Effect of disperse dye structure on dye sorption onto PLA fiber

The effect of the structure of various disperse dyes on their percentage sorption onto polylactide (PLA) is explained using molecular modeling. The interaction energies between the dyes and PLA have been calculated, and a linear equation has been developed to predict the percentage sorption on PLA based on the dye-PLA interaction energy. The predicted percentage sorption for a dye is shown to agree with its experimentally obtained percentage sorption on commercial PLA fabric and on PLA fiber extruded in our laboratory. Within the dyes, the functional groups that form the strongest interactions with PLA are -N(C(2)H(4)OCOCH(3))(2), -(CO)(2)NC(3)H(6)OCH(3), -SO(2)NHC(6)H(5), -NO(2), -CN(NH)C(6)H(4), and -CH(CO)(2)C(6)H(4), and the groups that form the weakest interactions with PLA are -Br and -Cl.     

A thermodynamic and kinetic study of hydride transfer of a caffeine derivative

One representative type of heterocyclic compound that can release a hydride ion is 7,8-dihydro-9-methylcaffeine (CAFH). The one-electron oxidation potential of CAFH [-0.294 (V vs Fc(+/0))] and the one-electron reduction potential of CAF(+) [-2.120 (V vs Fc(+/0))] were obtained using two different methods, CV and OSWV. Applying titration calorimetry data in thermodynamic cycles, the enthalpies of CAFH releasing a hydride ion [57.6 kcal/mol] and releasing a hydrogen atom [80.3 kcal/mol] and of its radical cation CAFH(?+) releasing a proton [33.0 kcal/mol] and releasing a hydrogen atom [38.4 kcal/mol] have been determined. Several conclusions can be drawn from the thermodynamic results: (1) CAFH is a very good single-electron donor whose single-electron oxidation potential is much less positive than that of NAD(P)H model compound BNAH [E(ox) = 0.219 V vs Fc(+/0)]. (2) The single-electron reduction potential of CAF(+) is much more negative than that of BNA(+) [E(red) = -1.419 V], which means that CAF(+) is not a good electron acceptor. Furthermore, CAFH is a very good hydride donor compared to BNAH. The results of non-steady-state kinetic studies, for the reaction of CAFH and AcrH(+)ClO(4)(-), show that the ratio of t(0.50)/t(0.05) is larger than 13.5 and the ratio of k(init)/k(pfo) is larger than 1. The pseudo-first-order rate constants obtained at different reaction stages decrease with the time, and the kinetic isotope was observed to be small at a short reaction time and slowly increases to 3.72 with the progress of the reaction. These kinetic results clearly display that the hydride transfer of CAFH to AcrH(+) in acetonitrile is not a one-step mechanism, while the thermodynamic results show that CAFH is a very good electron donor. The combination of the kinetic results with the thermodynamics analysis shows that the hydride transfer of the caffeine derivative CAFH takes place by a two-step reversible mechanism and there is an intermediate in the reaction.     

Adsorption of dye from wastewater using chitosan-CTAB modified bentonites

Multifunctional magnetic-fluorescent nanohybrids were successfully fabricated by a facile layer-by-layer (LBL) self-assembly of in situ generated Eu, Gd co-doped LaF(3) nanocrystals (LaF(3):Eu:Gd) on the surface of multi-walled carbon nanotubes (MWNTs). Photoluminescence (PL) quenching occurred when LaF(3):Eu:Gd nanoparticles were directly coated on the surface of MWNTs. By growth of a SiO(2) shell spacer between MWNTs and LaF(3):Eu:Gd nanocrystals, we circumvented the PL quenching and achieved the magnetic-fluorescent MWNTs. Moreover, the nanohybrids showed powerful T(1) and T(2)-weighted magnetic resonance imaging (MRI) signal in water and could be used as MRI contrast agents. As a result, the nanohybrids can be expected to act as a promising multimodal MRI/optical imaging probe.     

Adsorption of a reactive dye on chemically modified activated carbons--influence of pH

The surface chemistry of a commercial activated carbon with a slightly basic nature was modified by appropriate treatments in order to obtain two additional samples, respectively with acidic and basic properties, without changing its textural parameters significantly. Different techniques (N2 adsorption at 77 K, temperature programmed desorption, and determination of acidity, basicity, and pH at the point of zero charge) were used to characterize the adsorbents. Kinetic and equilibrium adsorption data of a selected textile reactive dye (Rifafix Red 3BN, C.I. reactive red 241) on the mentioned materials were obtained at the pH values of 2, 7, and 12. The kinetic curves are fitted using the second-order model. The respective rate constants seem to diminish progressively with the initial concentration for the more diluted solutions tested, reaching a constant value at higher concentrations, which depends on the experimental system under consideration (adsorbent and pH). In general, the Langmuir model provides the best fit for the equilibrium data. The different uptakes obtained are discussed in relation to the surface chemical properties of the adsorbents. It is shown that the adsorption of the reactive (anionic) dye on the basic sample (prepared by thermal treatment under H2 flow at 700 degrees C) is favored. This conclusion is explained on the basis of the dispersive and electrostatic interactions involved. Moreover, it is also shown that the optimal adsorption condition for all the activated carbons tested corresponds to solution pH values not higher than the pH(pzc) of the adsorbents, which may be interpreted by taking into account the electrostatic forces present.     

Adsorption behavior of uranium on polyvinyl alcohol-g-amidoxime: Physicochemical properties, kinetic and thermodynamic aspects

Amidoxime-based adsorbents are widely studied as the main adsorbent in the recovery of uranium from seawater.However,the adsorption rate and loading capacity of such adsorbents should be further improved due to the economic viability consideration.In this paper,polyvinyl alcohol functionalized with amidoxime(PVA-g-AO)has been prepared as a new adsorbent for uranium(Ⅵ)adsorption from aqueous solution.The physicochemical properties of PVA-g-AO were investigated using infrared spectroscopy(IR),scanning electron microscope(SEM),X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS).Results showed that the ligand monomers were successfully grafted onto the matrixes.The XRD and XPS analysis showed that uranium was adsorbed in metal ionic form rather than in crystal form.Uranyl(U(Ⅵ))adsorption properties onto PVA-g-AO were evaluated.The adsorption of U(Ⅵ)by PVA-g-AO was fast,with an equilibrium time of less than 50 min.Additionally the maximum adsorption capacity reached 42.84 mg/g at pH 4.0.     

Equilibrium, kinetic, and thermodynamic studies of Basic Blue 9 dye sorption on agro-industrial lignocellulosic materials

The sorptive potential of some lignocellulosic agro-industrial wastes (sunflower seed shells and corn cob) for Basic Blue 9 cationic dye removal from aqueous solutions was examined using the batch technique. The Freundlich, Langmuir, and Dubinin-Radushkevich isotherm models were used in order to determine the quantitative parameters of sorption. The Langmuir isotherm model indicated a maximum sorption capacity for these materials in the range of 40–50 mg dye per g (25°C), slightly higher for corn cob than for sunflower seed shells. The values of the thermodynamic parameters showed that the retention of cationic dye is a spontaneous and endothermic process. The application of pseudo-first order and pseudo-second order intraparticle diffusion models, and a Boyd — Reichenberg model for kinetic data interpretation suggested that sorption of Basic Blue 9 dye onto the studied materials is a process where both surface sorption and intraparticle diffusion contributed to the rate-limiting step. These lignocellulosic wastes can be used with good efficiency for dye removal from aqueous effluents.      

Kinetic study of the reaction between hydroxylated polybutadienes and isocyanates. 1. Reaction with tolylene diisocyanate (TDI)

A comparative kinetic study of the reaction of three different hydroxylated liquid polybutadienes (M _n ? 3000) — R - 45M, R-45HT, and H-034—and tolylene diisocyanate (TDI), was carried out in toluene solution. An analytical method was used to follow the kinetics of the reactions at four different temperatures. The reactions presented an apparent second-order rate law. In the second-order plots, a discontinuity was observed. The R-45M polybutadiene was about twice more reactive than R-45HT and H-034; these latter two polybutadienes presented similar reactivities.     

Adsorption kinetic, isotherm and thermodynamic studies of Sr2+ onto hexagonal tungsten oxide

Hexagonal tungsten oxide (hex-WO₃) with exchangeable sodium and ammonium cations located in hexagonal channel was synthesized by a facile hydrothermal treatment of sodium tungstate dihydrate in concentrated HCl solution in the presence of ammonium sulfate. An attempt was made to assess the potential of hex-WO₃ for the adsorption of Sr²⁺ ions from acidic radioactive waste solutions. Adsorption of Sr²⁺ reached equilibrium very quickly in 2 h in acidic aqueous solution. Maximum removal of Sr²⁺ ions occurred at pH 4. Equilibrium studies showed that the extent of Sr²⁺ ions uptake by hex-WO₃ was better described by the Freundlich isotherm in comparison with the Langmuir model. The thermodynamic parameters showed that the adsorption of Sr²⁺ ions onto hex-WO₃ was spontaneous and exothermic under the studied conditions.     

Adsorption of organochlorine pesticides on modified porous Al30/bentonite: Kinetic and thermodynamic studies

Adsorption of pesticides (heptachlor epoxide, dieldrin and endrin) onto modified bentonite by Keggin cation [Al₃₀O₈(OH)₅₆(H₂O)₂₄]¹⁸⁺ denoted Al₃₀ cation to form composite (Al₃₀/B), has been investigated as a possible alternative method for their removal from aqueous solutions. The study was aimed to use a low-cost material as a step towards cleaner environment. Interestingly, these chemical modifications altered the physicochemical characteristics of bentonite in term of morphology, surface area and functionality which has been confirmed by using nitrogen adsorption–desorption isotherm, scanning electronic microscopy (SEM) and X-ray diffraction (XRD). Gas chromatography coupled to mass spectrometry (GC–MS) was used to identify and analyze the pesticides. Different physicochemical parameters were analyzed: contact time, adsorbent dose, pH, and temperature. The results showed that the removal percentage of pesticides on Al₃₀/B was the highest at contact time of 5 h, adsorbent dosage of 25 mg, at pH 7.5, and at optimum temperature of 45 °C. Furthermore, the Kinetic study indicated that the adsorption of pesticides on Al₃₀/B was well adapted to the pseudo-first order kinetic with a correlation coefficient near unity. The results of adsorption were fitted to the Langmuir and Freundlich isotherms. The Freundlich model represented the adsorption process better than Langmuir model, with correlation coefficients (R²) values range from 0.986 to 0.989. The Thermodynamic study suggested that the adsorption of pesticides was chemisorption, spontaneous and endothermic process. Therefore, Al₃₀/B composite can be utilized effectively for removal of pesticides with efficiency up to 98%.     

Adsorption and activity of Candida rugosa lipase on polypropylene hollow fiber membrane modified with phospholipid analogous polymers

Efforts have recently been made toward the study of interactions of phospholipid with various enzymes. It seems that phospholipids may be directly involved in regulating the enzyme activity. In this work, three phospholipid analogous polymers (PAPs), containing hydrophobic octyloxy, dodecyloxy, and octadecyloxy groups (abbreviated as 8-PAP, 12-PAP, and 18-PAP, respectively), were tethered on polypropylene hollow fiber microfiltration membrane (PPHFMM) to create a biocompatible interface for lipase immobilization. Lipase from Candida rugosa was immobilized on these PPHFMMs by adsorption. The adsorption capacity, activity, and thermal stability of enzyme on the PAP-modified PPHFMMs were compared with those of enzyme on the nascent ones. It was found that, as for the PAP-modified PPHFMMs, the adsorption capacities of lipase are lower than that of the nascent ones, while the activity retention of immobilized lipase increases from 57.5% to 74.1%, 77.5%, and 83.2% respectively for the 8-PAP-, 12-PAP-, and 18-PAP-modified PPHFMMs. In addition, the experimental results of thermal stability show that the residual activity of the immobilized lipase at 50 degrees C for 2 h is 62% for the 8-PAP-modified PPHFMM, 59% for the 12-PAP-modified PPHFMM, and 66% for the 18-PAP-modified PPHFMM, which are also higher than that of the nascent ones.     

Clarification of coal-clay disperse systems with modified polyacrylamide flocculant

Modification of polyacrylamide under mild conditions was studied.     

Adsorption of U(IV) by several geomaterials: kinetic,adsorbent dosage and thermodynamic

Journal of Radioanalytical and Nuclear Chemistry - The behavior of U(IV) in the presence of several geomaterials (inorganic components of soils from an oyamel forest IMH(OF) and a semiarid zone...     

The use of starch‐modified magnetic Fe0 nanoparticles for naphthalene adsorption from water samples: Adsorption isotherm,kinetic and thermodynamic studies

This study was aimed at investigating the effectiveness of starch‐modified magnetic nanoparticles for the removal of naphthalene, which is a polycyclic aromatic hydrocarbon present in the majority of water sediments, from water resources. Magnetic Fe⁰ nanoparticles have recently been considered because of their high efficiency for contaminant removal. In the present study, Fe⁰ nanoparticles were synthesized using sulfate method and starch was used as a stabilizer. The size of the Fe⁰ nanoparticles was measured as approximately 45 nm using X‐ray diffraction and scanning electron microscopy analyses. The removal efficiency of naphthalene from water using the nanoparticles was evaluated based on various factors including the viscosity of naphthalene dissolved in water, and operation factors such as nanoparticle dosage, contact time, initial naphthalene concentration and pH in non‐continuous reactors were optimized. The results revealed that the starch‐modified nanoparticles have high efficiency for removal of dissolved naphthalene from aqueous solution. Under the optimum conditions, more than 99% of naphthalene at a pH of 5.0 with nanoparticle dosage of 0.05 g was removed from aqueous solution in 5 min. The equilibrium adsorption data were interpreted in terms of Langmuir, Freundlich and Temkin isotherm models and the goodness of fit was inspected using linear regression analysis. Our results indicated that the Langmuir model with maximum adsorption capacity was best fitted, suggesting monolayer adsorption. Moreover, it was found that the adsorption process followed the pseudo‐second‐order kinetic model. In addition, a thermodynamic study indicated that the adsorption process of naphthalene from aqueous solution by the starch‐modified nanoparticles was spontaneous and exothermic.     

Adsorption thermodynamic and desorption studies of U(VI) on modified silica gel (SiAPMS-HL)

In this study, the adsorption process was examined by various isotherm models Langmuir, Freundlich and Dubinin–Radushkevich and equilibrium data were successfully described by Langmuir model. Adsorption thermodynamics of uranium (VI) on modified silica gel (SiAPMS-HL) has been studied within a temperature range from 293 to 333 K and the thermodynamic parameters, such as equilibrium constant (K _D), standard free energy changes (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°), have been obtained. The desorption studies were conducted in batch system to investigate the kind, concentration and volume of the eluent.     

Hindered rotor models with variable kinetic functions for accurate thermodynamic and kinetic predictions

We present an extension of some popular hindered rotor (HR) models, namely, the one-dimensional HR (1DHR) and the degenerated two-dimensional HR (d2DHR) models, allowing for a simple and accurate treatment of internal rotations. This extension, based on the use of a variable kinetic function in the Hamiltonian instead of a constant reduced moment of inertia, is extremely suitable in the case of rocking/wagging motions involved in dissociation or atom transfer reactions. The variable kinetic function is first introduced in the framework of a classical 1DHR model. Then, an effective temperature and potential dependent constant is proposed in the cases of quantum 1DHR and classical d2DHR models. These methods are finally applied to the atom transfer reaction SiCl(3)+BCl(3)→SiCl(4)+BCl(2). We show, for this particular case, that a proper accounting of internal rotations greatly improves the accuracy of thermodynamic and kinetic predictions. Moreover, our results confirm (i) that using a suitably defined kinetic function appears to be very adapted to such problems; (ii) that the separability assumption of independent rotations seems justified; and (iii) that a quantum mechanical treatment is not a substantial improvement with respect to a classical one.     

Equilibrium,kinetic and thermodynamic studies of copper adsorption onto poly(n-vinylpyrrolidone) modified clay

We demonstrated in this study the removal of copper ions from aqueous solutions by a new and cost efficiency adsorbent based on poly(N-vinylpyrrolidone) modified sodium bentonite. The X-ray diffraction analysis confirmed that the poly(N-vinylpyrrolidone) is well intercalated in the clay inter-sheets. Adsorption of copper was analyzed by the atomic absorption spectroscopy technical.

Quantitative removal of copper in aqueous solution and the optimum conditions in batch experimental set-up were attained by following searching effects such as contact time, initial metal concentration, pH and temperature.

The elimination of this pollutant by this a new composite reached 3.27 mg.g^?1, which is more important than the amount of copper adsorbed by the non-modified clay (1.5 mg.g^?1). The experimental results showed that the equilibrium and shaking time was attained within 05 min. The better retention capacity of copper was obtained at pH between 4 and 5.8.

Equilibrium data were well fitted with the Langmuir, Freundlich and Elovich models.

Also, the pseudo first order and pseudo-second-order were also applied. The experimental data follow well the pseudo-second-order kinetics. The thermodynamic of this new adsorbent of copper shows spontaneous and exothermic process with a negative value of ΔS.     

Dyeing of multiple types of fabrics with a single reactive azo disperse dye

Three novel reactive azo disperse dyes were prepared using 7-acetamide-4-hydroxy-2-naphthalene sodium sulphate as the precursor. The structure of the dyes has the combined characteristics of reactive, disperse, and cationic dyes. Under alkaline conditions (pH 9), the dyes can be applied to cotton, silk, wool, and nylon. Under neutral conditions, they can be used to dye polyester. Under acidic conditions (pH 4.5), they can colour acrylic fabric after conversion of the tertiary amine group to the quaternary ammonium cation. The colour-fastness of the dyed fabrics were also evaluated.     

Adsorption and thermodynamic behavior of uranium on natural zeolite

Adsorptive behavior of natural clinoptilolite-rich zeolite from Balikesir deposites in Turkey was assessed for the removal of uranium from aqueous solutions. The uranium uptake and cation exchange capacities of zeolite were determined. The effect of initial uranium concentrations in solution was studied in detail at the optimum conditions determined before (pH 2.0, contact time: 60 minutes, temperature: 20 °C). The uptake equilibrium is best described by Langmuir adsorption isotherm. Some thermodynamic parameters (ΔH°, ΔS°, ΔG°) of the adsorption system were also determined. Application to fixation of uranium to zeolite was performed. The uptake of uranium complex on zeolite followed Langmuir adsorption isotherm for the initial concentration (25 to 100 μg/ml). Thermodynamic values of ΔG°, ΔS° and ΔH° found show the spontaneous and exothermic nature of the process of uranium ions uptake by natural zeolite. This revised version was published online in August 2006 with corrections to the Cover Date.