imide ionic liquid (MPPyrrTFSI) and lithium bis(trifluoromethanesulfon)imide salt (LiTFSI) was performed. Li|electrolyte|Li and LiC6|electrolyte|Li cells were galvanostatically charged/discharged in order to form solid electrolyte interphase (SEI) protecting layer. SEM images showed that the surface of both Li and LiC6 anodes was covered with small particles. The fitting procedure of electrochemical impedance data taken at different temperatures gave three resistances (R el, R SEI, R ct) and hence, three lnR = f(T ?1) straight lines of different slopes. Specific conductivity and activation energy of the conduction process of the liquid electrolyte, were ca. σ = 2.5 mS cm?1 (at T = 25.0 °C) and $ E_{\text{el}}^{\# } $  = 15 kJ mol?1. Activation energy for the conduction process in the SEI layer was ca. 56 kJ mol?1 in the case of the metallic lithium and 62 kJ mol?1 for the graphite anode. Activation energy of the charge transfer process, $ E_{\text{ct}}^{\# } $ , for Li and LiC6 anodes was 71 and 65 kJ mol?1, respectively. Analysis of literature data for different electrolytes suggests that the $ E_{\text{ct}}^{\# } $ value for Li+ reduction may be approximated by 57 ± 5 kJ mol?1. Activation energy for the diffusion processes in the graphite electrode, detected from the Warburg coefficient, was ca 74 kJ mol?1.  相似文献   

9.
The formation dynamics of calcium barium sulphoaluminate mineral with the composition of 2.75CaO·1.25BaO·3Al2O3·SO3 (C2.75B1.25A3 $\overline{\text{S}}$ S ¯ ) was studied. The results suggest that, under the preparative conditions, the formation of C2.75B1.25A3 $\overline{\text{S}}$ S ¯ mineral is controlled by a diffusion mechanism from 1,100 to 1,380 °C; and, the formation dynamics fits nicely with D 4 = 1 ? 2α/3 ? (1 ? α)2/3 = Kt. From 1,100 to 1,300 °C, the apparent activation energy is 227.45 kJ mol?1. From 1,300 to 1,380 °C, the apparent activation energy decreases to 175.94 kJ mol?1, making the formation of C2.75B1.25A3 $\overline{\text{S}}$ S ¯ mineral faster and easier.  相似文献   

10.
ABSTRACT

This study has evaluated the efficiency of Fenton process followed by coagulation to treat real effluent from fish farm. Fenton obtained Chemical Oxygen Demand and turbidity removal of 48% at (0.5 mg L?1 Fe2+ and 10 mmol H2O2). Fenton followed by coagulation reduced COD and turbidity by almost 100%. The process also decreased the concentrations of suspended solids, phosphate, nitrate, Biological Oxygen Demand, and nitrite. Ecotoxicology test indicated that the effluent treated with 0.5 mmol L?1 Fe2+ in 10 mmol L?1 H2O2 displayed the lowest toxicity. These findings can indicate an environmental friendly alternative to treat fish farm effluent.  相似文献   

11.
A new porous carbon with high surface area of 1,313.41 m2 g?1 with pore volume 1.359 cm3 g?1 has been synthesized from matured tea leaves by chemical activation method using phosphoric acid. The carbon was found to be highly efficient for removal of Cr(VI) from aqueous solution. The effects of various parameters such as contact time, initial metal ion concentration, pH, temperature and amount of adsorbent on the extent of adsorption were studied. Langmuir, Freundlich and Temkin adsorption models were used to interpret the experimental data. The adsorption data were best fitted with Langmuir isotherm model. The adsorption capacity of Cr(VI) onto the activated carbon calculated from Langmuir isotherm was found to be 30.8 mg g?1 at pH 4.8 and temperature 303 K. The adsorption capacity increases from 25.36 to 32.04 mg g?1 with an increase in temperature from 303 to 323 K at initial Cr(VI) concentration of 60 mg L?1. The adsorption process followed a pseudo second order kinetic model. Thermodynamic parameters ΔH0 (28.6 KJ mol?1), ΔG0 at three different temperatures [(?0.145, ?1.09, ?2.04) KJ mol?1] and ΔS0 (94.87 J mol?1 K?1) were calculated. These values confirm the adsorption process to be endothermic and spontaneous in nature.  相似文献   

12.
A metal-chelating superabsorbent hydrogel based on poly(2-acrylamido-2-methylpropanesulfonic acid-co-acrylic acid-co-acrylamide) grafted onto sodium alginate backbone, NaAlg-g-poly(AMPS-co-AA-co-AM) is prepared under microwave irradiation. The Taguchi method is used for the optimization of synthetic parameters of the hydrogel based on water absorbency. The Taguchi L9 (34) orthogonal array is chosen for experimental design. Mass concentrations of crosslinker MBA \(C_{\text{MBA}}\) initiator KPS \(C_{\text{KPS}}\), sodium alginate \(C_{\text{NaAlg}}\) and mass ratio of monomers \(C_{\text{AM/AA/AMPS}}\) are chosen as four factors. The analysis of variance of the test results indicates the following optimal conditions: 0.8 g L?1 of MBA, 0.9 g L?1 of KPS, 8 g L?1 of NaAlg and \(R_{\text{AM/AA/AMPS}}\) equals to 1:1.1:1.1. The maximum water absorbency of the optimized final hydrogel is found to be 822 g g?1. The relative thermal stability of the optimized hydrogel in comparison with sodium alginate is demonstrated via thermogravimetric analysis. The prepared hydrogel is characterized by FTIR spectroscopy and scanning electron microscopy. The influence of the environmental parameters on water absorbency such as the pH and the ionic force is also investigated. The optimized hydrogel is used as adsorbent for hazardous heavy metal ions Pb(II), Cd(II), Ni(II) and Cu(II) and their competitive adsorption is also discussed. Isotherm of adsorption and effect of pH, adsorption dosage and recyclability are investigated. The results show that the maximum adsorption capacities of lead and cadmium ions on the hydrogel are 628.93 and 456.62 mg g?1, respectively. The adsorption is well described by Langmuir isotherm model. The hydrogel is also utilized for the loading of potassium nitrate as an active agrochemical agent and the release of this active agent has also been investigated.  相似文献   

13.
A novel chelating resin with functional group containing S and N atoms was prepared using chloromethylated polystyrene and 2,5‐dimercapto‐1,3,4‐thiodiazole (also called bismuththiol I, BMT) as materials. Its structure was characterized by infrared spectra and elementary analysis. The results showed that the content of the functional group was 2.07 mmol BMT g?1 resin, 47% of which were in the form of monosubstitution (PS‐BMT‐1) and 53% in the form of double substitution (PS‐BMT‐2). The adsorption for mercury ion was investigated. The adsorption dynamics showed that the adsorption was controlled by liquid film diffusion. Increasing the temperature was beneficial to adsorption. The Langmuir model was much better than the Freundlich model to describe the isothermal process. The adsorption activation energy (Ea), ΔG, ΔH, and ΔS values calculated were 18.56 kJ·mol?1, ‐5.99 kJ·mol?1, 16.38 kJ·mol?1, and 37.36, J·mol?1·K?1, respectively. The chelating resin could be easily regenerated by 2% thiourea in 0.1 mol·L?1 HCl with higher effectiveness. Five adsorption–desorption cycles demonstrated that this resin was suitable for repeated use without considerable change in adsorption capacity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1646–1652, 2004  相似文献   

14.
15.
In the present investigation, attempts were made to color match mass colored polypropylene by the use of several colorimetric color matching procedures. A color matching procedure consisting of a rough match as a starting point and an iterative algorithm to achieve the exact match to any degree of accuracy was carried out. The rough match was calculated based on the Kubelka-Munk's one and two constant theories. Six different iteration procedures were utilized to achieve the exact match having ΔE2000 < 0.5. The results showed that the iterations based on Lab76 gave superior results showing the most potential for a recipe prediction system for a computer color matching procedure by giving the lowest average concentration difference, ΔCAVE, and the lowest color difference, ΔE2000, under the reference condition, i.e., D65/10°. In general and as expected, concentration predictions based on the one-constant theory were always inferior to the prediction based on the two-constant theory.  相似文献   

16.
《分离科学与技术》2012,47(1):203-222
Abstract

The decontamination of lead ions from aqueous media has been investigated using styrene‐divinylbenzene copolymer beads (St‐DVB) as an adsorbent. Various physico‐chemical parameters such as selection of appropriate electrolyte, contact time, amount of adsorbent, concentration of adsorbate, effect of foreign ions, and temperature were optimized to simulate the best conditions which can be used to decontaminate lead from aqueous media using St‐DVB beads as an adsorbent. The atomic absorption spectrometric technique was used to determine the distribution of lead. Maximum adsorption was observed at 0.001 mol L?1 acid solutions (HNO3, HCl, H2SO4 and HClO4) using 0.2 g of adsorbent for 4.83×10?5 mol L?1 lead concentration in two minutes equilibration time. The adsorption data followed the Freundlich, Langmuir, and Dubinin‐Radushkevich (D‐R) isotherms over the lead concentration range of 1.207×10?3 to 2.413×10?2 mol L?1. The characteristic Freundlich constants i.e. 1/n=0.164±0.012 and A=2.345×10?3±4.480×10?5 mol g?1 have been computed for the sorption system. Langmuir isotherm gave a saturated capacity of 0.971±0.011 mmol g?1, which suggests monolayer coverage of the surface. The sorption mean free energy from D‐R isotherm was found to be 18.26±0.75 kJ mol?1 indicating chemisorption involving chemical bonding for the adsorption process. The uptake of lead increases with the rise in temperature. Thermodynamic parameters i.e. ΔG, ΔH, and ΔS have also been calculated for the system. The sorption process was found to be exothermic. The developed procedure was successfully applied for the removal of lead ions from real battery wastewater samples.  相似文献   

17.
In this study, physical and thermodynamic properties of poly(2-phenyl-1,3-dioxolane-4-yl-methyl-methacrylate-co-styrene) (PDMMA-ST) were investigated by using inverse gas chromatography. Two groups of solvents with different chemical natures and polarities were used to obtain information about PDMMA-ST-solvent interactions: alcohols and alkanes. The specific retention volume (Vg 0), the sorption enthalpy (ΔH1 S), sorption free energy (ΔG1 S), sorption entropy (ΔS1 S), the weight fraction activity coefficients of solute probes at infinite dilution (Ω 1 ), and Flory-Huggins interaction parameters (χ 12 ) between polymer and solvents were determined for the interactions of PDMMA-ST with alcohols and alkanes by inverse gas chromatography in the temperature range of 333–473 K. Also, the solubility parameters of PDMMA-ST at infinite dilution were found by plotting the graph of [(δ 1 2/RT) - χ 12 /V1] versus solubility parameters, δ 1, of probes.  相似文献   

18.
《国际聚合物材料杂志》2012,61(12):1145-1154
Galactomannan, a water-soluble heteropolysaccharide, was isolated from the seed of Chinese traditional medicine fenugreek. The polysaccharide was characterized by using both chemical and chromatographic procedures, as well as FT-IR, 1H NMR, 13C NMR spectroscopy. The results showed that the polysaccharide consists of D-mannopyranose and D-galactopyranose residues with a molar ratio of 1.2:1.0. The main chain of this galactomannan comprises β-(1,4)-linked D-mannopyranose residues, in which 83.3% of the main chain is substituted at C-6 with a single residue of α-(1,6)-D-galactopyranose. The galactomannan had a molecular weight Mw of 3.23 × 105 g mol?1 and an intrinsic water viscosity of 235 mL g?1. Fenugreek gum (seed endosperm) contains 73.6% galactomannan. The viscosity of fenugreek gum at 1% concentration is 286 mPa.s (30°C, 170 s?1). The viscosity of the solutions decreased sharply as the rate of shear increased, but rose with increased concentration, and decreased as the temperature of fully hydrated gum solution was gradually raised from 30 to 90°C. Fenugreek gum can be a highly efficient water-thickening agents and can be used in food industry and drug delivery formulations.  相似文献   

19.
《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   

20.
BACKGROUND: Due to its strong colour, high concentrations of fluorides and chemical oxygen demand (CODCr) and large amount of suspended solids (SS), the waste‐water from carbon production (WCP) seriously affects the stability of the circulating system of Guizhou Branch, Aluminium Corporation of China. In this paper, the performance of a pilot‐scale (24 m3 d?1) combined treatment plant, consisting of chemical precipitation, coagulation, and Fenton oxidation, for the treatment of WCP was investigated. RESULTS: Lime precipitation and hydrated ferrous sulphate (HFS) coagulation, with polyacrylamide (PAM) as a coagulation aid, proved to be effective in the removal of colour (>70%), suspended solids (SS) (>90%) and fluoride (>80%) from the WCP. Subsequent Fenton oxidation combined with coagulation as a final treatment efficiently removed SS, F?, CODCr, dissolved organic carbon (DOC) and colour. The average total removal efficiencies of these parameters in the pilot‐scale combined technology were as follows: SS = 98.8%, F? = 95.7%, CODCr = 94.8%, DOC = 91.8% and colour = 98.3%, giving an average effluent quality: colour 24 (multiple), CODCr 168 mg L?1, DOC 80 mg L?1, F? 38 mg L?1 and SS 44 mg L?1, consistent with the reusable water limits for the process. CONCLUSIONS: The current experimental results and the economic evaluation suggest that the combined process could be advantageous and feasible for the treatment of WCP. Copyright © 2009 Society of Chemical Industry  相似文献   

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