Equilibrium Mixture Research Articles

Mono- and Bichromophores Formed from Perylene Monoimide Diesters: Competition between Intramolecular Charge Transfer and Intermolecular Singlet Exciton Fission.

Perylene monoimide diesters and the corresponding phenyl-linked bichromophores are strongly fluorescent in dilute solution with minimal triplet population after relaxation of the initial Franck-Condon state. The monomer forms nonemissive face-to-face dimers in solution, wherein illumination leads to formation of a spin-correlated, triplet pair with a yield of ca. 13% and with a time constant of 4 ± 1 ps. The triplet pair, which is localized on the aggregate, cannot separate and decays with a mean lifetime of 80 ± 10 ps. The relaxed S1 state of the weakly coupled, phenyl-linked bichromophores establishes an equilibrium with an intramolecular charge-transfer state over a hundred picoseconds or so, depending on the solvent and the geometry of the linkage. This equilibrium mixture, being dominated by the relaxed S1 state, decays on the nanosecond time scale in solution at room temperature without implication of a triplet state. Self-association occurs at higher concentration and, for the para-bridged bichromophore, leads to inefficient triplet formation in tetrahydrofuran at room temperature.

On thermodynamic processes, state equations and critical phenomena for homogeneous mixtures

In this paper, we study the thermodynamics of homogeneous mixtures in equilibrium. From the perspective of thermodynamics, substances are understood as Legendre submanifolds, which are equipped with a Riemannian structure in addition. We refer to these as Legendre-Riemannian manifolds. This Legendre structure reflects the law of conservation of energy, while the Riemannian structure corresponds to the second central moment of measurement of extensive quantities, indicating that we only consider stable states. Thermodynamic processes, such as chemical reactions, correspond to contact vector fields that preserve the law of energy conservation, or are contact. The presence of a Riemannian structure distinguishes between three classes of processes: positive, which increase the metric; neutral, which preserve the metric; and negative, which decrease the metric. We provide a detailed description of the processes and suggest a method for finding state equations for a homogeneous mixture in mechanical or chemical equilibrium.

Light-Induced Electron Transfer in a [NiFe] Hydrogenase Opens a Photochemical Shortcut for Catalytic Dihydrogen Cleavage.

[NiFe] hydrogenases catalyze the reversible cleavage of molecular hydrogen into protons and electrons. Here, we have studied the impact of temperature and illumination on an oxygen-tolerant and thermostable [NiFe] hydrogenase by IR and EPR spectroscopy. Equilibrium mixtures of two catalytic [NiFe] states, Nia-C and Nia-SR'', were found to drastically change with temperature, indicating a thermal exchange of electrons between the [NiFe] active site and iron-sulfur clusters of the enzyme. In addition, IR and EPR experiments performed under illumination revealed an unusual photochemical response of the enzyme. Nia-SR'', a fully reduced hydride intermediate of the catalytic cycle, was found to be reversibly photoconverted into another catalytic state, Nia-L. In contrast to the well-known photolysis of the more oxidized hydride intermediate Nia-C, photoconversion of Nia-SR'' into Nia-L is an active-site redox reaction that involves light-driven electron transfer towards the enzyme's iron-sulfur clusters. Omitting the ground-state intermediate Nia-C, this direct interconversion of these two states represents a potential photochemical shortcut of the catalytic cycle that integrates multiple redox sites of the enzyme. In total, our findings reveal the non-local redistribution of electrons via thermal and photochemical reaction channels and the potential of accelerating or controlling [NiFe] hydrogenases by light.

Refrachor (F) – seventy-year-old tool and a contemporary observation: estimation of equilibrium compositions of 1H- and 2H-tautomers of tetrazole and 1,2,3-triazole and imine–amine composition of acetaldimine–vinylamine tautomerism

Abstract Refrachor with a symbol F a new physical constant proposed for the first time in 1951 by Joshi and Tuli defined by the equation F = –P log( n D 20 ${n}_{\mathrm{D}}^{20}$ –1) where P is the parachor and n D 20 ${n}_{\mathrm{D}}^{20}$ is the refractive index, is now used in our present work to calculate the percentage composition of 1H- and 2H-tautomers of tetrazole, 1,2,3-triazole, and imine-enamine tautomerism of acetaldimine in their equilibrium mixtures.

Hindered intermolecular stacking of anti-parallel telomeric G-quadruplexes.

Telomeric G-quadruplexes (G4s) are non-canonical DNA structures composed of TTAGGG repeats. They are extensively studied both as biomolecules key for genome stability and as promising building blocks and functional elements in synthetic biology and nanotechnology. This is why it is extremely important to understand how the interaction between G4s is affected by their topology. We used small-angle x-ray scattering to investigate the end-to-end stacking of antiparallel telomeric G-quadruplexes formed by the sequence AG3(T2AG3)3. To represent the experimental data, we developed a highly efficient coarse-grained fitting tool, which successfully described the samples as an equilibrium mixture of monomeric and dimeric G4 species. Our findings indicate that the antiparallel topology prevents the formation of long multimeric structures under self-crowding conditions, unlike the hybrid/parallel structures formed by the same DNA sequence. This result supports the idea that the stacking of monomeric G-quadruplexes is strongly affected by the presence of diagonal loops.

Liquid–Liquid Equilibria in Mixtures of 2-Ethylhexanoic Acid, Ethanol, and Water

Liquid–Liquid Equilibria in Mixtures of 2-Ethylhexanoic Acid, Ethanol, and Water

Establishment of a one-dimensional model for CO2 Pipeline rupture process and design recommendations

Pipelines serve as a critical means of transporting CO2 within Carbon Capture, Utilization, and Storage (CCUS) technology. Elevated transport pressures may lead to unforeseen pipeline ruptures. To provide practical recommendations for the design of CO2 pipelines and mitigate the risk of ruptures, this study establishes a one-dimensional Homogeneous Equilibrium Mixture (HEM) model. The model is currently used to predict the decompression behavior in existing pure CO2 rupture tests. Future work will address rupture tests and predictions involving impure CO2. The results indicate that due to differences in pressure reduction caused by decompression waves, the likelihood of long-range ruptures occurring in density CO2 pipelines is lower compared to supercritical CO2 pipelines. The crack propagation velocity and crack arrest pressure of pipelines designed according to ASME B31.3 are calculated using the High Strength Line Pipe Committee (HLP) model. Although the crack propagation velocity is lower than the decompression wave speed, the crack arrest pressure may fall below the rupture pressure, with the pressure at 1.6 m from the rupture point remaining above the crack arrest level for 1 ms post-rupture, a duration that is especially prolonged in larger-diameter pipelines. It is recommended to consider additional thickness beyond the calculated minimum thickness.

A dynamic compositional equilibrium governs mRNA recognition by eIF3.

Eukaryotic translation initiation factor (eIF) 3 is a multi-subunit protein complex that binds both ribosomes and messenger RNAs (mRNAs) to drive a diverse set of mechanistic steps during translation of an mRNA into the protein it encodes. And yet, a unifying framework explaining how eIF3 performs these numerous activities is lacking. Using single-molecule light scattering microscopy, we demonstrate that Saccharomyces cerevisiae eIF3 is in dynamic exchange between the full complex, subcomplexes, and subunits. By extending our microscopy approach to an in vitro reconstituted eIF3 and complementing it with biochemical assays, we define the subspecies comprising this dynamic compositional equilibrium and show that mRNA binding by eIF3 is not driven by the full complex but instead by the eIF3a subunit within eIF3a-containing subcomplexes. Our findings provide a mechanistic model for the role of eIF3 in mRNA recruitment and establish a mechanistic framework for explaining and investigating the other activities of eIF3.

An NMR study on the keto-enol tautomerism of 1,3-dicarbonyl drug precursors.

The effective implementation of drug precursor legislation has driven the innovation and design of new alternative substances. The application of 1,3-dicarbonyl precursors as alternative precursors for the synthesis of 1-phenyl-2-propanone (P2P) and 3,4-methylenedioxyphenyl-2-propanone (MDP2P) has created new challenges to legal control. Their 1,3-dicarbonyl structure allows the precursors to exist as an equilibrium mixture of the tautomeric diketo and keto-enolic forms during the nuclear magnetic resonance (NMR) analysis. In this study, the keto-enol tautomerism of four 1,3-dicarbonyl drug pre-precursors, α-phenylacetoacetamide (APAA), methyl α-phenylacetoacetate (MAPA), ethyl α-phenylacetoacetate (EAPA), and methyl 2-(benzo[d][1,3]dioxol-5-yl)-3-oxobutanoate (MAMDPA) were investigated through NMR. One-dimensional (1D) and 2D NMR were combined to assign signals for the diketo and keto-enolic tautomers. Results showed that the keto-enol tautomerism was solvent-dependent but was also influenced by the substituent present in the molecule. Further, the analysis results indicated that majority of substances existed mainly in the diketo form. The enol-keto equilibrium constant (Keq) was stable in dimethyl sulfoxide-d6 and chloroform-d, while unstable for some compounds in acetone-d6 and deuterated methanol. The presence of impurities in the seized sample may disrupt the equilibrium between keto-enol tautomers in 1,3-dicarbonyl precursors. After the optimization of several key quantitative parameters, a quantitative NMR method for the quantification of 1,3-dicarbonyl drug precursors were also developed to facilitate their quantitative analysis. This is the first study to investigate the keto-enol tautomerism and quantification of 1,3-dicarbonyl drug precursors by NMR, providing a new approach for structure analysis and quantification of new precursor analogues.

Mathematical Model of Gasification of Solid Fuel

This paper presents an innovative mathematical model of solid fuel gasification, which is not described in the available literature. The calculation of the components of the heterogeneous phase (including both solid and gaseous phases) as well as the calculation of the homogeneous phase (only gaseous components) is based on the balance of the total amounts of carbon, oxygen, hydrogen, and nitrogen entering the reactor space. Additionally, this paper introduces a new method for calculating the composition of the gaseous phase, based on reducing the heterogeneous mixture (composed of solid and gaseous phases) to a homogeneous gaseous phase. This approach to calculating the gaseous phase composition in the solid fuel gasification process has not been found by the authors in the cited literature. This paper also presents a model for calculating the heterogeneous and gaseous phases using the number of moles that participate in the assumed chemical reactions of the solid fuel gasification process. This approach to calculating the composition of the heterogeneous and gaseous phases of the solid fuel gasification process is also not represented in the cited literature. For comparison with the literature data, municipal solid waste (MSW) and cashew nut shell (Cashew Shell Char (CNSC)) were used as fuels in the calculation of gasification composition. The results of the calculation of the gaseous phase composition using the model presented in the paper show good agreement with the data from the literature. The calculation of the composition of the heterogeneous mixture during the steam gasification of MSW (α = 0.4) shows the presence of a solid phase (carbon) up to approximately 735 °C. At that temperature, the synthetic gas contains only gaseous components: CO = 33.10%, H2 = 52.70%, CH4 = 2.54%, CO2 = 4.97, H2O = 5.93% and N2 = 0.76%. Increasing the temperature above 735 °C eliminates the solid phase from the equilibrium mixture. The literature data on solid fuel gasification generally do not consider the proportion of the solid phase (carbon) in the equilibrium mixture. To satisfy the material balance at the input and output of the gasification reactor, it is necessary to determine the proportion of the solid phase (carbon) in the equilibrium mixture. Since the proportion of the solid phase (carbon) in the heterogeneous equilibrium mixture can only be determined through measurement, the development and application of a mathematical model in engineering practice is of great importance, so this developed model can be considered a useful tool for simulating the influence of process parameters on gas characteristics.

Development Of An Endoscopic, Absorption Corrected And Calibrated OH Laser Induced Fluorescence Probe System for High Pressure Combustion Diagnostics

We present the design and preliminary results of an endoscopic OH laser-induced fluorescence (LIF) system that is capable of acquiring 1D-line measurements in high pressure combustion processes within large-scale test facilities. The system can be exploited to acquire line-of-sight OH-chemiluminescence images and absorption corrected absolute OH-species concentration from which additionally temperature distribution can be extracted in case of lean mixtures in chemical equilibrium. Different critical components, such as light guides for high power UV laser pulses and flexible UV image guides, were first tested and characterized in a laboratory setup. Optimization regarding pulse energy and beam quality led to the selection of an 1m long hollow core fiber for laser light delivery as a central element for the experimental setup despite high losses caused by bending the fiber. The image transfer is accomplished by a 7m long flexible UV image bundle, which is preferred to the use of a rigid borescope in harsh environments. We designed the endoscopic UV optics using readily available parts and achieved an approximated image resolution of 21.6 line pairs/mm. Additionally, post-processing methods, such as flat-field correction, can improve the image quality substantially and remove the pixilation effect of the fiber bundle structure nearly completely. To validate the complete system, probe-based qualitative OH-LIF measurements were performed in a well-known laminar flame of a matrix burner, which serves as a mock-up for anticipated applications in an industrial test environment with a technology readiness level (TRL) greater than 4. The final step consists of the integration of the miniaturized optics into a cooled probe system which protects the sensitive optics against the harsh environment of an aero-engine sector combustor. For this purpose, two probe systems were designed to include, on the one hand, the endoscope optics together with the fiber image bundle end tip and, on the other hand, the laser emitting and receiving system for performing an absorption measurement needed to quantify the recorded LIF signal.

An experimental and modelling investigation on the water content of CO2and CO2-rich mixtures using the differential scanning hygrometry (DSH) method

Monitoring humidity downstream to conditioning facilities and during transportation is essential for avoiding hydrate deposition. However, water inline monitoring under high pressure is still challenging in the CCS industry. This study presents an experimental and modelling investigation for enhancing field monitoring and model predictions. Measurements are performed using the Differential Scanning Hygrometry (DSH). This novel analytical approach has been successfully tested for measuring dew/frost temperatures for carbon dioxide, CH4+CO2, and CO2-rich mixtures in equilibrium with hydrates, free water and ice. Moreover, the DSH method has been applied for direct HP equilibrium temperature measurements. Also, this work compares three modified versions of the classical SRK EoS with the Multi-Fluid Helmholtz Energy Approximation (MFHEA). This evaluation includes Huron-Vidal and the EMS mixing rules and the cubic-plus association (CPA) approach. A thorough fitting process was carried out and, overall, comparisons with the experimental data showed that SRK + EMS yielded results as satisfactory as sCPA.

Application of thermodynamics at different scales to describe the behaviour of fast reacting binary mixtures in vapour-liquid equilibrium

The use of reactive working fluids in thermodynamic cycles is currently being considered as an alternative to inert working fluids, because of the preliminarily attested higher energy-efficiency potential. The current needs to simulate their use in thermodynamic cycles, which may operate in liquid, vapour or vapour-liquid state, are an accurate real-fluid equation of state and ideal gas thermochemical properties of each molecule constituting the mixture, to calculate the equilibrium constant. To this end, the appeal to a multi-scale theoretical methodology is paramount and its definition represents the objective of the present work. This methodology is applied and validated on the system N2O4 ⇌ 2NO2. Firstly, the equations solved for simultaneous two-phase and reaction equilibrium are presented. Secondly, ideal gas thermochemical properties of N2O4 and NO2 are computed at atomic scale by quantum mechanics simulations. Then, to apply the selected cubic equation of state, pure-component properties of the species forming the reactive mixture (critical point coordinates and acentric factor) are required as input. However, these properties are not measurable, since NO2 and N2O4 do not exist in nature as pure components. To get around this difficulty, the methodology relies on molecular Monte Carlo simulations of the pure N2O4 and NO2, as well as on the reactive N2O4 ⇌ 2NO2, enabling the determination of those missing pure-component properties and thus the calculation, on a macroscopic scale, of the reactive mixture properties. Finally, the comparison of calculated mixture properties with available experimental data leads to validate the accuracy of the proposed methodology.

Quantification of peracetic acid (PAA) in the H2O2 + acetic acid reaction by the wavelength shift analysis in near-UV/visible absorption region.

In our study, we present an innovative method for the analysis and real-time monitoring of peracetic acid (PAA) formation within the near-UV/Vis (visible) wavelength region. PAA's absorption spectrum, influenced by its presence in a complex quaternary equilibrium mixture with hydrogen peroxide (H2O2), acetic acid, and water, lacks discernible peaks. This inherent complexity challenges conventional analytical techniques like Beer's law, which rely on absorption intensity as a foundation. To address this challenge, we introduce a novel approach that centers on the analysis of blue shifts in absorption wavelengths, particularly at an absorbance of 0.8 a.u. This method significantly enhances the precision of calibration curves for both diluted PAA and H2O2, unveiling an exponential correlation between wavelength and the logarithm of concentration for both components. Significantly, our approach allows for real-time and accurate measurements, especially during the dynamic PAA formation reaction. Our results exhibit excellent agreement with data obtained from Fourier-transform infrared (FT-IR) spectroscopy, validating the reliability of our method. It's noteworthy that under stable PAA concentration conditions (after 12h of solution interaction), both traditional absorption method and our approach closely align with the FT-IR method. However, in dynamic scenarios (0-12h), the absorption method exhibits higher error rates compared to our approach. Additionally, the increased concentration of a catalyst, sulfuric acid (H2SO4), significantly reduces the errors in both methods, a finding that warrants further exploration. In summary, our study not only advances our understanding of PAA and its spectral behavior but also introduces innovative and precise methods for determining PAA concentration in complex solutions. These advancements hold the potential to revolutionize the field of chemical analysis and spectroscopy.

Steady states and kinetic modelling of the acid-catalysed ethanolysis of glucose, cellulose, and corn cob to ethyl levulinate.

Ethyl levulinate is a promising advanced biofuel and platform chemical that can be derived from lignocellulosic biomass by ethanolysis processes. It can be blended with both diesel and gasoline and, thus, used in conventional engines and infrastructure. Previously, it has been shown that alkyl levulinate/alcohol/alkyl ether mixtures exhibit significantly enhanced fuel properties relative to any of the individual fuel components, particularly when blended with conventional hydrocarbon liquid fuels. Consequently, this study specifically quantifies the three primary components of the alcoholysis reaction mixture: ethyl levulinate, diethyl ether, and ethanol. The steady state and kinetic phase fractions of ethyl levulinate and diethyl ether produced from glucose, cellulose, and corn cob with 0.5-2 mass% sulphuric acid in ethanol are determined for 5, 10, and 20 mass% of feedstock at 150 °C. Knowledge of the steady state equilibrium mixture fraction is specifically targeted due to its importance in assessing commercial-scale production and in modelling analysis as: (i) it defines the maximum yield possible at a given condition, and (ii) it is equitable to the minimum free energy state. Maximum steady state yields (mass%) of ethyl levulinate of (46.6 ± 3.7), (50.2 ± 5.4), and (27.0 ± 1.9)% are determined for glucose, cellulose, and corn cob, respectively. The conversion of glucose and cellulose to ethyl levulinate in the presence of ethanol and sulphuric acid is shown to be a catalytic process, where the ethyl levulinate yield is not dependent on the acid concentration. For corn-cob biomass, in a new and contrasting finding, the ethyl levulinate yield is shown to strongly depend on the acid concentration. This effect is also observed in the fractions of diethyl ether formed, providing strong evidence that the hydrogen cation is not being replenished in the ethanolysis process and the overall reaction with corncob is not wholly catalytic. Thus, for the acid catalysed alcoholysis of lignocellulosic biomass, acid concentration must be scaled with feedstock concentration. The critical corn cob-to-acid ratio that maximises ethyl levulinate yields while minimizing the formation of undesired co-products (diethyl ether) is in the range 10-20 : 1 at 150 °C. A detailed, hierarchical, mass-conserved chemical kinetic model capable of accurately predicting the relative abundance of the three primary components of the ethanolysis reaction: ethyl levulinate, diethyl ether, and ethanol, from the biochemical composition of the feedstock, is elucidated and validated.

Малопараметрическое уравнение состояния графита для описания поведения сплошных и пористых образцов в ударных волнах и волнах разгрузки

This study is aimed to obtain the parameters of the graphite equation of state represented as the Mie–Grüneisen equation of state. Graphite with metals and the porous graphite are considered as simple thermodynamically equilibrium mixtures. The equilibrium state is determined by the conditions of equal pressure, temperature, and velocity of the components in the mixture. Thus, the motion of the multicomponent medium can be described as the motion of a continuum with a special equation of state that takes into account the properties of the mixture components and their concentration, which significantly reduces the number of equations. For the Grüneisen parameter, a logarithmic dependence on density is used, which adequately describes the variation in the Grüneisen parameter for both normal and anomalous behavior of shock adiabats. The increasing scope of the equation of state is a result of comparing experimental data with calculations for the following: 1) shock-wave loading of porous materials to cover the range of higher temperatures; 2) double compression of the samples to cover the range of increased densities; 3) isentropic expansion of samples to cover the range of low densities; and 4) sound velocities, which characterize the compressibility of matter, slope of the Poisson adiabat on the shock adiabat, and propagation velocity of the weak shock waves and unloading waves through the compressed matter. The comprehensive analysis confirms that the proposed model of the equation of state for graphite is applicable to practical applications.

Fluorinated diaminobicyclooxacalixarene and diaminotetraoxacalixarenes: Synthesis and conformational behaviour

Polyfluorinated diaminotetraoxacalixarenes and diaminobicyclooxacalixarene were obtained in good yield by reduction of the corresponding dinitrooxacalixarenes with sodium dithionite. Fluorinated tetraoxacalix[4]arenes with nitro and amino groups located in the inner rim of the macrocycle exists in the solution as an equilibrium mixture of two conformers. For diaminotetraoxacalixarenes the conformational equilibrium is shifted towards conformers having a 1,3-alternate structure. The ESI-MS method shows the possibility of complexing fluorinated diaminotetraoxacalixarenes and diaminobicyclooxacalixarenes with metal cations.

Experimentally-measured rate parameters for vibrational quenching of CO by N2

Carbon monoxide is a trace species in Titan's atmosphere that is not consistently found in local thermodynamic equilibrium at all altitudes. Understanding how CO exchanges energy with atmospheric collision partners is therefore crucial for accurate atmospheric modelling. Particularly significant could be vibrational relaxation of CO by nitrogen due to the high collision frequency in Titan's N2-based atmosphere. Some CO(v)-N2 rate coefficients have never been experimentally measured while others were measured decades ago in low-precision experiments. In this work, we present precise experimental measurements of the rate coefficients for the quenching of CO(v = 1,2) by N2. To perform the experiment, an equilibrium mixture of CO, N2, O3, and bath gases was subjected to a temperature-jump, creating a small amount of vibrationally-excited CO. Transient diode laser absorption spectroscopy was then used to observe the evolving vibrational state populations as a function of time. The rate coefficients of interest were found by measuring quenching rate as a function of quencher concentrations. The rate coefficient for quenching of CO(v = 1) by N2 was measured to be k = (1.3 ± 0.2) x 10−14 cm3 molecule−1 s−1 and the rate coefficient for quenching of CO(v = 2) by N2 was measured to be k = (2.1 ± 0.5) x 10−13 cm3 molecule−1 s−1 at 315 K.

Computational Modeling of Walking Beam Type Reheat Furnace for the Prediction of Slab Heating and Scale Formation

Abstract Computational modeling using the high-viscosity laminar flow approach was applied to study the effect of slab crossing time on slab heating and scale growth. Simulation of an existing industrial walking beam reheating furnace with four zones, outer refractory body, skid, slab, and fluid zone is considered. The fuel used was a mixture of coke oven and blast furnace gas. Preheated air is supplied co-axially with the fuel mixture. The combustion simulation is performed using the constrained equilibrium mixture fraction model. From the results, it has been observed that with an increase in slab residence time, the slab temperature and scale growth increase across the slab. For the system considered, with a fuel mass flowrate of 70,000 kg/h, 150–180 min of slab crossing time is appropriate to obtain desired slab temperature at the discharge end. The overall equivalence ratio is taken as Φ = 1 (fuel/air ratio is the same as stoichiometric ratio). The maximum slab scale thickness is evaluated as 2.4 mm at the discharged end for 180 min of slab crossing time.

Modeling phase equilibria in mixtures of mono- and di-carboxylic acids with hydrocarbons

Modeling phase equilibria in mixtures of mono- and di-carboxylic acids with hydrocarbons