Insights into aqueous carbofuran removal by modified and non-modified rice husk biochars

Biochar has been considered as a potential sorbent for removal of frequently detected pesticides in water. In the present study, modified and non-modified rice husk biochars were used for aqueous carbofuran removal. Rice husk biochars were produced at 300, 500, and 700 °C in slow pyrolysis and further exposed to steam activation. Biochars were physicochemically characterized using proximate, ultimate, FTIR methods and used to examine equilibrium and dynamic adsorption of carbofuran. Increasing pyrolysis temperature led to a decrease of biochar yield and increase of porosity, surface area, and adsorption capacities which were further enhanced by steam activation. Carbofuran adsorption was pH-dependant, and the maximum (161 mg g^?1) occurred in the vicinity of pH 5, on steam-activated biochar produced at 700 °C. Freundlich model best fitted the sorption equilibrium data. Both chemisorption and physisorption interactions on heterogeneous adsorbent surface may involve in carbofuran adsorption. Langmuir kinetics could be applied to describe carbofuran adsorption in a fixed bed. A higher carbofuran volume was treated in a column bed by a steam-activated biochar versus non-activated biochars. Overall, steam-activated rice husk biochar can be highlighted as a promising low-cost sustainable material for aqueous carbofuran removal.     

Adsorption characteristics of Cu(II) from aqueous solution onto biochar derived from swine manure

The purpose of this study was to investigate adsorption characteristic of swine manure biochars pyrolyzed at 400 °C and 700 °C for the removal of Cu(II) ions from aqueous solutions. The biochars were characterized using BET surface area, Fourier transform infrared spectroscopy (FTIR), zeta potential, scanning electron microscopy/energy dispersive spectrometer (SEM–EDS), and X-ray diffraction (XRD). The adsorption of Cu(II) ions by batch method was carried out and the optimum conditions were investigated. The adsorption processes of these biochars are well described by a pseudo-second-order kinetic model, and the adsorption isotherm closely fitted the Sips model. Thermodynamic analysis suggested that the adsorption was endothermic. The maximum Cu(II) adsorption capacities of biochars derived from fresh and composted swine manure at 400 °C were 17.71 and 21.94 mg g^?1, respectively, which were higher than those at 700 °C. XRD patterns indicated that the silicate and phosphate particles within the biochars served as adsorption sites for Cu(II). The removal of Cu(II) ions from industrial effluent indicated that the fresh swine manure biochar pyrolyzed at 400 °C can be considered as an effective adsorbent.     

Properties of biochars from conventional and alternative feedstocks and their suitability for metal immobilization in industrial soil

In contaminated soils, excessive concentrations of metals and their high mobility pose a serious environmental risk. A suitable soil amendment can minimize the negative effect of metals in soil. This study investigated the effect of different biochars on metal (Cu, Pb, Zn) immobilization in industrial soil. Biochars produced at 300 and 600 °C from conventional (MS, maize silage; WP, wooden pellets) and alternative (SC, sewage sludge compost; DR, digestate residue) feedstocks were used as soil amendments at a dosage of 10 % (w/w). The type of feedstock and pyrolysis temperature affected the properties of the biochars and their ability to immobilize metal in soil. Compared to production at 300 °C, all biochars produced at 600 °C had higher pH (6.2–10.7), content of ash (7.2–69.0 %) and fixed carbon (21.1–56.7 %), but lower content of volatile matter (9.7–37.2 %). All biochars except DR biochar had lower dissolved organic carbon (DOC) content (1.4–2.3 g C/L) when made at 600 °C. Only MS and SC biochars had higher cation exchange capacity (25.2 and 44.7 cmol/kg, respectively) after charring at 600 °C. All biochars contained low concentrations of Cd, Cu, Ni, Pb and Zn; Cd was volatilized to the greatest extent during pyrolysis. Based on FTIR analysis and molar ratios of H/C and O/C, biochars had a greater degree of carbonization and aromaticity after charring at 600 °C. The efficiency of the biochars in metal immobilization depended mainly on their pH, ash content, and concentration of DOC. SC and DR biochars were more effective for Cu and Zn immobilization than MS and WP biochars, which makes them attractive options for large-scale soil amendment.     

Effect of Pinus radiata derived biochars on soil sorption and desorption of phenanthrene

Biochars are anthropogenic carbonaceous sorbent and their influences on the sorption of environmental contaminants need to be characterized. Here we evaluated the effect of Pinus radiata derived biochars on soil sorption and desorption of phenanthrene. Two biochars separately produced at 350 °C and 700 °C and three soils were tested. Biochar amendment generally enhanced the soil sorption of phenanthrene. The biochar produced at 700 °C generally showed a greater ability at enhancing a soil’s sorption ability than that prepared at 350 °C. The single-step desorption measurement showed an apparent hysteresis in biochar-amended soils. After 28 d equilibration, the sorptive capacity of biochar-amended soil (with an organic carbon content of 0.16%) significantly decreased. This study clearly suggested that biochar application enhanced soil sorption of hydrophobic organic compounds, but the magnitude of enhancement depended on the preparation of biochars, the indigenous soil organic carbon levels, and the contact time between soil and biochar.     

Pyrolysis temperature influences ameliorating effects of biochars on acidic soil

The biochars were prepared from straws of canola, corn, soybean, and peanut at different temperatures of 300, 500, and 700 °C by means of oxygen-limited pyrolysis. Amelioration effects of these biochars on an acidic Ultisol were investigated with incubation experiments, and application rate of biochars was 10 g/kg. The incorporation of these biochars induced the increase in soil pH, soil exchangeable base cations, base saturation, and cation exchange capacity and the decrease in soil exchangeable acidity and exchangeable Al. The ameliorating effects of biochars on acidic soil increased with increase in their pyrolysis temperature. The contribution of oxygen-containing functional groups on the biochars to their ameliorating effects on the acidic soil decreased with the rise in pyrolysis temperature, while the contribution from carbonates in the biochars changed oppositely. The incorporation of the biochars led to the decrease in soil reactive Al extracted by 0.5 mol/L CuCl₂, and the content of reactive Al was decreased with the increase in pyrolysis temperature of incorporated biochars. The biochars generated at 300 °C increased soil organically complexed Al due to ample quantity of oxygen-containing functional groups such as carboxylic and phenolic groups on the biochars, while the biochars generated at 500 and 700 °C accelerated the transformation of soil exchangeable Al to hydroxyl-Al polymers due to hydrolysis of Al at higher pH. Therefore, the crop straw-derived biochars can be used as amendments for acidic soils and the biochars generated at relatively high temperature have great ameliorating effects on the soils.     

Effects of production conditions on yield and physicochemical properties of biochars produced from rice husk and oil palm empty fruit bunches

Biochar is the bio-solid material produced by pyrolysis. The biochar properties are controlled by feedstock and pyrolysis variables. In this study, the impacts of these production variables on biochar yield and physicochemical properties including pH, cation exchange capacity (CEC), total organic carbon (TOC) content, surface area, and pore volume and size were investigated. Rice husk (RH) and oil palm empty fruit bunches (EFB) were used as biomass. The biochars were produced at temperature range of 300 to 700 °C, heating rate of 3 to 10 °C/min and retention time of 1 to 3 h. The pyrolysis conditions were optimized using response surface methodology (RSM) technique to maximize the values of the responses. Analysis of variance (ANOVA) of the results demonstrated that the data fitted well to the linear and quadratic equations. Temperature was found to be the most effective parameter on the responses followed by retention time and heating rate, sequentially. CEC, TOC, surface area, and pore characteristics were evaluated as biochar properties determining their sorption potential. The optimum conditions for the maximum values of the properties were temperatures of 700 and 493.44 °C and time of 3 and 1 h for RH and EFB biochars, respectively. Heating rate at 3 °C/min was found to be the best rate for both biochars. The structure of EFB biomass was more sensitive to heating than rice husk. The biomass type and the production variables were demonstrated as the direct effective factors on biochar yield and physicochemical properties.     

Effect of wheat and rice straw biochars on pyrazosulfuron-ethyl sorption and persistence in a sandy loam soil

The objective of this research was to investigate the effect of wheat and rice biochars on pyrazosulfuron-ethyl sorption in a sandy loam soil. Pyrazosulfuron-ethyl was poorly sorbed in the soil (3.5–8.6%) but biochar amendment increased the herbicide adsorption, and the effect varied with the nature of the feedstock and pyrolysis temperature. Biochars prepared at 600°C were more effective in adsorbing pyrazosulfuron-ethyl than biochars prepared at 400°C. Rice biochars were better than wheat biochars, and higher herbicide adsorption was attributed to the biochar surface area/porosity. The Freundlich constant 1/n suggested nonlinear isotherms, and nonlinearlity increased with increase in the level of biochar amendment. Desorption results suggested sorption of pyrazosulfuron-ethyl was partially irreversible, and the irreversibility increased with increase in the level of biochar. Both sorption and desorption of pyrazosulfuron-ethyl correlated well with the content of biochars. The free energy change (ΔG) indicated that the pyrazosulfuron-ethyl sorption process was exothermic, spontaneous and physical in nature. Persistence studies indicated that biochar (0.5%) amendment did not have significant effect on herbicide degradation, and its half-life values in the control, 0.5% WBC600- and RBC600-amended rice planted soils were 7, 8.6, and 10.4 days, respectively.     

Characterization of contaminants and evaluation of the suitability for land application of maize and sludge biochars

Prior to the application of biochar as an agricultural improver, attention should be paid to the potential introduction of toxicants and resulting unintended impacts on the environment. In the present study, the concentrations of polycyclic aromatic hydrocarbons (PAHs), heavy metals, and mineral elements were determined in maize and sludge biochars produced at 100 °C increments between 200 and 700 °C. The concentration ranges of total PAHs were 358–5,136 μg kg^?1 in maize biochars and 179–70,385 μg kg^?1 in sludge biochars. The total heavy metals were detected at the following concentrations (mg kg^?1): Cu, 20.4–56.7; Zn, 59.7–133; Pb, 1.44–3.50; Cd, <0.014; Cr, 8.08–21.4; Ni, 4.38–9.82 in maize biochars and Cu, 149–202; Zn, 735–986; Pb, 54.7–74.2; Cd, 1.06–1.38; Cr, 180–247; Ni, 41.1–56.1 in sludge biochars. The total concentrations of PAHs and heavy metals in all maize biochars and most sludge biochars were below the control standards of sludge for agricultural use in China, the USA, and Europe. The leachable Mn concentrations in sludge biochars produced at below 500 °C exceeded the groundwater or drinking water standards of these countries. Overall, all the maize biochars were acceptable for land application, but sludge biochars generated at temperatures between 200 and 500 °C were unsuitable for application as soil amendments due to their potential adverse effects on soil and groundwater quality.     

Effect of biochars on adsorption of Cu(II), Pb(II) and Cd(II) by three variable charge soils from southern China

The purpose of this study is to compare the relative contribution of different mechanisms to the enhanced adsorption of Cu(II), Pb(II) and Cd(II) by variable charge soils due to incorporation of biochars derived from crop straws. The biochars were prepared from the straws of canola and peanut using an oxygen-limited pyrolysis method at 350 °C. The effect of biochars on adsorption and desorption of Cu(II), Pb(II) and Cd(II) by and from three variable charge soils from southern China was investigated with batch experiments. Based on the desorption of pre-adsorbed heavy metals, the electrostatic and non-electrostatic adsorptions were separated. EDTA was used to replace the heavy metals complexed with biochars and to evaluate the complexing ability of the biochars with the metals. The incorporation of biochars increased the adsorption of Cu(II), Pb(II) and Cd(II) by the soil; peanut straw char induced a greater increase in the adsorption of the three metals. The increased percentage of Cd(II) adsorption induced by biochars was much greater than that for the adsorption of Cu(II) and Pb(II). Cu(II) adsorption on three variable charge soils was enhanced by the two biochars mainly through a non-electrostatic mechanism, while both electrostatic and non-electrostatic mechanisms contributed to the enhanced adsorption of Pb(II) and Cd(II) due to the biochars. Peanut straw char had a greater specific adsorption capacity than canola straw char and thus induced more non-electrostatic adsorption of Cu(II), Pb(II) and Cd(II) by the soils than did the canola straw char. The complexing ability of the biochars with Cu(II) and Pb(II) was much stronger than that with Cd(II) and thus induced more specific adsorption of Cu(II) and Pb(II) by the soils than that of Cd(II). Biochars increased heavy metal adsorption by the variable charge soils through electrostatic and non-electrostatic mechanisms, and the relative contribution of the two mechanisms varied with metals and biochars.     

Value of biochars from Miscanthus x giganteus cultivated on contaminated soils to decrease the availability of metals in multicontaminated aqueous solutions

The objective of this study was to evaluate the sorption efficiency of eight biochars, made from Miscanthus x giganteus cultivated on contaminated agricultural soil, in aqueous solutions contaminated with metals alone or mixed with polycyclic aromatic hydrocarbons. These biochars were produced in different pyrolysis conditions (temperature, 400/600 °C; heating rate, 5/10 °C min⁻¹; duration, 45/90 min) and compared with an uncontaminated commercialized biochar made of wood. The physicochemical characterization of the Miscanthus biochars confirmed the impact of the pyrolysis on the biochar parameters with substantial differences between the biochars in terms of pH, cation exchange capacity, and specific surface area. The sorption experiment showed higher sorption efficiency of Cd, Pb, and Zn for the Miscanthus biochars produced at 600 °C compared with the biochars produced at 400 °C when the aqueous solutions were mono- or multicontaminated. Furthermore, the desorption study showed that the sorption process was largely irreversible. Therefore, the high sorption capacity of Miscanthus biochars and the low sorption reversibility confirmed that these biochars are a suitable sorbent for metals.

     

Sorption of simazine to corn straw biochars prepared at different pyrolytic temperatures

Simazine sorption to corn straw biochars prepared at various temperatures (100-600 °C) was examined to understand its sorption behavior as influenced by characteristics of biochars. Biochars were characterized via elemental analysis, BET-N₂ surface area (SA), FTIR and ¹³C NMR. Freundlich and dual-mode models described sorption isotherms well. Positive correlation between log K_oc values and aromatic C contents and negative correlation between log K_oc values and (O + N)/C ratios indicate aromatic-rich biochars have high binding affinity to simazine (charge transfer (π-π*) interactions) and hydrophobic binding may overwhelm H-bonding, respectively. Dual-mode model results suggest adsorption contribution to total sorption increases with carbonization degree. Positive correlation between amounts of adsorption (Q_ad) and SA indicates pore-filling mechanism. Comparison between our results and those obtained with other sorbents indicates corn straw biochars produced at higher temperature can effectively retain simazine. These observations will be helpful for designing biochars as engineered sorbents to remove triazine herbicides.     

Effect of pH on surface characteristics of switchgrass-derived biochars produced by fast pyrolysis

Surface properties of switchgrass-derived biochars produced at fast pyrolysis temperatures of 450, 600 and 800 °C were characterized at different solution pHs in order to determine the structural and chemical changes of artificially-weathered biochars when incorporated into soil. As biochars were acidified from pH 7 to 3, crystalline minerals dissolved slowly releasing nutrients; however, residual minerals were still detected in biochars produced at higher pyrolysis temperatures after pH treatment. Moreover, the amount of exchangeable bases and other inorganic compounds released from the biochars increased when pH decreased. As minerals dissolved from the biochars, total surface area and pore volume were found to increase. Surface functional groups and water vapor adsorption capacity at 0.8 P/P_o also increased, whereas the potential CEC of biochars decreased due to the replacement of exchangeable sites by hydrogen ion. Therefore, during the aging process, it is predicted that soil-incorporated biochars will slowly release nutrients with changes in surface functionality and porosity, which are expected to enhance water holding capacity of soil and provide a beneficial habitat for microbial colonization.     

Efficient removal of uranium(VI) from aqueous systems by heat-treated carbon microspheres

In this study, uranium(VI) was successfully removed from aqueous solutions using heat-treated carbon microspheres based on a batch adsorption technique. Influence of the parameters, such as solution pH, contact time, initial uranium(VI) concentration, and temperature on the removal efficiency have been investigated in detail. The results reveal that the maximum adsorption capacity of the heat-treated carbon microspheres toward uranium(VI) is 92.08 mg g^?1, displaying a high efficiency for the removal of uranium(VI) from aqueous solution. The experimental data are analyzed using sorption kinetic models. It is revealed that the process obey the pseudo-second-order kinetic model, the determining step might be chemical sorption. The thermodynamic parameters, such as ΔH°, ΔS°, and ΔG° show that the process is endothermic and spontaneous. This work provides an efficient, fast, and convenient approach for the removal of uranium(VI) from aqueous solutions.     

Thermodynamic and kinetic studies of As(V) removal from water by zirconium oxide-coated marine sand

Arsenic contamination of groundwater is a major threat to human beings globally. Among various methods available for arsenic removal, adsorption is fast, inexpensive, selective, accurate, reproducible and eco-friendly in nature. The present paper describes removal of arsenate from water on zirconium oxide-coated sand (novel adsorbent). In the present work, zirconium oxide-coated sand was prepared and characterised by infrared and X-ray diffraction techniques. Batch experiments were performed to optimise different adsorption parameters such as initial arsenate concentration (100–1,000 μg/L), dose (1–8 g/L), pH of the solution (2–14), contact time (15–150 min.), and temperature (20, 30, 35 and 40 °C). The experimental data were analysed by Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. Furthermore, thermodynamic and kinetic parameters were evaluated to know the mode of adsorption between ZrOCMS and As(V). The maximum removal of arsenic, 97 %, was achieved at initial arsenic concentration of 200 μg/L, after 75 min at dosage of 5.0 g/L, pH?7.0 and 27?±?2 °C. For 600 μg/L concentration, the maximum Langmuir monolayer adsorption capacity was found to be 270 μg/g at 35 °C. Kinetic modelling data indicated that adsorption process followed pseudo-second-order kinetics. The mechanism is controlled by liquid film diffusion model. Thermodynamic parameter, ΔH°, was ?57.782, while the values of ΔG° were ?9.460, ?12.183, ?13.343 and ?13.905 kJ/mol at 20, 30, 35 and 40 °C, respectively, suggesting exothermic and spontaneous nature of the process. The change in entropy, ΔS°?=??0.23 kJ/mol indicated that the entropy decreased due to adsorption of arsenate ion onto the solid adsorbent. The results indicated that the reported zirconium oxide-coated marine sand (ZrOCMS) was good adsorbent with 97 % removal capacity at 200 μg/L concentration. It is interesting to note that the permissible limit of arsenic as per World Health Organization is 10 μg/L, and in real situation, this low concentration can be achieved through this adsorbent. Besides, the adsorption capacity showed that this adsorbent may be used for the removal of arsenic from any natural water resource.     

Biosorption and biodegradation of trichloroethylene by acclimated activated sludge

The biosorprion and biodegradation of trichloroethylene (TCE) was investigated. The experimental results showed that at 25°C the adsorption equilibrium of TCE at concentrations from 10 mg/L to 200 mg/L could be described by the Freundlich isotherm. Adsorption could complete within 15 min. Results indicated that glucose could serve as a co-substrate and enhance TCE biodegradation through co-metabolism. The TCE biodegradation conformed to the first-order reaction kinetic, and the rate constant was 0.3212 day⁻¹ at 25°C. In addition, results also indicated that TCE could serve as the sole substrate and be biodegraded under aerobic condition. No intermediate products such as DCE and VC were accumulated during the degradation.     

Studies on the removal of nickel from aqueous solutions using modified riverbed sand

This paper highlights the utility of riverbed sand (RS) for the treatment of Ni(II) from aqueous solutions. For enhancement of removal efficiency, RS was modified by simple methods. Raw and modified sands were characterized by scanning electron microscope (SEM), Energy Dispersive Spectroscopy (EDS), and Fourier Transform Infrared Spectroscopy (FTIR) to investigate the effect of modifying the surface of RS. For optimization of various important process parameters, batch mode experiments were conducted by choosing specific parameters such as pH (4.0–8.0), adsorbent dose (1.0–2.0 g), and metal ion concentrations (5–15 mg/L). Removal efficiency decreased from 68.76 to 54.09 % by increasing the concentration of Ni(II) in solution from 5 to 15 mg/L. Removal was found to be highly dependent on pH of aqueous solutions and maximum removal was achieved at pH 8.0. The process of removal follows first-order kinetics, and the value of rate constant was found to be 0.048 min^?1 at 5 mg/L and 25 °C. Value of intraparticle diffusion rate constant (k _id) was found to be 0.021 mg/g min^1/2 at 25 °C. Removal of Ni(II) decreased by increasing temperature which confirms exothermic nature of this system. For equilibrium studies, adsorption data was analyzed by Freundlich and Langmuir models. Thermodynamic studies for the present process were performed by determining the values of ΔG°, ΔH°, and ΔS°. Negative value of ?H° further confirms the exothermic nature of the removal process. The results of the present investigation indicate that modified riverbed sand (MRS) has high potential for the removal of Ni(II) from aqueous solutions, and resultant data can serve as baseline data for designing treatment plants at industrial scale.     

Biosorption characteristics of Bacillus gibsonii S-2 waste biomass for removal of lead (II) from aqueous solution

Lead (II) has been as one of the most toxic heavy metals because it is associated with many health hazards. Therefore, people are increasingly interested in discovering new methods for effectively and economically scavenging lead (II) from the aquatic system. Recent studies demonstrate biosorption is a promising technology for the treatment of pollutant streams. To apply these techniques, suitable adsorbents with high efficiency and low cost are demanded. The waste biomass of Bacillus gibsonii S-2 biosorbent was used as low-cost biosorbent to remove metallic cations lead (II) from aqueous solution. To optimize the maximum removal efficiency, the effect of pH and temperature on the adsorption process was studied. The isotherm models, kinetic models and thermodynamic parameters were analysed to describe the adsorptive behaviour of B. gibsonii S-2 biosorbent. The mechanisms of lead (II) biosorption were also analysed by FTIR and EDX. The results showed that the optimum pH values for the biosorption at three different temperatures, i.e. 20, 30 and 40 °C, were determined as 4. The equilibrium data were well fitted to Langmuir model, with the maximum lead (II) uptake capacities of 333.3 mg?g^?1. The kinetics for lead (II) biosorption followed the pseudo-second-order kinetic equation. The thermodynamic data showed that the biosorption process were endothermic (?G?<?0), spontaneous (?H?>?0) and irreversible (?S?>?0). The mechanism of lead (II) biosorption by the waste biomass of B. gibsonii S-2 biosorbent could be a combination of ion exchange and complexation with the functional groups present on the biosorbent surface. The application of the waste biomass of B. gibsonii S-2 for lead (II) adsorption, characterized with higher lead (II) sorption capacity and lower cost, may find potential application in industrial wastewater treatment.     

Removal of 2, 4‐D from aqueous solution by the adsorbents from spent bleaching earth

Abstract

The removal of 2, 4‐D (2, 4‐ dichlorophenoxyacetic acid) from aqueous solutions by activated spent bleaching earths (SBE) was studied at 20 °C. Experiments were performed as a function of time, initial concentration, dose and particle size of the adsorbent. The Langmuir and Freundlich adsorption equations were fitted by the adsorption data obtained. The values of Langmuir and Freundlich constants were determined. The adsorption kinetic was found to follow Lagergren equation. Both the boundary layer and intraparticle diffusion played important roles in the adsorption rate of 2, 4‐D. As the size of the adsorbent increased, the time to reach equilibrium increased but adsorption capacity decreased.     

Kinetic, equilibrium isotherm and thermodynamic studies of Cr(VI) adsorption onto low-cost adsorbent developed from peanut shell activated with phosphoric acid

A particular agricultural waste, peanut shell, has been used as precursor for activated carbon production by chemical activation with H₃PO₄. Unoxidized activated carbon was prepared in nitrogen atmosphere which was then heated in air at a desired temperature to get oxidized activated carbon. The prepared carbons were characterized for surface area, surface morphology, and pore volume and utilized for the removal of Cr(VI) from aqueous solution. Batch mode experiments were conducted to study the effects of pH, contact time, particle size, adsorbent dose, initial concentration of adsorbate, and temperature on the adsorption of Cr(VI). Cr(VI) adsorption was significantly dependent on solution pH, and the optimum adsorption was observed at pH 2. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to analyze the kinetic data obtained at different initial Cr(VI) concentrations. The adsorption kinetic data were described very well by the pseudo-second-order model. Equilibrium isotherm data were analyzed by the Langmuir, Freundlich, and Temkin models. The results showed that the Langmuir adsorption isotherm model fitted the data better in the temperature range studied. The adsorption capacity which was found to increase with temperature showed the endothermic nature of Cr(VI) adsorption. The thermodynamic parameters, such as Gibb’s Free energy change (ΔG°), standard enthalpy change (ΔH°), and standard entropy change (ΔS°) were evaluated.