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At least 73 records · Page 4

Thermodynamic Data to 20,000 K For Monatomic Gases

This report contains standard-state thermodynamic functions for 50 gaseous atomic elements plus deuterium and electron gas, 51 singly ionized positive ions, and 36 singly ionized negative ions. The data were generated by the NASA Lewis computer program PAC97, a modified version of PAC91 reported in McBride and Gordon. This report is being published primarily to document part of the data currently being used in several NASA Lewis computer programs. The data are presented in tabular and graphical format and are also represented in the form of least-squares coefficients. The tables give the following data as functions of temperature : heat capacity, enthalpy, entropy Gibbs energy, enthalpy of formation, and equilibrium constant. A brief discussion and a comparison of calculated results are given for several models for calculating ideal thermodynamic data for monatomic gases.

Gordon, Sanford↗

Size Exclusion Chromatography Studies of the Initial Self-Association Steps of Chicken Egg White Lysozyme Nucleation

Nucleation is one of the least understood aspects of crystallogenesis. In the case of macromolecule nucleation, this understanding is further hampered by uncertainty over what precisely is being discussed. We define the process of solute self-association (aggregation, oligomerization, interaction, clustering, etc.) whereby n-mers (n > or = 2) having a crystallographic or nascent crystallographic arrangement leading to the critical nucleus reversibly form in the solution, to be part of the nucleation process. This reversible self-association process is a fundamental part of the nucleation process, and occurs as a function of the solute concentration. In the case of chicken egg white lysozyme, a considerable body of experimental evidence leads us to the conclusion that it also forms the crystal growth units. Size exclusion chromatography is a simple and direct method for determining the equilibrium constants for the self-association process. A Pharmacia FPLC system was used to provide accurate solution flow rates. The column, injection valve, and sample loop were all mounted within a temperature-controlled chamber. Chromatographically re-purified lysozyme was first dialyzed against the column equilibration buffer, with injection onto the column after several hours pre-incubation at the running temperature. Preliminary experiments, were carried out using a Toyopearl HW-50F column (1 x 50cm), equilibrated with 0.1 M sodium acetate, 5% sodium chloride, pH 4.6, at 15C. Protein concentrations from 0.1 to 4 mg/ml were employed (C(sub sat) = 1.2 mg/ml). The data from several different protein preparations consistently shows a progressively decreasing elution volume with increasing protein concentration, indicating that reversible self-association is occurring. The dotted line indicates the monomeric lysozyme elution volume. However, lysozyme interacts with the column matrix in these experiments, which complicates data analysis.Accordingly, we are testing silica-based HPLC columns in an effort to eliminate this problem and substantially reduce the column volume and experimental run time. The results and data analysis from these and subsequent experiments will be presented.

Ewing, Felecia↗

Diffusion of Hydrogen in Silica under Transient Conditions

Development of hydrogen in sealed silica glass ampoules during annealing at elevated temperatures was investigated. The dependence of hydrogen pressure in the ampoules as a function of time, for different temperatures and ampoule parameters was measured. The process was modeled assuming chemical solution of hydrogen according to the reaction: silica + H2 = H- Si= + H-O-Si=. The equilibrium constant of the reaction was determined by fitting the theoretical curves to the experimental data. The Gibbs function for this reaction was estimated at deltaG = -25.8 + 54T.

Palosz, W.↗

Basal glycogenolysis in mouse skeletal muscle: in vitro model predicts in vivo fluxes

A previously published mammalian kinetic model of skeletal muscle glycogenolysis, consisting of literature in vitro parameters, was modified by substituting mouse specific Vmax values. The model demonstrates that glycogen breakdown to lactate is under ATPase control. Our criteria to test whether in vitro parameters could reproduce in vivo dynamics was the ability of the model to fit phosphocreatine (PCr) and inorganic phosphate (Pi) dynamic NMR data from ischemic basal mouse hindlimbs and predict biochemically-assayed lactate concentrations. Fitting was accomplished by optimizing four parameters--the ATPase rate coefficient, fraction of activated glycogen phosphorylase, and the equilibrium constants of creatine kinase and adenylate kinase (due to the absence of pH in the model). The optimized parameter values were physiologically reasonable, the resultant model fit the [PCr] and [Pi] timecourses well, and the model predicted the final measured lactate concentration. This result demonstrates that additional features of in vivo enzyme binding are not necessary for quantitative description of glycogenolytic dynamics.

Non-NASA Center↗

Concentration of simple aldehydes by sulfite-containing double-layer hydroxide minerals: implications for biopoesis

Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.

NASA Discipline Exobiology↗

The Combined Strength of Thermodynamics and Comparative Planetology: Application of Activity Models to Core Formation in Terrestrial Bodies

Recent models for accretion of terrestrial bodies involve metal-silicate equilibrium as the metallic core formed during growth. Most elements considered are either refractory or well studied elements for which effects of pressure, temperature, oxygen fugacity, and metallic liquid composition are well known. There are a large number of elements that are both siderophile and volatile, whose fate in such models is unknown, largely due to a lack of data at comparable conditions and com-positions (FeNi core with light elements such as S, C, Si, and O). We have focused on Ge, In, As, Sb and determined the effect of Si and C on metal-silicate partitioning, and developed a thermo-dynamic model that allows application of these new data to a wide range of planetary bodies. New experiments: We have previously carried out experiments with FeSi metallic liquid at C-saturated conditions at 1600 and 1800 C [4]. In a new series of experiments we investigate the effect of Si in carbon-free systems at 1600 C for comparison. Experiments were carried out at 1 GPa in MgO capsules using the same basaltic starting composition as in previous studies. The MgO capsule reacts with the silicate melt to form more MgO-rich liquids that have 22-26 wt% MgO. Experimental met-als and silicates were analyzed using a combination of electron microprobe analysis and laser ablation ICP-MS. Results: The new results can be interpreted by considering Ge as an example, in the simple exchange equilibrium Fe + GeO = FeO + Ge, where the equilibrium constant Kd can be examined as a function of Si content of the metal. The slope of lnKd vs. (1-XSi) for this new series allows derivation of the epsilon interaction parameter for each of these four elements and Si (both C-saturated and C-free).All four elements have positive epsilon values, indicating that Si causes a decrease in the partition coefficients; values are 6.6, 6.5, 27.8 and 25.2 for In, Ge, As, and Sb, respectively, at 1 GPa and 1600 C. As an example of how large the effect of Si can be, these epsilon values correspond to activity coefficients (gamma) for As of 0.01 when XSi = 0, and up to gamma = 23 when XSi = 0.2. Combining these new results with previous determinations [5,6] of epsilon parameters for S and C for these elements allows us calculate activity of Ge, In, As, and Sb in Fe-Ni-Si-S-C-O metallic liquids. We apply this new model to sever-al terrestrial bodies such as Earth (Si-rich core), Mars (S-rich core), Moon (S-, C-, and Si-poor core), and Vesta, and examine the resulting core and mantle concentrations of these elements. Mantle concentrations of these four elements are well explained for Earth and Mars in models that call for mid-mantle equilibration between Si-bearing and S-bearing FeNi cores, respectively. Modeling results for the Moon and Vesta will also be presented.

Righter, K.↗

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

humic acid↗

Grinding kinetics and equilibrium states

The temporary and permanent equilibrium occurring during the initial stage of cement grinding does not indicate the end of comminution, but rather an increased energy consumption during grinding. The constant dynamic equilibrium occurs after a long grinding period indicating the end of comminution for a given particle size. Grinding equilibrium curves can be constructed to show the stages of comminution and agglomeration for certain particle sizes.

Opoczky, L.↗

Stability of the equilibrium for atomic H in solid H2

The previously reported phenomenological rate process theory for the storage of atomic hydrogen free radicals in a tritium-impregnated crystalline molecular hydrogen solid is used to determine the dynamical stability of the constant uniform equilibrium solution. The analysis indicates that the equilibrium is unstable (thus, unattainable experimentally) for storage temperatures in a certain range (specifically between 0.134 and 0.80 K for 0.03% tritium by weight, and between 0.165 and 0.80 K for 1.20% tritium by weight), while being absolutely stable with respect to arbitrary small-amplitude perturbations for all storage temperatures below and above this range. The theory also predicts the maximum size for a stable H/H2 sample with an appreciable concentration of trapped H and a net excess rate of volumetric heating due to the tritium decay.

Rosen, G.↗

Steady evaporation and condensation of isolated clouds in hot plasma

The evaporation and condensation of an isolated cloud embedded in a thermally stable hot gas is studied under the assumption that the ambient hot gas is in thermal equilibrium at constant temperature and that the cloud is large enough that classical conduction is valid. It is found that the cloud will evaporate provided that it is smaller than the Field length, which gives the maximum range of thermal conduction. A large cloud can condense only if the pressure exceeds the saturated vapor pressure p(sat). The pressure required for condensation increases as the cloud radius decreases, until condensation becomes impossible. Since p(sat) is close to the maximum pressure at which the hot gas can exist in equilibrium, condensation is likely to occur under unsteady conditions. The Compton-bremsstrahlung case is treated as an example.

Mckee, Christopher F.↗

Hydrodynamic Models of Line-Driven Accretion Disk Winds III: Local Ionization Equilibrium

We present time-dependent numerical hydrodynamic models of line-driven accretion disk winds in cataclysmic variable systems and calculate wind mass-loss rates and terminal velocities. The models are 2.5-dimensional, include an energy balance condition with radiative heating and cooling processes, and includes local ionization equilibrium introducing time dependence and spatial dependence on the line radiation force parameters. The radiation field is assumed to originate in an optically thick accretion disk. Wind ion populations are calculated under the assumption that local ionization equilibrium is determined by photoionization and radiative recombination, similar to a photoionized nebula. We find a steady wind flowing from the accretion disk. Radiative heating tends to maintain the temperature in the higher density wind regions near the disk surface, rather than cooling adiabatically. For a disk luminosity L (sub disk) = solar luminosity, white dwarf mass M(sub wd) = 0.6 solar mass, and white dwarf radii R(sub wd) = 0.01 solar radius, we obtain a wind mass-loss rate of M(sub wind) = 4 x 10(exp -12) solar mass yr(exp -1) and a terminal velocity of approximately 3000 km per second. These results confirm the general velocity and density structures found in our earlier constant ionization equilibrium adiabatic CV wind models. Further we establish here 2.5D numerical models that can be extended to QSO/AGN winds where the local ionization equilibrium will play a crucial role in the overall dynamics.

Pereyra, Nicolas Antonio↗

The Gaseous Explosive Reaction : The Effect of Inert Gases

Attention is called in this report to previous investigations of gaseous explosive reactions carried out under constant volume conditions, where the effect of inert gases on the thermodynamic equilibrium was determined. The advantage of constant pressure methods over those of constant volume as applied to studies of the gaseous explosive reaction is pointed out and the possibility of realizing for this purpose a constant pressure bomb mentioned. The application of constant pressure methods to the study of gaseous explosive reactions, made possible by the use of a constant pressure bomb, led to the discovery of an important kinetic relation connecting the rate of propagation of the zone of explosive reaction within the active gases, with the initial concentrations of those gases: s = K(sub 1)(A)(sup n1)(B)(sup n2)(C)(sup n3)------. By a method analogous to that followed in determining the effect of inert gases on the equilibrium constant K, the present paper records an attempt to determine their kinetic effect upon the expression given above.

Stevens, F W↗

A system debugging model.

Consideration of the nature of the 'debugging' process applied to a new complex system during the initial period of its life. During this period failures and errors are corrected as they occur, with resulting improvement in the subsequent performance of the system. One mathematical idealization of this process leads to the assumption that system failure rate is decreasing with time. In practice, the debugging phase is considered completed when the failure rate reaches an equilibrium or constant value. Models are formulated for this phenomenon. Maximum likelihood estimates are obtained for relevant failure rate functions and for the end of the debugging period. A conservative upper confidence bound on the stable failure rate is obtained.

Barlow, R. E.↗

The numerical analysis of the rotational theory for the formation of lunar globules

The morphology of lunar globules is studied through the application of a numerical analysis of their rotation in space during cooling. It is assumed that molten rock is shot from the surface of the moon, solidifies in space above the moon and then falls back to the surface. The rotational theory studied makes the following assumptions: the volume of the molten rock does not change during cooling; the angular momentum is conserved; there are no internal motions because of the high viscosity of the molten rock, i.e., in equilibrium the globule is rotating as a rigid body; finally, the kinetic reaction of the globule to the forces is fast relative to the rate of cooling, i.e., the globule reaches equilibrium at constant energy. These assumptions are subjected to numerical analysis yielding good agreement between the actual globule shapes and the numerical results, but leaving some doubt as to the validity of the rotational theory due to the failure to establish the existence of true local minima and an incomplete understanding of the thermokentics.

Ross, J.↗

Effects of diffusion and mass flows on C IV and Si IV lines formed in the solar atmosphere

A model for the transition region is derived from an initial interpretation of EUV observations, assuming ionization equilibrium and constant elemental abundance with height. The effects of diffusion and mass flows are then included in the initial model and the emergent profiles of several C IV and Si IV lines are computed. It is found that diffusion and mass flows have a strong effect on both the emergent intensity and spectral shape of these lines. Diffusion acts to deplete the transition region of heavy ions to an extent which depends on the detailed temperature and density structure. The net effect is a weighting of the coronal emission relative to that in the transition. On the basis of the results, it is suggested that the downflows observed in the network in lines of C IV and Si IV could be due to gravitational settling of the ions following their injection, via diffusion, into the corona from spicules. When flows are superposed on the basic diffusion model, the rapid change in elemental abundance characteristic of the model is virtually eliminated and the coronal contribution to the emission in C IV and Si IV lines becomes negligible relative to that in the transition region. Flows have a strong effect on the computed line intensities and introduce large asymmetries into the line shapes.

Roussel-Dupre, R.↗

Periodic-disturbance accommodating control of the Space Station for asymptotic momentum management

Periodic-disturbance accommodating control is investigated for asymptotic momentum management of control moment gyros used as primary actuating devices for the Space Station. The proposed controller utilizes the concepts of quaternion feedback control and periodic-disturbance accommodation to achieve oscillations about the constant torque equilibrium attitude, while minimizing the control effort required. Three-axis coupled equations of motion, written in terms of quaternions, are derived for roll/yaw controller design and stability analysis. The quaternion feedback controller designed using the linear-quadratic regulator synthesis technique is shown to be robust for a wide range of pitch angles. It is also shown that the proposed controller tunes the open-loop unstable vehicle to a stable oscillatory motion which minimizes the control effort needed for steady-state operations.

Warren, Wayne↗