Thermodynamic Studies Research Articles

Polyethylene microplastics as adsorbent of diazinon in aqueous environments: optimization, and modeling, isotherm, kinetics, and thermodynamic studies

MPs have raised significant public concern due to their role as carriers of organic contaminants in aqueous solutions. DZN is a non-systemic organophosphorus pesticide that poses risks to human and environmental health. This study aimed to investigate the adsorption of DZN onto PE MPs by examining factors such as PE dose, reaction time, pesticide concentration, and pH through experimental runs based on the Box‒Behnken model. According to the Langmuir model, the maximum adsorption capacity of PE for DZN was 0.35 mg/g. The results indicated that the highest adsorption rate of DZN (92%) was observed in distilled water, while the lowest adsorption rate (57%) was observed in municipal wastewater. The ΔH° and ΔS° values were obtained as − 0.16 kJ/mol and 54.41 J/(mol K), respectively. Therefore, regarding negative ΔG° values, it can be concluded that the adsorption of DZN onto PE MPs is an exothermic, highly disordered, and spontaneous process. The findings indicate a reduction in the adsorption rate of DZN as the concentrations of interfering compounds increase. These findings offer understanding of the interaction between MPs and organic contaminants, emphasizing the need for further studies and approaches to reduce their harmful impact on human health and the environment.

Hybrid photocatalytic/photochemical degradation of 1,2-dichlorobenzene: kinetic, thermodynamic, operating cost, synergism and mineralization study

Hybrid photocatalytic/photochemical degradation of 1,2-dichlorobenzene: kinetic, thermodynamic, operating cost, synergism and mineralization study

Evaluating SiO2/Al2O3/poly(acrylic acid-co-glycidyl methacrylate) composite as a novel adsorbent for cobalt(II) radionuclides

Abstract A novel SiO2/Al2O3/poly(acrylic acid-co-glycidyl methacrylate), SiO2/Al2O3/P(AA-co-GMA), composite was synthesized and evaluated for its effectiveness in adsorbing Co(II) ions from aqueous solutions. The composite was analyzed using various techniques including FTIR, SEM, TGA, DTA, and XRD. The composite displays a high specific surface area of 17.451 m2/g, exceeding that of the corresponding copolymer, which measures 0.236 m2/g. Batch adsorption experiments were conducted to investigate the factors influencing the adsorption capacity of the composite for Co(II) ions. In the pH experiments, it was found that at a solution pH of 3.4, the P(AA-co-GMA) copolymer alone showed limited capability in adsorbing Co(II) ions, achieving only 3.82 mg/g. However, upon integration of SiO2/Al2O3 into the polymer matrix, the composite exhibited a significantly enhanced adsorption capacity of 103.54 mg/g. The adsorption process followed a pseudo-second-order kinetic model and attained equilibrium within 60 min. The Langmuir isotherm model was found to best describe the adsorption behavior, with a maximum adsorption capacity of 217.86 mg/g. The adsorption of Co(II) was significantly affected by the ionic strength, especially with Al3+ displaying a more pronounced impact on the adsorption of Co(II) ions compared to Na+, Ca2+, and Mg2+. Thermodynamic studies indicate that the adsorption process was spontaneous and endothermic. Overall, the SiO2/Al2O3/P(AA-co-GMA) composite material displayed significant adsorption ability for Co(II) ions, making it a suitable option for further development as an effective adsorbent in water treatment applications.

Numerical investigation of the effect of operating conditions on performance of PV-PCM system

The photovoltaic module only manages to convert around 15% of the incoming light into usable electricity and the rest is lost as heat, reducing the module's overall efficiency. Hybrid photovoltaic thermal systems are therefore the best way to collect thermal and electrical energy. The cooling and heat storage benefits of PV cells are amplified using phase change materials (PCMs). In this article, a simple two-dimensional CFD model to forecast the temperature of the PV where it contacts the PCM. The findings of the numerical simulations show that PV systems equipped with PCM have been studied under a variety of situations. A contemporary thermodynamic study is performed to examine system behaviour under different operating settings by investigating the effect of some rather crucial aspects that have not been taken into account before. The research takes into account three instances, each with its own unique combination of wind speed, ambient temperature, and sun irradiation. It has been shown that the solar radiation is a key component for growth in the PV temperature. The findings show that an increase in PV temperature of 5–7°C is caused by an increase in solar irradiance of 1000 W/m2. The rise in wind velocity, heat dissipation rate increases resulting to the fall in the temperature of the PCM and glass, the decrease in PCM temperature leads to a further drop in glass temperature. More so than wind speed or solar irradiation, ambient temperature determines how quickly PV glass heats up. Furthermore, at an ambient temperature of 35°C, PCM is found to melt entirely in 435 min, whereas at an ambient temperature of 30°C, PCM melts up to a liquid fraction of 0.77 min. Therefore, the efficiency of the PV system improves dramatically as the outside temperature is lowered.

Removal of Methylene Blue by Low-Cost Adsorbent Prepared from Jujube Stones: Kinetic and Thermodynamic Studies

Removal of Methylene Blue by Low-Cost Adsorbent Prepared from Jujube Stones: Kinetic and Thermodynamic Studies

Biomass derived carbon dots for enhanced wastewater remediation: ANN-optimized synthesis and cellular imaging applications

Water pollution is a significant problem in today’s modern world, with dye molecules being the most challenging pollutants to eliminate. Carbon dots (CDs) have demonstrated high efficacy in water and wastewater treatment. This research aimed to develop CDs using banana peel as a carbon precursor through a facile hydrothermal method. These CDs were utilized to eliminate methylene blue (MB) dye. The CDs exhibited blue fluorescence with an improved quantum yield (QY) of up to 19 %. They showed an adsorption efficiency of 71.942 mg g−1, with maximum adsorption occurring within a pH range from 2 to 10. The adsorption kinetic data were well described by the pseudo-second-order and Freundlich isotherm models. Thermodynamic studies revealed that the adsorption process was spontaneous and exothermic. Moreover, the CDs demonstrated excellent re-usability potential over five successive cycles of adsorption. Additionally, a prediction study was performed using an Artificial Neural Network (ANN) to forecast the adsorption of dye by CDs. The CDs were further investigated for cytotoxic properties and cellular internalization in breast cancer cells (MCF-7). The findings indicated that cellular viability significantly decreased with increasing dosage, reaching 50 % (IC50) at a concentration of 128 μg mL−1. Successful internalization of CDs by cancer cells with blue emission suggests their potential in biomedical applications. Thus, the synthesized nanomaterial is highly promising for both bio-sensing applications and wastewater treatment.

Kinetics and Thermodynamics Study of Ammonia Leaching on Spent LMR-NMC Battery Cathodes

The recycling of spent lithium NMC-type batteries, widely used in electric vehicles, presents a challenge due to manganese content, which complicates metal separation and purification. This study explored a selective leaching process using ammonia to recover metals from high-manganese-content LMR-NMC cathodes. By adjusting the (NH4)2SO4 reagent concentration to 1–2 M and maintaining the temperature between 50–80 °C, the recovery rates of lithium, nickel and cobalt metals were enhanced, leaving manganese primarily as residue in the form of Mn(OH)₂ and (NH4)2Mn(SO4)2. A kinetics model, integrating an equilibrium-shrinking core model with a modified temperature-dependent Arrhenius approach, accurately simulates the metal recovery. The activation energies of the forward leaching reactions of Li, Ni, and Co were respectively (1.4331±0.0036)×105, (1.5494±0.0034)×105, and (1.5743±0.0040)×105 J/mol, while those for the backward reactions were (5.3307±0.0041)×105, (2.4753±0.0093)×105, and (1.6289±0.0092)×105 J/mol, respectively. The leaching mechanism was found to be exothermic, which allows maximum recovery at low temperatures. The findings highlight ammonia’s effectiveness as a selective leachant, significantly reducing manganese in the leaching solution, and streamlining nickel and cobalt separation, thus enhancing the recycling process’s efficiency and sustainability.

Equilibrium and Thermodynamic Studies for the Removal of Eriochrome Black T dye from its Aqueous Solutions using Nano Carbon Prepared from Morus Nigra (Mulberry) Stem through two Stages of Carbonization

Equilibrium and Thermodynamic Studies for the Removal of Eriochrome Black T dye from its Aqueous Solutions using Nano Carbon Prepared from Morus Nigra (Mulberry) Stem through two Stages of Carbonization

Zeolite supported zinc oxide nanoparticles composite: Synthesis, characterization, and photocatalytic activity for methylene blue dye degradation

In the first stage of this study, zinc oxide nanoparticles (ZnO-NPs) were synthesized. The synthesized nanoparticles were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), selected area diffraction (SAED), and X-ray diffraction analyses (XRD). Subsequently, a composite material was obtained by coating ZnO-NPs with zeolite from Rátka, Hungary. The photocatalytic degradation of ZnO-NPs using Hungarian zeolite in the ZnO-Zeolite composite was investigated. The objective was to evaluate the efficacy of the ZnO-Zeolite composite in degrading methylene blue (MB) under ultraviolet-visible spectroscopy (UV). It was observed that the composite materials were influenced by the light source. The degradation rates showed that the ZnO-Zeolite composite with 100 mg L−1 MB achieved the highest photodegradation rate of 96.70 % when exposed to sunlight for 210 min. These findings indicate that the ZnO-Zeolite composite with a 1:5 ratio has the potential to significantly increase the photocatalytic activity, achieving a high yield of 96.70 % compared to raw zeolite. In the last stage of the study, equilibrium, kinetic, and thermodynamic studies were carried out. The photocatalytic maximum adsorption capacity of MB for the ZnO-Zeolite composite was calculated as qm= 41.32 mg g−1. In the adsorption and kinetic studies of the obtained composite, the best results were obtained with the Langmuir adsorption isotherm and pseudo-second-order kinetics. A desorption study has been conducted, and it has been determined that the composite can be reused for up to 7 cycles.

The sources and physical–chemical conditions of gold mineralization in the Qi189 porphyry deposit, Qiyugou gold orefield, Eastern Qinling

The Qiyugou gold orefield is situated in the Eastern Qinling. It is a magmatic hydrothermal system, which includes cryptoexplosive breccia-type, vein-type, and porphyry gold deposits. However, the gold sources and physical–chemical conditions of precipitation of the newly discovered porphyry gold deposit, the Qi189, have not yet been well studied. It also hinders the comprehensive understanding of magmatic–hydrothermal gold systems in the Qiyugou gold orefield. Thus, detailed field and microscopic observations, C–O–He–Ar isotopic analysis, in situ major/trace element analysis, and thermodynamic studies on the Qi189 porphyry gold deposit have been carried out in this study. This deposit has three hydrothermal stages: the (I) early quartz–K-feldspar–molybdenite–magnetite stage, (II) middle quartz–sericite–pyrite–Te–Bi-mineral stage, as well as (III) late calcite–quartz stage. The carbon and He–Ar isotopic compositions suggest deep-seated sources of ore-forming fluids with mantle component proportions of up to 37 %. Oxygen isotopic compositions indicate the gradual involvement of more meteoric water in ore-forming fluids during stages I–III. The meteoric water input and reduction in temperature and pressure in the early stage II increased oxygen fugacity and decreased the pH values of ore-forming fluids. Then, in hematite and sulfides formation during late stage II, the oxygen and sulfur fugacities of ore-forming fluids gradually decreased. Precipitation of native gold and Au-bearing telluride grains with quartz-sericite alteration in stage II is significant for Au enrichment, which occurred under acidic (pH = 3.64–5.71), low-logfO2 (<-34.86), low-logfS2 (−13.07 to −11.13) and low-logfTe2 (−15.55 to −10.32) conditions. Therefore, abundant mantle components and changes in the pH, logfO2, logfS2, and logfTe2 of the ore-forming fluids play important roles in gold enrichment. Combined with previous studies, this work also provides some new evidence for identifying a magmatic-hydrothermal gold system in this district, including similar sulfide trace elements, δ13CV-PDB compositions, and changes in logfO2 and logfS2 of various types of gold deposits in a gold orefield.

Adsorption isotherm, kinetic and thermodynamic studies for adsorption of fluoride on waste marble powder

Economically viable, efficient waste marble powder (WMP) for fluoride removal has been studied. A batch adsorption study has been carried out concerning contact time, initial concentration, adsorbent dosage, pH, and temperature. After using a batch adsorption mode, 97.13 % removal efficiency was observed with an adsorption capacity of 1.166 mg/g at the initial fluoride concentration of 6 mg/L, solution pH of 6, adsorbent dosage of 500 mg, temperature of 35 °C, and contact time of 60 min. According to kinetics studies, the experimental adsorption data fit well in a nonlinear pseudo-second order with the adjusted-R2 value 0.999, and the nonlinear Langmuir isotherm model fitted best with the adjusted-R2 value 0.988. The separation factor (RL) values were within the range of 0.178 - 0.086, suggesting a satisfactory uptake of fluoride ions. Thermodynamic analysis showed that the adsorption process was endothermic, and negative values of Gibbs free energy change (∆Go) indicated spontaneous fluoride adsorption. In contrast, a positive value of entropy change (∆So= 65.26) indicated arbitrary behaviour at the interface between the solid and the solution. Fluoride removal from aqueous solution was also studied using a continuous fixed-bed column. The Yoon-Nelson model, with a higher adjusted-R2 value of 0.9906, described the dynamics of the fluoride adsorption process better than the Adams-Bohart model because it had better predictions for the breakthrough curve. According to the regeneration analysis, 52 % of the adsorption rate with an adsorption capacity of 0.604 mg/g could be achieved even after five cycles of WMP regeneration.

Eco-friendly engineering of micro composite-based hydroxyapatite bio crystal and polyaniline for high removal of OG dye from wastewater: Adsorption mechanism and RSM@BBD optimization

The presence of harmful substances such as dyes in water systems poses a direct threat to the quality of people's lives and other organisms living in the ecosystem. Orange G (OG) is considered a hazardous dye. The existing paper attempts to evaluate a low-cost adsorbent for the effective removal of OG dye. The developed adsorbent Polyaniline@Hydroxyapatite extracted from Cilus Gilberti fish Scale (PANI@FHAP) was elaborated through the application of the in situ chemical polymerization method to incorporate PANI on the surface of naturally extracted hydroxyapatite FHAP. The good synthesis of PANI@FHAP was evaluated through multiple techniques including X-ray diffraction (XRD), Scanning electron microscopy coupled with energy dispersive X-ray spectrometry (SEM/EDS), Fourier Transforms Infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) coupled with thermal differential analysis (DTA) analysis. The results reveal a highly ordered disposition of PANI chains on FHAP, resulting in a well-coated FHAP in the PANI matrix. Furthermore, the presence of functional groups on the surface of PANI such as amine (-NH2) and imine (=NH) groups would facilitate the removal of OG dye from contaminated water. The adsorption of OG onto PANI@FHAP was conducted in batch mode and optimized through response surface methodology coupled with box-Behnken design (RSM/BBD) to investigate the effect of time, adsorbent dose, and initial concentration. The outcomes proved that OG adsorption follows a quadratic model (R2 = 0.989). The kinetic study revealed that the adsorption of OG fits the pseudo-second-order model. On the other hand, the isotherm study declared that the Freundlich model is best suited to the description of OG adsorption. For thermodynamic study, the adsorption of OG is spontaneous in nature and exothermic. Furthermore, the regeneration-reusability study indicates that PANI@FHAP could be regenerated and reused up to five successive cycles. Based on the FTIR spectrum of PANI@FHAP after OG adsorption, the mechanism governing OG adsorption is predominantly driven by π-π interaction, electrostatic interaction, and hydrogen bonding interactions. The obtained results suppose that PANI@FHAP adsorbent can be a competitive material in large-scale applications.

Thermodynamic Study of Adsorption behaviors of Trivalent Metal Ions onto Chelating Resin: Comparison between Scandium(III) and Other Metal Ions

Thermodynamic Study of Adsorption behaviors of Trivalent Metal Ions onto Chelating Resin: Comparison between Scandium(III) and Other Metal Ions

Remediation of Methyl Orange Dye in Aqueous Solutions by Green Microalgae (Bracteacoccus sp.): Optimization, Isotherm, Kinetic, and Thermodynamic Studies

Remediation of Methyl Orange Dye in Aqueous Solutions by Green Microalgae (Bracteacoccus sp.): Optimization, Isotherm, Kinetic, and Thermodynamic Studies

Adsorption of Cr(VI) from aqueous solutions using inorganic clays modified magnetic chitosan adsorbent: Kinetic and thermodynamic study

Inorganic clays modified magnetic chitosan adsorbent (ICMMCA) was successfully prepared and systematically characterized in chemical structure and morphology. Effect of variables including initial pH and concentration of Cr(VI) in the solution, adsorption time, adsorption temperature and coexisting ions on the performance of ICMMCA in Cr(VI) removal from water were evaluated. Furthermore, the kinetic and thermodynamic studies were conducted to elucidate the adsorption mechanisms and thermodynamic characteristics of the adsorption process. The results demonstrated that the maximum Cr(VI) adsorption capacity of 94.67 mg/g could be achieved when the adsorbent loading was 1 g/L, the initial concentration of Cr(VI) was 100 mg/L, the adsorption time was 60 min and solution pH was at 5. The adsorption data could be well fitted by the Freundlich isotherm model. The thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic in nature. The adsorption process could be described by the pseudo-second-order kinetic model.

EDTA functionalized pine needle biochar (EDTA@BC); a valorized bio-material for removal of Ni(II) from aqueous solution.

The preparation of ethylenediaminetetraacetic acid (EDTA) functionalized pine needles biochar (EDTA@BC) as a low-cost active adsorbent and its effectiveness in removing Ni(II) from aqueous solution at various conditions is reported in this paper. First, alkali activation was selected to render the pine needle biochar with an excellent porous structure and increased concentration of hydroxyl groups to facilitate grafting. Subsequently, a simple method was utilized to graft EDTA onto the biochar. The prepared EDTA@BC was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and energy dispersive x-ray spectrometry (EDX). Batch adsorption studies were conducted to assess the impact of various parameters such as solution pH, adsorbent dosage, adsorbate volume, and shaking time on the removal efficiency of Ni(II). At pH 6, 100 mg dosage, 4 mL of adsorbate volume, and 10 min of shaking time, the maximum removal efficiency of Ni(II) was observed to be 89%. EDTA@BC showed reasonable sorption performance still after the third cycle of regeneration. The effect of interfering ions such as Pb, Cr, Cu, and Hg was evaluated, resulting a decrease of 69%, 78%, 76%, and 68%, respectively, in its sorption capacity. The Langmuir model provided a better fit for Ni(II) in the concentration range of 0.1-2000 ppm under optimized conditions, with qmax of 46.69 ± 1.031 mg/g and KL of 0.001, compared with the Freundlich isotherm, which yielded n = 0.234 and χ2 = 2.7899, Temkin isotherm (R2 = 0.9520), and Redlich-Peterson isotherm (R2 = 0.9725). The removal of Ni(II) by EDTA@BC was found to be the pseudo-second-order kinetics. Thermodynamic studies indicated adsorption process to be endothermic and nonspontaneous. Hence, a sustainable valorized bio-material (EDTA@BC) is prepared having better sorption efficiency of Ni(II) from aqueous solution with possible wide applicability. RESEARCH HIGHLIGHTS: New EDTA functionalized indigenous pine needles biochar (EDTA@BC) was prepared. This low-cost active adsorbent found effective in removing Ni(II) from aqueous solution. FTIR, SEM, and EDX proved synthesis and uptake of Ni(II) from aqueous solution. Ni(II) removal, regeneration, interfering and adsorption studies were performed by UV-Vis spectroscopy.

Bio Fabrication of MgO Decorated Spinel Magnetite Nanoparticles for Efficient Removal of AO Dye: Isotherm, Kinetic, and Thermodynamic Study

Bio Fabrication of MgO Decorated Spinel Magnetite Nanoparticles for Efficient Removal of AO Dye: Isotherm, Kinetic, and Thermodynamic Study

Thermodynamic and kinetic study on the catalysis of tributyl aconitate by Amberlyst-15 in a cyclic fixed-bed reactor

Abstract Tributyl aconitate is a new type of alternative plasticizer to phthalates. Amberlyst-15 was used to catalyze the esterification of aconitic acid and n-butanol for the preparation of tributyl aconitate in a cyclic fixed-bed reactor. The influence of the reaction conditions on the conversion was investigated. The results showed that the conversion of aconitic acid increased significantly with the rise of temperature and catalyst loading. The reaction conditions were optimized as: temperature: 115 °C; initial mass ratio of AA and n-butanol: 1:4; catalyst loading: 25 %; reaction absolute pressure: 85 kPa; volume flow rate: 30 mL min−1. Thermodynamics and kinetics of the reaction was studied. The non-ideality of the reaction system was rectified using the UNIFAC group contribution method. The kinetic process was simulated using the pseudo-homogeneous (PH) model, Eley-Rideal (E-R) model, and Langmuir-Hinshelwood-Hougen-Watson (LHHW) model. The results revealed that the E-R model exhibited superior suitability in simulating the kinetic process.

Development of novel API-based deep eutectic solvents for esterification of high free fatty acid

Low-value feedstocks containing high free fatty acid (FFA) content are incompatible with direct alkali-catalysed transesterification, and require a deacidification step through esterification to reduce its FFA level. Herein, innovative acid catalysts were developed based on deep eutectic solvents (DESs) to pretreat low-quality palm oil (12.43 % FFA). DESs were formed using Brønsted acids (5-sulfosalicylic acid and benzenesulfonic acid) and an active pharmaceutical ingredient (paracetamol) at a 3:1 molar ratio. The DESs were characterized using ATR-FTIR and Hammett acidity function (H0). DES catalyst dosage, methanol requirement, reaction time and temperature parameters were optimized, and its recyclability was evaluated. The FFA contents were reduced to below the limit of < 2 % using acidic DESs at optimized conditions. Reaction kinetics revealed that DES-catalysed reactions followed the pseudo first order rate of reaction and required the lowest activation energy of 40.91 kJ/mol. Through the Eyring-Polanyi thermodynamic study, the DES-catalysed esterification reactions were endothermic (ΔH° > 0), non-spontaneous (ΔS° < 0 and ΔG° > 0) and endergonic. COSMO-RS computational calculations reveal the viable formation of the DESs based on its moieties, and supports the good solubility of the DESs in methanol. This study demonstrates the feasible valorisation of low-value feedstocks using innovative catalysts in enabling biodiesel production.

Thermogravimetric pyrolysis investigation of pistachio shell for its potential of thermal properties, kinetics and thermodynamics

In order to design and optimize thermochemical systems for the production of bioenergy understanding the energy capacity of the pistachio shell and its kinetics of degradation is crucial. The Thermogravimetric analysis at different heating rates of biomass was studied along with thermodynamic study, primary characterizations like the composition of biomass, heating value and a reaction mechanism-assisted kinetic model. Nitrogen gas flow rate is used for thermogravimetric analysis (TGA), which is performed at 10, 15, 20 and 30 ℃/min different heating rates from room temperature to 900 ℃. The output also shows that maximal degradation took place between 180 and 430 °C. The various iso-conversional models, such as Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS), Starink and Friedman, are used to calculate kinetic and thermodynamic parameters, which give the average value of activation energy as 172.29, 170.47, 169.79, and 193.25 kJ/mol. The average values of Gibbs free energy for the FWO, KAS, Starink and Friedman techniques were found to be 176.49, 1176.54, 176.29, and 175.78 kJ/mol, respectively.Graphical