Novel application of modified multiwalled carbon nanotubes as a solid phase extraction adsorbent for the determination of polyhalogenated organic pollutants in aqueous solution

This paper describes a novel application of pristine and chemically modified multiwalled carbon nanotubes (MWCNTs) as the packing materials for the determination of different polyhalogenated organic pollutants, pentachlorophenol, 2,4,5-trichlorophenol, 3,3′,4,4′-tetrachlorobiphenyl and 2,2′,5,5′-tetrabromobiphenyl, from aqueous solution based on solid phase extraction. The modified MWCNTs were characterized using different techniques and the results revealed the successful modification of the MWCNTs with octadecyl amine and poly(ethylene glycol), separately. Factors that maybe influence the preconcentration efficiency, such as sample flow rate, adsorbent mass, sample pH and sample volume, were studied. Desorption of the target analytes was studied using different solvents and the results showed that acetone was the best solvent for all the analytes compared with methanol and hexane. All the results indicated that the proposed method could be used for the simultaneous determination of different pollutants in environmental water samples at trace levels.     

Thermodynamic and kinetic parameters of ofloxacin adsorption from aqueous solution onto modified coal fly ash

Batch adsorption experiments were carried out for the removal of ofloxacin from aqueous solution using modified coal fly ash as adsorbent. The effects of various parameters such as contact time, initial solution concentration and temperature on the adsorption system were investigated. The optimum contact time was found to be 150 min. The adsorption isotherm data fit well with the Langmuir model, and the kinetic data fit well with the pseudo-second order and the intra-particle diffusion model. Intra-particle diffusion analysis demonstrates that ofloxacin diffuses quickly among the particles at the beginning of the adsorption process, and then the diffusion slows down and stabilizes. Thermodynamic parameters such as ΔG, ΔH, and ΔS were also calculated. The negative Gibbs free energy change and the positive enthalpy change indicated the spontaneous and endothermic nature of the adsorption, and the positive entropy change indicated that the adsorption process was aided by increased randomness.     

Kinetics and thermodynamic study of aniline adsorption by multi-walled carbon nanotubes from aqueous solution

Multi-walled carbon nanotubes (MWCNTs) were used in the adsorptive removal of aniline, an organic pollutant, from an aqueous solution. It was found that carbon nanotubes with a higher specific surface area adsorbed and removed more aniline from an aqueous solution. The adsorption was dependent on factors, such as MWCNTs dosage, contact time, aniline concentration, solution pH and temperature. The adsorption study was analyzed kinetically, and the results revealed that the adsorption followed pseudo-second order kinetics with good correlation coefficients. In addition, it was found that the adsorption of aniline occurred in two consecutive steps, including the slow intra-particle diffusion of aniline molecules through the nanotubes. Various thermodynamic parameters, including the Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°), were calculated. The results indicated that the spontaneity of the adsorption, exothermic nature of the adsorption and the decrease in the randomness reported as ΔG°, ΔH° and ΔS°, respectively, were all negative.     

Thermal properties of seed proteins

The sample of LiCoO₂ was synthesized, and the heat capacity was measured by adiabatic calorimetry between 13 and 300 K. The smoothed values of the heat capacity were calculated from the data. The thermodynamic functions, standard enthalpy, entropy and Gibbs energy, of LiCoO₂ were calculated from the heat capacity and the numerical values are tabulated at selected temperatures from 15 to 300 K. The heat capacity, enthalpy, entropy, and Gibbs energy at T=298.15 K are 71.57 J K^–1mol^–1, 9.853 kJ mol^–1, 52.45 J K^–1 mol^–1, –5.786 kJ mol^–1, respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preparation of magnetic composite adsorbents from laterite nickel ore for organic amine removal

Magnetic composite adsorbent (MCA) was prepared successfully using laterite nickel ore. The effectiveness of MCA as an adsorbent was evaluated for removal trimethylamine from aqueous environment. In this technological route, the utilization of solid wastes, wastewater treatment and adsorbent recovery were considered comprehensively. The MCA was characterized by techniques, including XRD, SEM, TEM, EDS, VSM and adsorption-desorption of nitrogen at 77 K. The adsorption processes were best described by pseudo-second-order kinetic model and controlled by intraparticle and surface diffusion processes. Langmuir and Freundlich isotherm models were used to match the adsorption equilibrium data. Freundlich isotherm was the best fitting curve for the sorption equilibrium data. The adsorption mechanism was further interpreted by Gibbs free energy, entropy and enthalpy calculated by thermodynamic equation. The negative values of Gibbs free energy changes (ΔG) manifest that the adsorbing process is spontaneous. The results show that laterite nickel ore can be made into MCA for organic amine removal from polluted water.     

Complexation of europium(III) with 2,2′-dipyridyl in Eu(An)<Subscript>3</Subscript>-2,2′-dipyridyl ethyl acetate systems

Complexation of europium(III) with 2,2′-dipyridyl in Eu(An)₃-2,2′-dipyridyl-ethyl acetate systems, where An is acetylacetonate, trichloroacetate, or trifluoroacetate ions, was studied by spectrophotometric methods. The stability constants of the complexes at different temperatures were determined, and Gibbs energy, enthalpy, and entropy changes in complexation were calculated. The influence of the initial organic ligands on complexation was elucidated.     

Diglycolamide functionalized multi-walled carbon nanotubes for removal of uranium from aqueous solution by adsorption

Diglycolamide functionalized multi-walled carbon nanotubes (DGA-MWCNTs) were synthesized by sequential chemical reactions for removal of uranium from aqueous solution. Characterization studies were carried out using FT-IR spectroscopy, XRD and SEM analysis. Adsorption of uranium from aqueous solution on this material was studied as a function of nitric acid concentration, adsorbent dose and initial uranium concentration. The uranium adsorption data on DGA-MWCNTs followed the Langmuir and Freundlich adsorption isotherms. The adsorption capacity of DGA-MWCNTs as well as adsorption isotherms and the effect of temperature on uranium ion adsorption were investigated. The standard enthalpy, entropy, and free energy of adsorption of the uranium with DGA-MWCNTs were calculated to be 6.09 kJ mole⁻¹, 0.106 kJ mole⁻¹ K⁻¹ and −25.51 kJ mole⁻¹ respectively at 298K. The results suggest that DGA-MWCNTs can be used as efficient adsorbent for uranium ion removal.     

The effect of counterions on the surface adsorption and micelle formation in mixed surfactant systems of dodecyl sulfates

 The surface tension of the aqueous solutions of sodium dodecyl sulfate (SDS) and tetramethylammonium dodecyl sulfate (TMADS) was measured as a function of total molality of the surfactants at fixed composition of TMADS at 298.15 K under atmospheric pressure. The phase diagrams of adsorption and of micelle formation, the activity coefficients, and the excess Gibbs energy were calculated to estimate the deviation from the ideal mixing quantitatively. The preferential adsorption and the micelle formation for TMA⁺ to Na⁺ is attributable to some extent to the hydrophobicity of the methyl groups of TMA⁺. The composition of TMA⁺ in the micelle is larger than that in the adsorbed film at equilibrium. That is, a larger hydrated counterion is more likely to exist in the micelle than in the adsorbed film owing to geometrical benefit. The negative values of the excess Gibbs energy of the adsorbed film and of the micelle arise from the positive ones of the excess entropy greater than that of excess enthalpy. The counterions of very similar size are mixed ideally in the micelle and the size effect appears sensitively in the adsorbed film. Received: 23 May 2001 Accepted: 16 July 2001     

Separation of U(IV) and U(VI) species by means of ion-exchange resins of the DGA-, TEVA- and UTEVA-type

The present paper deals with the retention of U(IV) and U(VI) species, both individually and in 1 :1 mixtures, on some ion-exchange resins of the normal DGA (N,N’,N’-tetra-n-octyldiglycolamide), TEVA- [trialkyl methyl-ammonium nitrate (or chloride)] and UTEVA-type (dipentyl pentylphosphonate), in different experimental conditions. The degree of retention, distribution constant, as well as enthalpy and entropy values which characterize the adsorption of uranium ions on these resins were calculated. By means of Langmuir relation, taking into account the experimental data, the maximum adsorption capacity, Langmuir constant and Gibbs free energy values for the studied processes are established.     

Biosorption studies of uranium (VI) on cross-linked chitosan: isotherm,kinetic and thermodynamic aspects

The cross-linked chitosan (CS) gels synthesized by using glutaraldehyde (GLA), epichlorohydrin (EC), and ethylene glycol diglycidyl ether (EGDE) as cross-linkers respectively were used to investigate the adsorption of U(VI) ions in an aqueous solution. The pure chitosan (PCS) and the cross-linked chitosan gels were characterized by FTIR and SEM analysis. The kinetic, thermodynamic adsorption and adsorption isotherms of U(VI) ions onto unmodified and modified cross-linked chitosan were studied in a batch adsorption experiments. The effect of pH, contact time and temperature on the adsorption capacity were also carried out. At the optimum pH, the maximum adsorbed amount of PCS, GLACS, ECCS and EGDECS were 483.05, 147.05, 344.83 and 67.56 mg/g, respectively. The uranium (VI) adsorption process of PCS and ECCS followed better with pseudo-second-order kinetic model, while GLACS and EGDECS followed pseudo-first-order kinetic model well. The results obtained from the equilibrium isotherms adsorption studied of U(VI) ions were analyzed in two adsorption models, namely, Langmuir and Freundlich isothms models, the results showed that the Langmuir isotherm had better conformity to the equilibrium data. The thermodynamic parameters such as enthalpy (ΔHo), entropy (ΔSo), and Gibbs free energy (ΔGo) showed that the adsorption process was both spontaneous and endothermic.     

Adsorption and Aggregation Properties of Some Polysorbates at Different Temperatures

Measurements of the surface tension of aqueous solutions of polysorbates (Tween 20, Tween 60 and Tween 80) at 293, 303 and 313 K were made. On the basis of the obtained results the Gibbs surface excess concentration of the Tweens at the water–air interface and critical micelle concentrations were determined. Knowing the Gibbs surface excess concentration and taking into account the difference between the limiting area occupied by water and Tween molecules at the water–air interface, the fraction occupied by Tween molecules was established. The limiting area occupied by the Tween molecule was calculated by applying the Joos equation. The area determined in such a way was confirmed by the calculations of cross section of Tween molecules based on the bond lengths and the angles between them as well as the average distance between the molecules, taking into account their different conformations. This area was used for calculation of the standard Gibbs energy of adsorption using the Langmuir equation. The standard Gibbs energy of Tweens adsorption at the water–air interface was also calculated from the hydrophobic part of Tween molecule–water interface tension and that of hydrophobic part. Using the determined values of standard Gibbs energy of adsorption at different temperatures, the standard enthalpy and entropy values were deduced. The standard thermodynamic functions of micellization were also determined and compared to the Gibbs energy of Tween molecules interactions through the water phase.     

Micellar properties of alkyldimethylphenylammonium bromides in water

The synthesis and methods applied for the purification of dodecyl-, tetradecyl-, and hexadecyldimethylphenylammonium bromides are described. The results of surface tension measurements of aqueous solutions of these surfactants show that slight amounts of strongly surface-active nonionic impurities are persistent in the crystalline materials presumably due to their low thermal stability. The Critical micelle concentration (cmc) and the degree of ionization (β) of the micelles of the salts studied in aqueous solutions were determined at 25 °C from specific conductivity versus molality plots. The temperature dependence of the cmc and of β of the tetradecyl homologue was measured in the range 4–34 °C. A minimum cmc amounting to 1.20 mmol/kg was determined at about 14 °C. The values of β were found to grow linearly with temperature. From these results, the standard Gibbs energy, the enthalpy and the entropy of the process of micellization were obtained by application of the pseudo-phase-separation model. Enthalpy and entropy show a compensation effect in their contribution to the Gibbs energy. At low temperatures the process of micellization is driven mainly by the entropic term, whereas with increasing temperature the enthalpic term becomes predominant. At the temperature of the minimum cmc, the value of the enthalpy is far from being zero because of the important contribution of the (β/T)R ln X _cmc term. Received: 27 July 1998 Accepted in revised form: 15 December 1998     

Temperature Dependence of Solubility for Ibuprofen in Some Organic and Aqueous Solvents

The thermodynamic functions—Gibbs energy, enthalpy, and entropy of solution—were evaluated from the solubilities of ibuprofen determined at several temperatures in the pure solvents: octanol, isopropyl myristate, chloroform, cyclohexane, and water. The organic solvent-saturated aqueous media and water-saturated organic solvents were also studied, except for cyclohexane. In aqueous media, the solubility was determined at pH = 7.4 and an ionic strength 0.15 mol-L^–1 (physiological values). The excess Gibbs energy and the activity coefficients of the solutes were also determined. The solubilities are higher in organic media such as chloroform and octanol than in aqueous media and cyclohexane.     

Simultaneous analysis of vitamins and caffeine in energy drinks by surfactant-mediated matrix-assisted laser desorption/ionization

As a new approach to rapid small-molecule analysis, surfactant-mediated matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI–TOF-MS) was successfully used in the analysis of caffeine and the vitamins riboflavin, nicotinamide, and pyridoxine in various energy drinks. Of five common MALDI matrices tested (α-cyano-4-hydroxycinnamic acid, sinapinic acid, 2,5-dihydroxybenzoic acid, dithranol, and 2′,4′,6′-trihydroxyacetophenone), α-cyano-4-hydroxycinnamic acid was found to be most suitable for analysis of high-sugar-containing energy drinks. Cetyltrimethylammonium bromide (CTAB) surfactant was used as a matrix-ion suppressor, at a matrix:surfactant mole ratio of approximately 500:1. The resulting mass spectra show very few matrix-related ions, while analyte signals were clearly observed. For comparative purposes the same analytes were identified and quantified in energy drinks by LC–ESI–MS with UV detection. Quantitatively the calibration curves of all four analytes showed a marked improvement when the surfactant-mediated method was used compared with traditional MALDI–TOF-MS; correlation coefficients of 0.989 (nicotinamide), 0.991 (pyridoxine), 0.983(caffeine) and 0.987 (riboflavin) were obtained. It was found that in quantitation of the energy drink analytes the surfactant-mediated MALDI–TOF-MS results were comparable with those from LC analysis. In reproducibility experiments RSD values ranged from 9.7 to 18.1%. The work has demonstrated that this mass spectrometric approach can be used as a rapid screening technique for fortified drinks.     

Adsorption of cesium (I) from aqueous solution using oxidized multiwall carbon nanotubes

Multiwall carbon nanotubes (MWCNTs) were modified by nitric acid solution and then used to study the adsorption of cesium from aqueous solution using a batch technique under ambient conditions. As produced and oxidized MWCNTs were characterized by nitrogen adsorption/desorption, Boehm’s titration method and Fourier transform infrared spectroscopy. The physical properties of MWCNTs such as functional groups, total number of acid sites and specific surface area were greatly improved after oxidation, and these were responsible for more sorption of cesium from aqueous solution and made them more dispersible in water. The adsorption of cesium ions as a function of contact time, initial concentration of cesium, pH, ionic strength and oxidized MWCNT concentrations was also investigated. The results showed that cesium adsorption percentage strongly depended on the pH value, oxidized MWCNT content and on the solution ionic strength. Kinetic data indicated that the adsorption process achieved equilibrium within 80 min. Equilibrium data for as produced and oxidized MWCNTs was well described by both Freundlich and Langmuir isotherms. The dominant mechanism of cesium adsorption on oxidized MWCNTs may be mainly attributed to ion exchange. This study suggests that oxidized MWCNTs can be a promising candidate for the removal of cesium from nuclear waste solution.     

Adsorption of cesium on a composite inorganic exchanger zirconium phosphate - ammonium molybdophosphate

The applicability of zirconium phosphate-ammonium molybdophosphate (ZrP-AMP) for the efficient removal of cesium from aqueous acidic solutions by adsorption has been investigated. The adsorption data analysis was carried out using the Freundlich, Dubinin-Raduskevich (D-R) and Langmuir isotherms for the uptake of Cs in the initial concentration range of 3.75^.10^-5-7.52^.10^-3 mol^.dm^-3 on the ZrP-AMP exchanger from nitric acid medium. The mean free energy (E) values for the adsorption of Cs were obtained from the D-R isotherm. Equilibrium adsorption values at different temperatures have been utilized to evaluate the change in enthalpy, entropy and free energy (ΔH°, ΔS°, ΔG°). The adsorption of cesium on the ZrP-AMP exchanger was found to be endothermic. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermodynamical characteristics of acid-base equilibria in glycyl-glycyl-glycine aqueous solutions at 298 K

The constants and enthalpies of acid dissociation of glycyl-glycyl-glycine peptide in aqueous solutions at 298.15 K and ionic strength values of 0.1, 0.5, and 1.0 M containing NaCl as a background electrolyte, were determined by potentiometry and calorimetry. The standard values of pK ₁^° and pK ₂^° constants, the change of Gibbs energy, enthalpy, and entropy for the dissociation processes were calculated. It was found that the acidic properties of the carboxylic group in aqueous solution subside upon the transition from α-amino acids to peptides due to the lower entropy effect of dissociation. It was concluded that the increase of dissociation constant of a protonated peptide amino group upon an increase in the length of its molecule is determined by entropy factor associated with the attenuation of amino group solvation.     

Comparison of the thermodynamic properties of structurally related amphiphilic antidepressants in aqueous solution

 The critical concentrations of amitriptyline, desipramine and nortriptyline hydrochlorides in aqueous solution were determined over the temperature range 288–313 K by a method based on deconvolution into Gaussians of the second derivate of the measured specific conductivity data. The mass-action model was used to calculate the thermodynamic quantities: standard free Gibbs energy, standard enthalpy and standard entropy of aggregate formation. The results are discussed in terms of the structure of the drug aggregates. Received: 12 June 2000 / in revised form: 10 October 2000 Accepted: 16 October 2000     

Adsorption and thermodynamic behavior of uranium(VI) on <Emphasis Type="Italic">Ulva sp</Emphasis>.-Na bentonite composite adsorbent

Summary The algae-clay composite adsorbent was tested for its ability to recover U(VI) from diluted aqueous solutions. Macro marine algae (Ulva sp.) and clay (Na bentonite) were used to prepare composite adsorbent. The ability of the composite adsorbent to adsorp uranium(VI) from aqueous solution has been studied at different optimized conditions of pH, concentration of U(VI), temperature, contact time. Parameters of desorption were also investigated to recover the adsorbed uranium. The adsorption patterns of uranium on the composite adsorbent followed the Freundlich and Dubinin-Radushkevich isotherms. The thermodynamic parameters such as the enthalpy ΔH, entropy ΔS and Gibbs free energy ΔG were calculated from the slope and intercept of lnK_d vs. 1/T plots. The results suggested that the Ulva sp.-Na bentonite composite adsorbent is suitable as sorbent material for recovery and biosorption/adsorption of uranium ions from aqueous solutions.     

氧化叔胺树脂的合成及其对苯酚的吸附性能研究

将D301树脂的叔胺基氧化，合成了大孔交联氧化叔胺树脂．比较D301树脂与氧化叔胺树脂对正己烷溶液中和水溶液苯酚的吸附性能，发现氧化叔胺树脂对苯酚的吸附量比D301树脂的有明显的增加．为弄清吸附量增加的原因，根据氧化叔胺树脂对正己烷溶液中苯酚的吸附等温线，利用热力学函数关系计算了等量吸附焓、吸附Gibbs自由能和吸附熵，发现叔胺树脂氧化后，与苯酚的相互作用和吸附的自发倾向增强，但吸附过程仍为氢键吸附．