Equilibrium, kinetic and thermodynamic studies on the adsorption of m-cresol onto micro- and mesoporous carbon

Investigations were conducted in batch mode to study the adsorption behaviour of m-cresol on a porous carbon prepared from rice husk (RHAC) by varying the parameters such as agitation time, m-cresol concentration (50-300 mg/l), pH (2.5-10) and temperature (293-323 K). Studies showed that the adsorption decreased with increase in pH and temperature. The isotherm data were fitted to Langmuir, Freundlich, and Dubinin-Radushkevic (D-R) models. The kinetic models such as pseudo-first-order, pseudo-second-order and intraparticle diffusion models were selected to understand the reaction pathways and mechanism of adsorption process. The thermodynamic equilibrium coefficients obtained at different temperatures were used to evaluate the thermodynamic constants DeltaG degrees, DeltaH degrees and DeltaS degrees. The sorption process was found to be exothermic in nature (DeltaH degrees : -23.46 to -25.40 kJ/mol) with a decrease in entropy (DeltaS degrees: -19.44 to -35.87 J/(mol K)). The negative value of Gibbs free energy, DeltaG degrees indicates that the adsorption occurs via a spontaneous process. The decrease in the value of -DeltaG degrees from 17.70 to 13.54 kJ/mol with increase in pH and temperature indicates that the adsorption of m-cresol onto activated carbon is less favourable at higher temperature and pH range. The influence of mesopore and a possible mechanism of adsorption is also suggested.     

Biosorption of copper ions from aqueous solution by Codium vermilara: Optimization,kinetic, isotherm and thermodynamic studies

In this investigation, the efficiency of Codium vermilara for copper ions removal from aqueous solution was studied. Central Composite Design has been used for the Response Surface Methodology and has been found to be an effective method for investigating the influences of various variables and their interactions on the efficiency of Cu²⁺ ions removal. The interactive impacts of four variables: algal dose, pH, initial concentrations of copper and contact time on the copper removal efficiency were assessed. Algal dose 0.75 g/L, pH 5.28, contact time 70.51 min, and copper concentration 48.75 mg/L were found to be the conditions of optimum biosorption. The efficiency of copper removal was found to be 85.5% under these optimum conditions. Copper removal on the biomass of C. vermilara followed well the kinetics of pseudo-first-order, Elvoish and Intraparticle diffusion. Compared to the other models, Dubinin-Radushkevich isotherm best suited the experimental data revealing that the adsorption mechanism was physical adsorption. Thermodynamic parameters exhibited non-spontaneous, randomness and endothermic biosorption of Cu²⁺ ions. Additionally, the biosorbent characterization was estimated by scanning electron microscopy and Fourier transform infrared analysis. Thus, C. vermilara could be used as possible biosorbent for removing heavy metals and other pollutants from the environment.     

Equilibrium, kinetic and thermodynamic studies on the adsorption of phenol onto chitin

The adsorption of phenol onto chitin, a naturally occurring material was studied as a function of initial pH, temperature and initial phenol concentration. The highest phenol adsorption capacity was determined as 21.5 mgg(-1) for 300 mgdm(-3) initial phenol concentration at pH 1.0 and 40 degrees C. Adsorption data were well described by the Freundlich Model, although they could be modeled by the Langmuir equation. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The pseudo-second-order kinetic model provided the best correlation of the experimental data compared to the pseudo-first-order model. The thermodynamic constants of the adsorption process; DeltaG degrees , DeltaH degrees and DeltaS degrees were evaluated as -19.4 kJmol(-1) (at 40 degrees C), 10.2 kJmol(-1) and 0.093 kJmol(-1)K(-1), respectively. These showed that adsorption of phenol on chitin was endothermic and spontaneous.     

Equilibrium,kinetic and thermodynamic studies on the adsorption of phenol onto graphene

Graphene, a new member of carbon family, has been prepared, characterized and used as adsorbent to remove phenol from aqueous solution. The effect parameters including pH, dosage, contact time, and temperature on the adsorption properties of phenol onto graphene were investigated. The results showed that the maximum adsorption capacity can reach 28.26 mg/g at the conditions of initial phenol concentration of 50 mg/L, pH 6.3 and 285 K. Adsorption data were well described by both Freundlich and Langmuir models. The kinetic study illustrated that the adsorption of phenol onto graphene fit the pseudo second-order model. The thermodynamic parameters indicated that the adsorption of phenol onto graphene was endothermic and spontaneous.     

Comparative study of the biosorption of Pb(II), Ni(II) and Cr(VI) ions onto S. cerevisiae: determination of biosorption heats

In this study, the biosorption of Pb(II), Ni(II) and Cr(VI) ions onto inactive Saccharomyces cerevisiae was investigated as a function of initial pH, initial metal ion concentration and temperature. The Langmuir model was applied to experimental equilibrium data of Pb(II), Ni(II) and Cr(VI) biosorption depending on temperature and the maximum metal ions uptake at optimum biosorption temperature of 25 °C, were found to be 270.3, 46.3 and 32.6 mg g⁻¹, respectively. Using the Langmuir constant, b values obtained at different temperatures, the biosorption heats of Pb(II), Ni(II) and Cr(VI) were determined as −1.125, −1.912 and −2.89 kcal mol⁻¹, respectively. The results indicated that the biosorption of Pb(II), Ni(II) and Cr(VI) ions to S. cerevisiae is by the physical adsorption and has an exothermic nature.     

Biosorption of nickel and copper onto treated alga (Undaria pinnatifida): application of isotherm and kinetic models

Biosorption of nickel and copper ions from aqueous solution onto treated alga biomass Undaria pinnatifida has been studied and the Langmuir, Freundlich and Temkine equilibrium isotherms, pseudo-first-order, pseudo-second-order and intra-particle diffusion kinetic model were determined respectively. Within the test range (initial concentration 5–50 mg/L, biosorption doze 0.1–0.5 g, pH 3–7), biosorption performance for metal ions showed an increase in specific metal uptake capacity with an increasing in initial ions concentration and decreasing in biosorbent doze. The optimized condition of pH value for nickel and copper is 4.7 and 4.0, respectively, while contact time is about 100 min. At equilibrium, the maximum total uptake by U. pinnatifida was 24.71 mg/g for nickel and 38.82 mg/g for copper. The results for nickel and copper fit well to the Langmuir and the Temkin isotherm, respectively. Pseudo-second-order model described well the sorption kinetic of nickel and copper ions in comparison to pseudo-first-order and intra-particle diffusion kinetic model.     

Equilibrium, kinetic and thermodynamic studies of adsorption of fluoride onto plaster of Paris

Batch sorption system using plaster of Paris as an adsorbent was investigated to remove fluoride ions from aqueous solutions. The system variables studied include initial concentration of the sorbate, agitation time, adsorbent dose, pH, co-ions and temperature. The experimental data fitted well to the Freundlich and Langmuir isotherms. Thermodynamic parameters such as DeltaH degrees , DeltaS degrees and DeltaG degrees were calculated indicating that the adsorption was a spontaneous and exothermic. Kinetic studies reveal that the adsorption is first order. A mechanism involving three stages (external surface adsorption, intraparticle diffusion and final equilibrium) has been proposed for the adsorption of F(-) onto plaster of Paris. XRD patterns of the adsorbent were recorded to get a better in sight into the mechanism of adsorption process.     

Adsorption of 4-chlorophenol from aqueous solutions by xad-4 resin: isotherm, kinetic, and thermodynamic analysis

Removal of 4-chlorophenol (4-CP) from synthetic aqueous solutions through adsorption on Amberlite XAD-4 resin, a non-ionic macroreticular resins, under batch equilibrium experimental conditions at 298, 308 and 318K was investigated. It is necessary to propose a suitable model to a better understanding on the mechanism of 4-CP adsorption. For this purpose, Langmiur, Freundlich, Toth, and Redlich-Peterson (RP) isotherm models were compared. The two and three parameters in the adopted adsorption isotherm models were determined by the help of MATLAB package program. It was determined that best fitted adsorption isotherm models were obtained to be in the order: Redlich-Peterson>Langmuir>Toth>Freundlich isotherms. The pseudo-second-order kinetic model provided the best correlation to the experimental results. Results of the intra-particle diffusion model show that the pore diffusion is not the only rate limiting step. The lower correlation of the data to the Bangham's equation also represents that the diffusion of the adsorbate into pores of the sorbent is not the only rate-controlling step. The thermodynamic constants of adsorption phenomena; DeltaG degrees, DeltaH degrees, and DeltaS degrees were found as -4.17 (at 298K) kJ/mol, -42.01 kJ/mol, and -0.127 kJ/(mol K), respectively. The results showed that adsorption of 4-CP on Amberlite XAD-4, a nonionic polymeric resin was exothermic and spontaneous.     

Carbonate effects and pH-dependence of uranium sorption onto bacteriogenic iron oxides: kinetic and equilibrium studies

The removal of U(VI) from groundwaters by adsorption onto bacteriogenic iron oxides (BIOS) has been investigated under batch mode. The adsorbent dosage, the uranium concentration, the concentration of carbonate and the use of a real groundwater spiked with uranium comprised the examined parameters. In addition, the effect of pH was examined in two different water matrixes, i.e., in distilled water and in real groundwater. Equilibrium studies were carried out to determine the maximum adsorption capacity of BIOS and the data correlated well with the Langmuir and Freundlich models. The presence of carbonate affected adversely the adsorption of U(VI) onto BIOS. The maximum adsorption capacity of BIOS was 9.25 mg g(-1) at 0.1mM carbonate concentration and decreased to 6.93 mg g(-1) at 0.5mM carbonate concentration, whereas at carbonate concentration of 2mM practically no adsorption occurred. The data were further analyzed using the pseudo-second order kinetic equation, which fitted best the experimental results. The initial adsorption rate (h) was found to increase with decreasing the concentration of carbonate in all cases. When experiments were accomplished in the absence of carbonate, the pH values did not have an effect on the adsorption of U(VI). However, the extent of U(VI) adsorption was strongly pH-dependent when the experiments were carried out in the real groundwater. The maximum adsorption capacity increased sharply as the pH decreased and optimum removal was obtained in the pH range 3.2-4.0, thus bacteriogenic iron oxides can found application in the removal of U(VI) by adsorption from low pH or low carbonate waters.     

Biosorption of zinc from aqueous solution using Azadirachta indica bark: equilibrium and kinetic studies

The removal of zinc ions from aqueous solutions on the biomass of Azadirachta indica bark has been studied by using batch adsorption technique. The biosorption studies were determined as a function of contact time, pH, initial metal ion concentration, average biosorbent size and biosorbent dosage. The equilibrium metal uptake was increased and percentage biosorption was decreased with an increase in the initial concentration and particle size of biosorbent. The maximum zinc biosorption occurred at pH 6 and percentage biosorption increases with increase in the biosorbent dosage. Experimental data obtained were tested with the adsorption models like Langmuir, Freundlich and Redlich-Peterson isotherms. Biosorption isothermal data were well interpreted by Langmuir model with maximum biosorption capacity of 33.49mg/g of zinc ions on A. indica bark biomass and kinetic data were properly fitted with the pseudo-second-order kinetic model.     

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.     

Equilibrium and kinetic studies for the biosorption system of copper(II) ion from aqueous solution using Tectona grandis L.f. leaves powder

The biosorption of copper(II) ions from aqueous solution by Tectona grandis L.f. was studied in a batch adsorption system as a function of pH, metal ion concentration, adsorbent concentration and adsorbent size. The biosorption capacities and rates of copper(II) ions onto T. grandis L.f. were evaluated. The Langmuir, Freundlich, Redlich-Peterson and Temkin adsorption models were applied to describe the isotherms and isotherm constants. Biosorption isothermal data could be well interpreted by the Langmuir model with maximum adsorption capacity of 15.43 mg/g of copper(II) ion on T. grandis L.f. leaves powder. The kinetic experimental data properly correlated with the second-order kinetic model. Various thermodynamic parameters such as deltaG(o), deltaH(o), and deltaS(o) were calculated indicating that this system was a spontaneous and exothermic process.     

Elucidation of the naproxen sodium adsorption onto activated carbon prepared from waste apricot: kinetic, equilibrium and thermodynamic characterization

In this study, activated carbon (WA11Zn5) was prepared from waste apricot, which is waste in apricot plants in Malatya, by chemical activation with ZnCl(2). BET surface area of activated carbon is determined as 1060 m(2)/g. The ability of WA11Zn5, to remove naproxen sodium from effluent solutions by adsorption has been studied. Equilibrium isotherms for the adsorption of naproxen sodium on activated carbon were measured experimentally. Results were analyzed by the Langmiur, Freundlich equation using linearized correlation coefficient at 298 K. The characteristic parameters for each isotherm have been determined. Langmiur equation is found to best represent the equilibrium data for naproxen sodium-WA11Zn5 systems. The monolayer adsorption capacity of WA11Zn5 for naproxen sodium was found to be 106.38 mg/g at 298 K. The process was favorable and spontaneous. The kinetics of adsorption of naproxen sodium have been discussed using three kinetic models, i.e., the pseudo first-order model, the pseudo second-order model, the intraparticle diffusion model. Kinetic parameters and correlation coefficients were determined. It was shown that the pseudo second-order kinetic equation could describe the adsorption kinetics for naproxen sodium onto WA11Zn5. The thermodynamic parameters, such as DeltaG degrees , DeltaS degrees and DeltaH degrees, were calculated. The thermodynamics of naproxen sodium-WA11Zn5 system indicates endothermic process.     

Effect of Aluminum and Silicon on Transformation Induced Plasticity of the TRIP Steel

With the sublattice model, equilibrium compositions of ferrite (a) and austenite (7) phases, as well as the volume percent of austenite (7) at 780℃ in different TRIP steels were calculated. Concentration profiles of carbon, Mn,Al and Si in the steels were also estimated under the lattice fixed frame of reference so as to understand the complex mechanical behavior of TRIP steels after different isothermal bainitic transformation treatments. The effect of Si and Mn on transformation induced plasticity (TRIP) was discussed according to thermodynamic and kinetic analyses. It is recognized that Al also induces phase transformation in the steels but its TRIP effect is not as strong as that of Si.     

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.     

Biosorption of copper (II) onto immobilized cells of Pycnoporus sanguineus from aqueous solution: equilibrium and kinetic studies

The ability of white-rot fungus, Pycnoporus sanguineus to adsorb copper (II) ions from aqueous solution is investigated in a batch system. The live fungus cells were immobilized into Ca-alginate gel to study the influence of pH, initial metal ions concentration, biomass loading and temperature on the biosorption capacity. The optimum uptake of Cu (II) ions was observed at pH 5 with a value of 2.76mg/g. Biosorption equilibrium data were best described by Langmuir isotherm model followed by Redlich-Peterson and Freundlich models, respectively. The biosorption kinetics followed the pseudo-second order and intraparticle diffusion equations. The thermodynamic parameters enthalpy change (10.16kJ/mol) and entropy change (33.78J/molK) were determined from the biosorption equilibrium data. The FTIR analysis showed that OH, NH, CH, CO, COOH and CN groups were involved in the biosorption of Cu (II) ions onto immobilized cells of P. sanguineus. The immobilized cells of P. sanguineus were capable of removing Cu (II) ions from aqueous solution.     

Adsorption of phenol by MMT-CTAB and WPT-CTAB: Equilibrium,kinetic, and thermodynamic study

In this study, the phenol adsorption capacity of cetyltrimethylammonium bromide modified clays (MMT-CTAB) and cetyltrimethylammonium bromide modified pulp tea (WPT-CTAB) were studied. In batch adsorption experiments performed with MMT-CTAB, the effects of parameters such contact time, phenol concentration, pH of solution and adsorbent dosage were investigated. The effect of temperature on phenol adsorption onto MMT-CTAB and WPT-CTAB was examined; equilibrium and thermodynamic studies were completed. The highest phenol removal was found at pH 4.0 for MMT-CTAB and WPT-CTAB. To analyze the kinetics of phenol adsorption onto MMT-CTAB, the pseudo first-order and pseudo second-order kinetic models were applied. The kinetic data fitted better to the pseudo second-order model than the pseudo first-order kinetic model for MMT-CTAB. The characterization of adsorbents in phenol adsorption was clarified with the FTIR technique. Thermodynamic parameters such as ΔH°, ΔS° and ΔG° were calculated for each adsorption process. The adsorption process was found to be exothermic and spontaneous for phenol adsorption by MMT-CTAB and WPT-CTAB. The results were analyzed with the Langmuir, Freundlich, Temkin and Harkins–Jura equations using linearized correlation coefficients at different temperatures. The Langmuir equation was found to best represent the equilibrium data for phenol adsorption onto MMT-CTAB and WPT-CTAB.     

Adsorption of BSA onto hexagonal mesoporous silicate loaded by APTES and tannin: Isotherm,thermodynamic and kinetic studies

In the present study, hexagonal mesoporous silica (HMS) was synthesized and modified by tannic acid as a natural poly-phenol and amine (TA-A-HMS) and was applied for the adsorption of bovine serum albumin (BSA) from aqueous media. To investigate the structure of HMS and TA-A-HMS, SEM, TEM, XRD, BET and FTIR analysis were applied. The effects of pH, adsorbent dosage, contact time and temperature on the BSA adsorption were studied. After modification, BET surface area of HMS was reduced from 885?m²/g to 51?m²/g which confirms the presence of tannin and amine groups that inhibit the adsorption of nitrogen molecules. According to the results of equilibrium data, it is shown that Langmuir isotherm with maximum adsorption capacity of 1000?mg/g is the predominant model and adsorption is mono-layer. Kinetic and thermodynamic studies also reveal that adsorption kinetic followed by pseudo-second order model and the adsorption process is exothermic.     

Equilibrium,kinetic and thermodynamic studies on the adsorption of 2-nitroaniline onto activated carbon prepared from cotton stalk fibre

Activated carbon prepared from cotton stalk fibre has been utilized as an adsorbent for the removal of 2-nitroaniline from aqueous solutions. The influence of adsorbent mass, contact time and temperature on the adsorption was investigated by conducting a series of batch adsorption experiments. The equilibrium data at different temperatures were fitted with the Langmuir, Freundlich, Tempkin, Redlich–Peterson and Langmuir–Freundlich models. The Langmuir–Freundlich isotherm was found to best describe the experimental data. The adsorption amount increased with increasing temperature. The maximum adsorption capacity of 2-nitroaniline was found to be 383 mg/g for initial 2-nitroaniline concentration of 200 mg/L at 45 °C. The kinetic rates were modeled by using the Lagergren-first-order, pseudo-second-order and Elovich models. The pseudo-second-order model was found to explain the adsorption kinetics most effectively. It was also found that the pore diffusion played an important role in the adsorption, and intraparticle diffusion was the rate-limiting step at the first 30 min for the temperatures of 25, 35 and 45 °C. FTIR and ¹³C NMR study revealed that the amino and isocyanate groups present on the surface of the adsorbent were involved in chemical interaction with 2-nitroaniline. The negative change in free energy (ΔG°) and positive change in enthalpy (ΔH°) indicated that the adsorption was a spontaneous and endothermic process.