Adsorption of Methylene Blue from Aqueous Solution on High Lime Fly Ash: Kinetic,Equilibrium, and Thermodynamic Studies

Kinetic, equilibrium, and thermodynamic studies were performed for the batch adsorption of methylene blue (MB) on the high lime fly ash as a low cost adsorbent material. The studied operating variables were adsorbent amount, contact time, dye concentration, and temperature. The kinetic data were analyzed using the pseudo-first order and pseudo-second order kinetic models and the adsorption kinetic was followed well by the pseudo-second order kinetic model. The equilibrium data were fitted with the Freundlich, Langmuir, and Dubinin Radushkevich (D–R) isotherms and the equilibrium data were found to be well represented by the Freundlich and D–R isotherms. Based on these two isotherms MB is taken by chemical ion exchange and active sites on the high lime fly ash have different affinities to MB molecules. Various thermodynamic parameters such as enthalpy of adsorption (ΔH°), free energy change (ΔG°), and entropy change (ΔS°) were investigated. The positive value of ΔH° and negative value of ΔG° indicate that the adsorption is endothermic and spontaneous. The positive value of ΔS° shows the increased randomness at the solid–liquid interface during the adsorption. A single-stage batch adsorber was also designed based on the Freundlich isotherm for the removal of MB by the high lime fly ash.     

Assessment of <Emphasis Type="Italic">Urtica</Emphasis> as a low-cost adsorbent for methylene blue removal: kinetic,equilibrium, and thermodynamic studies

Methylene blue (MB) removal using eco-friendly, cost-effective, and freely available Urtica was investigated. The morphology of the adsorbent surface and the nature of the possible Urtica and MB interactions were examined using SEM analysis and the FTIR technique, respectively. Various factors affecting MB adsorption such as adsorption time, initial MB concentration, temperature, and solution pH were investigated. The adsorption process was analysed using different kinetic models and isotherms. The results showed that the MB adsorption kinetic follows a pseudo-second-order kinetic model and the isotherm data fit the Langmuir isotherm well. Thermodynamic parameters, such as ΔG°, ΔH°, and ΔS°, were also evaluated, and the results indicated that the adsorption process is endothermic and spontaneous in nature. The MB adsorption capacity of Urtica was found to be as high as 101.01 mg g^?1, higher than those of many other adsorbents studied in the literature. This superior adsorption capacity, along with the ready availability of Urtica, render this adsorbent potentially suitable for practical applications.     

An evaluation of coal fly ash as an adsorbent for the removal of methylene blue from aqueous solutions: kinetic and thermodynamic studies

Abstract

In this study the effect of the dose and particle size of the adsorbent, initial dye concentration, initial pH, contact time and temperature were investigated for the removal of by means of fly ash (FA) methylene blue (MB) from an aqueous solution. The FA dose was found to be 2.0?g and the under 270 mesh sized particles were found to be effective particles for adsorption. The adsorption process reached its maximum value at 0.5?mg/L dye concentration and attained equilibrium within 10?minutes. The adsorption isotherm was found to follow the Langmuir model. The estimated adsorption free energy (ΔG^o), enthalpy change (ΔH^o), and entropy change (ΔS^o) for the adsorption process were ?37.77?kJ mol^?1, ?13.44?kJ mol^?1 and 122 J mol^?1 K^?1 respectively at 298 K. The maximum adsorption capacity is 0,12?mg g^?1 at 298 K and 0,07?mg g^?1 at 398 K. The adsorption process was exothermic, feasible and spontaneous. The positive value of ΔS^o shows the affinity of FA for MB while the low value of ΔG^o suggests a physical adsorption process.     

Kinetic of Patent Blue VF Adsorption from Aqueous Solution on Activated Bone Charcoal

The effect of temperature of activation on bone charcoal, used as adsorbent for the removal of Patent Blue VF from water solutions was studied. The adsorbent was characterized by FTIR, XRD, SEM and EDS. The kinetic of adsorption of dye was carried out at 10 °C and 45 °C. Carbonization temperature (600–1000 °C) of the adsorbent has significant effect on the removal of dye from water solutions. The first order kinetic, Elovich, Bangham, parabolic diffusion and power function equations were found to fit the kinetic data. Activation energies of adsorption (Δ≠) have higher values for the charcoal activated at high temperatures and the other thermodynamic parameters like ΔH≠, ΔS≠ and ΔG≠ were also found.     

Synthesis, characterization, and application of titanate nanotubes for Th(IV) adsorption

Titanate nanotubes (TNTs) have been synthesized by a hydrothermal method using rutile TiO₂ powder as titanium source. The determination of the structure and morphology was characterized by XRD, FTIR, SEM and TEM. The results indicate that the TNTs successfully synthesized under hydrothermal conditions of 150 °C. The adsorption of Th(IV) on TNTs was studied as a function of contact time, pH values, ionic strength, initial Th(IV) concentration and temperature under ambient conditions by using batch technique. The results indicate that adsorption of Th(IV) on TNTs is strongly dependent on pH values, but weakly dependent on ionic strength; Adsorption kinetics was better described by the pseudo-second-order model. The adsorption isotherms are simulated by Langmuir and Freundlich models well. ΔG°, ΔH° and ΔS° free energy were calculated from experimental data, The results indicate that the adsorption of Th(IV) on TNTs is an endothermic and a spontaneous process, and increases with increasing temperature. The adsorption of Th(IV) on TNTs is mainly dominated by chemical sorption or surface complexation.     

Modified Calcium Alginate Beads with Sodium Dodecyl Sulfate and Clay as Adsorbent for Removal of Methylene Blue

In present study, we have investigated the effect of an anionic surfactant sodium dodecyl sulfate (SDS) and clay on calcium alginate beads was studied to remove methylene blue (MB) and to improve the adsorption capacity. The effects of various experimental parameters, such as shaking rate, initial dye concentration, temperature, and pH on the adsorption rate, have been studied. Equilibrium studies showed that the sorption of the dye was enhanced in presence of SDS. Scanning electron microscope (SEM) analysis showed that SDS entrapped beads have more pores and cavities which could be responsible for improved adsorption of MB. The kinetics of cationic dye adsorption nicely followed pseudo-second-order process. The evaluated thermodynamic parameters (ΔG ^o, ΔH ^o, ΔS ^o) suggest endothermic adsorption of MB. The results revealed that the surfactant entrapped alginate could be considered as potential adsorbents for MB removal from aqueous solutions.     

Valorization of two waste streams into activated carbon and studying its adsorption kinetics,equilibrium isotherms and thermodynamics for methylene blue removal

Wastes must be managed properly to avoid negative impacts that may result. Open burning of waste causes air pollution which is particularly hazardous. Flies, mosquitoes and rats are major problems in poorly managed surroundings. Uncollected wastes often cause unsanitary conditions and hinder the efforts to keep streets and open spaces in a clean and attractive condition. During final disposal methane is generated, it is much more effective than carbon dioxide as a greenhouse gas, leading to climate change. Therefore, this study describes the possible valorization of two waste streams into activated carbon (AC) with added value due to copyrolysis. High efficiency activated carbon was prepared by the copyrolysis of palm stem waste and lubricating oil waste. The effects of the lubricating oil waste to palm stem ratio and the carbonization temperature on the yield and adsorption capacity of the activated carbon were investigated. The results indicated that the carbon yield depended strongly on both the carbonization temperature and the lubricating oil to palm stem ratio. The efficiency of the adsorption of methylene blue (MB) onto the prepared carbons increased when the lubricating oil to palm stem ratio increased due to synergistic effect. The effects of pH, contact time, and the initial adsorbate concentration on the adsorption of methylene blue were investigated. The maximum adsorption capacity (128.89 mg/g) of MB occurred at pH 8.0. The MB adsorption kinetics were analyzed using pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models. The results indicated that the adsorption of MB onto activated carbon is best described using a second order kinetic model. Adsorption data are well fitted with Langmuir and Freundlich isotherms. The thermodynamic parameters; ΔG°, ΔH° and ΔS° indicate that the adsorption is spontaneous and endothermic.     

Removal of uranium(VI) from aqueous solutions using nanoporous ZnO prepared with microwave-assisted combustion synthesis

The adsorption of the uranyl ions from aqueous solutions on the nanoporous ZnO powders has been investigated under different experimental conditions. The adsorption of uranyl on nanoporous ZnO powders were examined as a function of the contact times, pH of the solution, concentration of uranium(VI) and temperature. The ability of this material to remove U(VI) from aqueous solution was followed by a series of Langmuir and Freunlinch adsorption isotherms. The adsorption percent and distribution coefficient for nanoporous ZnO powders were 98.65 % ± 1.05 and 7,304 mL g^?1, respectively. The optimum conditions were found as at pH 5.0, contact time 1 h, at 1/5 Zn²⁺/urea ratio, 50 ppm U(VI) concentration and 303 K. The monomolecular adsorption capacity of nanoporous ZnO powders for U(VI) was found to be 1,111 mg g^?1 at 303 K. Using the thermodynamic equilibrium constants obtained at different temperatures, various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, have been calculated. Thermodynamic parameters (ΔH° = 28.1 kJ mol ^?1, ΔS° = 160.30 J mol^?1 K^?1, ΔG° = ?48.54 kJ mol^?1) showed the endothermic and spontaneous of the process. The results suggested that nanoporous ZnO powders was suitable as sorbent material for recovery and adsorption of U(VI) ions from aqueous solutions.     

Calorimetric study of poly(2-ethylhexyl acrylate) over the range from T → 0 to 350 K

For the first time, the heat capacity $ C_{\text{p}}^{^\circ } $ of poly(2-ethylhexyl acrylate) has been studied in an adiabatic vacuum calorimeter between 7 and 350 K, the standard thermodynamic functions: heat capacity $ C_{\text{p}}^{^\circ } $ (T), enthalpy H°(T) ? H°(0), entropy S°(T) ? S°(0), Gibbs function G°(T) ? H°(0) have been calculated from T → 0 to 350 K. The energy of combustion Δ_c U of the compound under study has been measured in a calorimeter with a stationary bomb and an isothermal shell. The standard enthalpy of combustion Δ_c H° and thermodynamic parameters of formation—enthalpy Δ_f H°, entropy Δ_f S°, Gibbs function Δ_f G°—at T = 298.15 K have been calculated. The results have been used to calculate the thermodynamic characteristics of 2-ethylhexyl acrylate bulk polymerization into poly(2-ethylhexyl acrylate) over the range from T → 0 to 350 K.     

Adsorption of methylene blue dye from aqueous solution by agricultural waste: Equilibrium,thermodynamics, kinetics,mechanism and process design

The adsorption of methylene blue (MB) dye from aqueous solution onto a cashew nut shell (CNS) was investigated as a function of parameters such as solution pH, CNS dose, contact time, initial MB dye concentration and temperature. The CNS was shown to be effective for the quantitative removal of MB dye, and the equilibrium was reached in 60 min. The experimental data were analysed by two-parameter isotherms (Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models) using nonlinear regression analysis. The characteristic parameters for each isotherm and the related correlation coefficients were determined. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were also evaluated, the sorption process was found to be spontaneous and exothermic. Pseudo-first-order, pseudo-second-order and Elovich kinetic models were used to analyze the adsorption process. The results of the kinetic study suggest that the adsorption of MB dye matches the pseudo-second-order equation, suggesting that the adsorption process is presumably chemisorption. The adsorption process was found to be controlled by both surface and pore diffusion. Analysis of adsorption data using a Boyd kinetic plot confirmed that the external mass transfer is a rate determining step in the sorption process. A single-stage batch adsorber was designed for different CNS doses to effluent volume ratios using the Freundlich equation. The results indicated that the CNS could be used effectively to adsorb MB dye from aqueous solutions.     

Thermodynamic studies of Ni(II) adsorption onto bentonite from aqueous solution

The adsorption behavior of Ni(II) onto bentonite was studied as a function of temperature under optimized conditions of shaking time, amount of adsorbent, pH, and concentration of the adsorbate. Thermodynamic parameters such as ΔH^°, ΔS^°, and ΔG^° were calculated from the slope and intercept of the linear plot of lgK_D against 1/T. Analysis of adsorption results obtained at T=(298, 303, 313, and 323) K showed that the adsorption pattern on bentonite followed the Langmuir, Freundlich, and D-R isotherms. A flame atomic absorption spectrophotometer was used for measuring the concentration of Ni(II).     

Potentiometric and Thermodynamic Studies of Some Metal–Cysteine Complexes

A new and simple potentiometric method is developed to determine the stability constants of cysteine complexes with Mn(II), Cu(II), Zn(II), Cd(II), and Ce(III) metal ions using a modified Bjerrum method. Potentiometric titrations were performed in water and water/dioxane mixtures at five different temperatures. The least and highest stable complexes were those of Cu(II) and Zn(II), respectively. Furthermore, by conducting the experiments at temperatures of 15, 20, 25, 35, and 45 °C, the thermodynamic parameters ΔH°, ΔS°, and ΔG° for the pertinent complexes were calculated. The results show that the ΔH° values of the complexes are positive except for Zn(II). Negative values of ΔG° are evidence for the spontaneity of the reactions.     

The adsorption of phosphamidon on the surface of antimony(V) phosphate: A thermodynamic study

The thermodynamics of the adsorption of phosphamidon on antimony(V) phosphate cation exchanger has been studied at 30, 45 and 50°C and the thermodynamic equilibrium constant (K₀), standard free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) have been calculated to predict its adsorption behaviour. All the data are adequately represented by the Freundlich isotherms.     

Determination of thermodynamic parameters for cloud point extraction of Arsenazo-III and Magdala Red dyes using mixed micelles: An essential requirement for high performance

A simple and low cost method for extraction and preconcentration of Arsenazo-III (ARS-III) and Magdala Red (MR) was developed by an efficient cloud point extraction (CPE) method using mixed micelles of Triton X–114 (TX–114) and cetyltrimethyl ammonium bromide (CTAB). Various parameters, such as pH/concentration of H₂SO₄, surfactant concentrations (TX-114 and CTAB), equilibrium temperature and time have been studied to maximise efficiency. Thermodynamic quantities like change in Gibbs free energy (ΔG⁰), change in enthalpy (ΔH⁰) and change in entropy (ΔS⁰) were calculated. The results show that the CPE of ARS-III and MR dye is feasible, spontaneous, and endothermic in the temperature range of (50–80) °C indicating good recoveries for the developed method. The effect of temperature, surfactant concentration and dye concentration on various thermodynamic quantities was investigated and it was found that ΔG⁰ values increased with temperature but decreased with surfactant and dye concentration. ΔH⁰ and ΔS⁰ values increased as surfactant concentration increased and decreased as dye concentration decreased. The recoveries were found to be the range from 90.02 – 101.03 % for ARS-III and 86.07–99.46 % for MR dyes which proves that the method is highly efficient.     

Liquid phase adsorption of Congo red dye on functionalized corn cobs

This study investigates the adsorption of Congo red (CR) dye onto corn cob based activated carbon (CCAC) in the batch process. The activated carbon was characterized using FTIR, SEM, and EDX techniques, respectively. The effect of operational parameters such as the initial dye concentration (10–50?mg/L), contact time (5–160 minutes), and solution temperature (30–50°C) were studied. The amount of the CR dye adsorbed was found to increase as these operational parameters increased. Kinetic data for CR dye adsorption onto CCAC were best represented by the pseudo second-order kinetic model. Four different isotherms namely Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich models were used to test the adsorption data. It fitted the Langmuir isotherm model most. Thermodynamic parameters such as ΔH⁰, ΔS⁰, and ΔG⁰ were evaluated. The adsorption process was found to be exothermic and spontaneous. The study shows that CCAC is an effective adsorbent for the adsorption of CR dye from aqueous solution.     

Interaction of poly(vinylpyrrolidone) with methyl orange and its homologs in aqueous solution over the temperature range 60–90°c

The binding of methyl orange, ethyl orange, propyl orange, and butyl orange by poly(vinylpyrrolidone) has been examined by a technique of equilibrium dialysis over a high temperature range (60–90°C). The first binding constants and the thermodynamic parameters in the course of the binding were evaluated. The results obtained at these temperatures were compared to those at lower ones (5–35°C) described previously in order to estimate the contribution of hydrophobic bonds to the binding. It was found that at the 60–90°C range complex formation between the dye and the macromolecule is associated with an exothermic enthalpy change and a positive entropy change. The enthalpy and entropy changes of the binding are of the order of ?4.5 kcal/mole and 6 eu, respectively, for each dye measured. Thus the binding is mainly enthalpy-controlled. Furthermore the effect of the alkyl chain length of the dye on both the ΔH° and ΔS° values is not pronounced. Also temperature dependences of the ΔH° and ΔS° terms were not observed. All these observations in the higher temperature range can be explained as a result of the disruption of water structure in the binding environment and hence a decrease in hydrophobic bond formation between the dye and the polymer.     

Thermodynamic parameters related to the specific adsorption of iodide ion on the mercury electrode

The thermodynamic functions for the specific adsorption of the iodide ion on mercury have been determined from capacity measurements at 5°C, 25°C and 45°C. The experimental values of the standard electrochemical free energy, enthalphy and entropy of adsorption at zero charge, Δ$\text{G}$⁰_I^?, Δ$\text{H}$⁰_I^?, and Δ$\text{S}$⁰_I^?, are in good agreement with previous values for chloride and thiocyanate ion adsorption. They show that most of the free energy change comes from the entropy change, suggesting that the structural contributions play an important role in the ion-specific adsorption. The thermodynamic functions are compared with the values calculated using the Andersen—Bockris model.     

Thermodynamic studies of hydrogen iodide in dioxane-water mixtures from electromotive force measurements

The standard potentials of the silver-silver iodide electrode were measured in 10,20,30 and 40% (w/w) dioxane-water mixtures at 15,25,35 and 45°C. These values have been used to determine the thermodynamic quantities ΔG_t°, ΔS_t°, ΔH_t° for the transfer of H⁺I^? from water to various dioxane-water mixtures. The ionic ΔG_t° values for H⁺, Cl^?, Br^? and I^? are determined using Feakins method. The chemical and electrical contributions of ΔG_t° are also calculated using the method proposed by Roy and co-workers. The significance of these thermodynamic functions is discussed in relation to the acid—base character of the solvents.     

Quartzite an efficient adsorbent for the removal of anionic and cationic dyes from aqueous solutions

Quartzite obtained from local source was investigated for the removal of anionic dye congo red (CR) and cationic dye malachite green (MG) as an adsorbent from aqueous solution in batch experiment. The adsorption process was studied as a function of dye concentration, contact time, pH and temperature. Adsorption process was described well by Langmuir and Freundlich isotherms. The adsorption capacity remained 666.7 mg/g for CR dye and 348.125 mg/g for MG dye. Data was analyzed thermodynamically, ΔH⁰ and ΔG⁰ values proved that adsorption of CR and MG is an endothermic and spontaneous process. Adsorption data fitted best in the pseudo-first order kinetic model. The adsorption data proved that quartzite exhibits the best adsorption capacity and can be utilized for the removal of anionic and cationic dyes.