Search Results (37)

On the basis of the theory of polyphase equilibrium and the utilization of the MetCal software platform (MetCal v7.81), we adopted the chemical equilibrium constant method and successfully constructed a multiphase equilibrium model and simulation system for the antimony–lead synergistic side-blown oxidation smelting process. In typical production conditions, which encompass factors such as the composition of raw material, the ratio of oxygen to material, and oxygen-enriched concentration, the equilibrium product composition and pivotal technical indices are modeled and computed. Calculation results indicated that, other than the trace elements in the smelting slag, the relative errors of the calculated values for the content of major elements in the antimony-rich crude lead and smelting slag were less than 10% of the measured value after average treatment in production. Therefore, our results showed that the developed model and system preferably embodied the practical production condition of the antimony–lead synergistic side-blown oxidation smelting process, which is capable of precisely forecasting the smelting outcomes and optimizing the process parameters, thereby offering effective guidance for the practical execution of the antimony–lead synergistic side-blown oxidation smelting process. Full article

In the present study, the Homotopy Levenberg−Marquardt Algorithm (HLMA) and the Parameter Variation Levenberg–Marquardt Algorithm (PV–LMA), both developed in the context of high-temperature composition, are proposed to address the equilibrium composition model of plasma under the condition of local thermodynamic and chemical equilibrium. This model is essentially a nonlinear system of weakly singular Jacobian matrices. The model was formulated on the basis of the Saha and Guldberg–Waage equations, integrated with Dalton’s law of partial pressures, stoichiometric equilibrium, and the law of conservation of charge, resulting in a nonlinear system of equations with a weakly singular Jacobian matrix. This weak singularity primarily arises due to significant discrepancies in the coefficients between the Saha equation and the Guldberg–Waage equation, attributed to differing chemical reaction energies. By contrast, the coefficients in the equations derived from the other three principles within the equilibrium composition model are predominantly single−digit constants, further contributing to the system’s weak singularity. The key to finding the numerical solution to nonlinear equations is to set reasonable initial values for the iterative solution process. Subsequently, the principle and process of the HLMA and PV–LMA algorithms are analyzed, alongside an analysis of the unique characteristics of plasma equilibrium composition at high temperatures. Finally, a solving method for an arc plasma equilibrium composition model based on high temperature composition is obtained. The results show that both HLMA and PV–LMA can solve the plasma equilibrium composition model. The fundamental principle underlying the homotopy calculation of the (n−1) −th iteration, which provides a reliable initial value for the n−th LM iteration, is particularly well suited for the solution of nonlinear equations. A comparison of the computational efficiency of HLMA and PV–LMA reveals that the latter exhibits superior performance. Both HLMA and PV–LMA demonstrate high computational accuracy, as evidenced by the fact that the variance of the system of equations ||F|| < 1 × 10⁻¹⁵. This finding serves to substantiate the accuracy and feasibility of the method proposed in this paper. Full article

In the present paper, a modification of the standard mean-field model is considered, allowing for the description of the formation of a dynamic equilibrium between infected and recovered persons in a population of constant size. The key point of this model is that it highlights two-infection transfer mechanisms depending on the physical nature of the contact between people. We separate the transfer mechanism related directly to the movement of people (the so-called transport processes) from the one occurring at zero relative speed of persons (the so-called social contacts). Under the framework of a physical chemical analogy, the dependencies for the infection transfer rate constants are proposed for both purely transport and social mechanisms of spread. These dependencies are used in discussing the formation of quasi-stationary states in the model, which can be interpreted as endemic equilibrium states. The stability of such endemic equilibria is studied by the method of Lyapunov function. Full article

A root factor for the accuracy of all quantum chemical calculations of nuclear magnetic resonance (NMR) chemical shifts is the quality of the molecular equilibrium geometry used. In turn, this quality depends largely on the basis set employed at the geometry optimization stage. This parameter represents the main subject of the present study, which is a continuation of our recent work, where new pecG-n (n = 1, 2) basis sets for the geometry optimization were introduced. A goal of this study was to compare the performance of our geometry-oriented pecG-n (n = 1, 2) basis sets against the other basis sets in massive calculations of ¹³C NMR shielding constants/chemical shifts in terms of their efficacy in reducing geometry factor errors. The testing was carried out with both large-sized biologically active natural products and medium-sized compounds with complicated electronic structures. The former were treated using the computation protocol based on the density functional theory (DFT) and considered in the theoretical benchmarking, while the latter were treated using the computational scheme based on the upper-hierarchy coupled cluster (CC) methods and were used in the practical benchmarking involving the comparison with experimental NMR data. Both the theoretical and practical analyses showed that the pecG-1 and pecG-2 basis sets resulted in substantially reduced geometry factor errors in the calculated ¹³C NMR chemical shifts/shielding constants compared to their commensurate analogs, with the pecG-2 basis set being the best of all the considered basis sets. Full article

In this study, the thermodynamic simulation model and system of the copper side-blown smelting process were established using the chemical equilibrium constant method, based on the process reaction mechanism, multiphase equilibrium principle, and MetCal software platform (MetCal v7.81). Under typical production conditions, the composition of the product and the distribution behavior of impurity elements were simulated. The results indicate that the average relative error between the calculated mass fractions of major elements such as Cu, S, Fe, SiO₂, CaO, MgO, and Al₂O₃ in copper matte and smelting slag, and the actual production values, is 4.25%. Additionally, the average relative error between the calculated distribution ratios of impurity elements such as Pb, Zn, As, Bi, Mo, Au, and Ag in copper matte and smelting slag, and the actual production data, is 6.74%. Therefore, this model and calculation system accurately reflects the actual production situation of the copper side-blown smelting process well and has potential to predict process output accurately while optimizing process parameters, effectively guiding production practice. Full article

Many physical and chemical properties of solids, such as strength, plasticity, dispersibility, solubility and dissolution are determined by defects in the crystal structure. The aim of this work is to study in situ dynamic, dispersion, chemical, biological and surface properties of lacosamide powder after a complete cycle of mechanical loading by laser scattering, electron microscopy, FR-IR and biopharmaceutical approaches. The SLS method demonstrated the spontaneous tendency toward surface-energy reduction due to aggregation during micronisation. DLS analysis showed conformational changes of colloidal particles as supramolecular complexes depending on the loading time on the solid. SEM analysis demonstrated the conglomeration of needle-like lacosamide particles after 60 min of milling time and the transition to a glassy state with isotropy of properties by the end of the tribochemistry cycle. The following dynamic properties of lacosamide were established: elastic and plastic deformation boundaries, region of inhomogeneous deformation and fracture point. The ratio of dissolution-rate constants in water of samples before and after a full cycle of loading was 2.4. The lacosamide sample, which underwent a full cycle of mechanical loading, showed improved kinetics of API release via analysis of dissolution profiles in 0.1 M HCl medium. The observed activation-energy values of the cell-death biosensor process in aqueous solutions of the lacosamide samples before and after the complete tribochemical cycle were 207 kJmol⁻¹ and 145 kJmol⁻¹, respectively. The equilibrium time of dissolution and activation of cell-biosensor death corresponding to 20 min of mechanical loading on a solid was determined. The current study may have important practical significance for the transformation and management of the properties of drug substances in solid form and in solutions and for increasing the strength of drug matrices by pre-strain hardening via structural rearrangements during mechanical loading. Full article

This study explores the potential corrosion inhibition mechanisms of alkanolammonium salts, exemplified by ethylethanolammonium 4-nitrobenzoate (EEA4NB), for carbon steel, utilizing experimental and theoretical methods. The interactions between metal and inhibitor, focusing on adsorption behavior in saline solutions, will be thoroughly investigated. Analysis of potentiodynamic polarization curves and electrochemical impedance spectroscopy reveals that the inhibition efficiency (IE) increases with the rising concentration of EEA4NB, reaching 96% at 5 × 10⁻³ M. Negative adsorption free energy and a high adsorption equilibrium constant suggest the spontaneous formation of a protective inhibitor layer on the metal surface, effectively blocking reaction sites and reducing the corrosion rate, according to the Langmuir isotherms model. As confirmed by scanning electron microscopy, physical and chemical interactions contribute to the adsorption mechanisms. Quantum chemical calculations explore the relationship between EEA4NB molecular configuration and inhibition efficiencies. The study emphasizes the potential efficacy of alkanolammonium salts, exemplified by EEA4NB, as effective corrosion inhibitors for carbon steel in aggressive environments. Full article

For decades, the comparison of experimental data with theoretical results in studying the biochemistry of vitamin B12 has been very confusing. While the methylcobalamin cofactor-dependent Methionine Synthase process can undergo unlimited turnovers, and some of the adenosylcobalamin-dependent processes run with close-to-unity equilibrium constants (e.g., with close-to-zero energy barriers), the DFT and QM/MM based on density functional theory, the most used and appreciated methods for calculating the electronic structure of molecules, have been showing a much shorter than experimental-determined Co-N distances in the vitamin B12 cofactors of Co⁺² and the inadequate large energetic barriers of their enzymology bioprocesses. The confusion was even larger since some in vitro experimental data showed large barriers to the vitamin B12 cofactor reactions (which in fact play a destructive role in the Methionine Synthase process and which barriers were caused mostly by the influence of the solvents in which the reaction took place). It reached the point where solid contributions to the study of the biochemical processes of vitamin B12 were almost officially questioning the correctness of the experimental determination of the Co-N chemical bond distances in the cobalt(II) cofactors of vitamin B12. Unexpectedly, all the theoretical biochemistry of the vitamin B12 cofactors began to agree with all in vivo experimental data only when they were treated with the MCSCF method, the method that considers the orbital mixing, or in other words, the Pseudo-Jahn–Teller Effect. MCSCF data establish unknown mechanistic details of the methyl radical and hydrogen transfers, the origin of the electronic transfers between bioreagents, and the nature and the relationship between the bioreactions. The Pseudo-Jahn–Teller Effect, e.g., orbital mixing, governs vitamin B12 chemistry in general and provides insight into particular details of vitamin B12-dependent reactions in the human body. It turns out that the DFT or QM/MM based on DFT method theoretical data are incongruent with the experimental data due to their limitations, e.g., the unaccounted-for effects of orbital mixing. Full article

The existing combustion kinetic modeling method which aims at developing phenomenological combustion mechanisms characterized by multiple reactions confronts several challenges, including the conflicts between computing resources and mechanism scales during numerical simulation, etc. In order to address these issues, the minimized reaction network method for complex combustion system modeling based on the principle of simultaneous chemical equilibrium is proposed, which is aimed to develop combustion mechanisms with minimal reaction steps under a limited number of species. The concept of mechanism resolution is proposed in this method, and the reaction network with minimal reaction steps under a given mechanism resolution is constructed so that the scale of mechanisms is compressed greatly. Meanwhile, distinguishing from other mechanisms, the reversible form of elementary reactions is adopted and the classical two-parameter (A, E_a) Arrhenius equation fits the rate constants. Typical n-alkanes including n-butane, n-heptane, n-octane, n-decane, n-dodecane and n-hexadecane were taken as examples to indicate the development process of mechanisms and systematic kinetic validations were carried out. Results show that this method leads to very compact mechanisms with satisfactory accuracy, and it eliminates the process of mechanism reduction and is beneficial for mechanism optimization. This method and the derived kinetic mechanisms are hoped to contribute to combustion engineering applications. Full article

A series of sorption materials based on layered double hydroxides (Co-Fe LDH, Ni-Fe LDH, and Zn-Ti LDH) were obtained by a facile and environmentally friendly method of coprecipitation. A low particle size of no more than 10 µm was achieved. The use of transition metals makes it possible to obtain compounds that are mechanically and chemically stable in aggressive environments. XRD analysis revealed that the compounds have a highly organized crystalline structure. Using SEM, it was determined that Co-Fe LDH and Ni-Fe LDH had a loose, highly dispersed surface structure, while Zn-Ti LDH had a monolithic surface structure. U(VI) adsorption on the obtained materials in solutions containing Na₂CO₃, Na₂SO₄, KNO₃, NaCl, K₃PO₄, and NaHCO_3, was studied in batch mode. The degree of purification in the presence of these salts reached 99.9%, while the distribution coefficient K_d reached 10⁵ mL/g. Sorption capacity q_max and equilibrium adsorption constants K_f and K_L for U(VI) adsorption in batch mode (for 24 h) from distilled and seawater were determined using the Freundlich and Langmuir equations. The highest sorption capacity of 101.6 mg/g in seawater and 114.1 mg/g in distilled water was registered for Co-Fe-LDH. The presence of competing ions in seawater can reduce sorption efficiency by up to 40%. The provided research allowed us to conclude that the obtained materials, Co-Fe LDH, Ni-Fe LDH, and Zn-Ti LDH are promising for the sorption removal of U(VI) from aqueous media of medium salinity. Full article

In 2012, Kim and Hirata derived two generalized Langevin equations (GLEs) for a biomolecule in water, one for the structural fluctuation of the biomolecule and the other for the density fluctuation of water, by projecting all the mechanical variables in phase space onto the two dynamic variables: the structural fluctuation defined by the displacement of atoms from their equilibrium positions, and the solvent density fluctuation. The equation has an expression similar to the classical Langevin equation (CLE) for a harmonic oscillator, possessing terms corresponding to the restoring force proportional to the structural fluctuation, as well as the frictional and random forces. However, there is a distinct difference between the two expressions that touches on the essential physics of the structural fluctuation, that is, the force constant, or Hessian, in the restoring force. In the CLE, this is given by the second derivative of the potential energy among atoms in a protein. So, the quadratic nature or the harmonicity is only valid at the minimum of the potential surface. On the contrary, the linearity of the restoring force in the GLE originates from the projection of the water’s degrees of freedom onto the protein’s degrees of freedom. Taking this into consideration, Kim and Hirata proposed an ansatz for the Hessian matrix. The ansatz is used to equate the Hessian matrix with the second derivative of the free-energy surface or the potential of the mean force of a protein in water, defined by the sum of the potential energy among atoms in a protein and the solvation free energy. Since the free energy can be calculated from the molecular mechanics and the RISM/3D-RISM theory, one can perform an analysis similar to the normal mode analysis (NMA) just by diagonalizing the Hessian matrix of the free energy. This method is referred to as the Generalized Langevin Mode Analysis (GLMA). This theory may be realized to explore a variety of biophysical processes, including protein folding, spectroscopy, and chemical reactions. The present article is devoted to reviewing the development of this theory, and to providing perspective in exploring life phenomena. Full article

With the increasingly complicated sources of lead smelting materials, it is becoming more difficult to optimize process parameters during the bottom-blowing lead oxidation smelting process. Building a bottom-blowing lead smelting thermodynamic model has significant importance for the green production of the lead smelting process. In this study, we built a multi-phase equilibrium thermodynamic model and simulation system for the oxygen-enriched bottom-blowing lead oxidation smelting process using the MetCal software platform (MetCal v7.81) according to the chemical equilibrium constant method. The equilibrium products composition and important technical indicators were calculated under factory operating conditions. Compared with the industrial data, the calculation results demonstrated that the average relative error of the calculation value of the mass fraction in the crude lead, lead-rich slag, and dust was 3.76%. The average relative error of important technical indicators, including dust rate, crude lead yield, lead-rich slag temperature, slag iron–silica ratio (R_Fe/SiO2), and slag calcium–silica ratio (R_CaO/SiO2), was 6.39%. As a result, the developed modeling and simulation system was able to reflect the current state of the oxygen-enriched bottom-blowing lead smelting. It also demonstrated the potential to enhance the smelting process and optimize the process parameters. Therefore, it is expected to provide a useful tool for thermodynamic analysis. Full article

Copper-centered carbene–metal–halides (CMHs) with cyclic (alkyl)(amino) carbenes (CAACs) are bright phosphorescent emitters and key precursors in the synthesis of the highly promising class of the materials carbene–metal–amides (CMAs) operating via thermally activated delayed fluorescence (TADF). Aiming to reveal the molecular geometry for CMH phosphors in the absence of the intermolecular contacts, we report here the equilibrium molecular structure of the (CAAC)Cu(I)Cl (1) molecule in the gas-phase. We demonstrate that linear geometry around a copper atom shows no distortions in the ground state. The structure of complex 1 has been determined using the electron diffraction method, supported by quantum chemical calculations with RI-MP2/def2-QZVPP level of theory and compared with the crystal structure determined by X-ray diffraction analysis. Mean vibrational amplitudes, u_ij,h1, and anharmonic vibrational corrections (r_ij,e • r_ij,a) were calculated for experimental temperature T = 20 °C, using quadratic and cubic force constants, respectively. The quantum theory of atoms in molecules (QTAIM) and natural bond order (NBO) analysis of wave function at MN15/def2TZVP level of theory revealed two Cu^…H, three H^…H, and one three-center H^…H^…H bond paths with bond critical points. NBO analysis also revealed three-center, four-electron hyperbonds, (3c4e), [π(N–C) n_π(Cu) ↔ n_π(N) π(N–Cu)], or [N–C: Cu ↔ N: C–Cu] and n_π(Cu) → π(C–N)* hyperconjugation, that is the delocalization of the lone electron pair of Cu atom into the antibonding orbital of C–N bond. Full article

This paper develops a chemical model for a closed constant-volume combustion of a gaseous mixture of methane and hydrogen. Since the combustion is strongly dependent on temperature, pressure and fuel composition, these had chosen the actual corresponding thermodynamic systems in this kind of combustion, i.e., spark ignition (SI) reciprocating engines, to assess combustion parameters and flue gas composition. The actual cycles impose extra restrictive operational conditions through the engine’s-volumetric-compression ratio, the geometry of the combustion volume, the preparation method of the mixture of methane and hydrogen, (e.g., one fueling way of a homogeneous mixture obtained in a specific device or by two separate fueling ways for components), the cooling system and the delivered power. The chemical model avoided the unknown influences in order to accurately explain the influence of hydrogen upon constant-volume combustion and flue gas composition. The model adopted hypotheses allowing to generalize evaluated results, i.e., the isentropic compression and expansion processes, in closed constant-volume combustion caused by two successive steps that obey the energy and mass conservation laws, and the flue gas exhaust, which is also described by two steps, i.e., isentropic expansion through the flow section of exhaust valves followed by a constant pressure stagnation (this process, in fact, corresponds to a direct throttling process). The chemical model assumed the homogeneous mixtures of gases with variable heat capacity functions of temperatures, the Mendeleev—Clapeyron ideal gas state equation, and the variable chemical equilibrium constants for the chosen chemical reactions. It was assumed that the flue gas chemistry prevails during isentropic expansion and during throttling of exhaust flue gas. The chemical model allowed for evaluation of flue gas composition and noxious emissions. The numerical results were compared with those recently reported in other parallel studies. Full article

The use of digital twins in smart power systems at the stages of the life cycle is promising. The dynamics of such systems (smart energy renewable sources, smart energy hydrogen systems, etc.), are determined mainly by the physical and chemical processes occurring inside the systems. The basis for developing digital twins is reliable mathematical models of the systems. In the present paper, the authors present a method of energy processes mathematical prototyping—an overall approach to modeling processes of various physical and chemical natures based on modern non-equilibrium thermodynamics, mechanics, and electrodynamics. Controlled parameters are connected with measured ones by developing a theoretically correct system of process dynamics equations with accuracy up to the experimentally studied properties of substances and processes. Subsequent transformation into particular mathematical models of a specific class of systems makes this approach widely applicable. The properties of substances and processes are given in the form of functional dependencies on the state of the system up to experimentally determined constant coefficients. The authors consider algorithms for identifying the constant coefficients of the functions of substances and processes properties, which complement the proposed unified approach of designing models of various physical and chemical nature systems. Full article