Adsorption of Cr(VI) on Stipa tenacissima L (Alfa): Characteristics,kinetics and thermodynamic studies

This study aims to remove ionic Cr(IV) from aqueous solution using Stipa tenacissima L as a biomass source. The Arabic name for the plant Stipa tenacissima L is HALFA (ALFA) ; it belongs to the category of biosorbents agro-industrial origin. Stipa tenacissima L is from the center of the province of Djelfa Algeria. This biomass was characterized by various analytical techniques such as scanning electron microscopy, energy dispersive spectroscopy and Fourier-transform infrared spectroscopy. In order to optimize the operating conditions for the determination of ions of Cr(VI), the initial concentration of Cr(VI) ions, temperature, pH of the solution and the solid/liquid ratio were individually studied. According to the results, a fix rate of about 90% was recorded. Optimum biosorption conditions were found to be pH ~1, C_o = 50 mg/L, R = 5 g/L and T = 296 K. It was found that biosorption of Cr(VI) ions onto biomass of Stipa tenacissima L was better suitable to Langmuir model. The correlation coefficients for the second-order kinetic model obtained were found to be 0.996 for all concentrations. These indicate that the biosorption system studied belongs to the second-order kinetic model. Thermodynamics parameters as enthalpy, entropy of system and free energy were evaluated, which confirms the feasibility of the process. An empirical modeling was performed by using a 2⁴ full factorial design, and the regression equation for adsorption chromium (VI) was determined from the data. The initial metal ion concentration has the most positive pronounced effect in increasing the chromium (VI) adsorption, whereas the pH and adsorbent dosage have the most negative effect on the process.     

Solvent extraction and separation of rare earths from chloride media using α-aminophosphonic acid extractant HEHAMP

Solvent extraction and separation of rare earths (REs: La ~ Lu, plus Y and Sc) by a novel synthesized extractant, (2-ethylhexylamino)methyl phosphonic acid mono-2-ethylhexyl ester (HEHAMP, abbreviated as H₂A₂), were investigated in chloride medium. The favorable separation factors (SFs) between adjacent heavy REs suggested that HEHAMP has a better separation performance than P507. The extracted complex of trivalent REs was determined to be REClH₂A₄ by the slope analysis method. Thermodynamic parameters (ΔH, ΔG, and ΔS) of Lu were calculated as 7.47 kJ mol^?1, ?6.05 kJ mol^?1, and 45.4 J mol^?1 K^?1 at 298.15 K, respectively, which indicate that the extraction reaction of Lu is an endothermic process. The loading capacity of 30% (v/v) HEHAMP toward Lu(III), Yb(III), and Y(III) was about 15.17 g Lu₂O₃/L, 14.46 g Yb₂O₃/L, and 12.64 g Y₂O₃/L, respectively. HCl is the most efficient stripping acid, and 92% of the loaded Yb(III) can be stripped by one-stage stripping with 2 mol/L HCl.     

Reactive Extraction of Formic Acid by using Tri Octyl Amine (TOA)

Abstract

Distribution of formic acid (methanoic acid) between water and tri octyl amine (TOA) dissolved in various alcohols (isoamyl alcohol, hexan-1-ol, octan-1-ol, nonan-1-ol, decan-1-ol) as diluents, as well as the extraction capacity of pure diluent alone have been studied at isothermal conditions. All measurements were carried out at 298.15 K. The difference between the physical extraction and reactive extraction was studied. The loading factor, T _T, extraction efficiency, D _E, modified separation factor, S _F, and, distribution coefficients, K _D were calculated. The isoamylalcohol was found most effective solvent with maximum distribution value of 14.521. Possible equilibrium complexation constants for (acid:amine) (5:1), (6:1), and (7:1) have been determined as values of about 21.8 × 10³, 15.6 × 10⁴, and 11.1 × 10⁵ for K₅₁, K₆₁, and K₇₁, respectively with isoamylalcohol. Furthermore, Linear Solvation Energy Relationship (LSER) model equation has been obtained to calculate distribution coefficients for alcohols with regression coefficient of 0.981.     

CORN GLUTEN HYDROLYSIS BY ALCALASE: KINETICS OF HYDROLYSIS

In the present study, the reaction kinetics of corn gluten hydrolysis by Alcalase, a bacterial protease produced by Bacillus licheniformis, was investigated. The reactions were carried out for 10 min in 0.1 L of aqueous solutions containing 10, 20, 30, 40, and 50 g protein L^?1 corn gluten at various temperature and pH values. The amount of enzyme added to the reaction solution was 0.25% (v/v). Also, to determine decay and product inhibition effects for Alcalase, a series of inhibition experiments were conducted with the addition of various amounts of hydrolysate. For each experimental run, both the amount of hydrolysis (meqv L^?1) and the soluble protein amount (g L^?1) were investigated with respect to time, and the initial reaction rates were determined from the slopes of the linear models that fitted to these experimental data. The kinetic parameters, K_m and V_max were estimated as 53.77 g L^?1 and 5.94 meqv L^?1min^?1. The type of inhibition for Alcalase was determined as uncompetitive, and the inhibition constant, K_i, was estimated as 44.68% (hydrolysate/substrate mixture).     

Multivariate Optimization and Adsorption Characterization of As(III) by Using Fraxinus Tree Leaves

This study introduces Fraxinus tree leaves as a new, efficient biosorbent of As(III). A suitable response surface was achieved by running a central composite design. Simultaneous optimization of both responses (R% and q) was carried out and 67% of the goal of desirability function was attained. The results obtained for simultaneous optimization are R = 70% and q = 80.6 mg g^?1 with 67% desirability in m = 600 mg L^?1 where s = 0.10 g and pH = 3.9. Langmuir and Freundlich isotherms model were applied in explaining the sorbent–sorbate equilibrium study, and maximum capacity uptake equals 99.97 mg g^?1 and K_L = 0.05 L mg^?1 has been obtained. Fourier Transfer Infra-Red (FT-IR) and kinetic results were considered to examine the functional groups involved and the adsorption mechanism.     

Comparative Study on Reactive Extraction of Picolinic Acid with Six Different Extractants (Phosphoric and Aminic) in Two Different Diluents (Benzene and Decan-1-ol)

The equilibrium study on reactive extraction of picolinic acid by six different extractants (phosphoric and aminic) dissolved in two different diluents (benzene and decane-1-ol) is carried out to evaluate the performance of extractants and diluents. The extraction ability in terms of the distribution coefficient (K _D) is found to be in the order of tri-n-octylamine (TOA) ≥ tri-n-dodecylamine (TDDA) > di-2-ehylhexyl phosphoric acid (D2EHPA) > tri-n-butyl phosphate (TBP) > tri-octyl methyl ammonium chloride (Aliquat 336) > tri-n-octyl phosphine oxide (TOPO) with both diluents. Decan-1-ol is found to be the better solvating medium for the acid-extractant complexes. A mathematical model based on mass action law is employed to estimate the values of partition coefficient (P) and dimerization constant (D) in physical extraction, and equilibrium extraction constants (K _E) in chemical extraction. The values of loading ratios (Z) less than 0.5 imply the formation of (1:1) acid:extractant solvates in the organic phase. Decan-1-ol with TOA is the most effective solvation medium with K _{D, max} = 9 at 0.01 kmol · m^?3 of picolinic acid and K _E = 19.448 m³ · kmol^?1.     

Mechanical Properties and Degrading Behaviors of Aluminum Hypophosphite-Poly(Lactic Acid) (PLA) Nanocomposites

The flame retardancy of poly(lactic acid) (PLA)/aluminum hypophosphite (AHP, phosphorous content = 41.87 wt.%) nanocomposites (PLA/(AHP-x), x = 15%, 20%, 25%; and x denotes the weight percentage content of AHP) was greatly enhanced by melt blending of AHP into PLA through twin-screw extruder and injection-molding process. The UL 94 V-0 flammability rating can be reached for PLA/(AHP-20%) with the LOI value over 28.8. The well dispersion of the AHP in PLA/(AHP-x) was investigated by FT-IR spectra under the line mapping model. Based on TGA results under a non-isothermal condition, the thermal degradation kinetics of PLA/(AHP-x) composites were studied by Kissinger’s, Ozawa’s and Flynn-Wall-Ozawa’s (FWO’s) methods. And those thermal degradation dynamic analyses showed lower activation energy (E_K or E_O) (from 155 to 122 kJ·mol^–1) corresponded to higher content of AHP (from 15 to 25 wt.%) for PLA/(AHP-x) nanocomposites. Kissinger’s, FWO’s and Coast-Redfern’s methods were used to discriminate the kinetic models and kinetic parameters for the thermal degradation of PLA/(AHP-x), which suggested conversion function G (α) = [-ln(1-α)]^2/3 or G (α) = α for the investigated process. The flame retardant PLA nanocomposites obtained in this study will become safety environment-friendly potential candidates in household and automobile engineering with high performance.     

Applied of central composite design for the optimization of removal yield of the ketoprofen (KTP) using electrocoagulation process

ABSTRACT

In this paper, the modeling and the optimization of the removal efficiency of ketoprofen (KTP) by the electrocoagulation process were studied. The central composite design experiments (CCD) method was used to study the main effects and the interaction effects between operational parameters and to optimize the value of each parameter. According to the regression equation obtained, the current density appears to be one of the most important parameters (b₂ = +22.11) controlling the removal efficiency of KTP. The positive sign of b₂ coefficient suggests that the increase of current density increases the yield of removal. The second signi?cant parameter with a negative effect was the initial KTP concentration (b₃ = ?16.27). This result suggests that the removal efficiency was inversely proportional to the initial concentration. In addition, according to the model, the most influencing interactions were pH-current density, pH-initial concentration, and current density-initial concentration. The model obtained by CCD led to the following optimal conditions for KTP removal e?ciency (96.70%): pH = 7, i = 24.04 mA cm^?2, and C₀ = 5 mg L^?1.     

Determination of the phospholipase activity of patatin by a continuous spectrophotometric assay

Patatin is a family of glycoproteins that accounts for 30–40% of the total soluble protein in potato (Solanum tuberosum L.) tubers. This protein has been reported to serve as a storage protein and also to exhibit lipid phospholipase activity. This paper describes a simple continuous spectrophotometric method for assaying patatin phospholipase activity. The procedure is based on a coupled enzymatic assay using [1,2-dilinoleoyl]PC as the phospholipase substrate and lipoxygenase as the coupling enzyme. In the procedure developed in this work, lipoxygenase oxidizes the linoleic acid released by the phospholipase activity of patatin. This activity can then be followed spectrophotometrically by recording the increase in absorbance at 234 nm that results from the formation of the corresponding hydroperoxide from linoleic acid by the action of lipoxygenase. The optimal assay concentrations of patatin and lipoxygenase were established. Phospholipase activity varied with pH, reaching its optimal value at pH 9.5. Scans of the deoxycholate concentration pointed to an optimal detergent concentration of 3 mM. Phospholipid hydrolysis followed classical Michaelis-Menten kinetics (V _m=9.8×10⁻³ μmol/min·μg protein, K _m=7.8 μM, V _m/K _m=1.3 min⁻¹·μg protein). This method proved to be specific since there was no activity in the absence of patatin. It also had the advantages of a short analysis time and the use of commercially nonradiolabeled and inexpensive substrates, which are, furthermore, natural substrates of phospholipase.     

Mathematical model of growth and polyhydroxybutyrate production using microbial fermentation of Bacillus subtilis

Poly-3-hydroxybutyrate (PHB) has been extensively utilized as a biodegradable plastic. The value of substrate inhibition constant (K_I) was also established in shake flask cultures by varying the initial glucose concentration (20–160?g/L) in growth media. Excess carbon source adversely affected the growth of Bacillus subtilis cultures. The production kinetics of PHB was studied using batch fermentation strategy for B. subtilis culture. Batch cultivation was also performed in a 5-L stirred tank bioreactor to obtain a Biomass and PHB yield of 5.25 and 1.6?g/L, respectively. The kinetic data of biomass, PHB production, and substrate consumption was used to estimate the optimized values of the growth and product formation kinetic parameters. Optimal values of kinetic parameters (µ_m value of 0.325, K_S value of 10.53?g/L for glucose, Y value of 0.183?g/g of glucose, K_I value of 105?g/L, m value of 0.12?g/(g h), k₁ of 0.36?g/g, and k₂ value was 0.12?g/(g h)) and the initial values of biomass, substrate and PHB concentration (X?=?0.14?g/L, S?=?9.99?g/L, and P?=?0.13?g/L) were utilized to obtain a modified mathematical model for PHB production. Statistical validity of the mathematical model simulations were measured using F-test. The F-test showed that the statistical validity of the model was more than 95% when compared with experimentally obtained values. This model also predicted that the production of PHB using B. subtilis cultures is mainly growth associated.     

Sorption of Silver Cations by Natural and Na-Exchanged Mordenite

Sorption of Ag⁺ by natural mordenite and its Na-exchanged form was investigated by the batch method. Maximum Ag⁺ uptake was observed at initial pH > 3.0 and contact time 90 min. The kinetic data fitted very well to the pseudo-second-order rate model with values of k ₂ from 37.31 to 0.487 and 48.32 to 0.491 g/meq min for the natural and Na-exchanged mordenite, respectively. The Langmuir model is in good correlation with the isotherm data up to initial concentration of 500 mg Ag⁺/L (q _m = 57.41 (natural sample) and 87.72 mg/g (Na-exchanged sample). The obtained data are promising for clean-up of polluted water.     

Application of Ni-doped ZnO nanorods for degradation of diazinon: Kinetics and by-products

The photocatalytic degradation of the organophosphorus insecticide diazinon in aqueous suspensions was studied by using Ni-doped ZnO nanorods as a photocatalyst. The effects of some operational parameters such as solution pH, nanocatalyst dosage, initial diazinon concentration, different purging gases, H₂O₂ concentration, and type of organic compounds on the removal efficiency were studied. Under optimal conditions: pH = 7, [Diazinon]₀ = 20 mg/L, nanocatalyst dosage = 0.2 g/L, H₂O₂ = 15 mM, 99.96% of the insecticide was removed after 120 min. Three kinetic models were developed for this process, and the findings showed that the diazinon removal rate obeyed the first-order kinetic.     

Removal of Copper and Lead from Aqueous Solution by Adsorption onto Cross-Linked Chitosan/Montmorillonite Nanocomposites in the Presence of Hydroxyl–Aluminum Oligomeric Cations: Equilibrium,Kinetic, and Thermodynamic Studies

Adsorption removal of Cu (II) and Pb (II) on cross-linked chitosan/Al₁₃-pillared montmorillonite (CCPM) was examined in solutions. The chitosan dosage was drastically reduced in the new nanocomposite, which is made from the treated clay (Al₁₃-pillared montmorillonite). Several important parameters that influenced the adsorption of Cu (II) and Pb (II) ions, such as cross-linked chitosan-to-clay ratio, pH, temperature, initial concentration, dosage, and contact time effect, were systematically investigated. Result showed that in the nanocomposite with cross-linked chitosan-to-clay ratio of 0.45:1, the maximum removal efficiencies of Cu (II) [pH 6.5, dosage 10 g/L, initial Cu (II) concentration 100 mg/L, contact time 2 h, 298 K] and Pb (II) [pH 6.0, dosage 5 g/L, initial Pb (II) concentration 100 mg/L, contact time 2 h, 298 K] were 96.0% and 99.5%, respectively. Kinetic and isotherm studies have indicated that the adsorption process of Cu (II) or Pb (II) nanocomposites was better fitted by the pseudo-second-order equation and the Freundlich equation, with chemical adsorptions as the rate-limiting step. The metal–ion affinity to the functional groups of CCPM followed the order Pb (II) > Cu (II). The thermodynamic parameters ΔH and ΔS values showed that the sorption process of Cu (II) or Pb (II) was spontaneous (ΔG < 0), was endothermic (ΔH < 0), and had decreased entropy (ΔS < 0). HNO₃ (0.1 M) could be a good desorbent in the recovery of metal ions after adsorption and regeneration of the adsorbent.     

Influence of Substituents on Phenols Extraction and Dissociation

Based on the systematic analysis of experimental data for liquid-liquid extraction of the substituted phenols, the F _α and F _μ parameters have been suggested to describe the dependence of log P ₀ (P ₀ is the distribution coefficient) from the energy of universal intermolecular interactions in solutions and the structural characteristics of solutions in non-polar and polar solvents correspondingly. The deviations from the dependences of log P₀ = f(F _α) and log P₀ = f(F _μ) show the contribution of specific interactions (H-bonds) to the process of extraction. The method is aimed at determination of the ionization constant of phenol (K _a ) on the basis of phenol distribution between the water and non-water solvents, which do not mix up with water. It is shown that the рK _a values of the substituted phenols obtained by the measurements in water and non-water solvents depend on σ⁰-constant. The influence of the amount of the same substituents in the phenol molecules on the рK _a values was studied.     

Caffeine Molecular Imprinted Microgel Spheres by Precipitation Polymerization

Imprinted uniform microgel spheres were prepared by precipitation polymerization. Acetonitrile was used as the dilute solvent with MAA as the monomer, EDMA as the crosslinker and caffeine as the print molecule. Comparison of caffeine adsorption on molecular imprinted and blank microgel spheres was made. Langmuir model was used to fit the adsorption data. It was found that the caffeine imprinted microgel spheres show specific binding sites to the target molecules. A binding study of caffeine on imprinted microgel spheres was made by Scatchard analysis; the dissociation constants (K_D) and the maximum binding capacity were K_D= 1.84×10⁻⁴mol/L,Q _max = 16.98 μmol/g for high affinity binding site and K_D=1.33×l0⁻³ mol/L, Q_max=46.84 μmol/g for lower affinity binding site, respectively This microgel spheres can be useful affinity adsorbents in further applications.     

The Kinetics of Melting Crystallization of Poly-L-Lactide

The influence of non-isothermal melt crystallization on thermal behavior and isothermal melt crystallization kinetics of poly-L-lactide (PLLA) were investigated by differential scanning calorimetry (DSC), polarizing micrograph (POM) and x-ray diffraction (XRD). Crystallization performed at lower cooling rates (2°C·min^?1) is accompanied by a variation of the kinetics around 118°C. The glass transition temperature of PLLA decreases with increase of cooling rate, and the crystallinity at the end of crystallization increases with decreasing cooling rate. The size of PLLA spherulites increases with a decrease in the cooling rate, and PLLA becomes almost amorphous cooled at rapid rate (>10°C·min^?1). PLLA exhibits an Avrami crystallization exponent n = 3.01±0.13 in isothermal crystallization in the range from 90°C to 140°C. According to Hoffman-Lauritzen theory, two crystallization regime are identified with a transition temperature occurring at 118°C, and the value of K_g(II)/K_g(III) is 2.17 [K_g(II) = 6.025 × 10⁵K², K_g(III) = 1.307 × 10⁶ K²].     

Hydrolysis of pentosans in bagasse pith

Work has been conducted on the hydrolysis of pentosans in bagasse pith as the first part of a study of the chemistry of bagasse processing aimed at establishing an integrated industry. Bagasse pith is the fine part screened out and discarded as waste during the preparation of raw material for bagasse pulping plant. By using dilute sulphuric acid at a concentration less than 2% by weight and at a temperature lower than 165°C, pith is hydrolysed to pentoses in a yield of 80–90% based on potential pentoses in pith. Hydrolysis of pentosans in pith, within the scope of experiment, seems to be a first order reaction. However, the semi-logarithmic time plot for the hydrolysis of potential pentoses in the residue consists of two straight lines of different slope. This may be explained on the assumption that bagasse pith contains two major fractions of pentosans that are hydrolysed at different rates. Saeman's equation for hydrolysis of wood with sulphuric acid may be adapted to represent dependence of rate constant K on acid concentration C and reaction temperature T in hydrolysis of the two major parts of pentosans in bagasse pith. K₁ = 6.4 × 10⁵C^1.02 exp (?6378/T) K₂ = 10.7C^0.363 exp (- 2826/T)     

Formation and relative reactivity of comonomer H-complexes in the radical copolymerization of acrylic acid with 1-vinyl-2-pyrrolidone

The dimerization constant (K_g) of acrylic acid and the association constant of the comonomer complex between acrylic acid and 1-vinyl-2-pyrrolidone (K₁) have been determined in chloroform by means of IR and ¹H NMR spectroscopy: K_d=(2.0±0.2) × 10³litre mol^?1 and K₁=68.5±0.5 litre mol^?1. A detailed equation for the copolymer composition considering the participation of the intermolecular complexes in the chain propagation has been derived with the help of a specific regular three addition states Markov chain. Applying a numerical procedure for fitting the experimental curve for the comonomer composition, this equation has been used in the estimation of the dimer and the comonomer complex relative reactivities. The considerably higher reactivities of the two complexes compared with that of the monomers are accounted for by the π-electrons' greater delocalization in the transition states involving the complexes species.     

Ion‐Exchange Separation of Pu from Macro Concentration of Th in HNO3 Medium

Abstract

Sorption behavior of Th and Pu from anion‐ as well as cation‐exchange resin was investigated from nitric acid medium by both batch and column methods. The anion‐exchange studies involved anionic nitrate complexes of Pu⁴⁺ and Th⁴⁺ sorbed onto DOWEX 1x4 resin (50–100 mesh), and the cation‐exchange studies involved the sorption of Pu³⁺ and Th⁴⁺ onto BIORAD AG 50Wx8 (50–100 mesh) or DOWEX 50Wx4 (50–100 mesh) resin. The batch data gave a separation factor (K _d,Pu/K _d,Th) of 22 for the anion‐exchange method and 0.017 for the cation‐exchange method at 3 and 2 M HNO₃, respectively. A two‐stage ion‐exchange separation method was developed for the quantitative separation of Pu (8 g/L) from a macro amount of Th (200 g/L) in nitric acid medium. The first step involved the quantitative sorption of plutonium from the mixture while about 90% of Th could be washed in 6 column volumes. The plutonium, eluted (as Pu³⁺) using 0.5 M HNO₃ + 0.2 M hydrazinium nitrate (HN) + 0.2 M hydroxyl ammonium nitrate (HAN), and the residual (～10%) Th were subsequently loaded onto a cation‐exchange column in the second step. Greater than 99% Pu was recovered with 2 M HNO₃ (in ～8 column volumes) containing 0.2 M HN + 0.2 M HAN. The final elution of thorium from the cation‐exchange column was achieved in about 6 column volumes of 1 M α‐hydroxy isobutyric acid. A (Pu, Th)O₂ fuel scrap sample was dissolved in 16 M HNO₃ containing 0.005 M HF and was used subsequently as the feed for the anion‐exchange column. The eluted Pu was subsequently loaded onto a cation‐exchange column for final purification. The recovery of plutonium and thorium was found to be >99% and >98%, respectively, while the respective decontamination factors were estimated to be 215 and 292.     

Uranyl Ion Uptake from Aqueous Solutions by Chemically Cross-linked Polyelectrolyte CAMA Hydrogels

Uranyl ion adsorption from aqueous solutions has been investigated by chemically cross-linked polyelectrolyte acrylamide/maleic acid (CAMA) hydrogels. CAMA hydrogels with various compositions were prepared from ternary mixtures of acrylamide (A), maleic acid (MA), and water by free radical polymerization in aqueous solution using multifunctional cross-linkers such as ethylene glycol dimethacrylate (EGDMA) and 1,4-butanediol dimethacrylate (BDMA). Uranyl ion adsorption from aqueous solutions was studied by batch sorption technique at 25°C. The effect of uranyl ion concentration and mass of adsorbent on the uranyl ion adsorption were examined. In the experiments of the sorption, L type sorption in the Giles classification system was found. Some binding parameters such as initial binding constant (K _i ), equilibrium constant (K), monolayer coverage (n), site-size (u), and maximum fractional occupancy (Ô) for CAMA hydrogel-uranyl ion binding system were calculated by using Langmuir linearization method. Finally, the amount of sorbed uranyl ion per gram of dry hydrogel (q) was calculated to be 3.29 × 10^?4 ? 15.87 × 10^?4 mol uranyl ion per gram for CAMA hydrogels. Adsorption of uranyl ion was changed range 8.17–48.10%.