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At least 37 records · Page 2

Comparison of Heterogeneous Langmuirian Models for Mixed-Gas Adsorption Equilibria

Mixed-gas adsorption remains a very active area of research, where newly proposed adsorption equilibrium models need to be compared to standards in the field. The generalized Langmuir (gL) isotherm, proposed by Hamid et al. to address adsorption of different size molecules on heterogeneous adsorbents without requiring evaluation of the Gibbs isotherm, has thus far been tested mainly against the adsorbed solution theory (AST). The gL isotherm was shown to be thermodynamically consistent and gave either better or similar representation than AST models. Here, the gL isotherm is contrasted with the Dual-Process Langmuir isotherm popularized by Ritter and his co-workers and the Loading Ratio Correlation popularized for simple mixtures, both of which are considered the “standard” models for process simulation. Furthermore, the comparison is based on their theoretical roots, interpretations, and representation of the equilibrium loading and the isosteric enthalpy of adsorption of unary, binary, and ternary mixtures of various gaseous adsorbates on different adsorbents over a range of experimental pressures and temperatures.

42 ENGINEERING↗

Barrier-free predictions of short-range ordering/clustering kinetics in binary FCC solid solutions

We present comparisons of kinetic Monte Carlo (kMC) simulations of isothermal short-range ordering (SRO) and clustering (SRC) kinetics in binary FCC alloys with a mean-field concentration wave (CW) model. We find that the CW model is able to give order-of-magnitude agreement with kMC simulations for ordering/clustering relaxation times over a wide range of temperatures and compositions. The advantage of the CW model is that it does not require parameterization of vacancy hopping energy barriers, which, for a concentrated alloy, becomes prohibitive. We assess limits in the accuracy of the model and discuss the effect of cooling rates as well as the extension to multi-component systems. Ultimately, the simplicity and performance of the CW model compared to kMC simulations suggests that it is a useful tool to connect with models of properties dependent on SRO/SRC as well as for designing thermal treatments to control formation of SRO/SRC.

36 MATERIALS SCIENCE↗

Predicting Multicomponent Aqueous Phase Adsorption Equilibria of Organic Acids Using the Generalized Brunauer–Emmett–Teller Isotherm Model

Here, to support process development of adsorptive separation of organic acids, this work presents a thermodynamic modeling methodology to predict multicomponent aqueous phase organic acid adsorption equilibria from single-component adsorption isotherms using the generalized Brunauer–Emmett–Teller isotherm model (gBET). With the organic acid fugacities rigorously accounting for the aqueous phase organic acid solution chemistry and solution nonideality, gBET precisely represents the single-component adsorption isotherms and accurately predicts the binary and ternary mixed-acid adsorption equilibria for the ranges of initial pH (∼3–7), acid concentration (100–400 mmol/L), and temperature (298.15–328.15 K) with less than 10% average absolute relative deviation. In addition, gBET with pH-independent parameters provides insights into the underlying adsorption phenomena, including the adsorbate loadings and compositions in the monolayer and subsequent layers under varying initial pH, temperature, concentration, and composition. The gBET model predictions outperform the predictions from the overloading model and the Ideal Dilute Solution Theory.

09 BIOMASS FUELS↗

Thermodynamic modeling of adsorption at the liquid-solid interface

Adsorptive separation techniques are significantly energy efficient in comparison to conventional thermal separation techniques such as distillation. Despite extensive research and development activities undertaken for mixed-gas adsorption, the use of adsorption techniques for the separation of multicomponent liquid mixtures is still limited. A major barrier is the lack of accurate adsorption thermodynamic models, which form the scientific foundation of process simulation of such systems, making the translation to industrial scale challenging. In this work, we have rigorously computed the surface excess of adsorption for six binary liquid mixtures on silica gel at 303 K using the frameworks of the generalized Langmuir isotherm (gL) and the adsorbed solution theory (AST). The six binary liquid mixtures were formed by the pair-wise combinations of four components: benzene, 1,2-dichloroethane, cyclohexane, and n-heptane. We have based our calculations by considering simultaneous equilibria of three phases: saturated vapor phase, bulk liquid phase, and adsorbed phase. Further, the composition of the corresponding saturated vapor phase was estimated by the Nonrandom Two-Liquid activity coefficient model and experimental vapor-liquid equilibria data. The activity coefficients of the adsorbed phase, the central issue of multicomponent adsorption thermodynamics, were calculated using the adsorption Nonrandom Two-Liquid activity coefficient model. Devoid of simplifying assumptions, gL and AST provide rigorous thermodynamic frameworks for adsorption equilibria of multicomponent liquid mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermosolutal convection during dendritic solidification

This paper presents a mathematical model for directional solidification of a binary alloy including a dendritic region underlying an all-liquid region. It is assumed initially that there exists a nonconvecting state with planar isotherms and isoconcentrates solidifying at a constant velocity. The stability of this system has been analyzed and nonlinear calculations are performed that show the effect of convection in the solidification process when the system is unstable. Results of calculations for various cases defined by the initial temperature gradient at the dendrite tips and varying strength of the gravitational field are presented for systems involving lead-tin alloys. The results show that the systems are stable for a gravitational constant of 0.0001 g(0) and that convection can be suppressed by appropriate choice of the container's size for higher values of the gravitational constant. It is also concluded that for the lead-tin systems considered, convection in the mushy zone is not significant below the upper 20 percent of the dendritic zone, if al all.

Heinrich, J. C.↗

Use of the Burton-prim-slichter Equation at High Growth Rates

The following must be assumed in order to derive the classic Burton-Prim-Slichter equation for segregation during crystal growth: isobaric, isothermal, isopotential or uncharged species, binary, planar interface, steady state, constant diffusion coefficient in fluid, no diffusion in crystal, no lateral convection within fluid film at interface with complete mixing beyond (stagnant film model), and either density, total concentration or partial molar volumes constant in the fluid phase. In addition, the effective distribution coefficient and the interfacial distribution coefficient must be defined properly. The velocity in the equation is the growth rate times a factor correcting for the difference in volumetric properties between crystal and fluid. The stagnant film thickness is found to be a function of freezing rate, with the precise functionality depending on the type of stirring occurring in the growth fluid.

Wilcox, W. R.↗

Simultaneous concentration and purification through gradient deformation chromatography

Mobile-phase additives, commonly used to modulate absorbate retention in gradient elution chromatography, are usually assumed to be either linearly retained or unretained. Previous theoretical work from our laboratory has shown that these modulators, such as salts in ion-exchange and hydrophobic interaction chromatography and organic modifiers in reversed-phase chromatography, can absorb nonlinearly, giving rise to gradient deformation. Consequently, adsorbate peaks that elute in the vicinity of the head of the deformed gradient may exhibit unusual shapes, form shoulders, and/or be concentrated. These effects for a reversed-phase sorbent with aqueous acetonitrile (ACN) as the modulator are verified experimentally. Gradient deformation is demonstrated experimentally and agrees with simulations based on ACN isotherm parameters that are independently determined from batch equilibrium studies using the layer model. Unusual absorbate peak shapes were found experimentally for single-component injections of phenylalanine, similar to those calculated by the simulations. A binary mixture of tryptophan and phenylalanine is used to demonstrate simultaneous concentration and separation, again in agreement with simulations. The possibility of gradient deformation in ion-exchange and hydrophobic interaction chromatography is discussed.

NASA Discipline Number 93-10↗

Finite element simulations of thermosolutal convection in vertical solidification of binary alloys

Dendritic vertical solidification of a binary alloy is modeled using the finite element method to assess the effect of thermosolutal convection in macrosegregation. The mathematical model assumes steady-state solidification with a planar, undeformable surface defined by the dendrite tips and the eutectic isotherm. The dendritic region is assumed to advance at a constant solidification velocity v. The stability of the modeled system has been investigated and nonlinear calculations performed that show finger-like convection when the system is unstable. Results for lead-tin alloys show that when the system is unstable, convection is only significant in the uppermost part of the mush and is entirely driven by convection in the bulk fluid.

Heinrich, J. C.↗

Comprehensive insights into competitive oxidation/sulfidation reactions on binary ferritic alloys at high temperatures

Interpreting high-temperature corrosion induced by mixed-gas atmospheres is challenging due to the different contributions of oxidizing gases. In this work, a comprehensive study on the combined oxidation/sulfidation using label molecules is presented. Fe-Cr model alloys with 2 wt% and 9 wt% Cr were isothermally exposed using a volumetric mixture of 0.5%S 16 O 2 /27%H 2 18 O and 0.5%S 16 O 2 /7%H 2 18 O at 650 °C for 5 h and then characterized by secondary ion mass spectroscopy (SIMS). Additionally, the reactions were followed in-situ utilizing energy dispersive X-ray diffraction. The study showed that both S 16 O 2 and H 2 18 O contribute to the oxidation of the alloys but to different extents depending on the Cr-content.

36 MATERIALS SCIENCE↗

Bridging confined phase behavior of CH 4 -CO 2 binary systems across scales

Phase behavior of confined fluids may deviate significantly from that of the bulk fluid due to the fluid-wall interactions being a significant portion of all intermolecular interactions under confinement. Despite recent advancements in understanding confined phase behavior of pure fluids, confined phase behavior of mixtures remains an understudied topic. In this work, we examine the confined phase behavior of a CH 4 -CO 2 binary system by combining Monte Carlo (MC) simulations, a cubic equation of state (EoS), and the lattice Boltzmann method (LBM). First, the effects of confinement on density and phase distribution in nano-size pores are established using Gibbs Ensemble MC calculations, which produce precise results of liquid and vapor confined pressures and account for the modification of the phase change location. By comparing the phase envelopes of bulk and confined mixtures at a fixed temperature, here it is observed that the phase envelopes shrink with reductions in pore size. Based on this observation, we extend a modified Peng-Robinson EoS, which was originally developed for pure fluids under confinement, to mixtures via van-der-Waals-type mixing rules and by accounting for shifts in the critical properties of confined CH 4 -CO 2 . The resulting phase envelopes are in good agreement with the MC data. In addition, a local density model is used in combination with the confined EoS to calculate adsorption isotherms of CH 4 -CO 2 mixtures and to characterize the behavior of confined matter in nanopores. Finally, we incorporate this EoS in a multicomponent multiphase LBM that uses a pseudopotential model to represent intermolecular forces. This workflow utilizes multiscale simulation techniques to bridge the behavior of multicomponent systems across scales and to shed light on the confined phase behavior of CH 4 -CO 2 binary systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A newly proposed isotherm model to predict Cs exchange with crystalline silicotitanate in tank waste simulants

The Zheng Anthony Miller (ZAM) computer model, a multicomponent ion exchange model used to predict the exchange of Group I metals onto crystalline silicotitanate (CST), has historically been used to predict Cs distribution coefficients from Hanford and Savannah River Site (SRS) tank waste simulants. Comparison of experimentally determined Cs distribution coefficients from tank waste simulants with ZAM isotherm model predictions indicate overprediction of Cs and K distribution coefficients for simple and complex simulants with the engineered form of CST. Additionally, recent changes in chemical composition/manufacturing of IONSIV TM R9140-B have resulted in increased Cs capacity from high-salt, highly alkaline solutions. Here, this work served to assess different isotherm models and refine equilibrium parameters to develop a model that can be applied to Hanford and SRS tank waste Cs removal efforts. Toward this goal, the Campbell Westesen Peterson (CWP) model was developed. This model utilized the experimentally determined Cs capacity, and simplified ZAM equilibria expressions to include only the binary substitution of Cs + or K + on the Na + sites. Equilibrium constants for these equations were refined using experimentally determined distribution coefficients. Overall, the CWP model significantly improved our ability to predict both Cs and K loading capacity from complex matrices.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Grain boundary segregation beyond the dilute limit: Separating the two contributions of site spectrality and solute interactions

Solute segregation at grain boundaries (GBs) is known to have a profound impact on material properties, and as such is becoming routinely used as an element in alloy design. Beyond the dilute limit, the extent of solute GB segregation is known to be concentration dependent. Using hybrid Monte Carlo/Molecular Statics simulations of Mg segregation in Al, in this work we decouple the two contributions to this composition dependence: (i) spectrality of atomic environments at the boundary and (ii) solute-solute interactions. Although only contribution (ii) is typically considered in the literature, we argue that both contributions are equally important to understand concentration dependence and correctly quantify GB solute segregation in a binary alloy. Finally, a thermodynamic segregation isotherm is outlined that accounts for both the spectrality of grain boundary sites and solute-solute interactions. Unlike classical isotherms like those of McLean or Fowler-Guggenheim, which can be successfully fitted to GB segregation data only over a limited range of composition and temperature, our proposed model is shown to be accurate across the composition-temperature space.

36 MATERIALS SCIENCE↗

Angular momentum transfer by gravitational torques and the evolution of binary protostars

The efficiency of angular momentum transport by gravitational torques is investigated semianalytically for two idealized models. The first model, a rotating ellipsoid embedded within another ellipsoid, is compared with numerical results for the fission instability of a radpidly-rotating polytrope. The fission instability is aborted by the rapid transfer of angular momentum outward by gravitational torques. The global rates of angular momentum transfer by gravitational torques in rotating gas clouds such as the presolar nebula are shown to be comparable to the rates assumed to be appropriate for transfer by turbulent stresses. The second model is a binary system embedded within a rotating ellipsoid. The binary orbital angular momentum decreases significantly when the phase angle with the ellipsoid is constant; the binary separation may then decrease by a factor of 100 within about an orbital period. For a variable phase angle, little secular loss of orbital angular momentum occurs. Binaries which form in the isothermal regime of the theory of hierarchical fragmentation will not undergo orbital decay, whereas very close binaries composed of nonisothermal fragments may decay and merge into single objects.

Boss, A. P.↗

Understanding the Puzzling X-Ray Spectrum of the SO Galaxy NGC 4382; NGC 43819: Spectral Analysis of the Prototypical Early Merger and ASCA Observations of a Dynamically Young Elliptical: NGC 4125

We have analyzed the ASCA observations of NGC 4382, NGC 4038/9, NGC 4125 and produced papers for publication. NGC 4382 is one of the E and SO galaxies detected with the lowest X-ray to optical luminosity ratio. These galaxies have a peculiar X-ray (0.1-3 keV) spectrum, with a significant excess of counts in the lowest spectral channels (less than 1 keV) relative to the spectral count distributions of X-ray brihter E and SO galaxies. Analyzing the ROSAT PSPC observation of NGC 4382 it was unclear whether this soft excess was due to a real very soft component in a multi-component spectrum, or reflected an extremely low metal abundance in an isothermal hot gas. Our ASCA observations show that the low-abundance single-temperature model does not fit well to the X-ray spectrum, in agreement with our previous suggestions. A better explanation is a composite spectrum with a very soft component (0.3 keV) in addition to a harder (5 keV) component from X-ray binaries. In this model, the abundance cannot be constrained. More complex spectral models are also possible. The ASCA observations of The Antennae - (NGC4038/9) show that at least two spectral components are required to describe the emission-thermal emission from a plasma at 0.8 keV, and a component at higher energies. The hot gas contributes about half of the flux in the 0.5 to 6 keV band. If the column density to the higher energy component is greater than 2 x 10 (exp 21) per square centimeter, then the fitted abundance in the hot gas component is less than 0.2 solar. This low abundance is not expected for the hot interstellar medium in NGC4038/9 in which supernovae and star formation (expected to enrich and heat the gas) are ongoing. We do not detect any spatial variations in the spectrum. We relate these findings to data obtained by other satellites (Einstein, ROSAT) for this interacting galaxy pair. NGC4125's ASCA data was analyzed jointly with its Beppo-SAX observation. A hard component (kT /sim 4-10 keV) is observed together with a thermal component with line emission.

Fabbiano, Giuseppina↗

Directional solidification with heat losses

The upward directional solidification of a dilute binary alloy in a tall, thin, two-dimensional slot is considered. Heat losses from the sidewalls produce curved isotherms, interface deformations, and melt convection. An asymptotic approach is used which relates the small heat loss to the thinness of the solidification cell, and solutions are obtained for the resulting melt convection, interface deflection, and the distribution of heat and solute. The model is compared to the numerical results of Chang and Brown (1983) which exclude the effects of solute buoyancy and thermodynamic equilibrium at the interface. The radial segregation at the interface (consistent with both interface shapes and temperature fields) is computed, and it is found that the radial segregation is independent of interfacial shapes; the radial segregation cannot be calculated from only a knowledge of the interface shape.

Brattkus, K.↗

Models for Galaxy halos in an open universe

The properties of simple, self-consistent infall models which embed an 'isothermal' dark halo in an open universe are presented. These models depend on one scaling parameter and two shape parameters. The first may be taken to be the circular velocity in the inner regions, and the others to be the density of the universe, Omega, and a measure, e, of the shape of orbits. These models provide a useful description of ensembles of satellite galaxies, or of binary galaxies, because they allow explicitly for the fact that such systems have orbital periods approaching the age of the universe and so cannot have a random orbital phase.

White, Simon D. M.↗

An automated multi-component gas adsorption system (MC GAS)

The knowledge gap on adsorption of complex mixtures in the literature relative to single component data represents a persistent obstacle to developing accurate process models for adsorption separations. The collection of mixed gas adsorption data is an imminent need for improved understanding of the behavior of adsorbent systems in these diverse adsorption applications. Current approaches to understanding mixture adsorption using predictive theories based on pure component adsorption experiments often fail to capture the behavior of more complex, non-ideal systems. In this work, we present an automated volumetric instrument for the measurement of mixed gas adsorption isotherms. This instrument was validated by comparison to other in-house instruments and data available in the literature, and the binary adsorption measurements were found to be thermodynamically consistent. The automation of this instrument allows for rapid collection of high-quality mixture adsorption data.

47 OTHER INSTRUMENTATION↗

The baroeffect and an appropriate momentum boundary condition

As disparate molecular weight gases isothermally diffuse between two ends of a capillary tube, they can support a pressure gradient. The magnitude of this pressure gradient depends critically on viscous wall stress and becomes a measure of the boundary condition. Here, a one-dimensional analytical model is proposed that allows for specular gas reflection from the wall. It explains anomalous (4/3) correction factors required previously to match experiment to baroeffect models. It predicts a new physical phenomenon, a surface-driven baroeffect for equal molecular weight gases. Diffusive slip contributions exceed the order of convective diffusion for Peclet number Pe less than 1 and approximately equal convective diffusion for Pe values between 1 and 4. For binary gases, this model further extends the baroeffect experiment as a means to find momentum accommodation coefficients, slip lengths, and external friction coefficients. A corrected binary diffusion coefficient is defined.

Noever, David A.↗