Application of the new thermodynamic approach to the description of superequivalent sorption by ion exchangers

Using the example of sorption systems with the participation of amino acids, it is shown that the novel thermodynamic approach to describing superequivalent sorption as a combination of ion exchange and nonexchangeable absorption allows us to adequately describe such equilibria. Results from calculating the activity coefficients of components of a sorbent phase and the thermodynamic constants of ion exchange equilibrium and the superequivalent absorption of phenylalanine by AV-17-8 anion exchange resin are presented.     

Misleading information on homogeneity and heterogeneity obtained from sorption isotherms

In this paper, the applications and the differences among the widely applied sorption isotherms (Langmuir isotherm for adsorption, competitive adsorption, ion exchange, Freundlich isotherm) are shown. The misleading information obtained by the formal applications of the isotherms is demonstrated using a simple mathematical model of homovalent ion exchange on homogeneous surface. This model calculation clearly reveals that when studying surface accumulation processes, the mechanism of the sorption process has to be determined. The correct thermodynamic interpretation of the data of sorption experiments is possible only if the isotherm is adapted to the sorption mechanism. It is emphasized that the regression values of the applied models themselves provide correct information neither on the surface heterogeneity nor the interactions among the sorbed species. The curved shape of an inadequate applied isotherm gives no information about the heterogeneity. In order to study the energy distribution of surface sites, the thermodynamic equations, including isotherms, has to be selected on the basis of sorption mechanism. All variable quantities involved in the given model (concentrations of the competing substances in all phases) have to be measured experimentally and included into the isotherm.     

Study of <Superscript>63</Superscript>Ni(II) sorption on CMC-bound bentonite from aqueous solutions

Bentonite was investigated to remove Ni(II) from aqueous solutions because of its strong sorption ability. Herein, bentonite was modified with sodium carboxymethylcellulose (CMC) and used as an adsorbent to remove Ni(II) from aqueous solutions. The results indicated that CMC-bentonite had higher sorption capacity than bare bentonite in the sorption of Ni(II) from aqueous solutions. Sorption of Ni(II) on CMC-bentonite was mainly dominated by ion exchange or outer-sphere surface complexation at low pH values, but by inner-sphere surface complexation or surface precipitation at high pH values. The thermodynamic data calculated from temperature dependent sorption isotherms indicated that the sorption of Ni(II) to CMC-bentonite hybrids was an spontaneous process and enhanced with increasing temperature.     

Sorption of radiocobalt(II) onto MWCNTs: effects of solid content, contact time, pH, ionic strength, humic acid and temperature

Multiwalled carbon nanotubes (MWCNTs) have attracted intense multidisciplinary study because of their special physicochemical properties. In this paper, the effect of solid content, contact time, pH, temperature and humic acid on radionuclide (⁶⁰Co(II)) on MWCNTs was studied by using batch technique. The results indicate that the sorption of Co(II) on MWCNTs can achieve sorption equilibration in short time and the kinetic sorption can be described by pseudo-second-order model well. The sorption of Co(II) on MWCNTs is strongly dependent on pH and independent of ionic strength, suggesting that the sorption of Co(II) on MWCNTs is mainly dominated by inner-sphere surface complexation rather than by outer-sphere surface complexation or ion exchange. The thermodynamic parameters calculated from the temperature-dependent sorption isotherms indicate that the sorption of Co(II) on MWCNTs was an endothermic and spontaneous process. The results of high sorption capacity of Co(II) suggest that MWCNTs can be used as efficient materials for the preconcentration of radiocobalt from large volumes of aqueous solutions in radionuclide polluted water.     

Removal of radiocobalt from aqueous solutions by kaolinite affected by solid content, pH, ionic strength, contact time and temperature

The kaolinite sample was characterized by Fourier transform infrared spectroscopy (FT-IR) and X-ray powder diffraction, and was applied as adsorbent for the removal of radiocobalt ions from radioactive wastewater. The results demonstrated that the sorption of Co(II) was strongly dependent on pH and ionic strength at low pH values, and independent of pH and ionic strength at high pH values. The sorption of Co(II) was dominated by outer-sphere surface complexation or ion exchange at low pH values, whereas inner-sphere surface complexation was the main sorption mechanism at high pH values. The sorption isotherms were well described by Langmuir, Freundlich and Dubinin–Radushkevich models. The thermodynamic parameters (i.e., ΔG°, ΔS°, ΔH°) calculated from the temperature-dependent sorption isotherms indicated that the sorption of Co(II) on kaolinite was an endothermic and spontaneous process. The results of high sorption capacity of kaolinite suggested that the kaolinite sample was a suitable material for the preconcentration of Co(II) from large volumes of aqueous solutions and as backfill materials in nuclear waste management.     

Fungal biomass with grafted poly(acrylic acid) for enhancement of Cu(II) and Cd(II) biosorption

The biomass of Penicillium chrysogenum was modified by graft polymerization of acrylic acid (AAc) on the surface of ozone-pretreated biomass. The sorption capacity for copper and cadmium increased significantly as a large number of carboxyl groups were present on the biomass surface, especially when the carboxylic acid group was converted to carboxylate ions using NaOH. When modeled using the Langmuir isotherm, the sorption capacities were 1.70 and 1.87 mmol g(-1) for copper and cadmium, respectively. The loaded biosorbent was regenerated using HCl solution and used repeatedly over five cycles with little loss of uptake capacity beyond the second cycle. The sorption of the two metals was time-dependent, and the kinetics fitted the pseudo-second-order equation well. The Freundlich, Langmuir, Temkin, and Dubinin-Redushkevich isotherms were used to model the metal sorption isotherms, and the thermodynamic parameters calculated show that the sorption was spontaneous and endothermic under the condition applied and that the biomass has similar sorption affinities for the two metals. Fourier transform infrared and X-ray photoelectron spectroscopy reveal that carboxyl, amide, and hydroxyl groups on the biomass surface were involved in the sorption of copper and cadmium and ion exchange and complexation dominated the sorption process.     

Sorption study of radionickel on attapulgite as a function of pH, ionic strength and temperature

Sorption of radionickel on attapulgite is studied as a function of contact time, ionic strength, pH and temperature. The results indicate that the sorption of Ni(II) on attapulgite is strongly ionic strength-dependent at pH <8, and independent of ionic strength at pH >8. Outer-sphere surface complexation or ion exchange contributes to Ni(II) sorption on attapulgite at pH <8, whereas the sorption of Ni(II) is mainly dominated by inner-sphere surface complexation at pH >8. The sorption of Ni(II) on attapulgite increases with increasing temperature, and the thermodynamic parameters (??H ⁰, ??G ⁰ and ??S ⁰) calculated from the temperature dependent sorption isotherms suggest that the sorption of Ni(II) on attapulgite is a spontaneous and endothermic process. The high sorption capacity of attapulgite suggests that attapulgite is a suitable material for the preconcentration and solidification of radionickel from large volumes of aqueous solutions.     

Impact of environmental conditions on the sorption behavior of Pb(II) onto attapulgite

This paper examined the application of attapulgite as an adsorbent for the removal of Pb(II) from heavy metal-contaminated water under various conditions. The sorption results indicated that the sorption of Pb(II) on attapulgite was strongly dependent on ionic strength at pH < 7.0. Outer-sphere surface complexation or ion exchange may be the main sorption mechanism of Pb(II) on attapulgite at low pH values. No drastic difference of Pb(II) sorption was observed at pH 7.0–10.0, and the sorption at pH > 10.0 was mainly dominated by inner-sphere surface complexation. The sorption of Pb(II) on attapulgite was affected by foreign ions in solution at pH < 7.0, and was not affected by foreign ions at pH > 7.0. The thermodynamic parameters (ΔH°, ΔS° and ΔG°) were evaluated from the temperature-dependent sorption isotherms, and the results indicated that the sorption process of Pb(II) on attapulgite was spontaneous and endothermic in nature.     

Sorption of anti-infective organic molecules from aqueous solutions onto zirconium phosphate

Amorphous zirconium phosphate (ZP), an inorganic ion exchange material of tetravalent metal acid (tma) salt, is synthesized by the sol-gel method and characterized by elemental analysis (ICP-AES), thermal analysis (TGA, DSC), FT-IR and X-ray diffraction studies. The resistivity of the material to acids, bases and organic solvents is assessed. The sorption behavior of the dyes acriflavin (AF) and brilliant green (BG) toward ZP was studied at 313, 323 and 333 K and the kinetic and thermodynamic parameters evaluated. Adsorption isotherms [Langmuir and Fruendlich], breakthrough capacity and elution behavior of these dyes are also studied. The sorption affinity of dyes towards ZP is BG > AF.     

Removal of U(VI) from aqueous solutions by using attapulgite/iron oxide magnetic nanocomposites

The attapulgite/iron oxide magnetic nanocomposites were prepared by coprecipitation method and characterized by scanning electron microscopy, X-ray diffraction, vibrating sample magnetometer and Fourier transform infrared sorption spectroscopy. The results of characterization showed that iron oxides were successfully deposited on the surfaces of attapulgite. The prepared magnetic nanocomposites were applied to remove radionuclide U(VI) ions from aqueous solutions by using batch technique and magnetic separation method. The results showed that the sorption of U(VI) on attapulgite/iron oxide magnetic composites was strongly dependent on ionic strength and pH at low pH values, and was independent of ionic strength at high pH values. The interaction of U(VI) with the magnetic nanocomposites was mainly dominated by outer-sphere surface complexation or ion exchange at low pH values, and was controlled by inner-sphere surface complexation or multinuclear surface complexation at high pH values. With increasing temperature, the sorption of U(VI) on attapulgite/iron oxide magnetic composites increased and the thermodynamic parameters calculated from the temperature dependent sorption isotherms suggested that the sorption of U(VI) on the magnetic nanocomposites was a spontaneous and endothermic process. The high sorption capacity and easy magnetic separation of the attapulgite/iron oxide magnetic composites make the material as suitable sorbent in nuclear waste management.     

Sorption of radiocobalt(II) from aqueous solutions to Na-attapulgite

The sorption of Co(II) on Na-attapulgite as a function of contact time, solid content, pH, ionic strength, foreign ions, fulvic acid (FA) and temperature under ambient conditions was studied. The kinetic of Co(II) sorption on Na-attapulgite was described well by pseudo-second-order model. The sorption of Co(II) on Na-attapulgite was strongly dependent on pH and ionic strength. The sorption of Co(II) was mainly dominated by outer-sphere surface complexation and/or ion exchange at low pH, whereas inner-sphere surface complexation or surface precipitation was the main sorption mechanism at high pH values. The presence of FA did not affect Co(II) sorption obviously at pH <7, and a negative effect was observed at pH >7. The Langmuir and Freundlich models were used to simulate the sorption data at different temperatures, and the results indicated that the Langmuir model simulated the data better than the Freundlich isotherm model. The thermodynamic parameters (∆G°, ∆S°, ∆H°) calculated from the temperature-dependent sorption isotherms indicated that the sorption of Co(II) on Na-attapulgite was an endothermic and spontaneous process. The results suggest that the attapulgite sample is a suitable material in the preconcentration and solidification of radiocobalt from large volumes of aqueous solutions.     

Sorption of uranium(VI) on Na-attapulgite as a function of contact time,solid content,pH, ionic strength,temperature and humic acid

Sorption of U(VI) from aqueous solution to Na-attapulgite was investigated at different experimental chemistry conditions by using batch technique. The attapulgite sample was characterized by FTIR and XRD. Sorption of U(VI) on attapulgite was strongly dependent on pH and ionic strength. The sorption of U(VI) on attapulgite increased quickly with rising pH at pH < 6, and decreased with increasing pH at pH > 7. The presence of humic acid (HA) enhanced the sorption of U(VI) on attapulgite obviously at low pH because of the strong complexation of surface adsorbed HA with U(VI) on attapulgite surface. Sorption of U(VI) on attapulgite was mainly dominated by ion exchange and/or outer-sphere surface complexation at low pH values, whereas the sorption was attributed to the inner-sphere surface complexation or precipitation at high pH values. The sorption increased with increasing temperature and the thermodynamic parameters calculated from the temperature dependent sorption isotherms suggested that the sorption of U(VI) on attapulgite was a spontaneous and endothermic process. The results indicate that attapulgite is a very suitable material for the preconcentration of U(VI) ions from large volumes of aqueous solutions.     

Investigation of Co(II) sorption on GMZ bentonite from aqueous solutions by batch experiments

In this study, a local bentonite from Gaomiaozi county (Inner Mongolia, China) was converted to Na-bentonite and was characterized by FTIR and XRD to determine its chemical constituents and micro-structure. The removal of cobalt from aqueous solutions by Na-bentonite was investigated as a function of contact time, pH, ionic strength, foreign ions and temperature by batch technique under ambient conditions. The results indicated that the sorption of Co(II) was strongly dependent on pH. At low pH, the sorption of Co(II) was dominated by outer-sphere surface complexation or ion exchange whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich, and D-R models were used to simulate the sorption isotherms of Co(II) at the temperatures of 293.15, 313.15 and 333.15 K, respectively. The thermodynamic parameters (∆G°, ∆S°, ∆H°) of Co(II) sorption on GMZ bentonite calculated from the temperature-dependent sorption isotherms indicated that the sorption of Co(II) on GMZ bentonite was an exothermic and spontaneous process. The Na-bentonite is a suitable material for the preconcentration and solidification of Co(II) from aqueous solutions.     

Purification of waste waters containing 60Co2+, 115mCd2+ and 203Hg2+ radioactive ions by ETS-4 titanosilicate

Summary The sorption of ⁶⁰Co²⁺, ^115mCd²⁺ and ²⁰³Hg²⁺ from diluted solutions (as analogues for radioactive waste waters) on ETS-4 microporous titanosilicate was studied at 277, 293, 313 and 333 K by measuring the sorption kinetics using a batch-method. The sorption of these radiocations was compared by means of the distribution coefficient and of the sorption capacity. The maximum sorption capacities follow the order: ²⁰³Hg²⁺>^115mCd²⁺3⁶⁰Co²⁺. The thermodynamic functions of the sorption processes have been estimated. The increase of the absolute value of DG° with increasing temperatures shows that higher temperatures favor ionic exchange.     

RECOVERY OF URANIUM FROM CARBONATE SOLUTIONS USING STRONGLY ABSIC ANION EXCHANGER Ⅰ.THE OPTIMUM RECOVERY PROCESSES AND COMPOSITION IN RESIN PHASE

A practical and econmical process for effectively recovering uranium from carbonate solutions is presented.The uranium complexes are made unstable by adjusting the pH of mixed solutions of Na2CO3 and NaHCO3 to about 7-8 by HCl and/or NaOH.Within this range of pH value,the super-equivalent uptake of uranium compared with exchange of Cl^- and UO2(CO3)3^4- can be worked out ,the total freee energy change takes on the minimum value ,the predominant species of uranium in resin phase may be U2O7^2- except for a little amount of UO2^2+.     

Characterization of radioactive cobalt on graphene oxide by macroscopic and spectroscopic techniques

Graphene oxide (GO) was synthesized using the modified Hummers method and characterized by XRD and FTIR. The sorption of ⁶⁰Co(II) on GO as a function of contact time, pH, polyacrylic acid, ionic strength, temperature and solution concentration was studied by batch technique. The sorption kinetics indicated that the sorption of ⁶⁰Co(II) on GO could be simulated by the pseudo-second-order model very well. The maximum sorption capacities of GO for ⁶⁰Co(II) calculated from Langmuir model at pH 6.40 and T = 300 K was ~62.0 mg/g. The thermodynamic parameters from the temperature-dependent sorption isotherms indicated that the ⁶⁰Co(II) sorption on GO was an endothermic and spontaneous process. The interaction mechanism between GO and Co(II) were outer-sphere surface complexation or ion exchange at pH <7, whereas the inner-sphere surface complexation was observed at pH 7–9 in terms of the analysis of XPS spectra.     

Impact of environmental conditions on the sorption behavior of Co(II) on Na-rectorite studied by batch experiments

The sorption of Co(II) from aqueous solution on Na-rectorite was investigated under ambient conditions. Experiments were carried out as a function of contact time, solid content, pH, ionic strength, foreign ions, fulvic acid and temperature. The results indicated that the sorption of Co(II) was strongly dependent on pH. At low pH the sorption was dominated by outer-sphere surface complexation or ion exchange, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms at three different temperatures. The thermodynamic data (∆G ⁰, ∆S ⁰, ∆H ⁰) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Co(II) on Na-rectorite was spontaneous and endothermic. Experimental results indicate that Na-rectorite is a suitable adsorbent for preconcentration and solidification of Co(II) from large volumes of aqueous solutions.