Thermodynamic Equilibrium Research Articles

Chemical abundances for a sample of FGK dwarfs in the Pleiades open cluster from APOGEE

ABSTRACT This paper presents chemical abundances of 12 elements (C, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, and Fe) for 80 FGK dwarfs in the Pleiades open cluster, which span a temperature range of $\sim$2000 K in T$_{\rm eff}$, using the high-resolution (R$\sim$22 500) near-infrared SDSS (Sloan Digital Sky Survey)-IV/APOGEE (Apache Point Observatory Galactic Evolution Experiment) spectra ($\lambda$1.51–1.69 $\mu$m). Using a 1D local thermodynamic equilibrium abundance analysis, we determine an overall metallicity of [Fe/H] = +0.03 $\pm$ 0.04 dex, with the elemental ratios [$\alpha$/Fe] = +0.01 $\pm$ 0.05, [odd-z/Fe] = –0.04 $\pm$ 0.08, and [iron peak/Fe] = –0.02 $\pm$ 0.08. These abundances for the Pleiades are in line with the abundances of other open clusters at similar galactocentric distances as presented in the literature. Examination of the abundances derived from each individual spectral line revealed that several of the stronger lines displayed trends of decreasing abundance with decreasing $T_{\rm eff}$. The list of spectral lines that yield abundances that are independent of $T_{\rm eff}$ are presented and used for deriving the final abundances. An investigation into possible causes of the temperature-dependent abundances derived from the stronger lines suggests that the radiative codes and the APOGEE line list we employ may inadequately model van der Waals broadening, in particular in the cooler K dwarfs.

Heterobimetallic NiFe Complex for Photocatalytic CO2 Reduction: United Efforts of NiFe Dual Sites.

Catalytic CO2 reduction poses a significant challenge for the conversion of CO2 into chemicals and fuels. Ni-Fe carbon monoxide dehydrogenase ([NiFe]-CODH) effectively mediates the reversible conversion of CO2 and CO at a nearly thermodynamic equilibrium potential, highlighting the heterobimetallic cooperation for the design of CO2 reduction catalysts. However, numerous NiFe biomimetic model complexes have realized little success in CO2 reduction catalysis, which underscores the crucial role of precise bimetallic configuration and functionality. Herein, we presented a heterobimetallic NiFe complex for the photocatalytic reduction of CO2 to CO, demonstrating significantly enhanced catalytic performance compared to the homonuclear NiNi catalyst. Photocatalytic and mechanistic investigations revealed that with the assistance of a redox-active phenanthroline ligand, NiFe achieves dual-site activation of CO2 through a pivotal intermediate, NiII(μ-CO22--κC:κO)FeII, where the Lewis acidity of the FeII site plays an important role, as corroborated in the homonuclear FeFe system. This study introduces the first heteronuclear NiFe molecular catalyst capable of efficiently catalyzing the reduction of CO2 to CO, deepening insights into heterobimetallic cooperation and offering a novel strategy for designing highly active and selective CO2 reduction catalysts.

Exergetic characterization of flat plate solar collector using genetic algorithm

With the rapid advancement of technology, the global demand for energy is increasing exponentially. It is crucial to focus on energy conservation and conversion across all sectors. This study conducted a second law or exergy analysis on a solar water heating system to uncover hidden losses during the process. To optimize exergetic efficiency, a genetic algorithm was employed to control the overall loss coefficient of a solar flat plate collector. Four decision variables were used in the genetic algorithm—heat flux rate, glass cover temperatures at the inlet and exit, and collector plate temperature to minimize the overall loss coefficient. Energy efficiency, entropy generation, and exergy destruction were estimated for various mass flow rates using thermodynamic equilibrium equations. Exergy correlations were developed concerning mass flow rate (0.001–0.009 kg/s), inlet temperature (300 K–360 K), collector plate area (1–10 m²), incident solar energy (400–900 W/m²), optical efficiency (0.4%–1%), and ambient temperature (300–315 K) under a range of initial conditions. It was found that exergy efficiency slightly increased (0.01%–0.08%) over a 12-h period. Although this increase is small, it can significantly contribute to energy conservation over the long term. The genetic algorithm predicted the minimum loss coefficient occurring during peak hours (12–14 p.m.) with respect to four decision variables. The results of this study were compared with existing literature and showed good agreement. In addition to the exergy analysis, an uncertainty error analysis was performed to assess the reliability and accuracy of the experimental measurements and computational predictions. By quantifying these uncertainties, the study ensured that the reported enhancements in exergy efficiency and the optimization results obtained through the genetic algorithm are robust and credible. This rigorous error analysis adds confidence to the findings, highlighting the potential for improved energy conservation in solar water heating systems.

Insight into the Course of the Ferrier Rearrangement Used to Obtain Untypical Diosgenyl Saponins.

The Ferrier rearrangement was utilized to obtain 2,3-unsaturated diosgenyl glycosides. This reaction proceeded with high stereoselectivity, yielding mostly saponins with an α configuration (hexoses) or predominantly with a β configuration (pentoses). The diversity of the glycals used and the glycosides obtained enabled a deep discussion of the Ferrier rearrangement mechanism. The mechanism was supported by DFT calculations concerning the intermediate ions. It was concluded that the vinylogous anomeric effect may influence the reactivity of the glycals. Two possible Ferrier rearrangement intermediates, dioxolenium and allyloxycarbenium ions, were hypothesized to exist in thermodynamic equilibrium that shifted toward the former. The allyloxycarbenium ion participates in the final rearrangement step and determines the reaction regioselectivity. Furthermore, the conformational stability of the 2,3-unsaturated pyranose ring determines the stereoselectivity of the reaction. Factors influencing this stability, as well as the NMR data enabling recognition of the 0H5 and 5H0 conformations, were identified. Chemoselective hydrogenation of 2,3-unsaturated diosgenyl glycosides provided a series of 2,3-dideoxy analogues. The anticancer, hemolytic, and antibacterial activities of the synthesized saponins are presented alongside a discussion of the structure-activity relationships.

Chemical composition of planetary hosts: C, N, and α-element abundances

Accurate atmospheric parameters and chemical composition of planet hosts play a major role in characterising exoplanets and understanding their formation and evolution. Our objective is to uniformly determine atmospheric parameters and chemical abundances of carbon (C), nitrogen (N), oxygen(O), and the alpha -elements, magnesium (Mg) and silicon (Si), along with C/O, N/O and Mg/Si abundance ratios for planet-hosting stars. In this analysis, we aim to investigate the potential links between stellar chemistry and the presence of planets. e tai Observatory telescope. The determination of stellar parameters was based on a standard analysis using equivalent widths and one-dimensional, plane-parallel model atmospheres calculated under the assumption of local thermodynamical equilibrium. The differential synthetic spectrum method was used to uniformly determine the carbon C(C2), nitrogen N(CN), oxygen O I magnesium Mg I, and silicon Si I elemental abundances as well as the C/O, N/O, and Mg/Si ratios. We analysed elemental abundances and ratios in dwarf and giant stars, finding that C/Fe O/Fe and Mg/Fe are lower in metal-rich dwarf hosts; whereas N/Fe is close to the Solar ratio. Giants show smaller scatter in C/Fe and O/Fe and lower than the Solar average C/Fe and C/O ratios. The (C+N+O) abundances increase with Fe/H in giant stars, with a minimal scatter. We also noted an overabundance of Mg and Si in planet-hosting stars, particularly at lower metallicities, and a lower Mg/Si ratio in stars with planets. In giants hosting high-mass planets, nitrogen shows a moderate positive relationship with planet mass. C/O and N/O ratios show moderate negative and positive slopes in giant stars, respectively. The Mg/Si ratio shows a negative correlation with planet mass across the entire stellar sample.

Clumped isotopes constrain thermogenic and secondary microbial methane origins in coal bed methane

Methane is an economic energy resource and potent greenhouse gas. Distinguishing secondary microbial methane from thermogenic gas is important for natural gas exploration and consideration of subsurface microbial activity in the global carbon cycle, but remains challenging. To understand controls on methane origins in natural gas systems, we investigated the methane clumped isotopologue distributions in the Qinshui Basin high-thermal maturity coal bed methane (CBM) reservoir. Here, near-equilibrium clumped isotopologues distribution (Δ13CH3D and Δ12CH2D2) inferred a temperature interval of 21.6–252.3 °C. The high-temperature thermodynamic equilibrium most likely represents original thermogenic CBM characteristics during coalification. The low-temperature equilibrium clumped isotopologue distributions suggest microbial alteration to CH4 isotopic bond ordering by increased enzymatically catalyzed isotopic exchange. The independent constraints from clumped isotopes, integrated with other geochemical and genomic evidence, confirm notable secondary microbial methane from biodegradation in the highly mature reservoir. Thus, methane clumped isotopes can be used as unequivocal tracers to distinguish secondary microbial methane from thermogenic gases and hence provide the ability to incorporate them separately into global methane budgets.

The solar beryllium abundance revisited with 3D non-LTE models

The present-day abundance of beryllium in the solar atmosphere provides clues about mixing mechanisms within stellar interiors. However, abundance determinations based on the Be II313.107 nm line are prone to systematic errors due to imperfect model spectra. These errors arise from missing continuous opacity in the UV, a significant unidentified blend at 313.102 nm, departures from local thermodynamic equilibrium (LTE), and microturbulence and macroturbulence fudge parameters associated with one-dimensional (1D) hydrostatic model atmospheres. Although these factors have been discussed in the literature, no study has yet accounted for all of them simultaneously. To address this, we present 3D non-LTE calculations for neutral and ionised beryllium in the Sun. We used these models to derive the present-day solar beryllium abundance, calibrating the missing opacity on high resolution solar irradiance data and the unidentified blend on the centre-to-limb variation. We find a surface abundance of 1.21 ± 0.05 dex, which is significantly lower than the value of 1.38 dex that has been commonly adopted since 2004. Taking the initial abundance via CI chondrites, our result implies that beryllium has been depleted from the surface by an extra 0.11 ± 0.06 dex, or 22 ± 11%, on top of any effects of atomic diffusion. This is in tension with standard solar models, which predict negligible depletion, as well as with contemporary solar models that have extra mixing calibrated on the abundances of helium and lithium, which predict excessive depletion. These discrepancies highlight the need for further improvements to the physics in solar and stellar models.

A Yebes W-band Line Survey towards an Unshocked Molecular Cloud of Supernova Remnant 3C 391: Evidence of Cosmic-Ray-Induced Chemistry

Cosmic rays (CRs) have strong influences on the chemistry of dense molecular clouds (MCs). To study the detailed chemistry induced by CRs, we conducted a Yebes W-band line survey towards an unshocked MC (which we named 3C391:NML) associated with supernova remnant 3C 391. We detected emission lines of 18 molecular species in total and estimated their column densities with local thermodynamic equilibrium (LTE) and non-LTE analysis. Using the abundance ratio N(HCO+)/N(CO) and an upper limit of N(DCO+)/N(HCO+), we estimated that the CR ionization rate of 3C391:NML is ζ ≳ 2.7 × 10−14 s−1 with an analytic method. However, we caution against adopting this value because chemical equilibrium, which is a prerequisite of using the equations, is not necessarily reached in 3C391:NML. We observed lower N(HCO+)/N(HOC+), higher N(HCS+)/N(CS), and higher X(l-C3H+) by an order of magnitude in 3C391:NML than the typical values in quiescent dense MCs. We found that an enhanced CR ionization rate (of order ∼10−15 or ∼10−14 s−1) is needed to reproduce the observation with a chemical model. This is higher than the values found in typical MCs by 2–3 orders of magnitude.

HR-GO

Context. Dwarf galaxy streams encode vast amounts of information essential to understanding early galaxy formation and nucleosynthesis channels. Due to the variation in the timescales of star formation history in their progenitors, stellar streams serve as ‘snapshots’ that record different stages of galactic chemical evolution. Aims. This study focusses on the Cetus stream, stripped from a low-mass dwarf galaxy. We aim to uncover its chemical evolution history as well as the different channels of its element production from detailed elemental abundances. Methods. We carried out a comprehensive analysis of the chemical composition of 22 member stars based on their high-resolution spectra. We derived abundances for up to 28 chemical species from C to Dy and, for 20 of them, we account for the departures from local thermodynamic equilibrium (NLTE effects). Results. We confirm that the Cetus stream has a mean metallicity of [Fe/H] = −2.11 ± 0.21. All observed Cetus stars are α enhanced with [α/Fe] ≃ 0.3. The absence of the α-‘knee’ implies that star formation stopped before iron production in type Ia supernovae (SNe Ia) became substantial. Neutron capture element abundances suggest that both the rapid (r-) and the main slow (s-) processes contributed to their origin. The decrease in [Eu/Ba] from a typical r-process value of [Eu/Ba] = 0.7–0.3 with increasing [Ba/H] indicates a distinct contribution of the r- and s-processes to the chemical composition of different Cetus stars. For barium, the r-process contribution varies from 100 to 20% in different sample stars, with an average value of 50%. Conclusions. Our abundance analysis indicates that the star formation in the Cetus progenitor ceased after the onset of the main s-process in low- to intermediate-mass asymptotic giant branch stars but before SNe Ia played an important role. A distinct evolution scenario is revealed by comparing the abundances in the Ursa Minor dwarf spheroidal galaxy, showing the diversity in – and uniqueness of – the chemical evolution of low-mass dwarf galaxies.

The AMBRE Project: Lead abundance in Galactic stars

Context. The chemical evolution of neutron capture elements in the Milky Way is still a matter of debate. Although more and more studies investigate their chemical behaviour, there is still a lack of a significant large sample of abundances of a key heavy element: lead. Aims. Lead is the final product of the s-process nucleosynthesis channel and is one of the most stable heavy elements. The goal of this article is to present the largest catalogue of homogeneous Pb abundances, in particular for metallicities higher than −1.0 dex, and then to study the lead content of the Milky Way. Methods. We analysed high-resolution spectra from the ESO UVES and FEROS archives. Atmospheric parameters were taken from the AMBRE parametrisation. We used the automated abundance method GAUGUIN to derive lead abundances in 653 slow-rotating FGK-type stars from the 368.34 nm Pb I line. Results. We present the largest catalogue of Local Thermodynamic Equilibrium (LTE) and non-LTE lead abundances ever published with metallicities ranging from −2.9 to 0.6 dex and [Pb/Fe] from −0.7 to 3.3 dex. Within this sample, no lead-enhanced Asymptotic Giant Branch (AGB) stars were found, but nine lead-enhanced metal-poor stars ([Pb/Fe] > 1.5) were detected. Most of them were already identified as carbon-enhanced metal-poor stars with enrichments in other s-process species. The lead abundance of 13 Gaia Benchmark Stars are also provided. We then investigated the Pb content of the Milky Way disc by computing vertical and radial gradients and found a slightly decreasing [Pb/Fe] radial trend with metallicity. This trend together with other related ratios ([Pb/Eu], [Pb/Ba], and [Pb/α]) are interpreted thanks to chemical evolution models. The two-infall model closely reproduces the observed trends with respect to the metallicity. It is also found that the AGB contribution to the Pb Galactic enrichment has to be strongly reduced. Moreover, the contribution of massive stars with rather high rotational velocities should be favoured in the low-metallicity regime.

Continuous near-equilibrium operation and model validation of a pilot-scale thermochemical energy storage reactor using CaO/Ca(OH)2

Thermochemical energy storage using the material system CaO/Ca(OH)2 is regarded as one of the most promising technologies for application temperatures between 400 °Cand600 °C. However, there is still a lack of information concerning the transfer of laboratory results to industrially-relevant conditions. This study addresses this research gap and provides data for a continuously operated pilot-scale fluidized-bed storage reactor (257 mm diameter, up to 31L fluidized bed volume maximal 700 °C and 6barg). The reactor is operated near the thermodynamic equilibrium at varying space times of the storage material (250–400 µm). The bed height is maintained at 390 mm during continuous operation. The results indicate good fluidization quality at steady-state operation for up to 9 h. Based on the results, a CSTR-type reactor model is proposed and validated, giving good results in predicting the fluidized bed’s steady-state conversion and temperature. The model is based on material and fluidization properties, such as the fluidized beds porosity, that are measured in dependence of temperature and superficial gas velocity. The simulation results indicate that the heat transfer characteristics are crucial for adequate storage power.

Equation of state of the relativistic electron–positron–photon plasma at arbitrary temperature and degeneracy

We consider the plasma made of relativistic electrons and positrons in thermodynamic equilibrium with photons at arbitrary temperature and degeneracy. We establish various thermodynamic identities as a function of the electron and positron chemical potentials and temperature. The high-temperature regime in which the electrons and positrons are ultrarelativistic is recovered. The excess of electrons with respect to positrons or the excess of positrons with respect to electrons depends on the thermodynamic conditions. Doing so, we go beyond what is usually found in the literature where only the high temperature regime is usually tackled.

Helium retention feature in the boron deposited layer on tungsten substrate by laser-induced breakdown spectroscopy and machine learning approach

ITER is designed for a burning plasma operation in which Tungsten (W) tiles are used as the first wall and diverter materials. Studying He dynamics in B-coated W wall is essential to understanding the effect of boronized plasma-facing components in fusion reactors, as these post-conditioning materials significantly influence helium retention and release. Plasma-wall interactions (PWI) are an important issue in ITER fusion reactors. PWI would lead to wall erosion and impurity redeposition. As a product of the D-T burning plasma, helium (He) ash would be retained or co-deposited on plasma-facing components (PFCs), affecting the stable operation of burning plasma. Laser-induced breakdown spectroscopy (LIBS) is proposed as a promising in-situ diagnostic approach for monitoring D/T and He retention and impurity deposition on PFCs of tokamak devices. In this study, the LIBS technique was used to investigate the helium retention feature in the boron (B) layer on tungsten substrate in 10−5 mbar. Five He-retention samples on the boron deposition layer on tungsten substrates were prepared by pulsed laser deposition (PLD) method at different ambient pressures in our lab. The investigations indicate that the atomic spectral line of helium (He-I 587.56 nm) was observed in the spectra of the first three laser shots. The depth profiles of He, B, and W in the boron-deposited layer on tungsten substrate were performed by LIBS to determine the co-deposition layer thickness. The concentration of He in the co-deposition layer samples measured by TDS is 7 × 1020 He/m2. The plasma parameters, such as plasma electron temperature and electron number density, were calculated to validate the local thermodynamic equilibrium. Machine learning (ML) algorithms are used to classify the co-deposits and substrates. The first three principal components (PC1, PC2 & PC3) of the unsupervised ML algorithm (PCA) give a classification accuracy of 91.7 %. The supervised ML algorithm neural network achieved training and testing accuracy of 100 % and 96.7 %, respectively.

Helium Abundance of the Sun: A Spectroscopic Analysis

Determining the He/H ratio in cool stars presents a fundamental astrophysical challenge. While this ratio is established for hot O and B stars, its extrapolation to cool stars remains uncertain due to the absence of helium lines in their observed spectra. We address this knowledge gap by focusing on the Sun as a representative cool star. We conduct spectroscopic analyses of the observed solar photospheric lines by utilizing a combination of MgH molecular lines and neutral Mg atomic lines including yet another combination of CH and C2 molecular lines with neutral C atomic lines. Our spectroscopic analyses were further exploited by adopting solar model atmospheres constructed for distinct He/H ratios to determine the solar photospheric helium abundance. The helium abundance is determined by enforcing the fact that for an adopted model atmosphere with an appropriate He/H ratio, the derived Mg abundance from the neutral Mg atomic lines and that from the MgH molecular lines must be the same. The same holds for the C abundance derived from neutral C atomic lines and that from CH lines of the CH molecular band and C2 lines from the C2 Swan band. The estimated He/H ratio for the Sun is discussed based on the one-dimensional local thermodynamic equilibrium model atmosphere. The helium abundance (He/H = 0.091−0.014+0.019 ) obtained for the Sun serves as a critical reference point to characterize the He/H ratio of cool stars across the range in their effective temperature.

Rigidity‐Driven Structural Isomers in the NaCl–Ga2S3 System: Implications for Energy Storage

Alternative energy sources require the search for innovative materials with promising functionalities. Systems with unusual chemical properties represent an insufficiently explored domain, concealing unexpected features. Using diffraction and Raman spectroscopy over a wide temperature range, supported by first‐principles simulations, a rare phenomenon is unveiled: phase‐dependent chemical interactions between binary components in the NaCl–Ga2S3 system. In this unique occurrence, previously intact binary crystalline species transform upon melting into mixed liquid structural isomers, forming bonds with new partners. The chemical combinatorics appears to be fully reversible for stable crystals and liquids. Despite this, rapidly frozen glasses out of thermodynamic equilibrium remain in a metastable isomeric state, offering remarkable properties, particularly a high room‐temperature Na+ conductivity, comparable to the best sodium halide superionic conductors and therefore encouraging for sodium solid‐state batteries and energy applications. A rigidity paradigm is responsible for the observed phenomenon, as the extremely constrained Ga2S3 crystal lattice does not survive viscous flow, breaking up at a short‐range level. The removal of rigidity constraints and dense packing leads to a significant increase in empty space, which is the origin of high sodium diffusivity. Broadly, the rigidity‐driven structural isomerism opens up an inspiring path to the discovery of atypical materials.

Full non-LTE spectral line formation

In the present paper we consider the full nonlocal thermodynamic equilibrium (non-LTE) radiation transfer problem. This formalism allows us to account for deviation from equilibrium distribution of both the radiation field and the massive particles. In the present study, two-level atoms with broadened upper level represent the massive particles. In the absence of velocity-changing collisions, we demonstrate the analytic equivalence of the full non-LTE source function with the corresponding standard non-LTE partial frequency redistribution (PFR) model. We present an iterative method based on operator splitting techniques that can be used to numerically solve the problem at hand. We benchmark it against the standard non-LTE transfer problem for a two-level atom with PFR. We illustrate the deviation of the velocity distribution function of excited atoms from the equilibrium distribution. We also discuss the dependence of the emission profile and the velocity distribution function on elastic collisions and velocity-changing collisions.

A reinvestigation on combined dry and wet adhesive contact considering surface tension

The present study theoretically explores combined dry and wet adhesive contact between a rigid sphere and elastic semi-half substrate, in which dry contact is encircled by liquid bridge. We consider threefold effects of liquid bridge on contact behavior, namely Laplace pressure induced by the curved surface of liquid meniscus, surface tension at the triple-phase junction and alternation of adhesion energy between solid surfaces ascribed to liquid immersion. A clear novelty in this study is the investigation on the effect of surface tension at the vapor-liquid-solid junction on the adhesive contact response, in contrast to previous studies. The model solution predicts that the contact behavior and adhesive strength are strongly dependent on surface wettability (manifested by contact angle), liquid volume and the contact system's rapidity in achieving thermodynamic equilibrium. It is found that the transition of the pull-off force is evidently different from Maugis-Dugdale model in terms of a couple of interesting characteristics. Moreover, it is unveiled that the jump instabilities and hysteresis of force-separation curves are highly affected by surface wettability and liquid volume. These theoretical results can not only shed lights on the mechanism of liquid-mediated adhesion employed by animals and plants, but also provide us inspiration for development of biomimetic adhesive devices.

Experimental investigation on product and temperature distribution in a continuous flow packed-bed reactor for dodecahydro-N-ethylcarbazole dehydrogenation

The dehydrogenation of dodecahydro-N-ethylcarbazole (H12-NEC) generates enormous gas accompanied by intense heat absorption, affecting heat and mass transfer in porous catalysts. A packed-bed reactor equipped with a temperature measurement device was designed to investigate the continuous flow dehydrogenation of H12-NEC. The effects of weight hourly space velocity (WHSV), reaction temperature, catalyst particle size, and pressure were evaluated. The results reveal that the volume flow rate of hydrogen will increase with the increase of WHSV. And the reduction of gas–liquid ratio and catalyst particle size facilitates heat transfer causing a more uniform axial temperature distribution within the reactor. As the temperature rises, the hydrogen yield increases along with more by-products. 456 K and 2 mm of catalyst particle size are determined to be the optimal reaction conditions in the study, achieving the hydrogen production rate of 9.61 molH2·gPd-1·h-1. With pressure increasing, the hydrogen yield gradually decreases, but the decreased evaporation of H12-NEC results in a smaller temperature difference between the reactor and heating wall. A comparison with the thermodynamic equilibrium model reveals that the effect of pressure on chemical equilibrium may be more significant than the temperature.

Ethanol removal by stripping with CO2 reduced-size bubbles: Mechanical and thermodynamic entrainments

The efficiency of stripping processes for volatile compounds is governed by mechanical and thermodynamic entrainments, which play crucial roles in ethanol removal during the extractive fermentation process. These mechanisms depend on variables such as bubble diameter, ethanol concentration, liquid volume, pressure, and temperature. However, the quantification of each of them separately and their dependence on bubble diameter have never been addressed. The present study proposes a new methodology to evaluate both mechanical and thermodynamic entrainments, based on experimental data and thermodynamic equilibrium analysis of the bubbles in reactors with working volumes of 10.0 and 50 L, aiming to clarify the role that bubble diameter (microbubbles, fine and coarse bubbles) plays in these mechanisms. The results indicated that thermodynamic equilibrium was reached for any size of bubbles up to 5 mm in diameter, under a wide range of experimental conditions with specific gas flow rates from 0.22 to 10 vvm. Equally important, mechanical entrainment was found to enrich the gas phase in ethanol by a factor of 15, representing a higher concentration factor than for thermodynamic entrainment, which was inconceivable initially. This introduces a new and promising approach to intensify the stripping process of volatile compounds by means of mechanical entrainment.

Probing the alkylidene carbene-strained alkyne equilibrium in polycyclic systems via the Fritsch-Buttenberg-Wiechell rearrangement.

Strained cycloalkynes are valuable building blocks in synthetic chemistry due to their high degree of reactivity and ability to form structurally complex scaffolds, common features of many pharmaceuticals and natural products. Alkylidene carbenes provide a pathway to the formation of strained cycloalkynes through Fritsch-Buttenberg-Wiechell rearrangements, but this strategy, like other methods of alkyne generation, is believed to depend upon a thermodynamic equilibrium that favors the alkyne over the carbene. Herein three highly strained, polycyclic alkynes, previously thought to be thermodynamically inaccessible, are generated under mild conditions and intercepted through Diels-Alder cycloaddition with a diene trapping agent. The use of a different trapping agent also allows for the interception of the alkylidene carbene, providing the first instance in which both an exocyclic alkylidene carbene and its cycloalkyne Fritsch-Buttenberg-Wiechell rearrangement product have been trapped.