Thermodynamic Equilibrium Model Research Articles

Thermodynamic equilibrium modeling of biomass gasification: Effects of operating conditions on gasifier performance

Biomass has remarkable potential to reduce harmful emissions and ensure stable and sustainable energy production. In this paper, various parameters such as operating temperature, type of gasifying agent, air–fuel ratio and steam-fuel ratio are investigated on the qualitative characteristics of the syngas obtained from biomass gasification. The qualitative indicators considered were the percentage of combustible components under the energy aspect and the percentage of undesirable components under the environmental aspect. The composition of the syngas was determined for a temperature range of 500–1000 °C as an equilibrium composition using the Gibbs free energy minimisation method. The results showed that increasing the gasification temperature above 900 °C had a positive effect on the energy and environmental properties of the syngas. Air and water vapour were selected as possible gasifying agents. The results showed that water vapour was significantly more favourable than air as a gasifying agent in terms of syngas quality. In the best case, the H2 yield for gasification with air is 35 %vol, while this value reaches 65 %vol for gasification with steam. In addition to the type, the ratio of the gasifying agent to the amount of fuel was also analysed. The analysis showed that it was more favourable to carry out the gasification process at lower air-to-fuel and steam-to-fuel ratios, which is consistent with the work of other authors.

The updated BOSZ synthetic stellar spectral library

The modeling of stellar spectra of flux standards observed by the Hubble and James Webb space telescopes requires a large synthetic spectral library that covers a wide atmospheric parameter range. The aim of this paper is to present and describe the calculation methods behind the updated version of the BOSZ synthetic spectral database, which was originally designed to fit the CALSPEC flux standards. These new local thermodynamic equilibrium (LTE) models incorporate both MARCS and ATLAS9 model atmospheres, updated continuous opacities, and 23 new molecular line lists. The new grid was calculated with Synspec using the LTE approximation and covers metallicities \ from $-$2.5 to 0.75 dex \ from $-$0.25 to 0.5 dex, and \ from $-$0.75 to 0.5 dex, providing spectra for 336 unique compositions. Calculations for stars between 2800 and 8000 K use MARCS model atmospheres, and ATLAS9 is used between 7500 and 16,000 K. The new BOSZ grid includes 628,620 synthetic spectra from 50 nm to 32 \ with models for 495 parameter pairs per composition and per microturbulent velocity. Each spectrum has eight different resolutions spanning a range from R = 500 to 50,000 as well as the original resolution of the synthesis. The microturbulent velocities are 0, 1, 2, and 4 kms. The new BOSZ grid extends the temperature range to cooler temperatures compared to the original grid because the updated molecular line lists make modeling possible for cooler stars. A publicly available and consistently calculated database of model spectra is important for many astrophysical analyses, for example spectroscopic surveys and the determination of stellar elemental compositions.

Biosolid Gasification Performance Prediction Using a Stoichiometric Thermodynamic Model.

The gasification process can recover energy from biosolids produced in wastewater treatment. This paper developed a stoichiometric thermodynamic equilibrium model for biosolid gasification based on the biosolid properties, thermodynamic database, and equilibrium constants. If the calculation result showed that the quantity of char was negative, the quantity of char was put to zero, and the simulation was carried out again. The model was first verified by woody gasification under isothermal conditions, and the influence of a given temperature on biosolid gasification was simulated. The model further investigated the effects of different feedstock types, moisture contents, equivalence ratios, and reaction extensions on the adiabatic temperature, exergy efficiency, and syngas properties under autothermal conditions. The four factors were all the main factors for adiabatic temperature. The exergy efficiency depended more on the operation conditions than on the feedstock type. The H2 concentration of the dry syngas in biosolid gasification exhibited a curve both against the given temperature under isothermal conditions and against the moisture content under autothermal conditions.

Equilibrium adsorption, kinetic, thermodynamic, and breakthrough curves modelling of acetaminophen on Elaeagnus Angustifolia L. seeds-based granular activated carbon

ABSTRACT The widespread presence of pharmaceutical compounds as emerging environmental contaminants in aquatic environments has become a significant concern in recent years. In this study, synthesised granular activated carbon (GAC) derived from Elaeagnus Angustifolia L. seeds was utilised as an adsorbent to remove an emerging contaminant, acetaminophen (commercially known as paracetamol). The operating conditions for the chemical synthesis of the GAC, utilising ZnCl2 as an activating agent, included an impregnation ratio of 1:1, carbonisation at 500°C for 1 hour, and a heating rate of 5 °C/min. The efficacy of this adsorbent was assessed through both batch and fixed-bed column adsorption experiments under various operational parameters, including adsorbent mass (1–6 g/L), contact time, pH (2–10), temperature (20–60°C), inlet acetaminophen concentration (20–150 mg/L), and flow rate (0.5–1.5 mL/min). The results indicate that acetaminophen was better adsorbed in its neutral form rather than in its dissociated state. The findings also revealed that both the Langmuir (two-parameter) and Sips (three-parameter) models provided the best fit for the static adsorption equilibrium data. Furthermore, kinetic analysis indicated that the experimental data were best modelled by the Elovich model and governed by both external diffusion and intraparticle diffusion mechanisms. Therefore, the Yan-Viraraghavan model provided a good fit for the experimental breakthrough curves under various operating conditions. However, the adsorbed amounts of acetaminophen obtained from the column experiment indicated that the high-adsorbed amount of 204.11 mg/g was achieved with an inlet acetaminophen concentration of 150 mg/L, a bed depth of 6 cm, and a flow rate of 0.5 mL/min. These results highlight the potential of the synthesised GAC as a promising adsorbent for pharmaceutical wastewater treatment using fixed-bed column systems.

Equilibrium adsorption, kinetic, thermodynamic, and breakthrough curves modelling of acetaminophen on Elaeagnus Angustifolia L. seeds-based granular activated carbon

ABSTRACT The widespread presence of pharmaceutical compounds as emerging environmental contaminants in aquatic environments has become a significant concern in recent years. In this study, synthesised granular activated carbon (GAC) derived from Elaeagnus Angustifolia L. seeds was utilised as an adsorbent to remove an emerging contaminant, acetaminophen (commercially known as paracetamol). The operating conditions for the chemical synthesis of the GAC, utilising ZnCl2 as an activating agent, included an impregnation ratio of 1:1, carbonisation at 500°C for 1 hour, and a heating rate of 5 °C/min. The efficacy of this adsorbent was assessed through both batch and fixed-bed column adsorption experiments under various operational parameters, including adsorbent mass (1–6 g/L), contact time, pH (2–10), temperature (20–60°C), inlet acetaminophen concentration (20–150 mg/L), and flow rate (0.5–1.5 mL/min). The results indicate that acetaminophen was better adsorbed in its neutral form rather than in its dissociated state. The findings also revealed that both the Langmuir (two-parameter) and Sips (three-parameter) models provided the best fit for the static adsorption equilibrium data. Furthermore, kinetic analysis indicated that the experimental data were best modelled by the Elovich model and governed by both external diffusion and intraparticle diffusion mechanisms. Therefore, the Yan-Viraraghavan model provided a good fit for the experimental breakthrough curves under various operating conditions. However, the adsorbed amounts of acetaminophen obtained from the column experiment indicated that the high-adsorbed amount of 204.11 mg/g was achieved with an inlet acetaminophen concentration of 150 mg/L, a bed depth of 6 cm, and a flow rate of 0.5 mL/min. These results highlight the potential of the synthesised GAC as a promising adsorbent for pharmaceutical wastewater treatment using fixed-bed column systems.

The rotation-tunneling spectrum of 3-hydroxypropenal and confirmation of its detection toward IRAS 16293-2422 B

Context. 3-Hydroxypropenal (HOCHCHCHO) is the lower energy tautomer of malonaldehyde which displays a complex rotation-tunneling spectrum. It was detected somewhat tentatively toward the solar-type protostellar system IRAS 16293-2422 with ALMA in the framework of the Protostellar Interferometric Line Survey (PILS). Several transitions, however, had large residuals, preventing not only their detection, but also the excitation temperature of the species from being determined unambiguously. Aims. We want to extend the existing rotational line list of 3-hydroxypropenal to shed more light on the recent observational results and to facilitate additional radio astronomical searches for this molecule. Methods. We recorded and analyzed the rotation-tunneling spectrum of 3-hydroxypropenal in the frequency regions between 150 and 330 GHz and between 400 and 660 GHz. Transitions were searched for in the PILS observations of IRAS 16293-2422. Local thermodynamic equilibrium (LTE) models were carried out and compared to the observations to constrain the excitation temperature. Additional transitions were searched for in other ALMA archival data of the same source to confirm the presence of 3-hydroxypropenal. Results. More than 7500 different spectral lines, corresponding to more than 11 500 transitions, were assigned in the course of our investigation with quantum numbers 2 ≤ J ≤ 100, Ka ≤ 59, and Kc ≤ 97, resulting in a greatly improved set of spectroscopic parameters. The comparison between the LTE models and the observations yields an excitation temperature of 125 K with a column density N = 1.0 × 1015 cm−2 for this species. We identified seven additional lines of 3-hydroxypropenal that show a good agreement with the model in the ALMA archive data. Conclusions. The calculated rotation-tunneling spectrum of 3-hydroxypropenal has sufficient accuracy for radio astronomical searches. With the solution of the excitation temperature conundrum and the detection of seven more lines, we consider the detection of 3-hydroxypropenal toward IRAS 16293-2422 as secure.

Regional potential of coastal ocean alkalinization with olivine within 100 years

The spreading of crushed olivine-rich rocks in coastal seas to accelerate weathering reactions sequesters atmospheric CO2 and reduces atmospheric CO2 concentrations. Their weathering rates depend on different factors, including temperature and the reaction surface area. Therefore, this study investigates the variations in olivine-based enhanced weathering rates across 13 regional coasts worldwide. In addition, it assesses the CO2 sequestration within 100 years and evaluates the maximum net-sequestration potential based on varying environmental conditions. Simulations were conducted using the geochemical thermodynamic equilibrium modeling software PHREEQC. A sensitivity analysis was performed, exploring various combinations of influencing parameters, including grain size, seawater temperature, and chemistry. The findings reveal significant variation in CO2 sequestration, ranging from 0.13 to 0.94 metric tons (t) of CO2 per ton of distributed olivine-rich rocks over 100 years. Warmer coastal regions exhibit higher CO2 sequestration capacities than temperate regions, with a difference of 0.4 t CO2/t olivine distributed. Sensitivity analysis shows that smaller grain sizes (10 µm) exhibit higher net CO2 sequestration rates (0.87 t/t) in olivine-based enhanced weathering across all conditions, attributed to their larger reactive surface area. However, in warmer seawater temperatures, olivine with slightly larger grain sizes (50 and 100 µm) displays still larger net CO2 sequestration rates (0.97 and 0.92 t/t), optimizing the efficiency of CO2 sequestration while reducing grinding energy requirements. While relying on a simplified sensitivity analysis that does not capture the full complexity of real-world environmental dynamics, this study contributes to understanding the variability and optimization of enhanced weathering for CO2 sequestration, supporting its potential as a sustainable CO2 removal strategy.

Chemical inventory of the envelope of the Class I protostar L1551 IRS 5

Episodic accretion in protostars leads to luminosity outbursts that end up heating their surroundings. This rise in temperature pushes the snow lines back, enabling the desorption of chemical species from dust grain surfaces, which may significantly alter the chemical history of the accreting envelope. However, a limited number of extensive chemical surveys of eruptive young stars have been performed thus far. In the present study, we carry out a large spectral survey of the binary Class I protostar L1551 IRS 5, known to be a FUor-like object, in the 3mm and 2mm bands with the IRAM-30m telescope. As a result, we detected more than 400 molecular lines. The source displays a great chemical richness with the detection of 75 species, including isotopologues. Among these species, there are 13 hydrocarbons, 25 N-bearing species, 30 O-bearing species, 15 S-bearing species, 12 deuterated molecules, and a total of 10 complex organic molecules (l-C$_4$H$_2$, CH$_3$CCH, CH$_2$DCCH, CH$_3$CHO, CH$_3$CN, CH$_3$OCH$_3$, CH$_3$OCHO, CH$_3$OH, CH$_2$DOH, and HC$_5$N). With the help of local thermodynamic equilibrium (LTE) and non-LTE models, we determined the column densities of most molecules as well as excitation and kinetic temperatures. While most of those molecules trace the cold envelope ($ 20$ K), the OCS and CH$_3$OH emission arise from the warm ($> 100$ K) innermost ($< 2$ regions. We compared the chemical inventory of L1551 IRS 5 and its column density ratios, including isotopic ratios, with other protostellar sources. A broad chemical diversity is seen among Class I objects. More observations with both single-dish telescopes and interferometers are needed to characterize the diversity in a larger sample of protostars, while more astrochemical models would help explain this diversity, in addition to the impact of luminosity outbursts on the chemistry of protostellar envelopes.

Diffusion in multicomponent mixed solvent electrolyte systems

Thermodynamic ideality is often assumed in diffusion calculation, implying concentrations are assumed equal to the activities with activity coefficients of one. A general set of diffusion flux and molar flux equations are developed, incorporating equilibrium thermodynamic models for non-ideal conditions in well-known non-equilibrium diffusion theory. Derivations are based on the Maxwell-Stefan friction theory with the chemical potential as the driving force. Isothermal and isobaric conditions are assumed, and the theory does not include the Soret coefficient or the Onsager formalism.In this work, Fick's law is derived from the general diffusion theory, also as a function of activity gradients. The results illustrate that concentration cannot just be substituted by activity. Using a similar approach demonstrates that the Nernst-Planck (NP) equation may be derived from the general theory incorporating terms for migration and convection. An extended NP equation is derived including the thermodynamic correction factors (TCF) to account for the non-ideality of the liquid. The derived equation shows the improvement of the self-diffusion terms and friction coefficients in the NP equation and that the TCF enhances the observed effective diffusivities.Examples of TCF are presented using the extended UNIQUAC thermodynamic model. This is done for the CO2-NaOH-monoethyleneglycol-water system, which is typically found in wet natural gas pipeline CO2 corrosion systems. pH-stabilization is classically used in the prevention of corrosion, but the results show that glycol has a noticeable effect of the diffusion on key components in the corrosion mechanism. A TCF of 0.4 to 1.3 may be expected. This indicates that the flux calculation deviates up to 60 % from the real-life scenario if ideality is assumed. The thermodynamic model may therefore improve the diffusion calculations considerably.

Thermodynamic and environmental analysis of integrated supercritical water gasification of sewage sludge for power and hydrogen production

Supercritical water gasification is a promising process for treating sewage sludge (SS) to obtain hydrogen and electrical energy. Here, a novel thermodynamic equilibrium model for supercritical water gasification of sewage sludge was developed and the thermodynamic and environmental effects of operating parameters on the system were investigated. The sensitivity analysis revealed that the optimum reaction condition for the system was: reaction temperature of 750 °C, preheated water to SS ratio of 1, and SS concentration of 25 %. Under this condition, the system energy efficiency and exergy efficiency were 44.74 % and 46.51 %, respectively, with H2 production of 103.19 kg/h and power generation of 2526.2 kW. The energy and exergy efficiencies could be improved by reducing the preheated water to SS ratio and increasing the reaction temperature and SS concentration. The heat exchangers and the heater were the key units causing exergy losses, accounting for 40.3 % and 19.5 % of the total exergy losses, respectively. When utilizing carbon capture and storage (CCS), the global warming potential (GWP) value was only 0.31 kg CO2-eq under the optimal operating parameters, which was 61.44 % less than without CCS.

Phase equilibrium data prediction and process optimizationin butadiene extraction process

In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction, a large amount of phase equilibrium data was collected in the context of the actual process of butadiene production by acetonitrile. The accuracy of five prediction methods, UNIFAC, UNIFAC-LL, UNIFAC-LBY, UNIFAC-DMD, and COSMO-RS, applied to the butadiene extraction process was verified using partial phase equilibrium data. The results showed that the UNIFAC-DMD method had the highest accuracy in predicting phase equilibrium data for the missing system. COSMO-RS predicted multiple systems showed good accuracy. And a large number of missing phase equilibrium data were estimated using the UNIFAC-DMD method and COSMO-RS method. The predicted phase equilibrium data were checked for consistency. The NRTL-RK and UNIQUAC thermodynamic models were used to correlate the phase equilibrium data. Industrial device simulations were used to verify the accuracy of the thermodynamic model applied to the butadiene extraction process. The simulation results showed that the average deviations of the simulated results using the correlated thermodynamic model from the actual values were less than 2% compared to that using the commercial simulation software Aspen Plus and its database. The average deviation was much smaller than that of the simulations using the Aspen Plus database (>10%), indicating that the obtained phase equilibrium data are highly accurate and reliable. The best phase equilibrium data and thermodynamic model parameters for butadiene extraction are provided. This improves the accuracy and reliability of the design, optimization and control of the process, and provides a basis and guarantee for developing a more environmentally friendly and economical butadiene extraction process.

Nitric Oxide Concentration: A New Data Set Derived From SABER Measurements

AbstractVertical profiles of nitric oxide (NO) concentration are derived between 120 and 250 km using updated NO emission rates measured by Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on the NASA Thermosphere Ionosphere Mesosphere Energetics and Dynamics satellite. The Naval Research Laboratory Mass Spectrometer Incoherent Scatter Radar (MSIS) 2.1 model is used to provide the required parameters of temperature, atomic oxygen number density, and molecule oxygen number density needed to derive the NO concentrations using a non‐local thermodynamic equilibrium (non‐LTE) model. The SABER NO concentration shows a significant correlation with solar activity with larger peak NO concentrations and higher altitude extent during solar maximum years compared to those during the solar minimum years. The SABER NO agrees well with the MSIS 2.1 NO at altitudes above 120 km for all latitudes, while the pronounced SABER‐MSIS NO discrepancy below 120 km is likely due to the temperature underestimation by MSIS 2.1. A detailed error analysis is presented and considers systematic and random errors in all the terms in the non‐LTE model used to derive the NO concentration. Random error in MSIS 2.1 temperature and atomic oxygen dominates the uncertainty in single NO profiles above 120 km. We estimated a systematic error up to ∼36% between 120 and 250 km during solar maximum years.

Highly efficient nitric oxide absorption by low viscosity superbase/amide deep eutectic solvents through mutual promotion effect

A series of low-viscous deep eutectic solvents (DESs) with superbase as HBA and amide as HBD were designed and prepared for NO absorption. Impressively, both a comparably low viscosity of 8.07 mPa∙s and a high absorption capacity of 6.43 mol∙kg−1 (∼0.19 kg/kg) at 293.2 K were achieved, which was superior to that of other reported absorbents. Through a combination of absorption experiments, FT-IR characterization, and thermodynamic modelling, the results indicated that such a high solubility for NO was originated from the mutual promotion effect between the superbase and the amide. Considering that chemical absorption occurred accompanied with physical one, a reaction equilibrium thermodynamic model (RETM) equation was derived to correlate the experiment solubility data, so that the thermodynamic parameters were obtained to evaluate the absorption process. The absorption-desorption cycle experiment revealed that the regeneration efficiency of the superbase/amide DESs could be high up to 90 %. Given the low viscosity, high absorption capacity and excellent recycle efficiency, the superbase/amide DES was considered as a promising candidate for NO capture and utilization.

Molecular and electrostatic origins of mixed salt partitioning phenomena in uncharged poly(ethylene oxide)-based membranes

Despite the increasing interest in membranes for water purification and resource recovery from aqueous electrolyte mixtures, few studies rigorously investigate the influence of salt solution composition (e.g., mole fraction and total salt concentration) on membrane material properties such as partition coefficients. Here, we systematically investigate the influence of solution composition on the partitioning of ionic species from binary aqueous salt solutions into crosslinked poly(ethylene glycol) diacrylate membranes at fixed ionic strength. These results are compared to partition coefficients observed for pure salt solutions. We observe large systematic deviations between the pure salt and mixed salt ion partition coefficients, indicating that the single salt partition coefficients that are often reported do not describe the more complex and realistic mixed salt scenario. Free energy calculations from molecular dynamics simulations, coupled with equilibrium thermodynamic modeling, indicate that mixed salt partitioning trends result from (i) different ions exhibiting different affinities for the membrane and (ii) the constraint of global electrical neutrality within the membrane. With this physical insight, we develop a simple approach to predicting the concentration of various ions in a membrane equilibrated with a mixed salt solution which requires no adjustable parameters.

Combined leaching and steam explosion pretreatment of lignocellulosic biomass for high quality feedstock for thermochemical applications

A novel pretreatment approach was developed in the present study to simultaneously reduce the content of inorganic troubling elements (TEs) and improve biomass energy density, i.e., combined leaching and steam explosion (SE) pretreatment with mechanical pressing. Three different high-ash-containing biomass feedstocks were studied – wheat straw (WS), spruce bark (SB), and empty fruit bunches of oil palm (EFB). Before studying the combined pretreatment, the impact of individual pretreatment was determined in-depth on biomass composition and ash-transformation behaviour. In leaching pretreatment, the effect of leaching with steam explosion condensate (SEC), dilute acetic acid and water was studied comprehensively. The solid (raw and treated) and liquid samples (leachate, SEC, hydrolysate) were characterized for a detailed comparative analysis. The ash-fusion and −transformation behaviour of raw and pretreated biomass was studied in-depth using advanced multicomponent thermodynamic equilibrium modelling (TEM) and push-rod dilatometry. After combined pretreatment, a considerably high reduction in TEs content was noted: 82–98 % K, 93–99 % Na, 80–99 % Cl, 34–90 % S, 3–77 % Mg, ash 43–63 %, 26–67 % P, and 19–63 % Ca. Simultaneously, heating values of all three feedstocks increased by 1.3–2.3 MJ/kg, reaching up to 20–22 MJ/kg. TEM results reveal that much lesser amounts of molten slag and volatile inorganic compounds were formed in pretreated samples compared to raw and SE biomass, such as K2Si5MgO12, KCl, KPMgO4, K2Si2O5, CaSiO3, and MgSiO3 in WS; Na2CO3, K2CO3, K2CaC2O6, KPMgO4, and CaCO3 in SB. Due to higher energy density and lower propensity towards ash-related issues, combined pretreated WS and SB have a high potential to be used in large-scale thermochemical applications.

Investigation of effective CO2 capture by ternary deep eutectic solvents based on superbase

The absorption and separation of CO2 is one of the main strategies to reduce carbon emissions and mitigate global climate change. In this context, a series of ternary superbase/betaine-based deep eutectic solvents (DESs) were synthesized to capture CO2, and their density, viscosity and thermal stability were investigated. The effects of temperature, pressure, different hydrogen bond donors (HBDs) and alkalinity of the superbase on their CO2 affinity were evaluated by the isovolumetric saturation method. The uptake of CO2 by the DES synthesized from betaine, 1,2-propanediol and 1,8-diazabicyclo(5.4.0)undec-7-ene reached a maximum of 1.5071 mol·kg−1 at 303.15 K and a pressure of 0.187 MPa. The simultaneous chemical and physical adsorption of CO2 by the ternary DESs was verified by FTIR spectroscopy, and the absorption mechanism was also proposed. The reaction equilibrium thermodynamic model (RETM) was improved to obtain the “Active DES” model, which was correlated with the experimentally determined CO2 solubility. The reaction equilibrium constants and Henry's law constants were obtained for each ternary system. The ternary superbase/betaine DESs proposed in this paper are green, economical and high-performance absorbers for capturing CO2.

How non-equilibrium aerosol chemistry impacts particle acidity: the GMXe AERosol CHEMistry (GMXe–AERCHEM, v1.0) sub-submodel of MESSy

Abstract. Aqueous-phase chemical processes in clouds, fog, and deliquescent aerosols are known to alter atmospheric composition and acidity significantly. Traditionally, global and regional models predict aerosol composition by relying on thermodynamic equilibrium models and neglect non-equilibrium processes. Here, we present the AERosol CHEMistry (GMXe–AERCHEM, v1.0) sub-submodel developed for the Modular Earth Submodel System (MESSy) as an add-on to the thermodynamic equilibrium model (i.e. ISORROPIA-II) used by MESSy's Global Modal-aerosol eXtension (GMXe) submodel. AERCHEM allows the representation of non-equilibrium aqueous-phase chemistry of varying complexity in deliquescent fine aerosols. We perform a global simulation for the year 2010 by using the available detailed kinetic model for the chemistry of inorganic and small oxygenated organics. We evaluate AERCHEM's performance by comparing the simulated concentrations of sulfate, nitrate, ammonium, and chloride to in situ measurements of three monitoring networks. Overall, AERCHEM reproduces observed concentrations reasonably well. We find that, especially in the USA, the consideration of non-equilibrium chemistry in deliquescent aerosols reduces the model bias for sulfate, nitrate, and ammonium when compared to simulated concentrations by ISORROPIA-II. Over most continental regions, fine-aerosol acidity simulated by AERCHEM is similar to the predictions by ISORROPIA-II, but simulated aerosol acidity tends to be slightly lower in most regions. The consideration of non-equilibrium chemistry in deliquescent aerosols leads to a significantly higher aerosol acidity in the marine boundary layer, which is in line with observations and recent literature. AERCHEM allows an investigation of the global-scale impact of aerosol non-equilibrium chemistry on atmospheric composition. This will aid in the exploration of key multiphase processes and improve the model predictions for oxidation capacity and aerosols in the troposphere.

NLTE modelling of water-rich exoplanet atmospheres. Cooling and heating rates

The hydrogen and water molecules respond very differently to the collisional-radiative processes taking place in planetary atmospheres. Naturally, the question arises whether H2O-rich atmospheres are more (or less) resilient to long-term mass loss than H2-dominated ones if they radiate away the incident stellar energy more (or less) efficiently. If confirmed, the finding would have implications on our understanding of the evolution of sub-Neptune exoplanets. As a key step towards answering this question, we present a non-local thermodynamic equilibrium (NLTE) model of H2O for the atmospheric region where the gas accelerates to escape the planet and conditions relevant to close-in sub-Neptunes. Our exploratory calculations for isothermal gas composed of H2, H2O and e− reveal that: (1) In the pressure region ∼10−2–10−4 dyn cm−2 where the stellar extreme-ultraviolet (XUV) photons are typically deposited in the atmosphere, H2O is in rotational LTE but vibrational NLTE. Vibrational LTE is facilitated by high H2O abundances and fractional ionizations, and we report critical densities for the LTE-NLTE transition; (2) Vibrational cooling may locally dominate over rotational cooling, partly because of the comparatively small opacities of ro-vibrational lines; (3) Even low H2O abundances notably enhance the cooling, foreseeably offsetting some of the stellar heating; (4) Heating due to the deposition of stellar infrared (IR) photons is significant at pressures ≳0.1 dyn cm−2. We estimate the contribution of H2O excitation to the internal energy of the gas and speculate on the photodissociation from the excited vibrational states. Ultimately, our findings motivate the consideration of NLTE in the mass loss rate calculations of H2O-rich atmospheres.

Melting and solidification dynamics during laser melting of reaction-based metal matrix composites uncovered by in-situ synchrotron X-ray diffraction

Laser additive manufacturing (AM) of reaction-based metal matrix composites (MMCs) involves highly complex and non-equilibrium material transformation behavior, including melting, dissolution, precipitation, and solidification. Yet, the dynamics and interplay of these phase transformation processes remain poorly understood, posing substantial challenges in identifying the microstructure formation mechanism, and predicting and controlling the microstructure in the printed parts. Here we performed the in-situ X-ray diffraction experiment to characterize the phase evolution dynamics of the 316L + 10 vol.%TiC system during laser melting, which provides direct and quantitative insights of the complex phase reaction and evolution dynamics under rapid heating and cooling conditions relevant to additive manufacturing of reaction-based MMCs. Further in-depth thermodynamic and kinetic calculations revealed that most of the phase evolution behavior observed in the in-situ X-ray diffraction experiment cannot be solely explained by widely used equilibrium thermodynamic models, and diffusion-controlled nonequilibrium dissolution and precipitation kinetics must be considered to elucidate the complex phase evolution behavior, including incomplete TiC dissolution, and three-step TiC precipitation. The three distinct types of precipitates generate unique hierarchical TiC micro- and nanostructures, which enhances the yield strength from 513 MPa to 877 MPa by 71 %, tensile strength from 628 MPa to 1054 MPa by 68 %, and Young's modulus from 193 GPa to 221 GPa by 14 %. The findings of our research provide the knowledge foundation for the design of unique microstructures and advanced MMC materials through laser AM.

Hydrogen-Rich Syngas Production from Gasification of Sewage Sludge: Catalonia Case

The continuous tightening of legislation regulating the agricultural usage of sewage sludge in the province of Catalonia (Spain) leads us to propose its gasification to produce hydrogen-rich syngas. A thermodynamic equilibrium model was developed using Aspen Plus® to simulate the air and steam gasification of sewage sludge from a wastewater treatment plant in Catalonia. The syngas generated is analyzed in terms of composition and lower heating value (LHV), as a function of equivalence ratio (ER), gasification temperature (Tgas), steam-to-biomass ratio (SBR), and moisture content (MC). Results show that air-blown gasification finds the highest LHV of 7.48 MJ/m3 at 1200 °C, ER of 0.2, and MC of 5%. Using steam as the gasifying agent, an LHV of 10.30 MJ/m3 is obtained at SBR of 0.2, MC of 5%, and 1200 °C. A maximum of 69.7% hydrogen molar fraction is obtained at 600 °C, MC of 25%, and SBR of 1.2. This study suggests using steam as a gasifying agent instead of air since it provides a higher LHV of the syngas as well as a hydrogen-richer syngas for the implementation of gasification as an alternative method to sewage sludge treatment in the region of Catalonia. Since the economic aspect should also be considered, in this regard, our sensitivity analysis provided important data demonstrating that it is possible to reduce the gasification temperature without significantly decreasing the LHV.