Biosorption of cadmium(II), zinc(II) and lead(II) by Penicillium simplicissimum: Isotherms, kinetics and thermodynamics

The isotherms, kinetics and thermodynamics of Cd(II), Zn(II) and Pb(II) biosorption by Penicillium simplicissimum were investigated in a batch system. The effects of pH, initial metal ions concentration, biomass dose, contact time, temperature and co-ions on the biosorption were studied. Adsorption data were well described by both the Redlich–Peterson and Langmuir model. Chemical ion-exchange was found to be an important process based on free energy value from Dubini–Radushkevich isotherm for all metal ions. The results of the kinetic studies of all metal ions at different temperature showed that the rate of adsorption followed the pseudo second-order kinetics well. The thermodynamics constants ΔG°, ΔH° and ΔS° of the adsorption process showed that biosorption of Cd(II), Zn(II) and Pb(II) ions on Penicillium simplicissimum were endothermic and spontaneous.     

Application of natural and modified hectorite clays as adsorbents to removal of Cr(VI) from aqueous solution–Thermodynamic and equilibrium study

A hectorite (H) clay sample has been modified with 2-mercaptobenzimidazole (MBI) using homogeneous and heterogeneous routes. Both modification methodologies resulted in similar products, named H_HOM and H_HET, respectively. These materials were characterized by CO₂ gas adsorption, elemental analysis, nuclear magnetic nuclei of carbon-13 and silicon-29. The effect of two variables (contact time and metal concentration) has been studied using batch technique at room temperature and pH 2.0. After achieving the best conditions for Cr(VI) adsorption, isotherms of this adsorbate on using the chosen adsorbents were obtained, which were fitted to non-linear Sips isotherm model. The maximum number of moles adsorbed was determined to be 11.63, 12.85 and 14.01 mmol g⁻¹ for H, H_HOM and H_HET, respectively, reflecting the maximum adsorption order of H_HET > H_HOM > H. The energetic effects (Δ_intH°, Δ_intG° and Δ_intS°) caused by chromium ion adsorption were determined through calorimetric titrations.     

Sorption of uranium(VI) from aqueous solutions by akaganeite

Removal of U(VI) ions from aqueous solutions was investigated using synthetic akaganeite-type nanocrystals. Nanocrystals of iron oxyhydroxides were synthesized with two different methods and then compared their adsorption capacities. Akaganeite (β-FeOOH) was synthesized in the laboratory by precipitation from aqueous solution of Fe(III) chloride and different precipitating agents. The relative importance of test parameters like solution pH, contact time, temperature and concentration of adsorbate on adsorption performance of akaganeite for U(VI) ion were studied. Typical adsorption isotherms (Langmuir, Freundlich, Dubinin-Raduskevich) were determined for the mechanism of sorption process. Also the thermodynamic constants (ΔH°, ΔS° and ΔG°) were calculated. The product materials were examined by powder X-ray diffraction for crystalline phase identification and scanning electron microscope (SEM).     

The study of adsorption characteristics Cu and Pb ions onto PHEMA and P(MMA-HEMA) surfaces from aqueous single solution

The adsorption characteristics of Cu²⁺ and Pb²⁺ ions onto poly2-hydroxyethyl methacrylate (PHEMA) and copolymer 2-hydroxyethyl methacrylate with monomer methyl methacrylate P(MMA-HEMA) adsorbent surfaces from aqueous single solution were investigated with respect to the changes in the pH of solution, adsorbent composition (changes in the weight percentage of MMA copolymerized with HEMA monomer), contact time and the temperature in the individual aqueous solutions. The linear correlation coefficients of Langmuir and Freundlich isotherms were obtained. The results revealed that the Langmuir isotherm fitted the experimental results better than the Freundlich isotherm. Using the Langmuir model equation, the monolayer adsorption capacity of PHEMA surface was found to be 0.840 and 3.037 mg/g for Cu²⁺ and Pb²⁺ ions and adsorption capacity of (PMMA-HEMA) was found to be 31.153 and 31.447 mg/g for Cu²⁺ and Pb²⁺ ions, respectively. Changes in the standard Gibbs free energy (ΔG⁰), standard enthalpy (ΔH⁰) and standard entropy (ΔS⁰) show that the adsorption of mentioned ions onto PHEMA and P(MMA-HEMA) are spontaneous and exothermic at 293–323 K.     

Preparation and application of acrylic acid grafted polytetrafluoroethylene fiber as a weak acid cation exchanger for adsorption of Er(III)

In this work, a weakly acidic ion exchange fiber (PTFE-g-AA) has been prepared by ⁶⁰Co irradiation grafting with acrylic acid (AA) onto the polytetrafluoroethylene (PTFE) fiber. The grafted fiber was characterized by FTIR, SEM and TGA technique. The exchange capacity of the PTFE-g-AA fiber is 3.87 mmol/g. The adsorbent material was employed for Er(III) uptaking by batch and column experiments. Kinetics studies showed that the adsorption process obeyed pseudo-second-order kinetics. The adsorption isotherms followed both the Freundlich model and Langmuir model. The maximum adsorption capacity of the PTFE-g-AA fiber for Er(III) was evaluated to be 142.0 mg/g for the Langmuir model. It was found that 0.75 M HCl–0.25 M NaCl solution provided effectiveness of the desorption of Er(III) from the PTFE-g-AA fiber. Various thermodynamic parameters such as standard enthalpy (ΔH⁰), standard entropy (ΔS⁰) and standard free energy (ΔG⁰) were evaluated. The adsorption of Er(III) on the PTFE-g-AA fiber was found to be endothermic in nature. The Thomas model was successfully applied to experimental data to predict the breakthrough curves and to determine the characteristics parameters of the column useful for process design.     

Removal of phenol from aqueous solutions by adsorption onto organomodified Tirebolu bentonite: Equilibrium, kinetic and thermodynamic study

A natural bentonite modified with a cationic surfactant, cetyl trimethylammonium bromide (CTAB), was used as an adsorbent for removal of phenol from aqueous solutions. The natural and modified bentonites (organobentonite) were characterized with some instrumental techniques (FTIR, XRD and SEM). Adsorption studies were performed in a batch system, and the effects of various experimental parameters such as solution pH, contact time, initial phenol concentration, organobentonite concentration, and temperature, etc. were evaluated upon the phenol adsorption onto organobentonite. Maximum phenol removal was observed at pH 9.0. Equilibrium was attained after contact of 1 h only. The adsorption isotherms were described by Langmuir and Freundlich isotherm models, and both model fitted well. The monolayer adsorption capacity of organobentonite was found to be 333 mg g⁻¹. Desorption of phenol from the loaded adsorbent was achieved by using 20% acetone solution. The kinetic studies indicated that the adsorption process was best described by the pseudo-second-order kinetics (R² > 0.99). Thermodynamic parameters including the Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were also calculated. These parameters indicated that adsorption of phenol onto organobentonite was feasible, spontaneous and exothermic in the temperature range of 0–40 °C.     

Interactive behavior of caffeine at a platinum electrode surface

Interactive behavior of caffeine at a charged platinum/solution interface was investigated in a wide temperature range, from 295 to 333 K, in a phosphate buffer solution pH 7.0. It was shown that the amount of adsorbed caffeine (surface concentration) is directly proportional to the measured adsorption surface charge density resulting from caffeine oxidation to theophilline. At low temperatures, a monolayer of caffeine molecules laying in a flat orientation on the Pt surface is adsorbed, while at higher temperatures, conformational changes occur, resulting in tilting of the adsorbed molecules to allow for higher surface concentrations to be achieved. A highly negative Gibbs energy of adsorption, ranging from −51.1 kJ mol⁻¹ at 295 K to −60.6 kJ mol⁻¹ at 333 K, demonstrated a high affinity of caffeine for the Pt surface. Although the adsorption process was found to be endothermic (ΔH_ADS = 20 kJ mol⁻¹), it was determined that a large positive change in the adsorption entropy (TΔS_ADS = 75 ± 3 kJ mol⁻¹) represents the driving force for the strong interaction of caffeine with Pt.     

Effective removal and fixation of Cr(VI) from aqueous solution with Friedel's salt

Friedel's salt (3CaO·Al₂O₃·CaCl₂·10H₂O or Ca₄Al₂(OH)₁₂Cl₂(H₂O)₄) is a calcium aluminate hydrate formed by hydrating cement or concrete in seawater at a low cost. In the current study, we carefully examined the adsorption behaviors of Friedel's salt for Cr(VI) from aqueous solution at different concentrations and various initial pHs. The adsorption kinetic data are well fitted with the pseudo-first-order Lageren equation at the initial Cr(VI) concentration from 0.10 to 8.00 mM. Both the experimental and modeled data indicate that Friedel's salt can adsorb a large amount of Cr(VI) (up to 1.4 mmol Cr(VI)/g) very quickly (t_1/2 = 2–3 min) with a very high efficiency (>99% Cr(VI) removal at [Cr] < 4.00 mM with 4.00 g/L of adsorbent) in the pH range of 4–10. In particular, the competitive adsorption tests show that the Cr(VI) removal efficiency is only slightly affected by the co-existence of Cl⁻ and HCO₃⁻. The Cr(VI)-fixation stability tests show that only less than 0.2% adsorbed Cr(VI) is leaching out in water at pH 4–10 for 24 h because the adsorption/exchange of Cr(VI) with Friedel's salt leads to the formation of a new stable phase (3CaO·Al₂O₃·CaCrO₄·10H₂O). This research thus suggests that Friedel's salt is a potential cost-effective adsorbent for Cr(VI) removal in wastewater treatment.     

The removal of an anionic red dye from aqueous solutions using chitosan beads-the role of experimental factors on adsorption using a full factorial design

A factorial design was employed to evaluate the quantitative removal of an anionic red dye from aqueous solutions on epichlorohydrin-cross-linked chitosan. The experimental factors and their respective levels studied were the initial dye concentration in solution (25 or 600 mg L⁻¹), the absence or the presence of the anionic surfactant sodium dodecylbenzenesulfonate (DBS) and the adsorption temperature (25 or 55 °C). The adsorption parameters were analyzed statistically using modeling polynomial equations. The results indicated that increasing the dye concentration from 25 to 600 mg L⁻¹ increases the dye adsorption whereas the presence of DBS increases it. The principal effect of temperature did not show a high statistical significance. The factorial results also demonstrate the existence of statistically significant binary interactions of the experimental factors. The adsorption thermodynamic parameters, namely Δ_adsH, Δ_adsG and Δ_adsS, were determined for all the factorial design results. Exothermic and endothermic values were found in relation to the Δ_adsH. The positive Δ_adsS values indicate that entropy is a driving force for adsorption. The Δ_adsG values are significantly affected by an important synergistic effect of the factors and not by the temperature changes alone.     

Adsorption of platinum (IV), palladium (II) and gold (III) from aqueous solutions onto L-lysine modified crosslinked chitosan resin

Crosslinked chitosan resin chemically modified with L-lysine has been used to investigate the adsorption of Pt(IV), Pd(II) and Au(III) from aqueous solutions. Batch adsorption studies were carried out with various parameters, such as initial metal ion concentration, contact time, pH and temperature. The maximum adsorption capacity was found at pH 1.0 for Pt(IV), at pH 2.0 for Au(III) and Pd(II). Langmuir and Freundlich isotherm models were applied to analyze the experimental data. The best interpretation for the experimental data was given by the Langmuir isotherm and the maximum adsorption capacity was found to be 129.26 mg/g for Pt(IV), 109.47 mg/g for Pd(II) and 70.34 mg/g for Au(III). The kinetic data was tested using pseudo-first-order and pseudo-second-order kinetic models. Kinetic data correlated well with the pseudo-second-order kinetic model, indicating that the chemical sorption was the rate-limiting step. Thermodynamic parameters like Gibbs free energy (DeltaG degrees), enthalpy (DeltaH degrees) and entropy (DeltaS degrees) were evaluated by applying the Van't Hoff equation. The thermodynamic study indicated that the adsorption process is spontaneous and exothermic in nature. The desorption studies were carried out using various reagents. The maximum percent desorption of precious metal ions were obtained when the reagent 0.7 M thiourea-2 M HCl was used.     

Synthesis and characterization of 3,6-bis(1H-1,2,3,4-tetrazol-5-ylamino)-1,2,4,5-tetrazine (BTATz): Novel high-nitrogen content insensitive high energy material

This paper reports the synthesis, characterization and thermolysis studies of 3,6-bis(1H-1,2,3,4-tetrazol-5-ylamino)-1,2,4,5-tetrazine (BTATz) and 3-(1H-1,2,3,4-tetrazol-5-ylamino)-6-(3,5-dimethyl-pyrazol-1-yl)-s-tetrazine monohydrate (TADPTz). The synthesized BTATz and TADPTz have been characterized by spectroscopic techniques and the data obtained confirm their structure. TGA and DSC results suggested that BTATz decomposes in the range 265–350 °C and TADPTz in the range 245–275 °C respectively. The calculated energy of activation of BTATz and TADPTz is 212.69 and 257.29 kJ/mol respectively. The experimentally determined ΔH_f value matches with theoretically computed heat of explosion. The computed volume of gases indicates that they can find application in gas generating compositions.     

Biosorption of total chromium from aqueous solution by red algae (Ceramium virgatum): equilibrium, kinetic and thermodynamic studies

This study focused on the biosorption of total chromium onto red algae (Ceramium virgatum) biomass from aqueous solution. Experimental parameters affecting biosorption process such as pH, contact time, biomass dosage and temperature were studied. Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were applied to describe the biosorption isotherms. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The biosorption capacity of C. virgatum biomass for total chromium was found to be 26.5 mg/g at pH 1.5 and 10 g/L biomass dosage, 90 min equilibrium time and 20 °C. From the D–R isotherm model, the mean free energy was calculated as 9.7 kJ/mol, indicating that the biosorption of total chromium was taken place by chemisorption. The calculated thermodynamic parameters (ΔG°, ΔH°and ΔS°) showed that the biosorption of total chromium onto C. virgatum biomass was feasible, spontaneous and exothermic at 20–50 °C. Kinetic evaluation of experimental data showed that the biosorption processes of total chromium followed well pseudo-second-order kinetics.     

Transient flow behaviour in a near alpha titanium alloy Timetal 834 in the dynamic strain aging regime

The transient flow behaviour in Timetal 834 titanium alloy was studied in the temperature range between 400 °C and 475 °C by means of stress relaxation and reloading during tensile testing at a strain rate of 6.67 × 10⁻⁴ s⁻¹. The increment in flow stress during reloading (Δσ_f) and the decrement in flow stress during stress relaxation (Δσ_r) were measured at different strains at each temperature. The observation of maximum value of Δσ_f and Δσ_r, normalized with respect to the Young's modulus at the corresponding temperature, confirmed that the maximum dynamic strain aging (DSA) effect in this alloy occurs at 450 °C.     

Sorption behavior of nano-TiO2 for the removal of selenium ions from aqueous solution

Titanium dioxide nanoparticles were employed for the sorption of selenium ions from aqueous solution. The process was studied in detail by varying the sorption time, pH, and temperature. The sorption was found to be fast, and to reach equilibrium basically within 5.0 min. The sorption has been optimized with respect to the pH, maximum sorption has been achieved from solution of pH 2–6. Sorbed Se(IV) and Se(VI) were desorbed with 2.0 mL 0.1 mol L⁻¹ NaOH. The kinetics and thermodynamics of the sorption of Se(IV) onto Nano-TiO₂ have been studied. The kinetic experimental data properly correlate with the second-order kinetic model (k₂ = 0.69 g mg⁻¹ min⁻¹, 293 K). The overall rate process appears to be influenced by both boundary layer diffusion and intraparticle diffusion. The sorption data could be well interpreted by the Langmuir sorption isotherm. The mean energy of adsorption (14.46 kJ mol⁻¹) was calculated from the Dubinin–Radushkevich (D–R) adsorption isotherm at room temperature. The thermodynamic parameters for the sorption were also determined, and the ΔH⁰ and ΔG⁰ values indicate exothermic behavior.     

Cr(VI) sorption behavior from aqueous solutions onto polymeric microcapsules containing a long-chain quaternary ammonium salt: Kinetics and thermodynamics analysis

This work studies the adsorption of Cr(VI) ions from an aqueous acid solution on hydrophobic polymeric microcapsules containing a long-chain quaternary ammonium salt-type extractant immobilized in their pore structure. The microcapsules were synthesized by adding the extractant Aliquat 336 during the in situ radical copolymerization of the monomers styrene (ST) and ethylene glycol dimethacrylate (EGDMA). The microcapsules, which had a spherical shape with a rough surface, behaved as efficient adsorbents for Cr(VI) at the tested temperatures. The results of kinetics experiments carried out at different temperatures showed that the adsorption process fits well to a pseudo-second-order with an activation energy of 82.7 kJ mol⁻¹, confirming that the sorption process is controlled by a chemisorption mechanism. Langmuir's isotherms were found to represent well the experimentally observed sorption data. Thermodynamics parameters, namely, changes in standard free energy (ΔG⁰), enthalpy (ΔH⁰), and entropy (ΔS⁰), are also calculated. The results indicate that the chemisorption process is spontaneous and exothermic. The entropy change value measured in this study shows that metal adsorbed on microcapsules leads to a less chaotic system than a liquid–liquid extraction system.     

Synthesis and characterization of CTAB-silica nanocapsules and its adsorption behavior towards Pd(II) ions in aqueous solution

The silica nanocapsules (SiNC) with CTAB (SiNC-CTAB) and free CTAB (SiNC-FREE) were prepared by the microemulsion polymerization process, in which the cetyltrimethylammonium bromide (CTAB) was used as a structure directive as well as a cationic functionalized agent. The structure and properties of these adsorbents were characterized by a field emission scanning electron microscope (FESEM), transmission electron microscope (TEM), nitrogen adsorption–desorption (NAD) analyzer, Fourier transform infrared (FTIR) spectrophotometer, thermogravimetric analyzer (TGA) and pH at point zero charges (pH_pzc) determination. The adsorbents were then characterized for their adsorption behavior towards Pd(II) ions in aqueous solution performed in a batch adsorption experiment. The maximum adsorption capacity of Pd(II) ions onto SiNC-CTAB obtained from the adsorption isotherm was 124.50 mg g⁻¹, which was over 2.4 times higher than that of the SiNC-FREE (51.28 mg g⁻¹). The diffusion modeling analysis by the Weber Morris model indicated that the film diffusion is the controlling step, while the chemical reaction modeling obeyed the pseudo-second order kinetic model. The SiNC-CTAB was found to be reusable in which a good adsorption performance of up to 4 adsorption cycles was observed.     

Chemically modified activated carbon with 1-acylthiosemicarbazide for selective solid-phase extraction and preconcentration of trace Cu(II), Hg(II) and Pb(II) from water samples

A new sorbent 1-acylthiosemicarbazide-modified activated carbon (AC-ATSC) was prepared as a solid-phase extractant and applied for removing of trace Cu(II), Hg(II) and Pb(II) prior to their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The separation/preconcentration conditions of analytes were investigated, including effects of pH, the shaking time, the sample flow rate and volume, the elution condition and the interfering ions. At pH 3, the maximum static adsorption capacity of Cu(II), Hg(II) and Pb(II) onto the AC-ATSC were 78.20, 67.80 and 48.56 mg g⁻¹, respectively. The adsorbed metal ions were quantitatively eluted by 3.0 mL of 2% CS(NH₂)₂ and 2.0 mol L⁻¹ HCl solution. Common coexisting ions did not interfere with the separation. According to the definition of IUPAC, the detection limits (3σ) of this method for Cu(II), Hg(II) and Pb(II) were 0.20, 0.12 and 0.45 ng mL⁻¹, respectively. The relative standard deviation under optimum conditions is less than 4.0% (n = 8). The prepared sorbent was applied for the preconcentration of trace Cu(II), Hg(II) and Pb(II) in certified and water samples with satisfactory results.     

Influence of straining and ageing on the room temperature mechanical properties of dual phase steel

In this work, changes in mechanical properties in dual phase steel containing 20% martensite volume fractions were observed at various ageing temperatures. For example, ΔY (increase in yield strength due to strain ageing), YS and UTS exhibit maximum values at ageing temperature of 100 °C for the pre-strains of 2 and 4%. This is due to the formation of solute atom atmospheres around dislocation. When the ageing temperature increased to 200 °C, yield strength decreased due to overageing resulted from tempering that starts in martensite phase.     

Composite adsorbent of CaCl2 and expanded graphite for adsorption ice maker on fishing boats

Adsorption performances and thermal conductivity were tested for three types of adsorbent: Pure CaCl₂ powder, simple composite adsorbent and consolidated composite adsorbent. The simple composite adsorbents show better adsorption performance because the additive of expanded graphite in CaCl₂ powder has restrained the agglomeration phenomenon in adsorption process and improved the adsorption performance of CaCl₂. The consolidated composite adsorbent are suitable to be used as adsorbent for ice maker on fishing boats because they have higher thermal conductivity, larger volumetric cooling capacity, higher SCP values and better anti-sway performance than simple composite adsorbents. Thermal conductivity of the consolidated composite adsorbent is 6.5–9.8 W m⁻¹ K⁻¹ depending on the molding pressure, ranging from 5 to 15 MPa, which is about 32 times higher than the thermal conductivity of CaCl₂ powder. The volumetric cooling capacity of consolidated composite adsorbent is about 52% higher than the best result obtained for CaCl₂ at the evaporating temperature of −10 °C. The SCP of the consolidated adsorbent increases of about 353% than CaCl₂ powder from simulation results at T_ad=30 °C and T_ev=−10 °C. The consolidated composite adsorbents have good anti-sway performance and they are not easy to be scattered out when the fishing boats sway on the sea.     

The influence of the synthesis routes of MgAl2O4 on its properties and behavior as support of dehydrogenation catalysts

In order to synthesize MgAl₂O₄, three methods were used: (a) a solid phase reaction of MgO and γ-Al₂O₃ oxides at 900 °C for 24 h (ceramic method), (b) wet milling during 24 h of the mixture of oxides followed by the reaction at 900 °C for 12 h (mechanochemical synthesis), and (c) coprecipitation of Mg(NO₃)₂·6H₂O and Al(NO₃)₃·9H₂O with ammonia solution followed by a calcination in a flow of air at 800 °C during 4 h (coprecipitation method). The synthesized materials were characterized by XRD, BET isotherm, isopropanol dehydration reaction, TGA/DTA and SEM. The results indicate that in all the cases the MgAl₂O₄ spinel was formed. Besides, a residue of MgO in the samples obtained by the ceramic method and mechanochemical synthesis was found, which was eliminated by purification. The surface area of MgAl₂O₄ obtained by mechanochemical synthesis and coprecipitation method are much higher than that of the spinel synthesized by the ceramic method. Pt (0.3%) catalysts were prepared by impregnating the three supports with H₂PtCl₆. The metallic dispersion of Pt/MgAl₂O₄ obtained by mechanochemical synthesis was higher than that of Pt catalysts supported on the other spinels, in agreement with the catalytic behavior observed in n-butane dehydrogenation reaction and test reactions of the metallic phase.