Do the Particles of an Ideal Gas Collide?

ERIC Educational Resources Information Center

Lesk, Arthur M.

1974-01-01

Describes the collisional properties as a logically essential component of the ideal gas model since an actual intraparticle process cannot support observable anisotropic velocity distributions without collisions taken into account. (CC)

How Is the Ideal Gas Law Explanatory?

ERIC Educational Resources Information Center

Woody, Andrea I.

2013-01-01

Using the ideal gas law as a comparative example, this essay reviews contemporary research in philosophy of science concerning scientific explanation. It outlines the inferential, causal, unification, and erotetic conceptions of explanation and discusses an alternative project, the functional perspective. In each case, the aim is to highlight…

Supersonic beams at high particle densities: model description beyond the ideal gas approximation.

PubMed

Christen, Wolfgang; Rademann, Klaus; Even, Uzi

2010-10-28

Supersonic molecular beams constitute a very powerful technique in modern chemical physics. They offer several unique features such as a directed, collision-free flow of particles, very high luminosity, and an unsurpassed strong adiabatic cooling during the jet expansion. While it is generally recognized that their maximum flow velocity depends on the molecular weight and the temperature of the working fluid in the stagnation reservoir, not a lot is known on the effects of elevated particle densities. Frequently, the characteristics of supersonic beams are treated in diverse approximations of an ideal gas expansion. In these simplified model descriptions, the real gas character of fluid systems is ignored, although particle associations are responsible for fundamental processes such as the formation of clusters, both in the reservoir at increased densities and during the jet expansion. In this contribution, the various assumptions of ideal gas treatments of supersonic beams and their shortcomings are reviewed. It is shown in detail that a straightforward thermodynamic approach considering the initial and final enthalpy is capable of characterizing the terminal mean beam velocity, even at the liquid-vapor phase boundary and the critical point. Fluid properties are obtained using the most accurate equations of state available at present. This procedure provides the opportunity to naturally include the dramatic effects of nonideal gas behavior for a large variety of fluid systems. Besides the prediction of the terminal flow velocity, thermodynamic models of isentropic jet expansions permit an estimate of the upper limit of the beam temperature and the amount of condensation in the beam. These descriptions can even be extended to include spinodal decomposition processes, thus providing a generally applicable tool for investigating the two-phase region of high supersaturations not easily accessible otherwise.

Gas flow headspace liquid phase microextraction.

PubMed

Yang, Cui; Qiu, Jinxue; Ren, Chunyan; Piao, Xiangfan; Li, Xifeng; Wu, Xue; Li, Donghao

2009-11-06

There is a trend towards the use of enrichment techniques such as microextraction in the analysis of trace chemicals. Based on the theory of ideal gases, theory of gas chromatography and the original headspace liquid phase microextraction (HS-LPME) technique, a simple gas flow headspace liquid phase microextraction (GF-HS-LPME) technique has been developed, where the extracting gas phase volume is increased using a gas flow. The system is an open system, where an inert gas containing the target compounds flows continuously through a special gas outlet channel (D=1.8mm), and the target compounds are trapped on a solvent microdrop (2.4 microL) hanging on the microsyringe tip, as a result, a high enrichment factor is obtained. The parameters affecting the enrichment factor, such as the gas flow rate, the position of the microdrop, the diameter of the gas outlet channel, the temperatures of the extracting solvent and of the sample, and the extraction time, were systematically optimized for four types of polycyclic aromatic hydrocarbons. The results were compared with results obtained from HS-LPME. Under the optimized conditions (where the extraction time and the volume of the extracting sample vial were fixed at 20min and 10mL, respectively), detection limits (S/N=3) were approximately a factor of 4 lower than those for the original HS-LPME technique. The method was validated by comparison of the GF-HS-LPME and HS-LPME techniques using data for PAHs from environmental sediment samples.

Condensation and critical exponents of an ideal non-Abelian gas

NASA Astrophysics Data System (ADS)

Talaei, Zahra; Mirza, Behrouz; Mohammadzadeh, Hosein

2017-11-01

We investigate an ideal gas obeying non-Abelian statistics and derive the expressions for some thermodynamic quantities. It is found that thermodynamic quantities are finite at the condensation point where their derivatives diverge and, near this point, they behave as \\vert T-Tc\\vert^{-ρ} in which Tc denotes the condensation temperature and ρ is a critical exponent. The critical exponents related to the heat capacity and compressibility are obtained by fitting numerical results and others are obtained using the scaling law hypothesis for a three-dimensional non-Abelian ideal gas. This set of critical exponents introduces a new universality class.

Determination of some pure compound ideal-gas enthalpies of formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steele, W. V.; Chirico, R. D.; Nguyen, A.

1989-06-01

The results of a study aimed at improvement of group-additivity methodology for estimation of thermodynamic properties of organic substances are reported. Specific weaknesses where ring corrections were unknown or next-nearest-neighbor interactions were only estimated because of lack of experimental data are addressed by experimental studies of enthalpies of combustion in the condensed- phase and vapor pressure measurements. Ideal-gas enthalpies of formation are reported for acrylamide, succinimide, ..gamma..-butyrolactone, 2-pyrrolidone, 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, 1,3-cyclohexadiene, 1,4-cyclohexadiene, and 1-methyl-1-phenylhydrazine. Ring corrections, group terms, and next-nearest-neighbor interaction terms useful in the application of group additivity correlations are derived. 44 refs., 2 figs., 59 tabs.

High School Forum. The Solution: "Derivation of the Ideal Gas Law."

ERIC Educational Resources Information Center

Herron, J. Dudley, Ed.

1980-01-01

Presents responses to an earlier report concerning a procedure for the derivation of the Ideal Gas Law from Charles', Boyle's, and other gas laws. Logic errors and solutions that work are discussed. (CS)

Effect of pairwise additivity on finite-temperature behavior of classical ideal gas

NASA Astrophysics Data System (ADS)

Shekaari, Ashkan; Jafari, Mahmoud

2018-05-01

Finite-temperature molecular dynamics simulations have been applied to inquire into the effect of pairwise additivity on the behavior of classical ideal gas within the temperature range of T = 250-4000 K via applying a variety of pair potentials and then examining the temperature dependence of a number of thermodynamical properties. Examining the compressibility factor reveals the most deviation from ideal-gas behavior for the Lennard-Jones system mainly due to the presence of both the attractive and repulsive terms. The systems with either attractive or repulsive intermolecular potentials are found to present no resemblance to real gases, but the most similarity to the ideal one as temperature rises.

Determination of ideal-gas enthalpies of formation for key compounds:

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steele, W.V.; Chirico, R.D.; Nguyen, A.

1991-10-01

The results of a study aimed at improvement of group-contribution methodology for estimation of thermodynamic properties of organic and organosilicon substances are reported. Specific weaknesses where particular group-contribution terms were unknown, or estimated because of lack of experimental data, are addressed by experimental studies of enthalpies of combustion in the condensed phase, vapor-pressure measurements, and differential scanning calorimetric (d.s.c.) heat-capacity measurements. Ideal-gas enthalpies of formation of ({plus minus})-butan-2-ol, tetradecan-1-ol, hexan-1,6-diol, methacrylamide, benzoyl formic acid, naphthalene-2,6-dicarboxylic acid dimethyl ester, and tetraethylsilane are reported. A crystalline-phase enthalpy of formation at 298.15 K was determined for naphthalene-2,6-dicarboxylic acid, which decomposed at 695 Kmore » before melting. The combustion calorimetry of tetraethylsilane used the proven fluorine-additivity methodology. Critical temperature and critical density were determined for tetraethylsilane with differential scanning calorimeter and the critical pressure was derived. Group-additivity parameters useful in the application of group- contribution correlations are derived. 112 refs., 13 figs., 19 tabs.« less

Modeling 3H-3He Gas-Liquid Phase Transport for Interpretation of Groundwater Age

NASA Astrophysics Data System (ADS)

Carle, S. F.; Esser, B.; Moran, J. E.

2009-12-01

California’s Groundwater Ambient Monitoring and Assessment (GAMA) Program has measured many hundreds of tritium (3H) and helium-3 (3He) concentrations in well water samples to derive estimates of groundwater age at production and monitoring wells in California basins. However, a 3H-3He age differs from an ideal groundwater age tracer in several respects: (1) the radioactive decay of 3H results in the accumulation of 3He being first-order with respect to 3H activity (versus a zero-order age-mass accumulation process for an ideal tracer), (2) surface concentrations of 3H as measured in precipitation over the last several decades have not been uniform, and (3) the 3H-3He “clock” begins at the water table and not at the ground surface where 3H source measurements are made. To better understand how these non-idealities affect interpretation of 3H-3He apparent groundwater age, we are modeling coupled gas-liquid phase flow and 3H-3He transport including processes of radiogenic decay, phase equilibrium, and molecular diffusion for water, air, 3H, and 3He components continuously through the vadose zone and saturated zone. Assessment of coupled liquid-gas phase processes enables consideration of 3H-3He residence time and dispersion within the vadose zone, including partitioning of tritiogenic 3He to the gas phase and subsequent diffusion into the atmosphere. The coupled gas-liquid phase modeling framework provides direct means to compare apparent 3H-3He age to ideal mean or advective groundwater ages for the same groundwater flow conditions. Examples are given for common groundwater flow systems involving areal recharge, discharge to streams or long-screened wells, and aquifer system heterogeneity. The Groundwater Ambient Monitoring and Assessment program is sponsored by the California State Water Resources Control Board and carried out in cooperation with the U.S. Geological Survey. This work was performed under the auspices of the U.S. Department of Energy by

Fluctuation theorem for the effusion of an ideal gas.

PubMed

Cleuren, B; Van den Broeck, C; Kawai, R

2006-08-01

The probability distribution of the entropy production for the effusion of an ideal gas between two compartments is calculated explicitly. The fluctuation theorem is verified. The analytic results are in good agreement with numerical data from hard disk molecular dynamics simulations.

Computer program for calculation of ideal gas thermodynamic data

NASA Technical Reports Server (NTRS)

Gordon, S.; Mc Bride, B. J.

1968-01-01

Computer program calculates ideal gas thermodynamic properties for any species for which molecular constant data is available. Partial functions and derivatives from formulas based on statistical mechanics are provided by the program which is written in FORTRAN 4 and MAP.

Renyi Entropy of the Ideal Gas in Finite Momentum Intervals

NASA Astrophysics Data System (ADS)

Bialas, A.; Czyz, W.

2003-06-01

Coincidence probabilities of multiparticle events, as measured in finite momentum intervals for Bose and Fermi ideal gas, are calculated and compared with the exact expressions given in statistical physics.

Use, misuse and extensions of "ideal gas" models of animal encounter.

PubMed

Hutchinson, John M C; Waser, Peter M

2007-08-01

Biologists have repeatedly rediscovered classical models from physics predicting collision rates in an ideal gas. These models, and their two-dimensional analogues, have been used to predict rates and durations of encounters among animals or social groups that move randomly and independently, given population density, velocity, and distance at which an encounter occurs. They have helped to separate cases of mixed-species association based on behavioural attraction from those that simply reflect high population densities, and to detect cases of attraction or avoidance among conspecifics. They have been used to estimate the impact of population density, speeds of movement and size on rates of encounter between members of the opposite sex, between gametes, between predators and prey, and between observers and the individuals that they are counting. One limitation of published models has been that they predict rates of encounter, but give no means of determining whether observations differ significantly from predictions. Another uncertainty is the robustness of the predictions when animal movements deviate from the model's assumptions in specific, biologically relevant ways. Here, we review applications of the ideal gas model, derive extensions of the model to cover some more realistic movement patterns, correct several errors that have arisen in the literature, and show how to generate confidence limits for expected rates of encounter among independently moving individuals. We illustrate these results using data from mangabey monkeys originally used along with the ideal gas model to argue that groups avoid each other. Although agent-based simulations provide a more flexible alternative approach, the ideal gas model remains both a valuable null model and a useful, less onerous, approximation to biological reality.

A Demonstration of Ideal Gas Principles Using a Football.

ERIC Educational Resources Information Center

Bare, William D.; Andrews, Lester

1999-01-01

Uses a true-to-life story of accusations made against a college football team to illustrate ideal gas laws. Students are asked to decide whether helium-filled footballs would increase punt distances and how to determine whether a football contained air or helium. (WRM)

Shock wave structure in an ideal dissociating gas

NASA Technical Reports Server (NTRS)

Liu, K. H.

1975-01-01

Composition changes within the shock layer due to chemical reactions are considered. The Lighthill ideal dissociating gas model was used in an effort to describe the oxygen type molecule. First, the two limiting cases, when the chemical reaction rates are very slow and very fast in comparison to local convective rates, are investigated. Then, the problem is solved for arbitrary chemical reaction rates.

Robotic kidney transplantation with regional hypothermia: evolution of a novel procedure utilizing the IDEAL guidelines (IDEAL phase 0 and 1).

PubMed

Menon, Mani; Abaza, Ronney; Sood, Akshay; Ahlawat, Rajesh; Ghani, Khurshid R; Jeong, Wooju; Kher, Vijay; Kumar, Ramesh K; Bhandari, Mahendra

2014-05-01

Surgical innovation is essential for progress of surgical science, but its implementation comes with potential harms during the learning phase. The Balliol Collaboration has recommended a set of guidelines (Innovation, Development, Exploration, Assessment, Long-term study [IDEAL]) that permit innovation while minimizing complications. To utilize the IDEAL model of surgical innovation in the development of a novel surgical technique, robotic kidney transplantation (RKT) with regional hypothermia, and describe the process of discovery and development. Phase 0 (simulation) studies included the establishment of techniques for pelvic cooling, graft placement in a robotic prostatectomy model, and simulation of the RKT procedure in a cadaveric model. Phase 1 (innovation) studies began in January 2013 and involved treatment of a highly selective small group of patients (n=7), using the principles utilized in the phase 0 studies, at a tertiary referral center. IDEAL model implementation in the development of RKT with regional hypothermia. For phase 0 studies, the outcomes evaluated included pelvic and body temperature measurements, and technical feasibility assessment. The primary outcome during phase 1 was post-transplant graft function. Other outcomes measured were operative and ischemic times, perioperative complications, and intracorporeal graft surface temperature. Phase 0 (simulation phase): Pelvic cooling to 15-20(o)C was achieved reproducibly. Using the surgical approach developed for robotic radical prostatectomy, vascular and ureterovesical anastomoses could be done without redocking the robot. Phase 1 (innovation phase): All patients underwent live-donor RKT in the lithotomy position. All grafts functioned immediately. Mean console, anastomotic, and warm ischemia times were 154 min, 29 min, and 2 min, respectively. One patient was re-explored on postoperative day 1. Adherence to the IDEAL guidelines put forth by the Balliol Collaboration provided a practical

Hyperpolarized (129) Xe imaging of the rat lung using spiral IDEAL.

PubMed

Doganay, Ozkan; Wade, Trevor; Hegarty, Elaine; McKenzie, Charles; Schulte, Rolf F; Santyr, Giles E

2016-08-01

To implement and optimize a single-shot spiral encoding strategy for rapid 2D IDEAL projection imaging of hyperpolarized (Hp) (129) Xe in the gas phase, and in the pulmonary tissue (PT) and red blood cells (RBCs) compartments of the rat lung, respectively. A theoretical and experimental point spread function analysis was used to optimize the spiral k-space read-out time in a phantom. Hp (129) Xe IDEAL images from five healthy rats were used to: (i) optimize flip angles by a Bloch equation analysis using measured kinetics of gas exchange and (ii) investigate the feasibility of the approach to characterize the exchange of Hp (129) Xe. A read-out time equal to approximately 1.8 × T2* was found to provide the best trade-off between spatial resolution and signal-to-noise ratio (SNR). Spiral IDEAL approaches that use the entire dissolved phase magnetization should give an SNR improvement of a factor of approximately three compared with Cartesian approaches with similar spatial resolution. The IDEAL strategy allowed imaging of gas, PT, and RBC compartments with sufficient SNR and temporal resolution to permit regional gas exchange measurements in healthy rats. Single-shot spiral IDEAL imaging of gas, PT and RBC compartments and gas exchange is feasible in rat lung using Hp (129) Xe. Magn Reson Med 76:566-576, 2016. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

Measurement of optical Feshbach resonances in an ideal gas.

PubMed

Blatt, S; Nicholson, T L; Bloom, B J; Williams, J R; Thomsen, J W; Julienne, P S; Ye, J

2011-08-12

Using a narrow intercombination line in alkaline earth atoms to mitigate large inelastic losses, we explore the optical Feshbach resonance effect in an ultracold gas of bosonic (88)Sr. A systematic measurement of three resonances allows precise determinations of the optical Feshbach resonance strength and scaling law, in agreement with coupled-channel theory. Resonant enhancement of the complex scattering length leads to thermalization mediated by elastic and inelastic collisions in an otherwise ideal gas. Optical Feshbach resonance could be used to control atomic interactions with high spatial and temporal resolution.

The energy density distribution of an ideal gas and Bernoulli’s equations

NASA Astrophysics Data System (ADS)

Santos, Leonardo S. F.

2018-05-01

This work discusses the energy density distribution in an ideal gas and the consequences of Bernoulli’s equation and the corresponding relation for compressible fluids. The aim of this work is to study how Bernoulli’s equation determines the energy flow in a fluid, although Bernoulli’s equation does not describe the energy density itself. The model from molecular dynamic considerations that describes an ideal gas at rest with uniform density is modified to explore the gas in motion with non-uniform density and gravitational effects. The difference between the component of the speed of a particle that is parallel to the gas speed and the gas speed itself is called ‘parallel random speed’. The pressure from the ‘parallel random speed’ is denominated as parallel pressure. The modified model predicts that the energy density is the sum of kinetic and potential gravitational energy densities plus two terms with static and parallel pressures. The application of Bernoulli’s equation and the corresponding relation for compressible fluids in the energy density expression has resulted in two new formulations. For incompressible and compressible gas, the energy density expressions are written as a function of stagnation, static and parallel pressures, without any dependence on kinetic or gravitational potential energy densities. These expressions of the energy density are the main contributions of this work. When the parallel pressure was uniform, the energy density distribution for incompressible approximation and compressible gas did not converge to zero for the limit of null static pressure. This result is rather unusual because the temperature tends to zero for null pressure. When the gas was considered incompressible and the parallel pressure was equal to static pressure, the energy density maintained this unusual behaviour with small pressures. If the parallel pressure was equal to static pressure, the energy density converged to zero for the limit of the

A notable difference between ideal gas and infinite molar volume limit of van der Waals gas

NASA Astrophysics Data System (ADS)

Liu, Q. H.; Shen, Y.; Bai, R. L.; Wang, X.

2010-05-01

The van der Waals equation of state does not sufficiently represent a gas unless a thermodynamic potential with two proper and independent variables is simultaneously determined. The limiting procedures under which the behaviour of the van der Waals gas approaches that of an ideal gas are letting two van der Waals coefficients be zero rather than letting the molar volume become infinitely large; otherwise, the partial derivative of internal energy with respect to pressure at a fixed temperature does not vanish.

Using Rubber-Elastic Material-Ideal Gas Analogies To Teach Introductory Thermodynamics. Part I: Equations of State.

ERIC Educational Resources Information Center

Smith, Brent

2002-01-01

Describes equations of state as a supplement to an introductory thermodynamics undergraduate course. Uses rubber-elastic materials (REM) which have strong analogies to the concept of an ideal gas and explains the molar basis of REM. Provides examples of the analogies between ideal gas and REM and mathematical analogies. (Contains 22 references.)…

Using Rubber-Elastic Material-Ideal Gas Analogies To Teach Introductory Thermodynamics. Part II: The Laws of Thermodynamics.

ERIC Educational Resources Information Center

Smith, Brent

2002-01-01

Describes the laws of thermodynamics as a supplement to an introductory thermodynamics undergraduate course. Uses rubber-elastic materials (REM) which have strong analogies to the concept of ideal gas. Provides examples of the analogies between ideal gas and REM and mathematical analogies. (YDS)

Numerical Analysis of an Impinging Jet Reactor for the CVD and Gas-Phase Nucleation of Titania

NASA Technical Reports Server (NTRS)

Gokoglu, Suleyman A.; Stewart, Gregory D.; Collins, Joshua; Rosner, Daniel E.

1994-01-01

We model a cold-wall atmospheric pressure impinging jet reactor to study the CVD and gas-phase nucleation of TiO2 from a titanium tetra-iso-propoxide (TTIP)/oxygen dilute source gas mixture in nitrogen. The mathematical model uses the computational code FIDAP and complements our recent asymptotic theory for high activation energy gas-phase reactions in thin chemically reacting sublayers. The numerical predictions highlight deviations from ideality in various regions inside the experimental reactor. Model predictions of deposition rates and the onset of gas-phase nucleation compare favorably with experiments. Although variable property effects on deposition rates are not significant (approximately 11 percent at 1000 K), the reduction rates due to Soret transport is substantial (approximately 75 percent at 1000 K).

Experimental Verification of Boyle's Law and the Ideal Gas Law

ERIC Educational Resources Information Center

Ivanov, Dragia Trifonov

2007-01-01

Two new experiments are offered concerning the experimental verification of Boyle's law and the ideal gas law. To carry out the experiments, glass tubes, water, a syringe and a metal manometer are used. The pressure of the saturated water vapour is taken into consideration. For educational purposes, the experiments are characterized by their…

Computations of ideal and real gas high altitude plume flows

NASA Technical Reports Server (NTRS)

Feiereisen, William J.; Venkatapathy, Ethiraj

1988-01-01

In the present work, complete flow fields around generic space vehicles in supersonic and hypersonic flight regimes are studied numerically. Numerical simulation is performed with a flux-split, time asymptotic viscous flow solver that incorporates a generalized equilibrium chemistry model. Solutions to generic problems at various altitude and flight conditions show the complexity of the flow, the equilibrium chemical dissociation and its effect on the overall flow field. Viscous ideal gas solutions are compared against equilibrium gas solutions to illustrate the effect of equilibrium chemistry. Improved solution accuracy is achieved through adaptive grid refinement.

Oscillatory conductive heat transfer for a fiber in an ideal gas

NASA Technical Reports Server (NTRS)

Kuntz, H. L.; Perreira, N. D.

1985-01-01

A description of the thermal effects created by placing a cylindrical fiber in an inviscid, ideal gas, through which an acoustic wave propagates, is presented. The fibers and the gas have finite heat capacities and thermal conductivities. Expressions for the temperature distribution in the gas and in the material are determined. The temperature distribution is caused by pressure oscillations in the gas which, in turn, are caused by the passage of an acoustic wave. The relative value of a dimensionless parameter is found to be indicative of whether the exact or approximate equations should be used in the solution. This parameter is a function of the thermal conductivities and heat capacities of the fiber and gas, the acoustic frequency, and the fiber diameter.

Microeconomics of the ideal gas like market models

NASA Astrophysics Data System (ADS)

Chakrabarti, Anindya S.; Chakrabarti, Bikas K.

2009-10-01

We develop a framework based on microeconomic theory from which the ideal gas like market models can be addressed. A kinetic exchange model based on that framework is proposed and its distributional features have been studied by considering its moments. Next, we derive the moments of the CC model (Eur. Phys. J. B 17 (2000) 167) as well. Some precise solutions are obtained which conform with the solutions obtained earlier. Finally, an output market is introduced with global price determination in the model with some necessary modifications.

Fluctuations in non-ideal pion gas with dynamically fixed particle number

NASA Astrophysics Data System (ADS)

Kolomeitsev, E. E.; Voskresensky, D. N.

2018-05-01

We consider a non-ideal hot pion gas with the dynamically fixed number of particles in the model with the λϕ4 interaction. The effective Lagrangian for the description of such a system is obtained after dropping the terms responsible for the change of the total particle number. Reactions π+π- ↔π0π0, which determine the isospin balance of the medium, are permitted. Within the self-consistent Hartree approximation we compute the effective pion mass, thermodynamic characteristics of the system and the variance of the particle number at temperatures above the critical point of the induced Bose-Einstein condensation when the pion chemical potential reaches the value of the effective pion mass. We analyze conditions for the condensate formation in the process of thermalization of an initially non-equilibrium pion gas. The normalized variance of the particle number increases with a temperature decrease but remains finite in the critical point of the Bose-Einstein condensation. This is due to the non-perturbative account of the interaction and is in contrast to the ideal-gas case. In the kinetic regime of the condensate formation the variance is shown to stay finite also.

Development of Modified Incompressible Ideal Gas Model for Natural Draft Cooling Tower Flow Simulation

NASA Astrophysics Data System (ADS)

Hyhlík, Tomáš

2018-06-01

The article deals with the development of incompressible ideal gas like model, which can be used as a part of mathematical model describing natural draft wet-cooling tower flow, heat and mass transfer. It is shown, based on the results of a complex mathematical model of natural draft wet-cooling tower flow, that behaviour of pressure, temperature and density is very similar to the case of hydrostatics of moist air, where heat and mass transfer in the fill zone must be taken into account. The behaviour inside the cooling tower is documented using density, pressure and temperature distributions. The proposed equation for the density is based on the same idea like the incompressible ideal gas model, which is only dependent on temperature, specific humidity and in this case on elevation. It is shown that normalized density difference of the density based on proposed model and density based on the nonsimplified model is in the order of 10-4. The classical incompressible ideal gas model, Boussinesq model and generalised Boussinesq model are also tested. These models show deviation in percentages.

From Free Expansion to Abrupt Compression of an Ideal Gas

ERIC Educational Resources Information Center

Anacleto, Joaquim; Pereira, Mario G.

2009-01-01

Using macroscopic thermodynamics, the general law for adiabatic processes carried out by an ideal gas was studied. It was shown that the process reversibility is characterized by the adiabatic reversibility coefficient r, in the range 0 [less than or equal] r [less than or equal] 1 for expansions and r [greater than or equal] 1 for compressions.…

Bose-Einstein condensation in the relativistic ideal Bose gas.

PubMed

Grether, M; de Llano, M; Baker, George A

2007-11-16

The Bose-Einstein condensation (BEC) critical temperature in a relativistic ideal Bose gas of identical bosons, with and without the antibosons expected to be pair-produced abundantly at sufficiently hot temperatures, is exactly calculated for all boson number densities, all boson point rest masses, and all temperatures. The Helmholtz free energy at the critical BEC temperature is lower with antibosons, thus implying that omitting antibosons always leads to the computation of a metastable state.

Computation of Phase Equilibria, State Diagrams and Gas/Particle Partitioning of Mixed Organic-Inorganic Aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.

2009-04-01

The chemical composition of organic-inorganic aerosols is linked to several processes and specific topics in the field of atmospheric aerosol science. Photochemical oxidation of organics in the gas phase lowers the volatility of semi-volatile compounds and contributes to the particulate matter by gas/particle partitioning. Heterogeneous chemistry and changes in the ambient relative humidity influence the aerosol composition as well. Molecular interactions between condensed phase species show typically non-ideal thermodynamic behavior. Liquid-liquid phase separations into a mainly polar, aqueous and a less polar, organic phase may considerably influence the gas/particle partitioning of semi-volatile organics and inorganics (Erdakos and Pankow, 2004; Chang and Pankow, 2006). Moreover, the phases present in the aerosol particles feed back on the heterogeneous, multi-phase chemistry, influence the scattering and absorption of radiation and affect the CCN ability of the particles. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy, enabling the calculation of activity coefficients. We use the group-contribution model AIOMFAC (Zuend et al., 2008) to calculate activity coefficients, chemical potentials and the total Gibbs energy of mixed organic-inorganic systems. This thermodynamic model was combined with a robust global optimization module to compute potential liquid-liquid (LLE) and vapor-liquid-liquid equilibria (VLLE) as a function of particle composition at room temperature. And related to that, the gas/particle partitioning of semi-volatile components. Furthermore, we compute the thermodynamic stability (spinodal limits) of single-phase solutions, which provides information on the process type and kinetics of a phase separation. References Chang, E. I. and Pankow, J. F.: Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part

Boltzmann equations for a binary one-dimensional ideal gas.

PubMed

Boozer, A D

2011-09-01

We consider a time-reversal invariant dynamical model of a binary ideal gas of N molecules in one spatial dimension. By making time-asymmetric assumptions about the behavior of the gas, we derive Boltzmann and anti-Boltzmann equations that describe the evolution of the single-molecule velocity distribution functions for an ensemble of such systems. We show that for a special class of initial states of the ensemble one can obtain an exact expression for the N-molecule velocity distribution function, and we use this expression to rigorously prove that the time-asymmetric assumptions needed to derive the Boltzmann and anti-Boltzmann equations hold in the limit of large N. Our results clarify some subtle issues regarding the origin of the time asymmetry of Boltzmann's H theorem.

How Incorrect Is the Classical Partition Function for the Ideal Gas?

ERIC Educational Resources Information Center

Kroemer, Herbert

1980-01-01

Discussed is the classical partition function for the ideal gas and how it differs from the exact value for bosons or fermions in the classical regime. The differences in the two values are negligible hence the classical treatment leads in the end to correct answers for all observables. (Author/DS)

Fluctuation theorem for entropy production during effusion of a relativistic ideal gas.

PubMed

Cleuren, B; Willaert, K; Engel, A; Van den Broeck, C

2008-02-01

The probability distribution of the entropy production for the effusion of a relativistic ideal gas is calculated explicitly. This result is then extended to include particle and antiparticle pair production and annihilation. In both cases, the fluctuation theorem is verified.

Cooking under Pressure: Applying the Ideal Gas Law in the Kitchen

ERIC Educational Resources Information Center

Chen, Ling; Anderson, Jennifer Y.; Wang, Diane R.

2010-01-01

This case study uses a daily cooking scenario to demonstrate how the boiling point of water is directly related to the external pressures in order to reinforce the concepts of boiling and boiling point, apply ideal gas law, and relate chemical reaction rates with temperatures. It also extends its teaching to autoclaves used to destroy…

Critical behavior of the ideal-gas Bose-Einstein condensation in the Apollonian network.

PubMed

de Oliveira, I N; dos Santos, T B; de Moura, F A B F; Lyra, M L; Serva, M

2013-08-01

We show that the ideal Boson gas displays a finite-temperature Bose-Einstein condensation transition in the complex Apollonian network exhibiting scale-free, small-world, and hierarchical properties. The single-particle tight-binding Hamiltonian with properly rescaled hopping amplitudes has a fractal-like energy spectrum. The energy spectrum is analytically demonstrated to be generated by a nonlinear mapping transformation. A finite-size scaling analysis over several orders of magnitudes of network sizes is shown to provide precise estimates for the exponents characterizing the condensed fraction, correlation size, and specific heat. The critical exponents, as well as the power-law behavior of the density of states at the bottom of the band, are similar to those of the ideal Boson gas in lattices with spectral dimension d(s)=2ln(3)/ln(9/5)~/=3.74.

Gas Phase Nanoparticle Synthesis

NASA Astrophysics Data System (ADS)

Granqvist, Claes; Kish, Laszlo; Marlow, William

This book deals with gas-phase nanoparticle synthesis and is intended for researchers and research students in nanomaterials science and engineering, condensed matter physics and chemistry, and aerosol science. Gas-phase nanoparticle synthesis is instrumental to nanotechnology - a field in current focus that raises hopes for environmentally benign, resource-lean manufacturing. Nanoparticles can be produced by many physical, chemical, and even biological routes. Gas-phase synthesis is particularly interesting since one can achieve accurate manufacturing control and hence industrial viability.

Quantized vortices in the ideal bose gas: a physical realization of random polynomials.

PubMed

Castin, Yvan; Hadzibabic, Zoran; Stock, Sabine; Dalibard, Jean; Stringari, Sandro

2006-02-03

We propose a physical system allowing one to experimentally observe the distribution of the complex zeros of a random polynomial. We consider a degenerate, rotating, quasi-ideal atomic Bose gas prepared in the lowest Landau level. Thermal fluctuations provide the randomness of the bosonic field and of the locations of the vortex cores. These vortices can be mapped to zeros of random polynomials, and observed in the density profile of the gas.

A Systematic Experimental Test of the Ideal Gas Equation for the General Chemistry Laboratory

NASA Astrophysics Data System (ADS)

Blanco, Luis H.; Romero, Carmen M.

1995-10-01

A set of experiments that examines each one of the terms of the ideal gas equation is described. Boyle's Law, Charles-Gay Lussac's Law, Amonton's Law, the number of moles or Molecular Weight, and the Gas Constant are studied. The experiments use very simple, easy to obtain equipment and common gases, mainly air. The results gathered by General Chemistry College students are satisfactory.

Molecular simulation of excess isotherm and excess enthalpy change in gas-phase adsorption.

PubMed

Do, D D; Do, H D; Nicholson, D

2009-01-29

We present a new approach to calculating excess isotherm and differential enthalpy of adsorption on surfaces or in confined spaces by the Monte Carlo molecular simulation method. The approach is very general and, most importantly, is unambiguous in its application to any configuration of solid structure (crystalline, graphite layer or disordered porous glass), to any type of fluid (simple or complex molecule), and to any operating conditions (subcritical or supercritical). The behavior of the adsorbed phase is studied using the partial molar energy of the simulation box. However, to characterize adsorption for comparison with experimental data, the isotherm is best described by the excess amount, and the enthalpy of adsorption is defined as the change in the total enthalpy of the simulation box with the change in the excess amount, keeping the total number (gas + adsorbed phases) constant. The excess quantities (capacity and energy) require a choice of a reference gaseous phase, which is defined as the adsorptive gas phase occupying the accessible volume and having a density equal to the bulk gas density. The accessible volume is defined as the mean volume space accessible to the center of mass of the adsorbate under consideration. With this choice, the excess isotherm passes through a maximum but always remains positive. This is in stark contrast to the literature where helium void volume is used (which is always greater than the accessible volume) and the resulting excess can be negative. Our definition of enthalpy change is equivalent to the difference between the partial molar enthalpy of the gas phase and the partial molar enthalpy of the adsorbed phase. There is no need to assume ideal gas or negligible molar volume of the adsorbed phase as is traditionally done in the literature. We illustrate this new approach with adsorption of argon, nitrogen, and carbon dioxide under subcritical and supercritical conditions.

Association between different phases of menstrual cycle and body image measures of perceived size, ideal size, and body dissatisfaction.

PubMed

Teixeira, André Luiz S; Dias, Marcelo Ricardo C; Damasceno, Vinícius O; Lamounier, Joel A; Gardner, Rick M

2013-12-01

The association between phases of the menstrual cycle and body image was investigated. 44 university women (M age = 23.3 yr., SD = 4.7) judged their perceived and ideal body size, and body dissatisfaction was calculated at each phase of the menstrual cycle, including premenstrual, menstrual, and intermenstrual. Participants selected one of nine figural drawings ranging from very thin to obese that represented their perceived size and ideal size. Body dissatisfaction was measured as the absolute difference between scores on perceived and ideal figural drawings. During each menstrual phase, anthropometric measures of weight, height, body mass index, circumference of waist and abdomen, and body composition were taken. There were no significant differences in any anthropometric measures between the three menstrual cycle phases. Perceived body size and body dissatisfaction were significantly different between menstrual phases, with the largest perceived body size and highest body dissatisfaction occurring during the menstrual phase. Ideal body size did not differ between menstrual phases, although participants desired a significantly smaller ideal size as compared to the perceived size.

Analytical theory of mesoscopic Bose-Einstein condensation in an ideal gas

NASA Astrophysics Data System (ADS)

Kocharovsky, Vitaly V.; Kocharovsky, Vladimir V.

2010-03-01

We find the universal structure and scaling of the Bose-Einstein condensation (BEC) statistics and thermodynamics (Gibbs free energy, average energy, heat capacity) for a mesoscopic canonical-ensemble ideal gas in a trap with an arbitrary number of atoms, any volume, and any temperature, including the whole critical region. We identify a universal constraint-cutoff mechanism that makes BEC fluctuations strongly non-Gaussian and is responsible for all unusual critical phenomena of the BEC phase transition in the ideal gas. The main result is an analytical solution to the problem of critical phenomena. It is derived by, first, calculating analytically the universal probability distribution of the noncondensate occupation, or a Landau function, and then using it for the analytical calculation of the universal functions for the particular physical quantities via the exact formulas which express the constraint-cutoff mechanism. We find asymptotics of that analytical solution as well as its simple analytical approximations which describe the universal structure of the critical region in terms of the parabolic cylinder or confluent hypergeometric functions. The obtained results for the order parameter, all higher-order moments of BEC fluctuations, and thermodynamic quantities perfectly match the known asymptotics outside the critical region for both low and high temperature limits. We suggest two- and three-level trap models of BEC and find their exact solutions in terms of the cutoff negative binomial distribution (which tends to the cutoff gamma distribution in the continuous limit) and the confluent hypergeometric distribution, respectively. Also, we present an exactly solvable cutoff Gaussian model of BEC in a degenerate interacting gas. All these exact solutions confirm the universality and constraint-cutoff origin of the strongly non-Gaussian BEC statistics. We introduce a regular refinement scheme for the condensate statistics approximations on the basis of the

Convection in an ideal gas at high Rayleigh numbers.

PubMed

Tilgner, A

2011-08-01

Numerical simulations of convection in a layer filled with ideal gas are presented. The control parameters are chosen such that there is a significant variation of density of the gas in going from the bottom to the top of the layer. The relations between the Rayleigh, Peclet, and Nusselt numbers depend on the density stratification. It is proposed to use a data reduction which accounts for the variable density by introducing into the scaling laws an effective density. The relevant density is the geometric mean of the maximum and minimum densities in the layer. A good fit to the data is then obtained with power laws with the same exponent as for fluids in the Boussinesq limit. Two relations connect the top and bottom boundary layers: The kinetic energy densities computed from free fall velocities are equal at the top and bottom, and the products of free fall velocities and maximum horizontal velocities are equal for both boundaries.

Simulation of ideal-gas flow by nitrogen and other selected gases at cryogenic temperatures. [transonic flow in cryogenic wind tunnels

NASA Technical Reports Server (NTRS)

Hall, R. M.; Adcock, J. B.

1981-01-01

The real gas behavior of nitrogen, the gas normally used in transonic cryogenic tunnels, is reported for the following flow processes: isentropic expansion, normal shocks, boundary layers, and interactions between shock waves and boundary layers. The only difference in predicted pressure ratio between nitrogen and an ideal gas which may limit the minimum operating temperature of transonic cryogenic wind tunnels occur at total pressures approaching 9 atm and total temperatures 10 K below the corresponding saturation temperature. These pressure differences approach 1 percent for both isentropic expansions and normal shocks. Alternative cryogenic test gases were also analyzed. Differences between air and an ideal diatomic gas are similar in magnitude to those for nitrogen and should present no difficulty. However, differences for helium and hydrogen are over an order of magnitude greater than those for nitrogen or air. It is concluded that helium and cryogenic hydrogen would not approximate the compressible flow of an ideal diatomic gas.

Comparison of electrical and optical characteristics in gas-phase and gas-liquid phase discharges

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qazi, H. I. A.; Li, He-Ping, E-mail: liheping@tsinghua.edu.cn; Zhang, Xiao-Fei

This paper presents an AC-excited argon discharge generated using a gas-liquid (two-phase) hybrid plasma reactor, which mainly consists of a powered needle electrode enclosed in a conical quartz tube and grounded deionized water electrode. The discharges in the gas-phase, as well as in the two-phase, exhibit two discharge modes, i.e., the low current glow-like diffuse mode and the high current streamer-like constrict mode, with a mode transition, which exhibits a negative resistance of the discharges. The optical emission spectral analysis shows that the stronger diffusion of the water vapor into the discharge region in the two-phase discharges boosts up themore » generation of OH (A–X) radicals, and consequently, leads to a higher rotational temperature in the water-phase plasma plume than that of the gas-phase discharges. Both the increase of the power input and the decrease of the argon flow rate result in the increase of the rotational temperature in the plasma plume of the water-phase discharge. The stable two-phase discharges with a long plasma plume in the water-phase under a low power input and gas flow rate may show a promising prospect for the degradation of organic pollutants, e.g., printing and dyeing wastewater, in the field of environmental protection.« less

How is the Ideal Gas Law Explanatory?

NASA Astrophysics Data System (ADS)

Woody, Andrea I.

2013-07-01

Using the ideal gas law as a comparative example, this essay reviews contemporary research in philosophy of science concerning scientific explanation. It outlines the inferential, causal, unification, and erotetic conceptions of explanation and discusses an alternative project, the functional perspective. In each case, the aim is to highlight insights from these investigations that are salient for pedagogical concerns. Perhaps most importantly, this essay argues that science teachers should be mindful of the normative and prescriptive components of explanatory discourse both in the classroom and in science more generally. Giving attention to this dimension of explanation not only will do justice to the nature of explanatory activity in science but also will support the development of robust reasoning skills in science students while helping them understand an important respect in which science is more than a straightforward collection of empirical facts, and consequently, science education involves more than simply learning them.

Cellular Analysis of Boltzmann Most Probable Ideal Gas Statistics

NASA Astrophysics Data System (ADS)

Cahill, Michael E.

2018-04-01

Exact treatment of Boltzmann's Most Probable Statistics for an Ideal Gas of Identical Mass Particles having Translational Kinetic Energy gives a Distribution Law for Velocity Phase Space Cell j which relates the Particle Energy and the Particle Population according toB e(j) = A - Ψ(n(j) + 1)where A & B are the Lagrange Multipliers and Ψ is the Digamma Function defined byΨ(x + 1) = d/dx ln(x!)A useful sufficiently accurate approximation for Ψ is given byΨ(x +1) ≈ ln(e-γ + x)where γ is the Euler constant (≈.5772156649) & so the above distribution equation is approximatelyB e(j) = A - ln(e-γ + n(j))which can be inverted to solve for n(j) givingn(j) = (eB (eH - e(j)) - 1) e-γwhere B eH = A + γ& where B eH is a unitless particle energy which replaces the parameter A. The 2 approximate distribution equations imply that eH is the highest particle energy and the highest particle population isnH = (eB eH - 1) e-γwhich is due to the facts that population becomes negative if e(j) > eH and kinetic energy becomes negative if n(j) > nH.An explicit construction of Cells in Velocity Space which are equal in volume and homogeneous for almost all cells is shown to be useful in the analysis.Plots for sample distribution properties using e(j) as the independent variable are presented.

Steady Secondary Flows Generated by Periodic Compression and Expansion of an Ideal Gas in a Pulse Tube

NASA Technical Reports Server (NTRS)

Lee, Jeffrey M.

1999-01-01

This study establishes a consistent set of differential equations for use in describing the steady secondary flows generated by periodic compression and expansion of an ideal gas in pulse tubes. Also considered is heat transfer between the gas and the tube wall of finite thickness. A small-amplitude series expansion solution in the inverse Strouhal number is proposed for the two-dimensional axisymmetric mass, momentum and energy equations. The anelastic approach applies when shock and acoustic energies are small compared with the energy needed to compress and expand the gas. An analytic solution to the ordered series is obtained in the strong temperature limit where the zeroth-order temperature is constant. The solution shows steady velocities increase linearly for small Valensi number and can be of order I for large Valensi number. A conversion of steady work flow to heat flow occurs whenever temperature, velocity or phase angle gradients are present. Steady enthalpy flow is reduced by heat transfer and is scaled by the Prandtl times Valensi numbers. Particle velocities from a smoke-wire experiment were compared with predictions for the basic and orifice pulse tube configurations. The theory accurately predicted the observed steady streaming.

Theoretical test of Jarzynski's equality for reversible volume-switching processes of an ideal gas system.

PubMed

Sung, Jaeyoung

2007-07-01

We present an exact theoretical test of Jarzynski's equality (JE) for reversible volume-switching processes of an ideal gas system. The exact analysis shows that the prediction of JE for the free energy difference is the same as the work done on the gas system during the reversible process that is dependent on the shape of path of the reversible volume-switching process.

Off-diagonal long-range order, cycle probabilities, and condensate fraction in the ideal Bose gas.

PubMed

Chevallier, Maguelonne; Krauth, Werner

2007-11-01

We discuss the relationship between the cycle probabilities in the path-integral representation of the ideal Bose gas, off-diagonal long-range order, and Bose-Einstein condensation. Starting from the Landsberg recursion relation for the canonic partition function, we use elementary considerations to show that in a box of size L3 the sum of the cycle probabilities of length k>L2 equals the off-diagonal long-range order parameter in the thermodynamic limit. For arbitrary systems of ideal bosons, the integer derivative of the cycle probabilities is related to the probability of condensing k bosons. We use this relation to derive the precise form of the pik in the thermodynamic limit. We also determine the function pik for arbitrary systems. Furthermore, we use the cycle probabilities to compute the probability distribution of the maximum-length cycles both at T=0, where the ideal Bose gas reduces to the study of random permutations, and at finite temperature. We close with comments on the cycle probabilities in interacting Bose gases.

An Introduction to the Gas Phase

NASA Astrophysics Data System (ADS)

Vallance, Claire

2017-11-01

'An Introduction to the Gas Phase' is adapted from a set of lecture notes for a core first year lecture course in physical chemistry taught at the University of Oxford. The book is intended to give a relatively concise introduction to the gas phase at a level suitable for any undergraduate scientist. After defining the gas phase, properties of gases such as temperature, pressure, and volume are discussed. The relationships between these properties are explained at a molecular level, and simple models are introduced that allow the various gas laws to be derived from first principles. Finally, the collisional behaviour of gases is used to explain a number of gas-phase phenomena, such as effusion, diffusion, and thermal conductivity.

Conical flow near singular rays. [shock generation in ideal gas

NASA Technical Reports Server (NTRS)

Zahalak, G. I.; Myers, M. K.

1974-01-01

The steady flow of an ideal gas past a conical body is investigated by the method of matched asymptotic expansions, with particular emphasis on the flow near the singular ray occurring in linearized theory. The first-order problem governing the flow in this region is formulated, leading to the equation of Kuo, and an approximate solution is obtained in the case of compressive flow behind the main front. This solution is compared with the results of previous investigations with a view to assessing the applicability of the Lighthill-Whitham theories.

Thermodynamics of an ideal generalized gas: II. Means of order alpha.

PubMed

Lavenda, B H

2005-11-01

The property that power means are monotonically increasing functions of their order is shown to be the basis of the second laws not only for processes involving heat conduction, but also for processes involving deformations. This generalizes earlier work involving only pure heat conduction and underlines the incomparability of the internal energy and adiabatic potentials when expressed as powers of the adiabatic variable. In an L-potential equilibration, the final state will be one of maximum entropy, whereas in an entropy equilibration, the final state will be one of minimum L. Unlike classical equilibrium thermodynamic phase space, which lacks an intrinsic metric structure insofar as distances and other geometrical concepts do not have an intrinsic thermodynamic significance in such spaces, a metric space can be constructed for the power means: the distance between means of different order is related to the Carnot efficiency. In the ideal classical gas limit, the average change in the entropy is shown to be proportional to the difference between the Shannon and Rényi entropies for nonextensive systems that are multifractal in nature. The L potential, like the internal energy, is a Schur convex function of the empirical temperature, which satisfies Jensen's inequality, and serves as a measure of the tendency to uniformity in processes involving pure thermal conduction.

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-05-01

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of the phase diagram. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation

Development and evaluation of the aerosol dynamic and gas phase chemistry model ADCHEM

NASA Astrophysics Data System (ADS)

Roldin, P.; Swietlicki, E.; Schurgers, G.; Arneth, A.; Lehtinen, K. E. J.; Boy, M.; Kulmala, M.

2010-08-01

The aim of this work was to develop a model ideally suited for detailed studies on aerosol dynamics, gas and particle phase chemistry within urban plumes, from local scale (1×1 km2) to regional or global scale. This article describes and evaluates the trajectory model for Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer (ADCHEM), which has been developed and used at Lund University since 2007. The model treats both vertical and horizontal dispersion perpendicular to an air mass trajectory (2-space dimensions), which is not treated in Lagrangian box-models (0-space dimensions). The Lagrangian approach enables a more detailed representation of the aerosol dynamics, gas and particle phase chemistry and a finer spatial and temporal resolution compared to that of available regional 3D-CTMs. These features make it among others ideally suited for urban plume studies. The aerosol dynamics model includes Brownian coagulation, dry deposition, wet deposition, in-cloud processing, condensation, evaporation, primary particle emissions and homogeneous nucleation. The gas phase chemistry model calculates the gas phase concentrations of 63 different species, using 119 different chemical reactions. Daily isoprene and monoterpene emissions from European forests were simulated separately with the vegetation model LPJ-GUESS, and included as input to ADCHEM. ADCHEM was used to simulate the ageing of the urban plumes from the city of Malmö in Southern Sweden (280 000 inhabitants). Several sensitivity tests were performed concerning the number of size bins, size structure method, coupled or uncoupled condensation, the volatility basis set (VBS) or traditional 2-product model for secondary organic aerosol formation, different aerosol dynamic processes and vertical and horizontal mixing. The simulations show that the full-stationary size structure gives accurate results with little numerical diffusion when more than 50 size bins are used between 1.5 and 2500 nm

Validation of the Jarzynski relation for a system with strong thermal coupling: an isothermal ideal gas model.

PubMed

Baule, A; Evans, R M L; Olmsted, P D

2006-12-01

We revisit the paradigm of an ideal gas under isothermal conditions. A moving piston performs work on an ideal gas in a container that is strongly coupled to a heat reservoir. The thermal coupling is modeled by stochastic scattering at the boundaries. In contrast to recent studies of an adiabatic ideal gas with a piston [R.C. Lua and A.Y. Grosberg, J. Phys. Chem. B 109, 6805 (2005); I. Bena, Europhys. Lett. 71, 879 (2005)], the container and piston stay in contact with the heat bath during the work process. Under this condition the heat reservoir as well as the system depend on the work parameter lambda and microscopic reversibility is broken for a moving piston. Our model is thus not included in the class of systems for which the nonequilibrium work theorem has been derived rigorously either by Hamiltonian [C. Jarzynski, J. Stat. Mech. (2004) P09005] or stochastic methods [G.E. Crooks, J. Stat. Phys. 90, 1481 (1998)]. Nevertheless the validity of the nonequilibrium work theorem is confirmed both numerically for a wide range of parameter values and analytically in the limit of a very fast moving piston, i.e., in the far nonequilibrium regime.

Stepwise Bose-Einstein Condensation in a Spinor Gas.

PubMed

Frapolli, C; Zibold, T; Invernizzi, A; Jiménez-García, K; Dalibard, J; Gerbier, F

2017-08-04

We observe multistep condensation of sodium atoms with spin F=1, where the different Zeeman components m_{F}=0,±1 condense sequentially as the temperature decreases. The precise sequence changes drastically depending on the magnetization m_{z} and on the quadratic Zeeman energy q (QZE) in an applied magnetic field. For large QZE, the overall structure of the phase diagram is the same as for an ideal spin-1 gas, although the precise locations of the phase boundaries are significantly shifted by interactions. For small QZE, antiferromagnetic interactions qualitatively change the phase diagram with respect to the ideal case, leading, for instance, to condensation in m_{F}=±1, a phenomenon that cannot occur for an ideal gas with q>0.

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-08-01

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system

Gas-Kinetic Theory Based Flux Splitting Method for Ideal Magnetohydrodynamics

NASA Technical Reports Server (NTRS)

Xu, Kun

1998-01-01

A gas-kinetic solver is developed for the ideal magnetohydrodynamics (MHD) equations. The new scheme is based on the direct splitting of the flux function of the MHD equations with the inclusion of "particle" collisions in the transport process. Consequently, the artificial dissipation in the new scheme is much reduced in comparison with the MHD Flux Vector Splitting Scheme. At the same time, the new scheme is compared with the well-developed Roe-type MHD solver. It is concluded that the kinetic MHD scheme is more robust and efficient than the Roe- type method, and the accuracy is competitive. In this paper the general principle of splitting the macroscopic flux function based on the gas-kinetic theory is presented. The flux construction strategy may shed some light on the possible modification of AUSM- and CUSP-type schemes for the compressible Euler equations, as well as to the development of new schemes for a non-strictly hyperbolic system.

Magnetogasdynamic spherical shock wave in a non-ideal gas under gravitational field with conductive and radiative heat fluxes

NASA Astrophysics Data System (ADS)

Nath, G.; Vishwakarma, J. P.

2016-11-01

Similarity solutions are obtained for the flow behind a spherical shock wave in a non-ideal gas under gravitational field with conductive and radiative heat fluxes, in the presence of a spatially decreasing azimuthal magnetic field. The shock wave is driven by a piston moving with time according to power law. The radiation is considered to be of the diffusion type for an optically thick grey gas model and the heat conduction is expressed in terms of Fourier's law for heat conduction. Similarity solutions exist only when the surrounding medium is of constant density. The gas is assumed to have infinite electrical conductivity and to obey a simplified van der Waals equation of state. It is shown that an increase of the gravitational parameter or the Alfven-Mach number or the parameter of the non-idealness of the gas decreases the compressibility of the gas in the flow-field behind the shock, and hence there is a decrease in the shock strength. The pressure and density vanish at the inner surface (piston) and hence a vacuum is formed at the center of symmetry. The shock waves in conducting non-ideal gas under gravitational field with conductive and radiative heat fluxes can be important for description of shocks in supernova explosions, in the study of a flare produced shock in the solar wind, central part of star burst galaxies, nuclear explosion etc. The solutions obtained can be used to interpret measurements carried out by space craft in the solar wind and in neighborhood of the Earth's magnetosphere.

Ballistic and diffusive dynamics in a two-dimensional ideal gas of macroscopic chaotic Faraday waves.

PubMed

Welch, Kyle J; Hastings-Hauss, Isaac; Parthasarathy, Raghuveer; Corwin, Eric I

2014-04-01

We have constructed a macroscopic driven system of chaotic Faraday waves whose statistical mechanics, we find, are surprisingly simple, mimicking those of a thermal gas. We use real-time tracking of a single floating probe, energy equipartition, and the Stokes-Einstein relation to define and measure a pseudotemperature and diffusion constant and then self-consistently determine a coefficient of viscous friction for a test particle in this pseudothermal gas. Because of its simplicity, this system can serve as a model for direct experimental investigation of nonequilibrium statistical mechanics, much as the ideal gas epitomizes equilibrium statistical mechanics.

Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roldin, P.; Eriksson, A. C.; Nordin, E. Z.

2014-08-11

We have developed the novel Aerosol Dynamics, gas- and particle- phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: 1) the mass transfer limited uptake of ammonia (NH3)more » and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), 2) the slow and almost particle size independent evaporation of α-pinene secondary organic aerosol (SOA) particles, and 3) the influence of chamber wall effects on the observed SOA formation in smog chambers.« less

Ideal Gas with a Varying (Negative Absolute) Temperature: an Alternative to Dark Energy?

NASA Astrophysics Data System (ADS)

Saha, Subhajit; Mondal, Anindita; Corda, Christian

2018-02-01

The present work is an attempt to investigate whether the evolutionary history of the Universe from the offset of inflation can be described by assuming the cosmic fluid to be an ideal gas with a specific gas constant but a varying negative absolute temperature (NAT). The motivation of this work is to search for an alternative to the "exotic" and "supernatural" dark energy (DE). In fact, the NAT works as an "effective quintessence" and there is need to deal neither with exotic matter like DE nor with modified gravity theories. For the sake of completeness, we release some clarifications on NATs in Section 3 of the paper.

Constant volume gas cell optical phase-shifter

DOEpatents

Phillion, Donald W.

2002-01-01

A constant volume gas cell optical phase-shifter, particularly applicable for phase-shifting interferometry, contains a sealed volume of atmospheric gas at a pressure somewhat different than atmospheric. An optical window is present at each end of the cell, and as the length of the cell is changed, the optical path length of a laser beam traversing the cell changes. The cell comprises movable coaxial tubes with seals and a volume equalizing opening. Because the cell is constant volume, the pressure, temperature, and density of the contained gas do not change as the cell changes length. This produces an exactly linear relationship between the change in the length of the gas cell and the change in optical phase of the laser beam traversing it. Because the refractive index difference between the gas inside and the atmosphere outside is very much the same, a large motion must be made to change the optical phase by the small fraction of a wavelength that is required by phase-shifting interferometry for its phase step. This motion can be made to great fractional accuracy.

Identifying and addressing student difficulties with the ideal gas law

NASA Astrophysics Data System (ADS)

Kautz, Christian Hans

This dissertation reports on an in-depth investigation of student understanding of the ideal gas law. The research and curriculum development were mostly conducted in the context of algebra- and calculus-based introductory physics courses and a sophomore-level thermal physics course. Research methods included individual demonstration interviews and written questions. Student difficulties with the quantities: pressure, volume, temperature, and the number of moles were identified. Data suggest that students' incorrect and incomplete microscopic models about gases contribute to the difficulties they have in answering questions posed in macroscopic terms. In addition, evidence for general reasoning difficulties is presented. These research results have guided the development of curriculum to address the student difficulties that have been identified.

CARBON DIOXIDE SEPARATION BY PHASE ENHANCED GAS-LIQUID ABSORPTION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang Hu

A new process called phase enhanced gas-liquid absorption has been developed in its early stage. It was found that adding another phase into the absorption system of gas/aqueous phase could enhance the absorption rate. A system with three phases was studied. In the system, gas phase was carbon dioxide. Two liquid phases were used. One was organic phase. Another was aqueous phase. By addition of organic phase into the absorption system of CO{sub 2}-aqueous phase, the absorption rate of CO{sub 2} was increased significantly. CO{sub 2} finally accumulated into aqueous phase. The experimental results proved that (1) Absorption rate ofmore » carbon dioxide was enhanced by adding organic phase into gas aqueous phase system; (2) Organic phase played the role of transportation of gas solute (CO{sub 2}). Carbon dioxide finally accumulated into aqueous phase.« less

Monopole excitations of a harmonically trapped one-dimensional Bose gas from the ideal gas to the Tonks-Girardeau regime.

PubMed

Choi, S; Dunjko, V; Zhang, Z D; Olshanii, M

2015-09-11

Using a time-dependent modified nonlinear Schrödinger equation (MNLSE)-where the conventional chemical potential proportional to the density is replaced by the one inferred from Lieb-Liniger's exact solution-we study frequencies of the collective monopole excitations of a one-dimensional Bose gas. We find that our method accurately reproduces the results of a recent experimental study [E. Haller et al., Science 325, 1224 (2009)] in the full spectrum of interaction regimes from the ideal gas, through the mean-field regime, through the mean-field Thomas-Fermi regime, all the way to the Tonks-Giradeau gas. While the former two are accessible by the standard time-dependent NLSE and inaccessible by the time-dependent local density approximation, the situation reverses in the latter case. However, the MNLSE is shown to treat all these regimes within a single numerical method.

Physiological gas exchange mapping of hyperpolarized 129 Xe using spiral-IDEAL and MOXE in a model of regional radiation-induced lung injury.

PubMed

Zanette, Brandon; Stirrat, Elaine; Jelveh, Salomeh; Hope, Andrew; Santyr, Giles

2018-02-01

To map physiological gas exchange parameters using dissolved hyperpolarized (HP) 129 Xe in a rat model of regional radiation-induced lung injury (RILI) with spiral-IDEAL and the model of xenon exchange (MOXE). Results are compared to quantitative histology of pulmonary tissue and red blood cell (RBC) distribution. Two cohorts (n = 6 each) of age-matched rats were used. One was irradiated in the right-medial lung, producing regional injury. Gas exchange was mapped 4 weeks postirradiation by imaging dissolved-phase HP 129 Xe using spiral-IDEAL at five gas exchange timepoints using a clinical 1.5 T scanner. Physiological lung parameters were extracted regionally on a voxel-wise basis using MOXE. Mean gas exchange parameters, specifically air-capillary barrier thickness (δ) and hematocrit (HCT) in the right-medial lung were compared to the contralateral lung as well as nonirradiated control animals. Whole-lung spectroscopic analysis of gas exchange was also performed. δ was significantly increased (1.43 ± 0.12 μm from 1.07 ± 0.09 μm) and HCT was significantly decreased (17.2 ± 1.2% from 23.6 ± 1.9%) in the right-medial lung (i.e., irradiated region) compared to the contralateral lung of the irradiated rats. These changes were not observed in healthy controls. δ and HCT correlated with histologically measured increases in pulmonary tissue heterogeneity (r = 0.77) and decreases in RBC distribution (r = 0.91), respectively. No changes were observed using whole-lung analysis. This work demonstrates the feasibility of mapping gas exchange using HP 129 Xe in an animal model of RILI 4 weeks postirradiation. Spatially resolved gas exchange mapping is sensitive to regional injury between cohorts that was undetected with whole-lung gas exchange analysis, in agreement with histology. Gas exchange mapping holds promise for assessing regional lung function in RILI and other pulmonary diseases. © 2017 The Authors. Medical Physics published by Wiley

Similarity solutions for unsteady flow behind an exponential shock in a self-gravitating non-ideal gas with azimuthal magnetic field

NASA Astrophysics Data System (ADS)

Nath, G.; Pathak, R. P.; Dutta, Mrityunjoy

2018-01-01

Similarity solutions for the flow of a non-ideal gas behind a strong exponential shock driven out by a piston (cylindrical or spherical) moving with time according to an exponential law is obtained. Solutions are obtained, in both the cases, when the flow between the shock and the piston is isothermal or adiabatic. The shock wave is driven by a piston moving with time according to an exponential law. Similarity solutions exist only when the surrounding medium is of constant density. The effects of variation of ambient magnetic field, non-idealness of the gas, adiabatic exponent and gravitational parameter are worked out in detail. It is shown that the increase in the non-idealness of the gas or the adiabatic exponent of the gas or presence of magnetic field have decaying effect on the shock wave. Consideration of the isothermal flow and the self-gravitational field increase the shock strength. Also, the consideration of isothermal flow or the presence of magnetic field removes the singularity in the density distribution, which arises in the case of adiabatic flow. The result of our study may be used to interpret measurements carried out by space craft in the solar wind and in neighborhood of the Earth's magnetosphere.

Giddings Austin chalk enters deep lean-gas phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moritis, G.

1995-12-25

Deep lean gas is the latest phase in the growth of the Giddings field Austin chalk play. The first phase involved drilling vertical oil and gas wells. Next came the horizontal well boom in the shallower Austin chalk area, which is still continuing. And now this third phase places horizontal laterals in the Austen chalk at about 14,000--15,000 ft to produce lean gas. The article describes the producing wells and gas gathering.

Fluctuation theorem for entropy production during effusion of an ideal gas with momentum transfer.

PubMed

Wood, Kevin; Van den Broeck, C; Kawai, R; Lindenberg, Katja

2007-06-01

We derive an exact expression for entropy production during effusion of an ideal gas driven by momentum transfer in addition to energy and particle flux. Following the treatment in Cleuren [Phys. Rev. E 74, 021117 (2006)], we construct a master equation formulation of the process and explicitly verify the thermodynamic fluctuation theorem, thereby directly exhibiting its extended applicability to particle flows and hence to hydrodynamic systems.

Probability theory for 3-layer remote sensing in ideal gas law environment.

PubMed

Ben-David, Avishai; Davidson, Charles E

2013-08-26

We extend the probability model for 3-layer radiative transfer [Opt. Express 20, 10004 (2012)] to ideal gas conditions where a correlation exists between transmission and temperature of each of the 3 layers. The effect on the probability density function for the at-sensor radiances is surprisingly small, and thus the added complexity of addressing the correlation can be avoided. The small overall effect is due to (a) small perturbations by the correlation on variance population parameters and (b) cancellation of perturbation terms that appear with opposite signs in the model moment expressions.

Heat-flow equation motivated by the ideal-gas shock wave.

PubMed

Holian, Brad Lee; Mareschal, Michel

2010-08-01

We present an equation for the heat-flux vector that goes beyond Fourier's Law of heat conduction, in order to model shockwave propagation in gases. Our approach is motivated by the observation of a disequilibrium among the three components of temperature, namely, the difference between the temperature component in the direction of a planar shock wave, versus those in the transverse directions. This difference is most prominent near the shock front. We test our heat-flow equation for the case of strong shock waves in the ideal gas, which has been studied in the past and compared to Navier-Stokes solutions. The new heat-flow treatment improves the agreement with nonequilibrium molecular-dynamics simulations of hard spheres under strong shockwave conditions.

University Students Explaining Adiabatic Compression of an Ideal Gas--A New Phenomenon in Introductory Thermal Physics

ERIC Educational Resources Information Center

Leinonen, Risto; Asikainen, Mervi A.; Hirvonen, Pekka E.

2012-01-01

This study focuses on second-year university students' explanations and reasoning related to adiabatic compression of an ideal gas. The phenomenon was new to the students, but it was one which they should have been capable of explaining using their previous upper secondary school knowledge. The students' explanations and reasoning were…

Definitive Ideal-Gas Thermochemical Functions of the H216O Molecule

NASA Astrophysics Data System (ADS)

Furtenbacher, Tibor; Szidarovszky, Tamás; Hrubý, Jan; Kyuberis, Aleksandra A.; Zobov, Nikolai F.; Polyansky, Oleg L.; Tennyson, Jonathan; Császár, Attila G.

2016-12-01

A much improved temperature-dependent ideal-gas internal partition function, Qint(T), of the H216O molecule is reported for temperatures between 0 and 6000 K. Determination of Qint(T) is principally based on the direct summation technique involving all accurate experimental energy levels known for H216O (almost 20 000 rovibrational energies including an almost complete list up to a relative energy of 7500 cm-1), augmented with a less accurate but complete list of first-principles computed rovibrational energy levels up to the first dissociation limit, about 41 000 cm-1 (the latter list includes close to one million bound rovibrational energy levels up to J = 69, where J is the rotational quantum number). Partition functions are developed for ortho- and para-H216O as well as for their equilibrium mixture. Unbound rovibrational states of H216O above the first dissociation limit are considered using an approximate model treatment. The effect of the excited electronic states on the thermochemical functions is neglected, as their contribution to the thermochemical functions is negligible even at the highest temperatures considered. Based on the high-accuracy Qint(T) and its first two moments, definitive results, in 1 K increments, are obtained for the following thermochemical functions: Gibbs energy, enthalpy, entropy, and isobaric heat capacity. Reliable uncertainties (approximately two standard deviations) are estimated as a function of temperature for each quantity determined. These uncertainties emphasize that the present results are the most accurate ideal-gas thermochemical functions ever produced for H216O. It is recommended that the new value determined for the standard molar enthalpy increment at 298.15 K, 9.904 04 ± 0.000 01 kJ mol-1, should replace the old CODATA datum, 9.905 ± 0.005 kJ mol-1.

Pressure Dependence of Gas-Phase Reaction Rates

ERIC Educational Resources Information Center

De Persis, Stephanie; Dollet, Alain; Teyssandier, Francis

2004-01-01

It is presented that only simple concepts, mainly taken from activated-complex or transition-state theory, are required to explain and analytically describe the influence of pressure on gas-phase reaction kinetics. The simplest kind of elementary gas-phase reaction is a unimolecular decomposition reaction.

Generic features of the wealth distribution in ideal-gas-like markets.

PubMed

Mohanty, P K

2006-07-01

We provide an exact solution to the ideal-gas-like models studied in econophysics to understand the microscopic origin of Pareto law. In these classes of models the key ingredient necessary for having a self-organized scale-free steady-state distribution is the trading or collision rule where agents or particles save a definite fraction of their wealth or energy and invest the rest for trading. Using a Gibbs ensemble approach we could obtain the exact distribution of wealth in this model. Moreover we show that in this model (a) good savers are always rich and (b) every agent poor or rich invests the same amount for trading. Nonlinear trading rules could alter the generic scenario observed here.

Propagation of exponential shock wave in an axisymmetric rotating non-ideal dusty gas

NASA Astrophysics Data System (ADS)

Nath, G.

2016-09-01

One-dimensional unsteady isothermal and adiabatic flow behind a strong exponential shock wave propagating in a rotational axisymmetric mixture of non-ideal gas and small solid particles, which has variable azimuthal and axial fluid velocities, is analyzed. The shock wave is driven out by a piston moving with time according to exponential law. The azimuthal and axial components of the fluid velocity in the ambient medium are assumed to be varying and obeying exponential laws. In the present work, small solid particles are considered as pseudo-fluid with the assumption that the equilibrium flow-conditions are maintained in the flow-field, and the viscous-stress and heat conduction of the mixture are negligible. Solutions are obtained in both the cases, when the flow between the shock and the piston is isothermal or adiabatic by taking into account the components of vorticity vector and compressibility. It is found that the assumption of zero temperature gradient brings a profound change in the density, axial component of vorticity vector and compressibility distributions as compared to that of the adiabatic case. To investigate the behavior of the flow variables and the influence on the shock wave propagation by the parameter of non-idealness of the gas overline{b} in the mixture as well as by the mass concentration of solid particles in the mixture Kp and by the ratio of the density of solid particles to the initial density of the gas G1 are worked out in detail. It is interesting to note that the shock strength increases with an increase in G1 ; whereas it decreases with an increase in overline{b} . Also, a comparison between the solutions in the cases of isothermal and adiabatic flows is made.

Magnetogasdynamics shock waves in a rotational axisymmetric non-ideal gas with increasing energy and conductive and radiative heat-fluxes

NASA Astrophysics Data System (ADS)

Nath, Gorakh

2016-07-01

Self-similar solutions are obtained for one-dimensional adiabatic flow behind a magnetogasdynamics cylindrical shock wave propagating in a rotational axisymmetric non ideal gas with increasing energy and conductive and radiative heat fluxes in presence of an azimuthal magnetic field. The fluid velocities and the azimuthal magnetic field in the ambient medium are assume to be varying and obeying power laws. In order to find the similarity solutions the angular velocity of the ambient medium is taken to be decreasing as the distance from the axis increases. The heat conduction is expressed in terms of Fourier's law and the radiation is considered to be the diffusion type for an optically thick grey gas model. The thermal conductivity and the absorption coefficient are assumed to vary with temperature and density. The effects of the presence of radiation and conduction, the non-idealness of the gas and the magnetic field on the shock propagation and the flow behind the shock are investigated.

Dynamical heterogeneity in a glass-forming ideal gas.

PubMed

Charbonneau, Patrick; Das, Chinmay; Frenkel, Daan

2008-07-01

We conduct a numerical study of the dynamical behavior of a system of three-dimensional "crosses," particles that consist of three mutually perpendicular line segments of length sigma rigidly joined at their midpoints. In an earlier study [W. van Ketel, Phys. Rev. Lett. 94, 135703 (2005)] we showed that this model has the structural properties of an ideal gas, yet the dynamical properties of a strong glass former. In the present paper we report an extensive study of the dynamical heterogeneities that appear in this system in the regime where glassy behavior sets in. On the one hand, we find that the propensity of a particle to diffuse is determined by the structure of its local environment. The local density around mobile particles is significantly less than the average density, but there is little clustering of mobile particles, and the clusters observed tend to be small. On the other hand, dynamical susceptibility results indicate that a large dynamical length scale develops even at moderate densities. This suggests that propensity and other mobility measures are an incomplete measure of the dynamical length scales in this system.

Speed of sound and ideal-gas heat capacity of freon R-236ea

NASA Astrophysics Data System (ADS)

Komarov, S. G.; Gruzdev, V. A.; Stankus, S. V.

2008-09-01

Speed of sound in the gaseous freon R-236ea with the purity of 99.68 mol. % has been measured by the method of ultrasonic interferometer in the range from 263 to 423 K and at pressures from 17 kPA to 4.2 MPa. Errors of temperature, pressure, and speed of sound measurement were estimated to be within +/- 20 mK, ± 1.5 kPa, and ±(0.1+0.2) % respectively. Temperature dependence of ideal-gas heat capacity of R-236ea has been calculated on the basis of the obtained data.

Modeling shock waves in an ideal gas: combining the Burnett approximation and Holian's conjecture.

PubMed

He, Yi-Guang; Tang, Xiu-Zhang; Pu, Yi-Kang

2008-07-01

We model a shock wave in an ideal gas by combining the Burnett approximation and Holian's conjecture. We use the temperature in the direction of shock propagation rather than the average temperature in the Burnett transport coefficients. The shock wave profiles and shock thickness are compared with other theories. The results are found to agree better with the nonequilibrium molecular dynamics (NEMD) and direct simulation Monte Carlo (DSMC) data than the Burnett equations and the modified Navier-Stokes theory.

The ‘ideal selectivity’ vs ‘true selectivity’ for permeation of gas mixture in nanoporous membranes

NASA Astrophysics Data System (ADS)

He, Zhou; Wang, Kean

2018-03-01

In this study, we proposed and validated a novel and non-destructive experimental technology for measuring the permeation of binary gas mixture in nanoporous membranes. The traditional time lag rig was modified to examine the permeation characteristics of each gas component as well as that of the binary gas mixtures. The difference in boiling points of each species were explored. Binary gas mixtures of CO2/He were permeated through the nanoporous carbon molecular sieve membrane (CMSM). The results showed that, due to the strong interaction among different molecules and with the porous network of the membrane, the measured perm-selectivity or ‘true selectivity’ of a binary mixture can significantly deviate from the ‘ideal selectivity’ calculated form the permeation flux of each pure species, and this deviation is a complicated function of the molecular properties and operation conditions.

A combustion model for studying the effects of ideal gas properties on jet noise

NASA Astrophysics Data System (ADS)

Jacobs, Jerin; Tinney, Charles

2016-11-01

A theoretical combustion model is developed to simulate the influence of ideal gas effects on various aeroacoustic parameters over a range of equivalence ratios. The motivation is to narrow the gap between laboratory and full-scale jet noise testing. The combustion model is used to model propane combustion in air and kerosene combustion in air. Gas properties from the combustion model are compared to real lab data acquired at the National Center for Physical Acoustics at the University of Mississippi as well as outputs from NASA's Chemical Equilibrium Analysis code. Different jet properties are then studied over a range of equivalence ratios and pressure ratios for propane combustion in air, kerosene combustion in air and heated air. The findings reveal negligible differences between the three constituents where the density and sound speed ratios are concerned. Albeit, the area ratio required for perfectly expanded flow is shown to be more sensitive to gas properties, relative to changes in the temperature ratio.

Floating liquid phase in sedimenting colloid-polymer mixtures.

PubMed

Schmidt, Matthias; Dijkstra, Marjolein; Hansen, Jean-Pierre

2004-08-20

Density functional theory and computer simulation are used to investigate sedimentation equilibria of colloid-polymer mixtures within the Asakura-Oosawa-Vrij model of hard sphere colloids and ideal polymers. When the ratio of buoyant masses of the two species is comparable to the ratio of differences in density of the coexisting bulk (colloid) gas and liquid phases, a stable "floating liquid" phase is found, i.e., a thin layer of liquid sandwiched between upper and lower gas phases. The full phase diagram of the mixture under gravity shows coexistence of this floating liquid phase with a single gas phase or a phase involving liquid-gas equilibrium; the phase coexistence lines meet at a triple point. This scenario remains valid for general asymmetric binary mixtures undergoing bulk phase separation.

Numerical estimation of ultrasonic production of hydrogen: Effect of ideal and real gas based models.

PubMed

Kerboua, Kaouther; Hamdaoui, Oualid

2018-01-01

Based on two different assumptions regarding the equation describing the state of the gases within an acoustic cavitation bubble, this paper studies the sonochemical production of hydrogen, through two numerical models treating the evolution of a chemical mechanism within a single bubble saturated with oxygen during an oscillation cycle in water. The first approach is built on an ideal gas model, while the second one is founded on Van der Waals equation, and the main objective was to analyze the effect of the considered state equation on the ultrasonic hydrogen production retrieved by simulation under various operating conditions. The obtained results show that even when the second approach gives higher values of temperature, pressure and total free radicals production, yield of hydrogen does not follow the same trend. When comparing the results released by both models regarding hydrogen production, it was noticed that the ratio of the molar amount of hydrogen is frequency and acoustic amplitude dependent. The use of Van der Waals equation leads to higher quantities of hydrogen under low acoustic amplitude and high frequencies, while employing ideal gas law based model gains the upper hand regarding hydrogen production at low frequencies and high acoustic amplitudes. Copyright © 2017 Elsevier B.V. All rights reserved.

Rigorous investigation of the reduced density matrix for the ideal Bose gas in harmonic traps by a loop-gas-like approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beau, Mathieu, E-mail: mbeau@stp.dias.ie; Savoie, Baptiste, E-mail: baptiste.savoie@gmail.com

2014-05-15

In this paper, we rigorously investigate the reduced density matrix (RDM) associated to the ideal Bose gas in harmonic traps. We present a method based on a sum-decomposition of the RDM allowing to treat not only the isotropic trap, but also general anisotropic traps. When focusing on the isotropic trap, the method is analogous to the loop-gas approach developed by Mullin [“The loop-gas approach to Bose-Einstein condensation for trapped particles,” Am. J. Phys. 68(2), 120 (2000)]. Turning to the case of anisotropic traps, we examine the RDM for some anisotropic trap models corresponding to some quasi-1D and quasi-2D regimes. Formore » such models, we bring out an additional contribution in the local density of particles which arises from the mesoscopic loops. The close connection with the occurrence of generalized-Bose-Einstein condensation is discussed. Our loop-gas-like approach provides relevant information which can help guide numerical investigations on highly anisotropic systems based on the Path Integral Monte Carlo method.« less

Interaction between phases in the liquid–gas system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berry, R. S., E-mail: bmsmirnov@gmail.com; Smirnov, B. M.

This work analyzes the equilibrium between a liquid and a gas over this liquid separated by an interface. Various gas forms exist inside the liquid: dissolved gas molecules attached to solvent molecules, free gas molecules, and gaseous bubbles. Thermodynamic equilibrium is maintained between two phases; the first phase is the liquid containing dissolved and free molecules, and the second phase is the gas over the liquid and bubbles inside it. Kinetics of gas transition between the internal and external gas proceeds through bubbles and includes the processes of bubbles floating up and bubble growth as a result of association duemore » to the Smoluchowski mechanism. Evolution of a gas in the liquid is considered using the example of oxygen in water, and numerical parameters of this system are given. In the regime under consideration for an oxygen–water system, transport of oxygen into the surrounding air proceeds through micron-size bubbles with lifetimes of hours. This regime is realized if the total number of oxygen molecules in water is small compared with the numbers of solvated and free molecules in the liquid.« less

CHEMKIN2. General Gas-Phase Chemical Kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rupley, F.M.

1992-01-24

CHEMKIN is a high-level tool for chemists to use to describe arbitrary gas-phase chemical reaction mechanisms and systems of governing equations. It remains, however, for the user to select and implement a solution method; this is not provided. It consists of two major components: the Interpreter and the Gas-phase Subroutine Library. The Interpreter reads a symbolic description of an arbitrary, user-specified chemical reaction mechanism. A data file is generated which forms a link to the Gas-phase Subroutine Library, a collection of about 200 modular subroutines which may be called to return thermodynamic properties, chemical production rates, derivatives of thermodynamic properties,more » derivatives of chemical production rates, or sensitivity parameters. Both single and double precision versions of CHEMKIN are included. Also provided is a set of FORTRAN subroutines for evaluating gas-phase transport properties such as thermal conductivities, viscosities, and diffusion coefficients. These properties are an important part of any computational simulation of a chemically reacting flow. The transport properties subroutines are designed to be used in conjunction with the CHEMKIN Subroutine Library. The transport properties depend on the state of the gas and on certain molecular parameters. The parameters considered are the Lennard-Jones potential well depth and collision diameter, the dipole moment, the polarizability, and the rotational relaxation collision number.« less

Ideal thermodynamic processes of oscillatory-flow regenerative engines will go to ideal stirling cycle?

NASA Astrophysics Data System (ADS)

Luo, Ercang

2012-06-01

This paper analyzes the thermodynamic cycle of oscillating-flow regenerative machines. Unlike the classical analysis of thermodynamic textbooks, the assumptions for pistons' movement limitations are not needed and only ideal flowing and heat transfer should be maintained in our present analysis. Under such simple assumptions, the meso-scale thermodynamic cycles of each gas parcel in typical locations of a regenerator are analyzed. It is observed that the gas parcels in the regenerator undergo Lorentz cycle in different temperature levels, whereas the locus of all gas parcels inside the regenerator is the Ericson-like thermodynamic cycle. Based on this new finding, the author argued that ideal oscillating-flow machines without heat transfer and flowing losses is not the Stirling cycle. However, this new thermodynamic cycle can still achieve the same efficiency of the Carnot heat engine and can be considered a new reversible thermodynamic cycle under two constant-temperature heat sinks.

Wide-range ideal 2D Rashba electron gas with large spin splitting in Bi2Se3/MoTe2 heterostructure

NASA Astrophysics Data System (ADS)

Wang, Te-Hsien; Jeng, Horng-Tay

2017-02-01

An application-expected ideal two-dimensional Rashba electron gas, i.e., nearly all the conduction electrons occupy the Rashba bands, is crucial for semiconductor spintronic applications. We demonstrate that such an ideal two-dimensional Rashba electron gas with a large Rashba splitting can be realized in a topological insulator Bi2Se3 ultrathin film grown on a transition metal dichalcogenides MoTe2 substrate through first-principle calculations. Our results show the Rashba bands exclusively over a very large energy interval of about 0.6 eV around the Fermi level within the MoTe2 semiconducting gap. Such a wide-range ideal two-dimensional Rashba electron gas with a large spin splitting, which is desirable for real devices utilizing the Rashba effect, has never been found before. Due to the strong spin-orbit coupling, the strength of the Rashba splitting is comparable with that of the heavy-metal surfaces such as Au and Bi surfaces, giving rise to a spin precession length as small as 10 nm. The maximum in-plane spin polarization of the inner (outer) Rashba band near the Γ point is about 70% (60%). The room-temperature coherence length is at least several times longer than the spin precession length, providing good coherency through the spin processing devices. The wide energy window for ideal Rashba bands, small spin precession length, as well as long spin coherence length in this two-dimensional topological insulator/transition metal dichalcogenides heterostructure pave the way for realizing an ultrathin nano-scale spintronic device such as the Datta-Das spin transistor at room-temperature.

Modeling the Phase Composition of Gas Condensate in Pipelines

NASA Astrophysics Data System (ADS)

Dudin, S. M.; Zemenkov, Yu D.; Shabarov, A. B.

2016-10-01

Gas condensate fields demonstrate a number of thermodynamic characteristics to be considered when they are developed, as well as when gas condensate is transported and processed. A complicated phase behavior of the gas condensate system, as well as the dependence of the extracted raw materials on the phase state of the deposit other conditions being equal, is a key aspect. Therefore, when designing gas condensate lines the crucial task is to select the most appropriate methods of calculating thermophysical properties and phase equilibrium of the transported gas condensate. The paper describes a physical-mathematical model of a gas-liquid flow in the gas condensate line. It was developed based on balance equations of conservation of mass, impulse and energy of the transported medium within the framework of a quasi-1D approach. Constitutive relationships are given separately, and practical recommendations on how to apply the research results are provided as well.

Configuration-specific kinetic theory applied to an ideal binary gas mixture.

PubMed

Wiseman, Floyd L

2006-10-05

This paper is the second in a two-part series dealing with the configuration-specific analyses for molecular collision events of hard, spherical molecules at thermal equilibrium. The first paper analyzed a single-component system, and the reader is referred to it for the fundamental concepts. In this paper, the expressions for the configuration-specific collision frequencies and the average line-of-centers collision angles and speeds are derived for an ideal binary gas mixture. The analyses show that the average line-of-centers quantities are all dependent upon the ratio of the masses of the two components, but not upon molecular size. Of course, the configuration-specific collision frequencies do depend on molecular size. The expression for the overall binary collision frequency is a simple sum of the configuration-specific collision frequencies and is identical to the conventional expression.

On the accuracy of Whitham's method. [for steady ideal gas flow past cones

NASA Technical Reports Server (NTRS)

Zahalak, G. I.; Myers, M. K.

1974-01-01

The steady flow of an ideal gas past a conical body is studied by the method of matched asymptotic expansions and by Whitham's method in order to assess the accuracy of the latter. It is found that while Whitham's method does not yield a correct asymptotic representation of the perturbation field to second order in regions where the flow ahead of the Mach cone of the apex is disturbed, it does correctly predict the changes of the second-order perturbation quantities across a shock (the first-order shock strength). The results of the analysis are illustrated by a special case of a flat, rectangular plate at incidence.

Studies in Three Phase Gas-Liquid Fluidised Systems

NASA Astrophysics Data System (ADS)

Awofisayo, Joyce Ololade

1992-01-01

Available from UMI in association with The British Library. The work is a logical continuation of research started at Aston some years ago when studies were conducted on fermentations in bubble columns. The present work highlights typical design and operating problems that could arise in such systems as waste water, chemical, biochemical and petroleum operations involving three-phase, gas-liquid -solid fluidisation; such systems are in increasing use. It is believed that this is one of few studies concerned with "true" three-phase, gas-liquid-solid fluidised systems, and that this work will contribute significantly to closing some of the gaps in knowledge in this area. The research work was experimentally based and involved studies of the hydrodynamic parameters, phase holdups (gas and solid), particle mixing and segregation, and phase flow dynamics (flow regime and circulation patterns). The studies have focused particularly on the solid behaviour and the influence of properties of solids present on the above parameters in three-phase, gas-liquid-solid fluidised systems containing single particle components and those containing binary and ternary mixtures of particles. All particles were near spherical in shape and two particle sizes and total concentration levels were used. Experiments were carried out in two- and three-dimensional bubble columns. Quantitative results are presented in graphical form and are supported by qualitative results from visual studies which are also shown as schematic diagrams and in photographic form. Gas and solid holdup results are compared for air-water containing single, binary and ternary component particle mixtures. It should be noted that the criteria for selection of the materials used are very important if true three-phase fluidisation is to be achieved: this is very evident when comparing the results with those in the literature. The fluid flow and circulation patterns observed were assessed for validation of the generally

Simulation Approach for Microscale Noncontinuum Gas-Phase Heat Transfer

NASA Astrophysics Data System (ADS)

Torczynski, J. R.; Gallis, M. A.

2008-11-01

In microscale thermal actuators, gas-phase heat transfer from the heated beams to the adjacent unheated substrate is often the main energy-loss mechanism. Since the beam-substrate gap is comparable to the molecular mean free path, noncontinuum gas effects are important. A simulation approach is presented in which gas-phase heat transfer is described by Fourier's law in the bulk gas and by a wall boundary condition that equates the normal heat flux to the product of the gas-solid temperature difference and a heat transfer coefficient. The dimensionless parameters in this heat transfer coefficient are determined by comparison to Direct Simulation Monte Carlo (DSMC) results for heat transfer from beams of rectangular cross section to the substrate at free-molecular to near-continuum gas pressures. This simulation approach produces reasonably accurate gas-phase heat-transfer results for wide ranges of beam geometries and gas pressures. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Numerical simulation of double front detonations in a non-ideal explosive with varying aluminum concentration

NASA Astrophysics Data System (ADS)

Kim, Wuhyun; Gwak, Min-Cheol; Yoh, Jack; Seoul National University Team

2017-06-01

The performance characteristics of aluminized HMX are considered by varying the aluminum (Al) concentration in a hybrid non-ideal detonation model. Two cardinal observations are reported: a decrease in detonation velocity with an increase in Al concentration and a double front detonation (DFD) feature when aerobic Al reaction occurs behind the front. While experimental studies have been reported on the effect of Al concentration on both gas-phase and solid-phase detonations, the numerical investigations were limited to only gas-phase detonation for the varying Al concentration. In the current study, a two-phase model is utilized for understanding the volumetric effects of Al concentration in the condensed phase detonations. A series of unconfined and confined rate sticks are considered for characterizing the performance of aluminized HMX with a maximum Al concentration of 50%. The simulated results are compared with the experimental data for 5%-25% concentrations, and the formation of DFD structure under varying Al concentration (0%-50%) in HMX is investigated.

Development of a Small, Inexpensive, and Field-deployable Gas Chromatograph for the Automated Collection, Separation, and Analysis of Gas-phase Organic Compounds

NASA Astrophysics Data System (ADS)

Skog, K.; Xiong, F.; Gentner, D. R.

2017-12-01

The identification and quantification of gas-phase organic compounds, like volatile organic compounds (VOCs), in the atmosphere relies on separation of complex mixtures and sensitive detection. Gas chromatography (GC) is widely applied, but relies on the need for high-purity compressed gases for separation and, often for detection. We have developed a low-cost, compact GC-based system for the collection and quantitative chemical speciation of complex mixtures of common atmospheric VOCs without the need for compressed high-purity gases or expensive detectors. We present results of lab and field testing against a commercially-available GC system. At optimized linear velocities challenging VOC pairs of similar volatility were resolved within 30 minutes, including n- and i-pentane; n-pentane and isoprene; and ethylbenzene and m/p-xylene. For 5-30 minute samples, we observe ppt-level detection limits for common VOCs such as benzene, toluene, ethylbenzene, xylenes, alpha-pinene, and limonene. We also present results of in-field use for VOC measurements. In all, this instrument is accurate, precise, small, and inexpensive (<$2500). Its lack of compressed gas cylinders make it ideal for field deployment and has been demonstrated to produce similar quality data to available GC technology.

On the use of pulsed Dielectric Barrier Discharges to control the gas-phase composition of atmospheric pressure air plasmas

NASA Astrophysics Data System (ADS)

Barni, R.; Biganzoli, I.; Dell'Orto, E.; Riccardi, C.

2014-11-01

We presents results obtained from the numerical simulation of the gas-phase chemical kinetics in atmospheric pressure air non-equilibrium plasmas. In particular we have addressed the effect of pulsed operation mode of a plane dielectric barrier discharge. It was conjectured that the large difference in the time scales involved in the fast dissociation of oxygen molecules in plasma and their subsequent reactions to produce ozone and nitrogen oxides, makes the presence of a continuously repeated plasma production unnecessary and a waste of electrical power and thus efficiency. In order to test such suggestion we have performed a numerical study of the composition and the temporal evolution of the gas-phase of atmospheric pressure air non-equilibrium plasmas. Comparison with experimental findings in a dielectric barrier discharge with an electrode configuration symmetrical and almost ideally plane is briefly addressed too, using plasma diagnostics to extract the properties of the single micro-discharges and a sensor to measure the concentration of ozone produced by the plasma.

Mutual influence of molecular diffusion in gas and surface phases

NASA Astrophysics Data System (ADS)

Hori, Takuma; Kamino, Takafumi; Yoshimoto, Yuta; Takagi, Shu; Kinefuchi, Ikuya

2018-01-01

We develop molecular transport simulation methods that simultaneously deal with gas- and surface-phase diffusions to determine the effect of surface diffusion on the overall diffusion coefficients. The phenomenon of surface diffusion is incorporated into the test particle method and the mean square displacement method, which are typically employed only for gas-phase transport. It is found that for a simple cylindrical pore, the diffusion coefficients in the presence of surface diffusion calculated by these two methods show good agreement. We also confirm that both methods reproduce the analytical solution. Then, the diffusion coefficients for ink-bottle-shaped pores are calculated using the developed method. Our results show that surface diffusion assists molecular transport in the gas phase. Moreover, the surface tortuosity factor, which is known to be uniquely determined by physical structure, is influenced by the presence of gas-phase diffusion. This mutual influence of gas-phase diffusion and surface diffusion indicates that their simultaneous calculation is necessary for an accurate evaluation of the diffusion coefficients.

Gas-Phase Infrared; JCAMP Format

National Institute of Standards and Technology Data Gateway

SRD 35 NIST/EPA Gas-Phase Infrared; JCAMP Format (PC database for purchase)   This data collection contains 5,228 infrared spectra in the JCAMP-DX (Joint Committee for Atomic and Molecular Physical Data "Data Exchange") format.

Understanding Gas-Phase Ammonia Chemistry in Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Chambers, Lauren; Oberg, Karin I.; Cleeves, Lauren Ilsedore

2017-01-01

Protoplanetary disks are dynamic regions of gas and dust around young stars, the remnants of star formation, that evolve and coagulate over millions of years in order to ultimately form planets. The chemical composition of protoplanetary disks is affected by both the chemical and physical conditions in which they develop, including the initial molecular abundances in the birth cloud, the spectrum and intensity of radiation from the host star and nearby systems, and mixing and turbulence within the disk. A more complete understanding of the chemical evolution of disks enables a more complete understanding of the chemical composition of planets that may form within them, and of their capability to support life. One element known to be essential for life on Earth is nitrogen, which often is present in the form of ammonia (NH3). Recent observations by Salinas et al. (2016) reveal a theoretical discrepancy in the gas-phase and ice-phase ammonia abundances in protoplanetary disks; while observations of comets and protostars estimate the ice-phase NH3/H2O ratio in disks to be 5%, Salinas reports a gas-phase NH3/H2O ratio of ~7-84% in the disk surrounding TW Hydra, a young nearby star. Through computational chemical modeling of the TW Hydra disk using a reaction network of over 5000 chemical reactions, I am investigating the possible sources of excess gas-phase NH3 by determining the primary reaction pathways of NH3 production; the downstream chemical effects of ionization by ultraviolet photons, X-rays, and cosmic rays; and the effects of altering the initial abundances of key molecules such as N and N2. Beyond providing a theoretical explanation for the NH3 ice/gas discrepancy, this new model may lead to fuller understanding of the gas-phase formation processes of all nitrogen hydrides (NHx), and thus fuller understanding of the nitrogen-bearing molecules that are fundamental for life as we know it.

Analysis of the gas phase reactivity of chlorosilanes.

PubMed

Ravasio, Stefano; Masi, Maurizio; Cavallotti, Carlo

2013-06-27

Trichlorosilane is the most used precursor to deposit silicon for photovoltaic applications. Despite of this, its gas phase and surface kinetics have not yet been completely understood. In the present work, it is reported a systematic investigation aimed at determining what is the dominant gas phase chemistry active during the chemical vapor deposition of Si from trichlorosilane. The gas phase mechanism was developed calculating the rate constant of each reaction using conventional transition state theory in the rigid rotor-harmonic oscillator approximation. Torsional vibrations were described using a hindered rotor model. Structures and vibrational frequencies of reactants and transition states were determined at the B3LYP/6-31+G(d,p) level, while potential energy surfaces and activation energies were computed at the CCSD(T) level using aug-cc-pVDZ and aug-cc-pVTZ basis sets extrapolating to the complete basis set limit. As gas phase and surface reactivities are mutually interlinked, simulations were performed using a microkinetic surface mechanism. It was found that the gas phase reactivity follows two different routes. The disilane mechanism, in which the formation of disilanes as reaction intermediates favors the conversion between the most stable monosilane species, and the radical pathway, initiated by the decomposition of Si2HCl5 and followed by a series of fast propagation reactions. Though both mechanisms are active during deposition, the simulations revealed that above a certain temperature and conversion threshold the radical mechanism provides a faster route for the conversion of SiHCl3 into SiCl4, a reaction that favors the overall Si deposition process as it is associated with the consumption of HCl, a fast etchant of Si. Also, this study shows that the formation of disilanes as reactant intermediates promotes significantly the gas phase reactivity, as they contribute both to the initiation of radical chain mechanisms and provide a catalytic route for

The Statistical Mechanics of Ideal MHD Turbulence

NASA Technical Reports Server (NTRS)

Shebalin, John V.

2003-01-01

Turbulence is a universal, nonlinear phenomenon found in all energetic fluid and plasma motion. In particular. understanding magneto hydrodynamic (MHD) turbulence and incorporating its effects in the computation and prediction of the flow of ionized gases in space, for example, are great challenges that must be met if such computations and predictions are to be meaningful. Although a general solution to the "problem of turbulence" does not exist in closed form, numerical integrations allow us to explore the phase space of solutions for both ideal and dissipative flows. For homogeneous, incompressible turbulence, Fourier methods are appropriate, and phase space is defined by the Fourier coefficients of the physical fields. In the case of ideal MHD flows, a fairly robust statistical mechanics has been developed, in which the symmetry and ergodic properties of phase space is understood. A discussion of these properties will illuminate our principal discovery: Coherent structure and randomness co-exist in ideal MHD turbulence. For dissipative flows, as opposed to ideal flows, progress beyond the dimensional analysis of Kolmogorov has been difficult. Here, some possible future directions that draw on the ideal results will also be discussed. Our conclusion will be that while ideal turbulence is now well understood, real turbulence still presents great challenges.

Molecular structure and conformational composition of 1,3-dihydroxyacetone studied by combined analysis of gas-phase electron diffraction data, rotational constants, and results of theoretical calculations. Ideal gas thermodynamic properties of 1,3-dihydroxyacetone.

PubMed

Dorofeeva, Olga V; Vogt, Natalja; Vogt, Jürgen; Popik, Mikhail V; Rykov, Anatolii N; Vilkov, Lev V

2007-07-19

The molecular structure of 1,3-dihydroxyacetone (DHA) has been studied by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) data, ab initio, and density functional theory calculations. The equilibrium re structure of DHA was determined by a joint analysis of the GED data and rotational constants taken from the literature. The anharmonic vibrational corrections to the internuclear distances (re-ra) and to the rotational constants (B(i)e-B(i)0) needed for the estimation of the re structure were calculated from the B3LYP/cc-pVTZ cubic force field. It was found that the experimental data are well reproduced by assuming that DHA consists of a mixture of three conformers. The most stable conformer of C2v symmetry has two hydrogen bonds, whereas the next two lowest energy conformers (Cs and C1 symmetry) have one hydrogen bond and their abundance is about 30% in total. A combined analysis of GED and MW data led to the following equilibrium structural parameters (re) of the most abundant conformer of DHA (the uncertainties in parentheses are 3 times the standard deviations): r(C=O)=1.215(2) A, r(C-C)=1.516(2) A, r(C-O)=1.393(2) A, r(C-H)=1.096(4) A, r(O-H)=0.967(4) A, angleC-C=O=119.9(2) degrees, angleC-C-O=111.0(2) degrees, angleC-C-H=108.2(7) degrees, angleC-O-H=106.5(7) degrees. These structural parameters reproduce the experimental B(i)0 values within 0.05 MHz. The experimental structural parameters are in good agreement with those obtained from theoretical calculations. Ideal gas thermodynamic functions (S degrees (T), C degrees p(T), and H degrees (T)-H degrees (0)) of DHA were calculated on the basis of experimental and theoretical molecular parameters obtained in this work. The enthalpy of formation of DHA, -523+/-4 kJ/mol, was calculated by the atomization procedure using the G3X method.

Ionic liquid stationary phases for gas chromatography.

PubMed

Poole, Colin F; Poole, Salwa K

2011-04-01

This article provides a summary of the development of ionic liquids as stationary phases for gas chromatography beginning with early work on packed columns that established details of the retention mechanism and established working methods to characterize selectivity differences compared with molecular stationary phases through the modern development of multi-centered cation and cross-linked ionic liquids for high-temperature applications in capillary gas chromatography. Since there are many reviews on ionic liquids dealing with all aspects of their chemical and physical properties, the emphasis in this article is placed on the role of gas chromatography played in the design of ionic liquids of low melting point, high thermal stability, high viscosity, and variable selectivity for separations. Ionic liquids provide unprecedented opportunities for extending the selectivity range and temperature-operating range of columns for gas chromatography, an area of separation science that has otherwise been almost stagnant for over a decade. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A generalized number theory problem applied to ideal liquids and to terminological lexis

NASA Astrophysics Data System (ADS)

Maslov, V. P.; Maslova, T. V.

2017-01-01

We consider the notion of number of degrees of freedom in number theory and thermodynamics. This notion is applied to notions of terminology such as terms, slogans, themes, rules, and regulations. Prohibitions are interpreted as restrictions on the number of degrees of freedom. We present a theorem on the small number of degrees of freedom as a consequence of the generalized partitio numerorum problem. We analyze the relationship between thermodynamically ideal liquids with the lexical background that a term acquires in the process of communication. Examples showing how this background may be enhanced are considered. We discuss the question of the coagulation of drops in connection with the forecast of analogs of the gas-ideal liquid phase transition in social-political processes.

Perturbative thermodynamic geometry of nonextensive ideal classical, Bose, and Fermi gases.

PubMed

Mohammadzadeh, Hosein; Adli, Fereshteh; Nouri, Sahereh

2016-12-01

We investigate perturbative thermodynamic geometry of nonextensive ideal classical, Bose, and Fermi gases. We show that the intrinsic statistical interaction of nonextensive Bose (Fermi) gas is attractive (repulsive) similar to the extensive case but the value of thermodynamic curvature is changed by a nonextensive parameter. In contrary to the extensive ideal classical gas, the nonextensive one may be divided to two different regimes. According to the deviation parameter of the system to the nonextensive case, one can find a special value of fugacity, z^{*}, where the sign of thermodynamic curvature is changed. Therefore, we argue that the nonextensive parameter induces an attractive (repulsive) statistical interaction for zz^{*}) for an ideal classical gas. Also, according to the singular point of thermodynamic curvature, we consider the condensation of nonextensive Boson gas.

An alternative expression to the Sackur-Tetrode entropy formula for an ideal gas

NASA Astrophysics Data System (ADS)

Nagata, Shoichi

2018-03-01

An expression for the entropy of a monoatomic classical ideal gas is known as the Sackur-Tetrode equation. This pioneering investigation about 100 years ago incorporates quantum considerations. The purpose of this paper is to provide an alternative expression for the entropy in terms of the Heisenberg uncertainty relation. The analysis is made on the basis of fluctuation theory, for a canonical system in thermal equilibrium at temperature T. This new formula indicates manifestly that the entropy of macroscopic world is recognized as a measure of uncertainty in microscopic quantum world. The entropy in the Sackur-Tetrode equation can be re-interpreted from a different perspective viewpoint. The emphasis is on the connection between the entropy and the uncertainty relation in quantum consideration.

The Noble Gas Record of Gas-Water Phase Interaction in the Tight-Gas-Sand Reservoirs of the Rocky Mountains

NASA Astrophysics Data System (ADS)

Ballentine, C. J.; Zhou, Z.; Harris, N. B.

2015-12-01

The mass of hydrocarbons that have migrated through tight-gas-sandstone systems before the permeability reduces to trap the hydrocarbon gases provides critical information in the hydrocarbon potential analysis of a basin. The noble gas content (Ne, Ar, Kr, Xe) of the groundwater has a unique isotopic and elemental composition. As gas migrates through the water column, the groundwater-derived noble gases partition into the hydrocarbon phase. Determination of the noble gases in the produced hydrocarbon phase then provides a record of the type of interaction (simple phase equilibrium or open system Rayleigh fractionation). The tight-gas-sand reservoirs of the Rocky Mountains represent one of the most significant gas resources in the United States. The producing reservoirs are generally developed in low permeability (averaging <0.1mD) Upper Cretaceous fluvial to marginal marine sandstones and commonly form isolated overpressured reservoir bodies encased in even lower permeability muddy sediments. We present noble gas data from producing fields in the Greater Green River Basin, Wyoming; the the Piceance Basin, Colorado; and in the Uinta Basin, Utah. The data is consistent from all three basins. We show how in each basin the noble gases record open system gas migration through a water column at maximum basin burial. The data within an open system model indicates that the gas now in-place represents the last ~10% of hydrocarbon gas to have passed through the water column, most likely prior to permeability closedown.

Spontaneous Growth and Mobilization of a Gas Phase in the Presence of Dense Non- Aqueous Phase Liquid (DNAPL)

NASA Astrophysics Data System (ADS)

Roy, J. W.; Smith, J. E.

2006-12-01

A number of mechanisms can lead to the presence of disconnected bubbles or ganglia of gas phase in groundwater. When associated with or near a DNAPL phase, the disconnected gas phase experiences mass transfer of dissolved gases including the volatile components of the DNAPL. The properties of the gas phase interface, such as interfacial tension and contact angle, can also be affected. This work addresses the behavior of spontaneous continual growth of initially trapped seed gas bubbles within DNAPL source zones. Three different experiments were performed in a 2-dimensional transparent flow cell 15 cm by 20 cm by 1.5 cm. In each case, a DNAPL pool was created within larger glass beads over smaller glass beads that served as a capillary barrier. The DNAPL consisted of either a 1:2 (v/v) tetrachloroethene (PCE) to benzene mixture, single component PCE, or single component TCE. The experiments effectively demonstrate spontaneous gas phase expansion and vertical advective mobilization of gas bubbles and ganglia above the DNAPL source zone. A cycle of gas phase growth and mobilization was facilitated by the presence of secondary seed bubbles left behind due to snap-off during vertical bubble (ganglion) mobilization. This gas phase growth process was relatively slow but continuous and could be expected to continue until the NAPL is completely dissolved. Some implications of the demonstrated behavior for water flow and mass transfer within and near the DNAPL source zone are highlighted.

Phase and flow behavior of mixed gas hydrate systems during gas injection

NASA Astrophysics Data System (ADS)

Darnell, K.; Flemings, P. B.; DiCarlo, D. A.

2017-12-01

We present one-dimensional, multi-phase flow model results for injections of carbon dioxide and nitrogen mixtures, or flue gas, into methane hydrate bearing reservoirs. Our flow model is coupled to a thermodynamic simulator that predicts phase stabilities as a function of composition, so multiple phases can appear, disappear, or change composition as the injection invades the reservoir. We show that the coupling of multi-phase fluid flow with phase behavior causes preferential phase fractionation in which each component flows through the system at different speeds and in different phases. We further demonstrate that phase and flow behavior within the reservoir are driven by hydrate stability of each individual component in addition to the hydrate stability of the injection composition. For example, if carbon dioxide and nitrogen are both individually hydrate stable at the reservoir P-T conditions, then any injection composition will convert all available water into hydrate and plug the reservoir. In contrast, if only carbon dioxide is hydrate stable at the reservoir P-T conditions, then nitrogen preferentially stays in the gaseous phase, while the carbon dioxide partitions into the hydrate and liquid water phases. For all injections of this type, methane originally held in hydrate is released by dissociation into the nitrogen-rich gaseous phase. The net consequence is that a gas phase composed of nitrogen and methane propagates through the reservoir in a fast-moving front. A slower-moving front lags behind where carbon dioxide and nitrogen form a mixed hydrate, but methane is absent due to dissociation-induced methane stripping from the first, fast-moving front. The entire composition path traces through the phase space as the flow develops with each front moving at different, constant velocities. This behavior is qualitatively similar to the dynamics present in enhanced oil recovery or enhanced coalbed methane recovery. These results explain why the inclusion of

Multiphase flow and transport caused by spontaneous gas phase growth in the presence of dense non-aqueous phase liquid

NASA Astrophysics Data System (ADS)

Roy, James W.; Smith, James E.

2007-01-01

Disconnected bubbles or ganglia of trapped gas may occur below the top of the capillary fringe through a number of mechanisms. In the presence of dense non-aqueous phase liquid (DNAPL), the disconnected gas phase experiences mass transfer of dissolved gases, including volatile components from the DNAPL. The properties of the gas phase interface can also change. This work shows for the first time that when seed gas bubbles exist spontaneous gas phase growth can be expected to occur and can significantly affect water-gas-DNAPL distributions, fluid flow, and mass transfer. Source zone behaviour was observed in three different experiments performed in a 2-dimensional flow cell. In each case, a DNAPL pool was created in a zone of larger glass beads over smaller glass beads, which served as a capillary barrier. In one experiment effluent water samples were analyzed to determine the vertical concentration profile of the plume above the pool. The experiments effectively demonstrated a) a cycle of spontaneous gas phase expansion and vertical advective mobilization of gas bubbles and ganglia above the DNAPL source zone, b) DNAPL redistribution caused by gas phase growth and mobilization, and c) that these processes can significantly affect mass transport from a NAPL source zone.

Multiphase flow and transport caused by spontaneous gas phase growth in the presence of dense non-aqueous phase liquid.

PubMed

Roy, James W; Smith, James E

2007-01-30

Disconnected bubbles or ganglia of trapped gas may occur below the top of the capillary fringe through a number of mechanisms. In the presence of dense non-aqueous phase liquid (DNAPL), the disconnected gas phase experiences mass transfer of dissolved gases, including volatile components from the DNAPL. The properties of the gas phase interface can also change. This work shows for the first time that when seed gas bubbles exist spontaneous gas phase growth can be expected to occur and can significantly affect water-gas-DNAPL distributions, fluid flow, and mass transfer. Source zone behaviour was observed in three different experiments performed in a 2-dimensional flow cell. In each case, a DNAPL pool was created in a zone of larger glass beads over smaller glass beads, which served as a capillary barrier. In one experiment effluent water samples were analyzed to determine the vertical concentration profile of the plume above the pool. The experiments effectively demonstrated a) a cycle of spontaneous gas phase expansion and vertical advective mobilization of gas bubbles and ganglia above the DNAPL source zone, b) DNAPL redistribution caused by gas phase growth and mobilization, and c) that these processes can significantly affect mass transport from a NAPL source zone.

A Uranyl Peroxide Dimer in the Gas Phase

DOE PAGES

Dau, Phuong D.; Dau, Phuong V.; Rao, Linfeng; ...

2017-03-14

For this study, the gas-phase uranyl peroxide dimer, [(UO 2) 2(O2)(L) 2] 2+ where L = 2,2'-trifluoroethylazanediyl)bis(N,N'-dimethylacetamide), was synthesized by electrospray ionization of a solution of UO 2 2+ and L. Collision-induced dissociation of this dimer resulted in endothermic O atom elimination to give [(UO 2) 2(O)(L) 2] 2+, which was found to spontaneously react with water via exothermic hydrolytic chemisorption to yield [(UO 2) 2(OH) 2(L) 2] 2+. Density functional theory computations of the energies for the gas-phase reactions are in accord with observations. The structures of the observed uranyl dimer were computed, with that of the peroxide ofmore » particular interest, as a basis to evaluate the formation of condensed phase uranyl peroxides with bent structures. The computed dihedral angle in [(UO 2) 2(O 2)(L) 2] 2+ is 145°, indicating a substantial deviation from the planar structure with a dihedral angle of 180°. Energies needed to induce bending in the most elementary gas-phase uranyl peroxide complex, [(UO 2) 2(O 2)] 2+, were computed. It was found that bending from the lowest-energy planar structure to dihedral angles up to 140° required energies of <10 kJ/mol. The gas-phase results demonstrate the inherent stability of the uranyl peroxide moiety and support the notion that the uranyl-peroxide-uranyl structural unit is intrinsically planar, with only minor energy perturbations needed to form the bent structures found in studtite and uranyl peroxide nanostructures.« less

Slippage and boundary layer probed in an almost ideal gas by a nanomechanical oscillator.

PubMed

Defoort, M; Lulla, K J; Crozes, T; Maillet, O; Bourgeois, O; Collin, E

2014-09-26

We measure the interaction between ⁴He gas at 4.2 K and a high-quality nanoelectromechanical string device for its first three symmetric modes (resonating at 2.2, 6.7, and 11 MHz with quality factor Q>0.1×10⁶) over almost 6 orders of magnitude in pressure. This fluid can be viewed as the best experimental implementation of an almost ideal monoatomic and inert gas of which properties are tabulated. The experiment ranges from high pressure where the flow is of laminar Stokes-type presenting slippage down to very low pressures where the flow is molecular. In the molecular regime, when the mean-free path is of the order of the distance between the suspended nanomechanical probe and the bottom of the trench, we resolve for the first time the signature of the boundary (Knudsen) layer onto the measured dissipation. Our results are discussed in the framework of the most recent theories investigating boundary effects in fluids (both analytic approaches and direct simulation Monte Carlo methods).

Numerical solutions of ideal quantum gas dynamical flows governed by semiclassical ellipsoidal-statistical distribution.

PubMed

Yang, Jaw-Yen; Yan, Chih-Yuan; Diaz, Manuel; Huang, Juan-Chen; Li, Zhihui; Zhang, Hanxin

2014-01-08

The ideal quantum gas dynamics as manifested by the semiclassical ellipsoidal-statistical (ES) equilibrium distribution derived in Wu et al. (Wu et al . 2012 Proc. R. Soc. A 468 , 1799-1823 (doi:10.1098/rspa.2011.0673)) is numerically studied for particles of three statistics. This anisotropic ES equilibrium distribution was derived using the maximum entropy principle and conserves the mass, momentum and energy, but differs from the standard Fermi-Dirac or Bose-Einstein distribution. The present numerical method combines the discrete velocity (or momentum) ordinate method in momentum space and the high-resolution shock-capturing method in physical space. A decoding procedure to obtain the necessary parameters for determining the ES distribution is also devised. Computations of two-dimensional Riemann problems are presented, and various contours of the quantities unique to this ES model are illustrated. The main flow features, such as shock waves, expansion waves and slip lines and their complex nonlinear interactions, are depicted and found to be consistent with existing calculations for a classical gas.

Numerical solutions of ideal quantum gas dynamical flows governed by semiclassical ellipsoidal-statistical distribution

PubMed Central

Yang, Jaw-Yen; Yan, Chih-Yuan; Diaz, Manuel; Huang, Juan-Chen; Li, Zhihui; Zhang, Hanxin

2014-01-01

The ideal quantum gas dynamics as manifested by the semiclassical ellipsoidal-statistical (ES) equilibrium distribution derived in Wu et al. (Wu et al. 2012 Proc. R. Soc. A 468, 1799–1823 (doi:10.1098/rspa.2011.0673)) is numerically studied for particles of three statistics. This anisotropic ES equilibrium distribution was derived using the maximum entropy principle and conserves the mass, momentum and energy, but differs from the standard Fermi–Dirac or Bose–Einstein distribution. The present numerical method combines the discrete velocity (or momentum) ordinate method in momentum space and the high-resolution shock-capturing method in physical space. A decoding procedure to obtain the necessary parameters for determining the ES distribution is also devised. Computations of two-dimensional Riemann problems are presented, and various contours of the quantities unique to this ES model are illustrated. The main flow features, such as shock waves, expansion waves and slip lines and their complex nonlinear interactions, are depicted and found to be consistent with existing calculations for a classical gas. PMID:24399919

Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol

PubMed Central

Axson, Jessica L.; Takahashi, Kaito; De Haan, David O.; Vaida, Veronica

2010-01-01

In aqueous solution, aldehydes, and to a lesser extent ketones, hydrate to form geminal diols. We investigate the hydration of methylglyoxal (MG) in the gas phase, a process not previously considered to occur in water-restricted environments. In this study, we spectroscopically identified methylglyoxal diol (MGD) and obtained the gas-phase partial pressures of MG and MGD. These results, in conjunction with the relative humidity, were used to obtain the equilibrium constant, KP, for the water-mediated hydration of MG in the gas phase. The Gibbs free energy for this process, ΔG°, obtained as a result, suggests a larger than expected gas-phase diol concentration. This may have significant implications for understanding the role of organics in atmospheric chemistry. PMID:20142510

Role of single-point mutations and deletions on transition temperatures in ideal proteinogenic heteropolymer chains in the gas phase.

PubMed

Olivares-Quiroz, L

2016-07-01

A coarse-grained statistical mechanics-based model for ideal heteropolymer proteinogenic chains of non-interacting residues is presented in terms of the size K of the chain and the set of helical propensities [Formula: see text] associated with each residue j along the chain. For this model, we provide an algorithm to compute the degeneracy tensor [Formula: see text] associated with energy level [Formula: see text] where [Formula: see text] is the number of residues with a native contact in a given conformation. From these results, we calculate the equilibrium partition function [Formula: see text] and characteristic temperature [Formula: see text] at which a transition from a low to a high entropy states is observed. The formalism is applied to analyze the effect on characteristic temperatures [Formula: see text] of single-point mutations and deletions of specific amino acids [Formula: see text] along the chain. Two probe systems are considered. First, we address the case of a random heteropolymer of size K and given helical propensities [Formula: see text] on a conformational phase space. Second, we focus our attention to a particular set of neuropentapeptides, [Met-5] and [Leu-5] enkephalins whose thermodynamic stability is a key feature on their coupling to [Formula: see text] and [Formula: see text] receptors and the triggering of biochemical responses.

Gas-phase and solution-phase polymerization of epoxides by Cr(salen) complexes: evidence for a dinuclear cationic mechanism.

PubMed

Schön, Eva; Zhang, Xiangyang; Zhou, Zhiping; Chisholm, Malcolm H; Chen, Peter

2004-11-15

The gas-phase reactions of a series of mass-selected mononuclear and dinuclear Cr(salen) complexes with propylene oxide suggest that the enhanced reactivity of the dinuclear complexes in gas-phase and in solution may derive from a dicationic mechanism in which the alkoxide chain is mu(2)-coordinated to two Lewis acidic metal centers. The double coordination is proposed to suppress backbiting, and hence chain-transfer in the gas-phase homopolymerization of epoxides.

Polymerization in the gas phase, in clusters, and on nanoparticle surfaces.

PubMed

El-Shall, M Samy

2008-07-01

Gas phase and cluster experiments provide unique opportunities to quantitatively study the effects of initiators, solvents, chain transfer agents, and inhibitors on the mechanisms of polymerization. Furthermore, a number of important phenomena, unique structures, and novel properties may exist during gas-phase and cluster polymerization. In this regime, the structure of the growing polymer may change dramatically and the rate coefficient may vary significantly upon the addition of a single molecule of the monomer. These changes would be reflected in the properties of the oligomers deposited from the gas phase. At low pressures, cationic and radical cationic polymerizations may proceed in the gas phase through elimination reactions. In the same systems at high pressure, however, the ionic intermediates may be stabilized, and addition without elimination may occur. In isolated van der Waals clusters of monomer molecules, sequential polymerization with several condensation steps can occur on a time scale of a few microseconds following the ionization of the gas-phase cluster. The cluster reactions, which bridge gas-phase and condensed-phase chemistry, allow examination of the effects of controlled states of aggregation. This Account describes several examples of gas-phase and cluster polymerization studies where the most significant results can be summarized as follows: (1) The carbocation polymerization of isobutene shows slower rates with increasing polymerization steps resulting from entropy barriers, which could explain the need for low temperatures for the efficient propagation of high molecular weight polymers. (2) Radical cation polymerization of propene can be initiated by partial charge transfer from an ionized aromatic molecule such as benzene coupled with covalent condensation of the associated propene molecules. This novel mechanism leads exclusively to the formation of propene oligomer ions and avoids other competitive products. (3) Structural information

Two-phase turbine engines. [using gas-liquid mixture accelerated in nozzles

NASA Technical Reports Server (NTRS)

Elliott, D. G.; Hays, L. G.

1976-01-01

A description is given of a two-phase turbine which utilizes a uniform mixture of gas and liquid accelerated in nozzles of the types reported by Elliott and Weinberg (1968). The mixture acts directly on an axial flow or tangential impulse turbine or is separated into gas and liquid streams which operate separately on a gas turbine and a hydraulic turbine. The basic two-phase cycles are examined, taking into account working fluids, aspects of nozzle expansion, details of turbine cycle operation, and the effect of mixture ratio variation. Attention is also given to two-phase nozzle efficiency, two-phase turbine operating characteristics and efficiencies, separator turbines, and impulse turbine experiments.

C-terminal peptide extension via gas-phase ion/ion reactions

PubMed Central

Peng, Zhou; McLuckey, Scott A.

2015-01-01

The formation of peptide bonds is of great importance from both a biological standpoint and in routine organic synthesis. Recent work from our group demonstrated the synthesis of peptides in the gas-phase via ion/ion reactions with sulfo-NHS reagents, which resulted in conjugation of individual amino acids or small peptides to the N-terminus of an existing ‘anchor’ peptide. Here, we demonstrate a complementary approach resulting in the C-terminal extension of peptides. Individual amino acids or short peptides can be prepared as reagents by incorporating gas phase-labile protecting groups to the reactive C-terminus and then converting the N-terminal amino groups to the active ketenimine reagent. Gas-phase ion/ion reactions between the anionic reagents and doubly protonated “anchor” peptide cations results in extension of the “anchor” peptide with new amide bond formation at the C-terminus. We have demonstrated that ion/ion reactions can be used as a fast, controlled, and efficient means for C-terminal peptide extension in the gas phase. PMID:26640400

Regioselectivity of pyridine deprotonation in the gas phase.

PubMed

Schafman, Bonnie S; Wenthold, Paul G

2007-03-02

The regioselective deprotonation of pyridine in the gas phase has been investigated by using chemical reactivity studies. The mixture of regioisomers, trapped as carboxylates, formed in an equilibrium mixture is determined to result from 70-80% deprotonation in the 4-position, and 20-30% deprotonation at the 3-position. The ion formed by deprotonation in the 2-position is not measurably deprotonated at equilibrium because the ion is destabilized by lone-pair repulsion. From the composition of the mixture, the gas-phase acidities (DeltaH degrees acid) at the 4-, 3-, and 2-positions are determined to be 389.9 +/- 2.0, 391.2-391.5, and >391.5 kcal/mol, respectively. The relative acidities of the 4- and 3-positions are explained by using Hammett-Taft parameters, derived by using the measured gas-phase acidities of pyridine carboxylic acids. The values of sigmaF and sigmaR are -0.18 and 0.74, respectively, showing the infused nitrogen in pyridine to have a strong pi electron-withdrawing effect, but with little sigma-inductive effect.

Investigation of Bose Condensation in Ideal Bose Gas Trapped under Generic Power Law Potential in d Dimension

NASA Astrophysics Data System (ADS)

Mehedi Faruk, Mir; Sazzad Hossain, Md.; Muktadir Rahman, Md.

2016-02-01

The changes in characteristics of Bose condensation of ideal Bose gas due to an external generic power law potential U=\\sumi=1dci\\vert xi/ai\\vertni are studied carefully. Detailed calculation of Kim et al. (J. Phys. Condens. Matter 11 (1999) 10269) yielded the hierarchy of condensation transitions with changing fractional dimensionality. In this manuscript, some theorems regarding specific heat at constant volume CV are presented. Careful examination of these theorems reveal the existence of hidden hierarchy of the condensation transition in trapped systems as well.

Fluctuating ideal-gas lattice Boltzmann method with fluctuation dissipation theorem for nonvanishing velocities.

PubMed

Kaehler, G; Wagner, A J

2013-06-01

Current implementations of fluctuating ideal-gas descriptions with the lattice Boltzmann methods are based on a fluctuation dissipation theorem, which, while greatly simplifying the implementation, strictly holds only for zero mean velocity and small fluctuations. We show how to derive the fluctuation dissipation theorem for all k, which was done only for k=0 in previous derivations. The consistent derivation requires, in principle, locally velocity-dependent multirelaxation time transforms. Such an implementation is computationally prohibitively expensive but, with a small computational trick, it is feasible to reproduce the correct FDT without overhead in computation time. It is then shown that the previous standard implementations perform poorly for non vanishing mean velocity as indicated by violations of Galilean invariance of measured structure factors. Results obtained with the method introduced here show a significant reduction of the Galilean invariance violations.

Gas and particulate phase products from the ozonolysis of acenaphthylene

NASA Astrophysics Data System (ADS)

Riva, Matthieu; Healy, Robert M.; Tomaz, Sophie; Flaud, Pierre-Marie; Perraudin, Emilie; Wenger, John C.; Villenave, Eric

2016-10-01

Polycyclic aromatic hydrocarbons (PAHs) are recognized as important secondary organic aerosol (SOA) precursors in the urban atmosphere. In this work, the gas-phase ozonolysis of acenaphthylene was investigated in an atmospheric simulation chamber using a proton transfer reaction time-of-flight-mass spectrometer (PTR-TOF-MS) and an aerosol time-of-flight-mass spectrometer (ATOFMS) for on-line characterization of the oxidation products in the gas and particle phases, respectively. SOA samples were also collected on filters and analyzed by ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) and gas chromatography/electron impact ionization-mass spectrometry (GC/EI-MS). The major gas-phase products included a range of oxygenated naphthalene derivatives such as 1,8-naphthalic anhydride, naphthalene 1,8-dicarbaldehyde and naphthaldehyde, as well as a secondary ozonide. Possible reaction mechanisms are proposed for the formation of these products and favoured pathways have been suggested. Many of these products were also found in the particle phase along with a range of oligomeric compounds. The same range of gas and particle phase products was observed in the presence and absence of excess cyclohexane, an OH scavenger, indicating that OH radical production from the ozonolysis of acenaphthylene is negligible. SOA yields in the range 23-37% were determined and indicate that acenaphthylene ozonolysis may contribute to part of the SOA observed in urban areas.

Non-ideal magnetohydrodynamics on a moving mesh

NASA Astrophysics Data System (ADS)

Marinacci, Federico; Vogelsberger, Mark; Kannan, Rahul; Mocz, Philip; Pakmor, Rüdiger; Springel, Volker

2018-05-01

In certain astrophysical systems, the commonly employed ideal magnetohydrodynamics (MHD) approximation breaks down. Here, we introduce novel explicit and implicit numerical schemes of ohmic resistivity terms in the moving-mesh code AREPO. We include these non-ideal terms for two MHD techniques: the Powell 8-wave formalism and a constrained transport scheme, which evolves the cell-centred magnetic vector potential. We test our implementation against problems of increasing complexity, such as one- and two-dimensional diffusion problems, and the evolution of progressive and stationary Alfvén waves. On these test problems, our implementation recovers the analytic solutions to second-order accuracy. As first applications, we investigate the tearing instability in magnetized plasmas and the gravitational collapse of a rotating magnetized gas cloud. In both systems, resistivity plays a key role. In the former case, it allows for the development of the tearing instability through reconnection of the magnetic field lines. In the latter, the adopted (constant) value of ohmic resistivity has an impact on both the gas distribution around the emerging protostar and the mass loading of magnetically driven outflows. Our new non-ideal MHD implementation opens up the possibility to study magneto-hydrodynamical systems on a moving mesh beyond the ideal MHD approximation.

Analysis of first and second order binary quantized digital phase-locked loops for ideal and white Gaussian noise inputs

NASA Technical Reports Server (NTRS)

Blasche, P. R.

1980-01-01

Specific configurations of first and second order all digital phase locked loops are analyzed for both ideal and additive white gaussian noise inputs. In addition, a design for a hardware digital phase locked loop capable of either first or second order operation is presented along with appropriate experimental data obtained from testing of the hardware loop. All parameters chosen for the analysis and the design of the digital phase locked loop are consistent with an application to an Omega navigation receiver although neither the analysis nor the design are limited to this application.

Gas-phase kinetics modifies the CCN activity of a biogenic SOA.

PubMed

Vizenor, A E; Asa-Awuku, A A

2018-02-28

Our current knowledge of cloud condensation nuclei (CCN) activity and the hygroscopicity of secondary organic aerosol (SOA) depends on the particle size and composition, explicitly, the thermodynamic properties of the aerosol solute and subsequent interactions with water. Here, we examine the CCN activation of 3 SOA systems (2 biogenic single precursor and 1 mixed precursor SOA system) in relation to gas-phase decay. Specifically, the relationship between time, gas-phase precursor decay and CCN activity of 100 nm SOA is studied. The studied SOA systems exhibit a time-dependent growth of CCN activity at an instrument supersaturation of ∼0.2%. As such, we define a critical activation time, t 50 , above which a 100 nm SOA particle will activate. The critical activation time for isoprene, longifolene and a mixture of the two precursor SOA is 2.01 hours, 2.53 hours and 3.17 hours, respectively. The activation times are then predicted with gas-phase kinetic data inferred from measurements of precursor decay. The gas-phase prediction of t 50 agrees well with CCN measured t 50 (within 0.05 hours of the actual critical times) and suggests that the gas-to-particle phase partitioning may be more significant for SOA CCN prediction than previously thought.

First steps towards a gas-phase acidity ladder for derivatized fullerene dications

NASA Astrophysics Data System (ADS)

Petrie, Simon; Javahery, Gholamreza; Bohme, Diethard K.

1993-03-01

C2+60 can be derivatized by gas-phase ion/molecule reactions with polar hydrogen-bearing molecules. The adduct dications so produced may then undergo proton transfer to neutrals. The occurrence or absence of proton transfer as a secondary process gives information on the gas-phase acidity of the dicationic species C60·(XH)2+in. We have performed studies using a selected-ion flow tube at 294 ± 2 K and 0.35 ± 0.01 Torr, and have used observed reactivity of such dicationic fullerene adducts to determine upper or lower limits to their apparent and absolute gas-phase acidities. We present also a rationale for assessing the proton-transfer reactivity of dications via the apparent gas-phase acidity of these species, rather than the traditional use of gas-phase basicities or proton affinities. We propose that further studies of proton transfer from polycharged fullerene adducts may provide considerable useful information to model the reactivity of polyprotonated proteins and other large molecular polycatiions which can now be produced by techniques such as electrospray ionization.

Processes forming Gas, Tar, and Coke in Cellulose Gasification from Gas-Phase Reactions of Levoglucosan as Intermediate.

PubMed

Fukutome, Asuka; Kawamoto, Haruo; Saka, Shiro

2015-07-08

The gas-phase pyrolysis of levoglucosan (LG), the major intermediate species during cellulose gasification, was studied experimentally over the temperature range of 400-900 °C. Gaseous LG did not produce any dehydration products, which include coke, furans, and aromatic substances, although these are characteristic products of the pyrolysis of molten LG. Alternatively, at >500 °C, gaseous LG produced only fragmentation products, such as noncondensable gases and condensable C1 -C3 fragments, as intermediates during noncondensable gas formation. Therefore, it was determined that secondary reactions of gaseous LG can result in the clean (tar- and coke-free) gasification of cellulose. Cooling of the remaining LG in the gas phase caused coke formation by the transition of the LG to the molten state. The molecular mechanisms that govern the gas- and molten-phase reactions of LG are discussed in terms of the acid catalyst effect of intermolecular hydrogen bonding to promote the molten-phase dehydration reactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel stationary phases based on asphaltenes for gas chromatography.

PubMed

Boczkaj, Grzegorz; Momotko, Malwina; Chruszczyk, Dorota; Przyjazny, Andrzej; Kamiński, Marian

2016-07-01

We present the results of investigations on the possibility of the application of the asphaltene fraction isolated from the oxidized residue from vacuum distillation of crude oil as a stationary phase for gas chromatography. The results of the investigation revealed that the asphaltene stationary phases can find use for the separation of a wide range of volatile organic compounds. The experimental values of Rohrschneider/McReynolds constants characterize the asphaltenes as stationary phases of medium polarity and selectivity similar to commercially available phases based on alkyl phthalates. Isolation of asphaltenes from the material obtained under controlled process conditions allows the production of a stationary phase having reproducible sorption properties and chromatographic columns having the same selectivity. Unique selectivity and high thermal stability make asphaltenes attractive as a material for stationary phases for gas chromatography. A low production cost from a readily available raw material (oxidized petroleum bitumens) is an important economic factor in case of application of the asphaltene stationary phases for preparative and process separations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

EPA GAS PHASE CHEMISTRY CHAMBER STUDIES

EPA Science Inventory

Gas-phase smog chamber experiments are being performed at EPA in order to evaluate a number of current chemical mechanisms for inclusion in EPA regulatory and research models. The smog chambers are 9000 L in volume and constructed of 2-mil teflon film. One of the chambers is co...

Fischer Indole Synthesis in the Gas Phase, the Solution Phase, and at the Electrospray Droplet Interface.

PubMed

Bain, Ryan M; Ayrton, Stephen T; Cooks, R Graham

2017-07-01

Previous reports have shown that reactions occurring in the microdroplets formed during electrospray ionization can, under the right conditions, exhibit significantly greater rates than the corresponding bulk solution-phase reactions. The observed acceleration under electrospray ionization could result from a solution-phase, a gas-phase, or an interfacial reaction. This study shows that a gas-phase ion/molecule (or ion/ion) reaction is not responsible for the observed rate enhancement in the particular case of the Fischer indole synthesis. The results show that the accelerated reaction proceeds in the microdroplets, and evidence is provided that an interfacial process is involved. Graphical Abstract .

Concurrence of aqueous and gas phase contamination of groundwater in the Wattenberg oil and gas field of northern Colorado.

PubMed

Li, Huishu; Son, Ji-Hee; Carlson, Kenneth H

2016-01-01

The potential impact of rapid development of unconventional oil and natural gas resources using hydraulic fracturing and horizontal drilling on regional groundwater quality has received significant attention. Major concerns are methane or oil/gas related hydrocarbon (such as TPHs, BTEX including benzene, toluene, ethybenzene and xylene) leaks into the aquifer due to the failure of casing and/or stray gas migration. Previously, we investigated the relationship between oil and gas activity and dissolved methane concentration in a drinking water aquifer with the major finding being the presence of thermogenic methane contamination, but did not find detectable concentrations of TPHs or BTEX. To understand if aqueous and gas phases from the producing formation were transported concurrently to drinking water aquifers without the presence of oil/gas related hydrocarbons, the ionic composition of three water groups was studied: (1) uncontaminated deep confined aquifer, (2) suspected contaminated groundwater - deep confined aquifer containing thermogenic methane, and (3) produced water from nearby oil and gas wells that would represent aqueous phase contaminants. On the basis of quantitative and spatial analysis, we identified that the "thermogenic methane contaminated" groundwater did not have similarities to produced water in terms of ionic character (e.g. Cl/TDS ratio), but rather to the "uncontaminated" groundwater. The analysis indicates that aquifer wells with demonstrated gas phase contamination have not been contacted by an aqueous phase from oil and gas operations according to the methodology we use in this study and the current groundwater quality data from COGCC. However, the research does not prove conclusively that this the case. The results may provide insight on contamination mechanisms since improperly sealed well casing may result in stray gas but not aqueous phase transport. Copyright © 2015 Elsevier Ltd. All rights reserved.

Harvesting Hydrogen Gas from Air Pollutants with an Unbiased Gas Phase Photoelectrochemical Cell.

PubMed

Verbruggen, Sammy W; Van Hal, Myrthe; Bosserez, Tom; Rongé, Jan; Hauchecorne, Birger; Martens, Johan A; Lenaerts, Silvia

2017-04-10

The concept of an all-gas-phase photoelectrochemical (PEC) cell producing hydrogen gas from volatile organic contaminated gas and light is presented. Without applying any external bias, organic contaminants are degraded and hydrogen gas is produced in separate electrode compartments. The system works most efficiently with organic pollutants in inert carrier gas. In the presence of oxygen, the cell performs less efficiently but still significant photocurrents are generated, showing the cell can be run on organic contaminated air. The purpose of this study is to demonstrate new application opportunities of PEC technology and to encourage further advancement toward PEC remediation of air pollution with the attractive feature of simultaneous energy recovery and pollution abatement. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational-hydrodynamic studies of the Noh compressible flow problem using non-ideal equations of state

NASA Astrophysics Data System (ADS)

Honnell, Kevin; Burnett, Sarah; Yorke, Chloe'; Howard, April; Ramsey, Scott

2017-06-01

The Noh problem is classic verification problem in the field of compressible flows. Simple to conceptualize, it is nonetheless difficult for numerical codes to predict correctly, making it an ideal code-verification test bed. In its original incarnation, the fluid is a simple ideal gas; once validated, however, these codes are often used to study highly non-ideal fluids and solids. In this work the classic Noh problem is extended beyond the commonly-studied polytropic ideal gas to more realistic equations of state (EOS) including the stiff gas, the Nobel-Abel gas, and the Carnahan-Starling hard-sphere fluid, thus enabling verification studies to be performed on more physically-realistic fluids. Exact solutions are compared with numerical results obtained from the Lagrangian hydrocode FLAG, developed at Los Alamos. For these more realistic EOSs, the simulation errors decreased in magnitude both at the origin and at the shock, but also spread more broadly about these points compared to the ideal EOS. The overall spatial convergence rate remained first order.

Interferograms, schlieren, and shadowgraphs constructed from real- and ideal-gas, two- and three-dimensional computed flowfields

NASA Technical Reports Server (NTRS)

Yates, Leslie A.

1993-01-01

The construction of interferograms, schlieren, and shadowgraphs from computed flowfield solutions permits one-to-one comparisons of computed and experimental results. A method of constructing these images from both ideal- and real-gas, two and three-dimensional computed flowfields is described. The computational grids can be structured or unstructured, and multiple grids are an option. Constructed images are shown for several types of computed flows including nozzle, wake, and reacting flows; comparisons to experimental images are also shown. In addition, th sensitivity of these images to errors in the flowfield solution is demonstrated, and the constructed images can be used to identify problem areas in the computations.

Interferograms, Schlieren, and Shadowgraphs Constructed from Real- and Ideal-Gas, Two- and Three-Dimensional Computed Flowfields

NASA Technical Reports Server (NTRS)

Yates, Leslie A.

1992-01-01

The construction of interferograms, schlieren, and shadowgraphs from computed flowfield solutions permits one-to-one comparisons of computed and experimental results. A method for constructing these images from both ideal- and real-gas, two- and three-dimensional computed flowfields is described. The computational grids can be structured or unstructured, and multiple grids are an option. Constructed images are shown for several types of computed flows including nozzle, wake, and reacting flows; comparisons to experimental images are also shown. In addition, the sensitivity of these images to errors in the flowfield solution is demonstrated, and the constructed images can be used to identify problem areas in the computations.

Ambient observations of dimers from terpene oxidation in the gas phase: Implications for new particle formation and growth: Ambient Observations of Gas-Phase Dimers

DOE PAGES

Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Yli-Juuti, Taina; ...

2017-03-28

Here, we present ambient observations of dimeric monoterpene oxidation products (C 16–20H yO 6–9) in gas and particle phases in the boreal forest in Finland in spring 2013 and 2014, detected with a chemical ionization mass spectrometer with a filter inlet for gases and aerosols employing acetate and iodide as reagent ions. These are among the first online dual-phase observations of such dimers in the atmosphere. Estimated saturation concentrations of 10 -15 to 10 -6 µg m -3 (based on observed thermal desorptions and group-contribution methods) and measured gas-phase concentrations of 10 -3 to 10 -2 µg m -3 (~10more » 6–10 7 molecules cm -3) corroborate a gas-phase formation mechanism. Regular new particle formation (NPF) events allowed insights into the potential role dimers may play for atmospheric NPF and growth. The observationally constrained Model for Acid-Base chemistry in NAnoparticle Growth indicates a contribution of ~5% to early stage particle growth from the ~60 gaseous dimer compounds.« less

Ambient observations of dimers from terpene oxidation in the gas phase: Implications for new particle formation and growth: Ambient Observations of Gas-Phase Dimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Yli-Juuti, Taina

Here, we present ambient observations of dimeric monoterpene oxidation products (C 16–20H yO 6–9) in gas and particle phases in the boreal forest in Finland in spring 2013 and 2014, detected with a chemical ionization mass spectrometer with a filter inlet for gases and aerosols employing acetate and iodide as reagent ions. These are among the first online dual-phase observations of such dimers in the atmosphere. Estimated saturation concentrations of 10 -15 to 10 -6 µg m -3 (based on observed thermal desorptions and group-contribution methods) and measured gas-phase concentrations of 10 -3 to 10 -2 µg m -3 (~10more » 6–10 7 molecules cm -3) corroborate a gas-phase formation mechanism. Regular new particle formation (NPF) events allowed insights into the potential role dimers may play for atmospheric NPF and growth. The observationally constrained Model for Acid-Base chemistry in NAnoparticle Growth indicates a contribution of ~5% to early stage particle growth from the ~60 gaseous dimer compounds.« less

Reticulated Vitreous Carbon Electrodes for Gas Phase Pulsed Corona Reactors.

DTIC Science & Technology

1999-01-01

AFRL-ML-TY-TP-1999-4546 RETICULATED VITREOUS CARBON ELECTRODES FOR GAS PHASE PULSED CORONA REACTORS B.R. LOCKE M. KIRKPATRICK H. HANSON W.C...SUBTITLE Reticulated Vitreous Carbon Electrodes for Gas Phase Pulsed Corona Reactors 6. AUTHOR(S) B.R. Locke, M. Kirkpatrick, H. Hanson, and W.C. Finney...incorporating reticulated vitreous carbon electrodes is demonstrated to be effective for the removal of nitrogen oxides from synthetic air mixtures

The effect of hydrate promoters on gas uptake.

PubMed

Xu, Chun-Gang; Yu, Yi-Song; Ding, Ya-Long; Cai, Jing; Li, Xiao-Sen

2017-08-16

Gas hydrate technology is considered as a promising technology in the fields of gas storage and transportation, gas separation and purification, seawater desalination, and phase-change thermal energy storage. However, to date, the technology is still not commercially used mainly due to the low gas hydrate formation rate and the low gas uptake. In this study, the effect of hydrate promoters on gas uptake was systematically studied and analyzed based on hydrate-based CH 4 storage and CO 2 capture from CO 2 /H 2 gas mixture experiments. Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and gas chromatography (GC) were employed to analyze the microstructures and gas compositions. The results indicate that the effect of the hydrate promoter on the gas uptake depends on the physical and chemical properties of the promoter and gas. A strong polar ionic promoter is not helpful towards obtaining the ideal gas uptake because a dense hydrate layer is easily formed at the gas-liquid interface, which hinders gas diffusion from the gas phase to the bulk solution. For a weak polar or non-polar promoter, the gas uptake depends on the dissolution characteristics among the different substances in the system. The lower the mutual solubility among the substances co-existing in the system, the higher the independence among the substances in the system; this is so that each phase has an equal chance to occupy the hydrate cages without or with small interactions, finally leading to a relatively high gas uptake.

Exploring the Ideal Gas Law through a Quantitative Gasometric Analysis of Nitrogen Produced by the Reaction of Sodium Nitrite with Sulfamic Acid

ERIC Educational Resources Information Center

Yu, Anne

2010-01-01

The gasometric analysis of nitrogen produced in a reaction between sodium nitrite, NaNO[superscript 2], and sulfamic acid, H(NH[superscript 2])SO[superscript 3], provides an alternative to more common general chemistry experiments used to study the ideal gas law, such as the experiment in which magnesium is reacted with hydrochloric acid. This…

DIPPR Project 871 For 1995 - Thermodynamic Properties and Ideal-Gas Enthalpies of Formation for Methyl Benzoate, Ethyl Benzoate, (R)-(+)-Limonene, Tert-Amyl Methyl Ether, Trans-Crotonaldehyde, and

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steele, W.V.

2002-07-01

Ideal-gas enthalpies of formation of methyl benzoate, ethyl benzoate, (R)-(+)-limonene, tert-amyl methyl ether, trans-crotonaldehyde, and diethylene glycol are reported. The standard energy of combustion and hence standard enthalpy of formation of each compound in the liquid phase has been measured using an oxygen rotating-bomb calorimeter without rotation. Vapor pressures were measured to a pressure limit of 270 kPa or the lower decomposition point for each of the six compounds using a twin ebulliometric apparatus. Liquid-phase densities along the saturation line were measured for each compound over a range of temperature (ambient to a maximum of 548 K). A differential scanningmore » calorimeter was used to measure two-phase (liquid + vapor) heat capacities for each compound in the temperature region ambient to the critical temperature or lower decomposition point. For methyl benzoate and tert-amyl methyl ether, critical temperatures and critical densities were determined from the DSC results and corresponding critical pressures derived from the fitting procedures. Fitting procedures were used to derive critical temperatures, critical pressures, and critical densities for each of the remaining compounds. The results of the measurements were combined to derive a series of thermophysical properties including critical temperature, critical density, critical pressure, acentric factor, enthalpies of vaporization (restricted to within {+-}50 K of the temperature region of the experimentally determined vapor pressures), and heat capacities along the saturation line. Wagner-type vapor-pressure equations were derived for each compound. All measured and derived values were compared with those obtained in a search of the literature. Recommended critical parameters are listed for each of the compounds studied. Group-additivity parameters, useful in the application of the Benson gas-phase group-contribution correlations, were derived.« less

Investigating gas-phase defect formation in late-stage solidification using a novel phase-field crystal alloy model

NASA Astrophysics Data System (ADS)

Wang, Nan; Smith, Nathan; Provatas, Nikolas

2017-09-01

We study late-stage solidification and the associated formation of defects in alloy materials using a novel model based on the phase-field-crystal technique. It is shown that our model successfully captures several important physical phenomena that occur in the late stages of solidification, including solidification shrinkage, liquid cavitation and microsegregation, all in a single framework. By examining the interplay of solidification shrinkage and solute segregation, this model reveals that the formation of gas pore defects at the late stage of solidification can lead to nucleation of second phase solid particles due to solute enrichment in the eutectic liquid driven by gas-phase nucleation and growth. We also predict a modification of the Gulliver-Scheil equation in the presence of gas pockets in confined liquid pools.

Gravitational Thermodynamics for Interstellar Gas and Weakly Degenerate Quantum Gas

NASA Astrophysics Data System (ADS)

Zhu, Ding Yu; Shen, Jian Qi

2016-03-01

The temperature distribution of an ideal gas in gravitational fields has been identified as a longstanding problem in thermodynamics and statistical physics. According to the principle of entropy increase (i.e., the principle of maximum entropy), we apply a variational principle to the thermodynamical entropy functional of an ideal gas and establish a relationship between temperature gradient and gravitational field strength. As an illustrative example, the temperature and density distributions of an ideal gas in two simple but typical gravitational fields (i.e., a uniform gravitational field and an inverse-square gravitational field) are considered on the basis of entropic and hydrostatic equilibrium conditions. The effect of temperature inhomogeneity in gravitational fields is also addressed for a weakly degenerate quantum gas (e.g., Fermi and Bose gas). The present gravitational thermodynamics of a gas would have potential applications in quantum fluids, e.g., Bose-Einstein condensates in Earth’s gravitational field and the temperature fluctuation spectrum in cosmic microwave background radiation.

Effect of initial densities in the lattice Boltzmann model for non-ideal fluid with curved interface

NASA Astrophysics Data System (ADS)

Gong, Jiaming; Oshima, Nobuyuki

2017-06-01

The effect of initial densities in a free energy based two-phase-flow lattice Boltzmann method for non-ideal fluids with a curved interface was investigated in the present work. To investigate this effect, the initial densities in the liquid and gas phases coming from the saturation points and the equilibrium state were adopted in the simulation of a static droplet in an open and a closed system. For the purpose of simplicity and easier comparison, the closed system is fabricated by the implementation of the periodic boundary condition at the inlet and outlet of a gas channel, and the open system is fabricated by the implementation of a constant flux boundary condition at the inlet and a free-out boundary condition at the outlet of the same gas channel. By comparing the simulation results from the two types of initial densities in the open and closed systems, it is proven that the commonly used saturation initial densities setting is the reason for droplet mass and volume variation which occurred in the simulation, particularly in the open system with a constant flux boundary condition. Such problems are believed to come from the curvature effect of the surface tension and can be greatly reduced by adopting the initial densities in the two phases from equilibrium state.

Gas purification in the dense phase at the CATS terminal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Openshaw, P.J.; Carnell, P.J.H.; Rhodes, E.F.

The purification and transportation of natural gas at very high pressures can help to minimize the capital cost of pipelines and processing equipment. However, complex mixtures of hydrocarbons undergo unusual phase changes, such as retrograde condensation, as the temperature and pressure are altered. The Central Area Transmission System (CATS) is a joint venture of Amoci, BG, Amerada Hess, Phillips, Agip and Fina operated by Amoco on behalf of the owners. The design of the CATS terminal has provided an interesting processing challenge. The terminal receives a total of 1.6 Bscf/d of rich gas from a number of offshore fields. Allmore » are relatively sweet but the small amounts of H{sub 2}S and Hg are removed. Fixed bed technology was selected as the most economic purification process, while minimizing hydrocarbon loss and operator involvement. Conventionally, the raw gas would be split into the different hydrocarbon fractions and each would be processed separately. This would require the installation of a large number of reactors. A more elegant solution is to treat the gas on arrival at the terminal in the dense phase. This option raised questions around whether a fixed bed would be prone to fouling, could the pressure drop be kept low enough to avoid phase separation and would inadvertent wetting by condensation cause problems. Details are given of the test work carried out to prove the viability of using fixed bed technology for dense phase gas processing, the eventual design adopted and the performance over the first year of service.« less

Computer code for gas-liquid two-phase vortex motions: GLVM

NASA Technical Reports Server (NTRS)

Yeh, T. T.

1986-01-01

A computer program aimed at the phase separation between gas and liquid at zero gravity, induced by vortex motion, is developed. It utilizes an explicit solution method for a set of equations describing rotating gas-liquid flows. The vortex motion is established by a tangential fluid injection. A Lax-Wendroff two-step (McCormack's) numerical scheme is used. The program can be used to study the fluid dynamical behavior of the rotational two-phase fluids in a cylindrical tank. It provides a quick/easy sensitivity test on various parameters and thus provides the guidance for the design and use of actual physical systems for handling two-phase fluids.

Energy Fluctuation of Ideal Fermi Gas Trapped under Generic Power Law Potential U=\\sum_{i=1}^{d} c_i\\vert x_{i}/a_{i}\\vert^{n_{i} } in d Dimensions

NASA Astrophysics Data System (ADS)

Mir, Mehedi Faruk; Muktadir Rahman, Md.; Dwaipayan, Debnath; Sakhawat Hossain Himel, Md.

2016-04-01

Energy fluctuation of ideal Fermi gas trapped under generic power law potential U=\\sumi=1d ci \\vertxi/ai \\vert n_i has been calculated in arbitrary dimensions. Energy fluctuation is scrutinized further in the degenerate limit μ ≫ KBT with the help of Sommerfeld expansion. The dependence of energy fluctuation on dimensionality and power law potential is studied in detail. Most importantly our general result can not only exactly reproduce the recently published result regarding free and harmonically trapped ideal Fermi gas in d = 3 but also can describe the outcome for any power law potential in arbitrary dimension.

Photoinduced Processes in Cobalt-Complexes: Condensed Phase and Gas Phase

NASA Astrophysics Data System (ADS)

Rupp, F.; Chevalier, K.; Wolf, M. M. N.; Krüger, H.-J.; Wüllen, C. v.; Nosenko, Y.; Niedner-Schatteburg, Y.; Riehn, C.; Diller, R.

2013-03-01

Femtosecond time-resolved, steady-state spectroscopic methods and quantum chemical calculations are employed to study ultrafast photoinduced processes in [Co(III)-(L-N4Me2)(dbc)](BPh4) and [Co(II)-(L-N4tBu2)(dbsq)](B(p-C6H4Cl)4) and to characterise the transient redox- and spin-states in condensed and gas phase.

Gas Phase Organophosphate Detection Using Enzymes Encapsulated Within Peptide Nanotubes

DTIC Science & Technology

2014-03-27

as gas and liquid chromatography, although very sensitive and reliable, have disadvantages. The US Air Force currently uses a field portable gas...biosensors to detect OPCs in liquid (Park et al., 2011; Stevens, 2012) and gas (Baker, 2013) phases. Detection is based upon a redox reaction... injecting a known volume of gas saturated at room temperature with malathion (vapor pressure = 25 ppbv), into a 40 ml vial purged with nitrogen at constant

Novel characterization of the aerosol and gas-phase composition of aerosolized jet fuel.

PubMed

Tremblay, Raphael T; Martin, Sheppard A; Fisher, Jeffrey W

2010-04-01

Few robust methods are available to characterize the composition of aerosolized complex hydrocarbon mixtures. The difficulty in separating the droplets from their surrounding vapors and preserving their content is challenging, more so with fuels, which contain hydrocarbons ranging from very low to very high volatility. Presented here is a novel method that uses commercially available absorbent tubes to measure a series of hydrocarbons in the vapor and droplets from aerosolized jet fuels. Aerosol composition and concentrations were calculated from the differential between measured total (aerosol and gas-phase) and measured gas-phase concentrations. Total samples were collected directly, whereas gas-phase only samples were collected behind a glass fiber filter to remove droplets. All samples were collected for 1 min at 400 ml min(-1) and quantified using thermal desorption-gas chromatography-mass spectrometry. This method was validated for the quantification of the vapor and droplet content from 4-h aerosolized jet fuel exposure to JP-8 and S-8 at total concentrations ranging from 200 to 1000 mg/m(3). Paired samples (gas-phase only and total) were collected every approximately 40 min. Calibrations were performed with neat fuel to calculate total concentration and also with a series of authentic standards to calculate specific compound concentrations. Accuracy was good when compared to an online GC-FID (gas chromatography-flame ionization detection) technique. Variability was 15% or less for total concentrations, the sum of all gas-phase compounds, and for most specific compound concentrations in both phases. Although validated for jet fuels, this method can be adapted to other hydrocarbon-based mixtures.

Scaling analysis of gas-liquid two-phase flow pattern in microgravity

NASA Technical Reports Server (NTRS)

Lee, Jinho

1993-01-01

A scaling analysis of gas-liquid two-phase flow pattern in microgravity, based on the dominant physical mechanism, was carried out with the goal of predicting the gas-liquid two-phase flow regime in a pipe under conditions of microgravity. The results demonstrated the effect of inlet geometry on the flow regime transition. A comparison of the predictions with existing experimental data showed good agreement.

DEMONSTRATION BULLETIN: GAS-PHASE CHEMICAL REDUCTION - ECO LOGIC INTERNATIONAL, INC.

EPA Science Inventory

The patented Eco Logic Process employs a gas-phase reduction reaction of hydrogen with organic and chlorinated organic compounds at elevated temperatures to convert aqueous and oily hazardous contaminants into a hydrocarbon-rich gas product. After passing through a scrubber, the ...

Investigation of mucus transport in an idealized lung airway model using multiphase CFD analysis

NASA Astrophysics Data System (ADS)

Rajendran, Rahul; Banerjee, Arindam

2015-11-01

Mucus, a Bingham fluid is transported in the pulmonary airways by consistent beating of the cilia and exhibits a wide range of physical properties in response to the core air flow and various pathological conditions. A better understanding of the interfacial instability is required as it plays a crucial role in gas transport, mixing, mucus clearance and drug delivery. In the current study, mucus is modelled as a Newtonian fluid and the two phase gas-liquid flow in the airways is investigated using an inhomogeneous Eulerian-Eulerian approach. The complex interface between the phases is tracked using the conventional VOF (Volume of Fluid) method. Results from our CFD simulations which are performed in idealized single and double bifurcation geometries will be presented and the influence of airflow rate, mucus layer thickness, mucus viscosity, airway geometry (branching & diameter) and surface tension on mucus flow behavior will be discussed. Mean mucus layer thickness, pressure drop due to momentum transfer & increased airway resistance, mucus transport speed and the flow morphology will be compared to existing experimental and theoretical data.

3D motion picture of transparent gas flow by parallel phase-shifting digital holography

NASA Astrophysics Data System (ADS)

Awatsuji, Yasuhiro; Fukuda, Takahito; Wang, Yexin; Xia, Peng; Kakue, Takashi; Nishio, Kenzo; Matoba, Osamu

2018-03-01

Parallel phase-shifting digital holography is a technique capable of recording three-dimensional (3D) motion picture of dynamic object, quantitatively. This technique can record single hologram of an object with an image sensor having a phase-shift array device and reconstructs the instantaneous 3D image of the object with a computer. In this technique, a single hologram in which the multiple holograms required for phase-shifting digital holography are multiplexed by using space-division multiplexing technique pixel by pixel. We demonstrate 3D motion picture of dynamic and transparent gas flow recorded and reconstructed by the technique. A compressed air duster was used to generate the gas flow. A motion picture of the hologram of the gas flow was recorded at 180,000 frames/s by parallel phase-shifting digital holography. The phase motion picture of the gas flow was reconstructed from the motion picture of the hologram. The Abel inversion was applied to the phase motion picture and then the 3D motion picture of the gas flow was obtained.

Gas phase oxidation downstream of a catalytic combustor

NASA Technical Reports Server (NTRS)

Tien, J. S.; Anderson, D. N.

1979-01-01

Effect of the length available for gas-phase reactions downstream of the catalytic reactor on the emission of CO and unburned hydrocarbons was investigated. A premixed, prevaporized propane/air feed to a 12/cm/diameter catalytic/reactor test section was used. The catalytic reactor was made of four 2.5 cm long monolithic catalyst elements. Four water cooled gas sampling probes were located at positions between 0 and 22 cm downstream of the catalytic reactor. Measurements of unburned hydrocarbon, CO, and CO2 were made. Tests were performed with an inlet air temperature of 800 K, a reference velocity of 10 m/s, pressures of 3 and 600,000 Pa, and fuel air equivalence ratios of 0.14 to 0.24. For very lean mixtures, hydrocarbon emissions were high and CO continued to be formed downstream of the catalytic reactor. At the highest equivalence ratios tested, hydrocarbon levels were much lower and CO was oxidized to CO2 in the gas phase downstream. To achieve acceptable emissions, a downstream region several times longer than the catalytic reactor could be required.

Receptors useful for gas phase chemical sensing

DOEpatents

Jaworski, Justyn W; Lee, Seung-Wuk; Majumdar, Arunava; Raorane, Digvijay A

2015-02-17

The invention provides for a receptor, capable of binding to a target molecule, linked to a hygroscopic polymer or hydrogel; and the use of this receptor in a device for detecting the target molecule in a gaseous and/or liquid phase. The invention also provides for a method for detecting the presence of a target molecule in the gas phase using the device. In particular, the receptor can be a peptide capable of binding a 2,4,6-trinitrotoluene (TNT) or 2,4,-dinitrotoluene (DNT).

A numerical study of an axisymmetric two-phase jet with allowance for the after-combustion of particles in the slipstream

NASA Astrophysics Data System (ADS)

Gilinskii, M. M.; Stasenko, A. L.; Tolstov, V. N.

A model is proposed which describes the gas thermodynamics of a nonuniform ideal gas mixture containing an oxidizer and finely dispersed particles, with allowance made for heat transfer between the phases. The results of a numerical study are presented for a supersonic two-phase jet where initially uniform particles are first accelerated, then enter the slipstream, and disappear as a result of oxidation.

Semiphenomenological model for gas-liquid phase transitions.

PubMed

Benilov, E S; Benilov, M S

2016-03-01

We examine a rarefied gas with inter-molecular attraction. It is argued that the attraction force amplifies random density fluctuations by pulling molecules from lower-density regions into high-density regions and thus may give rise to an instability. To describe this effect, we use a kinetic equation where the attraction force is taken into account in a way similar to how electromagnetic forces in plasma are treated in the Vlasov model. It is demonstrated that the instability occurs when the temperature T is lower than a certain threshold value T(s) depending on the gas density. It is further shown that, even if T is only marginally lower than T(s), the instability generates clusters with density much higher than that of the gas. These results suggest that the instability should be interpreted as a gas-liquid phase transition, with T(s) being the temperature of saturated vapor and the high-density clusters representing liquid droplets.

Determination of gas & liquid two-phase flow regime transitions in wellbore annulus by virtual mass force coefficient when gas cut

NASA Astrophysics Data System (ADS)

Qu, Junbo; Yan, Tie; Sun, Xiaofeng; Chen, Ye; Pan, Yi

2017-10-01

With the development of drilling technology to deeper stratum, overflowing especially gas cut occurs frequently, and then flow regime in wellbore annulus is from the original drilling fluid single-phase flow into gas & liquid two-phase flow. By using averaged two-fluid model equations and the basic principle of fluid mechanics to establish the continuity equations and momentum conservation equations of gas phase & liquid phase respectively. Relationship between pressure and density of gas & liquid was introduced to obtain hyperbolic equation, and get the expression of the dimensionless eigenvalue of the equation by using the characteristic line method, and analyze wellbore flow regime to get the critical gas content under different virtual mass force coefficients. Results show that the range of equation eigenvalues is getting smaller and smaller with the increase of gas content. When gas content reaches the critical point, the dimensionless eigenvalue of equation has no real solution, and the wellbore flow regime changed from bubble flow to bomb flow. When virtual mass force coefficients are 0.50, 0.60, 0.70 and 0.80 respectively, the critical gas contents are 0.32, 0.34, 0.37 and 0.39 respectively. The higher the coefficient of virtual mass force, the higher gas content in wellbore corresponding to the critical point of transition flow regime, which is in good agreement with previous experimental results. Therefore, it is possible to determine whether there is a real solution of the dimensionless eigenvalue of equation by virtual mass force coefficient and wellbore gas content, from which we can obtain the critical condition of wellbore flow regime transformation. It can provide theoretical support for the accurate judgment of the annular flow regime.

Mixed Stationary Liquid Phases for Gas-Liquid Chromatography.

ERIC Educational Resources Information Center

Koury, Albert M.; Parcher, Jon F.

1979-01-01

Describes a laboratory technique for use in an undergraduate instrumental analysis course that, using the interpretation of window diagrams, prepares a mixed liquid phase column for gas-liquid chromatography. A detailed procedure is provided. (BT)

Calorimetry of a Bose–Einstein-condensed photon gas

PubMed Central

Damm, Tobias; Schmitt, Julian; Liang, Qi; Dung, David; Vewinger, Frank; Weitz, Martin; Klaers, Jan

2016-01-01

Phase transitions, as the condensation of a gas to a liquid, are often revealed by a discontinuous behaviour of thermodynamic quantities. For liquid helium, for example, a divergence of the specific heat signals the transition from the normal fluid to the superfluid state. Apart from liquid helium, determining the specific heat of a Bose gas has proven to be a challenging task, for example, for ultracold atomic Bose gases. Here we examine the thermodynamic behaviour of a trapped two-dimensional photon gas, a system that allows us to spectroscopically determine the specific heat and the entropy of a nearly ideal Bose gas from the classical high temperature to the Bose-condensed quantum regime. The critical behaviour at the phase transition is clearly revealed by a cusp singularity of the specific heat. Regarded as a test of quantum statistical mechanics, our results demonstrate a quantitative agreement with its predictions at the microscopic level. PMID:27090978

Importance of the gas phase role to the prediction of energetic material behavior: An experimental study

NASA Astrophysics Data System (ADS)

Ali, A. N.; Son, S. F.; Asay, B. W.; Sander, R. K.

2005-03-01

Various thermal (radiative, conductive, and convective) initiation experiments are performed to demonstrate the importance of the gas phase role in combustion modeling of energetic materials (EM). A previously published condensed phase model that includes a predicted critical irradiance above which ignition is not possible is compared to experimental laser ignition results for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6-trinitrotoluene (TNT). Experimental results conflict with the predicted critical irradiance concept. The failure of the model is believed to result from a misconception about the role of the gas phase in the ignition process of energetic materials. The model assumes that ignition occurs at the surface and that evolution of gases inhibits ignition. High speed video of laser ignition, oven cook-off and hot wire ignition experiments captures the ignition of HMX and TNT in the gas phase. A laser ignition gap test is performed to further evaluate the effect of gas phase laser absorption and gas phase disruption on the ignition process. Results indicate that gas phase absorption of the laser energy is probably not the primary factor governing the gas phase ignition observations. It is discovered that a critical gap between an HMX pellet and a salt window of 6mm±0.4mm exists below which ignition by CO2 laser is not possible at the tested irradiances of 29W /cm2 and 38W/cm2 for HMX ignition. These observations demonstrate that a significant disruption of the gas phase, in certain scenarios, will inhibit ignition, independent of any condensed phase processes. These results underscore the importance of gas phase processes and illustrate that conditions can exist where simple condensed phase models are inadequate to accurately predict the behavior of energetic materials.

A complete equation of state for non-ideal condensed phase explosives

NASA Astrophysics Data System (ADS)

Wilkinson, S. D.; Braithwaite, M.; Nikiforakis, N.; Michael, L.

2017-12-01

The objective of this work is to improve the robustness and accuracy of numerical simulations of both ideal and non-ideal explosives by introducing temperature dependence in mechanical equations of state for reactants and products. To this end, we modify existing mechanical equations of state to appropriately approximate the temperature in the reaction zone. Mechanical equations of state of the Mie-Grüneisen form are developed with extensions, which allow the temperature to be evaluated appropriately and the temperature equilibrium condition to be applied robustly. Furthermore, the snow plow model is used to capture the effect of porosity on the reactant equation of state. We apply the methodology to predict the velocity of compliantly confined detonation waves. Once reaction rates are calibrated for unconfined detonation velocities, simulations of confined rate sticks and slabs are performed, and the experimental detonation velocities are matched without further parameter alteration, demonstrating the predictive capability of our simulations. We apply the same methodology to both ideal (PBX9502, a high explosive with principal ingredient TATB) and non-ideal (EM120D, an ANE or ammonium nitrate based emulsion) explosives.

Freeze drying for gas chromatography stationary phase deposition

DOEpatents

Sylwester, Alan P [Livermore, CA

2007-01-02

The present disclosure relates to methods for deposition of gas chromatography (GC) stationary phases into chromatography columns, for example gas chromatography columns. A chromatographic medium is dissolved or suspended in a solvent to form a composition. The composition may be inserted into a chromatographic column. Alternatively, portions of the chromatographic column may be exposed or filled with the composition. The composition is permitted to solidify, and at least a portion of the solvent is removed by vacuum sublimation.

Device for two-dimensional gas-phase separation and characterization of ion mixtures

DOEpatents

Tang, Keqi [Richland, WA; Shvartsburg, Alexandre A [Richland, WA; Smith, Richard D [Richland, WA

2006-12-12

The present invention relates to a device for separation and characterization of gas-phase ions. The device incorporates an ion source, a field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer, an ion mobility spectrometry (IMS) drift tube, and an ion detector. In one aspect of the invention, FAIMS operating voltages are electrically floated on top of the IMS drift voltage. In the other aspect, the FAIMS/IMS interface is implemented employing an electrodynamic ion funnel, including in particular an hourglass ion funnel. The present invention improves the efficiency (peak capacity) and sensitivity of gas-phase separations; the online FAIMS/IMS coupling creates a fundamentally novel two-dimensional gas-phase separation technology with high peak capacity, specificity, and exceptional throughput.

Chemical studies of elements with Z ⩾ 104 in gas phase

NASA Astrophysics Data System (ADS)

Türler, Andreas; Eichler, Robert; Yakushev, Alexander

2015-12-01

Chemical investigations of superheavy elements in the gas-phase, i.e. elements with Z ≥ 104, allow assessing the influence of relativistic effects on their chemical properties. Furthermore, for some superheavy elements and their compounds quite unique gas-phase chemical properties were predicted. The experimental verification of these properties yields supporting evidence for a firm assignment of the atomic number. Prominent examples are the high volatility observed for HsO4 or the very weak interaction of Cn with gold surfaces. The unique properties of HsO4 were exploited to discover the doubly-magic even-even nucleus 270Hs and the new isotope 271Hs. The combination of kinematic pre-separation and gas-phase chemistry allowed gaining access to a new class of relatively fragile compounds, the carbonyl complexes of elements Sg through Mt. A not yet resolved issue concerns the interaction of Fl with gold surfaces. While competing experiments agree on the fact that Fl is a volatile element, there are discrepancies concerning its adsorption on gold surfaces with respect to its daughter Cn. The elucidation of these and other questions amounts to the fascination that gas-phase chemical investigations exert on current research at the extreme limits of chemistry today.

The Ultrafast Wolff Rearrangement in the Gas Phase

NASA Astrophysics Data System (ADS)

Steinbacher, Andreas; Roeding, Sebastian; Brixner, Tobias; Nuernberger, Patrick

The Wolff rearrangement of gas-phase 5-diazo Meldrum's acid is disclosed with femtosecond ion spectroscopy. Distinct differences are found for 267 nm and 200 nm excitation, the latter leading to even two ultrafast rearrangement reactions.

An investigation into the flow behavior of a single phase gas system and a two phase gas/liquid system in normal gravity with nonuniform heating from above

NASA Technical Reports Server (NTRS)

Disimile, Peter J.; Heist, Timothy J.

1990-01-01

The fluid behavior in normal gravity of a single phase gas system and a two phase gas/liquid system in an enclosed circular cylinder heated suddenly and nonuniformly from above was investigated. Flow visualization was used to obtain qualitative data on both systems. The use of thermochromatic liquid crystal particles as liquid phase flow tracers was evaluated as a possible means of simultaneously gathering both flow pattern and temperature gradient data for the two phase system. The results of the flow visualization experiments performed on both systems can be used to gain a better understanding of the behavior of such systems in a reduced gravity environment and aid in the verification of a numerical model of the system.

Ideal walking dynamics via a gauged NJL model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rantaharju, Jarno; Pica, Claudio; Sannino, Francesco

According to the ideal walking technicolor paradigm, large mass anomalous dimensions arise in gauged Nambu–Jona-Lasinio (NJL) models when the four-fermion coupling is sufficiently strong to induce spontaneous symmetry breaking in an otherwise conformal gauge theory. Therefore, we study the SU(2) gauged NJL model with two adjoint fermions using lattice simulations. The model is in an infrared conformal phase at small NJL coupling while it displays a chirally broken phase at large NJL couplings. In the infrared conformal phase, we find that the mass anomalous dimension varies with the NJL coupling, reaching γm ~ 1 close to the chiral symmetry breakingmore » transition, de facto making the present model the first explicit realization of the ideal walking scenario.« less

Ideal walking dynamics via a gauged NJL model

DOE PAGES

Rantaharju, Jarno; Pica, Claudio; Sannino, Francesco

2017-07-25

According to the ideal walking technicolor paradigm, large mass anomalous dimensions arise in gauged Nambu–Jona-Lasinio (NJL) models when the four-fermion coupling is sufficiently strong to induce spontaneous symmetry breaking in an otherwise conformal gauge theory. Therefore, we study the SU(2) gauged NJL model with two adjoint fermions using lattice simulations. The model is in an infrared conformal phase at small NJL coupling while it displays a chirally broken phase at large NJL couplings. In the infrared conformal phase, we find that the mass anomalous dimension varies with the NJL coupling, reaching γm ~ 1 close to the chiral symmetry breakingmore » transition, de facto making the present model the first explicit realization of the ideal walking scenario.« less

Flow-pattern identification and nonlinear dynamics of gas-liquid two-phase flow in complex networks.

PubMed

Gao, Zhongke; Jin, Ningde

2009-06-01

The identification of flow pattern is a basic and important issue in multiphase systems. Because of the complexity of phase interaction in gas-liquid two-phase flow, it is difficult to discern its flow pattern objectively. In this paper, we make a systematic study on the vertical upward gas-liquid two-phase flow using complex network. Three unique network construction methods are proposed to build three types of networks, i.e., flow pattern complex network (FPCN), fluid dynamic complex network (FDCN), and fluid structure complex network (FSCN). Through detecting the community structure of FPCN by the community-detection algorithm based on K -mean clustering, useful and interesting results are found which can be used for identifying five vertical upward gas-liquid two-phase flow patterns. To investigate the dynamic characteristics of gas-liquid two-phase flow, we construct 50 FDCNs under different flow conditions, and find that the power-law exponent and the network information entropy, which are sensitive to the flow pattern transition, can both characterize the nonlinear dynamics of gas-liquid two-phase flow. Furthermore, we construct FSCN and demonstrate how network statistic can be used to reveal the fluid structure of gas-liquid two-phase flow. In this paper, from a different perspective, we not only introduce complex network theory to the study of gas-liquid two-phase flow but also indicate that complex network may be a powerful tool for exploring nonlinear time series in practice.

Multi-Scale Morphological Analysis of Conductance Signals in Vertical Upward Gas-Liquid Two-Phase Flow

NASA Astrophysics Data System (ADS)

Lian, Enyang; Ren, Yingyu; Han, Yunfeng; Liu, Weixin; Jin, Ningde; Zhao, Junying

2016-11-01

The multi-scale analysis is an important method for detecting nonlinear systems. In this study, we carry out experiments and measure the fluctuation signals from a rotating electric field conductance sensor with eight electrodes. We first use a recurrence plot to recognise flow patterns in vertical upward gas-liquid two-phase pipe flow from measured signals. Then we apply a multi-scale morphological analysis based on the first-order difference scatter plot to investigate the signals captured from the vertical upward gas-liquid two-phase flow loop test. We find that the invariant scaling exponent extracted from the multi-scale first-order difference scatter plot with the bisector of the second-fourth quadrant as the reference line is sensitive to the inhomogeneous distribution characteristics of the flow structure, and the variation trend of the exponent is helpful to understand the process of breakup and coalescence of the gas phase. In addition, we explore the dynamic mechanism influencing the inhomogeneous distribution of the gas phase in terms of adaptive optimal kernel time-frequency representation. The research indicates that the system energy is a factor influencing the distribution of the gas phase and the multi-scale morphological analysis based on the first-order difference scatter plot is an effective method for indicating the inhomogeneous distribution of the gas phase in gas-liquid two-phase flow.

Oriented xenon hydride molecules in the gas phase

NASA Astrophysics Data System (ADS)

Buck, Udo; Fárník, Michal

The production of the xenon hydride molecules HXeX with X = I and Cl in the gas phase is reviewed. These molecules are generated by the photolysis of the hydrogen halide HI and HCl molecules on the surface of large xenon Xen clusters. Molecular dynamics simulations show that the flexible H atoms react with the heavy XeX moiety and form the desired molecules with nearly no rotational motion. They are observed by photodissociation with subsequent detection of the kinetic energy of the H atom fragment. During the generating process, the cluster starts to evaporate and the hydride molecule is left essentially free. For further discrimination against the H atom fragments from HX, the HXeX molecules are oriented in a combined pulsed laser field and a weak electrostatic field. The three topics which represent the background of our experiments are briefly reviewed: the nature and generation of rare gas hydrides, the alignment and orientation of molecules in electric fields, and the photodissociation of selected molecules in rare gas clusters. The conditions for detecting them in the gas phase are discussed. This is the trade off between the stability, which requires high electron affinity, and the conditions for orientation, which necessitate large polarizability anisotropies and dipole moments. Finally the prospects of detecting other classes of molecules are discussed.

Gas Phase Reactivity of Carboxylates with N-Hydroxysuccinimide Esters

PubMed Central

Peng, Zhou; McGee, William M.; Bu, Jiexun; Barefoot, Nathan Z.; McLuckey, Scott A.

2015-01-01

N-hydroxysuccinimide (NHS) esters have been used for gas phase conjugation reactions with peptides at nucleophilic sites, such as primary amines (N-terminus, ε-amine of lysine) or guanidines, by forming amide bonds through a nucleophilic attack on the carbonyl carbon. The carboxylate has recently been found to also be a reactive nucleophile capable of initiating a similar nucleophilic attack to form a labile anhydride bond. The fragile bond is easily cleaved, resulting in an oxygen transfer from the carboxylate-containing species to the reagent, nominally observed as a water transfer. This reactivity is shown for both peptides and non-peptidic species. Reagents isotopically labeled with O18 were used to confirm reactivity. This constitutes an example of distinct differences in reactivity of carboxylates between the gas-phase, where they are shown to be reactive, and the solution-phase, where they are not regarded as reactive with NHS esters. PMID:25338221

The Heat Capacity of Ideal Gases

ERIC Educational Resources Information Center

Scott, Robert L.

2006-01-01

The heat capacity of an ideal gas has been shown to be calculable directly by statistical mechanics if the energies of the quantum states are known. However, unless one makes careful calculations, it is not easy for a student to understand the qualitative results. Why there are maxima (and occasionally minima) in heat capacity-temperature curves…

Monitoring gas-phase CO2 in the headspace of champagne glasses through combined diode laser spectrometry and micro-gas chromatography analysis.

PubMed

Moriaux, Anne-Laure; Vallon, Raphaël; Parvitte, Bertrand; Zeninari, Virginie; Liger-Belair, Gérard; Cilindre, Clara

2018-10-30

During Champagne or sparkling wine tasting, gas-phase CO 2 and volatile organic compounds invade the headspace above glasses, thus progressively modifying the chemical space perceived by the consumer. Gas-phase CO 2 in excess can even cause a very unpleasant tingling sensation perturbing both ortho- and retronasal olfactory perception. Monitoring as accurately as possible the level of gas-phase CO 2 above glasses is therefore a challenge of importance aimed at better understanding the close relationship between the release of CO 2 and a collection of various tasting parameters. Here, the concentration of CO 2 found in the headspace of champagne glasses served under multivariate conditions was accurately monitored, all along the 10 min following pouring, through a new combined approach by a CO 2 -Diode Laser Sensor and micro-gas chromatography. Our results show the strong impact of various tasting conditions (volume dispensed, intensity of effervescence, and glass shape) on the release of gas-phase CO 2 above the champagne surface. Copyright © 2018 Elsevier Ltd. All rights reserved.

Phase equilibrium of methane and nitrogen at low temperatures - Application to Titan

NASA Technical Reports Server (NTRS)

Kouvaris, Louis C.; Flasar, F. M.

1991-01-01

Since the vapor phase composition of Titan's methane-nitrogen lower atmosphere is uniquely determined as a function of the Gibbs phase rule, these data are presently computed via integration of the Gibbs-Duhem equation. The thermodynamic consistency of published measurements and calculations of the vapor phase composition is then examined, and the saturated mole fraction of gaseous methane is computed as a function of altitude up to the 700-mbar level. The mole fraction is found to lie approximately halfway between that computed from Raoult's law, for a gas in equilibrium with an ideal solution of liquid nitrogen and methane, and that for a gas in equilibrium with pure liquid methane.

Formation of complex organic molecules in cold objects: the role of gas-phase reactions

NASA Astrophysics Data System (ADS)

Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

2015-04-01

While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

Probing the regional distribution of pulmonary gas exchange through single-breath gas- and dissolved-phase 129Xe MR imaging.

PubMed

Kaushik, S Sivaram; Freeman, Matthew S; Cleveland, Zackary I; Davies, John; Stiles, Jane; Virgincar, Rohan S; Robertson, Scott H; He, Mu; Kelly, Kevin T; Foster, W Michael; McAdams, H Page; Driehuys, Bastiaan

2013-09-01

Although some central aspects of pulmonary function (ventilation and perfusion) are known to be heterogeneous, the distribution of diffusive gas exchange remains poorly characterized. A solution is offered by hyperpolarized 129Xe magnetic resonance (MR) imaging, because this gas can be separately detected in the lung's air spaces and dissolved in its tissues. Early dissolved-phase 129Xe images exhibited intensity gradients that favored the dependent lung. To quantitatively corroborate this finding, we developed an interleaved, three-dimensional radial sequence to image the gaseous and dissolved 129Xe distributions in the same breath. These images were normalized and divided to calculate "129Xe gas-transfer" maps. We hypothesized that, for healthy volunteers, 129Xe gas-transfer maps would retain the previously observed posture-dependent gradients. This was tested in nine subjects: when the subjects were supine, 129Xe gas transfer exhibited a posterior-anterior gradient of -2.00 ± 0.74%/cm; when the subjects were prone, the gradient reversed to 1.94 ± 1.14%/cm (P < 0.001). The 129Xe gas-transfer maps also exhibited significant heterogeneity, as measured by the coefficient of variation, that correlated with subject total lung capacity (r = 0.77, P = 0.015). Gas-transfer intensity varied nonmonotonically with slice position and increased in slices proximal to the main pulmonary arteries. Despite substantial heterogeneity, the mean gas transfer for all subjects was 1.00 ± 0.01 while supine and 1.01 ± 0.01 while prone (P = 0.25), indicating good "matching" between gas- and dissolved-phase distributions. This study demonstrates that single-breath gas- and dissolved-phase 129Xe MR imaging yields 129Xe gas-transfer maps that are sensitive to altered gas exchange caused by differences in lung inflation and posture.

Quantum-mechanical engines working with an ideal gas with a finite number of particles confined in a power-law trap

NASA Astrophysics Data System (ADS)

Wang, Jianhui; Ma, Yongli; He, Jizhou

2015-07-01

Based on quantum thermodynamic processes, we make a quantum-mechanical (QM) extension of the typical heat engine cycles, such as the Carnot, Brayton, Otto, Diesel cycles, etc., with no introduction of the concept of temperature. When these QM engine cycles are implemented by an ideal gas confined in an arbitrary power-law trap, a relation between the quantum adiabatic exponent and trap exponent is found. The differences and similarities between the efficiency of a given QM engine cycle and its classical counterpart are revealed and discussed.

Laboratory Studies on the Formation of Carbon-Bearing Molecules in Extraterrestrial Environments: From the Gas Phase to the Solid State

NASA Technical Reports Server (NTRS)

Jamieson, C. S.; Guo, Y.; Gu, X.; Zhang, F.; Bennett, C. J.; Kaiser, R. I.

2006-01-01

A detailed knowledge of the formation of carbon-bearing molecules in interstellar ices and in the gas phase of the interstellar medium is of paramount interest to understand the astrochemical evolution of extraterrestrial environments (1). This research also holds strong implications to comprehend the chemical processing of Solar System environments such as icy planets and their moons together with the atmospheres of planets and their satellites (2). Since the present composition of each interstellar and Solar System environment reflects the matter from which it was formed and the processes which have changed the chemical nature since the origin (solar wind, planetary magnetospheres, cosmic ray exposure, photolysis, chemical reactions), a detailed investigation of the physicochemical mechanisms altering the pristine environment is of paramount importance to grasp the contemporary composition. Once these underlying processes have been unraveled, we can identify those molecules, which belonged to the nascent setting, distinguish molecular species synthesized in a later stage, and predict the imminent chemical evolution of, for instance, molecular clouds. Laboratory experiments under controlled physicochemical conditions (temperature, pressure, chemical composition, high energy components) present ideal tools for simulating the chemical evolution of interstellar and Solar System environments. Here, laboratory experiments can predict where and how (reaction mechanisms; chemicals necessary) in extraterrestrial environments and in the interstellar medium complex, carbon bearing molecules can be formed on interstellar grains and in the gas phase. This paper overviews the experimental setups utilized in our laboratory to mimic the chemical processing of gas phase and solid state (ices) environments. These are a crossed molecular beams machine (3) and a surface scattering setup (4). We also present typical results of each setup (formation of amino acids, aldehydes, epoxides

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2

PubMed Central

Colombara, Diego; Berner, Ulrich; Ciccioli, Andrea; Malaquias, João C.; Bertram, Tobias; Crossay, Alexandre; Schöneich, Michael; Meadows, Helene J.; Regesch, David; Delsante, Simona; Gigli, Guido; Valle, Nathalie; Guillot, Jérome; El Adib, Brahime; Grysan, Patrick; Dale, Phillip J.

2017-01-01

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source. PMID:28233864

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2.

PubMed

Colombara, Diego; Berner, Ulrich; Ciccioli, Andrea; Malaquias, João C; Bertram, Tobias; Crossay, Alexandre; Schöneich, Michael; Meadows, Helene J; Regesch, David; Delsante, Simona; Gigli, Guido; Valle, Nathalie; Guillot, Jérome; El Adib, Brahime; Grysan, Patrick; Dale, Phillip J

2017-02-24

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se 2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu 2 ZnSnS 4 ) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.

Fluorescence Spectroscopy of Gas-phase Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

Thomas, J. D.; Witt, A. N.

2006-01-01

The purpose of this investigation was to produce fluorescence spectra of polycyclic aromatic hydrocarbon (PAH) molecules in the gas-phase for comparison with blue luminescence (BL) emission observed in astrophysical sources Vijh et al. (2004, 2005a,b). The BL occurs roughly from 350 to 450 nm, with a sharp peak near 380 nm. PAHs with three to four rings, e.g. anthracene and pyrene, were found to produce luminescence in the appropriate spectral region, based on existing studies. Relatively few studies of the gas-phase fluorescence of PAHs exist; those that do exist have dealt primarily with the same samples commonly available for purchase such as pyrene and anthracene. In an attempt to understand the chemistry of the nebular environment we also obtained several nitrogen substituted PAHs from our colleagues at NASA Ames. In order to simulate the astrophysical environment we also took spectra by heating the PAHs in a flame. The flame environment counteracts the formation of eximers and permits the spectroscopy of free-flying neutral molecules. Experiments with coal tar demonstrate that fluorescence spectroscopy reveals primarily the presence of the smallest molecules, which are most abundant and which possess the highest fluorescence efficiencies. One gas-phase PAH that seems to fit the BL spectrum most closely is phenanthridine. In view of the results from the spectroscopy of coal tar, a compound containing a mixture of PAHs ranging from small to very large PAH molecules, we can not preclude the presence of larger PAHs in interstellar sources exhibiting BL.

A facility for gas- and condensed-phase measurements behind shock waves

NASA Astrophysics Data System (ADS)

Petersen, Eric L.; Rickard, Matthew J. A.; Crofton, Mark W.; Abbey, Erin D.; Traum, Matthew J.; Kalitan, Danielle M.

2005-09-01

A shock-tube facility consisting of two, single-pulse shock tubes for the study of fundamental processes related to gas-phase chemical kinetics and the formation and reaction of solid and liquid aerosols at elevated temperatures is described. Recent upgrades and additions include a new high-vacuum system, a new gas-handling system, a new control system and electronics, an optimized velocity-detection scheme, a computer-based data acquisition system, several optical diagnostics, and new techniques and procedures for handling experiments involving gas/powder mixtures. Test times on the order of 3 ms are possible with reflected-shock pressures up to 100 atm and temperatures greater than 4000 K. Applications for the shock-tube facility include the study of ignition delay times of fuel/oxidizer mixtures, the measurement of chemical kinetic reaction rates, the study of fundamental particle formation from the gas phase, and solid-particle vaporization, among others. The diagnostic techniques include standard differential laser absorption, FM laser absorption spectroscopy, laser extinction for particle volume fraction and size, temporally and spectrally resolved emission from gas-phase species, and a scanning mobility particle sizer for particle size distributions. Details on the set-up and operation of the shock tube and diagnostics are given, the results of a detailed uncertainty analysis on the accuracy of the test temperature inferred from the incident-shock velocity are provided, and some recent results are presented.

GAS PHASE SELECTIVE PHOTOXIDATION OF ALCOHOLS USING LIGHT-ACTIVATED TITANIUM DIOXIDE AND MOLECULAR OXYGEN

EPA Science Inventory

Gas Phase Selective Oxidation of Alcohols Using Light-Activated Titanium Dioxide and Molecular Oxygen

Gas phase selective oxidations of various primary and secondary alcohols are studied in an indigenously built stainless steel up-flow photochemical reactor using ultravi...

Thermodynamics of ideal quantum gas with fractional statistics in D dimensions.

PubMed

Potter, Geoffrey G; Müller, Gerhard; Karbach, Michael

2007-06-01

We present exact and explicit results for the thermodynamic properties (isochores, isotherms, isobars, response functions, velocity of sound) of a quantum gas in dimensions D > or = 1 and with fractional exclusion statistics 0 < or = g < or =1 connecting bosons (g=0) and fermions (g=1) . In D=1 the results are equivalent to those of the Calogero-Sutherland model. Emphasis is given to the crossover between bosonlike and fermionlike features, caused by aspects of the statistical interaction that mimic long-range attraction and short-range repulsion. A phase transition along the isobar occurs at a nonzero temperature in all dimensions. The T dependence of the velocity of sound is in simple relation to isochores and isobars. The effects of soft container walls are accounted for rigorously for the case of a pure power-law potential.

The Grism Lens-Amplified Survey from Space (GLASS). II. Gas-Phase Metallicity and Radial Gradients in an Interacting System At Z ≃ 2

NASA Astrophysics Data System (ADS)

Jones, T.; Wang, X.; Schmidt, K. B.; Treu, T.; Brammer, G. B.; Bradač, M.; Dressler, A.; Henry, A. L.; Malkan, M. A.; Pentericci, L.; Trenti, M.

2015-03-01

We present spatially resolved gas-phase metallicity for a system of three galaxies at z = 1.85 detected in the Grism Lens-Amplified Survey from Space (GLASS). The combination of Hubble Space Telescope (HST’s) diffraction limit and strong gravitational lensing by the cluster MACS J0717+3745 results in a spatial resolution of ≃200-300 pc, enabling good spatial sampling despite the intrinsically small galaxy sizes. The galaxies in this system are separated by ≃50-200 kpc in projection and are likely in an early stage of interaction, evidenced by relatively high specific star formation rates. Their gas-phase metallicities are consistent with larger samples at similar redshift, star formation rate (SFR), and stellar mass. We obtain a precise measurement of the metallicity gradient for one galaxy and find a shallow slope compared to isolated galaxies at high redshift, consistent with a flattening of the gradient due to gravitational interaction. An alternative explanation for the shallow metallicity gradient and elevated SFR is rapid recycling of metal-enriched gas, but we find no evidence for enhanced gas-phase metallicities which should result from this effect. Notably, the measured stellar masses log {{M}*}/{{M}} = 7.2-9.1 probe to an order of magnitude below previous mass-metallicity studies at this redshift. The lowest mass galaxy has properties similar to those expected for Fornax at this redshift, indicating that GLASS is able to directly study the progenitors of local group dwarf galaxies on spatially resolved scales. Larger samples from the full GLASS survey will be ideal for studying the effects of feedback, and the time evolution of metallicity gradients. These initial results demonstrate the utility of HST spectroscopy combined with gravitational lensing for characterizing resolved physical properties of galaxies at high redshift.

Characterization of annular two-phase gas-liquid flows in microgravity

NASA Technical Reports Server (NTRS)

Bousman, W. Scott; Mcquillen, John B.

1994-01-01

A series of two-phase gas-liquid flow experiments were developed to study annular flows in microgravity using the NASA Lewis Learjet. A test section was built to measure the liquid film thickness around the perimeter of the tube permitting the three dimensional nature of the gas-liquid interface to be observed. A second test section was used to measure the film thickness, pressure drop and wall shear stress in annular microgravity two-phase flows. Three liquids were studied to determine the effects of liquid viscosity and surface tension. The result of this study provide insight into the wave characteristics, pressure drop and droplet entrainment in microgravity annular flows.

Cold flame on Biofilm - Transport of Plasma Chemistry from Gas to Liquid Phase

NASA Astrophysics Data System (ADS)

Kong, Michael

2014-10-01

One of the most active and fastest growing fields in low-temperature plasma science today is biological effects of gas plasmas and their translation in many challenges of societal importance such as healthcare, environment, agriculture, and nanoscale fabrication and synthesis. Using medicine as an example, there are already three FDA-approved plasma-based surgical procedures for tissue ablation and blood coagulation and at least five phase-II clinical trials on plasma-assisted wound healing therapies. A key driver for realizing the immense application potential of near room-temperature ambient pressure gas plasmas, commonly known as cold atmospheric plasmas or CAP, is to build a sizeable interdisciplinary knowledge base with which to unravel, optimize, and indeed design how reactive plasma species interact with cells and their key components such as protein and DNA. Whilst a logical objective, it is a formidable challenge not least since existing knowledge of gas discharges is largely in the gas-phase and therefore not directly applicable to cell-containing matters that are covered by or embedded in liquid (e.g. biofluid). Here, we study plasma inactivation of biofilms, a jelly-like structure that bacteria use to protect themselves and a major source of antimicrobial resistance. As 60--90% of biofilm is made of water, we develop a holistic model incorporating physics and chemistry in the upstream CAP-generating region, a plasma-exit region as a buffer for as-phase transport, and a downstream liquid region bordering the gas buffer region. A special model is developed to account for rapid chemical reactions accompanied the transport of gas-phase plasma species through the gas-liquid interface and for liquid-phase chemical reactions. Numerical simulation is used to illustrate how key reactive oxygen species (ROS) are transported into the liquid, and this is supported with experimental data of both biofilm inactivation using plasmas and electron spin spectroscopy (ESR

shock driven instability of a multi-phase particle-gas system

NASA Astrophysics Data System (ADS)

McFarland, Jacob; Black, Wolfgang; Dahal, Jeevan; Morgan, Brandon

2015-11-01

A computational study of a shock driven instability of a multiphse particle-gas system is presented. This instability can evolve in a similar fashion to the Richtmyer-Meshkov (RM) instability, but has addition parameters to be considered. Particle relaxation times, and density differences of the gas and particle-gas system can be adjusted to produce results which are different from the classical RM instability. We will show simulation results from the Ares code, developed at Lawrence Livermore National Laboratory, which uses a particle-in-cell approach to study the effects of the particle-gas system parameters. Mixing parameters will be presented to highlight the suppression of circulation and gas mixing by the particle phase.

Numerical Computation of Flame Spread over a Thin Solid in Forced Concurrent Flow with Gas-phase Radiation

NASA Technical Reports Server (NTRS)

Jiang, Ching-Biau; T'ien, James S.

1994-01-01

Excerpts from a paper describing the numerical examination of concurrent-flow flame spread over a thin solid in purely forced flow with gas-phase radiation are presented. The computational model solves the two-dimensional, elliptic, steady, and laminar conservation equations for mass, momentum, energy, and chemical species. Gas-phase combustion is modeled via a one-step, second order finite rate Arrhenius reaction. Gas-phase radiation considering gray non-scattering medium is solved by a S-N discrete ordinates method. A simplified solid phase treatment assumes a zeroth order pyrolysis relation and includes radiative interaction between the surface and the gas phase.

In Situ Environmental TEM in Imaging Gas and Liquid Phase Chemical Reactions for Materials Research.

PubMed

Wu, Jianbo; Shan, Hao; Chen, Wenlong; Gu, Xin; Tao, Peng; Song, Chengyi; Shang, Wen; Deng, Tao

2016-11-01

Gas and liquid phase chemical reactions cover a broad range of research areas in materials science and engineering, including the synthesis of nanomaterials and application of nanomaterials, for example, in the areas of sensing, energy storage and conversion, catalysis, and bio-related applications. Environmental transmission electron microscopy (ETEM) provides a unique opportunity for monitoring gas and liquid phase reactions because it enables the observation of those reactions at the ultra-high spatial resolution, which is not achievable through other techniques. Here, the fundamental science and technology developments of gas and liquid phase TEM that facilitate the mechanistic study of the gas and liquid phase chemical reactions are discussed. Combined with other characterization tools integrated in TEM, unprecedented material behaviors and reaction mechanisms are observed through the use of the in situ gas and liquid phase TEM. These observations and also the recent applications in this emerging area are described. The current challenges in the imaging process are also discussed, including the imaging speed, imaging resolution, and data management. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

3-D simulation of gases transport under condition of inert gas injection into goaf

NASA Astrophysics Data System (ADS)

Liu, Mao-Xi; Shi, Guo-Qing; Guo, Zhixiong; Wang, Yan-Ming; Ma, Li-Yang

2016-12-01

To prevent coal spontaneous combustion in mines, it is paramount to understand O2 gas distribution under condition of inert gas injection into goaf. In this study, the goaf was modeled as a 3-D porous medium based on stress distribution. The variation of O2 distribution influenced by CO2 or N2 injection was simulated based on the multi-component gases transport and the Navier-Stokes equations using Fluent. The numerical results without inert gas injection were compared with field measurements to validate the simulation model. Simulations with inert gas injection show that CO2 gas mainly accumulates at the goaf floor level; however, a notable portion of N2 gas moves upward. The evolution of the spontaneous combustion risky zone with continuous inert gas injection can be classified into three phases: slow inerting phase, rapid accelerating inerting phase, and stable inerting phase. The asphyxia zone with CO2 injection is about 1.25-2.4 times larger than that with N2 injection. The efficacy of preventing and putting out mine fires is strongly related with the inert gas injecting position. Ideal injections are located in the oxidation zone or the transitional zone between oxidation zone and heat dissipation zone.

A local leaky-box model for the local stellar surface density-gas surface density-gas phase metallicity relation

NASA Astrophysics Data System (ADS)

Zhu, Guangtun Ben; Barrera-Ballesteros, Jorge K.; Heckman, Timothy M.; Zakamska, Nadia L.; Sánchez, Sebastian F.; Yan, Renbin; Brinkmann, Jonathan

2017-07-01

We revisit the relation between the stellar surface density, the gas surface density and the gas-phase metallicity of typical disc galaxies in the local Universe with the SDSS-IV/MaNGA survey, using the star formation rate surface density as an indicator for the gas surface density. We show that these three local parameters form a tight relationship, confirming previous works (e.g. by the PINGS and CALIFA surveys), but with a larger sample. We present a new local leaky-box model, assuming star-formation history and chemical evolution is localized except for outflowing materials. We derive closed-form solutions for the evolution of stellar surface density, gas surface density and gas-phase metallicity, and show that these parameters form a tight relation independent of initial gas density and time. We show that, with canonical values of model parameters, this predicted relation match the observed one well. In addition, we briefly describe a pathway to improving the current semi-analytic models of galaxy formation by incorporating the local leaky-box model in the cosmological context, which can potentially explain simultaneously multiple properties of Milky Way-type disc galaxies, such as the size growth and the global stellar mass-gas metallicity relation.

Propagation characteristics of pulverized coal and gas two-phase flow during an outburst.

PubMed

Zhou, Aitao; Wang, Kai; Fan, Lingpeng; Tao, Bo

2017-01-01

Coal and gas outbursts are dynamic failures that can involve the ejection of thousands tons of pulverized coal, as well as considerable volumes of gas, into a limited working space within a short period. The two-phase flow of gas and pulverized coal that occurs during an outburst can lead to fatalities and destroy underground equipment. This article examines the interaction mechanism between pulverized coal and gas flow. Based on the role of gas expansion energy in the development stage of outbursts, a numerical simulation method is proposed for investigating the propagation characteristics of the two-phase flow. This simulation method was verified by a shock tube experiment involving pulverized coal and gas flow. The experimental and simulated results both demonstrate that the instantaneous ejection of pulverized coal and gas flow can form outburst shock waves. These are attenuated along the propagation direction, and the volume fraction of pulverized coal in the two-phase flow has significant influence on attenuation of the outburst shock wave. As a whole, pulverized coal flow has a negative impact on gas flow, which makes a great loss of large amounts of initial energy, blocking the propagation of gas flow. According to comparison of numerical results for different roadway types, the attenuation effect of T-type roadways is best. In the propagation of shock wave, reflection and diffraction of shock wave interact through the complex roadway types.

Propagation characteristics of pulverized coal and gas two-phase flow during an outburst

PubMed Central

Zhou, Aitao; Wang, Kai; Fan, Lingpeng; Tao, Bo

2017-01-01

Coal and gas outbursts are dynamic failures that can involve the ejection of thousands tons of pulverized coal, as well as considerable volumes of gas, into a limited working space within a short period. The two-phase flow of gas and pulverized coal that occurs during an outburst can lead to fatalities and destroy underground equipment. This article examines the interaction mechanism between pulverized coal and gas flow. Based on the role of gas expansion energy in the development stage of outbursts, a numerical simulation method is proposed for investigating the propagation characteristics of the two-phase flow. This simulation method was verified by a shock tube experiment involving pulverized coal and gas flow. The experimental and simulated results both demonstrate that the instantaneous ejection of pulverized coal and gas flow can form outburst shock waves. These are attenuated along the propagation direction, and the volume fraction of pulverized coal in the two-phase flow has significant influence on attenuation of the outburst shock wave. As a whole, pulverized coal flow has a negative impact on gas flow, which makes a great loss of large amounts of initial energy, blocking the propagation of gas flow. According to comparison of numerical results for different roadway types, the attenuation effect of T-type roadways is best. In the propagation of shock wave, reflection and diffraction of shock wave interact through the complex roadway types. PMID:28727738

Modeling Gas-Particle Partitioning of SOA: Effects of Aerosol Physical State and RH

NASA Astrophysics Data System (ADS)

Zuend, A.; Seinfeld, J.

2011-12-01

Aged tropospheric aerosol particles contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. In liquid aerosol particles non-ideal mixing of all species determines whether the condensed phase undergoes liquid-liquid phase separation or whether it is stable in a single mixed phase, and whether it contains solid salts in equilibrium with their saturated solution. The extended thermodynamic model AIOMFAC is able to predict such phase states by representing the variety of organic components using functional groups within a group-contribution concept. The number and composition of different condensed phases impacts the diversity of reaction media for multiphase chemistry and the gas-particle partitioning of semivolatile species. Recent studies show that under certain conditions biogenic and other organic-rich particles can be present in a highly viscous, semisolid or amorphous solid physical state, with consequences regarding reaction kinetics and mass transfer limitations. We present results of new gas-particle partitioning computations for aerosol chamber data using a model based on AIOMFAC activity coefficients and state-of-the-art vapor pressure estimation methods. Different environmental conditions in terms of temperature, relative humidity (RH), salt content, amount of precursor VOCs, and physical state of the particles are considered. We show how modifications of absorptive and adsorptive gas-particle mass transfer affects the total aerosol mass in the calculations and how the results of these modeling approaches compare to data of aerosol chamber experiments, such as alpha-pinene oxidation SOA. For a condensed phase in a mixed liquid state containing ammonium sulfate, the model predicts liquid-liquid phase separation up to high RH in case of, on average, moderately hydrophilic organic compounds, such as first generation oxidation products of alpha-pinene. The computations also reveal that treating liquid phases as ideal

Measurement of Biologically Available Naphthalene in Gas and Aqueous Phases by Use of a Pseudomonas putida Biosensor

PubMed Central

Werlen, Christoph; Jaspers, Marco C. M.; van der Meer, Jan Roelof

2004-01-01

Genetically constructed microbial biosensors for measuring organic pollutants are mostly applied in aqueous samples. Unfortunately, the detection limit of most biosensors is insufficient to detect pollutants at low but environmentally relevant concentrations. However, organic pollutants with low levels of water solubility often have significant gas-water partitioning coefficients, which in principle makes it possible to measure such compounds in the gas rather than the aqueous phase. Here we describe the first use of a microbial biosensor for measuring organic pollutants directly in the gas phase. For this purpose, we reconstructed a bioluminescent Pseudomonas putida naphthalene biosensor strain to carry the NAH7 plasmid and a chromosomally inserted gene fusion between the sal promoter and the luxAB genes. Specific calibration studies were performed with suspended and filter-immobilized biosensor cells, in aqueous solution and in the gas phase. Gas phase measurements with filter-immobilized biosensor cells in closed flasks, with a naphthalene-contaminated aqueous phase, showed that the biosensor cells can measure naphthalene effectively. The biosensor cells on the filter responded with increasing light output proportional to the naphthalene concentration added to the water phase, even though only a small proportion of the naphthalene was present in the gas phase. In fact, the biosensor cells could concentrate a larger proportion of naphthalene through the gas phase than in the aqueous suspension, probably due to faster transport of naphthalene to the cells in the gas phase. This led to a 10-fold lower detectable aqueous naphthalene concentration (50 nM instead of 0.5 μM). Thus, the use of bacterial biosensors for measuring organic pollutants in the gas phase is a valid method for increasing the sensitivity of these valuable biological devices. PMID:14711624

Heavy haze in winter Beijing driven by fast gas phase oxidation

NASA Astrophysics Data System (ADS)

Lu, K.; Tan, Z.; Wang, H.; Li, X.; Wu, Z.; Chen, Q.; Wu, Y.; Ma, X.; Liu, Y.; Chen, X.; Shang, D.; Dong, H.; Zeng, L.; Shao, M.; Hu, M.; Fuchs, H.; Novelli, A.; Broch, S.; Hofzumahaus, A.; Holland, F.; Rohrer, F.; Bohn, B.; Georgios, G.; Schmitt, S. H.; Schlag, P.; Kiendler-Scharr, A.; Wahner, A.; Zhang, Y.

2017-12-01

Heavy haze conditions were frequently presented in the airsheds of Beijing and surrounding areas, especially during winter time. To explore the trace gas oxidation and the subsequent formation of aerosols, a comprehensive field campaign was performed at a regional site (in the campus of University of Chinese Academy of Science, UCAS) in Beijing winter 2016. Serious haze pollution processes were often observed with the fast increase of inorganic salt (especially nitrate) and these pollutions were always associated with enhanced humidity and the concentrations of PAN (PeroxyAcyl Nitrates) which is normally a marker of gas phase oxidations from NOx and VOCs. Moreover, based on the measurements of OH, HO2, RO2, total OH reactivity, N2O5, NO, NO2, SO2, particle concentrations/distributions/chemical compositions, and meteorological parameters, the gas phase oxidation rates that leads to the formation of sulfate, nitrate and secondary organic aerosols were estimated. These determined formation rates were clearly enhanced by several folds during pollution episodes compared to that of the clean air masses. Preliminary analysis result showed that the gas phase formation potential of nitrate and secondary organic aerosols were larger than the observed concentrations of nitrate and SOA of which the excess production may be explained by deposition and dilution.

Polaronic exciton behavior in gas-phase water

NASA Astrophysics Data System (ADS)

Udal'tsov, Alexander V.

2018-03-01

Features of the absorption spectrum of gas-phase water in the energy range 7-10 eV have been considered applying polaronic exciton theory. The interaction of the incident photon generating polaronic exciton in water is described taking into account angular momentum of the electron so that polaronic exciton radii have been estimated in dependence on spin-orbit coupling under proton sharing. The suggested approach admits an estimate of kinetic and rotation energies of the polaronic exciton. As a result sixteen steps of half Compton wavelength, λC/2 = h/(2mec) changing polaronic exciton radius were found consistent with local maxima and shoulders in the spectrum. Thus, the absorption of gas-phase water in the energy range 8.5-10 eV has been interpreted in terms of polaronic exciton rotation mainly coupled with the proton sharing. The incident photon interaction with water is also considered in terms of Compton interaction, when the rotation energy plays a role like the energy loss of the incident photon under Compton scattering. The found symmetry and the other evidence allowed to conclude about polaronic exciton migration under the interaction angle 90°.

Analytical Phase Equilibrium Function for Mixtures Obeying Raoult's and Henry's Laws

NASA Astrophysics Data System (ADS)

Hayes, Robert

When a mixture of two substances exists in both the liquid and gas phase at equilibrium, Raoults and Henry's laws (ideal solution and ideal dilute solution approximations) can be used to estimate the gas and liquid mole fractions at the extremes of either very little solute or solvent. By assuming that a cubic polynomial can reasonably approximate the intermediate values to these extremes as a function of mole fraction, the cubic polynomial is solved and presented. A closed form equation approximating the pressure dependence on mole fraction of the constituents is thereby obtained. As a first approximation, this is a very simple and potentially useful means to estimate gas and liquid mole fractions of equilibrium mixtures. Mixtures with an azeotrope require additional attention if this type of approach is to be utilized. This work supported in part by federal Grant NRC-HQ-84-14-G-0059.

Dark current reduction of Ge photodetector by GeO₂ surface passivation and gas-phase doping.

PubMed

Takenaka, Mitsuru; Morii, Kiyohito; Sugiyama, Masakazu; Nakano, Yoshiaki; Takagi, Shinichi

2012-04-09

We have investigated the dark current of a germanium (Ge) photodetector (PD) with a GeO₂ surface passivation layer and a gas-phase-doped n+/p junction. The gas-phase-doped PN diodes exhibited a dark current of approximately two orders of magnitude lower than that of the diodes formed by a conventional ion implantation process, indicating that gas-phase doping is suitable for low-damage PN junction formation. The bulk leakage (Jbulk) and surface leakage (Jsurf) components of the dark current were also investigated. We have found that GeO₂ surface passivation can effectively suppress the dark current of a Ge PD in conjunction with gas-phase doping, and we have obtained extremely low values of Jbulk of 0.032 mA/cm² and Jsurf of 0.27 μA/cm.

Transport of Gas Phase Radionuclides in a Fractured, Low-Permeability Reservoir

NASA Astrophysics Data System (ADS)

Cooper, C. A.; Chapman, J.

2001-12-01

The U.S. Atomic Energy Commission (predecessor to the Department of Energy, DOE) oversaw a joint program between industry and government in the 1960s and 1970s to develop technology to enhance production from low-permeability gas reservoirs using nuclear stimulation rather than conventional means (e.g., hydraulic and/or acid fracturing). Project Rio Blanco, located in the Piceance Basin, Colorado, was the third experiment under the program. Three 30-kiloton nuclear explosives were placed in a 2134 m deep well at 1780, 1899, and 2039 m below the land surface and detonated in May 1973. Although the reservoir was extensively fractured, complications such as radionuclide contamination of the gas prevented production and subsequent development of the technology. Two-dimensional numerical simulations were conducted to identify the main transport processes that have occurred and are currently occurring in relation to the detonations, and to estimate the extent of contamination in the reservoir. Minor modifications were made to TOUGH2, the multiphase, multicomponent reservoir simulator developed at Lawrence Berkeley National Laboratories. The simulator allows the explicit incorporation of fractures, as well as heat transport, phase change, and first order radionuclide decay. For a fractured two-phase (liquid and gas) reservoir, the largest velocities are of gases through the fractures. In the gas phase, tritium and one isotope of krypton are the principle radionuclides of concern. However, in addition to existing as a fast pathway, fractures also permit matrix diffusion as a retardation mechanism. Another retardation mechanism is radionuclide decay. Simulations show that incorporation of fractures can significantly alter transport rates, and that radionuclides in the gas phase can preferentially migrate upward due to the downward gravity drainage of liquid water in the pores. This project was funded by the National Nuclear Security Administration, Nevada Operations Office

Unified first principles description from warm dense matter to ideal ionized gas plasma: electron-ion collisions induced friction.

PubMed

Dai, Jiayu; Hou, Yong; Yuan, Jianmin

2010-06-18

Electron-ion interactions are central to numerous phenomena in the warm dense matter (WDM) regime and at higher temperature. The electron-ion collisions induced friction at high temperature is introduced in the procedure of ab initio molecular dynamics using the Langevin equation based on density functional theory. In this framework, as a test for Fe and H up to 1000 eV, the equation of state and the transition of electronic structures of the materials with very wide density and temperature can be described, which covers a full range of WDM up to high energy density physics. A unified first principles description from condensed matter to ideal ionized gas plasma is constructed.

Atmospheric reactions of ortho cresol: Gas phase and aerosol products

NASA Astrophysics Data System (ADS)

Grosjean, Daniel

Photo-oxidation of ortho-cresol (0.5-1.1 ppm) and oxides of nitrogen (0.12-0.66 ppm) in air yielded the following gas-phase products: pyruvic acid, acetaldehyde, formaldehyde, peroxyacetylnitrate, nitrocresol and trace levels of nitric acid and methyl nitrate. particulate phase products included 2-hydroxy3-nitro toluene, 2-hydroxy-5-nitro toluene, 2-hydroxy-3,5-dinitrotoluene and, tentatively, several hydroxynitrocresol isomers. Yields of gas-phase products (0.8 % for pyruvic acid, 5-11 % for the sum of the aromatic ring fragmentation products) and of aerosol products (5-19% on a carbon basis, with particulate carbon formation rates of 30-80 μ g m -3 h -1) are discussed in terms of photochemical reaction pathways. From 60 to 89 % of the initial NO x was consumed in these reactions and a significant fraction of the reacted NO x could be accounted for as particulate nitro-aromatic products.

Analysis of Low-Pressure Gas-Phase Pyrolytic Reactions by Mass Spectrometric Techniques,

DTIC Science & Technology

1989-01-01

temperatures and pressures known only as a polymeric substance, is similarly obtained in high purity by heating the polymer to its melting point (105-110’ C...filaments for Curie- point pyrolysis’ J.Anal.Appl.Pyrolysis. 5 (1983) 1-7 (with Helge Egsgaard) 4) ’Heterogeneous catalysis in gas phase reactions studied...by Curie- point pyrolysis. Gas phase pyrolysis of methyl dithio- acetat’ J.Anal.Appl.Pyrolysis. 5 (1983) 257-259 (with Helge Egsgaard) 5) ’Continuous

Defect formation in fluoropolymer films at their condensation from a gas phase

NASA Astrophysics Data System (ADS)

Luchnikov, P. A.

2018-01-01

The questions of radiation defects, factors of influence of electronic high-frequency discharge plasma components on the molecular structure and properties of the fluoropolymer vacuum films synthesized on a substrate from a gas phase are considered. It is established that at sedimentation of fluoropolymer coverings from a gas phase in high-frequency discharge plasma in films there are radiation defects in molecular and supramolecular structure because of the influence of active plasma components which significantly influence their main properties.

New places and phases of CO-poor/CI-rich molecular gas in the Universe

NASA Astrophysics Data System (ADS)

Papadopoulos, Padelis P.; Bisbas, Thomas G.; Zhang, Zhiyu

2018-04-01

In this work we extend the work on the recently discovered role of Cosmic Rays (CRs) in regulating the average CO/H_2 abundance ratio in molecular clouds (and thus their CO line visibility) in starburst galaxies, and find that it can lead to a CO-poor/CI-rich H_2 gas phase even in environments with Galactic or in only modestly enhanced CR backgrounds expected in ordinary star-forming galaxies. Furthermore, the same CR-driven astro-chemistry raises the possibility of a widespread phase transition of molecular gas towards a CO-poor/CI-rich phase in: a) molecular gas outflows found in star-forming galaxies, b) active galactic nuclei (AGNs), and c) near synchrotron-emitting radio jets and the radio-loud cores of powerful radio galaxies. For main sequence galaxies we find that CRs can render some of their molecular gas mass CO-invisible, compounding the effects of low metallicities. Imaging the two fine structure lines of atomic carbon with resolution high enough to search beyond the CI/CO-bright line regions associated with central starbursts can reveal such a CO-poor/CI-rich molecular gas phase, provided that relative brightness sensitivity levels of Tb(CI 1 - 0)/Tb(CO J = 1 - 0) ˜0.15 are reached. The capability to search for such gas in the Galaxy is now at hand with the new high-frequency survey telescope HEAT deployed in Antarctica and future ones to be deployed in Dome A. ALMA can search for such gas in star-forming spiral disks, galactic molecular gas outflows and the CR-intense galactic and circumgalactic gas-rich environments of radio-loud objects.

Characterizing the correlations between local phase fractions of gas-liquid two-phase flow with wire-mesh sensor.

PubMed

Tan, C; Liu, W L; Dong, F

2016-06-28

Understanding of flow patterns and their transitions is significant to uncover the flow mechanics of two-phase flow. The local phase distribution and its fluctuations contain rich information regarding the flow structures. A wire-mesh sensor (WMS) was used to study the local phase fluctuations of horizontal gas-liquid two-phase flow, which was verified through comparing the reconstructed three-dimensional flow structure with photographs taken during the experiments. Each crossing point of the WMS is treated as a node, so the measurement on each node is the phase fraction in this local area. An undirected and unweighted flow pattern network was established based on connections that are formed by cross-correlating the time series of each node under different flow patterns. The structure of the flow pattern network reveals the relationship of the phase fluctuations at each node during flow pattern transition, which is then quantified by introducing the topological index of the complex network. The proposed analysis method using the WMS not only provides three-dimensional visualizations of the gas-liquid two-phase flow, but is also a thorough analysis for the structure of flow patterns and the characteristics of flow pattern transition. This article is part of the themed issue 'Supersensing through industrial process tomography'. © 2016 The Author(s).

The gas phase structure of α -pinene, a main biogenic volatile organic compound

NASA Astrophysics Data System (ADS)

Neeman, Elias M.; Avilés Moreno, Juan Ramón; Huet, Thérèse R.

2017-12-01

The gas phase structure of the bicyclic atmospheric aerosol precursor α-pinene was investigated employing a combination of quantum chemical calculation and Fourier transform microwave spectroscopy coupled to a supersonic jet expansion. The very weak rotational spectra of the parent species and all singly substituted 13C in natural abundance have been identified, from 2 to 20 GHz, and fitted to Watson's Hamiltonian model. The rotational constants were used together with geometrical parameters from density functional theory and ab initio calculations to determine the rs, r0, and rm(1 ) structures of the skeleton, without any structural assumption in the fit concerning the heavy atoms. The double C=C bond was found to belong to a quasiplanar skeleton structure containing 6 carbon atoms. Comparison with solid phase structure is reported. The significant differences of α-pinene in gas phase and other gas phase bicyclic monoterpene structures (β-pinene, nopinone, myrtenal, and bicyclo[3.1.1]heptane) are discussed.

Gas-liquid chromatography with a volatile "stationary" liquid phase.

PubMed

Wells, P S; Zhou, S; Parcher, J F

2002-05-01

A unique type of gas-liquid chromatography is described in which both mobile and "stationary" phases are composed of synthetic mixtures of helium and carbon dioxide. At temperatures below the critical point of the binary mixture and pressures above the vapor pressure of pure liquid carbon dioxide, helium and carbon dioxide can form two immiscible phases over extended composition ranges. A binary vapor phase enriched in helium can act as the mobile phase for chromatographic separations, whereas a CO2-rich liquid in equilibrium with the vapor phase, but condensed on the column wall, can act as a pseudostationary phase. Several examples of chromatographic separations obtained in "empty" capillary columns with no ordinary stationary liquid phase illustrate the range of conditions that produce such separations. In addition, several experiments are reported that confirm the proposed two-phase hypothesis. The possible consequences of the observed chromatographic phenomenon in the field of supercritical fluid chromatography with helium headspace carbon dioxide are discussed.

The physical chemistry of Criegee intermediates in the gas phase

DOE PAGES

Osborn, David L.; Taatjes, Craig A.

2015-07-24

Here, carbonyl oxides, also known as Criegee intermediates, are key intermediates in both gas phase ozonolysis of unsaturated hydrocarbons in the troposphere and solution phase organic synthesis via ozonolysis. Although the study of Criegee intermediates in both arenas has a long history, direct studies in the gas phase have only recently become possible through new methods of generating stabilised Criegee intermediates in sufficient quantities. This advance has catalysed a large number of new experimental and theoretical investigations of Criegee intermediate chemistry. In this article we review the physical chemistry of Criegee intermediates, focusing on their molecular structure, spectroscopy, unimolecular andmore » bimolecular reactions. These recent results have overturned conclusions from some previous studies, while confirming others, and have clarified areas of investigation that will be critical targets for future studies. In addition to expanding our fundamental understanding of Criegee intermediates, the rapidly expanding knowledge base will support increasingly predictive models of their impacts on society.« less

Solid phase microextraction for active or passive sampling of methyl bromide during fumigations

USDA-ARS?s Scientific Manuscript database

The high diffusivity and volatility of methyl bromide make it an ideal compound for Solid Phase Micro Extraction (SPME)-based sampling of air prior to gas-chromatographic quantifications. SPME fibers can be used as active methyl bromide samplers, with high capacities and an equilibrium time of 1-2 m...

Probing the energetics of dissociation of carbonic anhydrase-ligand complexes in the gas phase.

PubMed Central

Gao, J; Wu, Q; Carbeck, J; Lei, Q P; Smith, R D; Whitesides, G M

1999-01-01

This paper describes the use of electrospray ionization-Fourier transform ion cyclotron mass spectrometry (ESI-FTICR-MS) to study the relative stabilities of noncovalent complexes of carbonic anhydrase II (CAII, EC 4.2.1.1) and benzenesulfonamide inhibitors in the gas phase. Sustained off-resonance irradiation collision-induced dissociation (SORI-CID) was used to determine the energetics of dissociation of these CAII-sulfonamide complexes in the gas phase. When two molecules of a benzenesulfonamide (1) were bound simultaneously to one molecule of CAII, one of them was found to exhibit significantly weaker binding (DeltaE50 = 0.4 V, where E50 is defined as the amplitude of sustained off-resonance irradiation when 50% of the protein-ligand complexes are dissociated). In solution, the benzenesulfonamide group coordinates as an anion to a Zn(II) ion bound at the active site of the enzyme. The gas phase stability of the complex with the weakly bound inhibitor was the same as that of the inhibitor complexed with apoCAII (i.e., CAII with the Zn(II) ion removed from the binding site). These results indicate that specific interactions between the sulfonamide group on the inhibitor and the Zn(II) ion on CAII were preserved in the gas phase. Experiments also showed a higher gas phase stability for the complex of para-NO2-benzenesulfonamide-CAII than that for ortho-NO2-benzenesulfonamide-CAII complex. This result further suggests that steric interactions of the inhibitors with the binding pocket of CAII parallel those in solution. Overall, these results are consistent with the hypothesis that CAII retains, at least partially, the structure of its binding pocket in the gas phase on the time scale (seconds to minutes) of the ESI-FTICR measurements. PMID:10354450

Detection Of Gas-Phase Polymerization in SiH4 And GeH4

NASA Technical Reports Server (NTRS)

Shing, Yuh-Han; Perry, Joseph W.; Allevato, Camillo E.

1990-01-01

Inelastic scattering of laser light found to indicate onset of gas-phase polymerization in plasma-enhanced chemical-vapor deposition (PECVD) of photoconductive amorphous hydrogenated silicon/germanium alloy (a-SiGe:H) film. In PECVD process, film deposited from radio-frequency glow-discharge plasma of silane (SiH4) and germane (GeH4) diluted with hydrogen. Gas-phase polymerization undesirable because it causes formation of particulates and defective films.

Radioisotope measurements of the liquid-gas flow in the horizontal pipeline using phase method

NASA Astrophysics Data System (ADS)

Hanus, Robert; Zych, Marcin; Jaszczur, Marek; Petryka, Leszek; Świsulski, Dariusz

2018-06-01

The paper presents application of the gamma-absorption method to a two-phase liquid-gas flow investigation in a horizontal pipeline. The water-air mixture was examined by a set of two Am-241 radioactive sources and two NaI(Tl) scintillation probes. For analysis of the electrical signals obtained from detectors the cross-spectral density function (CSDF) was applied. Results of the gas phase average velocity measurements for CSDF were compared with results obtained by application of the classical cross-correlation function (CCF). It was found that the combined uncertainties of the gas-phase velocity in the presented experiments did not exceed 1.6% for CSDF method and 5.5% for CCF.

Determining phase diagrams of gas-liquid systems using a microfluidic PVT.

PubMed

Mostowfi, Farshid; Molla, Shahnawaz; Tabeling, Patrick

2012-11-07

A novel microfluidic device designed for analyzing phase diagrams of gas-liquid systems (PVT or pressure-volume-temperature measurements) is described. The method mimics the phase transition of a reservoir fluid as it travels through the wellbore from the formation to the surface. The device consists of a long serpentine microchannel etched in a silicon substrate. The local pressure inside the channel is measured using membrane-based optical pressure sensors positioned along the channel. Geometrical restrictions are placed along the microchannel in order to nucleate bubbles when nucleation conditions are met, thus preventing the development of a supersaturation state in the channel. We point out that a local equilibrium state between gas and liquid phases is achieved, which implies that equilibrium properties can be directly measured on the chip. We analyze different mixtures of hydrocarbon systems and, consistently with the preceding analysis, obtain excellent agreement between our technique and conventional measurements. From a practical viewpoint (important for the relevance of the technology), we observe that the measurement time of thermodynamic properties of gas-liquid systems is reduced from hours to minutes with the present device without compromising the measurement accuracy.

van der Waals Interactions in Hadron Resonance Gas: From Nuclear Matter to Lattice QCD.

PubMed

Vovchenko, Volodymyr; Gorenstein, Mark I; Stoecker, Horst

2017-05-05

An extension of the ideal hadron resonance gas (HRG) model is constructed which includes the attractive and repulsive van der Waals (VDW) interactions between baryons. This VDW-HRG model yields the nuclear liquid-gas transition at low temperatures and high baryon densities. The VDW parameters a and b are fixed by the ground state properties of nuclear matter, and the temperature dependence of various thermodynamic observables at zero chemical potential are calculated within the VDW-HRG model. Compared to the ideal HRG model, the inclusion of VDW interactions between baryons leads to a qualitatively different behavior of second and higher moments of fluctuations of conserved charges, in particular in the so-called crossover region T∼140-190  MeV. For many observables this behavior resembles closely the results obtained from lattice QCD simulations. This hadronic model also predicts nontrivial behavior of net-baryon fluctuations in the region of phase diagram probed by heavy-ion collision experiments. These results imply that VDW interactions play a crucial role in the thermodynamics of hadron gas. Thus, the commonly performed comparisons of the ideal HRG model with the lattice and heavy-ion data may lead to misconceptions and misleading conclusions.

Thermodynamics aspects of noise-induced phase synchronization

NASA Astrophysics Data System (ADS)

Pinto, Pedro D.; Oliveira, Fernando A.; Penna, André L. A.

2016-05-01

In this article, we present an approach for the thermodynamics of phase oscillators induced by an internal multiplicative noise. We analytically derive the free energy, entropy, internal energy, and specific heat. In this framework, the formulation of the first law of thermodynamics requires the definition of a synchronization field acting on the phase oscillators. By introducing the synchronization field, we have consistently obtained the susceptibility and analyzed its behavior. This allows us to characterize distinct phases in the system, which we have denoted as synchronized and parasynchronized phases, in analogy with magnetism. The system also shows a rich complex behavior, exhibiting ideal gas characteristics for low temperatures and susceptibility anomalies that are similar to those present in complex fluids such as water.

Thermodynamics aspects of noise-induced phase synchronization.

PubMed

Pinto, Pedro D; Oliveira, Fernando A; Penna, André L A

2016-05-01

In this article, we present an approach for the thermodynamics of phase oscillators induced by an internal multiplicative noise. We analytically derive the free energy, entropy, internal energy, and specific heat. In this framework, the formulation of the first law of thermodynamics requires the definition of a synchronization field acting on the phase oscillators. By introducing the synchronization field, we have consistently obtained the susceptibility and analyzed its behavior. This allows us to characterize distinct phases in the system, which we have denoted as synchronized and parasynchronized phases, in analogy with magnetism. The system also shows a rich complex behavior, exhibiting ideal gas characteristics for low temperatures and susceptibility anomalies that are similar to those present in complex fluids such as water.

Regio-Selective Intramolecular Hydrogen/Deuterium Exchange in Gas-Phase Electron Transfer Dissociation

NASA Astrophysics Data System (ADS)

Hamuro, Yoshitomo

2017-05-01

Protein backbone amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) typically utilizes enzymatic digestion after the exchange reaction and before MS analysis to improve data resolution. Gas-phase fragmentation of a peptic fragment prior to MS analysis is a promising technique to further increase the resolution. The biggest technical challenge for this method is elimination of intramolecular hydrogen/deuterium exchange (scrambling) in the gas phase. The scrambling obscures the location of deuterium. Jørgensen's group pioneered a method to minimize the scrambling in gas-phase electron capture/transfer dissociation. Despite active investigation, the mechanism of hydrogen scrambling is not well-understood. The difficulty stems from the fact that the degree of hydrogen scrambling depends on instruments, various parameters of mass analysis, and peptide analyzed. In most hydrogen scrambling investigations, the hydrogen scrambling is measured by the percentage of scrambling in a whole molecule. This paper demonstrates that the degree of intramolecular hydrogen/deuterium exchange depends on the nature of exchangeable hydrogen sites. The deuterium on Tyr amide of neurotensin (9-13), Arg-Pro-Tyr-Ile-Leu, migrated significantly faster than that on Ile or Leu amides, indicating the loss of deuterium from the original sites is not mere randomization of hydrogen and deuterium but more site-specific phenomena. This more precise approach may help understand the mechanism of intramolecular hydrogen exchange and provide higher confidence for the parameter optimization to eliminate intramolecular hydrogen/deuterium exchange during gas-phase fragmentation.

Regio-Selective Intramolecular Hydrogen/Deuterium Exchange in Gas-Phase Electron Transfer Dissociation.

PubMed

Hamuro, Yoshitomo

2017-05-01

Protein backbone amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) typically utilizes enzymatic digestion after the exchange reaction and before MS analysis to improve data resolution. Gas-phase fragmentation of a peptic fragment prior to MS analysis is a promising technique to further increase the resolution. The biggest technical challenge for this method is elimination of intramolecular hydrogen/deuterium exchange (scrambling) in the gas phase. The scrambling obscures the location of deuterium. Jørgensen's group pioneered a method to minimize the scrambling in gas-phase electron capture/transfer dissociation. Despite active investigation, the mechanism of hydrogen scrambling is not well-understood. The difficulty stems from the fact that the degree of hydrogen scrambling depends on instruments, various parameters of mass analysis, and peptide analyzed. In most hydrogen scrambling investigations, the hydrogen scrambling is measured by the percentage of scrambling in a whole molecule. This paper demonstrates that the degree of intramolecular hydrogen/deuterium exchange depends on the nature of exchangeable hydrogen sites. The deuterium on Tyr amide of neurotensin (9-13), Arg-Pro-Tyr-Ile-Leu, migrated significantly faster than that on Ile or Leu amides, indicating the loss of deuterium from the original sites is not mere randomization of hydrogen and deuterium but more site-specific phenomena. This more precise approach may help understand the mechanism of intramolecular hydrogen exchange and provide higher confidence for the parameter optimization to eliminate intramolecular hydrogen/deuterium exchange during gas-phase fragmentation. Graphical Abstract ᅟ.

Gas Phase Chromatography of some Group 4, 5, and 6 Halides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sylwester, Eric Robert

1998-10-01

Gas phase chromatography using The Heavy Element Volatility Instrument (HEVI) and the On Line Gas Apparatus (OLGA III) was used to determine volatilities of ZrBr 4, HfBr 4, RfBr 4, NbBr 5, TaOBr 3, HaCl 5, WBr 6, FrBr, and BiBr 3. Short-lived isotopes of Zr, Hf, Rf, Nb, Ta, Ha, W, and Bi were produced via compound nucleus reactions at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory and transported to the experimental apparatus using a He gas transport system. The isotopes were halogenated, separated from the other reaction products, and their volatilities determined by isothermal gas phase chromatography.more » Adsorption Enthalpy (ΔH a) values for these compounds were calculated using a Monte Carlo simulation program modeling the gas phase chromatography column. All bromides showed lower volatility than molecules of similar molecular structures formed as chlorides, but followed similar trends by central element. Tantalum was observed to form the oxybromide, analogous to the formation of the oxychloride under the same conditions. For the group 4 elements, the following order in volatility and ΔH a was observed: RfBr 4 > ZrBr 4 > HfBr 4. The ΔH a values determined for the group 4, 5, and 6 halides are in general agreement with other experimental data and theoretical predictions. Preliminary experiments were performed on Me-bromides. A new measurement of the half-life of 261Rf was performed. 261Rf was produced via the 248Cm( 18O, 5n) reaction and observed with a half-life of 74 -6 +7 seconds, in excellent agreement with the previous measurement of 78 -6 +11 seconds. We recommend a new half-life of 75±7 seconds for 261Rf based on these two measurements. Preliminary studies in transforming HEVI from an isothermal (constant temperature) gas phase chromatography instrument to a thermochromatographic (variable temperature) instrument have been completed. Thermochromatography is a technique that can be used to study the volatility and ΔH a of longer

Phase transitions in mixed gas hydrates: experimental observations versus calculated data.

PubMed

Schicks, Judith M; Naumann, Rudolf; Erzinger, Jörg; Hester, Keith C; Koh, Carolyn A; Sloan, E Dendy

2006-06-15

This paper presents the phase behavior of multicomponent gas hydrate systems formed from primarily methane with small amounts of ethane and propane. Experimental conditions were typically in a pressure range between 1 and 6 MPa, and the temperature range was between 260 and 290 K. These multicomponent systems have been investigated using a variety of techniques including microscopic observations, Raman spectroscopy, and X-ray diffraction. These techniques, used in combination, allowed for measurement of the hydrate structure and composition, while observing the morphology of the hydrate crystals measured. The hydrate formed immediately below the three-phase line (V-L --> V-L-H) and contained crystals that were both light and dark in appearance. The light crystals, which visually were a single solid phase, showed a spectroscopic indication for the presence of occluded free gas in the hydrate. In contrast, the dark crystals were measured to be structure II (sII) without the presence of these occluded phases. Along with hydrate measurements near the decomposition line, an unexpected transformation process was visually observed at P-T-conditions in the stability field of the hydrates. Larger crystallites transformed into a foamy solid upon cooling over this transition line (between 5 and 10 K below the decomposition temperature). Below the transition line, a mixture of sI and sII was detected. This is the first time that these multicomponent systems have been investigated at these pressure and temperature conditions using both visual and spectroscopic techniques. These techniques enabled us to observe and measure the unexpected transformation process showing coexistence of different gas hydrate phases.

A proof of the Biswas-Mitra-Bhattacharyya conjecture for the ideal quantum gas trapped under the generic power law potential U=\\sum\

NASA Astrophysics Data System (ADS)

Mehedi Faruk, Mir; Muktadir Rahman, Md

2016-03-01

The well known relation for ideal classical gas $\\Delta \\epsilon^2=kT^2 C_V$ which does not remain valid for quantum system is revisited. A new connection is established between energy fluctuation and specific heat for quantum gases, valid in the classical limit and the degenerate quantum regime as well. Most importantly the proposed Biswas-Mitra-Bhattacharyya (BMB) conjecture (Biswas $et.$ $al.$, J. Stat. Mech. P03013, 2015.) relating hump in energy fluctuation and discontinuity of specific heat is proved and precised in this manuscript.

Separation of gas from liquid in a two-phase flow system

NASA Technical Reports Server (NTRS)

Hayes, L. G.; Elliott, D. G.

1973-01-01

Separation system causes jets which leave two-phase nozzles to impinge on each other, so that liquid from jets tends to coalesce in center of combined jet streams while gas phase is forced to outer periphery. Thus, because liquid coalescence is achieved without resort to separation with solid surfaces, cycle efficiency is improved.

Comprehensive Analysis of the Gas- and Particle-Phase Products of VOC Oxidation

NASA Astrophysics Data System (ADS)

Bakker-Arkema, J.; Ziemann, P. J.

2017-12-01

Controlled environmental chamber studies are important for determining atmospheric reaction mechanisms and gas and aerosol products formed in the oxidation of volatile organic compounds (VOCs). Such information is necessary for developing detailed chemical models for use in predicting the atmospheric fate of VOCs and also secondary organic aerosol (SOA) formation. However, complete characterization of atmospheric oxidation reactions, including gas- and particle-phase product yields, and reaction branching ratios, are difficult to achieve. In this work, we investigated the reactions of terminal and internal alkenes with OH radicals in the presence of NOx in an attempt to fully characterize the chemistry of these systems while minimizing and accounting for the inherent uncertainties associated with environmental chamber experiments. Gas-phase products (aldehydes formed by alkoxy radical decomposition) and particle-phase products (alkyl nitrates, β-hydroxynitrates, dihydroxynitrates, 1,4-hydroxynitrates, 1,4-hydroxycarbonyls, and dihydroxycarbonyls) formed through pathways involving addition of OH to the C=C double bond as well as H-atom abstraction were identified and quantified using a suite of analytical techniques. Particle-phase products were analyzed in real time with a thermal desorption particle beam mass spectrometer; and off-line by collection onto filters, extraction, and subsequent analysis of functional groups by derivatization-spectrophotometric methods developed in our lab. Derivatized products were also separated by liquid chromatography for molecular quantitation by UV absorbance and identification using chemical ionization-ion trap mass spectrometry. Gas phase aldehydes were analyzed off-line by collection onto Tenax and a 5-channel denuder with subsequent analysis by gas chromatography, or by collection onto DNPH-coated cartridges and subsequent analysis by liquid chromatography. The full product identification and quantitation, with careful

Liquid and gas phase NMR spectra of 13CH313CHO acetaldehyde

NASA Astrophysics Data System (ADS)

Makulski, Włodzimierz; Wikieł, Agata J.

2018-01-01

The gas phase NMR experiments perform a vital role in establishing the magnetic shielding and spin-spin coupling constants which are free from intermolecular interactions, equivalent to the parameter of isolated molecules. This work is concerned with an acetaldehyde molecule. Small amounts of acetaldehyde 13CH313CHO in gaseous matrices of CO2 and Xe were studied using high-precision 1H and 13C NMR measurements. Results were extrapolated to the zero-density limit permitting the determinations of the 1H and 13C absolute nuclear magnetic shielding of an isolated acetaldehyde molecule. The difference between the experimental and recent theoretical DFT results is discussed. Several samples of 13CH313CHO dissolved in popular organic and inorganic solvents were also investigated. Gas-to-solution shifts show the influence of the association process when acetaldehyde is transferred from gas to liquid state. Several spin-spin coupling constants in the gas phase and in different solvents were precisely measured.

Neutral, ion gas-phase energetics and structural properties of hydroxybenzophenones.

PubMed

Dávalos, Juan Z; Guerrero, Andrés; Herrero, Rebeca; Jimenez, Pilar; Chana, Antonio; Abboud, José Luis M; Lima, Carlos F R A C; Santos, Luís M N B F; Lago, Alexsandre F

2010-04-16

We have carried out a study of the energetics, structural, and physical properties of o-, m-, and p-hydroxybenzophenone neutral molecules, C(13)H(10)O(2), and their corresponding anions. In particular, the standard enthalpies of formation in the gas phase at 298.15 K for all of these species were determined. A reliable experimental estimation of the enthalpy associated with intramolecular hydrogen bonding in chelated species was experimentally obtained. The gas-phase acidities (GA) of benzophenones, substituted phenols, and several aliphatic alcohols are compared with the corresponding aqueous acidities (pK(a)), covering a range of 278 kJ.mol(-1) in GA and 11.4 in pK(a). A computational study of the various species shed light on structural effects and further confirmed the self-consistency of the experimental results.

Statistical and Microscopic Approach to Gas Phase Chemical Kinetics.

ERIC Educational Resources Information Center

Perez, J. M.; Quereda, R.

1983-01-01

Describes advanced undergraduate laboratory exercise examining the dependence of the rate constants and the instantaneous concentrations with the nature and energy content in a gas-phase complex reaction. Computer program (with instructions and computation flow charts) used with the exercise is available from the author. (Author/JN)

Measurements of cross-sectional instantaneous phase distribution in gas-liquid pipe flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roitberg, E.; Shemer, L.; Barnea, D.

Two novel complementing methods that enable experimental study of gas and liquid phases distribution in two-phase pipe flow are considered. The first measuring technique uses a wire-mesh sensor that, in addition to providing data on instantaneous phase distribution in the pipe cross-section, also allows measuring instantaneous propagation velocities of the phase interface. A novel algorithm for processing the wire-mesh sensor data is suggested to determine the instantaneous boundaries of gas-liquid interface. The second method applied here takes advantage of the existence of sharp visible boundaries between the two phases. This optical instrument is based on a borescope that is connectedmore » to a digital video camera. Laser light sheet illumination makes it possible to obtain images in the illuminated pipe cross-section only. It is demonstrated that the wire-mesh-derived results based on application of the new algorithm improve the effective spatial resolution of the instrument and are in agreement with those obtained using the borescope. Advantages and limitations of both measuring techniques for the investigations of cross-sectional instantaneous phase distribution in two-phase pipe flows are discussed. (author)« less

Schlieren optical visualization for transient EHD induced flow in a stratified dielectric liquid under gas-phase ac corona discharges

NASA Astrophysics Data System (ADS)

Ohyama, R.; Inoue, K.; Chang, J. S.

2007-01-01

A flow pattern characterization of electrohydrodynamically (EHD) induced flow phenomena of a stratified dielectric fluid situated in an ac corona discharge field is conducted by a Schlieren optical system. A high voltage application to a needle-plate electrode arrangement in gas-phase normally initiates a conductive type EHD gas flow. Although the EHD gas flow motion initiated from the corona discharge electrode has been well known as corona wind, no comprehensive study has been conducted for an EHD fluid flow motion of the stratified dielectric liquid that is exposed to the gas-phase ac corona discharge. The experimentally observed result clearly presents the liquid-phase EHD flow phenomenon induced from the gas-phase EHD flow via an interfacial momentum transfer. The flow phenomenon is also discussed in terms of the gas-phase EHD number under the reduced gas pressure (reduced interfacial momentum transfer) conditions.

Closed-cage tungsten oxide clusters in the gas phase.

PubMed

Singh, D M David Jeba; Pradeep, T; Thirumoorthy, Krishnan; Balasubramanian, Krishnan

2010-05-06

During the course of a study on the clustering of W-Se and W-S mixtures in the gas phase using laser desorption ionization (LDI) mass spectrometry, we observed several anionic W-O clusters. Three distinct species, W(6)O(19)(-), W(13)O(29)(-), and W(14)O(32)(-), stand out as intense peaks in the regular mass spectral pattern of tungsten oxide clusters suggesting unusual stabilities for them. Moreover, these clusters do not fragment in the postsource decay analysis. While trying to understand the precursor material, which produced these clusters, we found the presence of nanoscale forms of tungsten oxide. The structure and thermodynamic parameters of tungsten clusters have been explored using relativistic quantum chemical methods. Our computed results of atomization energy are consistent with the observed LDI mass spectra. The computational results suggest that the clusters observed have closed-cage structure. These distinct W(13) and W(14) clusters were observed for the first time in the gas phase.

3-D Numerical Simulation for Gas-Liquid Two-Phase Flow in Aeration Tank

NASA Astrophysics Data System (ADS)

Xue, R.; Tian, R.; Yan, S. Y.; Li, S.

In the crafts of activated sludge treatment, oxygen supply and the suspending state of activated sludge are primary factors to keep biochemistry process carrying on normally. However, they are all controlled by aeration. So aeration is crucial. The paper focus on aeration, use CFD software to simulate the field of aeration tank which is designed by sludge load method. The main designed size of aeration tank is: total volume: 20 000 m3; corridor width: 8m; total length of corridors: 139m; number of corridors: 3; length of one single corridor: 48m; effective depth: 4.5m; additional depth: 0.5m. According to the similarity theory, a geometrical model is set up in proportion of 10:1. The way of liquid flow is submerge to avoid liquid flow out directly. The grid is plotted by dividing the whole computational area into two parts. The bottom part which contains gas pipe and gas exit hole and the above part which is the main area are plotted by tetrahedron and hexahedron respectively. In boundary conditions, gas is defined as the primary-phase, and liquid is defined as the secondary-phase. Choosing mixture model, two-phase flow field of aeration tank is simulated by solved the Continuity equation for the mixture, Momentum equation for the mixture, Volume fraction equation for the secondary phases and Relative velocity formula when gas velocity is 10m/s, 20m/s, 30m/s. what figure shows is the contour of velocity magnitude for the mixture phase when gas velocity is 20m/s. Through analysis, the simulation tendency is agreed with actual running of aeration tank. It is feasible to use mixture model to simulate flow field of aeration tank by fluent software. According to the simulation result, the better velocity of liquid or gas (the quantity of inlet air) can be chosen by lower cost, and also the performance of aeration tank can be forecast. It will be helpful for designing and operation.

Yb-doped large-mode-area laser fiber fabricated by halide-gas-phase-doping technique

NASA Astrophysics Data System (ADS)

Peng, Kun; Wang, Yuying; Ni, Li; Wang, Zhen; Gao, Cong; Zhan, Huan; Wang, Jianjun; Jing, Feng; Lin, Aoxiang

2015-06-01

In this manuscript, we designed a rare-earth-halide gas-phase-doping setup to fabricate a large-mode-area fiber for high power laser applications. YbCl3 and AlCl3 halides are evaporated, carried respectively and finally mixed with usual host gas material SiCl4 at the hot zone of MCVD system. Owing to the all-gas-phasing reaction process and environment, the home-made Yb-doped fiber preform has a homogeneous large core and modulated refractive index profile to keep high beam quality. The drawn fiber core has a small numerical aperture of 0.07 and high Yb concentration of 9500 ppm. By using a master oscillator power amplifier system, nearly kW-level (951 W) laser output power was obtained with a slope efficiency of 83.3% at 1063.8 nm, indicating the competition and potential of the halide-gas-phase-doping technique for high power laser fiber fabrication.

Methanol ice co-desorption as a mechanism to explain cold methanol in the gas-phase

NASA Astrophysics Data System (ADS)

Ligterink, N. F. W.; Walsh, C.; Bhuin, R. G.; Vissapragada, S.; van Scheltinga, J. Terwisscha; Linnartz, H.

2018-05-01

Context. Methanol is formed via surface reactions on icy dust grains. Methanol is also detected in the gas-phase at temperatures below its thermal desorption temperature and at levels higher than can be explained by pure gas-phase chemistry. The process that controls the transition from solid state to gas-phase methanol in cold environments is not understood. Aims: The goal of this work is to investigate whether thermal CO desorption provides an indirect pathway for methanol to co-desorb at low temperatures. Methods: Mixed CH3OH:CO/CH4 ices were heated under ultra-high vacuum conditions and ice contents are traced using RAIRS (reflection absorption IR spectroscopy), while desorbing species were detected mass spectrometrically. An updated gas-grain chemical network was used to test the impact of the results of these experiments. The physical model used is applicable for TW Hya, a protoplanetary disk in which cold gas-phase methanol has recently been detected. Results: Methanol release together with thermal CO desorption is found to be an ineffective process in the experiments, resulting in an upper limit of ≤ 7.3 × 10-7 CH3OH molecules per CO molecule over all ice mixtures considered. Chemical modelling based on the upper limits shows that co-desorption rates as low as 10-6 CH3OH molecules per CO molecule are high enough to release substantial amounts of methanol to the gas-phase at and around the location of the CO thermal desorption front in a protoplanetary disk. The impact of thermal co-desorption of CH3OH with CO as a grain-gas bridge mechanism is compared with that of UV induced photodesorption and chemisorption.

Parents of two-phase flow and theory of "gas-lift"

NASA Astrophysics Data System (ADS)

Zitek, Pavel; Valenta, Vaclav

2014-03-01

This paper gives a brief overview of types of two-phase flow. Subsequently, it deals with their mutual division and problems with accuracy boundaries among particular types. It also shows the case of water flow through a pipe with external heating and the gradual origination of all kinds of flow. We have met it in solution of safety condition of various stages in pressurized and boiling water reactors. In the MSR there is a problem in the solution of gas-lift using helium as a gas and its secondary usage for clearing of the fuel mixture from gaseous fission products. Theory of gas-lift is described.

Conformational Study of DNA Sugars: from the Gas Phase to Solution

NASA Astrophysics Data System (ADS)

Uriarte, Iciar; Vallejo-López, Montserrat; Cocinero, Emilio J.; Corzana, Francisco; Davis, Benjamin G.

2017-06-01

Sugars are versatile molecules that play a variety of roles in the organism. For example, they are important in energy storage processes or as structural scaffolds. Here, we focus on the monosaccharide present in DNA by addressing the conformational and puckering properties in the gas phase of α- and β-methyl-2-deoxy-ribofuranoside and α- and β-methyl-2-deoxy-ribopiranoside. Other sugars have been previously studied in the gas phase The work presented here stems from a combination of chemical synthesis, ultrafast vaporization methods, supersonic expansions, microwave spectroscopy (both chirped-pulsed and Balle-Flygare cavity-based spectrometers) and NMR spectroscopy. Previous studies in the gas phase had been performed on 2-deoxyribose, but only piranose forms were detected. However, thanks to the combination of these techniques, we have isolated and characterized for the first time the conformational landscape of the sugar present in DNA in its biologically relevant furanose form. Our gas phase study serves as a probe of the conformational preferences of these biomolecules under isolation conditions. Thanks to the NMR experiments, we can characterize the favored conformations in solution and extract the role of the solvent in the structure and puckering of the monosaccharides. E. J. Cocinero, A. Lesarri, P. Écija, F. J. Basterretxea, J.-U. Grabow, J. A. Fernández, F. Castaño, Angew. Chem. Int. Edit. 2012, 51, 3119. P. Écija, I. Uriarte, L. Spada, B. G. Davis, W. Caminati, F. J. Basterretxea, A. Lesarri, E. J. Cocinero, Chem. Commun. 2016, 52, 6241. I. Peña, E. J. Cocinero, C. Cabezas, A. Lesarri, S. Mata, P. Écija, A. M. Daly, Á. Cimas, C. Bermúdez, F. J. Basterretxea, S. Blanco, J. A. Fernández, J. C. López, F. Castaño, J. L. Alonso, Angew. Chem. Int. Edit. 2013, 52, 11840.

INVESTIGATION OF GAS-PHASE OZONE AS A POTENTIAL BIOCIDE

EPA Science Inventory

The paper presents data on the effect of ozone on both vegetative and spore-forming fungi as well as on spore-forming bacteria. (NOTE: Despite the wide use of ozone generators in indoor air cleaning, there is little research data on ozone's biocidal activity in the gas phase.) Dr...

Microfluidic and nanofluidic phase behaviour characterization for industrial CO2, oil and gas.

PubMed

Bao, Bo; Riordon, Jason; Mostowfi, Farshid; Sinton, David

2017-08-08

Microfluidic systems that leverage unique micro-scale phenomena have been developed to provide rapid, accurate and robust analysis, predominantly for biomedical applications. These attributes, in addition to the ability to access high temperatures and pressures, have motivated recent expanded applications in phase measurements relevant to industrial CO 2 , oil and gas applications. We here present a comprehensive review of this exciting new field, separating microfluidic and nanofluidic approaches. Microfluidics is practical, and provides similar phase properties analysis to established bulk methods with advantages in speed, control and sample size. Nanofluidic phase behaviour can deviate from bulk measurements, which is of particular relevance to emerging unconventional oil and gas production from nanoporous shale. In short, microfluidics offers a practical, compelling replacement of current bulk phase measurement systems, whereas nanofluidics is not practical, but uniquely provides insight into phase change phenomena at nanoscales. Challenges, trends and opportunities for phase measurements at both scales are highlighted.

Fundamental studies of gas phase ionic reactions by ion mobility spectrometry

NASA Technical Reports Server (NTRS)

Giles, K.; Knighton, W. B.; Sahlstrom, K. E.; Grimsrud, E. P.

1995-01-01

Ion mobility spectrometry (IMS) provides a promising approach to the study of gas phase ionic reactions in buffer gases at unusually high pressures. This point is illustrated here by studies of the Sn2 nucleophilic displacement reaction, Cl(-) + CH3Br yields Br + CH3Br, using IMS at atmospheric pressure. The equilibrium clustering reaction, Cl(-)(CHCI3)(n - 1) + CHCI3 yields Cl(-)(CHCI3)(n), where n = 1 and 2, and the effect of clustering on the Sn2 reaction with CH3Br have also been characterized by this IMS-based kinetic method. Present problems and anticipated improvements in the application of ion mobility spectrometry to studies of other gas phase ionic processes are discussed.

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1998-01-01

The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

Gas-phase chemistry in dense interstellar clouds including grain surface molecular depletion and desorption

NASA Technical Reports Server (NTRS)

Bergin, E. A.; Langer, W. D.; Goldsmith, P. F.

1995-01-01

We present time-dependent models of the chemical evolution of molecular clouds which include depletion of atoms and molecules onto grain surfaces and desorption, as well as gas-phase interactions. We have included three mechanisms to remove species from the grain mantles: thermal evaporation, cosmic-ray-induced heating, and photodesorption. A wide range of parameter space has been explored to examine the abundance of species present both on the grain mantles and in the gas phase as a function of both position in the cloud (visual extinction) and of evolutionary state (time). The dominant mechanism that removes molecules from the grain mantles is cosmic-ray desorption. At times greater than the depletion timescale, the abundances of some simple species agree with abundances observed in the cold dark cloud TMC-1. Even though cosmic-ray desorption preserves the gas-phase chemistry at late times, molecules do show significant depletions from the gas phase. Examination of the dependence of depletion as a function of density shows that when the density increases from 10(exp 3)/cc to 10(exp 5)/cc several species including HCO(+), HCN, and CN show gas-phase abundance reductions of over an order of magnitude. The CO: H2O ratio in the grain mantles for our standard model is on the order of 10:1, in reasonable agreement with observations of nonpolar CO ice features in rho Ophiuchus and Serpens. We have also examined the interdependence of CO depletion with the space density of molecular hydrogen and binding energy to the grain surface. We find that the observed depletion of CO in Taurus in inconsistent with CO bonding in an H2O rich mantle, in agreement with observations. We suggest that if interstellar grains consist of an outer layer of CO ice, then the binding energies for many species to the grain mantle may be lower than commonly used, and a significant portion of molecular material may be maintained in the gas phase.

Liquid-gas phase transition in asymmetric nuclear matter at finite temperature

NASA Astrophysics Data System (ADS)

Maruyama, Toshiki; Tatsumi, Toshitaka; Chiba, Satoshi

2010-03-01

Liquid-gas phase transition is discussed in warm asymmetric nuclear matter. Some peculiar features are figured out from the viewpoint of the basic thermodynamics about the phase equilibrium. We treat the mixed phase of the binary system based on the Gibbs conditions. When the Coulomb interaction is included, the mixed phase is no more uniform and the sequence of the pasta structures appears. Comparing the results with those given by the simple bulk calculation without the Coulomb interaction, we extract specific features of the pasta structures at finite temperature.

Measurement of Gas-Liquid Two-Phase Flow in Micro-Pipes by a Capacitance Sensor

PubMed Central

Ji, Haifeng; Li, Huajun; Huang, Zhiyao; Wang, Baoliang; Li, Haiqing

2014-01-01

A capacitance measurement system is developed for the measurement of gas-liquid two-phase flow in glass micro-pipes with inner diameters of 3.96, 2.65 and 1.56 mm, respectively. As a typical flow regime in a micro-pipe two-phase flow system, slug flow is chosen for this investigation. A capacitance sensor is designed and a high-resolution and high-speed capacitance measurement circuit is used to measure the small capacitance signals based on the differential sampling method. The performance and feasibility of the capacitance method are investigated and discussed. The capacitance signal is analyzed, which can reflect the voidage variation of two-phase flow. The gas slug velocity is determined through a cross-correlation technique using two identical capacitance sensors. The simulation and experimental results show that the presented capacitance measurement system is successful. Research work also verifies that the capacitance sensor is an effective method for the measurement of gas liquid two-phase flow parameters in micro-pipes. PMID:25587879

Measurement of gas-liquid two-phase flow in micro-pipes by a capacitance sensor.

PubMed

Ji, Haifeng; Li, Huajun; Huang, Zhiyao; Wang, Baoliang; Li, Haiqing

2014-11-26

A capacitance measurement system is developed for the measurement of gas-liquid two-phase flow in glass micro-pipes with inner diameters of 3.96, 2.65 and 1.56 mm, respectively. As a typical flow regime in a micro-pipe two-phase flow system, slug flow is chosen for this investigation. A capacitance sensor is designed and a high-resolution and high-speed capacitance measurement circuit is used to measure the small capacitance signals based on the differential sampling method. The performance and feasibility of the capacitance method are investigated and discussed. The capacitance signal is analyzed, which can reflect the voidage variation of two-phase flow. The gas slug velocity is determined through a cross-correlation technique using two identical capacitance sensors. The simulation and experimental results show that the presented capacitance measurement system is successful. Research work also verifies that the capacitance sensor is an effective method for the measurement of gas liquid two-phase flow parameters in micro-pipes.

Resolving Gas-Phase Metallicity In Galaxies

NASA Astrophysics Data System (ADS)

Carton, David

2017-06-01

Chapter 2: As part of the Bluedisk survey we analyse the radial gas-phase metallicity profiles of 50 late-type galaxies. We compare the metallicity profiles of a sample of HI-rich galaxies against a control sample of HI-'normal' galaxies. We find the metallicity gradient of a galaxy to be strongly correlated with its HI mass fraction {M}{HI}) / {M}_{\\ast}). We note that some galaxies exhibit a steeper metallicity profile in the outer disc than in the inner disc. These galaxies are found in both the HI-rich and control samples. This contradicts a previous indication that these outer drops are exclusive to HI-rich galaxies. These effects are not driven by bars, although we do find some indication that barred galaxies have flatter metallicity profiles. By applying a simple analytical model we are able to account for the variety of metallicity profiles that the two samples present. The success of this model implies that the metallicity in these isolated galaxies may be in a local equilibrium, regulated by star formation. This insight could provide an explanation of the observed local mass-metallicity relation. Chapter 3 We present a method to recover the gas-phase metallicity gradients from integral field spectroscopic (IFS) observations of barely resolved galaxies. We take a forward modelling approach and compare our models to the observed spatial distribution of emission line fluxes, accounting for the degrading effects of seeing and spatial binning. The method is flexible and is not limited to particular emission lines or instruments. We test the model through comparison to synthetic observations and use downgraded observations of nearby galaxies to validate this work. As a proof of concept we also apply the model to real IFS observations of high-redshift galaxies. From our testing we show that the inferred metallicity gradients and central metallicities are fairly insensitive to the assumptions made in the model and that they are reliably recovered for galaxies

A GAS-PHASE FORMATION ROUTE TO INTERSTELLAR TRANS-METHYL FORMATE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cole, Callie A.; Wehres, Nadine; Yang Zhibo

2012-07-20

The abundance of methyl formate in the interstellar medium has previously been underpredicted by chemical models. Additionally, grain surface chemistry cannot account for the relative abundance of the cis- and trans-conformers of methyl formate, and the trans-conformer is not even formed at detectable abundance on these surfaces. This highlights the importance of studying formation pathways to methyl formate in the gas phase. The rate constant and branching fractions are reported for the gas-phase reaction between protonated methanol and formic acid to form protonated trans-methyl formate and water as well as adduct ion: Rate constants were experimentally determined using a flowingmore » afterglow-selected ion flow tube apparatus at 300 K and a pressure of 530 mTorr helium. The results indicate a moderate overall rate constant of (3.19 {+-} 0.39) Multiplication-Sign 10{sup -10} cm{sup 3} s{sup -1} ({+-} 1{sigma}) and an average branching fraction of 0.05 {+-} 0.04 for protonated trans-methyl formate and 0.95 {+-} 0.04 for the adduct ion. These experimental results are reinforced by ab initio calculations at the MP2(full)/aug-cc-pVTZ level of theory to examine the reaction coordinate and complement previous density functional theory calculations. This study underscores the need for continued observational studies of trans-methyl formate and for the exploration of other gas-phase formation routes to complex organic molecules.« less

Laser Studies of Gas Phase Radical Reactions.

DTIC Science & Technology

1989-01-01

synchronised chopper ( Rofin 7500) to block the laser beam on alternate shots to allow background subtraction. Signal due to scattered laser light was...synchronised chopper ( Rofin 7500) to block the laser beam on alternate shots to allow background subtraction. Signal due to scattered laser light was...Cassufication) (U) Laser Studies of Gas Phase Radical Reactions 𔃼 ,ERSRP4AL UTHOR($) I3a. TYPE Of REPORT 13b. TIME COVERtD 14 D T8?’F JPORT (Year, Maonlth, Da

FAST TRACK COMMUNICATION: Gas liquid phase coexistence in a tetrahedral patchy particle model

NASA Astrophysics Data System (ADS)

Romano, Flavio; Tartaglia, Piero; Sciortino, Francesco

2007-08-01

We evaluate the location of the gas-liquid coexistence line and of the associated critical point for the primitive model for water (PMW), introduced by Kolafa and Nezbeda (1987 Mol. Phys. 61 161). Besides being a simple model for a molecular network forming liquid, the PMW is representative of patchy proteins and novel colloidal particles interacting with localized directional short-range attractions. We show that the gas-liquid phase separation is metastable, i.e. it takes place in the region of the phase diagram where the crystal phase is thermodynamically favoured, as in the case of particles interacting via short-range attractive spherical potentials. We do not observe crystallization close to the critical point. The region of gas-liquid instability of this patchy model is significantly reduced as compared to that from equivalent models of spherically interacting particles, confirming the possibility of observing kinetic arrest in a homogeneous sample driven by bonding as opposed to packing.

Gas-phase and particle-phase PCDD/F congener distributions in the flue gas from an iron ore sintering plant.

PubMed

Liu, Xiaolong; Ye, Meng; Wang, Xue; Liu, Wen; Zhu, Tingyu

2017-04-01

The activated carbon injection-circulating fluidized bed (ACI-CFB)-bag filter coupling technique was studied in an iron ore sintering plant. For comparison, the removal efficiencies under the conditions without or with ACI technology were both evaluated. It was found that the polychlorinated dibenzo-p-dioxins and dibenzofuran (PCDD/F) removal efficiency for total international toxic equivalence quantity (I-TEQ) concentration was improved from 91.61% to 97.36% when ACI was employed, revealing that ACI was very conducive to further controlling the PCDD/F emissions. Detailed congener distributions of PCDD/Fs in the gas-phase and particle-phase of the Inlet and Outlet samples were determined. Additionally, the PCDD/F distribution for the Fly ash-with ACI sample of was also studied. Copyright © 2016. Published by Elsevier B.V.

Some Fundamental Experiments on Apparent Dissolution Rate of Gas Phase in the Groundwater Recovery Processes of the Geological Disposal System - 12146

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoshii, Taiki; Niibori, Yuichi; Mimura, Hitoshi

The apparent dissolution rates of gas phase in the co-presence of solid phase were examined by in-room experiments in this study. The apparent dissolution rate of gas phase q (mol/m{sup 3}.s) was generally defined by q=aK{sub L}(γP{sub g}-c), where a (1/m) is specific surface area of the interface between gas and liquid phases, K{sub L} (m/s) is overall mass transfer coefficient, γ (mol/(Pa.m{sup 3})) is reciprocal number of Henry constant, P{sub g} (Pa) is partial pressure of gas phase, and c (mol/m{sup 3}) is the concentration of gas component in liquid phase. As a model gas, CO{sub 2} gas wasmore » used. For evaluating the values of K{sub L}, this study monitored pH or the migration rate of the interface between water/gas phases, using some experiments such as the packed beds and the micro channel consisting of granite chip and rubber sheet including a slit. In the results, the values of K{sub L} were distributed in the range from 5.0x10{sup -6} m/s to 5.0x10{sup -7} m/s. These values were small, in comparison with that (7.8x10{sup -4} m/s) obtained from the bubbling test where gas phase was continually injected into deionized water without solid phase. This means that the solid phase limits the local mixing of water phase near gas-liquid interfaces. (authors)« less

DEMONSTRATION OF FUEL CELLS TO RECOVER ENERGY FROM LANDFILL GAS: PHASE II. PRETREATMENT SYSTEM PERFORMANCE MEASUREMENT

EPA Science Inventory

The report describes Phase II of a demonstration of the utilization of commercial phosphoric acid fuel cells to recover energy from landfill gas. This phase consisted primarily of the construction and testing of a Gas Pretreatment Unit (GPU) whose function is to remove those impu...

Modifications to Langley 0.3-m TCT adaptive wall software for heavy gas test medium, phase 1 studies

NASA Technical Reports Server (NTRS)

Murthy, A. V.

1992-01-01

The scheme for two-dimensional wall adaptation with sulfur hexafluoride (SF6) as test gas in the NASA Langley Research Center 0.3-m Transonic Cryogenic Tunnel (0.3-m TCT) is presented. A unified version of the wall adaptation software has been developed to function in a dual gas operation mode (nitrogen or SF6). The feature of ideal gas calculations for nitrogen operation is retained. For SF6 operation, real gas properties have been computed using the departure function technique. Installation of the software on the 0.3-m TCT ModComp-A computer and preliminary validation with nitrogen operation were found to be satisfactory. Further validation and improvements to the software will be undertaken when the 0.3-m TCT is ready for operation with SF6 gas.

Not All Ideals are Equal: Intrinsic and Extrinsic Ideals in Relationships.

PubMed

Rodriguez, Lindsey M; Hadden, Benjamin W; Knee, C Raymond

2015-03-01

The ideal standards model suggests that greater consistency between ideal standards and actual perceptions of one's relationship predicts positive relationship evaluations; however, no research has evaluated whether this differs across types of ideals. A self-determination theory perspective was derived to test whether satisfaction of intrinsic ideals buffers the importance of extrinsic ideals. Participants (N=195) in committed relationships directly and indirectly reported the extent to which their partner met their ideal on two dimensions: intrinsic (e.g., warm, intimate) and extrinsic (e.g., attractive, successful). Relationship need fulfillment and relationship quality were also assessed. Hypotheses were largely supported, such that satisfaction of intrinsic ideals more strongly predicted relationship functioning, and satisfaction of intrinsic ideals buffered the relevance of extrinsic ideals for outcomes.

Not All Ideals are Equal: Intrinsic and Extrinsic Ideals in Relationships

PubMed Central

Rodriguez, Lindsey M.; Hadden, Benjamin W.; Knee, C. Raymond

2015-01-01

The ideal standards model suggests that greater consistency between ideal standards and actual perceptions of one’s relationship predicts positive relationship evaluations; however, no research has evaluated whether this differs across types of ideals. A self-determination theory perspective was derived to test whether satisfaction of intrinsic ideals buffers the importance of extrinsic ideals. Participants (N=195) in committed relationships directly and indirectly reported the extent to which their partner met their ideal on two dimensions: intrinsic (e.g., warm, intimate) and extrinsic (e.g., attractive, successful). Relationship need fulfillment and relationship quality were also assessed. Hypotheses were largely supported, such that satisfaction of intrinsic ideals more strongly predicted relationship functioning, and satisfaction of intrinsic ideals buffered the relevance of extrinsic ideals for outcomes. PMID:25821396

FIELD METHODS TO MEASURE CONTAMINANT REMOVAL EFFECTIVENESS OF GAS-PHASE AIR FILTRATION EQUIPMENT - PHASE 1: SEARCH OF LITERATURE AND PRIOR ART

EPA Science Inventory

The report, Phase 1 of a two-phase research project, gives results of a literature search into the
effectiveness of in-field gas-phase air filtration equipment (GPAFE) test methods, including required instrumentation and costs. GPAFE has been used in heating, ventilation, and ...

Gas holdup and flow regime transition in spider-sparger bubble column: effect of liquid phase properties

NASA Astrophysics Data System (ADS)

Besagni, G.; Inzoli, F.; De Guido, G.; Pellegrini, L. A.

2017-01-01

This paper discusses the effects of the liquid velocity and the liquid phase properties on the gas holdup and the flow regime transition in a large-diameter and large-scale counter-current two-phase bubble column. In particular, we compared and analysed the experimental data obtained in our previous experimental studies. The bubble column is 5.3 m in height, has an inner diameter of 0.24 m, it was operated with gas superficial velocities in the range of 0.004-0.20 m/s and, in the counter-current mode, the liquid was recirculated up to a superficial velocity of -0.09 m/s. Air was used as the dispersed phase and various fluids (tap water, aqueous solutions of sodium chloride, ethanol and monoethylene glycol) were employed as liquid phases. The experimental dataset consist in gas holdup measurements and was used to investigate the global fluid dynamics and the flow regime transition between the homogeneous flow regime and the transition flow regime. We found that the liquid velocity and the liquid phase properties significantly affect the gas holdup and the flow regime transition. In this respect, a possible relationship (based on the lift force) between the flow regime transition and the gas holdup was proposed.

Gas-phase abundances of refractory elements in planetary nebulae - A hot-wind model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shields, G.A.

Planetary nebulae (PN) characteristically show large gas-phase depletions of some refractory elements, with Fe/H and Ca/H concentration ratios approximately equal to -1.5. In contrast, the gas-phase abundance of carbon is large, with a C/H concentration ratio greater than approximately +0.3. This pattern is difficult to understand in terms of grain formation and destruction during PN formation. However, these abundances are consistent with a model (Kwok, Purton, and FitzGerald, 1978) in which the PN shell consists of material expelled as a wind during the red-giant phase and subsequently compressed and accelerated by the impact of a hot stellar wind from themore » central star.« less

The role of gas phase reactions in the deflagration-to-detonation transition of high energy propellants

NASA Technical Reports Server (NTRS)

Boggs, T. L.; Price, C. F.; Atwood, A. I.; Zurn, D. E.; Eisel, J. L.; Derr, R. L.

1980-01-01

The inadequacies of the two commonly used assumptions are shown, along with the need for considering gas phase reactions. Kinetic parameters that describe the gas phase reactions for several ingredients are provided, and the first steps in convective combustion leading to deflagration to detonation transition are described.

Exploring the Photoreduction of Au(III) Complexes in the Gas-Phase

NASA Astrophysics Data System (ADS)

Marcum, Jesse C.; Kaufman, Sydney H.; Weber, J. Mathias

2010-06-01

We have used photodissociation spectroscopy to probe the electronic structure and photoreduction of Au(III) in gas-phase complexes containing Cl- and OH-. The gas-phase electronic spectrum of [AuCl_4]- closely resembles the aqueous solution spectrum, showing a lack of strong solvatochromic shifts. Substitution of Cl- ligands with OH- results in a strong blue shift, in agreement with ligand-field theory. Upon excitation, [AuCl_4]- can dissociate by loss of either one or two neutral Cl atoms, resulting in the reduction of gold from Au(III) to Au(II) and Au(I) respectively. The hydroxide substituted complex, [AuCl_2(OH)_2]-, demonstrates similar behavior but the only observable fragment channel is the loss of two neutral OH ligands, leading only to Au(I).

Influence of the choice of gas-phase mechanism on predictions of key gaseous pollutants during the AQMEII phase-2 intercomparison

EPA Science Inventory

The formulations of tropospheric gas-phase chemistry (“mechanisms”)used in the regional-scale chemistry-transport models participating in theAir Quality Modelling Evaluation International Initiative (AQMEII) Phase2 are intercompared by the means of box model studies. Simulations ...

On the Equipartition of Kinetic Energy in an Ideal Gas Mixture

ERIC Educational Resources Information Center

Peliti, L.

2007-01-01

A refinement of an argument due to Maxwell for the equipartition of translational kinetic energy in a mixture of ideal gases with different masses is proposed. The argument is elementary, yet it may work as an illustration of the role of symmetry and independence postulates in kinetic theory. (Contains 1 figure.)

Unifying the microscopic picture of His-containing turns: from gas phase model peptides to crystallized proteins.

PubMed

Sohn, Woon Yong; Habka, Sana; Gloaguen, Eric; Mons, Michel

2017-07-14

The presence in crystallized proteins of a local anchoring between the side chain of a His residue, located in the central position of a γ- or β-turn, and its local main chain environment, was assessed by the comparison of protein structures with relevant isolated model peptides. Gas phase laser spectroscopy, combined with relevant quantum chemistry methods, was used to characterize the γ- and β-turn structures in these model peptides. A conformer-selective NH stretch infrared study provided evidence for the formation in vacuo of two types of short-range H-bonded motifs, labelled ε-6 δ and δ- δ 7/π H , bridging the His side chain (in its gauche+ rotamer) to the neighbouring NH(i) and CO(i) sites of the backbone; each side chain-backbone motif was found to be specific of the tautomer (ε or δ) adopted by the His side chain in its neutral form. A close comparison between β- and γ-turns, selected from the Protein Data Bank, and the gas phase models demonstrated that a significant proportion of the gauche+ His rotamer distribution of proteins was well described by the corresponding gas phase H-bonded structures. This is consistent with the persistence of local 6 δ and δ 7/π H intramolecular interactions in proteins, emphasizing the relevance of gas phase data to secondary structures that are poorly accessible to solvents, e.g., in the case of a specific compact topology (Xxx-His β-turns). Deviations from the gas phase structures were also observed, mainly in His-Xxx β-turns, and assigned to solvent accessible turn structures. They were well accounted for by theoretical models of microhydrated turns, in which a few solvent molecules take over the gas phase motifs, constituting a water-mediated local anchoring of the His side chain to the backbone. Finally, the present gas phase benchmark models also pinpointed weaknesses in the protein structure determination by X-ray diffraction analysis; in particular, besides the lack of tautomer information

Gas-fired duplex free-piston Stirling refrigerator

NASA Astrophysics Data System (ADS)

Urieli, L.

1984-03-01

The duplex free-piston Stirling refrigerator is a potentially high efficiency, high reliability device which is ideally suited to the home appliance field, in particular as a gas-fired refrigerator. It has significant advantages over other equivalent devices including freedom from halogenated hydrocarbons, extremely low temperatures available at a high efficiency, integrated water heating, and simple burner system control. The design and development of a portable working demonstration gas-fired duplex Stirling refrigeration unit is described. A unique combination of computer aided development and experimental development was used, enabling a continued interaction between the theoretical analysis and practical testing and evaluation. A universal test rig was developed in order to separately test and evaluate major subunits, enabling a smooth system integration phase.

Gas phase fractionation method using porous ceramic membrane

DOEpatents

Peterson, Reid A.; Hill, Jr., Charles G.; Anderson, Marc A.

1996-01-01

Flaw-free porous ceramic membranes fabricated from metal sols and coated onto a porous support are advantageously used in gas phase fractionation methods. Mean pore diameters of less than 40 .ANG., preferably 5-20 .ANG. and most preferably about 15 .ANG., are permeable at lower pressures than existing membranes. Condensation of gases in small pores and non-Knudsen membrane transport mechanisms are employed to facilitate and increase membrane permeability and permselectivity.

Degradation of volatile organic compounds in the gas phase by heterogeneous photocatalysis with titanium dioxide/ultraviolet light.

PubMed

Rochetto, Ursula Luana; Tomaz, Edson

2015-07-01

This work presents an overview over heterogeneous photocatalysis performed in gas phase towards the degradation of o-xylene, n-hexane, n-octane, n-decane, methylcyclohexane and 2,2,4-trimethylpentane. The experimental set-up composed by a titanium plug flow reactor vessel contained a quartz tube with a 100 W UV lamp placed at center position from 1.7 cm to the quartz wall. A titanium dioxide film was immobilized on the internal walls of the reactor and used as catalyst. All measurements were taken after reaching steady state condition and evaluated at the inlet and outlet of the system. Conversion rates were studied in a wide range of residence times yielding to a 90% or above conversion as from 20 seconds of residence time. During experiments the temperature of reactor's wall was monitored and remained between 52 and 62 °C. Temperature influence over degradation rates was negligible once a control experiment performed at 15 °C did not modify outgoing results. Humidity effect was also evaluated showing an ideal working range of 10-80% with abrupt conversion decay outside the range. By varying inlet concentration between 60 and 110 ppmv the VOC degradation curves remained unchanged. Loss over catalytic activity was only observed for o-xylene after 30 minutes of reaction, the catalyst was reactivated with a solution of hydrogen peroxide and UV light followed by additional deposition of the catalytic layer. The kinetic study suggests a first order reaction rate. The study of effective and economically viable techniques on the treatment of volatile organic compounds (VOCs) has being highlighted as an important parameter on the environmental research. The heterogeneous photocatalysis in gas phase was proved to be an effective process for the degradation of the nonaromatic VOCs tested, yielding high conversion values for the optimized systems.

Diurnal variability of gas phase and surface water ethanol in southeastern North Carolina, USA

NASA Astrophysics Data System (ADS)

Kieber, R. J.; Powell, J. P.; Foley, L.; Mead, R. N.; Willey, J. D.; Avery, G. B.

2017-11-01

Diurnal variations in gas phase and surface water concentrations of ethanol and acetaldehyde were investigated at five locations in southeastern North Carolina, USA. There were distinct diurnal oscillations observed in gas phase concentrations with maxima occurring in late afternoon suggesting that photochemical production is an important process in the cycling of these analytes in the troposphere. The rapid decrease in concentrations after the mid day maximum suggests that there is also an atmospheric photochemical sink for both analytes most likely involving photo produced hydroxyl radicals with a half-life on the order of hours rather than days at ground level. Ethanol concentrations in the surface microlayer taken at the same time as gas phase samples had a very similar diurnal profile suggesting photochemical processes, in addition to atmospheric deposition, play a role in the aqueous phase cycling of both analytes. The concentration of ethanol and acetaldehyde increased significantly in flasks containing freshwater collected from the Cape Fear River exposed to simulated sunlight for 6 h underscoring the importance of in situ photochemical production. Results of this study are significant because they represent the first simultaneous analyses of the temporal variability of ethanol and acetaldehyde concentrations in the gas and aqueous phases. These measurements are essential in order to better define the processes involved in the global biogeochemical cycling of ethanol both now and in the future as our use of the biofuel continues to grow.

Gas-phase reactions in extraterrestrial environments: laboratory investigations by crossed molecular beams.

PubMed

Balucani, Nadia; Casavecchia, Piergiorgio

2006-12-01

We have investigated gas-phase reactions of N((2)D) with the most abundant hydrocarbons in the atmosphere of Titan by the crossed molecular beam technique. In all cases, molecular products containing a novel CN bond are formed, thus suggesting possible routes of formation of gas-phase nitriles in the atmosphere of Titan and primordial Earth. The same approach has been recently extended to the study of radical-radical reactions, such as the reaction of atomic oxygen with the CH(3) and C(3)H(5) radicals. Products other than those already considered in the modeling of planetary atmospheres and interstellar medium have been identified.

Measuring Uptake Coefficients and Henry's Law Constants of Gas-Phase Species with Models for Secondary Organic Aerosol

NASA Astrophysics Data System (ADS)

Fairhurst, M. C.; Waring-Kidd, C.; Ezell, M. J.; Finlayson-Pitts, B. J.

2014-12-01

Volatile organic compounds (VOC) are oxidized in the atmosphere and their products contribute to secondary organic aerosol (SOA) formation. These particles have been shown to have effects on visibility, climate, and human health. Current models typically under-predict SOA concentrations from field measurements. Underestimation of these concentrations could be a result of how models treat particle growth. It is often assumed that particles grow via instantaneous thermal equilibrium partitioning between liquid particles and gas-phase species. Recent work has shown that growth may be better represented by irreversible, kinetically limited uptake of gas-phase species onto more viscous, tar-like SOA. However, uptake coefficients for these processes are not known. The goal of this project is to measure uptake coefficients and solubilities for different gases onto models serving as proxies for SOA and determine how they vary based on the chemical composition of the gas and the condensed phase. Experiments were conducted using two approaches: attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and a flow system coupled to a mass spectrometer. The ATR crystal was coated with the SOA proxy and the gas-phase species introduced via a custom flow system. Uptake of the gas-phase species was characterized by measuring the intensity of characteristic IR bands as a function of time, from which a Henry's law constant and initial estimate of uptake coefficients could be obtained. Uptake coefficients were also measured in a flow system where the walls of the flow tube were coated with the SOA proxy and gas-phase species introduced via a moveable inlet. Uptake coefficients were derived from the decay in gas-phase species measured by mass spectrometry. The results of this work will establish a structure-interaction relationship for uptake of gases into SOA that can be implemented into regional and global models.

Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler.

PubMed

Meischen, Sandra J; Van Pelt, Vincent J; Zarate, Eugene A; Stephens, Edward A

2004-01-01

Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.

Computational phase diagrams of noble gas hydrates under pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teeratchanan, Pattanasak, E-mail: s1270872@sms.ed.ac.uk; Hermann, Andreas, E-mail: a.hermann@ed.ac.uk

2015-10-21

We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-I{sub h}, ice-I{sub c}, ice-II, and C{sub 0} interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogenmore » hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C{sub 0} water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C{sub 0} hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.« less

Gas-Phase Hydrodesulfurization of JP-8 Light Fraction Using Steam Reformate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Xiwen; King, David L.

2006-10-11

Gas phase hydrodesulfurization of JP-8 light fraction was investigated over CoMo/Al2O3 and NiMo/Al2O3 catalysts. Use of a light fraction provides a fuel that is more easily desulfurized, and allows the process to operate in the vapor phase. This study investigated the utilization of reformate (syngas) from a steam reformer rather than pure H2 as gas feed to HDS unit. This is consistent with what might be available to the military during operation in the field. Dry syngas functions almost as well as pure H2 in the HDS reaction, and sulfur levels below 5ppmw are readily obtained from a feed initiallymore » containing 320ppmw sulfur. Addition of steam at 40 vol% to the gas feed has a significant negative impact on HDS performance with CoMo/Al2O3, but only a small effect with NiMo/Al2O3. The impacts of various process conditions on S removal efficiency were examined and will be described.« less

Efimov-driven phase transitions of the unitary Bose gas.

PubMed

Piatecki, Swann; Krauth, Werner

2014-03-20

Initially predicted in nuclear physics, Efimov trimers are bound configurations of three quantum particles that fall apart when any one of them is removed. They open a window into a rich quantum world that has become the focus of intense experimental and theoretical research, as the region of 'unitary' interactions, where Efimov trimers form, is now accessible in cold-atom experiments. Here we use a path-integral Monte Carlo algorithm backed up by theoretical arguments to show that unitary bosons undergo a first-order phase transition from a normal gas to a superfluid Efimov liquid, bound by the same effects as Efimov trimers. A triple point separates these two phases and another superfluid phase, the conventional Bose-Einstein condensate, whose coexistence line with the Efimov liquid ends in a critical point. We discuss the prospects of observing the proposed phase transitions in cold-atom systems.

Gas-liquid phase coexistence in quasi-two-dimensional Stockmayer fluids: A molecular dynamics study.

PubMed

Ouyang, Wen-Ze; Xu, Sheng-Hua; Sun, Zhi-Wei

2011-01-07

The Maxwell construction together with molecular dynamics simulation is used to study the gas-liquid phase coexistence of quasi-two-dimensional Stockmayer fluids. The phase coexistence curves and corresponding critical points under different dipole strength are obtained, and the critical properties are calculated. We investigate the dependence of the critical point and critical properties on the dipole strength. When the dipole strength is increased, the abrupt disappearance of the gas-liquid phase coexistence in quasi-two-dimensional Stockmayer fluids is not found. However, if the dipole strength is large enough, it does lead to the formation of very long reversible chains which makes the relaxation of the system very slow and the observation of phase coexistence rather difficult or even impossible.

Photoisomerization action spectroscopy of the carbocyanine dye DTC+ in the gas phase.

PubMed

Adamson, Brian D; Coughlan, Neville J A; da Silva, Gabriel; Bieske, Evan J

2013-12-19

Molecular photoisomerization plays a crucial role in diverse biological and technological contexts. Here, we combine ion mobility spectrometry and laser spectroscopy to characterize the photoisomerization of molecular cations in the gas phase. The target molecular ions, polymethine dye cations 3,3'-diethylthiacarbocyanine (DTC(+)), are propelled through helium buffer gas by an electric field and are photoisomerized by light from a tunable laser. Photoexcitation over the 450-570 nm range converts trans-DTC(+) to cis-DTC(+), noticeably modifying the ions' arrival time distribution. The photoisomerization action spectrum, which has a maximum at 535 nm, resembles the absorption spectrum of DTC(+) in solution but is shifted 25 nm to shorter wavelength. Comparisons between measured and calculated mobilities suggest that the photoisomer involves a twist about the second C-C bond in the methine chain (8,9-cis isomer) rather than a twist about the first methine C-C bond (2,8-cis isomer). It is postulated that the excited gas-phase ions internally convert from the S1 Franck-Condon region to the S0 manifold and explore the conformational landscape as they cool through He buffer gas collisions. Master equation simulations of the relaxation process in the S0 manifold suggest that the 8,9-cis isomer is preferred over the 2,8-cis isomer because it lies lower in energy and because it is separated from the trans isomer by a substantially higher barrier. The study demonstrates that the photoisomerization of molecular ions can be probed selectively in the gas phase, providing insights into photoisomerization mechanisms and information on the solvent-free absorption spectrum.

Recent progress of chiral stationary phases for separation of enantiomers in gas chromatography.

PubMed

Xie, Sheng-Ming; Yuan, Li-Ming

2017-01-01

Chromatography techniques based on chiral stationary phases are widely used for the separation of enantiomers. In particular, gas chromatography has developed rapidly in recent years due to its merits such as fast analysis speed, lower consumption of stationary phases and analytes, higher column efficiency, making it a better choice for chiral separation in diverse industries. This article summarizes recent progress of novel chiral stationary phases based on cyclofructan derivatives and chiral porous materials including chiral metal-organic frameworks, chiral porous organic frameworks, chiral inorganic mesoporous materials, and chiral porous organic cages in gas chromatography, covering original research papers published since 2010. The chiral recognition properties and mechanisms of separation toward enantiomers are also introduced. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Genealogical Tree of Ethanol: Gas-phase Formation of Glycolaldehyde, Acetic Acid, and Formic Acid

NASA Astrophysics Data System (ADS)

Skouteris, Dimitrios; Balucani, Nadia; Ceccarelli, Cecilia; Vazart, Fanny; Puzzarini, Cristina; Barone, Vincenzo; Codella, Claudio; Lefloch, Bertrand

2018-02-01

Despite the harsh conditions of the interstellar medium, chemistry thrives in it, especially in star-forming regions where several interstellar complex organic molecules (iCOMs) have been detected. Yet, how these species are synthesized is a mystery. The majority of current models claim that this happens on interstellar grain surfaces. Nevertheless, evidence is mounting that neutral gas-phase chemistry plays an important role. In this paper, we propose a new scheme for the gas-phase synthesis of glycolaldehyde, a species with a prebiotic potential and for which no gas-phase formation route was previously known. In the proposed scheme, the ancestor is ethanol and the glycolaldehyde sister species are acetic acid (another iCOM with unknown gas-phase formation routes) and formic acid. For the reactions of the new scheme with no available data, we have performed electronic structure and kinetics calculations deriving rate coefficients and branching ratios. Furthermore, after a careful review of the chemistry literature, we revised the available chemical networks, adding and correcting several reactions related to glycolaldehyde, acetic acid, and formic acid. The new chemical network has been used in an astrochemical model to predict the abundance of glycolaldehyde, acetic acid, and formic acid. The predicted abundance of glycolaldehyde depends on the ethanol abundance in the gas phase and is in excellent agreement with the measured one in hot corinos and shock sites. Our new model overpredicts the abundance of acetic acid and formic acid by about a factor of 10, which might imply a yet incomplete reaction network.

All-gas-phase synthesis of UiO-66 through modulated atomic layer deposition

PubMed Central

Lausund, Kristian Blindheim; Nilsen, Ola

2016-01-01

Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics. However, all-gas-phase deposition techniques are currently not available for such MOFs. We here report on thin-film deposition of the thermally and chemically stable UiO-66 in an all-gas-phase process by the aid of atomic layer deposition (ALD). Sequential reactions of ZrCl4 and 1,4-benzenedicarboxylic acid produce amorphous organic–inorganic hybrid films that are subsequently crystallized to the UiO-66 structure by treatment in acetic acid vapour. We also introduce a new approach to control the stoichiometry between metal clusters and organic linkers by modulation of the ALD growth with additional acetic acid pulses. An all-gas-phase synthesis technique for UiO-66 could enable implementations in microelectronics that are not compatible with solvothermal synthesis. Since this technique is ALD-based, it could also give enhanced thickness control and the possibility to coat irregular substrates with high aspect ratios. PMID:27876797

All-gas-phase synthesis of UiO-66 through modulated atomic layer deposition

NASA Astrophysics Data System (ADS)

Lausund, Kristian Blindheim; Nilsen, Ola

2016-11-01

Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics. However, all-gas-phase deposition techniques are currently not available for such MOFs. We here report on thin-film deposition of the thermally and chemically stable UiO-66 in an all-gas-phase process by the aid of atomic layer deposition (ALD). Sequential reactions of ZrCl4 and 1,4-benzenedicarboxylic acid produce amorphous organic-inorganic hybrid films that are subsequently crystallized to the UiO-66 structure by treatment in acetic acid vapour. We also introduce a new approach to control the stoichiometry between metal clusters and organic linkers by modulation of the ALD growth with additional acetic acid pulses. An all-gas-phase synthesis technique for UiO-66 could enable implementations in microelectronics that are not compatible with solvothermal synthesis. Since this technique is ALD-based, it could also give enhanced thickness control and the possibility to coat irregular substrates with high aspect ratios.

High-reliability gas-turbine combined-cycle development program: Phase II. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hecht, K.G.; Sanderson, R.A.; Smith, M.J.

This three-volume report presents the results of Phase II of the multiphase EPRI-sponsored High-Reliability Gas Turbine Combined-Cycle Development Program whose goal is to achieve a highly reliable gas turbine combined-cycle power plant, available by the mid-1980s, which would be an economically attractive baseload generation alternative for the electric utility industry. The Phase II program objective was to prepare the preliminary design of this power plant. This volume presents information of the reliability, availability, and maintainability (RAM) analysis of a representative plant and the preliminary design of the gas turbine, the gas turbine ancillaries, and the balance of plant including themore » steam turbine generator. To achieve the program goals, a gas turbine was incorporated which combined proven reliability characteristics with improved performance features. This gas turbine, designated the V84.3, is the result of a cooperative effort between Kraftwerk Union AG and United Technologies Corporation. Gas turbines of similar design operating in Europe under baseload conditions have demonstrated mean time between failures in excess of 40,000 hours. The reliability characteristics of the gas turbine ancillaries and balance-of-plant equipment were improved through system simplification and component redundancy and by selection of component with inherent high reliability. A digital control system was included with logic, communications, sensor redundancy, and mandual backup. An independent condition monitoring and diagnostic system was also included. Program results provide the preliminary design of a gas turbine combined-cycle baseload power plant. This power plant has a predicted mean time between failure of nearly twice the 3000-hour EPRI goal. The cost of added reliability features is offset by improved performance, which results in a comparable specific cost and an 8% lower cost of electricity compared to present market offerings.« less

Controllable fabrication of porous free-standing polypyrrole films via a gas phase polymerization.

PubMed

Lei, Junyu; Li, Zhicheng; Lu, Xiaofeng; Wang, Wei; Bian, Xiujie; Zheng, Tian; Xue, Yanpeng; Wang, Ce

2011-12-15

A facile gas phase polymerization method has been proposed in this work to fabricate porous free-standing polypyrrole (PPy) films. In the presence of pyrrole vapor, the films are obtained in the gas/water interface spontaneously through the interface polymerization with the oxidant of FeCl(3) in the water. Both the thickness of the film and the size of the pores could be controlled by adjusting the concentrations of the oxidant and the reaction time. The as-prepared PPy films exhibited a superhydrophilic behavior due to its composition and porous structures. We have demonstrated a possible formation mechanism for the porous free-standing PPy films. This gas phase polymerization is shown to be readily scalable to prepare large area of PPy films. Copyright © 2011 Elsevier Inc. All rights reserved.

Absorbance characteristics of a liquid-phase gas sensor based on gas-permeable liquid core waveguides.

PubMed

Peng, Pei; Wang, Wei; Zhang, Li; Su, Shiguang; Wang, Jiahui

2013-12-04

The absorbance characteristics and influential factors on these characteristics for a liquid-phase gas sensor, which is based on gas-permeable liquid core waveguides (LCWs), are studied from theoretical and experimental viewpoints in this paper. According to theory, it is predicted that absorbance is proportional to the analyte concentration, sampling time, analyte diffusion coefficient, and geometric factor of this device when the depletion layer of the analyte is ignored. The experimental results are in agreement with the theoretical hypothesis. According to the experimental results, absorbance is time-dependent and increasing linearly over time after the requisite response time with a linear correlation coefficient r(2)>0.999. In the linear region, the rate of absorbance change (RAC) indicates improved linearity with sample concentration and a relative higher sensitivity than instantaneous absorbance does. By using a core liquid that is more affinitive to the analyte, reducing wall thickness and the inner diameter of the tubing, or increasing sample flow rate limitedly, the response time can be decreased and the sensitivity can be increased. However, increasing the LCW length can only enhance sensitivity and has no effect on response time. For liquid phase detection, there is a maximum flow rate, and the absorbance will decrease beyond the stated limit. Under experimental conditions, hexane as the LCW core solvent, a tubing wall thickness of 0.1 mm, a length of 10 cm, and a flow rate of 12 mL min(-1), the detection results for the aqueous benzene sample demonstrate a response time of 4 min. Additionally, the standard curve for the RAC versus concentration is RAC=0.0267c+0.0351 (AU min(-1)), with r(2)=0.9922 within concentrations of 0.5-3.0 mg L(-1). The relative error for 0.5 mg L(-1) benzene (n=6) is 7.4±3.7%, and the LOD is 0.04 mg L(-1). This research can provide theoretical and practical guides for liquid-phase gas sensor design and development based on a

Exploring the relevance of gas-phase structures to biology: cold ion spectroscopy of the decapeptide neurokinin A.

PubMed

Pereverzev, A Y; Boyarkin, O V

2017-02-01

Linking the intrinsic tertiary structures of biomolecules to their native geometries is a central prerequisite for making gas-phase studies directly relevant to biology. The isolation of molecules in the gas phase eliminates hydrophilic interactions with solvents, to some extent mimicking a hydrophobic environment. Intrinsic structures therefore may resemble native ones for peptides that in vivo reside in a hydrophobic environment (e.g., binding pockets of receptors). In this study, we investigate doubly protonated neurokinin A (NKA) using IR-UV double resonance cold ion spectroscopy and find only five conformers of this decapeptide in the gas phase. In contrast, NMR data show that in aqueous solutions, NKA exhibits high conformational heterogeneity, which reduces to a few well-defined structures in hydrophobic micelles. Do the gas-phase structures of NKA resemble these native structures? The IR spectra reported here allow the validation of future structural calculations that may answer this question.

LOW COST IMAGER FOR POLLUTANT GAS LEAK DETECTION - PHASE II

EPA Science Inventory

An inexpensive imaging Instrument to quickly locate leaks of methane and other greenhouse and VOC gases would reduce the cost and effort expended by industry to comply with EPA regulations. In Phase I, of this WBIR program, a new gas leak visualization camera was demonstrated...

Gas-phase ion/ion reactions of peptides and proteins: acid/base, redox, and covalent chemistries

PubMed Central

Prentice, Boone M.

2013-01-01

Gas-phase ion/ion reactions are emerging as useful and flexible means for the manipulation and characterization of peptide and protein biopolymers. Acid/base-like chemical reactions (i.e., proton transfer reactions) and reduction/oxidation (redox) reactions (i.e., electron transfer reactions) represent relatively mature classes of gas-phase chemical reactions. Even so, especially in regards to redox chemistry, the widespread utility of these two types of chemistries is undergoing rapid growth and development. Additionally, a relatively new class of gas-phase ion/ion transformations is emerging which involves the selective formation of functional-group-specific covalent bonds. This feature details our current work and perspective on the developments and current capabilities of these three areas of ion/ion chemistry with an eye towards possible future directions of the field. PMID:23257901

Gas-phase ion/ion reactions of peptides and proteins: acid/base, redox, and covalent chemistries.

PubMed

Prentice, Boone M; McLuckey, Scott A

2013-02-01

Gas-phase ion/ion reactions are emerging as useful and flexible means for the manipulation and characterization of peptide and protein biopolymers. Acid/base-like chemical reactions (i.e., proton transfer reactions) and reduction/oxidation (redox) reactions (i.e., electron transfer reactions) represent relatively mature classes of gas-phase chemical reactions. Even so, especially in regards to redox chemistry, the widespread utility of these two types of chemistries is undergoing rapid growth and development. Additionally, a relatively new class of gas-phase ion/ion transformations is emerging which involves the selective formation of functional-group-specific covalent bonds. This feature details our current work and perspective on the developments and current capabilities of these three areas of ion/ion chemistry with an eye towards possible future directions of the field.

Gas-phase ozonolysis of ethene in the presence of carbonyl-oxide scavengers

NASA Astrophysics Data System (ADS)

Wolff, Silke; Boddenberg, Axel; Thamm, Jürgen; Turner, Walter V.; Gäb, Siegmar

Potential carbonyl-oxide scavengers are included in gas-phase ozonolysis experiments in an attempt to determine the extent to which the Criegee mechanism is involved. The scavengers selected are those whose reaction mechanism in the liquid phase is understood; water, hydrogen peroxide, alcohols and carboxylic acids have thus far been examined. The products of the ozonolysis of ethene in the gas phase depend on whether carbonyl-oxide scavengers are present. In the absence of scavengers, formaldehyde and formic acid are the major products, and only minor amounts of H 2O 2 and hydroxymethyl hydroperoxide are found. In the presence of a scavenger, certain products observed in addition to these can be regarded as arising from addition of the scavenger to the carbonyl oxide. Thus, H 2O 2 leads to the formation of hydroperoxymethyl hydroperoxide, while alcohols and formic acid give alkoxymethyl hydroperoxides and hydroperoxymethyl formate, respectively.

Real-Gas Correction Factors for Hypersonic Flow Parameters in Helium

NASA Technical Reports Server (NTRS)

Erickson, Wayne D.

1960-01-01

The real-gas hypersonic flow parameters for helium have been calculated for stagnation temperatures from 0 F to 600 F and stagnation pressures up to 6,000 pounds per square inch absolute. The results of these calculations are presented in the form of simple correction factors which must be applied to the tabulated ideal-gas parameters. It has been shown that the deviations from the ideal-gas law which exist at high pressures may cause a corresponding significant error in the hypersonic flow parameters when calculated as an ideal gas. For example the ratio of the free-stream static to stagnation pressure as calculated from the thermodynamic properties of helium for a stagnation temperature of 80 F and pressure of 4,000 pounds per square inch absolute was found to be approximately 13 percent greater than that determined from the ideal-gas tabulation with a specific heat ratio of 5/3.

Heat transfer in three-phase fluidization and bubble-columns with high gas holdups

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, S.; Kusakabe, K.; Fan, L.S.

1993-08-01

Bubble column and three-phase fluidized bed reactors have wide applications in biotechnological and petroleum processes (Deckwer, 1985; Fan, 1989). In such biotechnological processes as fermentation and waste water treatment, small bubbles of oxygen and/or nitrogen are introduced in the column to enhance oxygen transfer and to ensure the stability of immobilized cell particles. In addition, tiny bubbles are produced during the biological process due to the production of surface active compounds. The presence of these small bubbles causes an increase in the gas holdup of the system. High gas holdups are also characteristics of industrial processes such as coal liquefactionmore » and hydrotreating of residual oils. Good understanding of the transport properties of three-phase fluidized beds with high gas holdups is essential to the design, control and optimum operations of the commercial reactors employed in the above-mentioned processes. Heat-transfer studies in three-phase fluidized beds have been reviewed recently by Kim and Laurent (1991). Past studies focused primarily on the measurements of time-averaged heat transfer from the column wall to bed (Chiu and Ziegler 1983; Muroyama et al., 1986) or on immersed heating objects to bed (Baker et al., 1978; Kato et al., 1984) in aqueous systems. Recently, Kumar et al. (1992) provided a mechanistic understanding of the heat transfer in bubbly-liquid and liquid-solid systems. The purpose of this work is to investigate the heat transfer in a three-phase fluidized bed under high gas holdup conditions. The associated hydrodynamic behavior of the system is also studied.« less

Femtosecond gas phase electron diffraction with MeV electrons.

PubMed

Yang, Jie; Guehr, Markus; Vecchione, Theodore; Robinson, Matthew S; Li, Renkai; Hartmann, Nick; Shen, Xiaozhe; Coffee, Ryan; Corbett, Jeff; Fry, Alan; Gaffney, Kelly; Gorkhover, Tais; Hast, Carsten; Jobe, Keith; Makasyuk, Igor; Reid, Alexander; Robinson, Joseph; Vetter, Sharon; Wang, Fenglin; Weathersby, Stephen; Yoneda, Charles; Wang, Xijie; Centurion, Martin

2016-12-16

We present results on ultrafast gas electron diffraction (UGED) experiments with femtosecond resolution using the MeV electron gun at SLAC National Accelerator Laboratory. UGED is a promising method to investigate molecular dynamics in the gas phase because electron pulses can probe the structure with a high spatial resolution. Until recently, however, it was not possible for UGED to reach the relevant timescale for the motion of the nuclei during a molecular reaction. Using MeV electron pulses has allowed us to overcome the main challenges in reaching femtosecond resolution, namely delivering short electron pulses on a gas target, overcoming the effect of velocity mismatch between pump laser pulses and the probe electron pulses, and maintaining a low timing jitter. At electron kinetic energies above 3 MeV, the velocity mismatch between laser and electron pulses becomes negligible. The relativistic electrons are also less susceptible to temporal broadening due to the Coulomb force. One of the challenges of diffraction with relativistic electrons is that the small de Broglie wavelength results in very small diffraction angles. In this paper we describe the new setup and its characterization, including capturing static diffraction patterns of molecules in the gas phase, finding time-zero with sub-picosecond accuracy and first time-resolved diffraction experiments. The new device can achieve a temporal resolution of 100 fs root-mean-square, and sub-angstrom spatial resolution. The collimation of the beam is sufficient to measure the diffraction pattern, and the transverse coherence is on the order of 2 nm. Currently, the temporal resolution is limited both by the pulse duration of the electron pulse on target and by the timing jitter, while the spatial resolution is limited by the average electron beam current and the signal-to-noise ratio of the detection system. We also discuss plans for improving both the temporal resolution and the spatial resolution.

Evidence-Based Evaluation of Practice and Innovation in Physical Therapy Using the IDEAL-Physio Framework.

PubMed

Beard, David; Hamilton, David; Davies, Loretta; Cook, Jonathan; Hirst, Allison; McCulloch, Peter; Paez, Arsenio

2018-02-01

The IDEAL framework is an established method for initial and ongoing evaluations of innovation and practice for complex health care interventions. First derived for surgical sciences and embedded at a global level for evaluating surgery/surgical devices, the IDEAL framework is based on the principle that innovation and evaluation in clinical practice can, and should, evolve together in an ordered manner: from conception to development and then to validation by appropriate clinical studies and, finally, longer-term follow-up. This framework is highly suited to other complex, nonpharmacological interventions, such as physical therapist interventions. This perspective outlines the application of IDEAL to physical therapy in the new IDEAL-Physio framework. The IDEAL-Physio framework comprises 5 stages. In stage 1, the idea phase, formal data collection should begin. Stage 2a is the phase for iterative improvement and adjustment with thorough data recording. Stage 2b involves the onset of formal evaluation using systematically collected group or cohort data. Stage 3 is the phase for formal comparative assessment of treatment, usually involving randomized studies. Stage 4 involves long-term follow-up. The IDEAL-Physio framework is recommended as a method for guiding and evaluating both innovation and practice in physical therapy, with the overall goal of providing better evidence-based care. © 2017 American Physical Therapy Association.

Collisions of ideal gas molecules with a rough/fractal surface. A computational study.

PubMed

Panczyk, Tomasz

2007-02-01

The frequency of collisions of ideal gas molecules (argon) with a rough surface has been studied. The rough/fractal surface was created using random deposition technique. By applying various depositions, the roughness of the surface was controlled and, as a measure of the irregularity, the fractal dimensions of the surfaces were determined. The surfaces were next immersed in argon (under pressures 2 x 10(3) to 2 x 10(5) Pa) and the numbers of collisions with these surfaces were counted. The calculations were carried out using a simplified molecular dynamics simulation technique (only hard core repulsions were assumed). As a result, it was stated that the frequency of collisions is a linear function of pressure for all fractal dimensions studied (D = 2, ..., 2.5). The frequency per unit pressure is quite complex function of the fractal dimension; however, the changes of that frequency with the fractal dimension are not strong. It was found that the frequency of collisions is controlled by the number of weakly folded sites on the surfaces and there is some mapping between the shape of adsorption energy distribution functions and this number of weakly folded sites. The results for the rough/fractal surfaces were compared with the prediction given by the Langmuir-Hertz equation (valid for smooth surface), generally the departure from the Langmuir-Hertz equation is not higher than 48% for the studied systems (i.e. for the surfaces created using the random deposition technique).

Decay of the 3D inviscid liquid-gas two-phase flow model

NASA Astrophysics Data System (ADS)

Zhang, Yinghui

2016-06-01

We establish the optimal {Lp-L2(1 ≤ p < 6/5)} time decay rates of the solution to the Cauchy problem for the 3D inviscid liquid-gas two-phase flow model and analyze the influences of the damping on the qualitative behaviors of solution. Compared with the viscous liquid-gas two-phase flow model (Zhang and Zhu in J Differ Equ 258:2315-2338, 2015), our results imply that the friction effect of the damping is stronger than the dissipation effect of the viscosities and enhances the decay rate of the velocity. Our proof is based on Hodge decomposition technique, the {Lp-L2} estimates for the linearized equations and an elaborate energy method.

Laser spectroscopy of a halocarbocation in the gas phase: CH2I+.

PubMed

Tao, Chong; Mukarakate, Calvin; Reid, Scott A

2006-07-26

We report the first gas-phase observation of the electronic spectrum of a simple halocarbocation, CH2I+. The ion was generated rotationally cold (Trot approximately 20 K) using pulsed discharge methods and was detected via laser spectroscopy. The identity of the spectral carrier was confirmed by modeling the rotational contour observed in the excitation spectra and by comparison of ground state vibrational frequencies determined by single vibronic level emission spectroscopy with Density Functional Theory (DFT) predictions. The transition was assigned as 3A1 <-- X1A1. This initial detection of the electronic spectrum of a halocarbocation in the gas phase should open new avenues for study of the structure and reactivity of these important ions.

A Gas-Kinetic Method for Hyperbolic-Elliptic Equations and Its Application in Two-Phase Fluid Flow

NASA Technical Reports Server (NTRS)

Xu, Kun

1999-01-01

A gas-kinetic method for the hyperbolic-elliptic equations is presented in this paper. In the mixed type system, the co-existence and the phase transition between liquid and gas are described by the van der Waals-type equation of state (EOS). Due to the unstable mechanism for a fluid in the elliptic region, interface between the liquid and gas can be kept sharp through the condensation and evaporation process to remove the "averaged" numerical fluid away from the elliptic region, and the interface thickness depends on the numerical diffusion and stiffness of the phase change. A few examples are presented in this paper for both phase transition and multifluid interface problems.

Sex Education and Ideals

ERIC Educational Resources Information Center

de Ruyter, Doret J.; Spiecker, Ben

2008-01-01

This article argues that sex education should include sexual ideals. Sexual ideals are divided into sexual ideals in the strict sense and sexual ideals in the broad sense. It is argued that ideals that refer to the context that is deemed to be most ideal for the gratification of sexual ideals in the strict sense are rightfully called sexual…

Substellar fragmentation in self-gravitating fluids with a major phase transition

NASA Astrophysics Data System (ADS)

Füglistaler, A.; Pfenniger, D.

2015-06-01

Context. The observation of various ices in cold molecular clouds, the existence of ubiquitous substellar, cold H2 globules in planetary nebulae and supernova remnants, or the mere existence of comets suggest that the physics of very cold interstellar gas might be much richer than usually envisioned. At the extreme of low temperatures (≲10 K), H2 itself is subject to a phase transition crossing the entire cosmic gas density scale. Aims: This well-known, laboratory-based fact motivates us to study the ideal case of a cold neutral gaseous medium in interstellar conditions for which the bulk of the mass, instead of trace elements, is subject to a gas-liquid or gas-solid phase transition. Methods: On the one hand, the equilibrium of general non-ideal fluids is studied using the virial theorem and linear stability analysis. On the other hand, the non-linear dynamics is studied using computer simulations to characterize the expected formation of solid bodies analogous to comets. The simulations are run with a state-of-the-art molecular dynamics code (LAMMPS) using the Lennard-Jones inter-molecular potential. The long-range gravitational forces can be taken into account together with short-range molecular forces with finite limited computational resources, using super-molecules, provided the right scaling is followed. Results: The concept of super-molecule, where the phase transition conditions are preserved by the proper choice of the particle parameters, is tested with computer simulations, allowing us to correctly satisfy the Jeans instability criterion for one-phase fluids. The simulations show that fluids presenting a phase transition are gravitationally unstable as well, independent of the strength of the gravitational potential, producing two distinct kinds of substellar bodies, those dominated by gravity (planetoids) and those dominated by molecular attractive force (comets). Conclusions: Observations, formal analysis, and computer simulations suggest the

Ditechnetium heptoxide revisited: Solid-state, gas-phase, and theoretical studies

DOE PAGES

Childs, Bradley C.; Braband, Henrik; Lawler, Keith; ...

2016-10-04

Here, ditechnetium heptoxide was synthesized from the oxidation of TcO 2 with O 2 at 450 °C and characterized by single crystal X-ray diffraction (SCXRD), electron impact mass spectrometry (EI-MS) and theoretical methods. Refinement of the structure at 100 K indicates that Tc 2O 7 crystallizes as a molecular solid in the orthorhombic space group Pbca (a = 7.312(3) Å, b = 5.562(2) Å, c = 13.707(5) Å, V = 557.5(3) Å 3). The Tc 2O 7 molecule can be described as corner-sharing TcO4 tetrahedra (Tc---Tc = 3.698(1) Å and Tc-O Bri-Tc = 180.0°). The EI-MS spectrum of Tc 2Omore » 7 consists of both mononuclear and dinuclear species. The main dinuclear species in the gas-phase are Tc 2O 7 (100%) and Tc 2O 5 (56%), while the main mononuclear species are TcO 3 (33.9%) and TcO 2 (42.8%). The difference in the relative intensities of the M 2O 5 (M = Tc, Re) fragments (1.7% for Re) indicate that these Group 7 elements exhibit different gas phase chemistry. The solid-state structure of Tc 2O 7 was investigated by density functional theory (DFT) methods. The optimized structure of the Tc 2O 7 molecule is in good agreement with the experimental one. Simulations indicate that the more favorable geometry for the Tc 2O 7 molecule in the gas-phase is bent (Tc-O Bri-Tc = 156.5°), while linear (Tc-O Bri-Tc = 180.0°) is favored in the solid state.« less

Demonstrating the Gas Laws.

ERIC Educational Resources Information Center

Holko, David A.

1982-01-01

Presents a complete computer program demonstrating the relationship between volume/pressure for Boyle's Law, volume/temperature for Charles' Law, and volume/moles of gas for Avagadro's Law. The programing reinforces students' application of gas laws and equates a simulated moving piston to theoretical values derived using the ideal gas law.…

Experimental study on natural circulation precooling of cryogenic pump system with gas phase inlet reflux configuration

NASA Astrophysics Data System (ADS)

Chen, G. B.; Zhong, Y. K.; Zheng, X. L.; Li, Q. F.; Xie, X. M.; Gan, Z. H.; Huang, Y. H.; Tang, K.; Kong, B.; Qiu, L. M.

2003-12-01

A novel gas-phase inlet configuration in the natural circulation system instead of the liquid-phase inlet is introduced to cool down a cryogenic pump system from room temperature to cryogenic temperatures, effectively. The experimental apparatus is illustrated and test process is described. Heat transfer and pressure drop data during the cool-down process are recorded and portrayed. By contrast with liquid-phase inlet configuration, experimental results demonstrate that the natural circulation with the gas-phase inlet configuration is an easier and more controllable way to cool down the pump system and maintain it at cryogenic temperatures.

Supersonic flow of chemically reacting gas-particle mixtures. Volume 1: A theoretical analysis and development of the numerical solution

NASA Technical Reports Server (NTRS)

Penny, M. M.; Smith, S. D.; Anderson, P. G.; Sulyma, P. R.; Pearson, M. L.

1976-01-01

A numerical solution for chemically reacting supersonic gas-particle flows in rocket nozzles and exhaust plumes was described. The gas-particle flow solution is fully coupled in that the effects of particle drag and heat transfer between the gas and particle phases are treated. Gas and particles exchange momentum via the drag exerted on the gas by the particles. Energy is exchanged between the phases via heat transfer (convection and/or radiation). Thermochemistry calculations (chemical equilibrium, frozen or chemical kinetics) were shown to be uncoupled from the flow solution and, as such, can be solved separately. The solution to the set of governing equations is obtained by utilizing the method of characteristics. The equations cast in characteristic form are shown to be formally the same for ideal, frozen, chemical equilibrium and chemical non-equilibrium reacting gas mixtures. The particle distribution is represented in the numerical solution by a finite distribution of particle sizes.

Numerical modelling of underwater detonation of non-ideal condensed-phase explosives

NASA Astrophysics Data System (ADS)

Schoch, Stefan; Nikiforakis, Nikolaos

2015-01-01

The interest in underwater detonation tests originated from the military, since the expansion and subsequent collapse of the explosive bubble can cause considerable damage to surrounding structures or vessels. In military applications, the explosive is typically represented as a pre-burned material under high pressure, a reasonable assumption due to the short reaction zone lengths, and complete detonation of the unreacted explosive. Hence, numerical simulations of underwater detonation tests have been primarily concerned with the prediction of target loading and the damage incurred rather than the accurate modelling of the underwater detonation process. The mining industry in contrast has adopted the underwater detonation test as a means to experimentally characterise the energy output of their highly non-ideal explosives depending on explosive type and charge configuration. This characterisation requires a good understanding of how the charge shape, pond topography, charge depth, and additional charge confinement affect the energy release, some of which can be successfully quantified with the support of accurate numerical simulations. In this work, we propose a numerical framework which is able to capture the non-ideal explosive behaviour and in addition is capable of capturing both length scales: the reaction zone and the pond domain. The length scale problem is overcome with adaptive mesh refinement, which, along with the explosive model, is validated against experimental data of various TNT underwater detonations. The variety of detonation and bubble behaviour observed in non-ideal detonations is demonstrated in a parameter study over the reactivity of TNT. A representative underwater mining test containing an ammonium-nitrate fuel-oil ratestick charge is carried out to demonstrate that the presented method can be readily applied alongside experimental underwater detonation tests.

Chemkin-II: A Fortran chemical kinetics package for the analysis of gas-phase chemical kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kee, R.J.; Rupley, F.M.; Miller, J.A.

1989-09-01

This document is the user's manual for the second-generation Chemkin package. Chemkin is a software package for whose purpose is to facilitate the formation, solution, and interpretation of problems involving elementary gas-phase chemical kinetics. It provides an especially flexible and powerful tool for incorporating complex chemical kinetics into simulations of fluid dynamics. The package consists of two major software components: an Interpreter and Gas-Phase Subroutine Library. The Interpreter is a program that reads a symbolic description of an elementary, user-specified chemical reaction mechanism. One output from the Interpreter is a data file that forms a link to the Gas-Phase Subroutinemore » Library. This library is a collection of about 100 highly modular Fortran subroutines that may be called to return information on equation of state, thermodynamic properties, and chemical production rates.« less

Gas-Phase Amidation of Carboxylic Acids with Woodward’s Reagent K Ions

PubMed Central

Peng, Zhou; Pilo, Alice L.; Luongo, Carl A.; McLuckey, Scott A.

2015-01-01

Gas-phase amidation of carboxylic acids in multiply-charged peptides is demonstrated via ion/ion reactions with Woodward’s reagent K (wrk) in both positive and negative mode. Woodward’s reagent K, N-ethyl-3-phenylisoxazolium-3′-sulfonate, is a commonly used reagent that activates carboxylates to form amide bonds with amines in solution. Here, we demonstrate that the analogous gas-phase chemistry occurs upon reaction of the wrk ions and doubly protonated (or doubly deprotonated) peptide ions containing the carboxylic acid functionality. The reaction involves the formation of the enol ester intermediate in the electrostatic complex. Upon collisional activation, the ethyl amine on the reagent is transferred to the activated carbonyl carbon on the peptide, resulting in the formation of an ethyl amide (addition of 27 Da to the peptide) with loss of a neutral ketene derivative. Further collision-induced dissociation (CID) of the products and comparison with solution-phase amidation product confirms the structure of the ethyl amide. PMID:26122523

Laboratory Measurements of Gas Phase Pyrolysis Products from Southern Wildland Fuels using Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Scharko, N.; Safdari, S.; Danby, T. O.; Howarth, J.; Beiswenger, T. N.; Weise, D.; Myers, T. L.; Fletcher, T. H.; Johnson, T. J.

2017-12-01

Combustion is an oxidation reaction that occurs when there is less fuel available than oxidizers, while pyrolysis is a thermal decomposition process that occurs under "fuel rich" conditions where all of the available oxidizers are consumed leaving some fuel(s) either unreacted or partially reacted. Gas-phase combustion products from biomass burning experiments have been studied extensively; less is known, however, about pyrolysis processes and products. Pyrolysis is the initial reaction occurring in the burning process and generates products that are subsequently oxidized during combustion, yielding highly-oxidized chemicals. This laboratory study investigates the pyrolysis processes by using an FTIR spectrometer to detect and quantify the gas-phase products from thermal decomposition of intact understory fuels from forests in the southeastern United States. In particular, a laboratory flat-flame burner operating under fuel rich conditions (no oxygen) was used to heat individual leaves to cause decomposition. The gas-phase products were introduced to an 8 meter gas cell coupled to an infrared spectrometer were used to monitor the products. Trace gas emissions along with emission ratios, which are calculated by dividing the change in the amount of the trace gas by the change in the amount of CO, for the plant species, gallberry (Ilex glabra) and swampbay (Persea palustris) were determined. Preliminary measurements observed species such as CO2, CO, C2H2, C2H4, HCHO, CH3OH, isoprene, 1,3-butadiene, phenol and NH3 being produced as part of the thermal decomposition process. It is important to note that FTIR will not detect H2.

The gas-phase ozonolysis of α-humulene.

PubMed

Beck, M; Winterhalter, R; Herrmann, F; Moortgat, G K

2011-06-21

α-Humulene contains three double bonds (DB), and after ozonolysis of the first DB the first-generation products are still reactive towards O(3) and produce second- and third-generation products. The primary aim of this study consisted of identifying the products of the three generations, focusing on the carboxylic acids, which are known to have a high aerosol formation potential. The experiments were performed in a 570 litre spherical glass reactor at 295 K and 730 Torr. Initial mixing ratios were 260-2090 ppb for O(3) and 250-600 ppb for α-humulene in synthetic air. Reactants and gas-phase products were measured by in situ FTIR spectroscopy. Particulate products were sampled on Teflon filters, extracted with methanol and analyzed by LC-MS/MS-TOF. Using cyclohexane (10-100 ppm) as an OH-radical scavenger and by monitoring the yield of cyclohexanone by PTR-MS, an OH-yield of (10.5 ± 0.7)% was determined for the ozonolysis of the first DB, and (12.9 ± 0.7)% of the first-generation products. The rate constant of the reaction of O(3) with α-humulene is known as k(0) = 1.17 × 10(-14) cm(3) molecule(-1) s(-1) [Y. Shu and R. Atkinson, Int. J. Chem. Kinet., 1994, 26, 1193-1205]. The reaction rate constants of O(3) with the first-generation products and the second-generation products were, respectively, determined as k(1) = (3.6 ± 0.9) × 10(-16) and k(2) = (3.0 ± 0.7) × 10(-17) cm(3) molecule(-1) s(-1) by Facsimile-simulation of the observed ozone decay by FTIR. A total of 37 compounds in the aerosol phase and 5 products in the gas phase were tentatively identified: 25 compounds of the first-generation products contained C13-C15 species, 9 compounds of the second-generation products contained C8-C11 species, whereas 8 compounds of the third-generation products contained C4-C6 species. The products of all three generations consisted of a variety of dicarboxylic-, hydroxy-oxocarboxylic- and oxo-carboxylic acids. The formation mechanisms of some of the products are

Project ARGO: Gas phase formation in simulated microgravity

NASA Technical Reports Server (NTRS)

Powell, Michael R.; Waligora, James M.; Norfleet, William T.; Kumar, K. Vasantha

1993-01-01

The ARGO study investigated the reduced incidence of joint pain decompression sickness (DCS) encountered in microgravity as compared with an expected incidence of joint pain DCS experienced by test subjects in Earth-based laboratories (unit gravity) with similar protocols. Individuals who are decompressed from saturated conditions usually acquire joint pain DCS in the lower extremities. Our hypothesis is that the incidence of joint pain DCS can be limited by a significant reduction in the tissue gas micronuclei formed by stress-assisted nucleation. Reductions in dynamic and kinetic stresses in vivo are linked to hypokinetic and adynamic conditions of individuals in zero g. We employed the Doppler ultrasound bubble detection technique in simulated microgravity studies to determine quantitatively the degree of gas phase formation in the upper and lower extremities of test subjects during decompression. We found no evidence of right-to-left shunting through pulmonary vasculature. The volume of gas bubble following decompression was examined and compared with the number following saline contrast injection. From this, we predict a reduced incidence of DCS on orbit, although the incidence of predicted mild DCS still remains larger than that encountered on orbit.

An Ideal Molecular Sieve for Acetylene Removal from Ethylene with Record Selectivity and Productivity.

PubMed

Li, Bin; Cui, Xili; O'Nolan, Daniel; Wen, Hui-Min; Jiang, Mengdie; Krishna, Rajamani; Wu, Hui; Lin, Rui-Biao; Chen, Yu-Sheng; Yuan, Daqiang; Xing, Huabin; Zhou, Wei; Ren, Qilong; Qian, Guodong; Zaworotko, Michael J; Chen, Banglin

2017-12-01

Realization of ideal molecular sieves, in which the larger gas molecules are completely blocked without sacrificing high adsorption capacities of the preferred smaller gas molecules, can significantly reduce energy costs for gas separation and purification and thus facilitate a possible technological transformation from the traditional energy-intensive cryogenic distillation to the energy-efficient, adsorbent-based separation and purification in the future. Although extensive research endeavors are pursued to target ideal molecular sieves among diverse porous materials, over the past several decades, ideal molecular sieves for the separation and purification of light hydrocarbons are rarely realized. Herein, an ideal porous material, SIFSIX-14-Cu-i (also termed as UTSA-200), is reported with ultrafine tuning of pore size (3.4 Å) to effectively block ethylene (C 2 H 4 ) molecules but to take up a record-high amount of acetylene (C 2 H 2 , 58 cm 3 cm -3 under 0.01 bar and 298 K). The material therefore sets up new benchmarks for both the adsorption capacity and selectivity, and thus provides a record purification capacity for the removal of trace C 2 H 2 from C 2 H 4 with 1.18 mmol g -1 C 2 H 2 uptake capacity from a 1/99 C 2 H 2 /C 2 H 4 mixture to produce 99.9999% pure C 2 H 4 (much higher than the acceptable purity of 99.996% for polymer-grade C 2 H 4 ), as demonstrated by experimental breakthrough curves. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

COED Transactions, Vol. 8, No. 10, October 1976. The Computer Generation of Thermodynamic Phase Diagrams.

ERIC Educational Resources Information Center

Jolls, Kenneth R.; And Others

A technique is described for the generation of perspective views of three-dimensional models using computer graphics. The technique is applied to models of familiar thermodynamic phase diagrams and the results are presented for the ideal gas and van der Waals equations of state as well as the properties of liquid water and steam from the Steam…

Non-Ideal Compressible-Fluid Dynamics of Fast-Response Pressure Probes for Unsteady Flow Measurements in Turbomachinery

NASA Astrophysics Data System (ADS)

Gori, G.; Molesini, P.; Persico, G.; Guardone, A.

2017-03-01

The dynamic response of pressure probes for unsteady flow measurements in turbomachinery is investigated numerically for fluids operating in non-ideal thermodynamic conditions, which are relevant for e.g. Organic Rankine Cycles (ORC) and super-critical CO2 applications. The step response of a fast-response pressure probe is investigated numerically in order to assess the expected time response when operating in the non-ideal fluid regime. Numerical simulations are carried out exploiting the Non-Ideal Compressible Fluid-Dynamics (NICFD) solver embedded in the open-source fluid dynamics code SU2. The computational framework is assessed against available experimental data for air in dilute conditions. Then, polytropic ideal gas (PIG), i.e. constant specific heats, and Peng-Robinson Stryjek-Vera (PRSV) models are applied to simulate the flow field within the probe operating with siloxane fluid octamethyltrisiloxane (MDM). The step responses are found to depend mainly on the speed of sound of the working fluid, indicating that molecular complexity plays a major role in determining the promptness of the measurement devices. According to the PRSV model, non-ideal effects can increase the step response time with respect to the acoustic theory predictions. The fundamental derivative of gas-dynamic is confirmed to be the driving parameter for evaluating non-ideal thermodynamic effects related to the dynamic calibration of fast-response aerodynamic pressure probes.

Transferring pharmaceuticals into the gas phase

NASA Astrophysics Data System (ADS)

Christen, Wolfgang; Krause, Tim; Rademann, Klaus

2008-11-01

The dissolution of molecules of biological interest in supercritical carbon dioxide is investigated using pulsed molecular beam mass spectrometry. Due to the mild processing temperatures of most supercritical fluids, their adiabatic expansion into vacuum permits to transfer even thermally very sensitive substances into the gas phase, which is particularly attractive for pharmaceutical and biomedical applications. In addition, supercritical CO2constitutes a chemically inert solvent that is compatible with hydrocarbon-free ultrahigh vacuum conditions. Here, we report on the dissolution and pulsed supersonic jet expansion of caffeine (C8H10N4O2), the provitamin menadione (C11H8O2), and the amino acid derivative l-phenylalanine tert-butyl ester hydrochloride (C6H5CH2CH(NH2)COOC(CH3)3[dot operator]HCl), into vacuum. An on-axis residual gas analyzer is used to monitor the relative amounts of solute and solvent in the molecular beam as a function of solvent densityE The excellent selectivity and sensitivity provided by mass spectrometry permits to probe even trace amounts of solutes. The strong density variation of CO2 close to the critical point results in a pronounced pressure dependence of the relative ion currents of solute and solvent molecules, reflecting a substantial change in solubility.

Finite-Difference Solution for Laminar or Turbulent Boundary Layer Flow over Axisymmetric Bodies with Ideal Gas, CF4, or Equilibrium Air Chemistry

NASA Technical Reports Server (NTRS)

Hamilton, H. Harris, II; Millman, Daniel R.; Greendyke, Robert B.

1992-01-01

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Finite-difference solution for laminar or turbulent boundary layer flow over axisymmetric bodies with ideal gas, CF4, or equilibrium air chemistry

NASA Astrophysics Data System (ADS)

Hamilton, H. Harris, II; Millman, Daniel R.; Greendyke, Robert B.

1992-12-01

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

The Development of a Gas-Liquid Two-Phase Flow Sensor Applicable to CBM Wellbore Annulus.

PubMed

Wu, Chuan; Wen, Guojun; Han, Lei; Wu, Xiaoming

2016-11-18

The measurement of wellbore annulus gas-liquid two-phase flow in CBM (coalbed methane) wells is of great significance for reasonably developing gas drainage and extraction processes, estimating CBM output, judging the operating conditions of CBM wells and analyzing stratum conditions. Hence, a specially designed sensor is urgently needed for real-time measurement of gas-liquid two-phase flow in CBM wellbore annulus. Existing flow sensors fail to meet the requirements of the operating conditions of CBM wellbore annulus due to such factors as an inapplicable measurement principle, larger size, poor sealability, high installation accuracy, and higher requirements for fluid media. Therefore, based on the principle of a target flowmeter, this paper designs a new two-phase flow sensor that can identify and automatically calibrate different flow patterns of two-phase flows. Upon the successful development of the new flow sensor, lab and field tests were carried out, and the results show that the newly designed sensor, with a measurement accuracy of ±2.5%, can adapt to the operating conditions of CBM wells and is reliable for long-term work.

Gas and grain chemical composition in cold cores as predicted by the Nautilus three-phase model

NASA Astrophysics Data System (ADS)

Ruaud, Maxime; Wakelam, Valentine; Hersant, Franck

2016-07-01

We present an extended version of the two-phase gas-grain code NAUTILUS to the three-phase modelling of gas and grain chemistry of cold cores. In this model, both the mantle and the surface are considered as chemically active. We also take into account the competition among reaction, diffusion and evaporation. The model predictions are confronted to ice observations in the envelope of low-mass and massive young stellar objects as well as towards background stars. Modelled gas-phase abundances are compared to species observed towards TMC-1 (CP) and L134N dark clouds. We find that our model successfully reproduces the observed ice species. It is found that the reaction-diffusion competition strongly enhances reactions with barriers and more specifically reactions with H2, which is abundant on grains. This finding highlights the importance having a good approach to determine the abundance of H2 on grains. Consequently, it is found that the major N-bearing species on grains go from NH3 to N2 and HCN when the reaction-diffusion competition is taken into account. In the gas phase and before a few 105 yr, we find that the three-phase model does not have a strong impact on the observed species compared to the two-phase model. After this time, the computed abundances dramatically decrease due to the strong accretion on dust, which is not counterbalanced by the desorption less efficient than in the two-phase model. This strongly constrains the chemical age of cold cores to be of the order of few 105 yr.

Using artificial intelligence to improve identification of nanofluid gas-liquid two-phase flow pattern in mini-channel

NASA Astrophysics Data System (ADS)

Xiao, Jian; Luo, Xiaoping; Feng, Zhenfei; Zhang, Jinxin

2018-01-01

This work combines fuzzy logic and a support vector machine (SVM) with a principal component analysis (PCA) to create an artificial-intelligence system that identifies nanofluid gas-liquid two-phase flow states in a vertical mini-channel. Flow-pattern recognition requires finding the operational details of the process and doing computer simulations and image processing can be used to automate the description of flow patterns in nanofluid gas-liquid two-phase flow. This work uses fuzzy logic and a SVM with PCA to improve the accuracy with which the flow pattern of a nanofluid gas-liquid two-phase flow is identified. To acquire images of nanofluid gas-liquid two-phase flow patterns of flow boiling, a high-speed digital camera was used to record four different types of flow-pattern images, namely annular flow, bubbly flow, churn flow, and slug flow. The textural features extracted by processing the images of nanofluid gas-liquid two-phase flow patterns are used as inputs to various identification schemes such as fuzzy logic, SVM, and SVM with PCA to identify the type of flow pattern. The results indicate that the SVM with reduced characteristics of PCA provides the best identification accuracy and requires less calculation time than the other two schemes. The data reported herein should be very useful for the design and operation of industrial applications.

Kinetic modeling of secondary organic aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-08-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Kinetic modeling of Secondary Organic Aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-05-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Dual-phase gas-permeation flow-injection thermometric analysis for the determination of carbon dioxide.

PubMed

Liu, S J; Tubino, M

1998-11-01

A flow-injection configuration based on a dual-phase gas-permeation system from a liquid donor to a gas acceptor stream with a thermistor flow-through detector is proposed for the direct analysis of the gas in the acceptor. This system was applied for the determination of carbon dioxide (in the form of carbonate) using the following chemical reaction: CO(2)(g)+2NH(3)(g)+H(2)O(g)=(NH(4))(2)CO(3)(s), with a linear response from 1x10(-3) to 50x10(-3) mol l(-1) of CO(3)(2-). Carbon dioxide was produced in the liquid donor and permeated into the gaseous acceptor stream of air/water vapor. The detection limit is 1x10(-3) mol l(-1) of carbonate, and a sampling frequency of 60 h(-1) is achieved with a relative standard deviation of 4.1% for replicate injections. The dual-phase gas-permeation flow-injection manifold, along with the membrane and phase separations, as well as the chemical reaction, provides enhanced selectivity when compared with the system employing a liquid acceptor stream, as serious interferents in this system, for instance, acetate and formate, among others, do not interfere in the proposed system.

Vaccum Gas Tungsten Arc Welding, phase 1

NASA Astrophysics Data System (ADS)

Weeks, J. L.; Krotz, P. D.; Todd, D. T.; Liaw, Y. K.

1995-03-01

This two year program will investigate Vacuum Gas Tungsten Arc Welding (VGTAW) as a method to modify or improve the weldability of normally difficult-to-weld materials. VGTAW appears to offer a significant improvement in weldability because of the clean environment and lower heat input needed. The overall objective of the program is to develop the VGTAW technology and implement it into a manufacturing environment that will result in lower cost, better quality and higher reliability aerospace components for the space shuttle and other NASA space systems. Phase 1 of this program was aimed at demonstrating the process's ability to weld normally difficult-to-weld materials. Phase 2 will focus on further evaluation, a hardware demonstration and a plan to implement VGTAW technology into a manufacturing environment. During Phase 1, the following tasks were performed: (1) Task 11000 Facility Modification - an existing vacuum chamber was modified and adapted to a GTAW power supply; (2) Task 12000 Materials Selection - four difficult-to-weld materials typically used in the construction of aerospace hardware were chosen for study; (3) Task 13000 VGTAW Experiments - welding experiments were conducted under vacuum using the hollow tungsten electrode and evaluation. As a result of this effort, two materials, NARloy Z and Incoloy 903, were downselected for further characterization in Phase 2; and (4) Task 13100 Aluminum-Lithium Weld Studies - this task was added to the original work statement to investigate the effects of vacuum welding and weld pool vibration on aluminum-lithium alloys.

Vaccum Gas Tungsten Arc Welding, phase 1

NASA Technical Reports Server (NTRS)

Weeks, J. L.; Krotz, P. D.; Todd, D. T.; Liaw, Y. K.

1995-01-01

This two year program will investigate Vacuum Gas Tungsten Arc Welding (VGTAW) as a method to modify or improve the weldability of normally difficult-to-weld materials. VGTAW appears to offer a significant improvement in weldability because of the clean environment and lower heat input needed. The overall objective of the program is to develop the VGTAW technology and implement it into a manufacturing environment that will result in lower cost, better quality and higher reliability aerospace components for the space shuttle and other NASA space systems. Phase 1 of this program was aimed at demonstrating the process's ability to weld normally difficult-to-weld materials. Phase 2 will focus on further evaluation, a hardware demonstration and a plan to implement VGTAW technology into a manufacturing environment. During Phase 1, the following tasks were performed: (1) Task 11000 Facility Modification - an existing vacuum chamber was modified and adapted to a GTAW power supply; (2) Task 12000 Materials Selection - four difficult-to-weld materials typically used in the construction of aerospace hardware were chosen for study; (3) Task 13000 VGTAW Experiments - welding experiments were conducted under vacuum using the hollow tungsten electrode and evaluation. As a result of this effort, two materials, NARloy Z and Incoloy 903, were downselected for further characterization in Phase 2; and (4) Task 13100 Aluminum-Lithium Weld Studies - this task was added to the original work statement to investigate the effects of vacuum welding and weld pool vibration on aluminum-lithium alloys.

Droplet evaporation and combustion in a liquid-gas multiphase system

NASA Astrophysics Data System (ADS)

Muradoglu, Metin; Irfan, Muhammad

2017-11-01

Droplet evaporation and combustion in a liquid-gas multiphase system are studied computationally using a front-tracking method. One field formulation is used to solve the flow, energy and species equations with suitable jump conditions. Both phases are assumed to be incompressible; however, the divergence-free velocity field condition is modified to account for the phase change at the interface. Both temperature and species gradient driven phase change processes are simulated. Extensive validation studies are performed using the benchmark cases: The Stefan and the sucking interface problems, d2 law and wet bulb temperature comparison with the psychrometric chart values. The phase change solver is then extended to incorporate the burning process following the evaporation as a first step towards the development of a computational framework for spray combustion. We used detailed chemistry, variable transport properties and ideal gas behaviour for a n-heptane droplet combustion; the chemical kinetics being handled by the CHEMKIN. An operator-splitting approach is used to advance temperature and species mass fraction in time. The numerical results of the droplet burning rate, flame temperature and flame standoff ratio show good agreement with the experimental and previous numeric.

GAS-PHASE OXIDATION PRODUCTS OF BIPHENYL AND POLYCHLORINATED BIPHENYLS (R825377)

EPA Science Inventory

Our laboratory recently measured the gas-phase reaction rate constants of
polychlorinated biphenyls (PCBs) with the hydroxyl radical (OH) and concluded
that OH reactions are the primary removal pathway of PCBs from the atmosphere.
With the reaction system previousl...

LSPRAY: Lagrangian Spray Solver for Applications With Parallel Computing and Unstructured Gas-Phase Flow Solvers

NASA Technical Reports Server (NTRS)

Raju, Manthena S.

1998-01-01

Sprays occur in a wide variety of industrial and power applications and in the processing of materials. A liquid spray is a phase flow with a gas as the continuous phase and a liquid as the dispersed phase (in the form of droplets or ligaments). Interactions between the two phases, which are coupled through exchanges of mass, momentum, and energy, can occur in different ways at different times and locations involving various thermal, mass, and fluid dynamic factors. An understanding of the flow, combustion, and thermal properties of a rapidly vaporizing spray requires careful modeling of the rate-controlling processes associated with the spray's turbulent transport, mixing, chemical kinetics, evaporation, and spreading rates, as well as other phenomena. In an attempt to advance the state-of-the-art in multidimensional numerical methods, we at the NASA Lewis Research Center extended our previous work on sprays to unstructured grids and parallel computing. LSPRAY, which was developed by M.S. Raju of Nyma, Inc., is designed to be massively parallel and could easily be coupled with any existing gas-phase flow and/or Monte Carlo probability density function (PDF) solver. The LSPRAY solver accommodates the use of an unstructured mesh with mixed triangular, quadrilateral, and/or tetrahedral elements in the gas-phase solvers. It is used specifically for fuel sprays within gas turbine combustors, but it has many other uses. The spray model used in LSPRAY provided favorable results when applied to stratified-charge rotary combustion (Wankel) engines and several other confined and unconfined spray flames. The source code will be available with the National Combustion Code (NCC) as a complete package.

The Role of Multiple Representations in the Understanding of Ideal Gas Problems

ERIC Educational Resources Information Center

Madden, Sean P.; Jones, Loretta L.; Rahm, Jrene

2011-01-01

This study examined the representational competence of students as they solved problems dealing with the temperature-pressure relationship for ideal gases. Seven students enrolled in a first-semester general chemistry course and two advanced undergraduate science majors participated in the study. The written work and transcripts from videotaped…

Linking photochemistry in the gas and solution phase: S-H bond fission in p-methylthiophenol following UV photoexcitation.

PubMed

Oliver, Thomas A A; Zhang, Yuyuan; Ashfold, Michael N R; Bradforth, Stephen E

2011-01-01

Gas-phase H (Rydberg) atom photofragment translational spectroscopy and solution-phase femtosecond-pump dispersed-probe transient absorption techniques are applied to explore the excited state dynamics of p-methylthiophenol connecting the short time reactive dynamics in the two phases. The molecule is excited at a range of UV wavelengths from 286 to 193 nm. The experiments clearly demonstrate that photoexcitation results in S-H bond fission--both in the gas phase and in ethanol solution-and that the resulting p-methythiophenoxyl radical fragments are formed with significant vibrational excitation. In the gas phase, the recoil anisotropy of the H atom and the vibrational energy disposal in the p-MePhS radical products formed at the longer excitation wavelengths reveal the operation of two excited state dissociation mechanisms. The prompt excited state dissociation motif appears to map into the condensed phase also. In both phases, radicals are produced in both their ground and first excited electronic states; characteristic signatures for both sets of radical products are already apparent in the condensed phase studies after 50 fs. No evidence is seen for either solute ionisation or proton coupled electron transfer--two alternate mechanisms that have been proposed for similar heteroaromatics in solution. Therefore, at least for prompt S-H bond fissions, the direct observation of the dissociation process in solution confirms that the gas phase photofragmentation studies indeed provide important insights into the early time dynamics that transfer to the condensed phase.

Gas hydrate formation rates from dissolved-phase methane in porous laboratory specimens

USGS Publications Warehouse

Waite, William F.; Spangenberg, E.K.

2013-01-01

Marine sands highly saturated with gas hydrates are potential energy resources, likely forming from methane dissolved in pore water. Laboratory fabrication of gas hydrate-bearing sands formed from dissolved-phase methane usually requires 1–2 months to attain the high hydrate saturations characteristic of naturally occurring energy resource targets. A series of gas hydrate formation tests, in which methane-supersaturated water circulates through 100, 240, and 200,000 cm3 vessels containing glass beads or unconsolidated sand, show that the rate-limiting step is dissolving gaseous-phase methane into the circulating water to form methane-supersaturated fluid. This implies that laboratory and natural hydrate formation rates are primarily limited by methane availability. Developing effective techniques for dissolving gaseous methane into water will increase formation rates above our observed (1 ± 0.5) × 10−7 mol of methane consumed for hydrate formation per minute per cubic centimeter of pore space, which corresponds to a hydrate saturation increase of 2 ± 1% per day, regardless of specimen size.

Mimicking electrodeposition in the gas phase: a programmable concept for selected-area fabrication of multimaterial nanostructures.

PubMed

Cole, Jesse J; Lin, En-Chiang; Barry, Chad R; Jacobs, Heiko O

2010-05-21

An in situ gas-phase process that produces charged streams of Au, Si, TiO(2), ZnO, and Ge nanoparticles/clusters is reported together with a programmable concept for selected-area assembly/printing of more than one material type. The gas-phase process mimics solution electrodeposition whereby ions in the liquid phase are replaced with charged clusters in the gas phase. The pressure range in which the analogy applies is discussed and it is demonstrated that particles can be plated into pores vertically (minimum resolution 60 nm) or laterally to form low-resistivity (48 microOmega cm) interconnects. The process is applied to the formation of multimaterial nanoparticle films and sensors. The system works at atmospheric pressure and deposits material at room temperature onto electrically biased substrate regions. The combination of pumpless operation and parallel nozzle-free deposition provides a scalable tool for printable flexible electronics and the capability to mix and match materials.

Enhanced Lipidome Coverage in Shotgun Analyses by using Gas-Phase Fractionation

NASA Astrophysics Data System (ADS)

Nazari, Milad; Muddiman, David C.

2016-11-01

A high resolving power shotgun lipidomics strategy using gas-phase fractionation and data-dependent acquisition (DDA) was applied toward comprehensive characterization of lipids in a hen ovarian tissue in an untargeted fashion. Using this approach, a total of 822 unique lipids across a diverse range of lipid categories and classes were identified based on their MS/MS fragmentation patterns. Classes of glycerophospholipids and glycerolipids, such as glycerophosphocholines (PC), glycerophosphoethanolamines (PE), and triglycerides (TG), are often the most abundant peaks observed in shotgun lipidomics analyses. These ions suppress the signal from low abundance ions and hinder the chances of characterizing low abundant lipids when DDA is used. These issues were circumvented by utilizing gas-phase fractionation, where DDA was performed on narrow m/z ranges instead of a broad m/z range. Employing gas-phase fractionation resulted in an increase in sensitivity by more than an order of magnitude in both positive- and negative-ion modes. Furthermore, the enhanced sensitivity increased the number of lipids identified by a factor of ≈4, and facilitated identification of low abundant lipids from classes such as cardiolipins that are often difficult to observe in untargeted shotgun analyses and require sample-specific preparation steps prior to analysis. This method serves as a resource for comprehensive profiling of lipids from many different categories and classes in an untargeted manner, as well as for targeted and quantitative analyses of individual lipids. Furthermore, this comprehensive analysis of the lipidome can serve as a species- and tissue-specific database for confident identification of other MS-based datasets, such as mass spectrometry imaging.

Modeling the Transition From Predominantly Gas- to Predominantly Aerosol-Phase Products From OH Reactions With the Homologous Series of C10 to C15 n- Alkanes

NASA Astrophysics Data System (ADS)

Jordan, C. E.; Ziemann, P. J.; Griffin, R. J.; Lim, Y. B.; Atkinson, R.; Arey, J.

2006-12-01

Recent laboratory studies have shown significant formation of secondary organic aerosol (SOA) from OH reactions with a homologous series of n-alkanes. SOA mass yields of 56% were observed for pentadecane (C15), while only 0.5% yield was observed from octane (C8, the smallest alkane in the series). A rapid transition in SOA yield is observed from C10 to C13, with SOA yields increasing from 4% to 49%. In standard gas-aerosol partitioning theory, the vapor pressure controls the amount of material that can condense into the particle phase. However, the rapid transition observed here suggests there may also be a shift in the predominant reaction pathways for longer chain alkanes, leading to greater production of lower vapor pressure products. Here we present an investigation of the role of vapor pressure versus the role of shifting branching ratios to test the influence of each of these on SOA mass yields. We have added each of the alkanes in this series to the Caltech Atmospheric Chemistry Mechanism (CACM). This mechanism was developed in part to predict explicitly concentrations of secondary and tertiary semivolatile oxidation products that potentially form SOA. Although it is has been developed to lump similar compounds together for computational efficiency, it is nonetheless easily adapted and ideally suited for a detailed zero-dimensional modeling study of this kind. This gas-phase mechanism is linked to the aerosol partitioning module MPMPO (Model to Predict the Multi- phase Partitioning of Organics). MPMPO is a fully coupled module that allows the simultaneous partitioning of semi-volatile species to both an aqueous and an organic aerosol phase.

The gas phase origin of complex organic molecules precursors in prestellar cores

NASA Astrophysics Data System (ADS)

Bacmann, A.; Faure, A.

2015-05-01

Complex organic molecules (COMs) have long been observed in the warm regions surrounding nascent protostars. The recent discovery of oxygen-bearing COMs like methyl formate or dimethyl ether in prestellar cores (Bacmann et al. [2]), where gas and dust temperatures rarely exceed 10-15 K, has challenged the previously accepted models according to which COM formation relied on the diffusion of heavy radicals on warm (˜30 K) grains. Following these detections, new questions have arisen: do non-thermal processes play a role in increasing radical mobility or should new gas-phase routes be explored? The radicals involved in the formation of the aforementioned COMs, HCO and CH3O represent intermediate species in the grain-surface synthesis of methanol which proceeds via successive hydrogenations of CO molecules in the ice. We present here observations of methanol and its grain-surface precursors HCO, H2CO, CH3O in a sample of prestellar cores and derive their relative abundances. We find that the relative abundances HCO:H2CO:CH3O:CH3OH are constant across the core sample, close to 10:100:1:100. Our results also show that the amounts of HCO and CH3O are consistent with a gas-phase synthesis of these species from H2CO and CH3OH via radical-neutral or ion-molecule reactions followed by dissociative recombinations. Thus, while grain chemistry is necessary to explain the abundances of the parent volatile CH3OH, and possibly H2CO, the reactive species HCO and CH3O might be daughter molecules directly produced in the gas-phase.

Fragon: rapid high-resolution structure determination from ideal protein fragments.

PubMed

Jenkins, Huw T

2018-03-01

Correctly positioning ideal protein fragments by molecular replacement presents an attractive method for obtaining preliminary phases when no template structure for molecular replacement is available. This has been exploited in several existing pipelines. This paper presents a new pipeline, named Fragon, in which fragments (ideal α-helices or β-strands) are placed using Phaser and the phases calculated from these coordinates are then improved by the density-modification methods provided by ACORN. The reliable scoring algorithm provided by ACORN identifies success. In these cases, the resulting phases are usually of sufficient quality to enable automated model building of the entire structure. Fragon was evaluated against two test sets comprising mixed α/β folds and all-β folds at resolutions between 1.0 and 1.7 Å. Success rates of 61% for the mixed α/β test set and 30% for the all-β test set were achieved. In almost 70% of successful runs, fragment placement and density modification took less than 30 min on relatively modest four-core desktop computers. In all successful runs the best set of phases enabled automated model building with ARP/wARP to complete the structure.

Rate processes in gas phase

NASA Technical Reports Server (NTRS)

Hansen, C. F.

1983-01-01

Reaction-rate theory and experiment are given a critical review from the engineers' point of view. Rates of heavy-particle, collision-induced reaction in gas phase are formulated in terms of the cross sections and activation energies for reaction. The effect of cross section function shape and of excited state contributions to reaction both cause the slope of Arrhenius plots to differ from the true activation energy, except at low temperature. The master equations for chemically reacting gases are introduced, and dissociation and ionization reactions are shown to proceed primarily from excited states about kT from the dissociation or ionization limit. Collision-induced vibration, vibration-rotation, and pure rotation transitions are treated, including three-dimensional effects and conservation of energy, which have usually been ignored. The quantum theory of transitions at potential surface crossing is derived, and results are found to be in fair agreement with experiment in spite of some questionable approximations involved.

A method for direct, semi-quantitative analysis of gas phase samples using gas chromatography-inductively coupled plasma-mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carter, Kimberly E; Gerdes, Kirk

2013-07-01

A new and complete GC–ICP-MS method is described for direct analysis of trace metals in a gas phase process stream. The proposed method is derived from standard analytical procedures developed for ICP-MS, which are regularly exercised in standard ICP-MS laboratories. In order to implement the method, a series of empirical factors were generated to calibrate detector response with respect to a known concentration of an internal standard analyte. Calibrated responses are ultimately used to determine the concentration of metal analytes in a gas stream using a semi-quantitative algorithm. The method was verified using a traditional gas injection from a GCmore » sampling valve and a standard gas mixture containing either a 1 ppm Xe + Kr mix with helium balance or 100 ppm Xe with helium balance. Data collected for Xe and Kr gas analytes revealed that agreement of 6–20% with the actual concentration can be expected for various experimental conditions. To demonstrate the method using a relevant “unknown” gas mixture, experiments were performed for continuous 4 and 7 hour periods using a Hg-containing sample gas that was co-introduced into the GC sample loop with the xenon gas standard. System performance and detector response to the dilute concentration of the internal standard were pre-determined, which allowed semi-quantitative evaluation of the analyte. The calculated analyte concentrations varied during the course of the 4 hour experiment, particularly during the first hour of the analysis where the actual Hg concentration was under predicted by up to 72%. Calculated concentration improved to within 30–60% for data collected after the first hour of the experiment. Similar results were seen during the 7 hour test with the deviation from the actual concentration being 11–81% during the first hour and then decreasing for the remaining period. The method detection limit (MDL) was determined for the mercury by injecting the sample gas into the system following

Onset conditions for gas phase reaction and nucleation in the CVD of transition metal oxides

NASA Technical Reports Server (NTRS)

Collins, J.; Rosner, D. E.; Castillo, J.

1992-01-01

A combined experimental/theoretical study is presented of the onset conditions for gas phase reaction and particle nucleation in hot substrate/cold gas CVD of transition metal oxides. Homogeneous reaction onset conditions are predicted using a simple high activation energy reacting gas film theory. Experimental tests of the basic theory are underway using an axisymmetric impinging jet CVD reactor. No vapor phase ignition has yet been observed in the TiCl4/O2 system under accessible operating conditions (below substrate temperature Tw = 1700 K). The goal of this research is to provide CVD reactor design and operation guidelines for achieving acceptable deposit microstructures at the maximum deposition rate while simultaneously avoiding homogeneous reaction/nucleation and diffusional limitations.

A New Approach to Modeling Densities and Equilibria of Ice and Gas Hydrate Phases

NASA Astrophysics Data System (ADS)

Zyvoloski, G.; Lucia, A.; Lewis, K. C.

2011-12-01

The Gibbs-Helmholtz Constrained (GHC) equation is a new cubic equation of state that was recently derived by Lucia (2010) and Lucia et al. (2011) by constraining the energy parameter in the Soave form of the Redlich-Kwong equation to satisfy the Gibbs-Helmholtz equation. The key attributes of the GHC equation are: 1) It is a multi-scale equation because it uses the internal energy of departure, UD, as a natural bridge between the molecular and bulk phase length scales. 2) It does not require acentric factors, volume translation, regression of parameters to experimental data, binary (kij) interaction parameters, or other forms of empirical correlations. 3) It is a predictive equation of state because it uses a database of values of UD determined from NTP Monte Carlo simulations. 4) It can readily account for differences in molecular size and shape. 5) It has been successfully applied to non-electrolyte mixtures as well as weak and strong aqueous electrolyte mixtures over wide ranges of temperature, pressure and composition to predict liquid density and phase equilibrium with up to four phases. 6) It has been extensively validated with experimental data. 7) The AAD% error between predicted and experimental liquid density is 1% while the AAD% error in phase equilibrium predictions is 2.5%. 8) It has been used successfully within the subsurface flow simulation program FEHM. In this work we describe recent extensions of the multi-scale predictive GHC equation to modeling the phase densities and equilibrium behavior of hexagonal ice and gas hydrates. In particular, we show that radial distribution functions, which can be determined by NTP Monte Carlo simulations, can be used to establish correct standard state fugacities of 1h ice and gas hydrates. From this, it is straightforward to determine both the phase density of ice or gas hydrates as well as any equilibrium involving ice and/or hydrate phases. A number of numerical results for mixtures of N2, O2, CH4, CO2, water

Hydrodynamic behaviour and comparison of technologies for the removal of excess biomass in gas-phase biofilters.

PubMed

Mendoza, J A; Prado, O J; Veiga, M C; Kennes, C

2004-01-01

The hydrodynamic behaviour of a biofilter fed toluene and packed with an inert carrier was evaluated on start-up and after long-term operation, using both methane and styrene as tracers in Residence Time Distribution experiments. Results indicated some deviation from ideal plug flow behaviour after 2-year operation. It was also observed that the retention time of VOCs gradually increased with time and was significantly longer than the average residence time of the bulk gas phase. Non-ideal hydrodynamic behaviour in packed beds may be due to excess biomass accumulation and affects both reactor modeling and performance. Therefore, several methods were studied for the removal of biomass after long-term biofilter operation: filling with water and draining, backwashing, and air sparging. Several flow rates and temperatures (20-60 degrees C) were applied using either water or different chemicals (NaOH, NaOCl, HTAB) in aqueous solution. Usually, higher flow rates and higher temperatures allowed the removal of more biomass, but the efficiency of biomass removal was highly dependent on the pressure drop reached before the treatment. The filling/draining method was the least efficient for biomass removal, although the treatment did basically not generate any biological inhibition. The efficiency of backwashing and air sparging was relatively similar and was more effective when adding chemicals. However, treatments with chemicals resulted in a significant decrease of the biofilter's performance immediately after applying the treatment, needing periods of several days to recover the original performance. The effect of manually mixing the packing material was also evaluated in duplicate experiments. Quite large amounts of biomass were removed but disruption of the filter bed was observed. Batch assays were performed simultaneously in order to support and quantify the observed inhibitory effects of the different chemicals and temperatures used during the treatments.

Shock initiated reactions of reactive multi-phase blast explosives

NASA Astrophysics Data System (ADS)

Wilson, Dennis; Granier, John; Johnson, Richard; Littrell, Donald

2017-01-01

This paper describes a new class of non-ideal explosive compositions made of perfluoropolyether (PFPE), nanoaluminum, and a micron-size, high mass density, reactive metal. Unlike high explosives, these compositions release energy via a fast self-oxidized combustion wave rather than a true self-sustaining detonation. Their reaction rates are shock dependent and they can be overdriven to change their energy release rate. These compositions are fuel rich and have an extended aerobic energy release phase. The term "reactive multiphase blast" refers to the post-dispersion blast behavior: multiphase in that there are a gas phase that imparts pressure and a solid (particulate) phase that imparts energy and momentum [1]; and reactive in that the hot metal particles react with atmospheric oxygen and the explosive gas products to give an extended pressure pulse. Tantalum-based RMBX formulations were tested in two spherical core-shell configurations - an RMBX shell exploded by a high explosive core, and an RMBX core imploded by a high explosive shell. The fireball and blast characteristics were compared to a C-4 baseline charge.

Determination of gas phase protein ion densities via ion mobility analysis with charge reduction.

PubMed

Maisser, Anne; Premnath, Vinay; Ghosh, Abhimanyu; Nguyen, Tuan Anh; Attoui, Michel; Hogan, Christopher J

2011-12-28

We use a charge reduction electrospray (ESI) source and subsequent ion mobility analysis with a differential mobility analyzer (DMA, with detection via both a Faraday cage electrometer and a condensation particle counter) to infer the densities of single and multiprotein ions of cytochrome C, lysozyme, myoglobin, ovalbumin, and bovine serum albumin produced from non-denaturing (20 mM aqueous ammonium acetate) and denaturing (1 : 49.5 : 49.5, formic acid : methanol : water) ESI. Charge reduction is achieved through use of a Po-210 radioactive source, which generates roughly equal concentrations of positive and negative ions. Ions produced by the source collide with and reduce the charge on ESI generated drops, preventing Coulombic fissions, and unlike typical protein ESI, leading to gas-phase protein ions with +1 to +3 excess charges. Therefore, charge reduction serves to effectively mitigate any role that Coulombic stretching may play on the structure of the gas phase ions. Density inference is made via determination of the mobility diameter, and correspondingly the spherical equivalent protein volume. Through this approach it is found that for both non-denaturing and denaturing ESI-generated ions, gas-phase protein ions are relatively compact, with average densities of 0.97 g cm(-3) and 0.86 g cm(-3), respectively. Ions from non-denaturing ESI are found to be slightly more compact than predicted from the protein crystal structures, suggesting that low charge state protein ions in the gas phase are slightly denser than their solution conformations. While a slight difference is detected between the ions produced with non-denaturing and denaturing ESI, the denatured ions are found to be much more dense than those examined previously by drift tube mobility analysis, in which charge reduction was not employed. This indicates that Coulombic stretching is typically what leads to non-compact ions in the gas-phase, and suggests that for gas phase

Computation of three-phase capillary entry pressures and arc menisci configurations in pore geometries from 2D rock images: A combinatorial approach

NASA Astrophysics Data System (ADS)

Zhou, Yingfang; Helland, Johan Olav; Hatzignatiou, Dimitrios G.

2014-07-01

We present a semi-analytical, combinatorial approach to compute three-phase capillary entry pressures for gas invasion into pore throats with constant cross-sections of arbitrary shapes that are occupied by oil and/or water. For a specific set of three-phase capillary pressures, geometrically allowed gas/oil, oil/water and gas/water arc menisci are determined by moving two circles in opposite directions along the pore/solid boundary for each fluid pair such that the contact angle is defined at the front circular arcs. Intersections of the two circles determine the geometrically allowed arc menisci for each fluid pair. The resulting interfaces are combined systematically to allow for all geometrically possible three-phase configuration changes. The three-phase extension of the Mayer and Stowe - Princen method is adopted to calculate capillary entry pressures for all determined configuration candidates, from which the most favorable gas invasion configuration is determined. The model is validated by comparing computed three-phase capillary entry pressures and corresponding fluid configurations with analytical solutions in idealized triangular star-shaped pores. It is demonstrated that the model accounts for all scenarios that have been analyzed previously in these shapes. Finally, three-phase capillary entry pressures and associated fluid configurations are computed in throat cross-sections extracted from segmented SEM images of Bentheim sandstone. The computed gas/oil capillary entry pressures account for the expected dependence of oil/water capillary pressure in spreading and non-spreading fluid systems at the considered wetting conditions. Because these geometries are irregular and include constrictions, we introduce three-phase displacements that have not been identified previously in pore-network models that are based on idealized pore shapes. However, in the limited number of pore geometries considered in this work, we find that the favorable displacements are

The nonlinear model for emergence of stable conditions in gas mixture in force field

NASA Astrophysics Data System (ADS)

Kalutskov, Oleg; Uvarova, Liudmila

2016-06-01

The case of M-component liquid evaporation from the straight cylindrical capillary into N - component gas mixture in presence of external forces was reviewed. It is assumed that the gas mixture is not ideal. The stable states in gas phase can be formed during the evaporation process for the certain model parameter valuesbecause of the mass transfer initial equationsnonlinearity. The critical concentrations of the resulting gas mixture components (the critical component concentrations at which the stable states occur in mixture) were determined mathematically for the case of single-component fluid evaporation into two-component atmosphere. It was concluded that this equilibrium concentration ratio of the mixture components can be achieved by external force influence on the mass transfer processes. It is one of the ways to create sustainable gas clusters that can be used effectively in modern nanotechnology.

Solution and Gas-Phase H/D Exchange of Protein-Small-Molecule Complexes: Cex and Its Inhibitors

NASA Astrophysics Data System (ADS)

Kang, Yang; Terrier, Peran; Ding, Chuanfan; Douglas, D. J.

2012-01-01

The properties of noncovalent complexes of the enzyme exo-1,4-β-D-glycanase ("Cex") with three aza-sugar inhibitors, deoxynojirimycin (X2DNJ), isofagomine lactam (X2IL), and isofagomine (X2IF), have been studied with solution and gas-phase hydrogen deuterium exchange (H/Dx) and measurements of collision cross sections of gas-phase ions. In solution, complexes have lower H/Dx levels than free Cex because binding the inhibitors blocks some sites from H/Dx and reduces fluctuations of the protein. In mass spectra of complexes, abundant Cex ions are seen, which mostly are formed by dissociation of complexes in the ion sampling interface. Both complex ions and Cex ions formed from a solution containing complexes have lower cross sections than Cex ions from a solution of Cex alone. This suggests the Cex ions formed by dissociation "remember" their solution conformations. For a given charge, ions of the complexes have greater gas-phase H/Dx levels than ions of Cex. Unlike cross sections, H/Dx levels of the complexes do not correlate with the relative gas-phase binding strengths measured by MS/MS. Cex ions from solutions with or without inhibitors, which have different cross sections, show the same H/Dx level after 15 s, indicating the ions may fold or unfold on the seconds time scale of the H/Dx experiment. Thus, cross sections show that complexes have more compact conformations than free protein ions on the time scale of ca. 1 ms. The gas-phase H/Dx measurements show that at least some complexes retain different conformations from the Cex ions on a time scale of seconds.

Optical Absorptions of Oxygenated Carbon Chain Cations in the Gas Phase

NASA Astrophysics Data System (ADS)

Hardy, F.-X.; Rice, C. A.; Chakraborty, A.; Fulara, J.; Maier, J. P.

2016-06-01

The gas-phase electronic spectra of linear OC4O+ and a planar C6H2O+ isomer were obtained at a rotational temperature of ≈10 K. Absorption measurements in a 6 K neon matrix were followed by gas-phase observations in a cryogenic radiofrequency ion trap. The origin bands of the 1{}2{{{\\Pi }}}u ≤ftarrow X{}2{{{\\Pi }}}g transition of OC4O+ and the 1{}2A{}2 ≤ftarrow X{}2B1 of HCCC(CO)CCH+ lie at 417.31 ± 0.01 nm and 523.49 ± 0.01 nm, respectively. These constitute the first electronic spectra of oxygenated carbon chain cations studied under conditions that are relevant to the diffuse interstellar bands (DIBs), as both have a visible transition. The recent analysis of the 579.5 nm DIB indicates that small carriers, five to seven heavy atoms, continue to be possible candidates (Huang & Oka 2015). Astronomical implications are discussed regarding this kind of oxygenated molecules.

The VRT gas turbine combustor - Phase II

NASA Technical Reports Server (NTRS)

Melconian, Jerry O.; Mongia, Hukam C.; Nguyen, Hung L.

1992-01-01

An innovative annular combustor configuration is being developed for aircraft and other gas turbine engines. This design has the potential of permitting higher turbine inlet temperatures by reducing the pattern factor and providing a major reduction in NO(x) emission. The design concept is based on a Variable Residence Time (VRT) technique which allows large fuel particles adequate time to completely burn in the circumferentially mixed primary zone. High durability of the combustor is achieved by dual-function use of the incoming air. In Phase I, the feasibility of the concept was demonstrated by water analogue tests and 3D computer modeling. The flow pattern within the combustor was as predicted. The VRT combustor uses only half the number of fuel nozzles of the conventional configuration. In Phase II, hardware was designed, procured, and tested under conditions simulating typical supersonic civil aircraft cruise conditions to the limits of the rig. The test results confirmed many of the superior performance predictions of the VRT concept. The Hastelloy X liner showed no signs of distress after nearly six hours of tests using JP5 fuel.

Study of Hind Limb Tissue Gas Phase Formation in Response to Suspended Adynamia and Hypokinesia

NASA Technical Reports Server (NTRS)

Butler, Bruce D.

1996-01-01

The purpose of this study was to investigate the hypothesis that reduced joint/muscle activity (hypo kinesia) as well as reduced or null loading of limbs (adynamia) in gravity would result in reduced decompression-induced gas phase and symptoms of decompression sickness (DCS). Finding a correlation between the two phenomena would correspond to the proposed reduction in tissue gas phase formation in astronauts undergoing decompression during extravehicular activity (EVA) in microgravity. The observation may further explain the reported low incidence of DCS in space.

DYNAMIC MODELING STRATEGY FOR FLOW REGIME TRANSITION IN GAS-LIQUID TWO-PHASE FLOWS

DOE Office of Scientific and Technical Information (OSTI.GOV)

X. Wang; X. Sun; H. Zhao

In modeling gas-liquid two-phase flows, the concept of flow regime has been used to characterize the global interfacial structure of the flows. Nearly all constitutive relations that provide closures to the interfacial transfers in two-phase flow models, such as the two-fluid model, are often flow regime dependent. Currently, the determination of the flow regimes is primarily based on flow regime maps or transition criteria, which are developed for steady-state, fully-developed flows and widely applied in nuclear reactor system safety analysis codes, such as RELAP5. As two-phase flows are observed to be dynamic in nature (fully-developed two-phase flows generally do notmore » exist in real applications), it is of importance to model the flow regime transition dynamically for more accurate predictions of two-phase flows. The present work aims to develop a dynamic modeling strategy for determining flow regimes in gas-liquid two-phase flows through the introduction of interfacial area transport equations (IATEs) within the framework of a two-fluid model. The IATE is a transport equation that models the interfacial area concentration by considering the creation and destruction of the interfacial area, such as the fluid particle (bubble or liquid droplet) disintegration, boiling and evaporation; and fluid particle coalescence and condensation, respectively. For the flow regimes beyond bubbly flows, a two-group IATE has been proposed, in which bubbles are divided into two groups based on their size and shape (which are correlated), namely small bubbles and large bubbles. A preliminary approach to dynamically identifying the flow regimes is provided, in which discriminators are based on the predicted information, such as the void fraction and interfacial area concentration of small bubble and large bubble groups. This method is expected to be applied to computer codes to improve their predictive capabilities of gas-liquid two-phase flows, in particular for the

Effect of Grain Size on Differential Desorption of Volatile Species and on Non-ideal MHD Diffusivity

NASA Astrophysics Data System (ADS)

Zhao, Bo; Caselli, Paola; Li, Zhi-Yun

2018-05-01

We developed a chemical network for modeling the chemistry and non-ideal MHD effects from the collapsing dense molecular clouds to protostellar disks. First, we re-formulated the cosmic-ray desorption rate by considering the variations of desorption rate over the grain size distribution. We find that the differential desorption of volatile species is amplified by the grains larger than 0.1 μm, because larger grains are heated to a lower temperature by cosmic-rays and hence more sensitive to the variations in binding energies. As a result, atomic nitrogen N is ˜2 orders of magnitude more abundant than CO; N2H+ also becomes a few times more abundant than HCO+ due to the increased gas-phase N2. However, the changes in ionization fraction due to freeze-out and desorption only have minor effects on the non-ideal MHD diffusivities. Our chemical network confirms that the very small grains (VSGs: below a few 100 Å) weakens the efficiency of both ambipolar diffusion and Hall effect. In collapsing dense cores, a maximum ambipolar diffusion is achieved when truncating the MRN size distribution at 0.1 μm, and for a maximum Hall effect, the truncation occurs at 0.04 μm. We conclude that the grain size distribution is crucial to the differential depletion between CO and N2 related molecules, as well as to the non-ideal MHD diffusivities in dense cores.

Comprehensive Gas-Phase Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 2. Gas-Phase Hydrogen/Deuterium Exchange for Ion Population Estimation.

PubMed

Khakinejad, Mahdiar; Ghassabi Kondalaji, Samaneh; Tafreshian, Amirmahdi; Valentine, Stephen J

2017-05-01

Gas-phase hydrogen/deuterium exchange (HDX) using D 2 O reagent and collision cross-section (CCS) measurements are utilized to monitor the ion conformers of the model peptide acetyl-PAAAAKAAAAKAAAAKAAAAK. The measurements are carried out on a home-built ion mobility instrument coupled to a linear ion trap mass spectrometer containing electron transfer dissociation (ETD) capabilities. ETD is utilized to obtain per-residue deuterium uptake data for select ion conformers, and a new algorithm is presented for interpreting the HDX data. Using molecular dynamics (MD) production data and a hydrogen accessibility scoring (HAS)-number of effective collisions (NEC) model, hypothetical HDX behavior is attributed to various in-silico candidate (CCS match) structures. The HAS-NEC model is applied to all candidate structures, and non-negative linear regression is employed to determine structure contributions resulting in the best match to deuterium uptake. The accuracy of the HAS-NEC model is tested with the comparison of predicted and experimental isotopic envelopes for several of the observed c-ions. It is proposed that gas-phase HDX can be utilized effectively as a second criterion (after CCS matching) for filtering suitable MD candidate structures. In this study, the second step of structure elucidation, 13 nominal structures were selected (from a pool of 300 candidate structures) and each with a population contribution proposed for these ions. Graphical Abstract ᅟ.

Rapid removal of nitrobenzene in a three-phase ozone loaded system with gas-liquid-liquid

USGS Publications Warehouse

Li, Shiyin; Zhu, Jiangpeng; Wang, Guoxiang; Ni, Lixiao; Zhang, Yong; Green, Christopher T.

2015-01-01

This study explores the removal rate of nitrobenzene (NB) using a new gas-liquid-liquid (G-L-L) three-phase ozone loaded system consisting of a gaseous ozone, an aqueous solvent phase, and a fluorinated solvent phase (perfluorodecalin, or FDC). The removal rate of NB was quantified in relation to six factors including 1) initial pH, 2) initial NB dosage, 3) gaseous ozone dosage, 4) free radical scavenger, 5) FDC pre-aerated gaseous ozone, and 6) reuse of FDC. The NB removal rate is positively affected by the first three factors. Compared with the conventional gas-liquid (water) (G-L) two-phase ozonation system, the free radical scavenger (tertiary butyl alcohol) has much less influence on the removal rate of NB in the G-L-L system. The FDC loaded ozone acts as an ozone reservoir and serves as the main reactive phase in the G-L-L three-phase system. The reuse of FDC has little influence on the removal rate of NB. These experimental results suggest that the oxidation efficiency of ozonation in the G-L-L three-phase system is better than that in the conventional G-L two-phase system.

Protein and Peptide Gas-phase Structure Investigation Using Collision Cross Section Measurements and Hydrogen Deuterium Exchange

NASA Astrophysics Data System (ADS)

Khakinejad, Mahdiar

Protein and peptide gas-phase structure analysis provides the opportunity to study these species outside of their explicit environment where the interaction network with surrounding molecules makes the analysis difficult [1]. Although gas-phase structure analysis offers a unique opportunity to study the intrinsic behavior of these biomolecules [2-4], proteins and peptides exhibit very low vapor pressures [2]. Peptide and protein ions can be rendered in the gas-phase using electrospray ionization (ESI) [5]. There is a growing body of literature that shows proteins and peptides can maintain solution structures during the process of ESI and these structures can persist for a few hundred milliseconds [6-9]. Techniques for monitoring gas-phase protein and peptide ion structures are categorized as physical probes and chemical probes. Collision cross section (CCS) measurement, being a physical probe, is a powerful method to investigate gas-phase structure size [3, 7, 10-15]; however, CCS values alone do not establish a one to one relation with structure(i.e., the CCS value is an orientationally averaged value [15-18]. Here we propose the utility of gas-phase hydrogen deuterium exchange (HDX) as a second criterion of structure elucidation. The proposed approach incudes extensive MD simulations to sample biomolecular ion conformation space with the production of numerous, random in-silico structures. Subsequently a CCS can be calculated for these structures and theoretical CCS values are compared with experimental values to produce a pool of candidate structures. Utilizing a chemical reaction model based on the gas-phase HDX mechanism, the HDX kinetics behavior of these candidate structures are predicted and compared to experimental results to nominate the best in-silico structures which match (chemically and physically) with experimental observations. For the predictive approach to succeed, an extensive technique and method development is essential. To combine CCS

Analytical solutions for a soil vapor extraction model that incorporates gas phase dispersion and molecular diffusion

NASA Astrophysics Data System (ADS)

Huang, Junqi; Goltz, Mark N.

2017-06-01

To greatly simplify their solution, the equations describing radial advective/dispersive transport to an extraction well in a porous medium typically neglect molecular diffusion. While this simplification is appropriate to simulate transport in the saturated zone, it can result in significant errors when modeling gas phase transport in the vadose zone, as might be applied when simulating a soil vapor extraction (SVE) system to remediate vadose zone contamination. A new analytical solution for the equations describing radial gas phase transport of a sorbing contaminant to an extraction well is presented. The equations model advection, dispersion (including both mechanical dispersion and molecular diffusion), and rate-limited mass transfer of dissolved, separate phase, and sorbed contaminants into the gas phase. The model equations are analytically solved by using the Laplace transform with respect to time. The solutions are represented by confluent hypergeometric functions in the Laplace domain. The Laplace domain solutions are then evaluated using a numerical Laplace inversion algorithm. The solutions can be used to simulate the spatial distribution and the temporal evolution of contaminant concentrations during operation of a soil vapor extraction well. Results of model simulations show that the effect of gas phase molecular diffusion upon concentrations at the extraction well is relatively small, although the effect upon the distribution of concentrations in space is significant. This study provides a tool that can be useful in designing SVE remediation strategies, as well as verifying numerical models used to simulate SVE system performance.

Gas-phase cationic benzoylation of ambient aromatic substrates studied with the decay technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Occhiucci, G.; Cacace, F.; Speranza, M.

1986-03-05

The gas-phase benzoylation of typical ambient aromatic substrates PhY (Y = OH, OMe, and NH/sub 2/) has been investigated by a combination of the decay technique and of FT ICR mass spectrometry. Labeled phenylium ions, C/sub 6/X/sub 5//sup +/ (X = H and T), from the decay of multiply tritiated benzene, C/sub 6/X/sub 6/, have been allowed to react with excess CO-containing traces of PhY (Y = OH, OMe, and NH/sub 2/), in the pressure range from 90 to 650 torr. Radio GLC and HPLC of the tritiated products demonstrate two competitive reaction channels, i.e., phenylation and benzoylation of themore » aromatic substrates. The results indicate a sharp kinetic bias of the gaseous phenylium ions for the aromatic substrates, measured by an apparent k/sub CO//k/sub PhY/ ratio of 0.12 (Y = OH), 0.13 (Y = OMe), and 0.04 (Y = NH/sub 2/) in the systems at nearly atmospheric pressure. Gas-phase benzoylation displays a high intramolecular selectivity, occurring exclusively at the n-type center of PhOH and PhNH/sub 2/. In the case of PhOMe, appreciable ring benzoylation is observed, characterized by a remarkably high (up to 30:1) bias for the para position. The mechanistic features of the gas-phase benzoylation and phenylation processes, deduced from the decay and the ICR experiments, are discussed and compared with those of related aromatic acylation and alkylation reactions occurring in the dilute gas state. 30 references, 2 tables.« less

Synthesis of fullerene-like tantalum disulfide nanoparticles by a gas-phase reaction and laser ablation.

PubMed

Schuffenhauer, Christoph; Parkinson, Bruce A; Jin-Phillipp, Neng Yun; Joly-Pottuz, Lucile; Martin, Jean-Michel; Popovitz-Biro, Ronit; Tenne, Reshef

2005-11-01

Motivated by the discovery of the C(60) molecule (buckminsterfullerene), the search for inorganic counterparts of this closed-cage nanostructure started in 1992 with the discovery of nested fullerene-like nanoparticles of WS(2). Inorganic fullerene-like (IF) materials have since been found in numerous two-dimensional compounds and are available in a variety of shapes that offer major applications such as in lubricants and nanocomposites. Various synthetic methodologies have been employed to achieve the right conditions for the constricted or templated growth needed for the occurrence of this new phase. In this study, IF-TaS(2) is produced from a volatile chloride precursor in the gas phase and in small yield by room temperature laser ablation both in argon and in liquid CS(2). For the gas-phase reaction, a high yield of IF nanoparticles was obtained between 400 and 600 degrees C with a low concentration of the precursor gas. The average size and the yield of the IF-TaS(2) nanoparticles decrease with temperature. Above 600 degrees C, IF nanoparticles were found in low yields and at sizes below 20 nm. The stability of the IF nanoparticles produced by the gas-phase reaction is discussed in the light of two existing theoretical models. Laser ablation in argon leads to IF nanoparticles filled with clusters of TaS(2). Agglomeration of the nanoparticles can be avoided by laser ablation in liquid CS(2).

Time-resolved imaging of gas phase nanoparticle synthesis by laser ablation

NASA Astrophysics Data System (ADS)

Geohegan, David B.; Puretzky, Alex A.; Duscher, Gerd; Pennycook, Stephen J.

1998-06-01

The dynamics of nanoparticle formation, transport, and deposition by pulsed laser ablation of c-Si into 1-10 Torr He and Ar gases are revealed by imaging laser-induced photoluminescence and Rayleigh-scattered light from gas-suspended 1-10 nm SiOx particles. Two sets of dynamic phenomena are presented for times up to 15 s after KrF-laser ablation. Ablation of Si into heavier Ar results in a uniform, stationary plume of nanoparticles, while Si ablation into lighter He results in a turbulent ring of particles which propagates forward at 10 m/s. Nanoparticles unambiguously formed in the gas phase were collected on transmission electron microscope grids for Z-contrast imaging and electron energy loss spectroscopy analysis. The effects of gas flow on nanoparticle formation, photoluminescence, and collection are described.

Phase diagram and universality of the Lennard-Jones gas-liquid system.

PubMed

Watanabe, Hiroshi; Ito, Nobuyasu; Hu, Chin-Kun

2012-05-28

The gas-liquid phase transition of the three-dimensional Lennard-Jones particles system is studied by molecular dynamics simulations. The gas and liquid densities in the coexisting state are determined with high accuracy. The critical point is determined by the block density analysis of the Binder parameter with the aid of the law of rectilinear diameter. From the critical behavior of the gas-liquid coexisting density, the critical exponent of the order parameter is estimated to be β = 0.3285(7). Surface tension is estimated from interface broadening behavior due to capillary waves. From the critical behavior of the surface tension, the critical exponent of the correlation length is estimated to be ν = 0.63(4). The obtained values of β and ν are consistent with those of the Ising universality class.

Fluorometric method for the determination of gas-phase hydrogen peroxide

NASA Technical Reports Server (NTRS)

Kok, Gregory L.; Lazrus, Allan L.

1986-01-01

The fluorometric gas-phase hydrogen peroxide procedure is based on the technique used by Lazrus et. al. for the determination of H2O2 in the liquid phase. The analytical method utilizes the reaction of H2O2 with horseradish peroxidase and p-hydroxphenylacetic acid (POPHA) to form the fluorescent dimer of POPHA. The analytical reaction responds stoichiometrically to both H2O2 and some organic hydroperoxides. To discriminate H2O2 from organic hydroperoxides, catalase is used to preferentially destroy H2O2. Using a dual-channel flow system the H2O2 concentration is determined by difference.

Pore-scale interfacial dynamics during gas-supersaturated water injection in porous media - on nucleation, growth and advection of disconnected fluid phases (Invited)

NASA Astrophysics Data System (ADS)

Or, D.; Ioannidis, M.

2010-12-01

Degassing and in situ development of a mobile gas bubbles occur when injecting supersaturated aqueous phase into water-saturated porous media. Supersaturated water injection (SWI) has potentially significant applications in remediation of soils contaminated by non-aqueous phase liquids and in enhanced oil recovery. Pore network simulations indicate the formation of a region near the injection boundary where gas phase nuclei are activated and grow by mass transfer from the flowing supersaturated aqueous phase. Ramified clusters of gas-filled pores develop which, owing to the low prevailing Bond number, grow laterally to a significant extent prior to the onset of mobilization, and are thus likely to coalesce. Gas cluster mobilization invariably results in fragmentation and stranding, such that a macroscopic region containing few tenuously connected large gas clusters is established. Beyond this region, gas phase nucleation and mass transfer from the aqueous phase are limited by diminishing supply of dissolved gas. New insights into SWI dynamics are obtained using rapid micro-visualization in transparent glass micromodels. Using high-speed imaging, we observe the nucleation, initial growth and subsequent fate (mobilization, fragmentation, collision, coalescence and stranding) of CO2 bubbles and clusters of gas-filled pores and analyze cluster population statistics. We find significant support for the development of invasion-percolation-like patterns, but also report on hitherto unaccounted for gas bubble behavior. Additionally, we report for the first time on the acoustic emission signature of SWI in porous media and relate it to the dynamics of bubble nucleation and growth. Finally, we identify the pore-scale mechanisms associated with the mobilization and subsequent recovery of a residual non-aqueous phase liquid due to gas bubble dynamics during SWI.

Particle- and gas-phase PAHs toxicity equivalency quantity emitted by a non-road diesel engine with non-thermal plasma technology.

PubMed

Gao, Jianbing; Ma, Chaochen; Xing, Shikai; Zhang, Yajie; Liu, Jiangquan; Feng, Hao

2016-10-01

Polycyclic aromatic hydrocarbon (PAH) toxicity equivalency quantity (TEQ, denoted by benzo(a)pyrene equivalent (BaPeq) concentration) is more meaningful when evaluating the influence of non-road diesel engines PAH toxicity on environment. Particle- and gas-phase PAH BaPeq concentrations were calculated based on gas chromatography-mass spectrometer (GC-MS) results and toxic equivalency factors. A non-thermal plasma (NTP) reactor was applied to a non-road diesel engine to decrease PAH TEQ content. Only the gas-phase Nap BaPeq concentration increased slightly with the action of NTP at three different generator power outputs. BaP dominated the BaPeq concentration for 15 samples with, and without NTP except in the gas-phase at 4 kW. Almost all medium molecular weight (MMW) and high molecular weight (HMW) PAH TEQs increased for particle- and gas-phases at 3 kW power output compared to 2 kW without the use of NTP. Particle-phase Nap, Acp, and AcPy (low molecular weight, LMW) TEQ were under detection at 3 and 4 kW, while gas-phase BkF, IND, DBA, and BghiP (HMW) concentrations were below the limits of detection. The most abundant PAH TEQ compounds were MMW and HMW PAHs for gas- and particle-phase while they were BaA, CHR, BbF, BaP, and IND for PM aggregation. The total BaPeq emission factors were 15.1, 141.4, and 46.5 μg m(-3) at three engine loads, respectively. Significant BaPeq concentration percentage reduction was obtained (more than 80 and 60 %) with the use of NTP for particle- and gas-phases. A high TEQ content was observed for PM aggregation (38.8, 98.4, and 50.0 μg kg(-1)) which may have caused secondary PAH toxicity emissions. With the action of NTP, the breakup of MMW and HMW into LMW PAHs led to reduction of some PAH concentrations.

Investigation of the on-axis atom number density in the supersonic gas jet under high gas backing pressure by simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Guanglong; Xu, Yi; Cao, Yunjiu

The supersonic gas jets from conical nozzles are simulated using 2D model. The on-axis atom number density in gas jet is investigated in detail by comparing the simulated densities with the idealized densities of straight streamline model in scaling laws. It is found that the density is generally lower than the idealized one and the deviation between them is mainly dependent on the opening angle of conical nozzle, the nozzle length and the gas backing pressure. The density deviation is then used to discuss the deviation of the equivalent diameter of a conical nozzle from the idealized d{sub eq} inmore » scaling laws. The investigation on the lateral expansion of gas jet indicates the lateral expansion could be responsible for the behavior of the density deviation. These results could be useful for the estimation of cluster size and the understanding of experimental results in laser-cluster interaction experiments.« less

A Simple Approach to Characterize Gas-Aqueous Liquid Two-phase Flow Configuration Based on Discrete Solid-Liquid Contact Electrification.

PubMed

Choi, Dongwhi; Lee, Donghyeon; Kim, Dong Sung

2015-10-14

In this study, we first suggest a simple approach to characterize configuration of gas-aqueous liquid two-phase flow based on discrete solid-liquid contact electrification, which is a newly defined concept as a sequential process of solid-liquid contact and successive detachment of the contact liquid from the solid surface. This approach exhibits several advantages such as simple operation, precise measurement, and cost-effectiveness. By using electric potential that is spontaneously generated by discrete solid-liquid contact electrification, the configurations of the gas-aqueous liquid two-phase flow such as size of a gas slug and flow rate are precisely characterized. According to the experimental and numerical analyses on parameters that affect electric potential, gas slugs have been verified to behave similarly to point electric charges when the measuring point of the electric potential is far enough from the gas slug. In addition, the configuration of the gas-aqueous liquid two-phase microfluidic system with multiple gas slugs is also characterized by using the presented approach. For a proof-of-concept demonstration of using the proposed approach in a self-triggered sensor, a gas slug detector with a counter system is developed to show its practicality and applicability.

Online Measurements of Highly Oxidized Organics in the Gas and Particle phase during SOAS and SENEX

NASA Astrophysics Data System (ADS)

Lopez-Hilfiker, F.; Lee, B. H.; Mohr, C.; Ehn, M.; Rubach, F.; Mentel, T. F.; Kleist, E.; Thornton, J. A.

2014-12-01

We present measurements of a large suite of gas and particle phase organic compounds made with a Filter Inlet for Gas and AEROsol (FIGAERO) coupled to a high resolution time of flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington and with airborne HR-ToF-CIMS measurements. The FIGAERO instrument was deployed on the Jülich Plant Atmosphere Chamber to study α-pinene oxidation, and subsequently at the SMEAR II forest station in Hyytiälä, Finland and the SOAS ground site, in Brent Alabama. During the Southern Atmosphere Study, a gas-phase only version of the HR-ToF-CIMS was deployed on the NOAA WP-3 aircraft as part of SENEX. We focus here on highly oxygenated organic compounds derived from monoterpene oxidation detected both aloft during SENEX and at the ground-based site during SOAS. In both chamber and the atmosphere, many highly oxidized, low volatility compounds were observed in the gas and particles and many of the same compositions detected in the gas-phase were detected in the particles upon temperature programmed thermal desorption. The fraction of a given compound measured in the particle phase follows expected trends with elemental composition such as O/C ratios, but many compounds would not be well described by an absorptive partitioning model assuming unity activity coefficients. The detailed structure in the thermograms reveals a significant contribution from large molecular weight organics and/or oligomers in both chamber and ambient aerosol samples. Approximately 50% of the measured organics in the particle phase are associated with compounds having effective vapour pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. We discuss the implications of these findings for measurements of gas-particle partitioning and for evaluating the contribution of monoterpene oxidation to organic aerosol formation and growth. We also use the aircraft measurements and a

Why do disk galaxies present a common gas-phase metallicity gradient?

NASA Astrophysics Data System (ADS)

Chang, R.; Zhang, Shuhui; Shen, Shiyin; Yin, Jun; Hou, Jinliang

2017-03-01

CALIFA data show that isolated disk galaxies present a common gas-phase metallicity gradient, with a characteristic slope of -0.1dex/re between 0.3 and 2 disk effective radius re (Sanchez et al. 2014). Here we construct a simple model to investigate which processes regulate the formation and evolution.

Gas-phase infrared spectrum of phosphorus (III) oxycyanide, OPCN: experimental and theoretical investigations

NASA Astrophysics Data System (ADS)

Allaf, Abdul. W.; Kassem, M.; Alibrahim, M.; Boustani, Ihsan

1999-03-01

An attempt was made to observe the gas-phase infrared spectrum of Phosphorus (III) oxycyanide, OPCN for the first time. This molecule was produced by an on-line process using phosphorus (III) oxychloride, OPCl as precursor passed over heated AgCN. The products were characterised by the infrared spectra of their vapours. The low resolution gas-phase Fourier transform infrared spectrum shows two bands centered at 2165 and 1385 cm -1. These bands are assigned to, ν1 (CN stretch) and ν2 (OP stretch), respectively. Ab initio self-consistent-field (SCF) molecular orbital (MO) and Møller-Plesset second order perturbation theory (MP2) calculations were performed to determine the geometry, total energy and vibrational frequencies of OPCN.

Diffusion Monte Carlo simulations of gas phase and adsorbed D2-(H2)n clusters

NASA Astrophysics Data System (ADS)

Curotto, E.; Mella, M.

2018-03-01

We have computed ground state energies and analyzed radial distributions for several gas phase and adsorbed D2(H2)n and HD(H2)n clusters. An external model potential designed to mimic ionic adsorption sites inside porous materials is used [M. Mella and E. Curotto, J. Phys. Chem. A 121, 5005 (2017)]. The isotopic substitution lowers the ground state energies by the expected amount based on the mass differences when these are compared with the energies of the pure clusters in the gas phase. A similar impact is found for adsorbed aggregates. The dissociation energy of D2 from the adsorbed clusters is always much higher than that of H2 from both pure and doped aggregates. Radial distributions of D2 and H2 are compared for both the gas phase and adsorbed species. For the gas phase clusters, two types of hydrogen-hydrogen interactions are considered: one based on the assumption that rotations and translations are adiabatically decoupled and the other based on nonisotropic four-dimensional potential. In the gas phase clusters of sufficiently large size, we find the heavier isotopomer more likely to be near the center of mass. However, there is a considerable overlap among the radial distributions of the two species. For the adsorbed clusters, we invariably find the heavy isotope located closer to the attractive interaction source than H2, and at the periphery of the aggregate, H2 molecules being substantially excluded from the interaction with the source. This finding rationalizes the dissociation energy results. For D2-(H2)n clusters with n ≥12 , such preference leads to the desorption of D2 from the aggregate, a phenomenon driven by the minimization of the total energy that can be obtained by reducing the confinement of (H2)12. The same happens for (H2)13, indicating that such an effect may be quite general and impact on the absorption of quantum species inside porous materials.

Source characterization and exposure modeling of gas-phase polycyclic aromatic hydrocarbon (PAH) concentrations in Southern California

NASA Astrophysics Data System (ADS)

Masri, Shahir; Li, Lianfa; Dang, Andy; Chung, Judith H.; Chen, Jiu-Chiuan; Fan, Zhi-Hua (Tina); Wu, Jun

2018-03-01

Airborne exposures to polycyclic aromatic hydrocarbons (PAHs) are associated with adverse health outcomes. Because personal air measurements of PAHs are labor intensive and costly, spatial PAH exposure models are useful for epidemiological studies. However, few studies provide adequate spatial coverage to reflect intra-urban variability of ambient PAHs. In this study, we collected 39-40 weekly gas-phase PAH samples in southern California twice in summer and twice in winter, 2009, in order to characterize PAH source contributions and develop spatial models that can estimate gas-phase PAH concentrations at a high resolution. A spatial mixed regression model was constructed, including such variables as roadway, traffic, land-use, vegetation index, commercial cooking facilities, meteorology, and population density. Cross validation of the model resulted in an R2 of 0.66 for summer and 0.77 for winter. Results showed higher total PAH concentrations in winter. Pyrogenic sources, such as fossil fuels and diesel exhaust, were the most dominant contributors to total PAHs. PAH sources varied by season, with a higher fossil fuel and wood burning contribution in winter. Spatial autocorrelation accounted for a substantial amount of the variance in total PAH concentrations for both winter (56%) and summer (19%). In summer, other key variables explaining the variance included meteorological factors (9%), population density (15%), and roadway length (21%). In winter, the variance was also explained by traffic density (16%). In this study, source characterization confirmed the dominance of traffic and other fossil fuel sources to total measured gas-phase PAH concentrations while a spatial exposure model identified key predictors of PAH concentrations. Gas-phase PAH source characterization and exposure estimation is of high utility to epidemiologist and policy makers interested in understanding the health impacts of gas-phase PAHs and strategies to reduce emissions.

Source Characterization and Exposure Modeling of Gas-Phase Polycyclic Aromatic Hydrocarbon (PAH) Concentrations in Southern California.

PubMed

Masri, Shahir; Li, Lianfa; Dang, Andy; Chung, Judith H; Chen, Jiu-Chiuan; Fan, Zhi-Hua Tina; Wu, Jun

2018-03-01

Airborne exposures to polycyclic aromatic hydrocarbons (PAHs) are associated with adverse health outcomes. Because personal air measurements of PAHs are labor intensive and costly, spatial PAH exposure models are useful for epidemiological studies. However, few studies provide adequate spatial coverage to reflect intra-urban variability of ambient PAHs. In this study, we collected 39-40 weekly gas-phase PAH samples in southern California twice in summer and twice in winter, 2009, in order to characterize PAH source contributions and develop spatial models that can estimate gas-phase PAH concentrations at a high resolution. A spatial mixed regression model was constructed, including such variables as roadway, traffic, land-use, vegetation index, commercial cooking facilities, meteorology, and population density. Cross validation of the model resulted in an R 2 of 0.66 for summer and 0.77 for winter. Results showed higher total PAH concentrations in winter. Pyrogenic sources, such as fossil fuels and diesel exhaust, were the most dominant contributors to total PAHs. PAH sources varied by season, with a higher fossil fuel and wood burning contribution in winter. Spatial autocorrelation accounted for a substantial amount of the variance in total PAH concentrations for both winter (56%) and summer (19%). In summer, other key variables explaining the variance included meteorological factors (9%), population density (15%), and roadway length (21%). In winter, the variance was also explained by traffic density (16%). In this study, source characterization confirmed the dominance of traffic and other fossil fuel sources to total measured gas-phase PAH concentrations while a spatial exposure model identified key predictors of PAH concentrations. Gas-phase PAH source characterization and exposure estimation is of high utility to epidemiologist and policy makers interested in understanding the health impacts of gas-phase PAHs and strategies to reduce emissions.

A DMPA Langmuir monolayer study: from gas to solid phase. An atomistic description by molecular dynamics Simulation.

PubMed

Giner-Casares, J J; Camacho, L; Martín-Romero, M T; Cascales, J J López

2008-03-04

In this work, a DMPA Langmuir monolayer at the air/water interface was studied by molecular dynamics simulations. Thus, an atomistic picture of a Langmuir monolayer was drawn from its expanded gas phase to its final solid condensed one. In this sense, some properties of monolayers that were traditionally poorly or even not reproduced in computer simulations, such as lipid domain formation or pressure-area per lipid isotherm, were properly reproduced in this work. Thus, the physical laws that control the lipid domain formation in the gas phase and the structure of lipid monolayers from the gas to solid condensed phase were studied. Thanks to the atomistic information provided by the molecular dynamics simulations, we were able to add valuable information to the experimental description of these processes and to access experimental data related to the lipid monolayers in their expanded phase, which is difficult or inaccessible to study by experimental techniques. In this sense, properties such as lipids head hydration and lipid structure were studied.

Lattice model theory of the equation of state covering the gas, liquid, and solid phases

NASA Technical Reports Server (NTRS)

Bonavito, N. L.; Tanaka, T.; Chan, E. M.; Horiguchi, T.; Foreman, J. C.

1975-01-01

The three stable states of matter and the corresponding phase transitions were obtained with a single model. Patterned after Lennard-Jones and Devonshires's theory, a simple cubic lattice model containing two fcc sublattices (alpha and beta) is adopted. The interatomic potential is taken to be the Lennard-Jones (6-12) potential. Employing the cluster variation method, the Weiss and the pair approximations on the lattice gas failed to give the correct phase diagrams. Hybrid approximations were devised to describe the lattice term in the free energy. A lattice vibration term corresponding to a free volume correction is included semi-phenomenologically. The combinations of the lattice part and the free volume part yield the three states and the proper phase diagrams. To determine the coexistence regions, the equalities of the pressure and Gibbs free energy per molecule of the coexisting phases were utilized. The ordered branch of the free energy gives rise to the solid phase while the disordered branch yields the gas and liquid phases. It is observed that the triple point and the critical point quantities, the phase diagrams and the coexistence regions plotted are in good agreement with the experimental values and graphs for argon.

Kerr-AdS analogue of triple point and solid/liquid/gas phase transition

NASA Astrophysics Data System (ADS)

Altamirano, Natacha; Kubizňák, David; Mann, Robert B.; Sherkatghanad, Zeinab

2014-02-01

We study the thermodynamic behavior of multi-spinning d = 6 Kerr-anti de Sitter black holes in the canonical ensemble of fixed angular momenta J1 and J2. We find, dependent on the ratio q = J2/J1, qualitatively different interesting phenomena known from the ‘every day thermodynamics’ of simple substances. For q = 0 the system exhibits recently observed reentrant large/small/large black hole phase transitions, but for 0 < q ≪ 1 we find an analogue of a ‘solid/liquid’ phase transition. Furthermore, for q ∈ (0.00905, 0.0985) the system displays the presence of a large/intermediate/small black hole phase transition with two critical and one triple (or tricritical) points. This behavior is reminiscent of the solid/liquid/gas phase transition except that the coexistence line of small and intermediate black holes does not continue for an arbitrary value of pressure (similar to the solid/liquid coexistence line) but rather terminates at one of the critical points. Finally, for q > 0.0985 we observe the ‘standard liquid/gas behavior’ of the Van der Waals fluid.

Multi-Scale Long-Range Magnitude and Sign Correlations in Vertical Upward Oil-Gas-Water Three-Phase Flow

NASA Astrophysics Data System (ADS)

Zhao, An; Jin, Ning-de; Ren, Ying-yu; Zhu, Lei; Yang, Xia

2016-01-01

In this article we apply an approach to identify the oil-gas-water three-phase flow patterns in vertical upwards 20 mm inner-diameter pipe based on the conductance fluctuating signals. We use the approach to analyse the signals with long-range correlations by decomposing the signal increment series into magnitude and sign series and extracting their scaling properties. We find that the magnitude series relates to nonlinear properties of the original time series, whereas the sign series relates to the linear properties. The research shows that the oil-gas-water three-phase flows (slug flow, churn flow, bubble flow) can be classified by a combination of scaling exponents of magnitude and sign series. This study provides a new way of characterising linear and nonlinear properties embedded in oil-gas-water three-phase flows.

BUDHIES II: a phase-space view of H I gas stripping and star formation quenching in cluster galaxies

NASA Astrophysics Data System (ADS)

Jaffé, Yara L.; Smith, Rory; Candlish, Graeme N.; Poggianti, Bianca M.; Sheen, Yun-Kyeong; Verheijen, Marc A. W.

2015-04-01

We investigate the effect of ram-pressure from the intracluster medium on the stripping of H I gas in galaxies in a massive, relaxed, X-ray bright, galaxy cluster at z = 0.2 from the Blind Ultra Deep H I Environmental Survey (BUDHIES). We use cosmological simulations, and velocity versus position phase-space diagrams to infer the orbital histories of the cluster galaxies. In particular, we embed a simple analytical description of ram-pressure stripping in the simulations to identify the regions in phase-space where galaxies are more likely to have been sufficiently stripped of their H I gas to fall below the detection limit of our survey. We find a striking agreement between the model predictions and the observed location of H I-detected and non-detected blue (late-type) galaxies in phase-space, strongly implying that ram-pressure plays a key role in the gas removal from galaxies, and that this can happen during their first infall into the cluster. However, we also find a significant number of gas-poor, red (early-type) galaxies in the infall region of the cluster that cannot easily be explained with our model of ram-pressure stripping alone. We discuss different possible additional mechanisms that could be at play, including the pre-processing of galaxies in their previous environment. Our results are strengthened by the distribution of galaxy colours (optical and UV) in phase-space, that suggests that after a (gas-rich) field galaxy falls into the cluster, it will lose its gas via ram-pressure stripping, and as it settles into the cluster, its star formation will decay until it is completely quenched. Finally, this work demonstrates the utility of phase-space diagrams to analyse the physical processes driving the evolution of cluster galaxies, in particular H I gas stripping.

Robotic kidney transplantation with regional hypothermia: a step-by-step description of the Vattikuti Urology Institute-Medanta technique (IDEAL phase 2a).

PubMed

Menon, Mani; Sood, Akshay; Bhandari, Mahendra; Kher, Vijay; Ghosh, Prasun; Abaza, Ronney; Jeong, Wooju; Ghani, Khurshid R; Kumar, Ramesh K; Modi, Pranjal; Ahlawat, Rajesh

2014-05-01

We recently reported on preclinical and feasibility studies (Innovation, Development, Exploration, Assessment, Long-term study [IDEAL] phase 0-1) of the development of robotic kidney transplantation (RKT) with regional hypothermia. This paper presents the IDEAL phase 2a studies of technique development. To describe the technique of RKT with regional hypothermia developed at two tertiary care institutions (Vattikuti Urology Institute and Medanta Hospital). We report on the safety profile and early graft function in these patients. This is a prospective study of 50 consecutive patients who underwent live-donor RKT at Medanta Hospital following a 3-yr planning/simulation phase at the Vattikuti Urology Institute. Demographic details, and perioperative and postoperative outcomes are reported for the initial 25 recipients who have completed a minimum 6-mo follow-up. Positioning and port placement were similar to that used for robotic radical prostatectomy. Allograft cooling was achieved by ice slush delivered through a GelPOINT device. The accompanying video details the operative technique. The primary outcome was posttransplant graft function. Secondary outcomes included technical success or failure and complication rates. Fifty patients underwent RKT successfully, 7 in the phase 1 and 43 in the phase 2 stages of the study. For the initial 25 patients, mean console, warm ischemia, arterial, and venous anastomotic times were 135, 2.4, 12, and 13.4 min, respectively. All grafts were cooled to 18-20 °C with no change in core body temperature. All grafts functioned immediately posttransplant and the mean serum creatinine level at discharge was 1.3mg/dl (range: 0.8-3.1mg/dl). No patient developed anastomotic leaks, wound complications, or wound infections. At 6-mo of follow-up, no patient had developed a lymphocele detected on CT scanning. Two patients underwent re-exploration, and one patient died of congestive heart failure (1.5 mo posttransplant). RKT with regional

Modeling of heavy-gas effects on airfoil flows

NASA Technical Reports Server (NTRS)

Drela, Mark

1992-01-01

Thermodynamic models were constructed for a calorically imperfect gas and for a non-ideal gas. These were incorporated into a quasi one dimensional flow solver to develop an understanding of the differences in flow behavior between the new models and the perfect gas model. The models were also incorporated into a two dimensional flow solver to investigate their effects on transonic airfoil flows. Specifically, the calculations simulated airfoil testing in a proposed high Reynolds number heavy gas test facility. The results indicate that the non-idealities caused significant differences in the flow field, but that matching of an appropriate non-dimensional parameter led to flows similar to those in air.

Numerical modeling of experimental observations on gas formation and multi-phase flow of carbon dioxide in subsurface formations

NASA Astrophysics Data System (ADS)

Pawar, R.; Dash, Z.; Sakaki, T.; Plampin, M. R.; Lassen, R. N.; Illangasekare, T. H.; Zyvoloski, G.

2011-12-01

One of the concerns related to geologic CO2 sequestration is potential leakage of CO2 and its subsequent migration to shallow groundwater resources leading to geochemical impacts. Developing approaches to monitor CO2 migration in shallow aquifer and mitigate leakage impacts will require improving our understanding of gas phase formation and multi-phase flow subsequent to CO2 leakage in shallow aquifers. We are utilizing an integrated approach combining laboratory experiments and numerical simulations to characterize the multi-phase flow of CO2 in shallow aquifers. The laboratory experiments involve a series of highly controlled experiments in which CO2 dissolved water is injected in homogeneous and heterogeneous soil columns and tanks. The experimental results are used to study the effects of soil properties, temperature, pressure gradients and heterogeneities on gas formation and migration. We utilize the Finite Element Heat and Mass (FEHM) simulator (Zyvoloski et al, 2010) to numerically model the experimental results. The numerical models capture the physics of CO2 exsolution, multi-phase fluid flow as well as sand heterogeneity. Experimental observations of pressure, temperature and gas saturations are used to develop and constrain conceptual models for CO2 gas-phase formation and multi-phase CO2 flow in porous media. This talk will provide details of development of conceptual models based on experimental observation, development of numerical models for laboratory experiments and modelling results.

Surfactants from the gas phase may promote cloud droplet formation.

PubMed

Sareen, Neha; Schwier, Allison N; Lathem, Terry L; Nenes, Athanasios; McNeill, V Faye

2013-02-19

Clouds, a key component of the climate system, form when water vapor condenses upon atmospheric particulates termed cloud condensation nuclei (CCN). Variations in CCN concentrations can profoundly impact cloud properties, with important effects on local and global climate. Organic matter constitutes a significant fraction of tropospheric aerosol mass, and can influence CCN activity by depressing surface tension, contributing solute, and influencing droplet activation kinetics by forming a barrier to water uptake. We present direct evidence that two ubiquitous atmospheric trace gases, methylglyoxal (MG) and acetaldehyde, known to be surface-active, can enhance aerosol CCN activity upon uptake. This effect is demonstrated by exposing acidified ammonium sulfate particles to 250 parts per billion (ppb) or 8 ppb gas-phase MG and/or acetaldehyde in an aerosol reaction chamber for up to 5 h. For the more atmospherically relevant experiments, i.e., the 8-ppb organic precursor concentrations, significant enhancements in CCN activity, up to 7.5% reduction in critical dry diameter for activation, are observed over a timescale of hours, without any detectable limitation in activation kinetics. This reduction in critical diameter enhances the apparent particle hygroscopicity up to 26%, which for ambient aerosol would lead to cloud droplet number concentration increases of 8-10% on average. The observed enhancements exceed what would be expected based on Köhler theory and bulk properties. Therefore, the effect may be attributed to the adsorption of MG and acetaldehyde to the gas-aerosol interface, leading to surface tension depression of the aerosol. We conclude that gas-phase surfactants may enhance CCN activity in the atmosphere.

Determination of local values of gas and liquid mass flux in highly loaded two-phase flow

NASA Technical Reports Server (NTRS)

Burick, R. J.; Scheuerman, C. H.; Falk, A. Y.

1974-01-01

A measurement system using a deceleration probe was designed for determining the local values of gas and liquid mass flux in various gas/liquid droplet sprayfields. The system was used to characterize two-phase flowfields generated by gas/liquid rocket-motor injectors. Measurements were made at static pressures up to 500 psia and injected mass flow ratios up to 20. The measurement system can also be used at higher pressures and in gas/solid flowfields.

An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

NASA Technical Reports Server (NTRS)

Koontz, Steven L.; Davis, Dennis D.; Hansen, Merrill

1988-01-01

A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

Multiscale Aspects of Modeling Gas-Phase Nanoparticle Synthesis

PubMed Central

Buesser, B.; Gröhn, A.J.

2013-01-01

Aerosol reactors are utilized to manufacture nanoparticles in industrially relevant quantities. The development, understanding and scale-up of aerosol reactors can be facilitated with models and computer simulations. This review aims to provide an overview of recent developments of models and simulations and discuss their interconnection in a multiscale approach. A short introduction of the various aerosol reactor types and gas-phase particle dynamics is presented as a background for the later discussion of the models and simulations. Models are presented with decreasing time and length scales in sections on continuum, mesoscale, molecular dynamics and quantum mechanics models. PMID:23729992

Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Manhua; Wang, Xiang; Yeom, Younghoon

A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase id dispersed.

Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Manhua; Wang, Xiang; Yeom, Younghoon

A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase is dispersed.

Ideals versus reality: Are weight ideals associated with weight change in the population?

PubMed

Kärkkäinen, Ulla; Mustelin, Linda; Raevuori, Anu; Kaprio, Jaakko; Keski-Rahkonen, Anna

2016-04-01

To quantify weight ideals of young adults and to examine whether the discrepancy between actual and ideal weight is associated with 10-year body mass index (BMI) change in the population. This study comprised 4,964 adults from the prospective population-based FinnTwin16 study. They reported their actual and ideal body weight at age 24 (range 22-27) and 10 years later (attrition 24.6%). The correlates of discrepancy between actual and ideal body weight and the impact on subsequent BMI change were examined. The discrepancy between actual and ideal weight at 24 years was on average 3.9 kg (1.4 kg/m(2) ) among women and 1.2 kg (0.4 kg/m(2) ) among men. On average, participants gained weight during follow-up irrespective of baseline ideal weight: women ¯x = +4.8 kg (1.7 kg/m(2) , 95% CI 1.6-1.9 kg/m(2) ), men ¯x = +6.3 kg (2.0 kg/m(2) , 95% CI 1.8-2.1 kg/m(2) ). Weight ideals at 24 years were not correlated with 10-year weight change. At 34 years, just 13.2% of women and 18.9% of men were at or below the weight they had specified as their ideal weight at 24 years. Women and men adjusted their ideal weight upward over time. Irrespective of ideal weight at baseline, weight gain was nearly universal. Weight ideals were shifted upward over time. © 2016 The Obesity Society.

[Study of the phase transformation of TiO2 with in-situ XRD in different gas].

PubMed

Ma, Li-Jing; Guo, Lie-Jin

2011-04-01

TiO2 sample was prepared by sol-gel method from chloride titanium. The phase transformation of the prepared TiO2 sample was studied by in-situ XRD and normal XRD in different gas. The experimental results showed that the phase transformation temperatures of TiO2 were different under in-situ or normal XRD in different kinds of gas. The transformation of amorphous TiO2 to anatase was controlled by kinetics before 500 degrees C. In-situ XRD showed that the growth of anatase was inhibited, but the transformation of anatase to rutile was accelerated under inactive nitrogen in contrast to air. Also better crystal was obtained under hydrogen than in argon. These all showed that external oxygen might accelerate the growth of TiO2, but reduced gas might partly counteract the negative influence of lack of external oxygen. The mechanism of phase transformation of TiO2 was studied by in-situ XRD in order to control the structure in situ.

Density-driven transport of gas phase chemicals in unsaturated soils

NASA Astrophysics Data System (ADS)

Fen, Chiu-Shia; Sun, Yong-tai; Cheng, Yuen; Chen, Yuanchin; Yang, Whaiwan; Pan, Changtai

2018-01-01

Variations of gas phase density are responsible for advective and diffusive transports of organic vapors in unsaturated soils. Laboratory experiments were conducted to explore dense gas transport (sulfur hexafluoride, SF6) from different source densities through a nitrogen gas-dry soil column. Gas pressures and SF6 densities at transient state were measured along the soil column for three transport configurations (horizontal, vertically upward and vertically downward transport). These measurements and others reported in the literature were compared with simulation results obtained from two models based on different diffusion approaches: the dusty gas model (DGM) equations and a Fickian-type molar fraction-based diffusion expression. The results show that the DGM and Fickian-based models predicted similar dense gas density profiles which matched the measured data well for horizontal transport of dense gas at low to high source densities, despite the pressure variations predicted in the soil column were opposite to the measurements. The pressure evolutions predicted by both models were in trend similar to the measured ones for vertical transport of dense gas. However, differences between the dense gas densities predicted by the DGM and Fickian-based models were discernible for vertically upward transport of dense gas even at low source densities, as the DGM-based predictions matched the measured data better than the Fickian results did. For vertically downward transport, the dense gas densities predicted by both models were not greatly different from our experimental measurements, but substantially greater than the observations obtained from the literature, especially at high source densities. Further research will be necessary for exploring factors affecting downward transport of dense gas in soil columns. Use of the measured data to compute flux components of SF6 showed that the magnitudes of diffusive flux component based on the Fickian-type diffusion expressions

Evaluation of hydrogen as a cryogenic wind tunnel test gas

NASA Technical Reports Server (NTRS)

Haut, R. C.

1977-01-01

The nondimensional ratios used to describe various flow situations in hydrogen were determined and compared with the corresponding ideal diatomic gas ratios. The results were used to examine different inviscid flow configurations. The relatively high value of the characteristic rotational temperature causes the behavior of hydrogen, under cryogenic conditions, to deviate substantially from the behavior of an ideal diatomic gas in the compressible flow regime. Therefore, if an idea diatomic gas is to be modeled, cryogenic hydrogen is unacceptable as a wind tunnel test gas in a compressible flow situation.

Impact of Gas-Phase Mechanisms on Weather Research Forecasting Model with Chemistry (WRF/Chem) Predictions: Mechanism Implementation and Comparative Evaluation

EPA Science Inventory

Gas-phase mechanisms provide important oxidant and gaseous precursors for secondary aerosol formation. Different gas-phase mechanisms may lead to different predictions of gases, aerosols, and aerosol direct and indirect effects. In this study, WRF/Chem-MADRID simulations are cond...

Effect of duty-cycles on the air plasma gas-phase of dielectric barrier discharges

NASA Astrophysics Data System (ADS)

Barni, R.; Biganzoli, I.; Dell'Orto, E. C.; Riccardi, C.

2015-10-01

An experimental investigation concerning the effects of a duty-cycle in the supply of a dielectric barrier discharge in atmospheric pressure air has been performed. Electrical characteristics of the discharge have been measured, focusing mainly on the statistical properties of the current filaments and on dielectric surface charging, both affected by the frequent repetition of breakdown imposed by the duty-cycle. Information on the gas-phase composition was gathered too. In particular, a strong enhancement in the ozone formation rate is observed when suitable long pauses separate the active discharge phases. A simulation of the chemical kinetics in the gas-phase, based on a simplified discharge modeling, is briefly described in order to shed light on the observed increase in ozone production. The effect of a duty-cycle on surface modification of polymeric films in order to increase their wettability has been investigated too.

Supramolecular reactivity in the gas phase: investigating the intrinsic properties of non-covalent complexes.

PubMed

Cera, Luca; Schalley, Christoph A

2014-03-21

The high vacuum inside a mass spectrometer offers unique conditions to broaden our view on the reactivity of supramolecules. Because dynamic exchange processes between complexes are efficiently suppressed, the intrinsic and intramolecular reactivity of the complexes of interest is observed. Besides this, the significantly higher strength of non-covalent interactions in the absence of competing solvent allows processes to occur that are unable to compete in solution. The present review highlights a series of examples illustrating different aspects of supramolecular gas-phase reactivity ranging from the dissociation and formation of covalent bonds in non-covalent complexes through the reactivity in the restricted inner phase of container molecules and step-by-step mechanistic studies of organocatalytic reaction cycles to cage contraction reactions, processes induced by electron capture, and finally dynamic molecular motion within non-covalent complexes as unravelled by hydrogen-deuterium exchange processes performed in the gas phase.

Development and evaluation of the aerosol dynamics and gas phase chemistry model ADCHEM

NASA Astrophysics Data System (ADS)

Roldin, P.; Swietlicki, E.; Schurgers, G.; Arneth, A.; Lehtinen, K. E. J.; Boy, M.; Kulmala, M.

2011-06-01

The aim of this work was to develop a model suited for detailed studies of aerosol dynamics, gas and particle phase chemistry within urban plumes, from local scale (1 × 1 km2) to regional scale. This article describes and evaluates the trajectory model for Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer (ADCHEM). The model treats both vertical and horizontal dispersion perpendicular to an air mass trajectory (2-space dimensions). The Lagrangian approach enables a more detailed representation of the aerosol dynamics, gas and particle phase chemistry and a finer spatial and temporal resolution compared to that of available regional 3D-CTMs. These features make it among others well suited for urban plume studies. The aerosol dynamics model includes Brownian coagulation, dry deposition, wet deposition, in-cloud processing, condensation, evaporation, primary particle emissions and homogeneous nucleation. The organic mass partitioning was either modeled with a 2-dimensional volatility basis set (2D-VBS) or with the traditional two-product model approach. In ADCHEM these models consider the diffusion limited and particle size dependent condensation and evaporation of 110 and 40 different organic compounds respectively. The gas phase chemistry model calculates the gas phase concentrations of 61 different species, using 130 different chemical reactions. Daily isoprene and monoterpene emissions from European forests were simulated separately with the vegetation model LPJ-GUESS, and included as input to ADCHEM. ADCHEM was used to simulate the ageing of the urban plumes from the city of Malmö in southern Sweden (280 000 inhabitants). Several sensitivity tests were performed concerning the number of size bins, size structure method, aerosol dynamic processes, vertical and horizontal mixing, coupled or uncoupled condensation and the secondary organic aerosol formation. The simulations show that the full-stationary size structure gives accurate results

Massive Fermi gas in the expanding universe

NASA Astrophysics Data System (ADS)

Trautner, Andreas

2017-03-01

The behavior of a decoupled ideal Fermi gas in a homogeneously expanding three-dimensional volume is investigated, starting from an equilibrium spectrum. In case the gas is massless and/or completely degenerate, the spectrum of the gas can be described by an effective temperature and/or an effective chemical potential, both of which scale down with the volume expansion. In contrast, the spectrum of a decoupled massive and non-degenerate gas can only be described by an effective temperature if there are strong enough self-interactions such as to maintain an equilibrium distribution. Assuming perpetual equilibration, we study a decoupled gas which is relativistic at decoupling and then is red-shifted until it becomes non-relativistic. We find expressions for the effective temperature and effective chemical potential which allow us to calculate the final spectrum for arbitrary initial conditions. This calculation is enabled by a new expansion of the Fermi-Dirac integral, which is for our purpose superior to the well-known Sommerfeld expansion. We also compute the behavior of the phase space density under expansion and compare it to the case of real temperature and real chemical potential. Using our results for the degenerate case, we also obtain the mean relic velocity of the recently proposed non-thermal cosmic neutrino background.

A Simple Approach to Characterize Gas-Aqueous Liquid Two-phase Flow Configuration Based on Discrete Solid-Liquid Contact Electrification

PubMed Central

Choi, Dongwhi; Lee, Donghyeon; Sung Kim, Dong

2015-01-01

In this study, we first suggest a simple approach to characterize configuration of gas-aqueous liquid two–phase flow based on discrete solid-liquid contact electrification, which is a newly defined concept as a sequential process of solid-liquid contact and successive detachment of the contact liquid from the solid surface. This approach exhibits several advantages such as simple operation, precise measurement, and cost-effectiveness. By using electric potential that is spontaneously generated by discrete solid–liquid contact electrification, the configurations of the gas-aqueous liquid two-phase flow such as size of a gas slug and flow rate are precisely characterized. According to the experimental and numerical analyses on parameters that affect electric potential, gas slugs have been verified to behave similarly to point electric charges when the measuring point of the electric potential is far enough from the gas slug. In addition, the configuration of the gas-aqueous liquid two-phase microfluidic system with multiple gas slugs is also characterized by using the presented approach. For a proof-of-concept demonstration of using the proposed approach in a self-triggered sensor, a gas slug detector with a counter system is developed to show its practicality and applicability. PMID:26462437

Evaluation of ionic liquid stationary phases for one dimensional gas chromatography-mass spectrometry and comprehensive two dimensional gas chromatographic analyses of fatty acids in marine biota.

PubMed

Gu, Qun; David, Frank; Lynen, Frédéric; Vanormelingen, Pieter; Vyverman, Wim; Rumpel, Klaus; Xu, Guowang; Sandra, Pat

2011-05-20

Ionic liquid stationary phases were tested for one dimensional gas chromatography-mass spectrometry (GC-MS) and comprehensive two dimensional gas chromatography (GC×GC) of fatty acid methyl esters from algae. In comparison with polyethylene glycol and cyanopropyl substituted polar stationary phases, ionic liquid stationary phases SLB-IL 82 and SLB-IL 100 showed comparable resolution, but lower column bleeding with MS detection, resulting in better sensitivity. The selectivity and polarity of the ionic liquid phases are similar to a highly polar biscyanopropyl-silicone phase (e.g. HP-88). In GC×GC, using an apolar polydimethyl siloxane×polar ionic liquid column combination, an excellent group-type separation of fatty acids with different carbon numbers and number of unsaturations was obtained, providing information that is complementary to GC-MS identification. Copyright © 2011 Elsevier B.V. All rights reserved.

Intramolecular π-π Interactions in Flexibly Linked Partially Fluorinated Bisarenes in the Gas Phase.

PubMed

Blomeyer, Sebastian; Linnemannstöns, Marvin; Nissen, Jan Hendrick; Paulus, Jannik; Neumann, Beate; Stammler, Hans-Georg; Mitzel, Norbert W

2017-10-16

Three compounds with phenyl and pentafluorophenyl rings bridged by (CH 2 ) 3 and (CH 2 ) 2 SiMe 2 units were synthesized by hydrosilylation and C-C coupling reactions. Their solid-state structures are dominated by intermolecular π stacking interactions, primarily leading to dimeric or chain-type aggregates. Analysis of free molecules in the gas phase by electron diffraction revealed the most abundant conformer to be significantly stabilized by intramolecular π-π interactions. For the silicon compounds, structures characterized by σ-π interactions between methyl and pentafluorophenyl groups are second lowest in energy and cannot be excluded completely by the gas electron diffraction experiments. C 6 H 5 (CH 2 ) 3 C 6 F 5 , in contrast, is present as a single conformer. The gas-phase structures served as a reference for the evaluation of a series of (dispersion-corrected) quantum-chemical calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mutual optical intensity propagation through non-ideal mirrors

DOE PAGES

Meng, Xiangyu; Shi, Xianbo; Wang, Yong; ...

2017-08-18

The mutual optical intensity (MOI) model is extended to include the propagation of partially coherent radiation through non-ideal mirrors. The propagation of the MOI from the incident to the exit plane of the mirror is realised by local ray tracing. The effects of figure errors can be expressed as phase shifts obtained by either the phase projection approach or the direct path length method. Using the MOI model, the effects of figure errors are studied for diffraction-limited cases using elliptical cylinder mirrors. Figure errors with low spatial frequencies can vary the intensity distribution, redistribute the local coherence function and distortmore » the wavefront, but have no effect on the global degree of coherence. The MOI model is benchmarked againstHYBRIDand the multi-electronSynchrotron Radiation Workshop(SRW) code. The results show that the MOI model gives accurate results under different coherence conditions of the beam. Other than intensity profiles, the MOI model can also provide the wavefront and the local coherence function at any location along the beamline. The capability of tuning the trade-off between accuracy and efficiency makes the MOI model an ideal tool for beamline design and optimization.« less

(Fuzzy) Ideals of BN-Algebras

PubMed Central

Walendziak, Andrzej

2015-01-01

The notions of an ideal and a fuzzy ideal in BN-algebras are introduced. The properties and characterizations of them are investigated. The concepts of normal ideals and normal congruences of a BN-algebra are also studied, the properties of them are displayed, and a one-to-one correspondence between them is presented. Conditions for a fuzzy set to be a fuzzy ideal are given. The relationships between ideals and fuzzy ideals of a BN-algebra are established. The homomorphic properties of fuzzy ideals of a BN-algebra are provided. Finally, characterizations of Noetherian BN-algebras and Artinian BN-algebras via fuzzy ideals are obtained. PMID:26125050

Modélisation et simulation numérique du changement de phase liquide vapeur en cavité

NASA Astrophysics Data System (ADS)

Daru, Virginie; Duluc, Marie-Christine; Le Maître, Olivier; Juric, Damir; Le Quéré, Patrick

2006-01-01

A model for the simulation of boiling flow with phase change in a closed cavity is presented. A front-tracking method is used to deal with the liquid-vapor interface. The liquid phase is incompressible while the vapor phase is weakly compressible and obeys to the perfect gas law. This model can deal with large density ratio ( ρ/ρ≃1000) flows while accounting for the saturation curve. Computations are performed on a 1D validation case, idealizing a pressure cooker. Results are compared with a low Mach number approximation. To cite this article: V. Daru et al., C. R. Mecanique 334 (2006).

Secondary organic aerosol formation from low-NO(x) photooxidation of dodecane: evolution of multigeneration gas-phase chemistry and aerosol composition.

PubMed

Yee, Lindsay D; Craven, Jill S; Loza, Christine L; Schilling, Katherine A; Ng, Nga Lee; Canagaratna, Manjula R; Ziemann, Paul J; Flagan, Richard C; Seinfeld, John H

2012-06-21

The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes.

Analysis of senior high school student understanding on gas kinetic theory material

NASA Astrophysics Data System (ADS)

Anri, Y.; Maknun, J.; Chandra, D. T.

2018-05-01

The purpose of this research conducted to find out student understanding profile about gas kinetic theory. Particularly, on ideal gas law material, ideal gas equations and kinetic energy of ideal gas. This research was conducted on student of class XII in one of the schools in Bandung. This research is a descriptive research. The data of this research collected by using test instrument which was the essay that has been developed by the researcher based on Bloom’s Taxonomy revised. Based on the analysis result to student answer, this research discovered that whole student has low understanding in the material of gas kinetic theory. This low understanding caused of the misconception of the student, student attitude on physic subjects, and teacher teaching method who are less helpful in obtaining clear pictures in material being taught.

ANALYSIS OF A GAS-PHASE PARTITIONING TRACER TEST CONDUCTED IN AN UNSATURATED FRACTURED-CLAY FORMATION

EPA Science Inventory

The gas-phase partitioning tracer method was used to estimate non-aqueous phase liquid (NAPL), water, and air saturations in the vadose zone at a chlorinated-solvent contaminated field site in Tucson, AZ. The tracer test was conducted in a fractured-clay system that is the confin...

Phase considerations in the gas/particle partitioning of organic amines in the atmosphere

NASA Astrophysics Data System (ADS)