Temperature-dependent Equilibrium Research Articles

Fractionation of iron and titanium isotopes by ilmenite and the isotopic compositions of lunar magma ocean cumulates

Basaltic volcanism on the Moon produced low- and high-Ti mare basalt suites that are also distinct with respect to their iron, titanium, and magnesium isotopic compositions. Here, the equilibrium fractionation of Fe and Ti isotopes between ilmenite and melt was experimentally investigated in order to evaluate the role of ilmenite in generating the isotopic compositional variability among the lunar mare basalts. Ilmenite crystallization experiments were conducted using two bulk compositions: an ilmenite-saturated basaltic andesite and an ilmenite-saturated Apollo 14 black glass, and the Fe and Ti isotopic compositions of the experimental ilmenites and glass (quenched melt) were analyzed using solution MC-ICPMS after hand-picking. Additionally, Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements on synthetic ilmenite were conducted and compared to previous NRIXS measurements on synthetic lunar glasses in order to derive temperature-dependent equilibrium ilmenite-melt Fe isotopic fractionations. Experimentally determined ilmenite-melt fractionations were then incorporated into a lunar magma ocean crystallization model that tracks the major element and isotopic compositional evolution of lunar magma ocean cumulates and residual liquid. There is good agreement between the Fe equilibrium isotopic fractionation measured by NRIXS and the laboratory equilibration experiments, and we find that the isotopic fractionation is sensitive to ilmenite compositional differences (0 vs. 10% Fe3+). Further, the light Ti isotopic composition of ilmenite relative to the melt (Δ49Ti=ilmenite-melt−0.09±0.03‰ at 1100∘C) is consistent with the higher coordination of Ti in ilmenite relative to melts and results of previous studies. The modeled Ti isotopic compositions for lunar magma ocean cumulates display Ti isotopic variability sufficient to explain the low- and high-Ti mare basalt sources. However, the difference in Fe isotopic composition between the low- and high-Ti mare basalts cannot be attributed solely to ilmenite fractionation. Instead, Fe isotopic fractionation by additional products of lunar magma ocean crystallization, such as clinopyroxene, is required to generate the inferred Fe and Mg isotopic variability in the lunar mantle. Alternatively, the Fe and Mg isotopic compositions of the lunar mare basalts may indicate Fe-Mg interdiffusion has occurred in the Ti-rich component of the mare basalt source regions via reaction between ilmenite cumulates and the olivine- and pyroxene-rich lunar mantle.

Barium isotope fractionation during granitic magmatism and potential of δ138/134Ba for distinguishing magmatic-hydrothermal transition in granitic magma systems

The geochemistry of Ba is commonly used to study igneous processes and fluid-melt interaction in subduction zone and granitic environments. Recent advances in analytical techniques have also indicated that Ba isotope geochemistry has the potential to significantly augment these studies. Understanding the Ba isotope fractionation mechanisms is thus critical if this potential is to be fully realized. Hence, we have used the first-principles calculations based on the density functional theory (DFT) and long-time ab initio molecular dynamics (AIMD) simulation to calculate Ba isotope fractionation during felsic magma evolution. In fluids, the reduced partition function ratio (β factor) of aqueous Ba2+ is highly variable, depending on the coordination number (n) of H2O in the first hydration shell. At ambient surface conditions on the Earth, n = 8 best represents the aqueous Ba2+ species in natural fluid, and the temperature-dependent equilibrium Ba isotope fractionation between barite/witherite and fluids can be described by the relationships: 103lnαwitherite-fluid = −0.00009×(106/T2)2 + 0.0603×(106/T2) + 0.0003 and 103lnαbarite-fluid = −0.0001×(106/T2)2 + 0.0648×(106/T2) + 0.0004, which is consistent with previous theoretical and experimental studies. In hydrothermal fluids, the hydration number of Ba2+ varies from 4 to 6 at high P-T, and the cumulative average of 103lnβ is derived to be 0.0798 ± 0.005‰ in 923.15 K and 0.2 GPa. In silicate minerals, the enrichment of heavy Ba isotopes decreases in the sequence of muscovite > microcline ≈ celsian ≈ sanbornite > barylite > phlogopite. Variations in Ba concentrations and the degree of Al-Si disordering only induce limited Ba isotope fractionation, which would be hard to distinguish analytically. At high temperatures (> 600 °C), the melt phase is enriched in heavy Ba isotopes relative to any coexisting aqueous fluid and crystallizing minerals. During the early stages of felsic magma differentiation involving plagioclase crystallization as the main mineral, the δ138/134Ba and concentration in the residual melt remain close to their initial values, but any fluid exsolved from the melt will have light δ138/134Ba values. The high Ba distribution coefficient of K-feldspar means that the resultant K-feldspar granite inherits > 90% of the Ba contained in the initial magma reservoir. Hence, the δ138/134Ba of K-feldspar is close to that of the initial melt. During the final stage of felsic magma evolution, mixing of exsolved fluids from deeper reservoirs may significantly reduce the δ138/134Ba of the now Ba-depleted melt, and can account for the low δ138/134Ba values measured in highly differentiated leucogranites and pegmatites.

Schlenk-Type Equilibria of Grignard-Analogous Arylberyllium Complexes: Steric Effects.

The presence of complex Schlenk equilibria is a central property of synthetically invaluable Grignard reagents substantially affecting their reactivity and selectivity in chemical transformations. In this work, the steric effects of aryl substituents on the Schlenk-type equilibria of their lighter congeners, arylberyllium bromides, are systematically studied. Combination of diarylberyllium complexes Ar2 Be(OEt2 ) (1Ar, Ar=Tip, Tcpp; Tip=2,4,6-iPr3 C6 H3 , Tcpp=2,4,6-Cyp3 C6 H3 , Cyp=c-C5 H9 ), containing sterically demanding aryl groups, and BeBr2 (OEt2 )2 (2) affords the Grignard-analogous arylberyllium bromides ArBeBr(OEt2 ) (3Ar, Ar=Tip, Tcpp). In contrast, Mes2 Be(OEt2 ) (1Mes, Mes=2,4,6-Me3 C6 H3 ) and 2 exist in a temperature-dependent equilibrium with MesBeBr(OEt2 ) (3Mes) and free OEt2 . Ph2 Be(OEt2 ) (1Ph) reacts with 2 to afford dimeric [PhBeBr(OEt2 )]2 ([3Ph]2 ). Moreover, the influence of replacing the OEt2 donor by an N-heterocyclic carbene, IPr2 Me2 (IPr2 Me2 =C(iPrNCMe)2 ), on the redistribution reactions was investigated. The solution- and solid-state structures of the diarylberyllium and arylberyllium bromide complexes were comprehensively characterized using multinuclear (1 H, 9 Be, 13 C) NMR spectroscopic methods and single-crystal X-ray diffraction, while DFT calculations were employed to support the experimental findings.

Quantitative Electromerism of a Well-defined Mononuclear Copper Complex Through Reversible Intramolecular Metal-Ligand Electron Transfer.

Copper amine oxidases are enzymes that exhibit in their active site a mononuclear copper complex and a 2,4,5-trihydroxyphenylalanine quinone (TPQ) cofactor; in the oxidative half of the catalytic cycle, the enzymes regulate their activity by a temperature-dependent electron transfer equilibrium between the CuII complex with the reduced, aminoquinol form of the cofactor and the reactive CuI complex with the corresponding oxidized, semiquinone form of the cofactor. Here, we report the first mononuclear copper complex with redox-active ligands showing quantitative, reversible electromerism between a CuII eletromer with reduced, neutral ligand and a CuI electromer with an oxidized, radical monocationic ligand. The CuII form, being exclusively present at low temperature, exhibits a lower enthalpy (like the enzymes), but the CuI complex exhibits a higher entropy and is exclusively present at room temperature in CH2Cl2 solution. Further analysis, based on six different copper complexes, discloses a large solvent effect on electromerism.

Benchmarking First-Principles Reaction Equilibrium Composition Prediction.

The availability of thermochemical properties allows for the prediction of the equilibrium compositions of chemical reactions. The accurate prediction of these can be crucial for the design of new chemical synthesis routes. However, for new processes, these data are generally not completely available. A solution is the use of thermochemistry calculated from first-principles methods such as Density Functional Theory (DFT). Before this can be used reliably, it needs to be systematically benchmarked. Although various studies have examined the accuracy of DFT from an energetic point of view, few studies have considered its accuracy in predicting the temperature-dependent equilibrium composition. In this work, we collected 117 molecules for which experimental thermochemical data were available. From these, we constructed 2648 reactions. These experimentally constructed reactions were then benchmarked against DFT for 6 exchange-correlation functionals and 3 quality of basis sets. We show that, in reactions that do not show temperature dependence in the equilibrium composition below 1000 K, over 90% are predicted correctly. Temperature-dependent equilibrium compositions typically demonstrate correct qualitative behavior. Lastly, we show that the errors are equally caused by errors in the vibrational spectrum and the DFT electronic ground state energy.

Exploring the Limits of Intramolecular London Dispersion Stabilization with Bulky Dispersion Energy Donors in Alkane Solution

We present an experimental study of a cyclooctatetraene-based molecular balance disubstituted with increasingly bulky tert-butyl (tBu), adamantyl (Ad), and diamantyl (Dia) substituents in the 1,4-/1,6-positions for which we determined the valence-bond shift equilibrium in n-hexane (hex), n-octane (oct), and n-dodecane (dod). Computations including implicit and explicit solvation support our temperature-dependent NMR equilibrium measurements indicating that the more sterically crowded 1,6-isomer is always favored, irrespective of solvent, and that the free energy is quite insensitive to substituent size.

Charmonium, Bc and X(3872) Transport at the LHC

We deploy a kinetic-rate equation to evaluate the transport of J/ψ, ψ(2S), Bc and X (3872) in ultrarelativistic heavy-ion collisions and compare their production yields to experimental data from the Large Hadron Collider. The rate equation has two main transport parameters: the equilibrium limit and reaction rate for each state. The temperature-dependent equilibrium limits include charm- and bottom-quark fugacities based on their initial production. The reaction rates for charmonia, bottomonia and Bc rely on charm- and bottomquark masses and binding energies from a thermodynamic T-matrix approach. For the X (3872) particle, internal structure information is encoded in reaction rates and initial conditions in the hadronic phase via two different scenarios: a loosely bound hadronic molecule vs. a compact tetraquark.

Temperature-dependent micromagnetic model of the antiferromagnet Mn2Au : A multiscale approach

Antiferromagnets (AFMs) are strong candidates for the future spintronic and memory applications largely because of their inherently fast dynamics and lack of stray fields, with ${\mathrm{Mn}}_{2}\mathrm{Au}$ being one of the most promising. For the numerical modeling of magnetic material properties, it is common to use ab initio methods, atomistic models, and micromagnetics. However, each method alone describes the physics within certain limits. Multiscale methods bridging the gap between these three approaches have been already proposed for ferromagnetic materials. Here we present a complete multiscale model of the AFM ${\mathrm{Mn}}_{2}\mathrm{Au}$ as an exemplar material, starting with results from ab initio methods going via atomistic spin dynamics (ASD) to an AFM Landau-Lifshitz-Bloch (AFM-LLB) model. First, bulk ${\mathrm{Mn}}_{2}\mathrm{Au}$ is modelled using a classical spin Hamiltonian constructed based on earlier first-principles calculations. Second, this spin model is used in the stochastic Landau-Lifshitz-Gilbert to calculate temperature-dependent equilibrium properties, such as magnetization and magnetic susceptibilities. Third, the temperature-dependent micromagnetic parameters are used in the AFM-LLB. We validate our approach by comparing the ASD and AFM-LLB models for three paradigmatic cases: (i) damped magnetic oscillations, (ii) magnetization dynamics following a heat pulse resembling pump-probe experiments, and (iii) magnetic domain wall motion under thermal gradients.

Construction of the spectral function from noncommuting spectral moment matrices

The LDA+U method is widely used to study the properties of realistic solids with strong electron correlations. One of its main shortcomings is that it does not provide direct access to the temperature dependence of material properties such as the Dzyaloshinskii-Moriya interaction, the anomalous Hall conductivity, and the spin-orbit torque. While the method of spectral moments allows us in principle to compute these quantities directly at finite temperatures, the standard two-pole approximation can be applied only to Hamiltonians that are effectively of single-band type. We do a first step to explore if the method of spectral moments may replace the LDA+U method in first-principles calculations of correlated solids with many bands in cases where the direct assessment of the temperature dependence of equilibrium and response functions is desired: The spectral moments of many-band Hamiltonians of correlated electrons do not commute and therefore they do not possess a system of common eigenvectors. We show that nevertheless the spectral function may be constructed from the spectral moments by solving a system of coupled non-linear equations. Additionally, we show how to compute the anomalous Hall conductivity of correlated electrons from this spectral function. We demonstrate the method for the Hubbard-Rashba model, where the standard two-pole approximation cannot be applied, because spin-orbit interaction (SOI)couples the spin-up and the spin-down bands. In the quest for new quantum states that arise from the combination of SOI and correlation effects, the Hartree-Fock approximation is frequently used to obtain a first approximation for the phase diagram. We propose that using the many-band generalization of the selfconsistent moment method instead of Hartree-Fock in such exploratory model calculations may improve the accuracy significantly, while keeping the computational burden low.

Adducts of Diaminophosphines with Organoboranes

AbstractReactions of chlorodiaminophosphines (R2N)2PCl (R=Et, iPr) with organoborohydrides M[BR′nH4‐n] (M=Na, Li; n=1–3; R′=alkyl, Ph, CN) proceed via H/Cl metathesis to furnish secondary phosphines and boranes which may either combine to afford isolable donor‐acceptor adducts (R2N)2P(H)−BR′nH3‐n, coexist without any sign of mutual interaction, or give rise to mixtures comprising both a labile phosphine borane and its constituents in a temperature dependent equilibrium. Stable phosphine complexes of BH2CN and BH2Ph react with KN(SiMe3)2 under PH‐bond metalation to afford spectroscopically detectable diaminophosphide boranes whose usability as nucleophilic building blocks is illustrated by trapping one specimen in a PC‐bond formation reaction with an alkyl halide. The selectivity of the individual H/Cl‐metathesis and electrophilic substitution steps as well as the thermal stability of the various reaction products depend subtly on the Lewis acidity of the borane fragment and on steric factors. Several complexes of (iPr2N)‐substituted phosphines with cyano‐ and phenylborane were characterized by single‐crystal XRD.

Methanol Decomposition on Copper Surfaces under Ambient Conditions: Mechanism, Surface Kinetics, and Structure Sensitivity

Here, we study the adsorption of methanol vapor under ambient pressure and temperature conditions on low-index Cu surfaces using surface-sensitive infrared (IR) and X-ray spectroscopy techniques. The first step of methanol decomposition, i.e., breaking of the O–H bond to form surface-bound methoxy, readily occurs under ambient conditions. Time-lapse IR spectra clearly indicate a gradually decreasing methoxy coverage, which does not obey well-established kinetic models. We rationalize the initial temperature-independent, high, nonequilibrium coverage of methoxy by a H-bonded methanol assembly in the precursor state. A temperature-dependent equilibrium coverage is achieved as the excess methoxy is eliminated gradually via further dehydrogenation to CO that desorbs to the gas phase. The kinetics of this process displays a significant structure sensitivity with considerably faster kinetics on the Cu(110) surface compared to Cu(111) and Cu(100) surfaces.

Reversible thermochromism, two-way mechanofluorochromism and tunable wavelength mechanoluminescence on tetraarylimidazole polymorphs

1, 2, 4, 5-tetraarylimidazole with 4-dimethylaminobiphenyl and 4-cyanophenyl (IMP) respectively introduced at N1 and C2 atom on imidazole core is prepared and two polymorphs correspondingly emit blue (IMP-B) and green (IMP-G) fluorescence are obtained by slow volatilization from solution. The solution-state emission displays the heavily solvatochromic effect as well as the unique solvent- and temperature-dependent LE, ICT and TICT emission equilibrium. X-ray crystallographic analysis, theoretic calculations and temperature-dependent emission decay spectra consistently support the assumption that the emission of IMP-B and IMP-G should respectively originate from LE and TICT state in.crystalline phase. For IMP-G crystal, it displays a reversible theromochromism by annealing-cooling cycles. Under force stimuli, IMP-B and IMP-G crystals present red- and blue-shifted MFC activity. The ground sample selectively pass through the two different routes to be recovered into the original crystalline phase, including transformation into IMP-B by annealing and into IMP-G by vapor fumigation. In spite of centrosymmetric space groups in both crystals, they still exhibit bright ML emission whose wavelength is nearly identical to that of fluorescence on each crystal. It is deduced that polar couples packed by molecules in two crystals may well account for the ML effect on the double polymorphs.

Phase State and Thermodynamic Properties of Proxy Sea Spray Aerosol Interfaces Derived from Temperature-Dependent Equilibrium Spreading Pressure

Phase State and Thermodynamic Properties of Proxy Sea Spray Aerosol Interfaces Derived from Temperature-Dependent Equilibrium Spreading Pressure

Density functional theory calculations of nitrogen and oxygen equilibrium isotope fractionations in NO3−–NO2−–H2O aqueous system reveal inverse kinetic isotope effects during nitrite oxidation

Nitrate and nitrite play key roles in the nitrogen cycle on Earth's surface. The isotope fractionation during nitrate reduction on enzymatic level involves multiple steps, including transfer of free NO3− to the activate site on nitrate reductase and NO2− equilibration with ambient water. However, the isotope fractionation factors of 15N and 18O among NO3−, NO2−, and H2O molecules in aqueous phases are poorly constrained. It strongly impedes the understanding of the involved processes and using stable isotopes to quantitatively examine the biogeochemical nitrogen cycle. In this contribution, we employ the density functional theory method with the Urey-Bigeleisen-Goeppert-Mayer model to predict the nitrogen and oxygen equilibrium isotope fractionation factors of NO3−, NO2−, and H2O molecules in gaseous and aqueous phases. Our calculation results show that the solvent effect has a large influence on equilibrium isotope fractionation for oxygen in water (+10.1‰ between liquid and vapor water at 25 °C), which is different to the little solvent effects on both oxygen and nitrogen in nitrate and nitrite. The calculated temperature-dependent equilibrium isotope fractionations between nitrogen of NO3− and NO2−, and oxygen of H2O and NO2− are consistent with previous laboratory experiments. Our results confirm that the oxygen equilibrium isotope fractionations between NO3− and NO2− should be +9.4‰ at 25 °C. Integrating the new results and previously reported kinetic isotope effects of nitrate reduction, we demonstrate inverse kinetic isotope effects for both nitrogen (+15.4‰) and oxygen (+5.2‰) during nitrite oxidation, which falls in the range of previous experiments. The new results enable us to use both nitrogen and oxygen isotopes as a bonded isotope tool to quantitatively assess the nitrogen cycle in low-temperature environments.

Modeling Differential Enthalpy of Absorption of CO2 with Piperazine as a Function of Temperature.

Temperature-dependent correlations for equilibrium constants (ln K) and heat of absorption (ΔHabs) of different reactions (i.e., deprotonation, double deprotonation, carbamate formation, protonated carbamate formation, dicarbamate formation) involved in the piperazine (PZ)/CO2/H2O system have been calculated using computational chemistry based ln K values input to the Gibbs–Helmholtz equation. This work also presents an extensive study of gaseous phase free energy and enthalpy for different reactions using composite (G3MP2B3, G3MP2, CBS-QB3, and G4MP2) and density functional theory [B3LYP/6-311++G(d,p)] methods. The explicit solvation shell (ESS) model and SM8T solvation free energy coupled with gaseous phase density functional theory calculations give temperature-dependent reaction equilibrium constants for different reactions. Calculated individual and overall reaction equilibrium constants and enthalpies of different reactions involved in CO2 absorption in piperazine solution are compared against experimental data, where available, in the temperature range 273.15–373 K. Postcombustion CO2 capture (PCC) is a temperature swing absorption–desorption process. The enthalpy of the solution directly correlates with the steam requirement of the amine regeneration step. Temperature-dependent correlations for ln K and ΔHabs calculated using computational chemistry tools can help evaluate potential PCC solvents’ thermodynamics and cost-efficiency. These correlations can also be employed in thermodynamic models (e.g., e-UNIQUAC, e-NRTL) to better understand postcombustion CO2 capture solvent chemistry.

Fast prediction of phase equilibrium at varying temperatures for use in multi-component phase field models

A new method for temperature-dependent phase equilibrium prediction for use in multi-component phase field models of solidification is proposed. The method consists of two parts. First, the convex hull method is applied to predict the phase equilibrium at a single temperature. Second, a set of linear equations is developed to extend the equilibrium calculation over a range of temperatures. These linear equations are derived as an extension of the equation used for solidification of binary alloys in approximating the equilibrium state of multi-component systems. Phase field simulations of solidification of a Ti-Al-V-Fe alloy are performed to demonstrate the effectiveness of the present approach under isothermal and continuous cooling conditions. The results are compared against Thermo-Calc calculations, and indicate that a high accuracy of equilibrium prediction is achieved at a single and multiple temperatures, thus demonstrating that this approach can be successfully applied to the multi-component phase field models.

Characterization of Dislocations in hcp ^4hbox {He} by Torsional Oscillator and Thermal Conductivity Measurements

We apply two complementary techniques for the characterization of mobile dislocations in samples of hcp ^4hbox {He} with the concentration of ^3hbox {He} sim 3times 10^{-7}, grown by the blocked capillary method at molar volume 19.5 hbox {cm}^3,hbox {mol}^{-1}, before and after annealing at temperatures 1.8–2.0 K, and also after work hardening by high-amplitude twisting at 0.03 K and successive recovery at 0.5–1.0 K. The first technique relies on the elastic response of solid helium to oscillatory twisting at frequencies 161 Hz and 931 Hz at temperatures below 1 K, where this response is affected by the presence of mobile dislocations with variable amounts of trapped ^3hbox {He} impurities. Monitoring the non-equilibrium amplitude dependence after moderate forcing allows to compute the length distribution n(L) of mobile dislocations (Iwasa in J Low Temp Phys 171:30, 2013; Fefferman et al. in Phys Rev B 89:014105, 2014). We also test methods of determining n(L) from the equilibrium temperature dependence of either real or imaginary part of the shear modulus at small strain amplitudes, based on the values of the damping force measured by Fefferman et al. [2]. The second technique utilizes measurements of thermal conductivity at temperatures below 0.4 K, i.e., of the dislocation-limited mean free path of thermal transverse phonons (Greenberg and Armstrong in Phys Rev B 20:1049, 1979; Armstrong et al. in Phys Rev B 20:1061, 1979). During a prolonged AC-twisting at a high amplitude of strain exceeding the yield stress, long dislocations disappear being replaced by many short ones which remain mobile. However, upon stopping this twisting, the majority of dislocations become immobilized until the sample is warmed up above 0.5 K to speed-up the recovery of dislocations to their mobile state (Day et al. in Phys Rev B 79:214524, 2009; Beamish and Franck in Phys Rev B 26:6104, 1982). This is different from the immobilization of dislocations by trapped ^3hbox {He} impurities, routinely observed at smaller strain amplitudes, which is characterized by much shorter relaxation times to effectively un-trap ^3hbox {He} atoms and make dislocations mobile again. We investigated the dynamics of the recovery of cold-worked samples, during which short segments quickly disappear, while the longest one appear after longer annealing times; the activation energy was estimated to be 22 K—pointing at the thermal vacancy-assisted process. A complementary characterization by the scattering rate of thermal transverse phonons off crystalline defects rules out non-interacting mobile dislocations as the dominant scatterer. The main conclusion is that while many properties of the sample are consistent with the theory of Granato and Lücke of isolated gliding dislocations (Granato and Lücke in J Appl Phys 27:583, 1956), several observations at low temperatures (^3hbox {He}-independent immobilization of dislocations after stopping high-amplitude twisting, sporadic avalanche-like relaxation of strain, flat temperature dependence of the phonon scattering rate) point at the presence of interacting dislocations, probably arranged into dislocation walls.

Silver isotope fractionation in ore-forming hydrothermal systems

The behavior of silver in hydrothermal ore-forming systems has been the subject of numerous studies. Equilibrium and Rayleigh-type isotope fractionation of silver during transport- and deposition-related processes in silver-bearing hydrothermal ore-forming systems are investigated experimentally and theoretically in this study. The results of open-system evaporation experiments in a simple Ag+–H2O system show that the transfer kinetics of silver from liquid to vapor follows a second-order kinetic reaction model with activation energy (Ea) values of 131.20 ± 14.63 kJ·mol−1 and 145.38 ± 2.93 kJ·mol−1 in neutral and acidic solutions, respectively. No loss of silver from the solution was observed during surface evaporation, and the rate constant, ka, increased exponentially with temperature above 343 K at ambient pressure. During vapor–liquid separation, the vapor is enriched in 107Ag, whereas the liquid is enriched in 109Ag. The silver isotope fractionation follows a Rayleigh-type fractionation model with αvapor-liquid factors of 0.99936–0.99985 at 373 K under neutral and acidic conditions, respectively, whereas the temperature-dependent equilibrium isotope fractionation follows the relationship, 1000lnαvapor-liquid = −0.0039 × 106/T2 – 0.0037 based on density functional theory (DFT) calculations. This explains the relatively narrow interval of δ109Ag values (from −0.3 to +0.4‰) analyzed in Ag-bearing veins from hydrothermal ore-deposits. Based on the bond-strength of Ag to the nearest atoms in minerals, the 109Ag enrichment decreases in the order pyrargyrite, argentite, proustite, stephanite, native silver, iodargyrite, chlorargyrite. The equilibrium silver isotope fractionation between fluid and mineral during ore formation can be considerable depending on the temperature, the nature of the silver-bearing mineral deposited, whether or not there is vapor–liquid phase separation, and whether there is a reduction of oxidized silver (Ag(+1)) to the reduced form Ag(0). Consequently, the source signatures of δ109Ag are altered significantly by transport- and deposition-related processes during ore formation (e.g., boiling, precipitation and reduction). A new silver isotope-geothermometer is proposed based on the equilibrium silver isotope fractionation between argentite and stephanite. This geothermometer, which employs the relationship 1000lnαargentite-stephanite = 0.0128 × 106/T2 + 0.0014, can be used to constrain temperature in silver-bearing hydrothermal systems provided that argentite and stephanite are in equilibrium.

Assessment of Sieverts Law Assumptions and 'n' Values in Palladium Membranes: Experimental and Theoretical Analyses.

Palladium and palladium alloy membranes are superior materials for hydrogen purification, removal, or reaction processes. Sieverts’ Law suggests that the flux of hydrogen through such membranes is proportional to the difference between the feed and permeate side partial pressures, each raised to the 0.5 power (n = 0.5). Sieverts’ Law is widely applied in analyzing the steady state hydrogen permeation through Pd-based membranes, even in some cases where the assumptions made in deriving Sieverts’ Law do not apply. Often permeation data are fit to the model allowing the pressure exponent (n) to vary. This study experimentally assessed the validity of Sieverts’ Law as hydrogen was separated from other gases and theoretically modelled the effects of pressure and temperature on the assumptions and hence the accuracy of the 0.5-power law even with pure hydrogen feed. Hydrogen fluxes through Pd and Pd-Ag alloy foils from feed mixtures (5–83% helium in hydrogen; 473–573 K; with and without a sweep gas) were measured to study the effect of concentration polarization (CP) on hydrogen permeance and the applicability of Sieverts’ Law under such conditions. Concentration polarization was found to dominate hydrogen transport under some experimental conditions, particularly when feed concentrations of hydrogen were low. All mixture feed experiments showed deviation from Sieverts’ Law. For example, the hydrogen flux through Pd foil was found to be proportional to the partial pressure difference (n ≈ 1) rather than being proportional to the difference in the square root of the partial pressures (n = 0.5), as suggested by Sieverts’ Law, indicating the high degree of concentration polarization. A theoretical model accounting for Langmuir adsorption with temperature dependent adsorption equilibrium coefficient was made and used to assess the effect of varying feed pressure from 1–136 atm at fixed temperature, and of varying temperature from 298 to 1273 K at fixed pressure. Adsorption effects, which dominate at high pressure and at low temperature, result in pressure exponents (n) values less than 0.5. With better understanding of the transport steps, a qualitative analysis of literature (n) values of 0.5, 0.5 < n < 1, and n > 1, was conducted suggesting the role of each condition or step on the hydrogen transport based on the empirically fit exponent value.

CriTER-A: A Novel Temperature-Dependent Noncoding RNA Switch in the Telomeric Transcriptome of Chironomus riparius.

The telomeric transcriptome of Chironomus riparius has been involved in thermal stress response. One of the telomeric transcripts, the so-called CriTER-A variant, is highly overexpressed upon heat shock. On the other hand, its homologous variant CriTER-B, which is the most frequently encoded noncoding RNA in the telomeres of C. riparius, is only slightly affected by thermal stress. Interestingly, both transcripts show high sequence homology, but less is known about their folding and how this could influence their differential behaviour. Our study suggests that CriTER-A folds as two different conformers, whose relative proportion is influenced by temperature conditions. Meanwhile, the CriTER-B variant shows only one dominant conformer. Thus, a temperature-dependent conformational equilibrium can be established for CriTER-A, suggesting a putative functional role of the telomeric transcriptome in relation to thermal stress that could rely on the structure–function relationship of the CriTER-A transcripts.