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1.
The ferrocene-ferricinium electrode (Pt/Foc, Fic+) was investigated in water, acetonitrile, ethanol, DMSO and DMF using single scan cyclic voltammetry and phase sensitive ac polarography. The oxidation-reduction is pseudo-reversible in all five solvents with an electrochemical rate constant of approximately 10−2 cm/s. In all solvents a slow irreversible chemical step involving the ferricinium cation follows electron transfer, so that slow cyclic voltammetry or polarography rather than potentiometry is preferred if ferrocene is to be used as a reference electrode in non-aqueous solvents.

The Strehlow assumption, ΔGtr(Foc) = ΔGtr(Fic+ gives very different free energies of transfer of single ions from non-aqueous solvents to water when compared with the TATB assumption that ΔGtr(Ph4As+) = ΔGtr(Ph4B). This discrepancy is likely to be because ferricinium is only a moderately large cation, so that ΔGtr(Fic+) is less positive than ΔGtr(Foc) for transfer to water. The discrepancy is not because of abnormal electrochemical behavior of the Pt/Foc, Fic+ electrode in water or other solvents. Values of E° vs nhe, H2O in a variety of solvents based on the TATB assumption are presented.  相似文献   


2.
The aim of this research work is to investigate sorption characteristic of beach sand for the removal of Zn(II) ions from aqueous solutions. The sorption of Zn(II) ions by batch dynamic method is carried out using dilute solutions (10−4 M) of nitric, hydrochloric and perchloric acids along with deionized water and from buffers of pH 2–10. Maximum sorption is noticed from deionized water (88.3%) using 30 min shaking time. Two equations, i.e. Morris–Weber and Lagergren have been tested to track the kinetics of removal process. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) model are subjected to sorption data to estimate sorption capacity, intensity and energy. The thermodynamic parameters ΔH, ΔS and ΔG are evaluated. The influence of common ions on the sorption of Zn(II) ions is also examined. Some ions reduce the sorption while most of the ions tested have very little effect. It can be concluded that beach sand has potential to remove Zn(II) ions from aqueous solutions at very low concentrations and for the treatment of industrial effluent carrying Zn(II) ions.  相似文献   

3.
Adsorption of metals by clay minerals is a complex process controlled by a number of environmental variables. The present work investigates the removal of Cu(II) ions from an aqueous solution by kaolinite, montmorillonite, and their poly(oxo zirconium) and tetrabutylammonium derivatives. The entry of ZrO and TBA into the layers of both kaolinite and montmorillonite was confirmed by XRD measurement. The specific surface areas of kaolinite, ZrO-kaolinite, TBA-kaolinite, montmorillonite, ZrO-montmorillonite, TBA-montmorillonite were 3.8, 13.4, 14.0, 19.8, 35.8 and 42.2 m2/g, respectively. The cation exchange capacity (CEC) was measured as 11.3, 10.2, 3.9, 153.0, 73.2 and 47.6 meq/100 g for kaolinite, ZrO-kaolinite, TBA-kaolinite, montmorillonite, ZrO-montmorillonite, TBA-montmorillonite, respectively. Adsorption increased with pH till Cu(II) ions became insoluble in alkaline medium. The kinetics of the interactions suggests that the interactions could be best represented by a mechanism based on second order kinetics (k2 = 7.7 × 10−2 to 15.4 × 10−2 g mg−1 min−1). The adsorption followed Langmuir isotherm model with monolayer adsorption capacity of 3.0–28.8 mg g−1. The process was endothermic with ΔH in the range 29.2–50.7 kJ mol−1 accompanied by increase in entropy and decrease in Gibbs energy. The results have shown that kaolinite, montmorillonite and their poly(oxo zirconium) and tetrabutyl-ammonium derivatives could be used as adsorbents for separation of Cu(II) from aqueous solution.  相似文献   

4.
To get the low temperature sulfur resistant V2O5/TiO2 catalysts quantum chemical calculation study was carried out. After selecting suitable promoters (Se, Sb, Cu, S, B, Bi, Pb and P), respective metal promoted V2O5/TiO2 catalysts were prepared by impregnation method and characterized by X-ray diffraction (XRD) and Brunner Emmett Teller surface area (BET-SA). Se, Sb, Cu, S promoted V2O5/TiO2 catalysts showed high catalytic activity for NH3 selective catalytic reduction (NH3-SCR) of NOx carried at temperatures between 150 and 400 °C. The conversion efficiency followed in the order of Se > Sb > S > V2O5/TiO2 > Cu but Se was excluded because of its high vapor pressure. An optimal 2 wt% ‘Sb’ loading was found over V2O5/TiO2 for maximum NOx conversion, which also showed high resistance to SO2 in presence of water when compared to other metal promoters. In situ electrical conductivity measurement was carried out for Sb(2%)/V2O5/TiO2 and compared with commercial W(10%)V2O5/TiO2 catalyst. High electrical conductivity difference (ΔG) for Sb(2%)/V2O5/TiO2 catalyst with temperature was observed. SO2 deactivation experiments were carried out for Sb(2%)/V2O5/TiO2 and W(10%)/V2O5/TiO2 at a temperature of 230 °C for 90 h, resulted Sb(2%)/V2O5/TiO2 was efficient catalyst. BET-SA, X-ray photoelectron spectroscopy (XPS) and carbon, hydrogen, nitrogen and sulfur (CHNS) elemental analysis of spent catalysts well proved the presence of high ammonium sulfate salts over W(10%)/V2O5/TiO2 than Sb(2%)/V2O5/TiO2 catalyst.  相似文献   

5.
Spent brewery grains (SBG), a by-product of the brewing process, were tested as an adsorbent of acid orange 7 dye (AO7), a monoazo acid dye currently used in paper and textile industries. The presence of AO7 in these effluents causes obvious environmental problems.

Kinetics studies of adsorption of AO7 to SBG (3.75%, m/v) were carried out at 20 °C, using aqueous solutions with different AO7 concentrations (30–834 mg/L). For every situations tested, no significant variation in residual AO7 concentration in solution was detected after 1 h contact between the dye and the adsorbent. The adsorption process followed a pseudo-first order model.

The equilibrium process showed to be well described by both Freundlich and Langmuir isotherm models, at 20 and 30 °C. The maximum adsorption capacity was estimated to be 30.5 mg AO7/g SBG, at 30 °C.

Free energy of adsorption (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) changes were calculated to predict the nature of adsorption. The estimated values for ΔG° were −22.78 and −24.53 kJ/mol, respectively, at 293.3 K (20 °C) and 303.3 K (30 °C), which are rather low indicating that a spontaneous process occurred. The enthalpy changes and entropy of adsorption were 28.66 and 175.36 J/mol K, respectively. The positive value for ΔH° indicates that the adsorption of AO7 dye to SBG is an endothermic process. The positive value of entropy reflects the affinity of the adsorbent for AO7 dye.

The obtained results are very promising since: (i) high levels of colour removal (>90%) were achieved with low contact times adsorbent/dye (less than 1 h contact); and (ii) the whole SBG can be successfully used as adsorbent of AO7 dye in aqueous solution without needing any previous treatments such as milling and/or sieving. Spent grains, being a cheap, and easily available material, can be an alternative for more costly adsorbents used for dye removal in wastewater treatment processes.  相似文献   


6.
Cu(II) complexes of an aminic polymer containing sulphone have been studied at 25°C in aqueous solution at different pH's by potentiometric, calorimetric, visible and e.p.r. spectroscopic techniques. The potentiometric and spectroscopic data reveal the presence of two different complexes: the first CuL2+ (L refers to the repeating unit of the polymer) presents a ‘sharp’ stability constant. This indicates that logβ is unaffected by pH at different polymer/Cu(II) molar ratios. This species reaches a maximum concentration of 30% with respect to the ligand. From e.p.r. measurements, spectrophotometric and calorimetric data we can hypothesize the coordination of one nitrogen and one oxygen probably belonging to the sulphone. The second is a dihydroxo complex Cu(OH)2L whose stability constant is ‘apparent’ and decreases with increasing pH, while ΔH0 is ‘sharp’. E.p.r. and visible spectroscopic parameters are reported and the thermodynamic data are discussed.  相似文献   

7.
The adsorption of Cu(II) ions onto chitosan and cross-linked chitosan beads has been investigated. Chitosan beads were cross-linked with glutaraldehyde (GLA), epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE) in order to obtain sorbents that are insoluble in aqueous acidic and basic solution. Batch adsorption experiments were carried out as a function of pH, agitation period, agitation rate and concentration of Cu(II) ions. A pH of 6.0 was found to be a optimum for Cu(II) adsorption on chitosan and cross-linked chitosan beads. Isotherm studies indicate Cu(II) can be effectively removed by chitosan and cross-linked chitosan beads. Adsorption isothermal data could be well interpreted by the Langmuir equation. Langmuir constants have been determined for chitosan and cross-linked chitosan beads. The experimental data of the adsorption equilibrium from Cu(II) solution correlated well with the Langmuir isotherm equation. The uptakes of Cu(II) ions on chitosan beads were 80.71 mg Cu(II)/g chitosan, on chitosan-GLA beads were 59.67 mg Cu(II)/g chitosan-GLA, on chitosan-ECH beads were 62.47 mg Cu(II)/g chitosan-ECH and on chitosan-EGDE beads were 45.94 mg Cu(II)/g chitosan-EGDE. The Cu(II) ions can be removed from the chitosan and cross-linked chitosan beads rapidly by treatment with an aqueous EDTA solution and at the same time the chitosan and cross-linked chitosan beads can be regenerated and also can be used again to adsorb heavy metal ions.  相似文献   

8.
Complexes of type [M(SAH)(OH2)], where M is Mn(II),Co(II),Ni(II) and Cu(II), and SAH is the Schiff-base formed by condensation of salicylaldehyde (2 equiv.) and hydrazine (1 equiv.), bis(salicylaldiminato)hydrazone, or “2-({(z)-2-[(E)-1-(2-hydroxyphenyl)methylidene]hydrazono}methyl)phenol” have been prepared and characterized by elemental analysis, IR, UV–vis spectroscopy, conductometric, small area X-ray photoelectron spectroscopy and magnetic measurements. Elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). The results indicate that the Schiff-base ligand coordinates through one azomethine nitrogen and two phenolic oxygen to the metal ions. Conductance measurements suggest the non-electrolytic nature of the complexes. The atomic concentration of the complexes showed the ratio of M:N:O = 1:2:3, that indicates that a water molecule was in the complex. Alumina-supported complexes “[M(SAH)OH2]-Al2O3” catalyze the oxidation of cyclohexene with tert-butylhydroperoxide (TBHP). The major products of the reaction were 2-cyclohexene-1-ol, 2-cyclohexene-1-one and 2-cyclohexene-1-(tert-butylperoxy). The influence of solvent on the oxidation reaction has been studied. [M(SAH)OH2]-Al2O3 shows significantly higher catalytic activity than other alumina-supported complexes. These catalysts can also be reused in the oxidation of cyclohexene several times. The new materials “[M(SAH)OH2]-Al2O3” were characterized by several techniques: chemical analysis and spectroscopic methods (FT-IR, UV–vis, XRD, DRS).  相似文献   

9.
In aqueous potassium nitrate the complexes Cu(dip)(gly) Cl. 1.5 H2O, Cu(dip)(alan) Cl. 1.5 H2O, Cu(dip)(val) Cl.3 H2O, Cu(dip)(ser) Cl H2O have been observed to undergo single step two electron irreversible electroreduction at dme. From the characteristics of irreversible wave, the rate constant kr for each complex has been calculated at reference potential −0.2142V vs sce. It is observed that the electroreduction of the complexes Cu(dip)(gly) Cl.1.5 H2O, Cu(dip)(alan) Cl. 1.5H2O does not follow a particular reaction mechanism with temperature. It has been also observed that the half-wave potential shifts towards more negative side as the ligand field band shifts to higher energy side. A correlation between electrode behaviour characteristics and spectral characteristics has been attempted. A possible electron transfer mechanism has been suggested on the basis of orientation of orbitals towards the electrode. The stability constant data obtained from the literature also support the proposed mechanism.  相似文献   

10.
A low-pressure steady-state technique has been used to investigate the rates and mechanisms of the oxidation of isobutane over H3[PMo12O40], CuH4[PMo12O40]2, Cu2H2[PMo12O40]2, Cu2.5H[PMo12O40]2, and Cu3[PMo12O40]2. Observed oxidation products over all catalysts are methacrolein, 3-methyl-2-oxetanone, acetic acid, carbon dioxide and water. The most selective catalyst for methacrolein formation at low temperatures (<496 °C) is Cu2.5H[PMo12O40]2, where both Cu(II) reduction and acid sites play a role. The least active catalyst at low temperatures is phosphomolybdic acid followed by Cu3[PMo12O40]2. This activity is reversed at higher temperatures. The 3-methyl-2-oxetanone is a unique product and is likely to be the precursor to methacrylic acid. Acetic acid is also probably a precursor to complete oxidation. Catalyst deactivation or restructuring is significant only over H3[PMo12O40].  相似文献   

11.
The removal of Fe(III), Cu(II), and Cd(II) ions from aqueous solutions was investigated with a crossflow filtration technique. Alginic acid (AA)/cellulose composite membranes were used for retention. In the filtration of Fe(III) solutions, the effects of the crossflow velocity, applied pressure, AA content of the membranes, and pH on the retention percentage and the permeate flux were examined. The maximum retention percentage was found to be 89% for a 1 × 10?4M Fe(III) solution at the flow velocity of 100 mL/min and the pressure of 60 kPa with 0.50% (w/v) AA/cellulose composite membranes at pH 3. Aqueous solutions of Cu(II) and Cd(II) were filtered at the flow velocity of 100 mL/min and pressure of 10 kPa. The effects of the AA content of the membranes and pH of the waste medium on the retention percentage and the permeate flux were determined. For 1 × 10?4M Cu(II) and Cd(II) solutions, the maximum retention percentages were found to be 94 and 75%, respectively, at pH 7 with 0.50% (w/v) AA/cellulose composite membranes. When metal‐ion mixtures were used, the retention percentages of Fe(III), Cu(II), and Cd(II) were found to be 89, 48, and 10%, respectively, at pH 3 with 0.50% (w/v) AA/cellulose composite membranes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

12.
The electrode kinetics of the Pb(II)/Pb(Hg) system has been studied in DMSO and DMSO-water mixtures using the faradaic impedance measurements. With the increase of the mole fraction of the organic component in the mixture rate constant decreases steadily from 2 cm s?1 in pure water to 5 × 10?2 cm s?1 in DMSO in rough proportion to the coverage of the electrode by DMSO. The change of the kinetics with the solvent composition was discussed in the frame of existing models.Basing on the determined potentials of the Pb(II)/Pb(Hg) electrode expressed vs the ferrocinium ion/ferrocene electrode potential, the free energy of transfer of Pb(II) from water to DMSO and its mixtures was calculated and discussed.  相似文献   

13.
Polypyrrole coated oxidized multiwalled carbon nanotubes (oMWCNT/Ppy) were applied to determine the adsorption characteristics of Pb(II) and Cu(II) from their aqueous solutions. Structural and morphological characterization studies using scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared and Raman spectroscopy showed successful preparation of the oMWCNT/Ppy composite. The influence of pH, contact time, and initial metal ion concentration on the adsorption of Pb(II) and Cu(II) was studied. The adsorption processes fitted well with Langmuir isotherm and pseudo-second-order kinetic models. The maximum adsorption capacities for Pb(II) and Cu(II) were determined as 26.32 and 24.39 mg/g, respectively. Desorption studies indicated that the oMWCNT/Ppy composite could be reused for five cycles with minimum loss of its initial adsorption capacity.  相似文献   

14.
F. Sundardi 《Polymer》1979,20(12):1522-1526
A theoretical analysis of radiation grafting kinetics has been made in terms of the quantitative interrelationship between the degree of grafting (Gf), the grafting periods (t) grafting temperature (T) and the monomer content in the polymeric system (M). Poly(ethylene terephthalate) fibres and a number of hydrophilic monomers have been employed for these experiments. The grafting reactions were initiated by trapped radicals produced by irradiation of the polymeric system under vacuum at room temperature. Experimental results showed that the monomer content in the fibres obeyed the Arrhenius relationship. The overall activation energy of the grafting reaction has been calculated. Grafting reactions can proceed only if ΔEt > ΔEp + ΔEM. This termination activation energy ΔEt is a function of the state of polymeric system.  相似文献   

15.
Heavy metal ion is one of the major environmental pollutants. In this study, a Cu(II) ions imprinted magnetic chitosan beads are prepared to use chitosan as functional monomer, Cu(II) ions as template, Fe3O4 as magnetic core and epichlorohydrin and glutaraldehyde as crosslinker, which can be used for removal Cu(II) ions from wastewater. The kinetic study shows that the adsorption process follows the pseudo-second-order kinetic equations. The adsorption isotherm study shows that the Langmuir isotherm equation best fits for the monolayer adsorption processes. The selective adsorption properties are performed in Cu(II)/Zn(II), Cu(II)/Ni(II), and Cu(II)/Co(II) binary systems. The results shows that the IIMCD has a high selectivity for Cu(II) ions in binary systems. The mechanism of IIMCD recognition Cu(II) ions is also discussed. The results show that the IIMCD adsorption Cu(II) ions is an enthalpy controlled process. The absolute value of ΔH (Cu(II)) and ΔS(Cu(II)) is greater than ΔH (Zn(II), Ni(II), Co(II)) and ΔS (Zn(II), Ni(II), Co(II)), respectively, this indicates that the Cu(II) ions have a good spatial matching with imprinted holes on IIMCD. The FTIR and XPS also demonstrates the strongly combination of function groups on imprinted holes in the suitable space position. Finally, the IIMCD can be regenerated and reused for 10 times without a significantly decreasing in adsorption capacity. This information can be used for further application in the selective removal of Cu(II) ions from industrial wastewater.  相似文献   

16.
Five cationic transition metal (ethylenediamine) complexes (M=Cr(III), Co(III), Ni(II), and Cu(II)):paramolybdate anion (Mo7O246−) have been synthesis and characterized via their elemental analysis, magnetic susceptibility (μeff), thermal analysis (TG and DTA), FTIR spectra, and X-ray diffraction (XRD). The FTIR study suggests that the compounds prepared be of the ion-pair type ([M(en)n]m·Mo7O24). Thermal study showed that molybdenum in the Cr(III), and Co(III) compounds is reduced from oxidation state (VI) to (V) at high temperature. The stoichiometries of the resulting mixed oxides at elevated temperatures (500–750°C) are: Cr2O3·7MoO2.5, Co2O3·7MoO2.5, 6CoOCl·7MoO2.5, 3NiO·7MoO3 and 3CuO·7MoO3. Above 750°C the molybdenum oxide in the ion-pair compounds start the sublimation process. X-ray diffraction of [Cr(en)3]·Mo7O24, [Co(en)3]·Mo7O24, and [Cu(en)2(H2O)2]3·Mo7O24 shows that these complexes are crystalline solids with a similar structure, while the [Ni(en)(H2O)4]3·Mo7O24, and [Co(en)(H2O)2Cl2]6·Mo7O24 ion-pair compounds display a different structure.

A novel technique based on photocatalysis to eliminate Cr(VI) ions, a toxic pollutant in the environment, was applied. The photoreduction of Cr(VI) to Cr(III) ion in aqueous suspensions using new-mixed oxides as photocatalysts (Cr2O3·MoO2.5, Co2O3·MoO2.5, NiO·MoO3, and CuO·MoO3) under air-equilibration and irradiation by a medium pressure mercury lamp (UV–VIS) was investigated.  相似文献   


17.
Galvanostatic single-pulse, rotating-disc and chronopotentiometric measurements on etched polycrystalline copper electrodes in semimolar mixed solutions of CuSO4, MgSO4 and H2SO4 at 25°C have yielded kinetic parameters and specific rate data for either of the two consecutive charge-transfer steps of the Cu(I)/Cu(II) electrode. The ion-transfer step Cu/Cu(I), but not the electron-transfer step Cu/Cu(II), depends on a surface factor for crystal growth and demolition. Some information on this factor is obtained. Comparisons are made to the solid Ni/Ni(II) electrode and to the liquid Cu(Hg)/Cu(II) electrode.  相似文献   

18.
The kinetics of the electrode reaction of the Ni(II)/Ni(Hg) system in DMF and its mixtures with water at different concentrations of several background electrolytes has been studied.

Similarly to aqueous solutions, at higher background electrolyte concentrations the charge transfer step is preceded by a chemical reaction. It was deduced that this proceeding reaction is due to slow dissociation of the solvent molecule in the S1N process.

The change of a solvent from water to 70 vol.% of DMF decreases the standard rate constant (ks) for about one order of magnitude. At larger DMF content ks is virtually independent of the solvent composition. The change of ks with the DMF content was explained by assuming the resolvation of Ni(II) ions at the electrode surface in proportion to the surface coverage of the electrode molecules of both solvents.  相似文献   


19.
In this work, an adsorbent, which we call MnPT, was prepared by combining MnO2, polyethylenimine and tannic acid, and exhibited efficient performance for Cu(II) and Cr(VI) removal from aqueous solution. The oxygen/nitrogen-containing functional groups on the surface of MnPT might increase the enrichment of metal ions by complexation. The maximum adsorption capacities of MnPT for Cu(II) and Cr(VI) were 121.5 and 790.2 mg·g1, respectively. The surface complexation formation model was used to elucidate the physicochemical interplay in the process of Cu(II) and Cr(VI) co-adsorption on MnPT. Electrostatic force, solvation action, adsorbate–adsorbate lateral interaction, and complexation were involved in the spontaneous adsorption process. Physical electrostatic action was dominant in the initial stage, whereas chemical action was the driving force leading to adsorption equilibrium. It should be noted that after adsorption on the surface of MnPT, Cr(VI) reacted with some reducing functional groups (hydroxylamine-NH2) and was converted into Cr(III). The adsorption capacity declined by 12% after recycling five times. Understanding the adsorption mechanism might provide a technical basis for the procedural design of heavy metal adsorbents. This MnPT nanocomposite has been proven to be a low-cost, efficient, and promising adsorbent for removing heavy metal ions from wastewater.  相似文献   

20.
Ion‐imprinted chitosan (CS) microspheres (MIPs) were prepared with Cu(II) as a template and epichlorohydrin as a crosslinker for the selective separation of Cu(II) from aqueous solution. The microspheres showed a higher adsorption capacity and selectivity for the Cu(II) ions than nonimprinted chitosan microspheres (NMIPs) without a template. The results show that the adsorption of Cu(II) on the CS microspheres was affected by the initial pH value, initial Cu(II) concentration, and temperature. The kinetic parameters of the adsorption process indicated that the adsorption followed a second‐order adsorption process. Equilibrium experiments showed very good fits with the Langmuir isotherm equation for the monolayer adsorption process. The maximum sorption capacity calculated from the Langmuir isotherm was 201.66 mg/g for the Cu–MIPs and 189.51 mg/g for the NMIPs; these values were close to the experimental ones. The selectivity coefficients of Cu(II) and other metal ions on the NMIPs indicated a preference for Cu(II). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

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