Phosphating Process Research Articles

Mining and industrial processing wastes of phosphate rocks in Egypt: potentiality of rare earth elements

Abstract Globally, Egypt ranked the eighth position in the production of phosphorus with about 5 million tons annually. Phosphate ore is considered one of the commonest sources of rare earth elements (REEs). Mining and industrial processes (beneficiation) of phosphate ore produce huge amounts of wastes in different sizes. The present study aims to evaluate the potentiality of the phosphate ore wastes as a source of rare earth elements (REEs). The study targeted some phosphate production sites in Egypt, including: Abu Tartur, West and East El-Sebaiya phosphate mines, in addition to the fertilizers factory in Assiut. The collected waste samples, during 2023, were analyzed in terms of mineralogical composition using XRD (X-Ray Diffraction) and chemical composition using XRF (X-Ray Fluorescence). The results of chemical analysis recorded the highest concentrations of Y, Ce, La, Nd, Sc, Sm, U, and Th in Abu Tartur waste samples, while the lowest concentrations were recorded in the fertilizers factory waste samples. These wastes contain higher concentrations of REEs than the Algerian and USA wastes. Furthermore, an enrichment of the mostly environmental hazardous elements As, Cr, Cd, Pb, and Se are detected in Abu Tartur and West and East El-Sebaiya. Thus, the wastes from the industry and mining processing of phosphate represented a vital economic source for the production of REEs. The use of wastes for production of trace and rare earth elements represents an economic and environmental add value for phosphate industry.

Regulation of nano FePO4 precursors and exploration of influencing mechanisms in LiFePO4/C cathode

The iron phosphate (FePO4) process route has become the predominant method for synthesizing lithium iron phosphate (LiFePO4) due to its established technology and controllability.

Reverse growth surface planarization mechanism and high-efficiency polishing of KDP

ABSTRACT This paper proposes a reverse growth surface planarization mechanism for achieving high-efficiency precision processing of the potassium dihydrogen phosphate (KDP) crystal. The KDP crystal reverse growth has ordered and controllable characteristics similar to growth, which differs from the disordered and random dissolution in the natural state. Experiments are conducted using a high-precision annular polisher to investigate the surface characteristics, material removal, and surface planarization of different crystallographic planes in reverse growth. The repeat utilization of polishing liquids is studied to reduce processing costs. The difference in material removal and surface roughness of different crystallographic planes obtained from the same reverse growth polishing process is within 8%. The suitable undersaturation range for reverse growth surface planarization is 0.01–0.18, with a maximum material removal rate of 90 μm/min, 50 times that of the microemulsion polishing methods. Finally, a mirror-like KDP crystal surface is obtained with a surface roughness Ra of 0.00975 μm.

Characterisation of zinc phosphate coating deposited on carbon steel wire rod using an accelerator-side and iron-side phosphating solution

ABSTRACT Accelerator-side phosphating solutions are widely used for zinc phosphate conversion coating on carbon steel wire rods to impart good lubrication and corrosion resistance during wire drawing of steel. But on the accelerator side, the use of nitrite and nitrate as accelerator agents has challenges of high process temperature, liberation of nitrous gases and high sludge generation. For these challenges, the iron-side phosphating process is used as one of the solutions where the bath is maintained at a higher iron level and aeration is done to oxidise ferrous iron instead of an accelerator. In the literature, details of different processes and bath composition are available but their effects on the characteristics of zinc phosphate coating deposited on the carbon steel wire rod are not available. In this paper, zinc phosphate coating was deposited on different grades and sizes of wire rods using accelerator-side and iron-side phosphate solutions and their effect on coating weight and other coating characteristics was studied using SEM, EDS and Tafel polarisation experiments.

Green preparation of high-efficiency mesoporous MoP electrocatalyst for hydrogen evolution

The production of hydrogen generation catalysts through inexpensive, green and sustainable route is urgently needed in the context of “double carbon”. In this work, a new mesoporous transition metal phosphide (P–MoP@C) as electrocatalytic hydrogen evolution catalyst was prepared by a soft template method using polyoxometalate (POM), biomass gallic acid and ammonium polyphosphate through one-step phosphating and calcination process. The mesoporous structure is formed by organic-organic self-assembly strategy facilitated by strong hydrogen bonding between the pyrogallol group on gallic acid and the block copolymer. P–MoP@C shows good catalytic and stability properties, with overpotentials of 149 and 162 mV in alkaline and acidic solutions, respectively, at a current density of 10 mA cm−2. The mesoporous structure adds up to the quantity of exposed active sites, accelerates the electron transfer rate, and improves the catalytic performance of P–MoP@C. The use of plant polyphenols as a carbon source for the synthesis of green and environmentally friendly hydrogen evolution catalysts provides some reference value for large-scale industrial production.

Phosphatization in the São Pedro and São Paulo Archipelago (SPSPA), Equatorial Atlantic, Brazil: Insights from guano leaching and chemical weathering

This research explores the phosphatization process in the São Pedro and São Paulo Archipelago (SPSPA), located in the Equatorial Atlantic, by analyzing the geochemical interactions between guano coatings and the underlying rocks. The study also examines the geochemical characteristics of the substrates, assessing the behavior of major, minor, trace, and rare earth elements, and determines the degree of weathering degradation of guano crusts, speleothems, peridotites and carbonate sedimentary rocks affected by environmental factors as rain, wind and halmyrolysis. The distribution of chemical elements in water-soluble, adsorbed, acid-extractable/exchangeable, readily acid and reducible, acid oxidizable, and residual phases were investigated. The principal findings of this method show that elevated Na levels are leached in water-soluble fractions, thereby highlighting the occurrence of rapid and active geochemical cycling, which is influenced by seawater. In contrast, in more acidic environments (pH close 4.8 to 2.0), considerable amounts of macroelements like P, Fe, Mg, Al, and Mn are found in association with remaining phases, indicating a slower and more incremental geochemical cycle of mature guano in the input and output systems of these nutrients in the archipelago. The mineralogy, as indicated by the presence of mafic minerals such as olivine, augite, and Cr-spinel, as well as phosphates including fluorapatite, collinsite, and spheniscidite, also supports this finding. The findings underscore the complex interplay between biological activities and geochemical processes, which influence the elemental dynamics in the phosphate-rich rocks of the SPSPA at depth. This study not only enhances our understanding of phosphatization processes but also offers important insights into the sustainable management of marine resources in environmentally sensitive areas. The research underscores the necessity of considering biological and environmental variables when examining geochemical cycles, particularly in regions exhibiting distinctive geological and biological interactions that challenge the prevailing models, such as those identified in the ASPSP.

Treating waste with waste: New insight into phosphorus removal by graphitic carbon nitride modified water treatment sludge-based ceramsite

This study developed a novel ceramsite adsorbent, combining water treatment sludge (WTS) and graphite carbon nitride, which aimed at removing phosphate from wastewater to realize the sustainable development strategy of ‘treating waste with waste’. The optimal conditions for the preparation of N-modified WTS (NWTS)-based ceramsite were determined as follows: NWTS: bentonite: CaCO3=1:0.4:0.5, preheating at 450 °C for 15 min, and calcinating at 1100 °C for 15 min. The study examined the effects of pH, ceramsite dosage, initial phosphorus concentration, and temperature on phosphate removal, and it assessed the potential risk of heavy metal release from the ceramsite during application. The result indicated that phosphorus adsorption of the ceramsite reached 0.5 mg/g at pH=6, T=303 K, Pinitial=1 mg/L and dosage of 2 g/L, achieving 100% removal efficiency. The adsorption process of phosphate by ceramsite followed pseudo-second order kinetic and the Sips model, suggesting that the adsorption mechanism involved multilayer chemisorption. Ligand exchange reaction was the primary driver of adsorption, with hydrogen bonding further augmenting the adsorption efficiency. Additionally, the heavy metal content released by the ceramsite was significantly below the relevant standard limits, confirming its excellent feasibility and safety. These characteristics suggested that the ceramsite adsorbent had broad application potential in actual wastewater treatment process.

A novel RuP2-infused heteroatom-doped porous carbon for high-durability lithium-sulfur batteries

Nitrogen and phosphorus co-doped three-dimensional porous carbon encapsulated ruthenium diphosphide (PCS900@RuP2-2) is successfully synthesized via a phytic acid-assisted phosphating process. The resulting RuP2 nanoparticles, ranging in size from 10 to 50 nm, are encapsulated within a carbon matrix, providing a stable catalytic structure. Nitrogen adsorption and desorption tests reveal that PCS900@RuP2-2/S possesses a high specific surface area and a rich micro/mesoporous structure. This high porosity facilitates multi-directional ion diffusion and offers ample buffer space to accommodate sulfur volume expansion during cycling. Density functional theory (DFT) calculations confirm that PCS900@RuP2-2/S enables efficient adsorption of soluble polysulfides, thereby minimizing the notorious "shuttle effect." Electrochemical testing demonstrates the remarkable durability of PCS900@RuP2-2/S. After 500 cycles at a 1 C current density, the reversible capacity remains at 511.6 mAh g⁻¹, with an average capacity decay rate of just 0.047 % per cycle. Even under heavy sulfur loading conditions (4.2 mg cm⁻²), the composite maintains a high reversible capacity of 386.6 mAh g⁻¹ after 500 cycles. The combination of high porosity, stable catalytic structure, and efficient redox reaction facilitation contributes to the exceptional performance and longevity of PCS900@RuP2–2/S.

Arsenic content in tissues, Fungus combs, Herbs, Termite mounds and Soils of termites of the genus Macrotermes and assessment of the health risk associated with their food use in the industrial zone of the Societe Nouvelle Des phosphates du Togo (SNPT)

Arsenic is present in different environmental matrices of the phosphate mining and processing area of the Société Nouvelle des Phosphates du Togo; including termite tissues, termite waste, termite mounds, termite Fungus combs, soils and nearby herbs. Arsenic levels vary across matrices, with termite waste having the highest concentration (approximately 27.01 mg/kg) compared to the outside herbs, which have the lowest. Phosphate mining sites, including Hahotoé-Kpogamé and Akoumapé, have higher levels of As contamination in soils and termite tissues compared to the phosphate processing site. A positive correlation is observed between As levels in termite tissues and termite waste; suggesting an ability of termites to eliminate arsenic via their waste. Regarding health risks, the hazard quotient (HQ) for arsenic in termites exceeds 1, and for non-threshold effects, the excess individual risk (EIR) assessment gives EIR > 10-4 in both adults and children; which would mean that termite consumption poses a significant health risk, including cancer risks for human populations, particularly children. However, it should be noted that the estimation in this study includes total As (organic and inorganic). Since the toxicological reference values were calculated on the basis of inorganic arsenic, which presents more hazard and whose fraction represents 10% of total As, the daily exposure dose values for adults and children represent 1.40.10-4 mg/kg/d and 1.02.10-4 mg/kg/d of inorganic arsenic, respectively. These doses will then become lower than the toxicological reference value (TRV) with the consequence of hazard quotient (HQ) lower than 1 and resulting in low risks of carcinogenic effects. It is therefore necessary to specifically determine the inorganic fraction to refine the risk assessment and to extend this study to other trace elements in the prospected area.

Ionic liquid-assisted controlled synthesis of multi-site Ni2P as a bifunctional catalyst for electrocatalytic water splitting

It is crucial to develop effective electrocatalysts with multiple active sites for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in order to promote the advance energy conversion and development of sustainable energy technology. Here, we synthesized hierarchical nanostructured Ni2P on carbon cloth using ionic liquid (IL) assisted sacrificial template strategy through a simple two-step hydrothermal phosphatization process, which served as an electrode for enhancing bifunctional water electrolysis. By changing the content of ionic liquids in the solvent, the morphology of Ni(OH)2 precursors could be regulated, thereby altering the morphology of Ni2P. Ni2P exhibited remarkable electrocatalytic activity towards HER in acidic electrolytes with an overpotential of 132 mV at a current density of 10 mA cm−2, as well as OER in alkaline media with the overpotential of 309 mV. The excellent electrocatalytic activity of the Ni2P-2 could be attributed to its hierarchical nanostructure providing abundant active sites, which benefits from the structural end-capping effect of ILs.

Enhanced oxygen evolution reaction performance using amorphous hollow cerium-doped cobalt phosphate derived from ZIF-67 structures

A major obstacle in achieving massive operations water splitting is the slow rate of the anodic reaction. To address this issue, metal phosphates have been extensively employed as efficient materials for the oxygen evolution reaction (OER). In this study, ZIF-67 structures were synthesized in both single-metal and bimetallic forms with different molar ratios of cerium. The structure with the best electrochemical activity ((5 present) cerium doped ZIF-67 ((5)CeZIF-67)) was subjected to a phosphatization process, resulting in the formation of the amorphous and hollow cerium doped cobalt phosphate (Ce-CPO) structure as a novel and highly efficient OER electrocatalyst. To the best of authors knowledge, this is the first report on the synthesis and application of Ce-CPO structure for boosting OER process. This resultant structure exhibited suitable electrochemical performance in the oxygen evolution reaction (OER), achieving an overpotential of 286 mV at a current density of 30 mA cm−2 and a Tafel slope of 74.4 mV decade−1. Furthermore, the final structure demonstrated satisfactory stability during a 10 h operation period. The notable improvement in the Ce-CPO structure was due to the use of a bimetallic framework combined with phosphorus and an amorphous porous structure. The distinctive configuration achieved greatly amplifies the effective surface area, hence improving electron transfer. The findings of this research can contribute to the development of electrodes with improved performance in OER.

Calcium silicate hydrate complex konjac glucomannan-based hydrogel selectively adsorbed phosphate in low alkalinity solution

The selective recovery of phosphate from wastewater can manage nutrients and realize the recycling of phosphorus resources. In this study, a novel konjac glucomannan/pectin/calcium silicate composite hydrogel (KP-CSH) was developed for efficient recovery of phosphate in aqueous solution. The amount of alkali released after the reaction of KP-CSH in a neutral solution was small (the pH of the solution after the reaction was < 9). In a wide initial pH range (3–10), the adsorption capacity of KP-CSH in 50 mg-P/L phosphate solution reached 39∼45 mg-P/g. Besides, even if the pH of the solution after the reaction was less than 8, it could still well adsorb phosphate. The kinetic and isothermal adsorption experiments indicated that the adsorption process of phosphate by KP-CSH was chemical adsorption, and the maximum adsorption capacity was 61.2 mg-P/g. KP-CSH preferentially adsorbed phosphate even in the presence of high concentrations of competitive ions. In the actual biogas slurry, KP-CSH also exhibited the strongest selectivity/affinity for phosphate, and its distribution coefficient (Kd) was significantly higher than that of other co-existing anions and cations. The adsorption mechanism analysis indicated that Ca was the main adsorption site of KP-CSH, and that the adsorption process of target pollutants mainly involved ligand exchange and the intra-sphere complexation. Further plant seed germination and seedling growth experiments suggested that KP-CSH after phosphate recovery did not exert a negative effect on the growth of plant seedlings, and increased the chlorophyll content of seedling leaves. These results demonstrate that KP-CSH is a potential adsorbent for efficient phosphate recovery, which can be used as a slow-release phosphate fertilizer after recovering phosphate.

Hydro Geochemical Characteristics and Mineralization Process of Groundwater in the Phosphatic Basin of Gafsa, Southwestern Tunisia

The present study examines the water quality in the Quaternary Mio-Plio-Quaternary aquifer of the mining basin of Gafsa using a hydrochemical approach and multivariate statistical methods, to assess groundwater mineralization processes. Results from the analysis of groundwater quality collected during the winter (January 2020) and summer (June 2021) seasons reveal a pronounced stability in geochemical parameters, emphasizing a noteworthy consistency in water composition between the two seasons, with the dominance of the Na-Ca-Mg-SO4-Cl facies, in addition to the fact that all year round these concentrations are beyond their respective WHO limits. Despite the intensive extractive and transformation phosphate industry, the prolonged interaction of water with geological formations is the primary factor controlling their high mineralization. This results from the dissolution of carbonates (calcite, dolomite), gypsum, and halite. The results of the PCA represent two correlation classes. Class 1 comprises major elements sulfate, chloride, sodium, magnesium, and calcium strongly correlated with electrical conductivity (EC) and total dissolved solids (TDS). This correlation is indicative of the water mineralization process. Class 2 includes major elements nitrate and potassium weakly correlated with (TDS) and (EC) As regards heavy metals, their concentrations fall consistently below their respective potability standards established by the WHO across all water sampling points. Meanwhile, fluoride (F-) concentrations exhibited values ranging from (1.6 mg·L−1 to 2.9 mg·L−1) in the winter of January 2020 and (1 to 2.9 mg·L−1) in the summer of June 2021, surpassing its WHO limit (1.5 mg·L−1) in almost all water samples. These findings allow us to conclude that the high mineralization of these waters is acquired due to the dissolution of carbonates (calcite, dolomite), gypsum, and halite due to their prolonged interaction with the geological formations. The deterioration of groundwater quality in the Gafsa mining basin associated with phosphate extraction and processing activities appears to be primarily due to the intensive exploitation of deep-water resources.

Optimization of the two-step coating formation process for ZK21 magnesium alloy

Abstract The primary hindrance to the broader utilization of magnesium alloys lies in their insufficient corrosion resistance. This research initiative introduced an advanced two-phase methodology incorporating phosphating and alkali heating to produce a protective Ca-P coating on the surface of magnesium alloys. This innovative approach not only bolsters their corrosion resistance but also facilitates controlled degradation in bodily fluid environments. Following a 60-minute phosphating process in a solution with a pH level of 3, the resultant Ca-P coating achieved full coverage over the magnesium alloy surface, displaying commendable coating density and uniformity. Subsequent treatment with alkali heating for 30 minutes further enhanced the density and smoothness of the coating. Analysis utilizing EDS and XRD revealed that the primary constituents of the phosphate magnesium alloy and the phosphate + alkali heated magnesium alloy coating were DCPD and HA, respectively. Corrosion degradation assessments conducted in SBF solution validated that the two-step coating formation method significantly fortified the corrosion resistance of magnesium alloys.

Sludge-derived alginate-like extracellular polymers (ALE) for preparation of Fe-ALE and FeCaMg-ALE: Application to the adsorption of phosphate

Excess phosphorus (P) in wastewater has potential risk of causing harmful algal bloom and eutrophication in receiving wastewater. In this study, alginate-like extracellular polymers (ALE) derived from conventional activated sludge were modified with ionic cross-linking agents (Fe3+, Ca2+, and Mg2+) to develop Fe-ALE and FeCaMg-ALE for the adsorption of phosphate from wastewater. The adsorption process of phosphate by Fe-ALE and FeCaMg-ALE can be well described by pseudo-second-order kinetics and Freundlich isotherm model with a high level of accuracy, indicating that the adsorption processes were chemical, multi-layer adsorption process. The maximum adsorption capacity of dry Fe-ALE and FeCaMg-ALE concerning phosphate were 15.06 and 20.10 mg/g, respectively at 298 K. The adsorption capacity remained relatively consistent across a pH range of 2.0–11.0. FT-IR, XRD, SEM coupled with XPS analysis demonstrated the ALE had been successfully compounded with Fe3+ or Fe3+/Ca2+/Mg2+. Based on the experimental results and characteristic analysis, the main mechanism of phosphate by Fe-ALE and FeCaMg-ALE are physical filling, electrostatic attraction, ligand exchange and precipitation reaction. This work provides a new perspective for preparing ALE-based adsorbent using conventional activated sludge as raw material, realizing the treatment of waste with waste and effectively recovering phosphate from wastewater.

Co(PO3)2@CoP Heterojunction in CoPO/GC/NF Nanoarrays Modulate Proton Hydrogen-Promoted Electrocatalytic Hydrodechlorination.

Cobalt phosphide has received much attention as an efficient catalyst for electrocatalytic hydrodechlorination (EHDC). However, the active species proton hydrogen (H*) is consumed by the hydrogen evolution reaction (HER). Herein, we report a crystal regulation strategy for cobalt phosphate/graphitic nanocarbon/nickel foam (CoPO/GC/NF) catalysts applied for the EHDC of 2,4-dichlorophenoxyacetic acid (2,4-D). Characterization revealed that during the high-temperature phosphatization process, CoPO/GC/NF catalysts developed Co(PO3)2@CoP heterojunctions, enhancing charge transfer at the electrolyte-catalyst interface and water dissociation. The interaction between Co(PO3)2 and CoP induced the reconstitution of CoP into the Co-OH species, which facilitated the production of H* by accelerating the Volmer step, enhancing EHDC activity. Furthermore, Co(PO3)2 species improve the catalyst tolerance, with CoPO/GC/NF(450) maintaining over 71% yield of phenoxyacetic acid (PA) in continuous testing for up to 80 h under high-salt conditions. This work clarifies the surface transformation process of CoP/GC/NF during hydrodechlorination and demonstrates great potential for chlorophenol wastewater remediation.

Precisely Designed Ultra-Small CoP Nanoparticles-Decorated Hollow Carbon Nanospheres as Highly Efficient Host in Lithium-Sulfur Batteries.

Designing porous carbon materials with metal phosphides as host materials holds promise for enhancing the cyclability and durability of lithium-sulfur (Li-S) batteries by mitigating sulfur poisoning and exhibiting high electrocatalytic activity. Nevertheless, it is urgent to precisely control the size of metal phosphides to further optimize the polysulfide conversion reaction kinetics of Li-S batteries. Herein, a subtlety regulation strategy was proposed to obtain ultra-small CoP nanoparticles-decorated hollow carbon nanospheres (CoP@C) by using spherical polyelectrolyte brush (SPB) as the template with stabilizing assistance from polydopamine coating, which also works as carbon source. Leveraging the electrostatic interaction between SPB and Co2+, ultra-small Co particles with sizes measuring 5.5±2.6 nm were endowed after calcination. Subsequently, through a gas-solid phosphating process, these Co particles were converted into CoP nanoparticles with significantly finer sizes (7.1±3.1 nm) compared to state-of-the-art approaches. By uniformly distributing the electrocatalyst nanoparticles on hollow carbon nanospheres, CoP@C facilitated the acceleration of Li-ion diffusion and enhanced the conversion reaction kinetics of polysulfides through adsorption-diffusion synergy. As a result, Li-S batteries utilizing the CoP@C/S cathode demonstrated an initial specific discharge capacity of 850.0 mAh g-1 at 1.0 C, with a low-capacity decay rate of 0.03 % per cycle.

Improving the phosphating process for Ca-P coating on ZK21 biomedical magnesium alloy

Improving the phosphating process for Ca-P coating on ZK21 biomedical magnesium alloy

Core–Shell Co‐CoxP Nanoparticle‐Embedded N‐Doped Carbon Nanowhiskers Hollow Sphere for Efficient Oxygen Evolution Electrocatalysis

AbstractThe development of efficient oxygen evolution reaction (OER) electrocatalysts is critical to overcome the efficiency bottleneck in hydrogen generation via water electrolysis. Hollow nanostructured materials have emerged as a hot topic for electrocatalysis research because of their advantages, including abundant active sites, a large contact area between the catalyst and the electrolyte, and a short transmission path. As highly efficient and stable OER electrocatalysts, cobalt‐based nanostructured materials have attracted more and more attention. In this work, cobalt metal/cobalt phosphides/nitrogen‐doped carbon composites (Co‐CoxP/NC) with a hierarchical hollow structure are designed by using hollow ZIF‐67 microspheres as precursors. By coating ZIF‐8 on the surface of hollow ZIF‐67 microspheres and further carbonizing, carbon nanowhiskers are successfully formed on the surface of hollow carbon spheres under the catalytic effect of Co nanoparticles at a high temperature. In the subsequent phosphating process, solid Co nanocrystalline particles are transformed into core–shell CoP and Co2P nanoparticles on account of the Kirkendall effect. Through the optimization of the microstructure of the material and the synergistic effect of transition metal, transition metal phosphide, and nitrogen doping, the overpotential of the optimal material is only 287 mV at 10 mA cm−2 current density in 1 m KOH.

Solubility of codeine phosphate in ethylene glycol + N-methyl-2-pyrrolidone mixtures at different temperatures

ABSTRACT The primary objective of the present study is to systematically investigate the solubility data and thermodynamic properties associated with codeine phosphate within mixtures comprising ethylene glycol (EG) and N-methyl-2-pyrrolidone (NMP) under atmospheric pressure conditions within the temperature range of 293.2–313.2 K. The analysis reveals a discernible positive correlation with both temperature and the ratio of EG. Mathematical models are employed for the purpose of correlating the obtained data, and the reliability of these models is rigorously assessed through the computation of mean relative deviations for back-calculated values. Additionally, the density values of codeine phosphate saturated mixtures are meticulously measured and subsequently correlated utilising the Jouyban-Acree model. Furthermore, the apparent thermodynamic properties governing the solubilisation process of codeine phosphate, including standard enthalpy, entropy and Gibbs free energy, are computed through the application of Gibbs and van’t Hoff equations, and the obtained results are comprehensively documented.