Thermodynamic Information Research Articles

Stochastic Electrochemical Measurement of a Biofouling Layer on Gold.

Adsorption of a biofouling layer on the surface of biosensors decreases the electrochemical activity and hence shortens the service life of biosensors, particularly implantable and wearable biosensors. Real-time quantification of the loss of activity is important for in situ assessment of performance while presenting an opportunity to compensate for the loss of activity and recalibrate the sensor to extend the service life. Here, we introduce an electrochemical noise measurement technique as a tool for the quantification of the formation of a biofouling layer on the surface of gold. The technique uniquely affords thermodynamic and kinetic information without applying an external bias (potential and/or current), hence allowing the system to be appraised in its innate state. The technique relies on the analysis of non-faradaic current and potential fluctuations that are intrinsically generated by the interaction of charged species at the electrode surface, i.e., gold. An analytical model is extended to explain the significance of parameters drawn from statistical analysis of the noise signal. This concept is then examined in buffered media in the presence of albumin, a common protein in the blood and a known source of a fouling layer in biological systems. Results indicate that the statistical analysis of the noise signal can quantify the loss of electrochemical activity, which is also corroborated by impedance spectroscopy as a complementary technique.

Thermodynamic information geometry of criticality, fluctuation anomaly and hyperscaling breakdown in the spin-3/2 chain

Equilibrium state space geometry is worked out for the exactly solved one-dimensional spin-3/2 lattice with a Blume–Emery–Griffiths (BEG) Hamiltonian as well as a more general one with a non-zero field coupled to the octopole moments. The phase behaviour of the spin-3/2 chain is revisited and novel observations of anomaly in the hyperscaling relation and in the decay of fluctuations are reported for the first time. Using the method of constrained fluctuations developed earlier in Sahay (2017); Sanwari and Sahay (2022) three appropriate state space sectional curvatures and a 3d curvature are shown to separately encode dipolar, quadrupolar and octopolar correlations both near and away from pseudo-criticality. In all observations of hyperscaling breakdown the 3d scalar curvature is found to encode the correlation length while the relevant sectional curvature equals the inverse of singular free energy. For parameter values where the order parameter fluctuation anomalously decays despite a divergence in its correlation length the relevant scalar curvature undergoes a sign change to positive values, signalling a possible change in the nature of the underlying statistical interactions.

Inconsistency between the micropolar theory and non-equilibrium thermodynamics in the case of polar fluids

Abstract The balance equation of angular momentum in anisotropic fluids includes a couple stress contribution, also responsible for an antisymmetric contribution to the force stress tensor. We herein derive all balance equations for the simplest anisotropic fluid, i.e., a polar fluid, using the GENERIC formalism of non-equilibrium thermodynamics. In doing so, we find that there is an inconsistency between the internal energy density evolution equation derived using non-equilibrium thermodynamics and the one usually considered in micropolar theory.

Hydrodynamic density functional theory of simple dissipative fluids

In this paper, a statistical physical derivation of thermodynamically consistent fluid mechanical equations is presented for non-isothermal viscous molecular fluids. The coarse-graining process is based on (i) the adiabatic expansion of the one-particle probability density function around local thermodynamic equilibrium, (ii) the assumption of decoupled particle positions and momenta, and (iii) the variational principle. It is shown that there exists a class of free energy functionals for which the conventional thermodynamic formalism can be naturally adopted for non-equilibrium scenarios, and describes entropy monotonic fluid flow in isolated systems. Furthermore, the analysis of the general continuum equations revealed the possibility of a non-local transport mode of energy in highly compressible dense fluids.

A new experimental setup for combined fast differential scanning calorimetry and X-ray photon correlation spectroscopy.

Synchrotron-radiation-based techniques are a powerful tool for the investigation of materials. In particular, the availability of highly brilliant sources has opened the possibility to develop techniques sensitive to dynamics at the atomic scale such as X-ray photon correlation spectroscopy (XPCS). XPCS is particularly relevant in the study of glasses, which have been often investigated at the macroscopic scale by, for example, differential scanning calorimetry. Here, we show how to adapt a Flash calorimeter to combine XPCS and calorimetric scans. This setup paves the way to novel experiments requiring dynamical and thermodynamic information, ranging from the study of the crystallization kinetics to the study of the glass transition in systems that can be vitrified thanks to the high cooling rates reachable with an ultrafast calorimeter.

Microcalorimetry Techniques for Studying Interactions at Solid–Liquid Interface: A Review

Solid–liquid interfacial phenomena play an essential role in our everyday lives and are often regarded as the outcome of interactions at the solid–liquid interface. However, the intricately intrinsic mechanism underlying interfacial interactions renders in situ simulations and direct measurements challenging. As an effective analytic method for studying solid–liquid interfacial interactions, microcalorimetry can provide the most basic thermodynamic information (including changes in enthalpy, entropy, and Gibbs free energy during solid–liquid binding/separation processes), which is extremely crucial for understanding interaction directionality and limitation. This review is dedicated to highlighting the pivotal role of microcalorimetry in studying solid–liquid immersion and adsorption processes. Specifically, we provide an overview of the commonly employed microcalorimetric methods, including differential scanning calorimetry (DSC), isothermal titration calorimetry (ITC), and immersion microcalorimetry (IM), and delve into the influence factors of enthalpy change, and finally discuss the specific applications of microcalorimetry in studying various solid–liquid binding processes. There remains a vast expanse of thermodynamic information regarding solid–liquid interactions that await exploration via calorimetry.

Interaction between water and point defects inside volume-constrained α-quartz: An ab initio molecular dynamics study at 300 K

Quartz-based minerals in earth’s crust are well-known to contain water-related defects within their volume-constrained lattice, and they are responsible for strength-loss. Experimental observations of natural α-quartz indicate that such defects appear as hydroxyl groups attached to Si atoms, called Griggs defect (Si-OH), and molecular water (H2O) located at the interstitial sites. However, factors contributing to the formation of Griggs and interstitial H2O defects remain unclear. For example, the role of point defects like vacancy sites (O2− and Si4+), and substitutional (Al3+) and interstitial (Li+, K+, Ca2+, Mg2+, etc.) ions has remained largely unexplored. Here, we performed ab initio molecular dynamics at 300 K to examine the energetics and structure of water-related defects in volume-constrained α-quartz. Several configurations were systematically interrogated by incorporating interstitial H2O, O2− and Si4+ vacancies, substitutional Al3+, and interstitial Li+, Ca2+ and Mg2+ ions within α-quartz. Interstitial H2O defect was found to be energetically favorable in the presence of Substitutional Al3+, and interstitial Ca2+, Mg2+, and Li1+. In the presence of O2− and Si4+ vacancies, H2O showed a strong tendency to dissociate into OH—to form Griggs defect—and a proton; even in the presence of substitutional and interstitial ions. These ions distorted the α-quartz lattice and, in the extreme case, disrupted long-range order to form local amorphous domains; consistent with experimental reports. Our study provides an initial framework for understanding the impact of water within the crystal lattice of an anhydrous silicate mineral such as quartz. We provide not only thermodynamic and process-related information on observed defects, but also provides guidelines for future studies of water’s impact on the behavior of silicate minerals.

AbLEF: antibody language ensemble fusion for thermodynamically empowered property predictions.

Pre-trained protein language and/or structural models are often fine-tuned on drug development properties (i.e. developability properties) to accelerate drug discovery initiatives. However, these models generally rely on a single structural conformation and/or a single sequence as a molecular representation. We present a physics-based model, whereby 3D conformational ensemble representations are fused by a transformer-based architecture and concatenated to a language representation to predict antibody protein properties. Antibody language ensemble fusion enables the direct infusion of thermodynamic information into latent space and this enhances property prediction by explicitly infusing dynamic molecular behavior that occurs during experimental measurement. We showcase the antibody language ensemble fusion model on two developability properties: hydrophobic interaction chromatography retention time and temperature of aggregation (Tagg). We find that (i) 3D conformational ensembles that are generated from molecular simulation can further improve antibody property prediction for small datasets, (ii) the performance benefit from 3D conformational ensembles matches shallow machine learning methods in the small data regime, and (iii) fine-tuned large protein language models can match smaller antibody-specific language models at predicting antibody properties. AbLEF codebase is available at https://github.com/merck/AbLEF.

Four Generations of Volcano Plots for the Oxygen Evolution Reaction: Beyond Proton-Coupled Electron Transfer Steps?

ConspectusDue to its importance for electrolyzers or metal-air batteries for energy conversion or storage, there is huge interest in the development of high-performance materials for the oxygen evolution reaction (OER). Theoretical investigations have aided the search for active material motifs through the construction of volcano plots for the kinetically sluggish OER, which involves the transfer of four proton-electron pairs to form a single oxygen molecule. The theory-driven volcano approach has gained unprecedented popularity in the catalysis and energy communities, largely due to its simplicity, as adsorption free energies can be used to approximate the electrocatalytic activity by heuristic descriptors.In the last two decades, the binding-energy-based volcano method has witnessed a renaissance with special concepts being developed to incorporate missing factors into the analysis. To this end, this Account summarizes and discusses the different generations of volcano plots for the example of the OER. While first-generation methods relied on the assessment of the thermodynamic information for the OER reaction intermediates by means of scaling relations, the second and third generations developed strategies to include overpotential and kinetic effects into the analysis of activity trends. Finally, the fourth generation of volcano approaches allowed the incorporation of various mechanistic pathways into the volcano methodology, thus paving the path toward data- and mechanistic-driven volcano plots in electrocatalysis.Although the concept of volcano plots has been significantly expanded in recent years, further research activities are discussed by challenging one of the main paradigms of the volcano concept. To date, the evaluation of activity trends relies on the assumption of proton-coupled electron transfer steps (CPET), even though there is experimental evidence of sequential proton-electron transfer (SPET) steps. While the computational assessment of SPET for solid-state electrodes is ambitious, it is strongly suggested to comprehend their importance in energy conversion and storage processes, including the OER. This can be achieved by knowledge transfer from homogeneous to heterogeneous electrocatalysis and by focusing on the material class of single-atom catalysts in which the active center is well defined. The derived concept of how to analyze the importance of SPET for mechanistic pathways in the OER over solid-state electrodes could further shape our understanding of the proton-electron transfer steps at electrified solid/liquid interfaces, which is crucial for further progress toward sustainable energy and climate neutrality.

Conductometric investigation of nano MnSO4 association parameters and complex formation with glycylglycine in aqueous and methanol-water mixtures: Thermodynamic parameters and potential applications

This study aimed to investigate the ion pair association values and association parameters of nano MnSO4 in water and methanol-water mixtures (20 % and 40 % methanol by mass percentage) at varying temperatures (298.15, 303.15, 308.15, and 313.15 K) using the conductometric technique. Additionally, the parameters for complex formation between nano MnSO4 and glycylglycine as a ligand were determined. The focus was on elucidating the thermodynamic formation parameters for the nano Mn2+-glycylglycine interaction, with particular emphasis on comparing the 1: 1 and 1: 2 (M: L) complexes to understand the complexation behavior more comprehensively. The results indicated that the complexation process was spontaneous, as evidenced by negative ΔGf (formation free energy change) values, which increased with temperature, highlighting the enhanced spontaneity of the process. The findings provide valuable insights into designing new materials and procedures by enhancing our understanding of the complexation behavior of nano MnSO4 with ligands like glycylglycine, thus contributing to advancements in various applications such as chemical synthesis, medicines, and environmental remediation. By elucidating the thermodynamic aspects of these interactions, the study aimed to provide valuable information that could be utilized in practical applications and further research endeavors.

Artificial Intelligence-Assisted Multiparameter Size Discrimination of Silver Nanoparticles through Electrochemical Collision.

Single particle collision is an important tool for size analysis at the individual particle level; however, due to complex dynamic behaviors of nanoparticles on the surface of an electrode, the accuracy of size discrimination is limited. A silver (Ag) nanoparticle (NP) was chosen as the research target, and the dynamic behavior of Ag NPs was simplified by enhancing adsorption between Ag NP and Au ultramicroelectrode (UME) in alkaline media. Immediately after, accurate dynamic and thermodynamic information on single Ag NP was accurately extracted from collision events, including current intensity, transferred charge, and duration time. On the basis that there were differences between parameters of different-sized Ag NPs, multiparameter size discrimination was proposed, which improved the accuracy compared to single-parameter discrimination. More intriguingly, multiparameter analysis was combined with artificial intelligence, a tool adept at processing multidimensional data, for the first time. Finally, artificial intelligence-assisted multiparameter size discrimination was successfully used to intelligently distinguish mixed Ag NPs, with an optimal accuracy of more than 95%. To sum up, the artificial intelligence-assisted multiparameter method showed an excellent ability to quickly achieve the most accurate size discrimination of nanoparticles at the level of individual particle and provide an effective guidance for the application of nanoparticles.

Thermodynamic formalism on the Skorokhod space: the continuous-time Ruelle operator, entropy, pressure, entropy production and expansiveness

Thermodynamic formalism on the Skorokhod space: the continuous-time Ruelle operator, entropy, pressure, entropy production and expansiveness

Recent University Research, Implementation and Education in Support of Pyrometallurgical Lead Processing

The increasing chemical complexity of lead process streams encountered in industrial high temperature processing operations, as the result of declining primary resources, increased metal recycling and increased overall range of metals in modern devices has highlighted the urgent need for new predictive tools, fundamental phase equilibria and thermodynamic information and thermodynamic models to characterise the chemical behaviour of these systems. The paper examines recent progress in experimental and thermodynamic modelling research on process fundamentals, the availability of advanced, predictive computer-based tools and the implementation of the research outcomes into industrial practice. A wide range of chemical systems and phase assemblages have been studied. Some examples are taken from the current research program at PYROSEARCH, which involves the characterisation of multi-component, multi-phase gas-slag-matte-speiss-metal-solids systems with the PbO-ZnO-“Cu2O”-FeO-Fe2O3-CaO-Al2O3-MgO-SiO2-S as major and As-Sn-Sb-Bi-Ag-Au-Ni-Co-Cr-Na as minor elements with focus on systems directly relevant to lead primary and recycling pyrometallurgical processes. Examples of the application of advanced analytical techniques to fundamental and applied industrial research are also given. The implementation of new research outcomes into industrial practice depends critically on commitments by research staff as well as industry management and the availability of well-trained metallurgical engineers. We examine the current status of research implementation, university research, metallurgical engineering education and the availability of suitable educational pathways and initiatives that can be taken to increase undergraduate enrolments. Active engagement and support by industry is critical in ensuring the continuation of academic programs and advanced technical skills required by the industry.

Fundamental experimental and thermodynamic modelling study in support of the lead battery recycling slag

Antimony, tin, and other higher value metals, as well as elements such as arsenic and lead, can be found in the slags produced during the lead battery recycling process. Gopher Resources operates lead battery recycling furnaces that use sodium slag systems for which there has been less thermodynamic research than more common slag systems. Better thermodynamic information could help improve the process efficiency and control of these furnaces, as well as the recovery of higher value metals. The present study focuses on experimental research and thermodynamic modeling of slags belonging to the Na-Si-Fe-O system, with minor elements including S, Sb, Sn, Pb, and As. Examples of important systems studied extensively for the first time include Fe-Sb-Si-O and Na-Sn-Si-O. Phase equilibria methods are used to determine all the interaction parameters between the impurity metals and the main components of the slag. The experimental methodology involves equilibration, quenching, and electron-probe X-ray microanalysis of the samples. The modified Quasichemical model is used to describe the thermodynamics of the slags. The model also takes into account possible formation of matte/metal/speiss liquids, and numerous solid phases, which is important for understanding of fundamentals operation of various process units.

صدفة الحلزون (ذو الناب المدبب) كممتز منخفض التكلفة لإزالة صبغة السفرانين من محاليلها المائية

في هذا البحث ، تم استخدام مسحوق قشرة الحلزون كمادة مازة لصبغة السفرانين بسبب تكلفته المنخفضة وكفاءته العالية وكذلك قدرته العالية على الامتصاص. أجريت التجارب في درجة حرارة 298 كلفن لمعرفة تأثير الأس الهيدروجيني ،الوزن ،القوة الأيونية، زمن التوازن ودرجة الحرارة. كما تم تنفيذ أفضل الظروف لامتزاز صبغة السفرانين بوزن 0.0200 جم من مسحوق قشرة الحلزون. كانت نسبة الإزالة 96.09٪ بتركيز 9.0000 ملجم / لتر و 20 دقيقة كوقت اتزان عند درجة الحرارة 298 كلفن. الهدف من الدراسة هو تحليل ايزوثيرم متساوي درجة حرارة . تم تحليل البيانات التي تم جمعها من التجارب وفق نماذج الامتزاز الثلاثة: Langmuir و Temkin و Freundlich. كانت البيانات مناسبة لتساوي درجة حرارة Freundlich. توضح المعلومات الديناميكية الحرارية المحسوبة للعملية أن عملية الإزالة تحدث من خلال التبادل النشط للجزيئات العشوائية.

Added Value of Three‐Dimensional Horizontal Winds From Geostationary Interferometric Infrared Sounder for Typhoon Forecast in a Regional NWP Model

AbstractHigh temporal resolution geostationary hyperspectral infrared sounders can simultaneously profile atmospheric temperature and moisture, and track moisture features to provide 3D horizontal winds in clear and partially cloudy scenarios. The thermodynamic information obtained has been integral to enhancing tropical cyclone (TC) forecasts. However, the potential benefits derived from the dynamic information provided by geostationary hyperspectral infrared sounders (GeoHIS) are yet to be fully comprehended for numerical weather prediction (NWP). With the re‐estimated observation error and multivariate hydrometeor background error covariance, the 3D horizontal winds from the Geostationary Interferometric Infrared Sounder (GIIRS) are synergistically assimilated with the hydrometeor information. The impact of the GIIRS‐derived 3D horizontal wind assimilation on Typhoon Maria (2018) and Lekima (2019) analysis and forecast are evaluated. The results show that the assimilating GIIRS‐derived 3D horizontal wind notably reduces the RMSEs of analysis and forecast, particularly in the U and V components. The improvement in accuracy of large‐scale fields substantially enhances the forecasts of typhoons' track and maximum wind speed, as well as the central sea‐level pressure. Moreover, the prediction of the spatial distribution and intensity for landfall precipitation is also improved. The detailed diagnoses of the Maria show that a more southerly subtropical high generated by the additional horizontal wind assimilation improves the rainfall spatial distribution, and the reasonable water vapor transportation caused by the improved dynamic conditions corrects the precipitation intensity. This work highlights the importance of dynamic information in TC forecasting and emphasizes the need for efficient and high‐precision 3D wind measurements to improve NWP.

Introducing the concept of generalized thermal diffusivity to understand coupled heat–charge transport in ionic solutions

A theoretical framework addressing the coupled thermal and charge transport phenomena in ionic solutions is here developed. Starting from the microscopic definitions of thermal and charge currents from Onsager formulation of non-equilibrium thermodynamics, a unique, very general and compact form of the governing differential equation for the evolution of a temperature profile is derived. In particular, the concept of generalized thermal diffusivity is introduced to capture the overall effect of the coupling between heat and charge transport in a single phenomenological coefficient as well as to shed light on the non-equivalent situations of concurrent or discordant heat and charge currents. To validate our theoretical framework, an ionic salt solution of NaCl in water is investigated.

THERMODYNAMIC FORMALISM FOR AMENABLE GROUPS AND COUNTABLE STATE SPACES

Abstract Given the full shift over a countable state space on a countable amenable group, we develop its thermodynamic formalism. First, we introduce the concept of pressure and, using tiling techniques, prove its existence and further properties, such as an infimum rule. Next, we extend the definitions of different notions of Gibbs measures and prove their existence and equivalence, given some regularity and normalization criteria on the potential. Finally, we provide a family of potentials that nontrivially satisfy the conditions for having this equivalence and a nonempty range of inverse temperatures where uniqueness holds.

The Physics behind Precipitation Onset Bias in CMIP6 Models: The Pseudo-Entrainment Diagnostic and Trade-Offs between Lapse Rate and Humidity

Abstract Conditional instability and the buoyancy of plumes drive moist convection but have a variety of representations in model convective schemes. Vertical thermodynamic structure information from Atmospheric Radiation Measurement (ARM) sites and reanalysis (ERA5), satellite-derived precipitation (TRMM3b42), and diagnostics relevant for plume buoyancy are used to assess climate models. Previous work has shown that CMIP6 models represent moist convective processes more accurately than their CMIP5 counterparts. However, certain biases in convective onset remain pervasive among generations of CMIP modeling efforts. We diagnose these biases in a cohort of nine CMIP6 models with subdaily output, assessing conditional instability in profiles of equivalent potential temperature, θe, and saturation equivalent potential temperature, θes, in comparison to a plume model with different mixing assumptions. Most models capture qualitative aspects of the θes vertical structure, including a substantial decrease with height in the lower free troposphere associated with the entrainment of subsaturated air. We define a “pseudo-entrainment” diagnostic that combines subsaturation and a θes measure of conditional instability similar to what entrainment would produce under the small-buoyancy approximation. This captures the trade-off between larger θes lapse rates (entrainment of dry air) and small subsaturation (permits positive buoyancy despite high entrainment). This pseudo-entrainment diagnostic is also a reasonable indicator of the critical value of integrated buoyancy for precipitation onset. Models with poor θe/θes structure (those using variants of the Tiedtke scheme) or low entrainment runs of CAM5, and models with low subsaturation, such as NASA-GISS, lie outside the observational range in this diagnostic.

Investigating maximum temperature lift potential of the adsorption heat transformer cycle using IUPAC classified isotherms

Adsorption heat transformer (AHT) cycle is capable of upgrading the low-grade waste heat to a higher temperature. The maximum temperature lift of the AHT cycle can represent its theoretical performance limit. However, such a metric is currently absent from the literature due to the scarcity of fundamental studies on the heat upgrading sorption cycles. Therefore, in the present study, three models are proposed to derive the ‘maximum temperature lift’ of a typical AHT cycle: (i) heat engine heat pump representation, (ii) the 2nd law of thermodynamic formulation, and (iii) complete preheating. The first two models are developed based on the reversible cycle approach, whereas the 3rd model incorporates adsorbed phase properties. Thus, the first two models might be considered as the formulations for the thermodynamic temperature limit (lift) of an AHT cycle while the 3rd model is specific to the nature of a particular adsorbent + adsorbate pair which might be close to practical applications. The reversible models predict a maximum temperature lift of 22∘C to 58∘C for heat source temperatures between 50∘C to 80∘C. The 3rd model exhibits lower values of maximum temperature lift compared to the reversible models, owing to the inclusion of material properties in its formulation. The performance of the models is demonstrated by determining the maximum temperature lift of four water-based adsorption working pairs, each featuring distinct IUPAC (International Union of Pure and Applied Chemistry) isotherm types. This study will help propel the working pair selection and the thermodynamic modeling of sorption cycles to achieve its near maximum capability.