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1.
The nature of adsorption behavior of Au(III) on polyurethane (PUR) foam was studied in 0.2M HCl aqueous solution. The effect of shaking time and amount of adsorbent were optimized for 3.16·10−5M solution of Au(III) in 0.2M HCl. The classical Freundlich and Langmuir adsorption isotherms have been employed successfully. The Freundlich parameters 1/n and adsorption capacityK are 0.488±0.016 and (1.40±0.22)·10−2 mol·g−1, respectively. The Langmuir constants of saturation capacityM and binding energyb are (1.66±0.08)·10−4mol·g−1 and 40294±2947 l·g−1, respectively, indicating the monolayer chemical sorption. The mean free energy (E) of adsorption of Au(III) on PUR foam has been evaluated using D-R isotherm and found to be 11.5±0.16 kJ·mol−1 reflecting the ion exchange type of chemical adsorption. The effect of temperature on the adsorption has also been studied. the isosteric heat of adsorption was found to be 44.03±1.66 kJ·mol−1. The thermodynamic parameters of ΔG, ΔH, ΔS and equilibrium constantK c have been calculated. The negative values of ΔG, ΔH and ΔS support that the adsorption of Au(III) on PUR foam is spontaneous, exothermic and of ion exchange chemisorption. The nature of the Au(III) species sorbed on PUR foam have been discussed.  相似文献   

2.
Summary The sorption of Eu(III) ions onto PAN loaded PUF has been optimized and investigated under the influence of various temperatures, i.e., 303, 313 and 323 K. Maximum retention (>96%) of Eu(III) ions (1.79. 10-5M) onto PAN loaded PUF (7.75 mg. ml-1) was achieved after 30-minute equilibration time from pH 7 buffer solution. The variation of sorption with temperature yields the thermodynamic parameters ΔH=79±2 kJ. mol-1, ΔS=276±7 kJ. mol-1. K-1and ΔG=-1.4±0.1 kJ. mol-1at 298 K. The positive value of enthalpy and negative free energy show endothermic and spontaneous nature of sorption, respectively. The sorption data followed Freundlich, Dubinin-Radushkevich (D-R) and Langmuir isotherms at all the three given temperatures. The Freundlich constant 1/n=0.70, 0.62 and 0.55 and sorption capacities Cm=10.8 mmol. g-1, 6.1 mmol. g-1and 4.4 mmol. g-1, respectively, decreased with increasing temperature. Similarly, the sorption capacities of D-R isotherm Xm=197.6 μmol. g-1, 201.2 μmol. g-1and 137.4 μmol. g-1, also decreased with temperature. However, the sorption free energy E=10.2 kJ. mol-1, 11.2 kJ. mol-1and 12.7 kJ. mol-1, increased with temperature. The monolayer coverage (Q) computed from Langmuir isotherm was 11.1±0.6 μmol. g-1and remains constant at all the three temperatures investigated. However, the binding energy constant bincreased with temperature. The relationship of bwith temperature and differential heat of adsorption (ΔHdiff) have been evaluated and discussed.  相似文献   

3.
Titanium dioxide nanoparticles were employed for the sorption of Ge(IV) ions from aqueous solution. The process was studied in detail by varying the sorption time, pH, and temperature. The sorption process was found to be fast, equilibrium was reached within 3 min. A maximum sorption could be achieved from solution when the pH ranges between 4.0 and 11.0. Sorbed Ge(IV) ions can be completely desorbed with 2 mL of 0.3 mol L−1 K3PO4-1.0 mol L−1 H2SO4 mixture solution. The kinetic experimental data properly correlate with the second-order kinetic model (k 2 = 0.88 g mg−1 min−1 (25°C)), Reichenberg equation and Morris-Weber model. The estimated E a for Ge(IV) adsorption on nano-TiO2 was 19.66 kJ mol−1. The overall rate process appears to be influenced by intra-particle diffusion. The sorption data could be well interpreted with the Langmuir and Dubinin-Radushkevich (D-R) type sorption isotherms. The D-R parameters were calculated to be K = −0.00321 mol2 kJ−2, q m = 0.59 mmol g−1 and E = 12.48 kJ mol−1 at room temperature. Furthermore, the thermodynamic parameters were also determined, and the ΔH 0 and ΔG 0 values indicated a spontaneous exothermic behavior.  相似文献   

4.
Rice husk, an agricultural waste product, was studied as a potential decontaminant for chromium in the effluents of leather tanning industries. Physico-chemical parameters such as selection of appropriate electrolyte, shaking time, concentration of adsorbent and adsorbate were studied to optimize the best conditions in which this material can be utilized on commercial scale for the decontamination of effluents. The radiotracer technique was used to determine the distribution of chromium. In certain cases atomic absorption spectrophotometry was also employed. Maximum adsorption was observed at 0.01 mol·dm−3 acid solutions (HNO3, HCl, H2SO4 and HClO4) using 3.0 g of adsorbent for 2.73·10−3 mol·dm−3 chromium concentration in five minutes equilibration time. Studies show that the adsorption decreases with the increase in the concentrations of all the acids. The adsorption data follows the Freundlich isotherm over the range of 2.73·10−3 to 2.73·10−2 mol·dm−3 chromium concentration. The characteristic Freundlich constants, i.e., 1/n=0.86±0.06 andA=2.35±0.06 mmol·g−1 have been computed for the sorption system. Thermodynamic parameters, i.e., ΔG 0, ΔS 0 and ΔH 0 have also been calculated for the system. Application of the method to a test case of a medium size industry showed that 21 kg of rice husk was sufficient to maintain the NEQS limits of chromium for industrial effluents.  相似文献   

5.
1 Introduction Studies on the interaction of the complexes formed between proteins and amphiphilic molecules in aque- ous solutions have become a new focus and great pro- gress has been made in recent years[1―5]. An under- standing of these systems is of great importance in many biological processes and clinical use of drugs. The globular anionic protein human serum albumin (HSA) is widely used as a protein model in many studies[1―4,6]. Its principal function is to transport fatty acids an…  相似文献   

6.
The sorption of Cd(II) on Haro river sand from deionized water is reported. The sorption system obeyed according to the Freundlich and Dubinin–Radushkevich (D-R) isotherms. The Freundlich parameters 1/n = 0.67±0.05 and of A = 1.38±1.14 mmole·g-1 have been ascertained. D-R isotherm yields the values of = -0.003741±0.000321 kJ2·mole-2, X m = 0.23±0.21 mole·g-1 and of E = 11.6±0.5 kJ·mole-1. The influence of common anions and cations on the sorption was examined. Trivalent Bi enhances the sorption whereas Fe, Cr, Al and chromate ions reduce the sorption significantly. Hf(IV) and Ag(I) indicate substantial sorption (61–98%) whereas Gd(III), Re(VII) and Sc(III) show low sorption (<5%). The elements having low sorption can be separated from elements indicating higher sorption using Haro river sand column.  相似文献   

7.
A new tripodal rhodamine B derivative 2 was designed and synthesized by tripodal trialdehyde and rhodamine B hydrazide for the first time. This derivative could be used as a fluorescent chemosensor for the selective and sensitive determination of copper(II) in Tris-HCl buffer and ethanol aqueous mixed media. Under the optimum conditions described herein, fluorescence enhancement at 557/577 nm was linearly related to the concentration of copper(II) in the range of 0.10 to 10.00×10−5 mol·L−1, with a correlation coefficient of R 2=0.9964 (n=15) and a detection limit of 1.129×10−7 mol·L−1 (the relative standard deviation for five repeated measurements at 4.00×10−5 mol·L−1 Cu(II) was 2.2%). The absorbance measurements at 557 nm were linearly related to the concentration of Cu(II) in the range of 0.50 to 25.00×10−5 mol·L−1, with a correlation coefficient of R 2=0.9948 (n=13) and a detection limit of 3.338×10−7mol·L−1. Supported by the Foundation of the Governor of Guizhou Province, China (Grant No. 200617) and the Talented Person Foundation of Guizhou University (Grant No. 2007039)  相似文献   

8.
The reaction of the · OH radical with the oxalate ion in an acidic aqueous solution was studied by pulse radiolysis. The rate constant for the reaction of formation of the radical HOOC-COO·(λmax = 250 nm, ɛ = 1800 L mol−1 cm−1) is (5.0±0.5)·107 L mol−1 s−1. In the reaction with the hydrogen ion (k = 1.1·107 L mol−1 s−1), the radical HOOC-COO· is transformed into a nonidentified radical designated arbitrarily as H+(HOOC-COO)· (λmax = 260 nm, ɛ = 4000 L mol−1 cm−1). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1165–1167, June, 2008.  相似文献   

9.
The sorption of anions H2PO4 , HPO4 2−, PO4 3−, [Fe(CN)6]3−, and [Fe(CN)6]4− from aqueous solutions on the surface of FeIII and ZrIV oxyhydroxide hydrogels freshly precipitated at pH 4–13 was studied. The region of sorbate concentrations was from 0.00025 to 0.06 mol L−1. The plots of the anion uptakes vs. their equilibrium concentrations are represented by isotherms of the first type, which are well described by the Langmuir equation if the quantity of the amount adsorbed is expressed as mol-site g−1. The maximum uptakes and constants of the Langmuir equation were calculated. The phosphate anions occupy the same number of sorption sites on the sorbents precipitated at different pH. The average specific content of sorption sites for the ferro- and zirconogels in the metastability period is independent of the pH of their precipitation, being 3.1·10−3 and 3.2·10−3 mol-site g−1, respectively. The [Fe(CN)6]3− and [Fe(CN)6]4− anions are sorbed only on the positively charged sites of the hydrogels and occupy not more than 2·10 mol-site g−1 in the studied interval of pH of precipitation. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1736—1741, August, 2005.  相似文献   

10.
Batch experiments aimed at the sorption of Pb(II) onto peat were performed from an aqueous solution in both the absence and presence of common complexing agents (acetate or citrate). The influence of the initial pH of the solution, metal ion concentration and contact time on the sorption efficiency of Pb(II) was examined at ambient temperature (18 ± 0.5) °C for each experiment. The results showed that the presence of acetate improved the efficiency of the sorption process, while the presence of citrate in the aqueous solution decreased the efficiency of the Pb(II) sorption onto peat. The equilibrium data fitted well with the Langmuir isotherm model and confirmed the monolayer sorption of uncomplexed and complexed Pb(II) species onto peat. The values of maximum sorption capacities (q max) were 135.13 mg g−1 for Pb(II) complexed with acetate, q > 79.36 mg g−1 for uncomplexed Pb, q > 38.46 mg g−1 for Pb(II) complexed with citrate. The kinetics of Pb(II) sorption onto peat, in both the absence and presence of complexing agents, indicated a pseudosecond order mechanism. Analysis of IR spectra showed that carboxylic and hydroxyl groups had an important role in the binding process of Pb(II) species onto peat.  相似文献   

11.
The lead (II) biosorption potential of Aspergillus parasiticus fungal biomass has been investigated in a batch system. The initial pH, biosorbent dosage, contact time, initial metal ion concentrations and temperature were studied to optimize the biosorption conditions. The maximum lead (II) biosorption capacity of the fungal biosorbent was found as 4.02 × 10−4 mol g−1 at pH 5.0 and 20°C. The biosorption equilibrium was reached in 70 min. Equilibrium biosorption data were followed by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. In regeneration experiments, no significant loss of sorption performance was observed during four biosorption-desorption cycles. The interactions between lead (II) ions and biosorbent were also examined by FTIR and EDAX analysis. The results revealed that biosorption process could be described by ion exchange as dominant mechanism as well as complexation for this biosorbent. The ion exchange mechanism was confirmed by E value obtained from D-R isotherm model as well.  相似文献   

12.
Solubility product (Lu(OH)3(s)⇆Lu3++3OH) and first hydrolysis (Lu3++H2O⇆Lu(OH)2++H+) constants were determined for an initial lutetium concentration range from 3.72·10−5 mol·dm−3 to 2.09·10−3 mol·dm−3. Measurements were made in 2 mol·dm−3 NaClO4 ionic strength, under CO2-free conditions and temperature was controlled at 303 K. Solubility diagrams (pLuaq vs. pC H) were determined by means of a radiochemical method using 177Lu. The pC H for the beginning of precipitation and solubility product constant were determined from these diagrams and both the first hydrolysis and solubility product constants were calculated by fitting the diagrams to the solubility equation. The pC H values of precipitation increases inversely to [Lu3+]initial and the values for the first hydrolysis and solubility product constants were log10 β* Lu,H = −7.92±0.07 and log10 K*sp,Lu(OH)3 = −23.37±0.14. Individual solubility values for pC H range between the beginning of precipitation and 8.5 were S Lu3+ = 3.5·10−7 mol·dm−3, S Lu(OH)2+ = 6.2·10−7 mol·dm−3, and then total solubility was 9.7·10−7 mol·dm−3.  相似文献   

13.
The sorption of caesium and strontium from its aqueous solutions by ten clinoptilolite-and mordenite-containing sedimentary materials from Slovakia, Bulgaria, Ukraine and Greece was investigated by batch-type procedure and radiotracer techniques. The concentration of the solutions, that were performed in and without the presence of competing cations (0.005 mol·dm−3 KCl) varied between 1·10−4 and 5·10−2 mol·dm−3. The uptake and distribution coefficient (K d ) values determined for the materials of the different origin, were correlated with their mineralogical composition and gross cation exchange capacity (CEC). The identification of the specific uptake sites was attempted on the basis of the sorption isotherms and the content of exchangeable cations. The experimental results provide information on the suitability of the individual materials for the treatment of radioactive wastes and their application as backfills in potential nuclear waste repositories.  相似文献   

14.
Summary The sorption of microquantities of Tm(III) ions on washed polyurethane foam (PUF) from a mixture of aqueous solution and ethanol containing PAN was examined. The maximum sorption of 3.18. 10-6M solution of Tm(III) ions was observed at pH 8 with 30-minute equilibration time. The optimum ratio of aqueous-ethanol phase for the sorption of Tm(III) ions was found to be 3:1 v/v, respectively. The sorption rate of metal ions on PUF is followed a first order kinetics and obeyed the equation for an intra particle diffusion process. The equilibrium concentration data of Tm(III) ions could be described satisfactorily by several adsorption isotherms. The Freundlich adsorption isotherm constants 1/nand KFare 0.66±0.02 and (5.7±0.3). 10-3mol. g-1, respectively. The Langmuir isotherm constants for monolayer coverage (Q) and binding strength of sorption (b) are (2.5±0.7). 10-5mol. g-1and (1.6±0.1). 104l. mol-1, respectively. The sorption capacity derived from Dubinin-Radushkevich (D-R) isotherm is (1.7±0.2). 10-4mol. g-1and the sorption free energy (E) is 9.8±0.2 kJ. mol-1indicating chemisorption phenomena. The thermodynamic parameters indicate that the sorption of Tm(III) ions onto PUF is endothermic, entropy driven and spontaneous in nature.  相似文献   

15.
The kinetics of self-termination of benzophenone oxide (BPO) in the liquid phase was studied by flash photolysis. The extinction coefficient of BPO (ε) was found to be virtually independent of the solvent nature, ε=(1.9±0.1)·103 L mol−1 cm−1. The rate constant of the BPO self-temination increases from 1.8·107 (MeCN) and 7.4·107 (C6H6) to 1.5·109 (n-decane) and 2.0·109 L mol−1 s−1 (n-pentane) at 293±2 K. Solvation of BPO promotes a polar state of the molecule in MeCN and C6H6. In nonpolar hydrocarbons, a great contribution is made by the biradical structure resulting in an increase in the rate constant and a shift of the absorption maximum to the long-wave region (from 410 nm in MeCN to 425 nm inn-pentane). In solutions of benzene and acetonitrile, benzophenone oxide reacts with the parent diazo compound with a rate constant of (2–4)·105 L mol−1 s−1 (293±2 K) along with the self-termination. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1329–1332, July, 1998.  相似文献   

16.
Polymorphism of paracetamol   总被引:1,自引:0,他引:1  
The thermodynamic relationship between crystal modifications of paracetamol was studied by alternative methods. Temperature dependence of saturated vapor pressure for polymorphic modifications of the drug paracetamol (acetaminophen) was mea sured and thermodynamic functions of the sublimation process calculated. Solution calorimetry was carried out for the two modifications in the same solvent. Thermodynamic parameters for sublimation for form I (monoclinic) were found: ΔG sub298=60.0 kJ mol−1; ΔH sub298=117.9±0.7 kJ mol−1; ΔS sub298=190±2 J mol−1 K−1. For the orthorhombic modification (form II), the saturated vapor pressure could only be studied at 391 K. Phase transition enthalpy at 298 K, ΔH tr298(I→II)=2.0±0.4 kJ mol−1, was derived as the difference between the solution enthalpies of the noted polymorphs in the same solution (methanol). Based on ΔH tr298 (I→II), differences between temperature dependencies of heat capacities of both modifications and the vapor pressure value of form II at 391 K, the temperature dependence of saturated vapor pressure and thermodynamic sublimation parameters for modification II were also estimated (ΔG sub298=56.1 kJ mol−1; ΔH sub298=115.9±0.9 kJ mol−1; ΔS sub298=200±3 J mol−1 K−1). The results indicate that the modifications are monotropically related, which is in contrast to findings recently reported found by classical thermochemical methods.  相似文献   

17.
Condensed and gas phase enthalpies of formation of 3:4,5:6-dibenzo-2-hydroxymethylene-cyclohepta-3,5-dienenone (1, (−199.1 ± 16.4), (−70.5 ± 20.5) kJ mol−1, respectively) and 3,4,6,7-dibenzobicyclo[3.2.1]nona-3,6-dien-2-one (2, (−79.7 ± 22.9), (20.1 ± 23.1) kJ mol−1) are reported. Sublimation enthalpies at T=298.15 K for these compounds were evaluated by combining the fusion enthalpies at T = 298.15 K (1, (12.5 ± 1.8); 2, (5.3 ± 1.7) kJ mol−1) adjusted from DSC measurements at the melting temperature (1, (T fus, 357.7 K, 16.9 ± 1.3 kJ mol−1)); 2, (T fus, 383.3 K, 10.9 ± 0.1) kJ mol−1) with the vaporization enthalpies at T = 298.15 K (1, (116.1 ± 12.1); 2, (94.5 ± 2.2) kJ mol−1) measured by correlation-gas chromatography. The vaporization enthalpies of benzoin ((98.5 ± 12.5) kJ mol−1) and 7-heptadecanone ((94.5 ± 1.8) kJ mol−1) at T = 298.15 K and the fusion enthalpy of phenyl salicylate (T fus, 312.7 K, 18.4 ± 0.5) kJ mol−1) were also determined for the correlations. The crystal structure of 1 was determined by X-ray crystallography. Compound 1 exists entirely in the enol form and resembles the crystal structure found for benzoylacetone.  相似文献   

18.
This paper discusses the sorption properties for U(VI) by alginate coated CaSO4·2H2O sepiolite and calcined diatomite earth (Kieselguhr) (ACSD). The removal of U(VI) from aqueous solution by sorption onto ACSF in a single component system with various contact times, pH, temperatures, and initial concentrations of U(VI) was investigated. The sorption patterns of uranium on the composite adsorbent followed the Langmuir, Freundlich and Dubinin-Radushkhevic (D-R) isotherms. The Freundlich, Langmuir, and D-R models have been applied and the data correlated well with Freundlich model and that the sorption was physical in nature (sorption energy, E a = 17.05 kJ/mol). The thermodynamic parameters such as variation of enthalpy ΔH, variation of entropy ΔS and variation of Gibbs free energy ΔG were calculated from the slope and intercept of lnK 0 vs. 1/T plots. Thermodynamic parameters (ΔH ads = 31.83 kJ/mol, ΔS ads = 167 J/mol·K, ΔG o ads (293.15 K) = −17.94 kJ/mol) showed the endothermic heat of sorption and the feasibility of the process. The thermodynamics of U(VI) ion/ACSD system indicates the spontaneous and endothermic nature of the process. It was noted that an increase in temperature resulted in a higher uranium loading per unit weight of the adsorbent.  相似文献   

19.
Hydroxyl radicals were generated radiolytically in N2O-saturated aqueous solutions of the aminoglycoside antibiotic, gentamycin. Using the pulse radiolysis technique, the rate constant of OH radicals with gentamycin determined was 1.2·109 dm3·mol−1·s−1. Upon.OH attack a transient species with an absorption maximum at 270 nm is observed which decays by second-order kinetics within the solute concentration range of 3.2·10−5 to 1·10−3mol·dm−3. Transient species undergoes transformation to a permanent product absorbing between 260 and 340 nm with maximum absorption at 300 nm. Rate constant of the reaction of bimolecular decay of gentamycin radicals, k (Gen.+Gen.) was found to be ≈ 1.4·107 dm3·mol−1·s−1.  相似文献   

20.
The kinetics of the oxidation of promazine by trisoxalatocobaltate(III) were studied in the presence of a large excess of the cobalt(III) in tris buffer solution using u.v.–vis spectroscopy ([CoIII] = (0.6 − 2) × 10−3 M, [ptz] = 6 × 10−5 M, pH = 6.6–7.8, I = 0.1 M (NaCl), T = 288−308 K, l = 1 cm). The reaction proceeds via two consecutive reversible steps. In the first step, the reaction leads to formation of cobalt(II) species and a stable cationic radical. In the second step, cobalt(III) is reduced to cobalt(II) ion and a promazine radical is oxidized to the promazine 5-oxide. Linear dependences of the pseudo-first-order rate constants (k 1 and k 2) on [CoIII] with a non-zero intercept were established for both redox processes. Rates of reactions decreased with increasing concentration of the H+ ion indicating that the promazine and its radical exist in equilibrium with their deprotonated forms, which are reactive reducing species. The activation parameters for reactions studied were as follows: ΔH = 44 ± 1 kJ mol−1, ΔS = −100 ± 4 JK−1 mol−1 for the first step and ΔH = 25 ± 1 kJ mol−1, ΔS = −169 ± 4 J K−1 mol−1 for the second step, respectively. Mechanistic consequences of all the results are discussed.  相似文献   

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