Rational extended thermodynamics of a rarefied polyatomic gas with molecular relaxation processes

NASA Astrophysics Data System (ADS)

Arima, Takashi; Ruggeri, Tommaso; Sugiyama, Masaru

2017-10-01

We present a more refined version of rational extended thermodynamics of rarefied polyatomic gases in which molecular rotational and vibrational relaxation processes are treated individually. In this case, we need a triple hierarchy of the moment system and the system of balance equations is closed via the maximum entropy principle. Three different types of the production terms in the system, which are suggested by a generalized BGK-type collision term in the Boltzmann equation, are adopted. In particular, the rational extended thermodynamic theory with seven independent fields (ET7) is analyzed in detail. Finally, the dispersion relation of ultrasonic wave derived from the ET7 theory is confirmed by the experimental data for CO2, Cl2, and Br2 gases.

Kinetic theory of two-temperature polyatomic plasmas

NASA Astrophysics Data System (ADS)

Orlac'h, Jean-Maxime; Giovangigli, Vincent; Novikova, Tatiana; Roca i Cabarrocas, Pere

2018-03-01

We investigate the kinetic theory of two-temperature plasmas for reactive polyatomic gas mixtures. The Knudsen number is taken proportional to the square root of the mass ratio between electrons and heavy-species, and thermal non-equilibrium between electrons and heavy species is allowed. The kinetic non-equilibrium framework also requires a weak coupling between electrons and internal energy modes of heavy species. The zeroth-order and first-order fluid equations are derived by using a generalized Chapman-Enskog method. Expressions for transport fluxes are obtained in terms of macroscopic variable gradients and the corresponding transport coefficients are expressed as bracket products of species perturbed distribution functions. The theory derived in this paper provides a consistent fluid model for non-thermal multicomponent plasmas.

Rayleigh-Brillouin light scattering spectroscopy of nitrous oxide (N2O)

NASA Astrophysics Data System (ADS)

Wang, Y.; Liang, K.; van de Water, W.; Marques, W.; Ubachs, W.

2018-02-01

High signal-to-noise and high-resolution light scattering spectra are measured for nitrous oxide (N2O) gas at an incident wavelength of 403.00 nm, at 90° scattering, at room temperature and at gas pressures in the range 0.5 - 4 bar. The resulting Rayleigh-Brillouin light scattering spectra are compared to a number of models describing in an approximate manner the collisional dynamics and energy transfer in this gaseous medium of this polyatomic molecular species. The Tenti-S6 model, based on macroscopic gas transport coefficients, reproduces the scattering profiles in the entire pressure range at less than 2% deviation at a similar level as does the alternative kinetic Grad's 6-moment model, which is based on the internal collisional relaxation as a decisive parameter. A hydrodynamic model fails to reproduce experimental spectra for the low pressures of 0.5-1 bar, but yields very good agreement ( < 1%) in the pressure range 2 - 4 bar. While these three models have a different physical basis the internal molecular relaxation derived can for all three be described in terms of a bulk viscosity of ηb ∼(6 ± 2) ×10-5 Pa · s. A 'rough-sphere' model, previously shown to be effective to describe light scattering in SF6 gas, is not found to be suitable, likely in view of the non-sphericity and asymmetry of the N-N-O structured linear polyatomic molecule.

Energy partitioning in polyatomic chemical reactions: Quantum state resolved studies of highly exothermic atom abstraction reactions from molecules in the gas phase and at the gas-liquid interface

NASA Astrophysics Data System (ADS)

Zolot, Alexander M.

This thesis recounts a series of experiments that interrogate the dynamics of elementary chemical reactions using quantum state resolved measurements of gas-phase products. The gas-phase reactions F + HCl → HF + Cl and F + H2O → HF + OH are studied using crossed supersonic jets under single collision conditions. Infrared (IR) laser absorption probes HF product with near shot-noise limited sensitivity and high resolution, capable of resolving rovibrational states and Doppler lineshapes. Both reactions yield inverted vibrational populations. For the HCl reaction, strongly bimodal rotational distributions are observed, suggesting microscopic branching of the reaction mechanism. Alternatively, such structure may result from a quantum-resonance mediated reaction similar to those found in the well-characterized F + HD system. For the H2O reaction, a small, but significant, branching into v = 2 is particularly remarkable because this manifold is accessible only via the additional center of mass collision energy in the crossed jets. Rotationally hyperthermal HF is also observed. Ab initio calculations of the transition state geometry suggest mechanisms for both rotational and vibrational excitation. Exothermic chemical reaction dynamics at the gas-liquid interface have been investigated by colliding a supersonic jet of F atoms with liquid squalane (C30H62), a low vapor pressure hydrocarbon compatible with the high vacuum environment. IR spectroscopy provides absolute HF( v,J) product densities and Doppler resolved velocity component distributions perpendicular to the surface normal. Compared to analogous gas-phase F + hydrocarbon reactions, the liquid surface is a more effective "heat sink," yet vibrationally excited populations reveal incomplete thermal accommodation with the surface. Non-Boltzmann J-state populations and hot Doppler lineshapes that broaden with HF excitation indicate two competing scattering mechanisms: (i) a direct reactive scattering channel, whereby newly formed molecules leave the surface without equilibrating, and (ii) a partially accommodated fraction that shares vibrational, rotational, and translational energy with the liquid surface before returning to the gas phase. Finally, a velocity map ion imaging apparatus has been implemented to investigate reaction dynamics in crossed molecular beams. Resonantly enhanced multiphoton ionization (REMPI) results in rotational, vibrational, and electronic state selectivity. Velocity map imaging measurements provide differential cross sections and information about the internal energy distribution of the undetected collision partner.

Prospects for P-bearing molecules in cometary atmospheres

NASA Astrophysics Data System (ADS)

Boice, Daniel; de Almeida, Amaury

Phosphorus is a key element in all known forms of life and phosphorus-bearing compounds have been observed in space. Phosphorus is ubiquitous in meteorites, albeit in small quantities, with phosphates being found in stoney meteorites and phosphides have been identified in iron meteorites. It has been detected as part of the dust component in comet Halley but searches for P-bearing species in the gas phase in comets have been unsuccessful. Based of its moderate cosmic abundance (eighteenth most abundant element, [P]/[N] = 4 x 10-3 ) and the positive identification of P-bearing species in the interstellar medium (such as, PN, PC, HCP and PO), we would expect simple molecules, diatomics (like PH, PO, PC, PS), triatomics (like HCP and PH2 ), and possibly other polyatomics (like phosphine PH3 and diphosphine P2 H4 ), to exist in cometary ices, hence released into the gas phase upon ice sublimation. Our fluid dynamics model with chemistry of cometary comae (SUISEI) has been adapted to study this problem. SUISEI produces cometocentric abundances of the coma gas species; velocities of the bulk gas, light atomic and molecular hydrogen with escape, and electrons; gas and electron temperatures; column densities to facilitate comparison with observations; coma energy budget quantities; attenuation of the solar irradiance; and other quantities that can be related readily to observations. We present results from the first quantitative study of phosphorus-bearing molecules in comets to identify likely species containing phosphorus to aid in future searches for this important element in comets, possibly shedding light on issues of comet formation (time and place) and matters of the prebiotic to biotic evolution of life. Acknowledgements. This work was supported by the NSF Planetary Astronomy Program.

Comparison of cross sections from the quasi-classical trajectory method and the j(z)-conserving centrifugal sudden approximation with accurate quantum results for an atom-rigid nonlinear polyatomic collision

NASA Technical Reports Server (NTRS)

Schwenke, David W.

1993-01-01

We report the results of a series of calculations of state-to-state integral cross sections for collisions between O and nonvibrating H2O in the gas phase on a model nonreactive potential energy surface. The dynamical methods used include converged quantum mechanical scattering calculations, the j(z) conserving centrifugal sudden (j(z)-CCS) approximation, and quasi-classical trajectory (QCT) calculations. We consider three total energies 0.001, 0.002, and 0.005 E(h) and the nine initial states with rotational angular momentum less than or equal to 2 (h/2 pi). The j(z)-CCS approximation gives good results, while the QCT method can be quite unreliable for transitions to specific rotational sublevels. However, the QCT cross sections summed over final sublevels and averaged over initial sublevels are in better agreement with the quantum results.

Imaging CF3I conical intersection and photodissociation dynamics by ultrafast electron diffraction

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

Yang, Jie

Conical intersections play a critical role in excited state dynamics of polyatomic molecules, as they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wavepacket trajectories through these intersections directly. Here we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF3I molecules using ultrafast gas phase electron diffraction. In the two-photon channel, we have mapped out the real space trajectories of a coherent nuclear wavepacket, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitationmore » of both the umbrella and the breathing vibrational modes in the CF3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab-initio nonadiabatic dynamics calculations.« less

Optimal control of the population dynamics of the ground vibrational state of a polyatomic molecule

NASA Astrophysics Data System (ADS)

de Clercq, Ludwig E.; Botha, Lourens R.; Rohwer, Erich G.; Uys, Hermann; Du Plessis, Anton

2011-03-01

Simulating coherent control with femtosecond pulses on a polyatomic molecule with anharmonic splitting was demonstrated. The simulation mimicked pulse shaping of a Spatial Light Modulator (SLM) and the interaction was described with the Von Neumann equation. A transform limited pulse with a fluence of 600 J/m2 produced 18% of the population in an arbitrarily chosen upper vibrational state, n =2. Phase only and amplitude only shaped pulse produced optimum values of 60% and 40% respectively, of the population in the vibrational state, n=2, after interaction with the ultra short pulse. The combination of phase and amplitude shaping produced the best results, 80% of the population was in the targeted vibrational state, n=2, after interaction. These simulations were carried out with all the population initially in the ground vibrational level. It was found that even at room temperatures (300 Kelvin) that the population in the selected level is comparable with the case where all population is initially in the ground vibrational state. With a 10% noise added to the amplitude and phase masks, selective excitation of the targeted vibrational state is still possible.

Prebiotic chemical evolution in the astrophysical context.

PubMed

Ziurys, L M; Adande, G R; Edwards, J L; Schmidt, D R; Halfen, D T; Woolf, N J

2015-06-01

An ever increasing amount of molecular material is being discovered in the interstellar medium, associated with the birth and death of stars and planetary systems. Radio and millimeter-wave astronomical observations, made possible by high-resolution laboratory spectroscopy, uniquely trace the history of gas-phase molecules with biogenic elements. Using a combination of both disciplines, the full extent of the cycling of molecular matter, from circumstellar ejecta of dying stars - objects which expel large amounts of carbon - to nascent solar systems, has been investigated. Such stellar ejecta have been found to exhibit a rich and varied chemical content. Observations demonstrate that this molecular material is passed onto planetary nebulae, the final phase of stellar evolution. Here the star sheds almost its entire original mass, becoming an ultraviolet-emitting white dwarf. Molecules such as H2CO, HCN, HCO(+), and CCH are present in significant concentrations across the entire age span of such nebulae. These data suggest that gas-phase polyatomic, carbon-containing molecules survive the planetary nebula phase and subsequently are transported into the interstellar medium, seeding the chemistry of diffuse and then dense clouds. The extent of the chemical complexity in dense clouds is unknown, hindered by the high spectral line density. Organic species such as acetamide and methyl amine are present in such objects, and NH2CHO has a wide Galactic distribution. However, organophosphorus compounds have not yet been detected in dense clouds. Based on carbon and nitrogen isotope ratios, molecular material from the ISM appears to become incorporated into solar system planetesimals. It is therefore likely that interstellar synthesis influences prebiotic chemistry on planet surfaces.

Wavepacket dynamics and the multi-configurational time-dependent Hartree approach

NASA Astrophysics Data System (ADS)

Manthe, Uwe

2017-06-01

Multi-configurational time-dependent Hartree (MCTDH) based approaches are efficient, accurate, and versatile methods for high-dimensional quantum dynamics simulations. Applications range from detailed investigations of polyatomic reaction processes in the gas phase to high-dimensional simulations studying the dynamics of condensed phase systems described by typical solid state physics model Hamiltonians. The present article presents an overview of the different areas of application and provides a comprehensive review of the underlying theory. The concepts and guiding ideas underlying the MCTDH approach and its multi-mode and multi-layer extensions are discussed in detail. The general structure of the equations of motion is highlighted. The representation of the Hamiltonian and the correlated discrete variable representation (CDVR), which provides an efficient multi-dimensional quadrature in MCTDH calculations, are discussed. Methods which facilitate the calculation of eigenstates, the evaluation of correlation functions, and the efficient representation of thermal ensembles in MCTDH calculations are described. Different schemes for the treatment of indistinguishable particles in MCTDH calculations and recent developments towards a unified multi-layer MCTDH theory for systems including bosons and fermions are discussed.

Determination of low concentrations of iron, arsenic, selenium, cadmium, and other trace elements in natural samples using an octopole collision/reaction cell equipped quadrupole-inductively coupled plasma mass spectrometer.

PubMed

Dial, Angela R; Misra, Sambuddha; Landing, William M

2015-04-30

Accurate determination of trace metals has many applications in environmental and life sciences, such as constraining the cycling of essential micronutrients in biological production and employing trace metals as tracers for anthropogenic pollution. Analysis of elements such as Fe, As, Se, and Cd is challenged by the formation of polyatomic mass spectrometric interferences, which are overcome in this study. We utilized an Octopole Collision/Reaction Cell (CRC)-equipped Quadrupole-Inductively Coupled Plasma Mass Spectrometer for the rapid analysis of small volume samples (~250 μL) in a variety of matrices containing HNO3 and/or HCl. Efficient elimination of polyatomic interferences was demonstrated by the use of the CRC in Reaction Mode (RM; H2 gas) and in Collision-Reaction Mode (CRM; H2 and He gas), in addition to hot plasma (RF power 1500 W) and cool plasma (600 W) conditions. It was found that cool plasma conditions with RM achieved the greatest signal sensitivity while maintaining low detection limits (i.e. (56) Fe in 0.44 M HNO3 has a sensitivity of 160,000 counts per second (cps)-per-1 µg L(-1) and a limit of detection (LoD) of 0.86 ng L(-1) ). The average external precision was ≤ ~10% for minor (≤10 µg L(-1) ) elements measured in a 1:100 dilution of NIST 1643e and for iron in rainwater samples under all instrumental operating conditions. An improved method has been demonstrated for the rapid multi-element analysis of trace metals that are challenged by polyatomic mass spectrometric interferences, with a focus on (56) Fe, (75) As, (78) Se and (111) Cd. This method can contribute to aqueous environmental geochemistry and chemical oceanography, as well as other fields such as forensic chemistry, agriculture, food chemistry, and pharmaceutical sciences. Copyright © 2015 John Wiley & Sons, Ltd.

An Update on the Non-Mass-Dependent Isotope Fractionation under Thermal Gradient

NASA Technical Reports Server (NTRS)

Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard; Liu, Yun

2013-01-01

Mass flow and compositional gradient (elemental and isotope separation) occurs when flu-id(s) or gas(es) in an enclosure is subjected to a thermal gradient, and the phenomenon is named thermal diffusion. Gas phase thermal diffusion has been theoretically and experimentally studied for more than a century, although there has not been a satisfactory theory to date. Nevertheless, for isotopic system, the Chapman-Enskog theory predicts that the mass difference is the only term in the thermal diffusion separation factors that differs one isotope pair to another,with the assumptions that the molecules are spherical and systematic (monoatomic-like structure) and the particle collision is elastic. Our previous report indicates factors may be playing a role because the Non-Mass Dependent (NMD) effect is found for both symmetric and asymmetric, linear and spherical polyatomic molecules over a wide range of temperature (-196C to +237C). The observed NMD phenomenon in the simple thermal-diffusion experiments demands quantitative validation and theoretical explanation. Besides the pressure and temperature dependency illustrated in our previous reports, efforts are made in this study to address issues such as the role of convection or molecular structure and whether it is a transient, non-equilibrium effect only.

Method for preparation and readout of polyatomic molecules in single quantum states

NASA Astrophysics Data System (ADS)

Patterson, David

2018-03-01

Polyatomic molecular ions contain many desirable attributes of a useful quantum system, including rich internal degrees of freedom and highly controllable coupling to the environment. To date, the vast majority of state-specific experimental work on molecular ions has concentrated on diatomic species. The ability to prepare and read out polyatomic molecules in single quantum states would enable diverse experimental avenues not available with diatomics, including new applications in precision measurement, sensitive chemical and chiral analysis at the single-molecule level, and precise studies of Hz-level molecular tunneling dynamics. While cooling the motional state of a polyatomic ion via sympathetic cooling with a laser-cooled atomic ion is straightforward, coupling this motional state to the internal state of the molecule has proven challenging. Here we propose a method for readout and projective measurement of the internal state of a trapped polyatomic ion. The method exploits the rich manifold of technically accessible rotational states in the molecule to realize robust state preparation and readout with far less stringent engineering than quantum logic methods recently demonstrated on diatomic molecules. The method can be applied to any reasonably small (≲10 atoms) polyatomic ion with an anisotropic polarizability.

Three milieux for interstellar chemistry: gas, dust, and ice

NASA Astrophysics Data System (ADS)

Herbst, Eric

The interdisciplinary science of astrochemistry is 45 years of age, if we pinpoint its origin to have occurred when the first polyatomic molecules were detected in the interstellar gas. Since that time, the field has grown remarkably from an esoteric area of research to one that unites scientists around the globe. Almost 200 different molecules have been detected in the gas-phase of interstellar clouds, mainly by rotational spectroscopy, while dust particles and their icy mantles in colder regions can be probed by vibrational spectroscopy. Astrochemistry is exciting to scientists in a number of different fields. Astronomers are interested in molecular spectra from the heavens because such spectra are excellent probes of the physical conditions where molecules exist, while chemists are interested in the exotic molecules, their spectra, and the unusual chemical processes that produce and destroy them under conditions often very different from those on our home planet. Chemical simulations involving thousands of reactions are now used to calculate concentrations and spectra of interstellar molecules as functions of time. Even biologists share an interest in the subject, because the interstellar clouds of gas and dust, portions of which collapse to form stars and planetary systems, contain organic molecules that may become part of the initial inventory of new planets and may indeed be the precursors of life. An irresistible subject to its practitioners, astrochemistry is proving to be exciting to a much wider audience. In this perspective article, the field is first introduced, and the emphasis is then placed on the three environments in which chemistry occurs in the interstellar medium: the gas phase, the surfaces of bare dust particles, and the ice mantles that cover bare grains in cold dense interstellar clouds. What we do know and what we do not know is distinguished. The status of chemical simulations for a variety of interstellar sources having to do with stellar and planetary evolution is surveyed. An optimistic view of the future of astrochemistry ends the article.

Investigation of the ellipsoidal-statistical Bhatnagar-Gross-Krook kinetic model applied to gas-phase transport of heat and tangential momentum between parallel walls

NASA Astrophysics Data System (ADS)

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

2011-03-01

The ellipsoidal-statistical Bhatnagar-Gross-Krook (ES-BGK) kinetic model is investigated for steady gas-phase transport of heat, tangential momentum, and mass between parallel walls (i.e., Fourier, Couette, and Fickian flows). This investigation extends the original study of Cercignani and Tironi, who first applied the ES-BGK model to heat transport (i.e., Fourier flow) shortly after this model was proposed by Holway. The ES-BGK model is implemented in a molecular-gas-dynamics code so that results from this model can be compared directly to results from the full Boltzmann collision term, as computed by the same code with the direct simulation Monte Carlo (DSMC) algorithm of Bird. A gas of monatomic molecules is considered. These molecules collide in a pairwise fashion according to either the Maxwell or the hard-sphere interaction and reflect from the walls according to the Cercignani-Lampis-Lord model with unity accommodation coefficients. Simulations are performed at pressures from near-free-molecular to near-continuum. Unlike the BGK model, the ES-BGK model produces heat-flux and shear-stress values that both agree closely with the DSMC values at all pressures. However, for both interactions, the ES-BGK model produces molecular-velocity-distribution functions that are qualitatively similar to those determined for the Maxwell interaction from Chapman-Enskog theory for small wall temperature differences and moment-hierarchy theory for large wall temperature differences. Moreover, the ES-BGK model does not produce accurate values of the mass self-diffusion coefficient for either interaction. Nevertheless, given its reasonable accuracy for heat and tangential-momentum transport, its sound theoretical foundation (it obeys the H-theorem), and its available extension to polyatomic molecules, the ES-BGK model may be a useful method for simulating certain classes of single-species noncontinuum gas flows, as Cercignani suggested.

New emission features in the 11-13 micron region and their relationship to polycyclic aromatic hydrocarbons

NASA Technical Reports Server (NTRS)

Witteborn, F. C.; Sandford, S. A.; Bregman, J. D.; Allamandola, L. J.; Cohen, M.; Wooden, D. H.; Graps, A. L.

1989-01-01

Moderate-resolution spectra of NGC 7027, HD 44179, IRAS 2182+5050, and BD +30 deg 3639 are presented, showing that the 11.3-micron feature actually peaks at 11.22 microns. Evidence is found for new emission features near 11.9 and 12.7 microns, supporting an origin from PAHs. Also, the observed asymmetry of the 11.3-micron band is consistent with the anharmonicity expected in the C-H out-of-plane bending mode in PAHs. The analysis of the 11-13-micron emission suggests that the molecular structures of the most intensely emitting free PAHs vary between the high-excitation environment in NGC 7027 and the low-excitation but high-flux environment close to HD 44179. In addition, a series of regularly spaced features between 10 and 11 microns is detected in the spectrum of HD 44179, suggesting that a simple polyatomic hydride is present in the object's gas phase.

Rapid-Adiabatic Control of Ro-Vibrational Populations in Polyatomic Molecules

NASA Astrophysics Data System (ADS)

Zak, Emil J.; Yachmenev, Andrey

2017-06-01

We present a simple method for control of ro-vibrational populations in polyatomic molecules in the presence of inhomogeneous electric fields [1]. Cooling and trapping of heavy polar polyatomic molecules has become one of the frontier goals in high-resolution molecular spectroscopy, especially in the context of parity violation measurement in chiral compounds [2]. A key step toward reaching this goal would be development of a robust and efficient protocol for control of populations of ro-vibrational states in polyatomic, often floppy molecules. Here we demonstrate a modification of the stark-chirped rapid-adiabatic-passage technique (SCRAP) [3], designed for achieving high levels of control of ro-vibrational populations over a selected region in space. The new method employs inhomogeneous electric fields to generate space- and time- controlled Stark-shifts of energy levels in molecules. Adiabatic passage between ro-vibrational states is enabled by the pump pulse, which raises the value of the Rabi frequency. This Stark-chirped population transfer can be used in manipulation of population differences between high-field-seeking and low-field-seeking states of molecules in the Stark decelerator [4]. Appropriate timing of voltages on electric rods located along the decelerator combined with a single pump laser renders our method as potentially more efficient than traditional Stark decelerator techniques. Simulations for NH_3 show significant improvement in effectiveness of cooling, with respect to the standard 'moving-potential' method [5]. At the same time a high phase-space acceptance of the molecular packet is maintained. E. J. Zak, A. Yachmenev (submitted). C. Medcraft, R. Wolf, M. Schnell, Angew. Chem. Int. Ed., 53, 43, 11656-11659 (2014) M. Oberst, H. Munch, T. Halfman, PRL 99, 173001 (2007). K. Wohlfart, F. Grätz, F. Filsinger, H. Haak, G. Meijer, J. Küpper, Phys. Rev. A 77, 031404(R) (2008). H. L. Bethlem, F. M. H. Crompvoets, R. T. Jongma, S. Y. T. van de Meerakker, G. Meijer, Phys. Rev. A, 65, 053416 (2002).

Earle K. Plyler Prize Lecture: The Three Pillars of Ultrafast Molecular Science - Time, Phase, Intensity

NASA Astrophysics Data System (ADS)

Stolow, Albert

We discuss the probing and control of molecular wavepacket dynamics in the context of three main `pillars' of light-matter interaction: time, phase, intensity. Time: Using short, coherent laser pulses and perturbative matter-field interactions, we study molecular wavepackets with a focus on the ultrafast non-Born-Oppenheimer dynamics, that is, the coupling of electronic and nuclear motions. Time-Resolved Photoelectron Spectroscopy (TRPES) is a powerful ultrafast probe of these processes in polyatomic molecules because it is sensitive both electronic and vibrational dynamics. Ideally, one would like to observe these ultrafast processes from the molecule's point of view - the Molecular Frame - thereby avoiding loss of information due to orientational averaging. This can be achieved by Time-Resolved Coincidence Imaging Spectroscopy (TRCIS) which images 3D recoil vectors of both photofragments and photoelectrons, in coincidence and as a function of time, permitting direct Molecular Frame imaging of valence electronic dynamics during a molecular dynamics. Phase: Using intermediate strength non-perturbative interactions, we apply the second order (polarizability) Non-Resonant Dynamic Stark Effect (NRDSE) to control molecular dynamics without any net absorption of light. NRDSE is also the interaction underlying molecular alignment and applies to field-free 1D of linear molecules and field-free 3D alignment of general (asymmetric) molecules. Using laser alignment, we can transiently fix a molecule in space, yielding a more general approach to direct Molecular Frame imaging of valence electronic dynamics during a chemical reaction. Intensity: In strong (ionizing) laser fields, a new laser-matter physics emerges for polyatomic systems wherein both the single active electron picture and the adiabatic electron response, both implicit in the standard 3-step models, can fail dramatically. This has important consequences for all attosecond strong field spectroscopies of polyatomic molecules, including high harmonic generation (HHG). We discuss an experimental method, Channel-Resolved Above Threshold Ionization (CRATI), which directly unveils the electronic channels participating in the attosecond molecular strong field ionization response [10]. This work was supported by the National Research Council of Canada and the Natural Sciences & Engineering Research Council.

Attosecond-recollision-controlled selective fragmentation of polyatomic molecules.

PubMed

Xie, Xinhua; Doblhoff-Dier, Katharina; Roither, Stefan; Schöffler, Markus S; Kartashov, Daniil; Xu, Huailiang; Rathje, Tim; Paulus, Gerhard G; Baltuška, Andrius; Gräfe, Stefanie; Kitzler, Markus

2012-12-14

Control over various fragmentation reactions of a series of polyatomic molecules (acetylene, ethylene, 1,3-butadiene) by the optical waveform of intense few-cycle laser pulses is demonstrated experimentally. We show both experimentally and theoretically that the responsible mechanism is inelastic ionization from inner-valence molecular orbitals by recolliding electron wave packets, whose recollision energy in few-cycle ionizing laser pulses strongly depends on the optical waveform. Our work demonstrates an efficient and selective way of predetermining fragmentation and isomerization reactions in polyatomic molecules on subfemtosecond time scales.

A table of polyatomic interferences in ICP-MS

USGS Publications Warehouse

May, Thomas W.; Wiedmeyer, Ray H.

1998-01-01

Spectroscopic interferences are probably the largest class of interferences in ICP-MS and are caused by atomic or molecular ions that have the same mass-to-charge as analytes of interest. Current ICP-MS instrumental software corrects for all known atomic “isobaric” interferences, or those caused by overlapping isotopes of different elements, but does not correct for most polyatomic interferences. Such interferences are caused by polyatomic ions that are formed from precursors having numerous sources, such as the sample matrix, reagents used for preparation, plasma gases, and entrained atmospheric gases.

Rotation driven translational diffusion of polyatomic ions in water: A novel mechanism for breakdown of Stokes-Einstein relation

NASA Astrophysics Data System (ADS)

Banerjee, Puja; Yashonath, Subramanian; Bagchi, Biman

2017-04-01

While most of the existing theoretical and simulation studies have focused on simple, spherical, halide and alkali ions, many chemically, biologically, and industrially relevant electrolytes involve complex non-spherical polyatomic ions like nitrate, chlorate, and sulfate to name only a few. Interestingly, some polyatomic ions in spite of being larger in size show anomalously high diffusivity and therefore cause a breakdown of the venerable Stokes-Einstein (S-E) relation between the size and diffusivity. Here we report a detailed analysis of the dynamics of anions in aqueous potassium nitrate (KNO3) and aqueous potassium acetate (CH3COOK) solutions. The two ions, nitrate (-NO3) and acetate (CH3-CO2 ), with their similar size show a large difference in diffusivity values. We present evidence that the translational motion of these polyatomic ions is coupled to the rotational motion of the ion. We show that unlike the acetate ion, nitrate ion with a symmetric charge distribution among all periphery oxygen atoms shows a faster rotational motion with large amplitude rotational jumps which enhances its translational motion due to translational-rotational coupling. By creating a family of modified-charge model systems, we have analysed the rotational motion of asymmetric polyatomic ions and the contribution of it to the translational motion. These model systems help clarifying and establishing the relative contribution of rotational motion in enhancing the diffusivity of the nitrate ion over the value predicted by the S-E relation and also over the other polyatomic ions having asymmetric charge distribution like the acetate ion. In the latter case, reduced rotational motion results in lower diffusivity values than those with symmetric charge distribution. We propose translational-rotational coupling as a general mechanism of the breakdown of the S-E relation in the case of polyatomic ions.

Rotation driven translational diffusion of polyatomic ions in water: A novel mechanism for breakdown of Stokes-Einstein relation.

PubMed

Banerjee, Puja; Yashonath, Subramanian; Bagchi, Biman

2017-04-28

While most of the existing theoretical and simulation studies have focused on simple, spherical, halide and alkali ions, many chemically, biologically, and industrially relevant electrolytes involve complex non-spherical polyatomic ions like nitrate, chlorate, and sulfate to name only a few. Interestingly, some polyatomic ions in spite of being larger in size show anomalously high diffusivity and therefore cause a breakdown of the venerable Stokes-Einstein (S-E) relation between the size and diffusivity. Here we report a detailed analysis of the dynamics of anions in aqueous potassium nitrate (KNO 3 ) and aqueous potassium acetate (CH 3 COOK) solutions. The two ions, nitrate (NO3-) and acetate (CH 3 CO2-), with their similar size show a large difference in diffusivity values. We present evidence that the translational motion of these polyatomic ions is coupled to the rotational motion of the ion. We show that unlike the acetate ion, nitrate ion with a symmetric charge distribution among all periphery oxygen atoms shows a faster rotational motion with large amplitude rotational jumps which enhances its translational motion due to translational-rotational coupling. By creating a family of modified-charge model systems, we have analysed the rotational motion of asymmetric polyatomic ions and the contribution of it to the translational motion. These model systems help clarifying and establishing the relative contribution of rotational motion in enhancing the diffusivity of the nitrate ion over the value predicted by the S-E relation and also over the other polyatomic ions having asymmetric charge distribution like the acetate ion. In the latter case, reduced rotational motion results in lower diffusivity values than those with symmetric charge distribution. We propose translational-rotational coupling as a general mechanism of the breakdown of the S-E relation in the case of polyatomic ions.

Study of Pair and many-body interactions in rare-gas halide atom clusters using negative ion zero electron kinetic energy (ZEKE) and threshold photodetachment spectroscopy

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

Yourshaw, Ivan

1998-07-09

The diatomic halogen atom-rare gas diatomic complexes KrBr -, XeBr -, and KrCl - are studied in this work by zero electron kinetic energy (ZEKE) spectroscopy in order to characterize the weak intermolecular diatomic potentials of these species. Also, the ZEKE and threshold photodetachment spectra of the polyatomic clusters Ar nBr - (n = 2-9) and Ar nI - (n = 2-19) are studied to obtain information about the non-additive effects on the interactions among the atoms. This work is part of an ongoing effort to characterize the pair and many-body potentials of the complete series of rare gas halidemore » clusters. In these studies we obtain information about both the anionic and neutral clusters.« less

Creation of Rydberg Polarons in a Bose Gas

NASA Astrophysics Data System (ADS)

Camargo, F.; Schmidt, R.; Whalen, J. D.; Ding, R.; Woehl, G.; Yoshida, S.; Burgdörfer, J.; Dunning, F. B.; Sadeghpour, H. R.; Demler, E.; Killian, T. C.

2018-02-01

We report spectroscopic observation of Rydberg polarons in an atomic Bose gas. Polarons are created by excitation of Rydberg atoms as impurities in a strontium Bose-Einstein condensate. They are distinguished from previously studied polarons by macroscopic occupation of bound molecular states that arise from scattering of the weakly bound Rydberg electron from ground-state atoms. The absence of a p -wave resonance in the low-energy electron-atom scattering in Sr introduces a universal behavior in the Rydberg spectral line shape and in scaling of the spectral width (narrowing) with the Rydberg principal quantum number, n . Spectral features are described with a functional determinant approach (FDA) that solves an extended Fröhlich Hamiltonian for a mobile impurity in a Bose gas. Excited states of polyatomic Rydberg molecules (trimers, tetrameters, and pentamers) are experimentally resolved and accurately reproduced with a FDA.

Higher sensitivity secondary ion mass spectrometry of biological molecules for high resolution, chemically specific imaging.

PubMed

McDonnell, Liam A; Heeren, Ron M A; de Lange, Robert P J; Fletcher, Ian W

2006-09-01

To expand the role of high spatial resolution secondary ion mass spectrometry (SIMS) in biological studies, numerous developments have been reported in recent years for enhancing the molecular ion yield of high mass molecules. These include both surface modification, including matrix-enhanced SIMS and metal-assisted SIMS, and polyatomic primary ions. Using rat brain tissue sections and a bismuth primary ion gun able to produce atomic and polyatomic primary ions, we report here how the sensitivity enhancements provided by these developments are additive. Combined surface modification and polyatomic primary ions provided approximately 15.8 times more signal than using atomic primary ions on the raw sample, whereas surface modification and polyatomic primary ions yield approximately 3.8 and approximately 8.4 times more signal. This higher sensitivity is used to generate chemically specific images of higher mass biomolecules using a single molecular ion peak.

New approach in direct-simulation of gas mixtures

NASA Technical Reports Server (NTRS)

Chung, Chan-Hong; De Witt, Kenneth J.; Jeng, Duen-Ren

1991-01-01

Results are reported for an investigation of a new direct-simulation Monte Carlo method by which energy transfer and chemical reactions are calculated. The new method, which reduces to the variable cross-section hard sphere model as a special case, allows different viscosity-temperature exponents for each species in a gas mixture when combined with a modified Larsen-Borgnakke phenomenological model. This removes the most serious limitation of the usefulness of the model for engineering simulations. The necessary kinetic theory for the application of the new method to mixtures of monatomic or polyatomic gases is presented, including gas mixtures involving chemical reactions. Calculations are made for the relaxation of a diatomic gas mixture, a plane shock wave in a gas mixture, and a chemically reacting gas flow along the stagnation streamline in front of a hypersonic vehicle. Calculated results show that the introduction of different molecular interactions for each species in a gas mixture produces significant differences in comparison with a common molecular interaction for all species in the mixture. This effect should not be neglected for accurate DSMC simulations in an engineering context.

Channel-resolved photo- and Auger-electron spectroscopy of halogenated hydrocarbons

NASA Astrophysics Data System (ADS)

Ablikim, Utuq; Kaderiya, B.; Kumarapan, V.; Kushawaha, R.; Rudenko, A.; Rolles, D.; Xiong, H.; Berrah, N.; Bomme, C.; Savelyev, E.; Kilcoyne, D.

2016-05-01

Inner-shell photoelectron and Auger electron spectra of polyatomic molecules such as halogenated hydrocarbons are typically hard to interpret and assign due to many overlapping states that form broad bands even in high-resolution measurements. With the help of electron-ion-ion coincidence measurements performed using the velocity map imaging technique, we are able to detect high-energy (<= 150 eV) photo- and Auger electrons in coincidence with two- or many-body ionic fragmentation channels. Such channel-resolved measurements allow disentangling the overlapping electronic structures and help assigning individual components of the electron spectra to specific potential surfaces and final states. In this work, we present measurements on CH3 I, CH2 IBr, and CH2 ICl molecules in the gas-phase using soft x-ray light provided by the Advanced Light Source at LBNL. This project is supported by the DOE, Office of Science, BES, Division of Chemical, Geological and Biological Sciences under Award Number DE-FG02-86ER13491 (U.A., B.K., V.K., A.R., D.R.) and Award Number DE-SC0012376 (H.X., N.B.).

New Ro-Vibrational Kinetic Energy Operators using Polyspherical Coordinates for Polyatomic Molecules

NASA Technical Reports Server (NTRS)

Schwenke, David W.; Kwak, Dochan (Technical Monitor)

2002-01-01

We illustrate how one can easily derive kinetic energy operators for polyatomic molecules using polyspherical coordinates with very general choices for z-axis embeddings arid angles used to specify relative orientations of internal vectors. Computer algebra is not required.

Measurements of Polyatomic Molecule Formation on an Icy Grain Analog Using Fast Atoms

NASA Technical Reports Server (NTRS)

Chutjian, A.; Madsunkov, S.; Shortt, B. J.; MacAskill, J. A.; Darrach, M. R.

2006-01-01

Carbon dioxide has been produced from the impact of a monoenergetic O(P-3) beam upon a surface cooled to 4.8 K and covered with a CO ice. Using temperature-programmed desorption and mass spectrometer detection, we have detected increasing amounts of CO2 formation with O(P-3) energies of 2, 5, 10, and 14 eV. This is the first measurement of polyatomic molecule formation on a surface with superthermal atoms. The goal of this work is to detect other polyatomic species, such as CH3OH, which can be formed under conditions that simulate the grain temperature, surface coverage, and superthermal atoms present in shock-heated circumstellar and interstellar regions.

Enthalpic parameters of interaction between diglycylglycine and polyatomic alcohols in aqueous solutions

NASA Astrophysics Data System (ADS)

Mezhevoi, I. N.; Badelin, V. G.

2015-12-01

Integral enthalpies of solution Δsol H m of diglycylglycine in aqueous solutions of glycerol, ethylene glycol, and 1,2-propylene glycol are measured via solution calorimetry. The experimental data are used to calculate the standard enthalpies of solution (Δsol H°) and transfer (Δtr H°) of the tripeptide from water to aqueous solutions of polyatomic alcohols. The enthalpic pairwise coefficients h xy of interactions between the tripeptide and polyatomic alcohol molecules are calculated using the McMillan-Mayer solution theory and are found to have positive values. The findings are discussed using the theory of estimating various types of interactions in ternary systems and the effect the structural features of interacting biomolecules have on the thermochemical parameters of diglycylglycine dissolution.

Climate-chemical interactions and effects of changing atmospheric trace gases

NASA Technical Reports Server (NTRS)

Ramanathan, V.; Callis, L.; Cess, R.; Hansen, J.; Isaksen, I.

1987-01-01

The paper considers trace gas-climate effects including the greenhouse effect of polyatomic trace gases, the nature of the radiative-chemical interactions, and radiative-dynamical interactions in the stratosphere, and the role of these effects in governing stratospheric climate change. Special consideration is given to recent developments in the investigations of the role of oceans in governing the transient climate responses, and a time-dependent estimate of the potential trace gas warming from the preindustrial era to the early 21st century. The importance of interacting modeling and observational efforts is emphasized. One of the problems remaining on the observational front is the lack of certainty in current estimates of the rate of growth of CO, O3, and NOx; the primary challenge is the design of a strategy that will minimize the sampling errors.

The creation of hypersonic flows by a powerful impulse capillary discharge

NASA Astrophysics Data System (ADS)

Pashchina, A. S.; Karmatsky, R. E.; Klimov, A. I.

2017-11-01

The possibility of using a powerful pulsed capillary discharge to produce quasi-stationary highspeed plasma flows with characteristic Mach numbers M = 3-10 and temperatures T = 3000-6000 K has been experimentally substantiated. In a rarefied gas atmosphere ( p ∞ < 10 Torr), the transverse size of flow exceeds d < 3 cm and the duration of the working cycle can be brought to hundreds of milliseconds, which is of interest in problems of laboratory modeling of physical-chemical and gas-dynamic effects of interaction of bodies with hypersonic flows. Strong temperature nonequilibrium has been found (with the ratio between the vibrational and rotational temperatures reaching T v/ T r = 3 and more) and anomalously low values of the effective adiabatic index, which indicates an intensive formation of polyatomic molecules and condensed particles in a carbon-containing plasma.

Electrondriven processes in polyatomic molecules

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

McKoy, Vincent

2017-03-20

This project developed and applied scalable computational methods to obtain information about low-energy electron collisions with larger polyatomic molecules. Such collisions are important in modeling radiation damage to living systems, in spark ignition and combustion, and in plasma processing of materials. The focus of the project was to develop efficient methods that could be used to obtain both fundamental scientific insights and data of practical value to applications.

Physics with Cold Molecules Using Buffer Gas Cooling: Precision Measurement, Collisions, and Laser Cooling

NASA Astrophysics Data System (ADS)

Hutzler, Nicholas R.; Doyle, John M.

2014-06-01

Cryogenic buffer gas cooled beams and cells can be used to study many species, from atoms and polar molecules to biomolecules. We report on recent applications of this technique to improve the limit on the electron electric dipole moment [1], load polar molecules into a magnetic trap through optical pumping [2], perform chirally sensitive microwave spectroscopy on polyatomic molecules [3], progress towards magneto-optical trapping of polar molecules [4], and studies of atom-molecule sticking [5]. [1] The ACME Collaboration: J. Baron et al., Science 343, p. 269 (2014) [2] B. Hemmerling et al., arXiv:1310.2669, to appear in Phys. Rev. Lett. [3] D. Patterson, M. Schnell, & J. M. Doyle, Nature 497, p. 475 (2013) [4] H. Lu et al., arXiv:1310.3239, to appear in New. J. Phys. [5] J. Piskorski et al., under preparation

Radiative interactions in molecular gases under local and nonlocal thermodynamic equilibrium conditions

NASA Technical Reports Server (NTRS)

Tiwari, S. N.; Jha, M. K.

1993-01-01

Basic formulations, analyses, and numerical procedures are presented to investigate radiative heat interactions in diatomic and polyatomic gases under local and nonlocal thermodynamic equilibrium conditions. Essential governing equations are presented for both gray and nongray gases. Information is provided on absorption models, relaxation times, and transfer equations. Radiative flux equations are developed which are applicable under local and nonlocal thermodynamic equilibrium conditions. The problem is solved for fully developed laminar incompressible flows between two parallel plates under the boundary condition of a uniform surface heat flux. For specific applications, three diatomic and three polyatomic gases are considered. The results are obtained numerically by employing the method of variation of parameters. The results are compared under local and nonlocal thermodynamic equilibrium conditions at different temperature and pressure conditions. Both gray and nongray studies are conducted extensively for all molecular gases considered. The particular gases selected for this investigation are CO, NO, OH, CO2, H2O, and CH4. The temperature and pressure range considered are 300-2000 K and 0.1-10 atmosphere, respectively. In general, results demonstrate that the gray gas approximation overestimates the effect of radiative interaction for all conditions. The conditions of NLTE, however, result in underestimation of radiative interactions. The method developed for this study can be extended to solve complex problems of radiative heat transfer involving nonequilibrium phenomena.

Detection of anions by normal Raman spectroscopy and surface-enhanced Raman spectroscopy of cationic-coated substrates.

PubMed

Mosier-Boss, P A; Lieberman, S H

2003-09-01

The use of normal Raman spectroscopy and surface-enhanced Raman spectroscopy (SERS) of cationic-coated silver and gold substrates to detect polyatomic anions in aqueous environments is examined. For normal Raman spectroscopy, using near-infrared excitation, linear concentration responses were observed. Detection limits varied from 84 ppm for perchlorate to 2600 ppm for phosphate. In general, detection limits in the ppb to ppm concentration range for the polyatomic anions were achieved using cationic-coated SERS substrates. Adsorption of the polyatomic anions on the cationic-coated SERS substrates was described by a Frumkin isotherm. The SERS technique could not be used to detect dichromate, as this anion reacted with the coatings to form thiol esters. A competitive complexation method was used to evaluate the interaction of chloride ion with the cationic coatings. Hydrogen bonding and pi-pi interactions play significant roles in the selectivity of the cationic coatings.

Final Report

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

McLuckey, Scott

2016-08-30

The overall objectives of this research effort were to expand the capabilities of spectroscopic and ion chemistry tools for the structural characterization of polyatomic ions of relevance to the broad mission of the Department of Energy. Mass spectrometry currently plays an important role in virtually all of the molecular sciences by virtue of the value of the accurate measurement of mass and the structural information that can be derived from various structural probes based on, for example, ion chemistry, ion mobility, and ion spectroscopy. Mass spectrometry has long played important roles in supporting the missions of the Department of Energymore » and its predecessor agencies, particularly in the area of isotopic analysis of nuclides. Molecular mass spectrometry has played increasingly important roles is many aspects of the production and use of energy as the nation has diversified its energy portfolio. There is an ongoing need for the expansion of the measurement capabilities associated with molecular mass spectrometry that involves both technological developments as well as improved understanding of the chemical and physical processes that take place upon ionization and ion analysis in a mass spectrometer. Advances in mass spectrometry have impacted science broadly and further advances will be required to meet the needs of current energy and environmental research. This program has historically focused on the structural characterization of polyatomic ions, usually within the context of a tandem mass spectrometry experiment. A wide variety of physical and chemical processes can take place within a mass spectrometer and advantage can be taken of such processes to enhance the quality and quantity of information that can be derived for a given chemical system of interest. For example, ions can undergo interactions with neutral molecules/atoms, light, surfaces, electrons, or oppositely charged ions. The outcomes of all such interactions can be sensitive to the structures of the ions and are therefore candidates for probes of ion structure. This program has historically focused on the chemistry and physics associated with ion/neutral interactions at both low and high translational energies, and ion/ion reactions. The former area has involved the study of ion/molecule reactions at thermal energies and the extensive study of collisional activation under a wide variety of conditions. A major area of emphasis has been collisional activation in electrodynamic ion traps. The study of gas-phase ion/ion reactions within the context of tandem mass spectrometry was initiated in this program and has grown to be a major research area in this group. Most of the focus in ion/ion chemistry has been on proton transfer and electron transfer reactions and some of the work in the previous budget period was directed, in particular, to fundamental aspects of electron transfer. Recently, the discovery of selective covalent ion/ion reactions has opened up new vistas for research that will expand significantly the capabilities of tandem mass spectrometry for the structural characterization of polyatomic ions.« less

Interstellar H3+

PubMed Central

Oka, Takeshi

2006-01-01

Protonated molecular hydrogen, H3+, is the simplest polyatomic molecule. It is the most abundantly produced interstellar molecule, next only to H2, although its steady state concentration is low because of its extremely high chemical reactivity. H3+ is a strong acid (proton donor) and initiates chains of ion-molecule reactions in interstellar space thus leading to formation of complex molecules. Here, I summarize the understandings on this fundamental species in interstellar space obtained from our infrared observations since its discovery in 1996 and discuss the recent observations and analyses of H3+ in the Central Molecular Zone near the Galatic center that led to a revelation of a vast amount of warm and diffuse gas existing in the region. PMID:16894171

Computer program for calculating and fitting thermodynamic functions

NASA Technical Reports Server (NTRS)

Mcbride, Bonnie J.; Gordon, Sanford

1992-01-01

A computer program is described which (1) calculates thermodynamic functions (heat capacity, enthalpy, entropy, and free energy) for several optional forms of the partition function, (2) fits these functions to empirical equations by means of a least-squares fit, and (3) calculates, as a function of temperture, heats of formation and equilibrium constants. The program provides several methods for calculating ideal gas properties. For monatomic gases, three methods are given which differ in the technique used for truncating the partition function. For diatomic and polyatomic molecules, five methods are given which differ in the corrections to the rigid-rotator harmonic-oscillator approximation. A method for estimating thermodynamic functions for some species is also given.

Use of a single trajectory to study product energy partitioning in unimolecular dissociation: mass effects for halogenated alkanes.

PubMed

Sun, Lipeng; Park, Kyoyeon; Song, Kihyung; Setser, Donald W; Hase, William L

2006-02-14

A single trajectory (ST) direct dynamics approach is compared with quasiclassical trajectory (QCT) direct dynamics calculations for determining product energy partitioning in unimolecular dissociation. Three comparisons are made by simulating C(2)H(5)F-->HF + C(2)H(4) product energy partitioning for the MP26-31G(*) and MP26-311 + + G(**) potential energy surfaces (PESs) and using the MP26-31G(*) PES for C(2)H(5)F dissociation as a model to simulate CHCl(2)CCl(3)-->HCl + C(2)Cl(4) dissociation and its product energy partitioning. The trajectories are initiated at the transition state with fixed energy in reaction-coordinate translation E(t) (double dagger). The QCT simulations have zero-point energy (ZPE) in the vibrational modes orthogonal to the reaction coordinate, while there is no ZPE for the STs. A semiquantitative agreement is obtained between the ST and QCT average percent product energy partitionings. The ST approach is used to study mass effects for product energy partitioning in HX(X = F or Cl) elimination from halogenated alkanes by using the MP26-31G(*) PES for C(2)H(5)F dissociation and varying the masses of the C, H, and F atoms. There is, at most, only a small mass effect for partitioning of energy to HX vibration and rotation. In contrast, there are substantial mass effects for partitioning to relative translation and the polyatomic product's vibration and rotation. If the center of mass of the polyatomic product is located away from the C atom from which HX recoils, the polyatomic has substantial rotation energy. Polyatomic products, with heavy atoms such as Cl atoms replacing the H atoms, receive substantial vibration energy that is primarily transferred to the wag-bend motions. For E(t) (double dagger) of 1.0 kcalmol, the ST calculations give average percent partitionings to relative translation, polyatomic vibration, polyatomic rotation, HX vibration, and HX rotation of 74.9%, 6.8%, 1.5%, 14.4%, and 2.4% for C(2)H(5)F dissociation and 39.7%, 38.1%, 0.2%, 16.1%, and 5.9% for a model of CHCl(2)CCl(3) dissociation.

Computation of Thermally Perfect Properties of Oblique Shock Waves

NASA Technical Reports Server (NTRS)

Tatum, Kenneth E.

1996-01-01

A set of compressible flow relations describing flow properties across oblique shock waves, derived for a thermally perfect, calorically imperfect gas, is applied within the existing thermally perfect gas (TPG) computer code. The relations are based upon a value of cp expressed as a polynomial function of temperature. The updated code produces tables of compressible flow properties of oblique shock waves, as well as the original properties of normal shock waves and basic isentropic flow, in a format similar to the tables for normal shock waves found in NACA Rep. 1135. The code results are validated in both the calorically perfect and the calorically imperfect, thermally perfect temperature regimes through comparisons with the theoretical methods of NACA Rep. 1135, and with a state-of-the-art computational fluid dynamics code. The advantages of the TPG code for oblique shock wave calculations, as well as for the properties of isentropic flow and normal shock waves, are its ease of use, and its applicability to any type of gas (monatomic, diatomic, triatomic, polyatomic, or any specified mixture thereof).

Electron Scattering Studies of Gas Phase Molecular Structure at High Temperature

NASA Astrophysics Data System (ADS)

Mawhorter, Richard J., Jr.

A high precision counting electron diffraction study of the structure of gaseous sulfur dioxide as a function of temperature from 300(DEGREES) to 1000(DEGREES)K is presented. The results agree well with current theory, and yield insight into the effects of anharmonicity on molecular structure. Another aspect of molecular structure is the molecular charge density distribution. The difference (DELTA)(sigma) is between the electron scattering cross sections for the actual molecule and independent atom model (IAM) are a sensitive measure of the change in this distribution due to bond formation. These difference cross sections have been calculated using ab initio methods, and the results for a wide range of simple polyatomic molecules are presented. Such calculations are routinely done for a single, fixed molecular geometry, an approach which neglects the effects of the vibrational motion of real molecules. The effect of vibrational averaging is studied in detail for the three normal vibrational modes of H(,2)O in the ground state. The effects are small, lending credence to the practice of comparing cross sections calculated at a fixed geometry with inherently averaged experimental data. The efficacy of the standard formula used to account for vibrational averaging in the IAM is also examined. Finally, the nature of the ionic bond is probed with an experimental study of the structure of alkali chlorides, NaCl, KCl, RbCl, and CsCl, in the gas phase. Temperatures from 840-960(DEGREES)K were required to achieve the necessary vapor pressures of approximately 0.01 torr. A planar rhombic structure for the dimer molecule is confirmed, with a fairly uniform decrease of the chlorine-alkali-chlorine angle as the alkalis increase in size. The experiment also yields information on the amount of dimer present in the vapor, and these results are compared with thermodynamic values.

Mass Dependency of Isotope Fractionation of Gases Under Thermal Gradient and Its Possible Implications for Planetary Atmosphere Escaping Process

NASA Technical Reports Server (NTRS)

Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard

2014-01-01

Physical processes that unmix elements/isotopes of gas molecules involve phase changes, diffusion (chemical or thermal), effusion and gravitational settling. Some of those play significant roles for the evolution of chemical and isotopic compositions of gases in planetary bodies which lead to better understanding of surface paleoclimatic conditions, e.g. gas bubbles in Antarctic ice, and planetary evolution, e.g. the solar-wind erosion induced gas escaping from exosphere on terrestrial planets.. A mass dependent relationship is always expected for the kinetic isotope fractionations during these simple physical processes, according to the kinetic theory of gases by Chapman, Enskog and others [3-5]. For O-bearing (O16, -O17, -O18) molecules the alpha O-17/ alpha O-18 is expected at 0.5 to 0.515, and for S-bearing (S32,-S33. -S34, -S36) molecules, the alpha S-33/ alpha S-34 is expected at 0.5 to 0.508, where alpha is the isotope fractionation factor associated with unmixing processes. Thus, one isotope pair is generally proxied to yield all the information for the physical history of the gases. However, we recently] reported the violation of mass law for isotope fractionation among isotope pairs of multiple isotope system during gas diffusion or convection under thermal gradient (Thermal Gradient Induced Non-Mass Dependent effect, TGI-NMD). The mechanism(s) that is responsible to such striking observation remains unanswered. In our past studies, we investigated polyatomic molecules, O2 and SF6, and we suggested that nuclear spin effect could be responsible to the observed NMD effect in a way of changing diffusion coefficients of certain molecules, owing to the fact of negligible delta S-36 anomaly for SF6.. On the other hand, our results also showed that for both diffusion and convection under thermal gradient, this NMD effect is increased by lower gas pressure, bigger temperature gradient and lower average temperature, which indicate that the nuclear spin effect may not be the significant contributor as the energies involved in the hyperfine effect are much smaller than those with molecular collisions, especially under convective conditions.

Surface patterning of GaAs under irradiation with very heavy polyatomic Au ions

NASA Astrophysics Data System (ADS)

Bischoff, L.; Böttger, R.; Heinig, K.-H.; Facsko, S.; Pilz, W.

2014-08-01

Self-organization of surface patterns on GaAs under irradiation with heavy polyatomic Au ions has been observed. The patterns depend on the ion mass, and the substrate temperature as well as the incidence angle of the ions. At room temperature, under normal incidence the surface remains flat, whereas above 200 °C nanodroplets of Ga appear after irradiation with monatomic, biatomic as well as triatomic Au ions of kinetic energies in the range of 10-30 keV per atom. In the intermediate temperature range of 100-200 °C meander- and dot-like patterns form, which are not related to Ga excess. Under oblique ion incidence up to 45° from the surface normal, at room temperature the surface remains flat for mon- and polyatomic Au ions. For bi- and triatomic ions in the range of 60° ≤ α ≤ 70° ripple patterns have been found, which become shingle-like for α ≥ 80°, whereas the surface remains flat for monatomic ions.

Calculations on Isotope Separation by Laser Induced Photodissociation of Polyatomic Molecules. Final Report

DOE R&D Accomplishments Database

Lamb, W. E. Jr.

1978-11-01

This report describes research on the theory of isotope separation produced by the illumination of polyatomic molecules by intense infrared laser radiation. Newton`s equations of motion were integrated for the atoms of the SF{sub 6} molecule including the laser field interaction. The first year`s work has been largely dedicated to obtaining a suitable interatomic potential valid for arbitrary configurations of the seven particles. This potential gives the correct symmetry of the molecule, the equilibrium configuration, the frequencies of the six distinct normal modes of oscillation and the correct (or assumed) value of the total potential energy of the molecule. Other conditions can easily be imposed in order to obtain a more refined potential energy function, for example, by making allowance for anharmonicity data. A suitable expression was also obtained for the interaction energy between a laser field and the polyatomic molecule. The electromagnetic field is treated classically, and it would be easily possible to treat the cases of time dependent pulses, frequency modulation and noise.

Molecular extended thermodynamics of rarefied polyatomic gases and wave velocities for increasing number of moments

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

Arima, Takashi, E-mail: tks@stat.nitech.ac.jp; Mentrelli, Andrea, E-mail: andrea.mentrelli@unibo.it; Ruggeri, Tommaso, E-mail: tommaso.ruggeri@unibo.it

Molecular extended thermodynamics of rarefied polyatomic gases is characterized by two hierarchies of equations for moments of a suitable distribution function in which the internal degrees of freedom of a molecule is taken into account. On the basis of physical relevance the truncation orders of the two hierarchies are proven to be not independent on each other, and the closure procedures based on the maximum entropy principle (MEP) and on the entropy principle (EP) are proven to be equivalent. The characteristic velocities of the emerging hyperbolic system of differential equations are compared to those obtained for monatomic gases and themore » lower bound estimate for the maximum equilibrium characteristic velocity established for monatomic gases (characterized by only one hierarchy for moments with truncation order of moments N) by Boillat and Ruggeri (1997) (λ{sub (N)}{sup E,max})/(c{sub 0}) ⩾√(6/5 (N−1/2 )),(c{sub 0}=√(5/3 k/m T)) is proven to hold also for rarefied polyatomic gases independently from the degrees of freedom of a molecule. -- Highlights: •Molecular extended thermodynamics of rarefied polyatomic gases is studied. •The relation between two hierarchies of equations for moments is derived. •The equivalence of maximum entropy principle and entropy principle is proven. •The characteristic velocities are compared to those of monatomic gases. •The lower bound of the maximum characteristic velocity is estimated.« less

Polyatomic ions from a high current ion implanter driven by a liquid metal ion source.

PubMed

Pilz, W; Laufer, P; Tajmar, M; Böttger, R; Bischoff, L

2017-12-01

High current liquid metal ion sources are well known and found their first application as field emission electric propulsion thrusters in space technology. The aim of this work is the adaption of such kind of sources in broad ion beam technology. Surface patterning based on self-organized nano-structures on, e.g., semiconductor materials formed by heavy mono- or polyatomic ion irradiation from liquid metal (alloy) ion sources (LMAISs) is a very promising technique. LMAISs are nearly the only type of sources delivering polyatomic ions from about half of the periodic table elements. To overcome the lack of only very small treated areas by applying a focused ion beam equipped with such sources, the technology taken from space propulsion systems was transferred into a large single-end ion implanter. The main component is an ion beam injector based on high current LMAISs combined with suited ion optics allocating ion currents in the μA range in a nearly parallel beam of a few mm in diameter. Different types of LMAIS (needle, porous emitter, and capillary) are presented and characterized. The ion beam injector design is specified as well as the implementation of this module into a 200 kV high current ion implanter operating at the HZDR Ion Beam Center. Finally, the obtained results of large area surface modification of Ge using polyatomic Bi 2 + ions at room temperature from a GaBi capillary LMAIS will be presented and discussed.

Polyatomic ions from a high current ion implanter driven by a liquid metal ion source

NASA Astrophysics Data System (ADS)

Pilz, W.; Laufer, P.; Tajmar, M.; Böttger, R.; Bischoff, L.

2017-12-01

High current liquid metal ion sources are well known and found their first application as field emission electric propulsion thrusters in space technology. The aim of this work is the adaption of such kind of sources in broad ion beam technology. Surface patterning based on self-organized nano-structures on, e.g., semiconductor materials formed by heavy mono- or polyatomic ion irradiation from liquid metal (alloy) ion sources (LMAISs) is a very promising technique. LMAISs are nearly the only type of sources delivering polyatomic ions from about half of the periodic table elements. To overcome the lack of only very small treated areas by applying a focused ion beam equipped with such sources, the technology taken from space propulsion systems was transferred into a large single-end ion implanter. The main component is an ion beam injector based on high current LMAISs combined with suited ion optics allocating ion currents in the μA range in a nearly parallel beam of a few mm in diameter. Different types of LMAIS (needle, porous emitter, and capillary) are presented and characterized. The ion beam injector design is specified as well as the implementation of this module into a 200 kV high current ion implanter operating at the HZDR Ion Beam Center. Finally, the obtained results of large area surface modification of Ge using polyatomic Bi2+ ions at room temperature from a GaBi capillary LMAIS will be presented and discussed.

Constructing polyatomic potential energy surfaces by interpolating diabatic Hamiltonian matrices with demonstration on green fluorescent protein chromophore

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

Park, Jae Woo; Rhee, Young Min, E-mail: ymrhee@postech.ac.kr; Department of Chemistry, Pohang University of Science and Technology

2014-04-28

Simulating molecular dynamics directly on quantum chemically obtained potential energy surfaces is generally time consuming. The cost becomes overwhelming especially when excited state dynamics is aimed with multiple electronic states. The interpolated potential has been suggested as a remedy for the cost issue in various simulation settings ranging from fast gas phase reactions of small molecules to relatively slow condensed phase dynamics with complex surrounding. Here, we present a scheme for interpolating multiple electronic surfaces of a relatively large molecule, with an intention of applying it to studying nonadiabatic behaviors. The scheme starts with adiabatic potential information and its diabaticmore » transformation, both of which can be readily obtained, in principle, with quantum chemical calculations. The adiabatic energies and their derivatives on each interpolation center are combined with the derivative coupling vectors to generate the corresponding diabatic Hamiltonian and its derivatives, and they are subsequently adopted in producing a globally defined diabatic Hamiltonian function. As a demonstration, we employ the scheme to build an interpolated Hamiltonian of a relatively large chromophore, para-hydroxybenzylidene imidazolinone, in reference to its all-atom analytical surface model. We show that the interpolation is indeed reliable enough to reproduce important features of the reference surface model, such as its adiabatic energies and derivative couplings. In addition, nonadiabatic surface hopping simulations with interpolation yield population transfer dynamics that is well in accord with the result generated with the reference analytic surface. With these, we conclude by suggesting that the interpolation of diabatic Hamiltonians will be applicable for studying nonadiabatic behaviors of sizeable molecules.« less

Macroscopic descriptions of rarefied gases from the elimination of fast variables

NASA Astrophysics Data System (ADS)

Dellar, Paul J.

2007-10-01

The Boltzmann equation describing a dilute monatomic gas is equivalent to an infinite hierarchy of evolution equations for successive moments of the distribution function. The five moments giving the macroscopic mass, momentum, and energy densities are unaffected by collisions between atoms, while all other moments naturally evolve on a fast collisional time scale. We show that the macroscopic equations of Chen, Rao, and Spiegel [Phys. Lett. A 271, 87 (2000)], like the familiar Navier-Stokes-Fourier equations, emerge from using a systematic procedure to eliminate the higher moments, leaving closed evolution equations for the five moments unaffected by collisions. The two equation sets differ through their treatment of contributions from the temperature to the momentum and energy fluxes. Using moment equations offers a definitive treatment of the Prandtl number problem using model collision operators, greatly reduces the labor of deriving equations for different collision operators, and clarifies the role of solvability conditions applied to the distribution function. The original Chen-Rao-Spiegel approach offers greatly improved agreement with experiments for the phase speed of ultrasound, but when corrected to match the Navier-Stokes-Fourier equations at low frequencies, it then underestimates the phase speed at high frequencies. Our introduction of a translational temperature, as in the kinetic theory of polyatomic gases, motivates a distinction in the energy flux between advection of internal energy and the work done by the pressure. Exploiting this distinction yields macroscopic equations that offer further improvement in agreement with experimental data, and arise more naturally as an approximation to the infinite hierarchy of evolution equations for moments.

The effects of focusing power on TEA CO2 laser-induced gas breakdown and the consequent pulse shaping effects

NASA Astrophysics Data System (ADS)

Beheshtipour, Saleheh; Safari, Ebrahim; Majdabadi, Abbas; Silakhori, Kaveh

2018-02-01

Transversely Excited Atmospheric (TEA) CO2 laser pulses were used in order to generate an optical breakdown in a variety of mono- and polyatomic molecules using different focusing powers. The dependence of the spark kernel geometry and the transmitted pulse shapes on the focusing power as well as the pressure, molecular weight, and ionization energy of the gases was investigated in detail. Partial removal of the transmitted pulse tail in the 0.05-2.6 μs range together with shortened spikes in the 10-60 ns range has been observed by applying a 2.5 cm focal length lens for all the gases. At higher focal lengths, this effect is only incompletely observed for He gas. Spatial-temporal analyses of the laser beams and the relevant plasma plumes indicate that this behavior is due to the drop in the plasma density below the critical level, before the laser pulse tail is completed.

General features of the dissociative recombination of polyatomic molecules

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

Pratt, S. T.; Jungen, Ch.; Schneider, I. F.

We discuss some aspects of a simple expression for the low-energy dissociative recombination cross section that applies when the recombination process is dominated by the indirect mechanism. In most previous applications, this expression has been applied to capture into vibrationally excited Rydberg states with the assumption that capture is always followed by prompt dissociation. Here we consider the dissociative recombination of larger polyatomic ions and electrons. More specifically, we consider capture into electronically core-excited Rydberg states, and begin to assess its potential importance for larger systems.

General features of the dissociative recombination of polyatomic molecules

DOE PAGES

Pratt, S. T.; Jungen, Ch.; Schneider, I. F.; ...

2015-01-29

We discuss some aspects of a simple expression for the low-energy dissociative recombination cross section that applies when the recombination process is dominated by the indirect mechanism. In most previous applications, this expression has been applied to capture into vibrationally excited Rydberg states with the assumption that capture is always followed by prompt dissociation. Here we consider the dissociative recombination of larger polyatomic ions and electrons. More specifically, we consider capture into electronically core-excited Rydberg states, and begin to assess its potential importance for larger systems.

A molecular theory of liquid interfaces.

PubMed

Kovalenko, Andriy; Hirata, Fumio

2005-04-21

We propose a site site generalization of the Lovett-Mow-Buff-Wertheim integro-differential equation for the one-particle density distributions to polyatomic fluids. The method provides microscopic description of liquid interfaces of molecular fluids and solutions. It uses the inhomogeneous site-site direct correlation function of molecular fluid consistently constructed by nonlinear interpolation between the homogeneous ones. The site site correlations of the coexisting bulk phases are obtained from the reference interaction site model (RISM) integral equation with our closure approximation. For illustration, we calculated the structure of the planar liquid-vapor as well as liquid-liquid interfaces of n-hexane and methanol at ambient conditions.

Characterising molecules for fundamental physics: an accurate spectroscopic model of methyltrioxorhenium derived from new infrared and millimetre-wave measurements.

PubMed

Asselin, Pierre; Berger, Yann; Huet, Thérèse R; Margulès, Laurent; Motiyenko, Roman; Hendricks, Richard J; Tarbutt, Michael R; Tokunaga, Sean K; Darquié, Benoît

2017-02-08

Precise spectroscopic analysis of polyatomic molecules enables many striking advances in physical chemistry and fundamental physics. We use several new high-resolution spectroscopic devices to improve our understanding of the rotational and rovibrational structure of methyltrioxorhenium (MTO), the achiral parent of a family of large oxorhenium compounds that are ideal candidate species for a planned measurement of parity violation in chiral molecules. Using millimetre-wave and infrared spectroscopy in a pulsed supersonic jet, a cryogenic buffer gas cell, and room temperature absorption cells, we probe the ground state and the Re[double bond, length as m-dash]O antisymmetric and symmetric stretching excited states of both CH 3 187 ReO 3 and CH 3 185 ReO 3 isotopologues in the gas phase with unprecedented precision. By extending the rotational spectra to the 150-300 GHz range, we characterize the ground state rotational and hyperfine structure up to J = 43 and K = 41, resulting in refinements to the rotational, quartic and hyperfine parameters, and the determination of sextic parameters and a centrifugal distortion correction to the quadrupolar hyperfine constant. We obtain rovibrational data for temperatures between 6 and 300 K in the 970-1015 cm -1 range, at resolutions down to 8 MHz and accuracies of 30 MHz. We use these data to determine more precise excited-state rotational, Coriolis and quartic parameters, as well as the ground-state centrifugal distortion parameter D K of the 187 Re isotopologue. We also account for hyperfine structure in the rovibrational transitions and hence determine the upper state rhenium atom quadrupole coupling constant eQq'.

Computation of Thermally Perfect Compressible Flow Properties

NASA Technical Reports Server (NTRS)

Witte, David W.; Tatum, Kenneth E.; Williams, S. Blake

1996-01-01

A set of compressible flow relations for a thermally perfect, calorically imperfect gas are derived for a value of c(sub p) (specific heat at constant pressure) expressed as a polynomial function of temperature and developed into a computer program, referred to as the Thermally Perfect Gas (TPG) code. The code is available free from the NASA Langley Software Server at URL http://www.larc.nasa.gov/LSS. The code produces tables of compressible flow properties similar to those found in NACA Report 1135. Unlike the NACA Report 1135 tables which are valid only in the calorically perfect temperature regime the TPG code results are also valid in the thermally perfect, calorically imperfect temperature regime, giving the TPG code a considerably larger range of temperature application. Accuracy of the TPG code in the calorically perfect and in the thermally perfect, calorically imperfect temperature regimes are verified by comparisons with the methods of NACA Report 1135. The advantages of the TPG code compared to the thermally perfect, calorically imperfect method of NACA Report 1135 are its applicability to any type of gas (monatomic, diatomic, triatomic, or polyatomic) or any specified mixture of gases, ease-of-use, and tabulated results.

Predicting absorption and dispersion in acoustics by direct simulation Monte Carlo: Quantum and classical models for molecular relaxation.

PubMed

Hanford, Amanda D; O'Connor, Patrick D; Anderson, James B; Long, Lyle N

2008-06-01

In the current study, real gas effects in the propagation of sound waves are simulated using the direct simulation Monte Carlo method for a wide range of frequencies. This particle method allows for treatment of acoustic phenomena at high Knudsen numbers, corresponding to low densities and a high ratio of the molecular mean free path to wavelength. Different methods to model the internal degrees of freedom of diatomic molecules and the exchange of translational, rotational and vibrational energies in collisions are employed in the current simulations of a diatomic gas. One of these methods is the fully classical rigid-rotor/harmonic-oscillator model for rotation and vibration. A second method takes into account the discrete quantum energy levels for vibration with the closely spaced rotational levels classically treated. This method gives a more realistic representation of the internal structure of diatomic and polyatomic molecules. Applications of these methods are investigated in diatomic nitrogen gas in order to study the propagation of sound and its attenuation and dispersion along with their dependence on temperature. With the direct simulation method, significant deviations from continuum predictions are also observed for high Knudsen number flows.

Discrete Velocity Models for Polyatomic Molecules Without Nonphysical Collision Invariants

NASA Astrophysics Data System (ADS)

Bernhoff, Niclas

2018-05-01

An important aspect of constructing discrete velocity models (DVMs) for the Boltzmann equation is to obtain the right number of collision invariants. Unlike for the Boltzmann equation, for DVMs there can appear extra collision invariants, so called spurious collision invariants, in plus to the physical ones. A DVM with only physical collision invariants, and hence, without spurious ones, is called normal. The construction of such normal DVMs has been studied a lot in the literature for single species, but also for binary mixtures and recently extensively for multicomponent mixtures. In this paper, we address ways of constructing normal DVMs for polyatomic molecules (here represented by that each molecule has an internal energy, to account for non-translational energies, which can change during collisions), under the assumption that the set of allowed internal energies are finite. We present general algorithms for constructing such models, but we also give concrete examples of such constructions. This approach can also be combined with similar constructions of multicomponent mixtures to obtain multicomponent mixtures with polyatomic molecules, which is also briefly outlined. Then also, chemical reactions can be added.

Silicon isotope ratio measurements by inductively coupled plasma tandem mass spectrometry for alteration studies of nuclear waste glasses.

PubMed

Gourgiotis, Alkiviadis; Ducasse, Thomas; Barker, Evelyne; Jollivet, Patrick; Gin, Stéphane; Bassot, Sylvain; Cazala, Charlotte

2017-02-15

High-level, long-lived nuclear waste arising from spent fuel reprocessing is vitrified in silicate glasses for final disposal in deep geologic formations. In order to better understand the mechanisms driving glass dissolution, glass alteration studies, based on silicon isotope ratio monitoring of 29 Si-doped aqueous solutions, were carried out in laboratories. This work explores the capabilities of the new type of quadrupole-based ICP-MS, the Agilent 8800 tandem quadrupole ICP-MS/MS, for accurate silicon isotope ratio determination for alteration studies of nuclear waste glasses. In order to avoid silicon polyatomic interferences, a new analytical method was developed using O 2 as the reaction gas in the Octopole Reaction System (ORS), and silicon isotopes were measured in mass-shift mode. A careful analysis of the potential polyatomic interferences on SiO + and SiO 2 + ion species was performed, and we found that SiO + ion species suffer from important polyatomic interferences coming from the matrix of sample and standard solutions (0.5M HNO 3 ). For SiO 2 + , no interferences were detected, and thus, these ion species were chosen for silicon isotope ratio determination. A number of key settings for accurate isotope ratio analysis like, detector dead time, integration time, number of sweeps, wait time offset, memory blank and instrumental mass fractionation, were considered and optimized. Particular attention was paid to the optimization of abundance sensitivity of the quadrupole mass filter before the ORS. We showed that poor abundance sensitivity leads to a significant shift of the data away from the Exponential Mass Fractionation Law (EMFL) due to the spectral overlaps of silicon isotopes combined with different oxygen isotopes (i.e. 28 Si 16 O 18 O + , 30 Si 16 O 16 O + ). The developed method was validated by measuring a series of reference solutions with different 29 Si enrichment. Isotope ratio trueness, uncertainty and repeatability were found to be <0.2%, <0.5% and <0.6%, respectively. These performances meet the requirements of the studies of nuclear glasses alteration and open up possibilities to use this method for precise determination of silicon content in natural samples by Isotope Dilution. Copyright © 2016 Elsevier B.V. All rights reserved.

Kinetics and thermochemistry of polyatomic free radicals: New results and new understandings

NASA Technical Reports Server (NTRS)

Gutman, David; Slagle, Irene R.

1990-01-01

An experimental facility for the study of the chemical kinetics of polyatomic free radicals is described which consists of a heatable tubular reactor coupled to a photoionization mass spectrometer. Its use in different kinds of chemical kinetic studies is also discussed. Examples presented include studies of the C2H3 + O2, C2H3 + HC1, CH3 + O, and CH3 + CH3 reactions. The heat of formation of C2H3 was obtained from the results of the study of the C2H3 + HC1 reaction.

New Cs sputter ion source with polyatomic ion beams for secondary ion mass spectrometry applications

NASA Astrophysics Data System (ADS)

Belykh, S. F.; Palitsin, V. V.; Veryovkin, I. V.; Kovarsky, A. P.; Chang, R. J. H.; Adriaens, A.; Dowsett, M. G.; Adams, F.

2007-08-01

A simple design for a cesium sputter ion source compatible with vacuum and ion-optical systems as well as with electronics of the commercially available Cameca IMS-4f instrument is reported. This ion source has been tested with the cluster primary ions of Sin- and Cun-. Our experiments with surface characterization and depth profiling conducted to date demonstrate improvements of the analytical capabilities of the secondary ion mass spectrometry instrument due to the nonadditive enhancement of secondary ion emission and shorter ion ranges of polyatomic projectiles compared to atomic ones with the same impact energy.

Polyatomic interferences on high precision uranium isotope ratio measurements by MC-ICP-MS: Applications to environmental sampling for nuclear safeguards

DOE PAGES

Pollington, Anthony D.; Kinman, William S.; Hanson, Susan K.; ...

2015-09-04

Modern mass spectrometry and separation techniques have made measurement of major uranium isotope ratios a routine task; however accurate and precise measurement of the minor uranium isotopes remains a challenge as sample size decreases. One particular challenge is the presence of isobaric interferences and their impact on the accuracy of minor isotope 234U and 236U measurements. Furthermore, we present techniques used for routine U isotopic analysis of environmental nuclear safeguards samples and evaluate polyatomic interferences that negatively impact accuracy as well as methods to mitigate their impacts.

Computation of Electron Impact Ionization Cross sections of Iron Hydrogen Clusters - Relevance in Fusion Plasmas

NASA Astrophysics Data System (ADS)

Patel, Umang; Joshipura, K. N.

2017-04-01

Plasma-wall interaction (PWI) is one of the key issues in nuclear fusion research. In nuclear fusion devices, such as the JET tokamak or the ITER, first-wall materials will be directly exposed to plasma components. Erosion of first-wall materials is a consequence of the impact of hydrogen and its isotopes as main constituents of the hot plasma. Besides the formation of gas-phase atomic species in various charge states, di- and polyatomic molecular species are expected to be formed via PWI processes. These compounds may profoundly disturb the fusion plasma, may lead to unfavorable re-deposition of materials and composites in other areas of the vessel. Interaction between atoms, molecules as well transport of impurities are of interest for modelling of fusion plasma. Qion by electron impact are such process also important in low temperature plasma processing, astrophysics etc. We reported electron impact Qionfor iron hydrogen clusters, FeHn (n = 1 to 10) from ionization threshold to 2000 eV. A semi empirical approach called Complex Scattering Potential - Ionization Contribution (CSP-ic) has been employed for the reported calculation. In context of fusion relevant species Qion were reported for beryllium and its hydrides, tungsten and its oxides and cluster of beryllium-tungsten by Huber et al.. Iron hydrogen clusters are another such species whose Qion were calculated through DM and BEB formalisms, same has been compared with present calculations.

Linearization of calibration curves by aerosol carrier effect of CCl 4 vapor in electrothermal vaporization inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Kántor, Tibor; de Loos-Vollebregt, Margaretha T. C.

2005-03-01

Carbon tetrachloride vapor as gaseous phase modifier in a graphite furnace electrothermal vaporizer (GFETV) converts heavy volatile analyte forms to volatile and medium volatile chlorides and produces aerosol carrier effect, the latter being a less generally recognized benefit. However, the possible increase of polyatomic interferences in inductively coupled plasma mass spectrometry (GFETV-ICP-MS) by chlorine and carbon containing species due to CCl 4 vapor introduction has been discouraging with the use of low resolution, quadrupole type MS equipment. Being aware of this possible handicap, it was aimed at to investigate the feasibility of the use of this halogenating agent in ICP-MS with regard of possible hazards to the instrument, and also to explore the advantages under these specific conditions. With sample gas flow (inner gas flow) rate not higher than 900 ml min -1 Ar in the torch and 3 ml min -1 CCl 4 vapor flow rate in the furnace, the long-term stability of the instrument was ensured and the following benefits by the halocarbon were observed. The non-linearity error (defined in the text) of the calibration curves (signal versus mass functions) with matrix-free solution standards was 30-70% without, and 1-5% with CCl 4 vapor introduction, respectively, at 1 ng mass of Cu, Fe, Mn and Pb analytes. The sensitivity for these elements increased by 2-4-fold with chlorination, while the relative standard deviation (RSD) was essentially the same (2-5%) for the two cases in comparison. A vaporization temperature of 2650 °C was required for Cr in Ar atmosphere, while 2200 °C was sufficient in Ar + CCl 4 atmosphere to attain complete vaporization. Improvements in linear response and sensitivity were the highest for this least volatile element. The pyrolytic graphite layer inside the graphite tube was protected by the halocarbon, and tube life time was further increased by using traces of hydrocarbon vapor in the external sheath gas of the graphite furnace. Details of the modification of the gas supply for HGA-600MS furnace and the design of the volatilization device are described.

Various continuum approaches for studying shock wave structure in carbon dioxide

NASA Astrophysics Data System (ADS)

Alekseev, I. V.; Kosareva, A. A.; Kustova, E. V.; Nagnibeda, E. A.

2018-05-01

Shock wave structure in carbon dioxide is studied using different continuum models within the framework of one-temperature thermal equilibrium flow description. Navier-Stokes and Euler equations as well as commonly used Rankine-Hugoniot equations with different specific heat ratios are used to find the gas-dynamic parameters behind the shock wave. The accuracy of the Rankine-Hugoniot relations in polyatomic gases is assessed, and it is shown that they give a considerable error in the predicted values of fluid-dynamic variables. The effect of bulk viscosity on the shock wave structure in CO2 is evaluated. Taking into account bulk viscosity yields a significant increase in the shock wave width; for the complete model, the shock wave thickness varies non-monotonically with the Mach number.

Evaporation of Lennard-Jones fluids.

PubMed

Cheng, Shengfeng; Lechman, Jeremy B; Plimpton, Steven J; Grest, Gary S

2011-06-14

Evaporation and condensation at a liquid/vapor interface are ubiquitous interphase mass and energy transfer phenomena that are still not well understood. We have carried out large scale molecular dynamics simulations of Lennard-Jones (LJ) fluids composed of monomers, dimers, or trimers to investigate these processes with molecular detail. For LJ monomers in contact with a vacuum, the evaporation rate is found to be very high with significant evaporative cooling and an accompanying density gradient in the liquid domain near the liquid/vapor interface. Increasing the chain length to just dimers significantly reduces the evaporation rate. We confirm that mechanical equilibrium plays a key role in determining the evaporation rate and the density and temperature profiles across the liquid/vapor interface. The velocity distributions of evaporated molecules and the evaporation and condensation coefficients are measured and compared to the predictions of an existing model based on kinetic theory of gases. Our results indicate that for both monatomic and polyatomic molecules, the evaporation and condensation coefficients are equal when systems are not far from equilibrium and smaller than one, and decrease with increasing temperature. For the same reduced temperature T/T(c), where T(c) is the critical temperature, these two coefficients are higher for LJ dimers and trimers than for monomers, in contrast to the traditional viewpoint that they are close to unity for monatomic molecules and decrease for polyatomic molecules. Furthermore, data for the two coefficients collapse onto a master curve when plotted against a translational length ratio between the liquid and vapor phase.

Studies of electron-polyatomic-molecule collisions Applications to e-CH4

NASA Technical Reports Server (NTRS)

Lima, M. A. P.; Gibson, T. L.; Mckoy, V.; Huo, W. M.

1985-01-01

The first application of the Schwinger multichannel formulation to low-energy electron collisions with a nonlinear polyatomic target is reported. Integral and differential cross sections are obtained for e-CH4 collisions from 3 to 20 eV at the static-plus-exchange interaction level. In these studies, the exchange potential is directly evaluated and not approximated by local models. An interesting feature of the small-angle differential cross section is ascribed to polarization effects and not reproduced at the static-plus-exchange level. These differential cross sections are found to be in reasonable agreement with existing measurements at 7.5 eV and higher energies.

Proposed Molecular Beam Determination of Energy Partition in the Photodissociation of Polyatomic Molecules

DOE R&D Accomplishments Database

Zare, P. N.; Herschbach, D. R.

1964-01-29

Conventional photochemical experiments give no information about the partitioning of energy between translational recoil and internal excitation of the fragment molecules formed in photodissociation of a polyatomic molecule. In a molecular beam experiment, it becomes possible to determine the energy partition from the form of the laboratory angular distribution of one of the photodissociation products. A general kinematic analysis is worked out in detail, and the uncertainty introduced by the finite angular resolution of the apparatus and the velocity spread in the parent beam is examined. The experimental requirements are evaluated for he photolysis of methyl iodide by the 2537 angstrom Hg line.

Negative ions of polyatomic molecules.

PubMed Central

Christophorou, L G

1980-01-01

In this paper general concepts relating to, and recent advances in, the study of negative ions of polyatomic molecules area discussed with emphasis on halocarbons. The topics dealt with in the paper are as follows: basic electron attachment processes, modes of electron capture by molecules, short-lived transient negative ions, dissociative electron attachment to ground-state molecules and to "hot" molecules (effects of temperature on electron attachment), parent negative ions, effect of density, nature, and state of the medium on electron attachment, electron attachment to electronically excited molecules, the binding of attached electrons to molecules ("electron affinity"), and the basic and the applied significance of negative-ion studies. PMID:7428744

Metal-assisted SIMS and cluster ion bombardment for ion yield enhancement

NASA Astrophysics Data System (ADS)

Heile, A.; Lipinsky, D.; Wehbe, N.; Delcorte, A.; Bertrand, P.; Felten, A.; Houssiau, L.; Pireaux, J.-J.; De Mondt, R.; Van Vaeck, L.; Arlinghaus, H. F.

2008-12-01

In addition to structural information, a detailed knowledge of the local chemical environment proves to be of ever greater importance, for example for the development of new types of materials as well as for specific modifications of surfaces and interfaces in multiple fields of materials science or various biomedical and chemical applications. But the ongoing miniaturization and therefore reduction of the amount of material available for analysis constitute a challenge to the detection limits of analytical methods. In the case of time-of-flight secondary ion mass spectrometry (TOF-SIMS), several methods of secondary ion yield enhancement have been proposed. This paper focuses on the investigation of the effects of two of these methods, metal-assisted SIMS and polyatomic primary ion bombardment. For this purpose, thicker layers of polystyrene (PS), both pristine and metallized with different amounts of gold, were analyzed using monoatomic (Ar +, Ga +, Xe +, Bi +) and polyatomic (SF 5+, Bi 3+, C 60+) primary ions. It was found that polyatomic ions generally induce a significant increase of the secondary ion yield. On the other hand, with gold deposition, a yield enhancement can only be detected for monoatomic ion bombardment.

Overset grid implementation of the complex Kohn variational method for electron-polyatomic molecule scattering

NASA Astrophysics Data System (ADS)

McCurdy, C. William; Lucchese, Robert L.; Greenman, Loren

2017-04-01

The complex Kohn variational method, which represents the continuum wave function in each channel using a combination of Gaussians and Bessel or Coulomb functions, has been successful in numerous applications to electron-polyatomic molecule scattering and molecular photoionization. The hybrid basis representation limits it to relatively low energies (< 50 eV) , requires an approximation to exchange matrix elements involving continuum functions, and hampers its coupling to modern electronic structure codes for the description of correlated target states. We describe a successful implementation of the method using completely adaptive overset grids to describe continuum functions, in which spherical subgrids are placed on every atomic center to complement a spherical master grid that describes the behavior at large distances. An accurate method for applying the free-particle Green's function on the grid eliminates the need to operate explicitly with the kinetic energy, enabling a rapidly convergent Arnoldi algorithm for solving linear equations on the grid, and no approximations to exchange operators are made. Results for electron scattering from several polyatomic molecules will be presented. Army Research Office, MURI, WN911NF-14-1-0383 and U. S. DOE DE-SC0012198 (at Texas A&M).

Rotational dynamics of polyatomic ions in aqueous solutions: From continuum model to mode-coupling theory, aided by computer simulations.

PubMed

Banerjee, Puja; Bagchi, Biman

2018-06-14

Due to the presence of the rotational mode and the distributed surface charges, the dynamical behavior of polyatomic ions in water differs considerably from those of the monatomic ions. However, their fascinating dynamical properties have drawn scant attention. We carry out theoretical and computational studies of a series of well-known polyatomic ions, namely, sulfate, nitrate, and acetate ions. All three ions exhibit different rotational diffusivity, with that of the nitrate ion being considerably larger than the other two. They all defy the hydrodynamic laws of size dependence. Study of the local structure around the ions provides valuable insight into the origin of these differences. We carry out a detailed study of the rotational diffusion of these ions by extensive computer simulation and by using the theoretical approaches of the dielectric friction developed by Fatuzzo-Mason (FM) and Nee-Zwanzig (NZ), and subsequently generalized by Alavi and Waldeck. A critical element of the FM-NZ theory is the decomposition of the total rotational friction, ζ Rot , into Stokes and dielectric parts. The study shows a dominant role of dielectric friction in the sense that if the ions are made neutral, the nature of diffusion changes and the values become much larger. Our analyses further reveal that the decomposition of total friction into the Stokes and dielectric friction breaks down for sulfate ions but remains semi-quantitatively valid for nitrate and acetate ions. We discuss the relationship between translational and rotational dielectric friction on rigid spherical ions. We develop a self-consistent mode-coupling theory (SC-MCT) formalism that could provide a unified view of rotational friction of polyatomic ions in polar medium. Our SC-MCT shows that the breakdown can be attributed to the change in the microscopic structural features. The mode-coupling theory helps in elucidating the role of coupling between translational and rotational motion of these ions. In fact, these two motions self-consistently determine the value of each other. The reference interaction site model-based MCT suggests an interesting relation between the torque-torque and the force-force time correlation function with the proportionality constant being determined by the geometry and the charge distribution of the polyatomic molecule. We point out several parallelisms between the theories of translational and rotation friction calculations of ions in polar liquids.

Millimeter-wave Absorption Studies of Molecules in Diffuse Clouds

NASA Astrophysics Data System (ADS)

Lucas, Robert; Liszt, Harvey S.

1999-10-01

With IRAM instruments in the last few years, we have been using compact extragalactic millimeter wave radio sources as background objects to study the absorption spectrum of diffuse interstellar gas at millimeter wavelengths. The molecular content of interstellar gas has turned out to be unexpectedly rich. Simple polyatomic molecules such as HCO+, C2H are quite ubiquitous near the Galactic plane (beta < 15o), and many species are detected in some directions (CO, HCO+, H2CO, HCN, HNC, CN, C2H, C3H2, H2S, CS, HCS+, SO, SiO). Remarkable proportionality relations are found between related species such as HCO+ and OH, or CN, HCN and HNC. The high abundance of some species is still a challenge for current models of diffuse cloud chemistry. A factor of 10 increase in the sensitivity will make such studies achievable in denser clouds, where the chemistry is still more active and where abundances are nowadays only available by emission measurements, and thus subject to uncertainties due to sometimes poorly understood line formation and excitation conditions.

Femtosecond response of polyatomic molecules to ultra-intense hard X-rays.

PubMed

Rudenko, A; Inhester, L; Hanasaki, K; Li, X; Robatjazi, S J; Erk, B; Boll, R; Toyota, K; Hao, Y; Vendrell, O; Bomme, C; Savelyev, E; Rudek, B; Foucar, L; Southworth, S H; Lehmann, C S; Kraessig, B; Marchenko, T; Simon, M; Ueda, K; Ferguson, K R; Bucher, M; Gorkhover, T; Carron, S; Alonso-Mori, R; Koglin, J E; Correa, J; Williams, G J; Boutet, S; Young, L; Bostedt, C; Son, S-K; Santra, R; Rolles, D

2017-06-01

X-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions. Many imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 10 20 watts per square centimetre). However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption, which in a heteronuclear molecular system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge. In serial femtosecond crystallography of biological objects-an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure-the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects and has been suggested as a way of phasing the diffraction data. On the basis of experiments using either soft or less-intense hard X-rays, it is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 10 20 watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.

Femtosecond response of polyatomic molecules to ultra-intense hard X-rays

DOE PAGES

Rudenko, A.; Inhester, L.; Hanasaki, K.; ...

2017-05-31

We report x-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions. Many imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 10 20 watts per square centimetre). However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption, which in a heteronuclear molecularmore » system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge. In serial femtosecond crystallography of biological objects—an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure—the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects and has been suggested as a way of phasing the diffraction data. On the basis of experiments using either soft or less-intense hard X-rays, it is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 10 20 watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Fnally, our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.« less

Femtosecond response of polyatomic molecules to ultra-intense hard X-rays

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

Rudenko, A.; Inhester, L.; Hanasaki, K.

We report x-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions. Many imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 10 20 watts per square centimetre). However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption, which in a heteronuclear molecularmore » system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge. In serial femtosecond crystallography of biological objects—an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure—the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects and has been suggested as a way of phasing the diffraction data. On the basis of experiments using either soft or less-intense hard X-rays, it is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 10 20 watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Fnally, our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.« less

A density functional theory based approach for predicting melting points of ionic liquids

DOE PAGES

Chen, Lihua; Bryantsev, Vyacheslav S.

2017-01-17

Accurate prediction of melting points of ILs is important both from the fundamental point of view and from the practical perspective for screening ILs with low melting points and broadening their utilization in a wider temperature range. In this work, we present an ab initio approach to calculating melting points of ILs with known crystal structures and illustrate its application for a series of 11 ILs containing imidazolium/pyrrolidinium cations and halide/polyatomic fluoro-containing anions. The melting point is determined as a temperature at which the Gibbs free energy of fusion is zero. The Gibbs free energy of fusion can be expressedmore » through the use of the Born-Fajans-Haber cycle via the lattice free energy of forming a solid IL from gaseous phase ions and the sum of the solvation free energies of ions comprising IL. Dispersion-corrected density functional theory (DFT) involving (semi)local (PBE-D3) and hybrid exchange-correlation (HSE06-D3) functionals is applied to estimate the lattice enthalpy, entropy, and free energy. The ions solvation free energies are calculated with the SMD-generic-IL solvation model at the M06-2X/6-31+G(d) level of theory under standard conditions. The melting points of ILs computed with the HSE06-D3 functional are in good agreement with the experimental data, with a mean absolute error of 30.5 K and a mean relative error of 8.5%. The model is capable of accurately reproducing the trends in melting points upon variation of alkyl substituents in organic cations and replacement one anion by another. The results verify that the lattice energies of ILs containing polyatomic fluoro-containing anions can be approximated reasonably well using the volume-based thermodynamic approach. However, there is no correlation of the computed lattice energies with molecular volume for ILs containing halide anions. Moreover, entropies of solid ILs follow two different linear relationships with molecular volume for halides and polyatomic fluoro-containing anions. As a result, continuous progress in predicting crystal structures of organic salts with halide anions will be a key factor for successful prediction of melting points with no prior knowledge of the crystal structure.« less

A density functional theory based approach for predicting melting points of ionic liquids

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

Chen, Lihua; Bryantsev, Vyacheslav S.

Accurate prediction of melting points of ILs is important both from the fundamental point of view and from the practical perspective for screening ILs with low melting points and broadening their utilization in a wider temperature range. In this work, we present an ab initio approach to calculating melting points of ILs with known crystal structures and illustrate its application for a series of 11 ILs containing imidazolium/pyrrolidinium cations and halide/polyatomic fluoro-containing anions. The melting point is determined as a temperature at which the Gibbs free energy of fusion is zero. The Gibbs free energy of fusion can be expressedmore » through the use of the Born-Fajans-Haber cycle via the lattice free energy of forming a solid IL from gaseous phase ions and the sum of the solvation free energies of ions comprising IL. Dispersion-corrected density functional theory (DFT) involving (semi)local (PBE-D3) and hybrid exchange-correlation (HSE06-D3) functionals is applied to estimate the lattice enthalpy, entropy, and free energy. The ions solvation free energies are calculated with the SMD-generic-IL solvation model at the M06-2X/6-31+G(d) level of theory under standard conditions. The melting points of ILs computed with the HSE06-D3 functional are in good agreement with the experimental data, with a mean absolute error of 30.5 K and a mean relative error of 8.5%. The model is capable of accurately reproducing the trends in melting points upon variation of alkyl substituents in organic cations and replacement one anion by another. The results verify that the lattice energies of ILs containing polyatomic fluoro-containing anions can be approximated reasonably well using the volume-based thermodynamic approach. However, there is no correlation of the computed lattice energies with molecular volume for ILs containing halide anions. Moreover, entropies of solid ILs follow two different linear relationships with molecular volume for halides and polyatomic fluoro-containing anions. As a result, continuous progress in predicting crystal structures of organic salts with halide anions will be a key factor for successful prediction of melting points with no prior knowledge of the crystal structure.« less

Following the Interstellar History of Carbon: From the Interiors of Stars to the Surfaces of Planets.

PubMed

Ziurys, L M; Halfen, D T; Geppert, W; Aikawa, Y

2016-12-01

The chemical history of carbon is traced from its origin in stellar nucleosynthesis to its delivery to planet surfaces. The molecular carriers of this element are examined at each stage in the cycling of interstellar organic material and their eventual incorporation into solar system bodies. The connection between the various interstellar carbon reservoirs is also examined. Carbon has two stellar sources: supernova explosions and mass loss from evolved stars. In the latter case, the carbon is dredged up from the interior and then ejected into a circumstellar envelope, where a rich and unusual C-based chemistry occurs. This molecular material is eventually released into the general interstellar medium through planetary nebulae. It is first incorporated into diffuse clouds, where carbon is found in polyatomic molecules such as H 2 CO, HCN, HNC, c-C 3 H 2 , and even C 60 + . These objects then collapse into dense clouds, the sites of star and planet formation. Such clouds foster an active organic chemistry, producing compounds with a wide range of functional groups with both gas-phase and surface mechanisms. As stars and planets form, the chemical composition is altered by increasing stellar radiation, as well as possibly by reactions in the presolar nebula. Some molecular, carbon-rich material remains pristine, however, encapsulated in comets, meteorites, and interplanetary dust particles, and is delivered to planet surfaces. Key Words: Carbon isotopes-Prebiotic evolution-Interstellar molecules-Comets-Meteorites. Astrobiology 16, 997-1012.

Experimental and Theoretical Studies of Interstellar Grains. Ph.D. Thesis - Maryland Univ., College Park, 1982

NASA Technical Reports Server (NTRS)

Nuth, J. A., III

1981-01-01

Steady state vibrational populations of SiO and CO in dilute black body radiation fields were calculated as a function of total pressure, kinetic temperature and chemical composition of the gas. Approximate calculations for polyatomic molecules are presented. Vibrational disequilibrium becomes increasingly significant as total pressure and radiation density decrease. Many regions of postulated grain formation are found to be far from thermal equilibrium before the onset of nucleation. Calculations based upon classical nucleation theory or equilibrium thermodynamics are expected to be of dubious value in such regions. Laboratory measurements of the extinction of small iron and magnetite grains were made from 195 nm to 830 nm and found to be consistent with predictions based upon published optical constants. This implies that small iron particles are not responsible for the 220 nm interstellar extinction features. Additional measurements are discussed.

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

Cui, Jie; Krems, Roman V.; Li, Zhiying

We use classical trajectory calculations to study the effects of the interaction strength and the geometry of rigid polyatomic molecules on the formation of long-lived collision complexes at low collision energies. We first compare the results of the calculations for collisions of benzene molecules with rare gas atoms He, Ne, Ar, Kr, and Xe. The comparison illustrates that the mean lifetimes of the collision complexes increase monotonically with the strength of the atom–molecule interaction. We then compare the results of the atom–benzene calculations with those for benzene–benzene collisions. The comparison illustrates that the mean lifetimes of the benzene–benzene collision complexesmore » are significantly reduced due to non-ergodic effects prohibiting the molecules from sampling the entire configuration space. We find that the thermally averaged lifetimes of the benzene–benzene collisions are much shorter than those for Xe with benzene and similar to those for Ne with benzene.« less

Theoretical investigation of gas-surface interactions

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.

1990-01-01

A Dirac-Hartree-Fock code was developed for polyatomic molecules. The program uses integrals over symmetry-adapted real spherical harmonic Gaussian basis functions generated by a modification of the MOLECULE integrals program. A single Gaussian function is used for the nuclear charge distribution, to ensure proper boundary conditions at the nuclei. The Gaussian primitive functions are chosen to satisfy the kinetic balance condition. However, contracted functions which do not necessarily satisfy this condition may be used. The Fock matrix is constructed in the scalar basis and transformed to a jj-coupled 2-spinor basis before diagonalization. The program was tested against numerical results for atoms with a Gaussian nucleus and diatomic molecules with point nuclei. The energies converge on the numerical values as the basis set size is increased. Full use of molecular symmetry (restricted to D sub 2h and subgroups) is yet to be implemented.

Computational design of surfaces, nanostructures and optoelectronic materials

NASA Astrophysics Data System (ADS)

Choudhary, Kamal

Properties of engineering materials are generally influenced by defects such as point defects (vacancies, interstitials, substitutional defects), line defects (dislocations), planar defects (grain boundaries, free surfaces/nanostructures, interfaces, stacking faults) and volume defects (voids). Classical physics based molecular dynamics and quantum physics based density functional theory can be useful in designing materials with controlled defect properties. In this thesis, empirical potential based molecular dynamics was used to study the surface modification of polymers due to energetic polyatomic ion, thermodynamics and mechanics of metal-ceramic interfaces and nanostructures, while density functional theory was used to screen substituents in optoelectronic materials. Firstly, polyatomic ion-beams were deposited on polymer surfaces and the resulting chemical modifications of the surface were examined. In particular, S, SC and SH were deposited on amorphous polystyrene (PS), and C2H, CH3, and C3H5 were deposited on amorphous poly (methyl methacrylate) (PMMA) using molecular dynamics simulations with classical reactive empirical many-body (REBO) potentials. The objective of this work was to elucidate the mechanisms by which the polymer surface modification took place. The results of the work could be used in tailoring the incident energy and/or constituents of ion beam for obtaining a particular chemistry inside the polymer surface. Secondly, a new Al-O-N empirical potential was developed within the charge optimized many body (COMB) formalism. This potential was then used to examine the thermodynamic stability of interfaces and mechanical properties of nanostructures composed of aluminum, its oxide and its nitride. The potentials were tested for these materials based on surface energies, defect energies, bulk phase stability, the mechanical properties of the most stable bulk phase, its phonon properties as well as with a genetic algorithm based evolution theory of the materials to ensure that no spurious phases had a lower cohesive energy. Thirdly, lanthanide doped and co-doped Y3Al5O 12 were examined using density functional theory (DFT) with semi-local and local functional. Theoretical results were compared and validated with experimental data and new co-doped materials with high efficiency were predicted. Finally, Transition element doped CH3NH3PbI3 were studied with DFT for validation of the model with experimental data and replacement materials for toxic Pb were predicted.

An On-the-Fly Surface-Hopping Program JADE for Nonadiabatic Molecular Dynamics of Polyatomic Systems: Implementation and Applications.

PubMed

Du, Likai; Lan, Zhenggang

2015-04-14

Nonadiabatic dynamics simulations have rapidly become an indispensable tool for understanding ultrafast photochemical processes in complex systems. Here, we present our recently developed on-the-fly nonadiabatic dynamics package, JADE, which allows researchers to perform nonadiabatic excited-state dynamics simulations of polyatomic systems at an all-atomic level. The nonadiabatic dynamics is based on Tully's surface-hopping approach. Currently, several electronic structure methods (CIS, TDHF, TDDFT(RPA/TDA), and ADC(2)) are supported, especially TDDFT, aiming at performing nonadiabatic dynamics on medium- to large-sized molecules. The JADE package has been interfaced with several quantum chemistry codes, including Turbomole, Gaussian, and Gamess (US). To consider environmental effects, the Langevin dynamics was introduced as an easy-to-use scheme into the standard surface-hopping dynamics. The JADE package is mainly written in Fortran for greater numerical performance and Python for flexible interface construction, with the intent of providing open-source, easy-to-use, well-modularized, and intuitive software in the field of simulations of photochemical and photophysical processes. To illustrate the possible applications of the JADE package, we present a few applications of excited-state dynamics for various polyatomic systems, such as the methaniminium cation, fullerene (C20), p-dimethylaminobenzonitrile (DMABN) and its primary amino derivative aminobenzonitrile (ABN), and 10-hydroxybenzo[h]quinoline (10-HBQ).

Static time-of-flight secondary ion mass spectrometry analysis of microelectronics related substrates using a polyatomic ion source

NASA Astrophysics Data System (ADS)

Ravanel, X.; Trouiller, C.; Juhel, M.; Wyon, C.; Kwakman, L. F. Tz.; Léonard, D.

2008-12-01

Recent time-of-flight secondary ion mass spectrometry studies using primary ion cluster sources such as Au n+, SF 5+, Bi n+ or C 60+ have shown the great advantages in terms of secondary ion yield enhancement and ion formation efficiency of polyatomic ion sources as compared to monoatomic ion sources like the commonly used Ga +. In this work, the effective gains provided by such a source in the static ToF-SIMS analysis of microelectronics devices were investigated. Firstly, the influence of the number of atoms in the primary cluster ion on secondary ion formation was studied for physically adsorbed di-isononyl phthalate (DNP) (plasticizer) and perfluoropolyether (PFPE). A drastic increase in secondary ion formation efficiency and a much lower detection limit were observed when using a polyatomic primary ion. Moreover, the yield of the higher mass species was much enhanced indicating a lower degree of fragmentation that can be explained by the fact that the primary ion energy is spread out more widely, or that there is a lower energy per incoming ion. Secondly, the influence of the number of Bi atoms in the Bi n primary ion on the information depth was studied using reference thermally grown silicon oxide samples. The information depth provided by a Bi n cluster was shown to be lowered when the number of atoms in the aggregate was increased.

Data Needs for Stellar Atmosphere and Spectrum Modeling

NASA Technical Reports Server (NTRS)

Short, C. I.

2006-01-01

The main data need for stellar atmosphere and spectrum modeling remains atomic and molecular transition data, particularly energy levels and transition cross-sections. We emphasize that data is needed for bound-free (b - f) as well as bound-bound (b - b), and collisional as well as radiative transitions. Data is now needed for polyatomic molecules as well as atoms, ions, and diatomic molecules. In addition, data for the formation of, and extinction due to, liquid and solid phase dust grains is needed. A prioritization of species and data types is presented, and gives emphasis to Fe group elements, and elements important for the investigation of nucleosynthesis and Galactic chemical evolution, such as the -elements and n-capture elements. Special data needs for topical problems in the modeling of cool stars and brown dwarfs are described.

Simplified model to describe the dissociative recombination of linear polyatomic ions of astrophysical interest

NASA Astrophysics Data System (ADS)

Douguet, N.; Fonseca dos Santos, S.; Kokoouline, V.; Orel, A. E.

2015-01-01

We present results of a theoretical study on dissociative recombination of the HCNH+, HCO+ and N2H+ linear polyatomic ions at low energies using a simple theoretical model. In the present study, the indirect mechanism for recombination proceeds through the capture of the incoming electron in excited vibrational Rydberg states attached to the degenerate transverse modes of the linear ions. The strength of the non-adiabatic coupling responsible for dissociative recombination is determined directly from the near-threshold scattering matrix obtained numerically using the complex Kohn variational method. The final cross sections for the process are compared with available experimental data. It is demonstrated that at low collision energies, the major contribution to the dissociative recombination cross section is due to the indirect mechanism.

A BGK model for reactive mixtures of polyatomic gases with continuous internal energy

NASA Astrophysics Data System (ADS)

Bisi, M.; Monaco, R.; Soares, A. J.

2018-03-01

In this paper we derive a BGK relaxation model for a mixture of polyatomic gases with a continuous structure of internal energies. The emphasis of the paper is on the case of a quaternary mixture undergoing a reversible chemical reaction of bimolecular type. For such a mixture we prove an H -theorem and characterize the equilibrium solutions with the related mass action law of chemical kinetics. Further, a Chapman-Enskog asymptotic analysis is performed in view of computing the first-order non-equilibrium corrections to the distribution functions and investigating the transport properties of the reactive mixture. The chemical reaction rate is explicitly derived at the first order and the balance equations for the constituent number densities are derived at the Euler level.

Comprehensive mass spectrometric analysis of novel organic semiconductor molecules

NASA Astrophysics Data System (ADS)

Prada, Svitlana

This work presents a comprehensive mass spectrometry (MS) study of novel organic semiconductor molecules including ion mobility/reactivity measurements and trace elemental analysis. The organic molecules investigated here are important semiconductor materials for molecular electronic devices such as Organic Field-Effect Transistors (OFETs) and Light Emitted Diodes (LED). A high-performance orthogonal time-of flight mass spectrometer (TOF-MS) in combination with a matrix assisted laser desorption/ionization (MALDI) source operating at elevated pressure was used to perform MALDI/TOF analyses of pentacene and some of its derivatives with and without an added matrix. The observation of ion-molecule reactions between "cold" analyte ions and neutral analyte molecules in the gas phase has provided some insight into the mechanism of pentacene cluster formation and its functionalized derivatives. Furthermore, some of the matrices employed to assist the desorption/ionization process of these compounds were observed to influence the outcome via ion-molecule reactions of analyte ions and matrix molecules in the gas phase. The stability and reactivity of the compounds and their clusters in the MALDI plume during gas-phase expansion were evaluated; possible structures of the resulting clusters are discussed. The MALDI/TOF technique was also helpful in distinguishing between two isomeric forms of bis-[(triisopropylsilyl)-ethynyl]-pentacene. Furthermore, we reported ion mobility measurements of functionalized pentacene ions with a modified triple quadrupole mass spectrometer fitted with an ion molecule reactor (IMR). The IMR is equipped with a variable axial electrostatic drift field (ADF) and is able to trap ions for a prolong period of time. These capabilities were successfully employed in the measurement of ion mobilities in different modes of the IMR operation. Theoretical modeling of the drift dynamics and the special localization of the large ion packet was successfully implemented. The contribution of the quadrupole RF field to the drift dynamics also was taken into consideration. The IMR was successfully employed in the ion-molecule reactions study of four functionalized pentacene derivatives such as TIPS, o-TIPS, 6,13-bis-[(triisopropylsilyl)-ethynyl]-pentacene-2,3-dicarbonitrile (TIPS(CN)2), and 6,13-bis-[(triisopropylsilyl)-ethynyl]-pentacene-2,3,9,10-tetracarbonitrile (TIPS(CN)4). Details of the IMR operation in this mode are extensively discussed. The purity of the starting material is one of the most important parameters for the fabrication of a molecular electronic device. We report the method of determination of trace elemental impurities (Li, Na, Al, Mg, Be, Pb, Mn, Co, Ti, Sn, Cu, Cr, V, Zn, Fe, Ca, K and Ni) in organic semiconductor materials, such as Tetracene, Anthracene, Pentacene, TIPS and Rubrene, using an inductively coupled plasma quadrupole mass spectrometer (ICP-MS) fitted with a dynamic reaction cell (DRC). The determination of Fe, Ca, K and Ni in the organic semiconductor materials was carried out using NH3 as a reaction gas in the DRC mode to obviate the effect of polyatomic isobaric interferences. The other trace elements such as Li, Na, Al, Mg, Be, Pb, Mn, Co, Ti, Sn, Cu, Cr, V and Zn have been determined under standard operating conditions.

The Ionic Building Blocks of Life: Exploring Astrochemistry through Mass Spectrometry

NASA Astrophysics Data System (ADS)

Cole, Callie A.

The first polyatomic molecule was discovered in interstellar space in 1968, catalyzing the growth of a new scientific field called astrochemistry. Since its inception, collaborations among laboratory chemists, astrophysical modelers, and observational astronomers in this field have led to the detection of nearly 200 molecules in the interstellar medium (ISM). Similarly, detections of complex biomolecules in cometary dust and meteorites have sparked theories of the origin of terrestrial life, a central focus of the recently-established field of astrobiology. Chemical processing occurs in a variety of environments within our galaxy. The purpose of this work is to explore the chemistry of ions and molecules that are pertinent to a multitude of these regions including nebulae, prestellar cores, and the atmosphere of Saturn's moon, Titan. This thesis presents mass spectrometric investigations of gas-phase ion chemistry that contribute to the fields of both astrochemistry and astrobiology. Many gas-phase chemical reactions are initiated by ions due to the attractive forces induced by their charge on a reacting partner. This attraction often lowers the barriers of ion-neutral reactions, and can lead to high reaction rates even at low temperatures. The ions examined herein increase in complexity starting with simple species (CN-) and concluding with larger biomolecules, the deprotonated nucleobases. This work begins with a series of Flowing Afterglow-Selected Ion Flow Tube (FA-SIFT) experiments exploring nitrogen-containing carbanion (C xNy-) chemistry and the formation of interstellar propene and methyl formate (Chapters 3 and 4). Reactions between CxN y- and H atoms reveal pathways for destruction of several CxN- and CxN2 - anions, but no reactions are observed for CxN3 - species. Two previously-proposed reactions between organic cations and H2 are shown to be immeasurably slow and unlikely to produce propene. Lastly, a reaction pathway producing protonated trans-methyl formate is experimentally and computationally verified. The later chapters describe studies of heterocyclic biomolecules performed using a modified ion trap apparatus. These ions include deprotonated azoles, pyrimidines, and purines (Chapters 5-7). In addition to their reactivity, the dissociation processes and fragments of these anions provide clues to potential precursors and abiotic syntheses. Notably, nearly all fragments observed are detected interstellar species.

Rate constants for the slow Mu + propane abstraction reaction at 300 K by diamagnetic RF resonance.

PubMed

Fleming, Donald G; Cottrell, Stephen P; McKenzie, Iain; Ghandi, Khashayar

2015-08-14

The study of kinetic isotope effects for H-atom abstraction rates by incident H-atoms from the homologous series of lower mass alkanes (CH4, C2H6 and, here, C3H8) provides important tests of reaction rate theory on polyatomic systems. With a mass of only 0.114 amu, the most sensitive test is provided by the rates of the Mu atom. Abstraction of H by Mu can be highly endoergic, due to the large zero-point energy shift in the MuH bond formed, which also gives rise to high activation energies from similar zero-point energy corrections at the transition state. Rates are then far too slow near 300 K to be measured by conventional TF-μSR techniques that follow the disappearance of the spin-polarised Mu atom with time. Reported here is the first measurement of a slow Mu reaction rate in the gas phase by the technique of diamagnetic radio frequency (RF) resonance, where the amplitude of the MuH product formed in the Mu + C3H8 reaction is followed with time. The measured rate constant, kMu = (6.8 ± 0.5) × 10(-16) cm(3) s(-1) at 300 K, is surprisingly only about a factor of three slower than that expected for H + C3H8, indicating a dominant contribution from quantum tunneling in the Mu reaction, consistent with elementary transition state theory calculations of the kMu/kH kinetic isotope effect.

Molecular ion yield enhancement induced by gold deposition in static secondary ion mass spectrometry

NASA Astrophysics Data System (ADS)

Wehbe, Nimer; Delcorte, Arnaud; Heile, Andreas; Arlinghaus, Heinrich F.; Bertrand, Patrick

2008-12-01

Static ToF-SIMS was used to evaluate the effect of gold condensation as a sample treatment prior to analysis. The experiments were carried out with a model molecular layer (Triacontane M = 422.4 Da), upon atomic (In +) and polyatomic (Bi 3+) projectile bombardment. The results indicate that the effect of molecular ion yield improvement using gold metallization exists only under atomic projectile impact. While the quasi-molecular ion (M+Au) + signal can become two orders of magnitude larger than that of the deprotonated molecular ion from the pristine sample under In + bombardment, it barely reaches the initial intensity of (M-H) + when Bi 3+ projectiles are used. The differences observed for mono- and polyatomic primary ion bombardment might be explained by differences in near-surface energy deposition, which influences the sputtering and ionization processes.

Potential energy surfaces and reaction dynamics of polyatomic molecules

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

Chang, Yan-Tyng

A simple empirical valence bond (EVB) model approach is suggested for constructing global potential energy surfaces for reactions of polyatomic molecular systems. This approach produces smooth and continuous potential surfaces which can be directly utilized in a dynamical study. Two types of reactions are of special interest, the unimolecular dissociation and the unimolecular isomerization. For the first type, the molecular dissociation dynamics of formaldehyde on the ground electronic surface is investigated through classical trajectory calculations on EVB surfaces. The product state distributions and vector correlations obtained from this study suggest very similar behaviors seen in the experiments. The intramolecular hydrogenmore » atom transfer in the formic acid dimer is an example of the isomerization reaction. High level ab initio quantum chemistry calculations are performed to obtain optimized equilibrium and transition state dimer geometries and also the harmonic frequencies.« less

An exact variational method to calculate rovibrational spectra of polyatomic molecules with large amplitude motion

NASA Astrophysics Data System (ADS)

Yu, Hua-Gen

2016-08-01

We report a new full-dimensional variational algorithm to calculate rovibrational spectra of polyatomic molecules using an exact quantum mechanical Hamiltonian. The rovibrational Hamiltonian of system is derived in a set of orthogonal polyspherical coordinates in the body-fixed frame. It is expressed in an explicitly Hermitian form. The Hamiltonian has a universal formulation regardless of the choice of orthogonal polyspherical coordinates and the number of atoms in molecule, which is suitable for developing a general program to study the spectra of many polyatomic systems. An efficient coupled-state approach is also proposed to solve the eigenvalue problem of the Hamiltonian using a multi-layer Lanczos iterative diagonalization approach via a set of direct product basis set in three coordinate groups: radial coordinates, angular variables, and overall rotational angles. A simple set of symmetric top rotational functions is used for the overall rotation whereas a potential-optimized discrete variable representation method is employed in radial coordinates. A set of contracted vibrationally diabatic basis functions is adopted in internal angular variables. Those diabatic functions are first computed using a neural network iterative diagonalization method based on a reduced-dimension Hamiltonian but only once. The final rovibrational energies are computed using a modified Lanczos method for a given total angular momentum J, which is usually fast. Two numerical applications to CH4 and H2CO are given, together with a comparison with previous results.

An exact variational method to calculate rovibrational spectra of polyatomic molecules with large amplitude motion

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

Yu, Hua-Gen, E-mail: hgy@bnl.gov

We report a new full-dimensional variational algorithm to calculate rovibrational spectra of polyatomic molecules using an exact quantum mechanical Hamiltonian. The rovibrational Hamiltonian of system is derived in a set of orthogonal polyspherical coordinates in the body-fixed frame. It is expressed in an explicitly Hermitian form. The Hamiltonian has a universal formulation regardless of the choice of orthogonal polyspherical coordinates and the number of atoms in molecule, which is suitable for developing a general program to study the spectra of many polyatomic systems. An efficient coupled-state approach is also proposed to solve the eigenvalue problem of the Hamiltonian using amore » multi-layer Lanczos iterative diagonalization approach via a set of direct product basis set in three coordinate groups: radial coordinates, angular variables, and overall rotational angles. A simple set of symmetric top rotational functions is used for the overall rotation whereas a potential-optimized discrete variable representation method is employed in radial coordinates. A set of contracted vibrationally diabatic basis functions is adopted in internal angular variables. Those diabatic functions are first computed using a neural network iterative diagonalization method based on a reduced-dimension Hamiltonian but only once. The final rovibrational energies are computed using a modified Lanczos method for a given total angular momentum J, which is usually fast. Two numerical applications to CH{sub 4} and H{sub 2}CO are given, together with a comparison with previous results.« less

THE DYNAMICS OF HYDROGEN ATOM ABSTRACTION FROM POLYATOMIC MOLECULES.

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

LIU,X.; SUITS,A.G.

2002-11-21

The hydrogen atom abstraction reaction is an important fundamental process that is extensively involved in atmospheric and combustion chemistry. The practical significance of this type of reaction with polyatomic hydrocarbons is manifest, which has led to many kinetics studies. The detailed understanding of these reactions requires corresponding dynamics studies. However, in comparison to the A + HX {radical} AH + X reactions, the study of the dynamics of A + HR {yields} AH + R reactions is much more difficult, both experimentally and theoretically (here and in the following, A stands for an atom, X stands for a halogen atom,more » and R stands for a polyatomic hydrocarbon radical). The complication stems from the structured R, in contrast to the structureless X. First of all, there are many internal degrees of freedom in R that can participate in the reaction. In addition, there are different carbon sites from which an H atom can be abstracted, and the dynamics are correspondingly different; there are also multiple identical carbon sites in HR and in the picture of a local reaction, there exist competitions between neighboring H atoms, and so on. Despite this complexity, there have been continuing efforts to obtain insight into the dynamics of these reactions. In this chapter, some examples are presented, including the reactions of ground state H, Cl, and O atoms, with particular focus on our recent work using imaging to obtain the differential cross sections for these reactions.« less

Mechanistic insights related to the design and construction of lithium single ion conductors

NASA Astrophysics Data System (ADS)

Spahlinger, Gregory

Lithium single ion conductors are a class of electrolytes, typically designed for lithium ion batteries, with the potential to improve the performance of these batteries. The benefits of single ion conductors arise out of the fact that their immobile anions are not capable of concentrating near the anode of the battery, causing an increase in resistance as the battery is discharged. Unfortunately lithium single ion conductors suffer severe drawbacks in their conductivity which have been attributed to diverse causes. Because of the low success rate of single ion conductors in the literature and previous work in the Baker group, I have chosen to investigate mechanistic questions related to the design and construction of these materials, without engineering new materials. An attractive design strategy for the screening of immobile anion moieties for single ion conductors would be the use of the copper catalyzed alkyne azide (CUAAC) "click" reaction in order to efficiently introduce anions onto a polymer or nanoparticle support in a way that is efficient and tunable. A variable added by this strategy would be the presence of a 1,2,3-triazole moiety which is without any significant precedent in the lithium ion electrolyte literature. In order to assess the impact of the triazole in on the conductivity of an electrolyte a series of model compounds were synthesized containing a variable number of triazoles in an otherwise poly(ethylene glycol) like oligomer chain. The model compounds were subjected to differential scanning calorimetry, electrochemical impedance spectroscopy, and in one case single crystal X-ray diffraction, and solvent shells were modeled for lithium with and without triazoles using ab initio quantum chemistry calculations. It was concluded that the triazole is not significantly stronger than an ether oxygen as a ligand in the electrolytes, however the triazole has a substantial dipole which exerts some deleterious effects on the conductivity, leading to an increase in the Arrhenius activation energy for the process. These effects are balanced by an increase in the pre-exponential factor which leads to "compensation behavior" due to the dependence of that quantity on the dipole density in the material. The observed effect is one of a lower conductivity for the model compounds relative to poly(ethylene glycol)dimethyl ether 500 at room temperature, which converges to roughly the same conductivity around 80 °C. In synthetic studies, attempts were made to synthesize N-triflylpropanesultam (TPS) a five membered heterocycle whose nucleophilic ring opening would yield a desirable anion for use in single ion conductors. TPS proved to be significantly more difficult to open than expected, which prompted a computational study. In order to study the nucleofugality of polyatomic anionic leaving groups derived from oxygen and nitrogen, a contingent of 19 methylating agents consisting of amines or alcohols activated with carbonyl or sulfonyl substituents has been examined via ab initio calculations. Gas phase activation energies for alkylation of ammonia, and gas phase methyl cation affinitys were calculated. It was found that polyatomic anionic leaving groups derived from nitrogen will have higher activation energies for Menshutkin (SN2) alkylation even when they have similar methyl cation affinities. This inherent deficit in the nucleofugality of nitrogen derived leaving groups appears to be a result of the way bond cleavage is synchronized with bond formation to the incoming ammonia nucleophile. Additionally the second sulfonyl group present in a sulfonimide appears to be less effective at activating nitrogen due to a preference for tetrahedral geometries at nitrogen in the transition states of sulfonamide groups. Optimal delocalization of electron density is therefore frustrated due to the symmetry of the leaving group.

Ion-neutral potential models in atmospheric pressure ion mobility time-of-flight mass spectrometry IM(tof)MS.

PubMed

Steiner, Wes E; English, William A; Hill, Herbert H

2006-02-09

The ion mobilities and their respective masses of several classes of amines (primary, secondary, and tertiary) were measured by electrospray ionization atmospheric pressure ion mobility time-of-flight mass spectrometry IM(tof)MS. The experimental data obtained were comparatively analyzed by the one-temperature kinetic theory of Chapman-Enskog. Several theoretical models were used to estimate the collision cross-sections; they include the rigid-sphere, polarization-limit, 12-6-4, and 12-4 potential models. These models were investigated to represent the interaction potentials contained within the collision integral that occurs between the polyatomic ions and the neutral drift gas molecules. The effectiveness of these collision cross-section models on predicting the mobility of these amine ions was explored. Moreover, the effects of drift gas selectivity on the reduced-mass term and in the collision cross-section term was examined. Use of a series of drift gases, namely, helium, neon, argon, nitrogen, and carbon dioxide, made it possible to distinguish between mass effects and polarizability effects. It was found that the modified 12-4 potential that compensates for the center of charge not being at the same location as the centers of mass showed improved agreement over the other collision cross-section models with respect to experimental data.

Fundamental and methodological investigations for the improvement of elemental analysis by inductively coupled plasma mass soectrometry

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

Ebert, Christopher Hysjulien

This dissertation describes a variety of studies meant to improve the analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation (LA) ICP-MS. The emission behavior of individual droplets and LA generated particles in an ICP is studied using a high-speed, high frame rate digital camera. Phenomena are observed during the ablation of silicate glass that would cause elemental fractionation during analysis by ICP-MS. Preliminary work for ICP torch developments specifically tailored for the improvement of LA sample introduction are presented. An abnormal scarcity of metal-argon polyatomic ions (MAr{sup +}) is observed during ICP-MS analysis. Evidence shows thatmore » MAr{sup +} ions are dissociated by collisions with background gas in a shockwave near the tip of the skimmer cone. Method development towards the improvement of LA-ICP-MS for environmental monitoring is described. A method is developed to trap small particles in a collodion matrix and analyze each particle individually by LA-ICP-MS.« less

Dissipation dynamics of field-free molecular alignment for symmetric-top molecules: Ethane (C2H6)

NASA Astrophysics Data System (ADS)

Zhang, H.; Billard, F.; Yu, X.; Faucher, O.; Lavorel, B.

2018-03-01

The field-free molecular alignment of symmetric-top molecules, ethane, induced by intense non-resonant linearly polarized femtosecond laser pulses is investigated experimentally in the presence of collisional relaxation. The dissipation dynamics of field-free molecular alignment are measured by the balanced detection of ultrafast molecular birefringence of ethane gas samples at high pressures. By separating the molecular alignment into the permanent alignment and the transient alignment, the decay time-constants of both components are quantified at the same pressure. It is observed that the permanent alignment always decays slower compared to the transient alignment within the measured pressure range. This demonstrates that the propensity of molecules to conserve the orientation of angular momentum during collisions, previously observed for linear species, is also applicable to symmetric-top molecules. The results of this work provide valuable information for further theoretical understanding of collisional relaxation within nonlinear polyatomic molecules, which are expected to present interesting and nontrivial features due to an extra rotational degree of freedom.

Thermomagnetic torques in polyatomic gases

NASA Technical Reports Server (NTRS)

Hildebrandt, A. F.; Wood, C. T.

1972-01-01

The application of the Scott effect to the dynamics of galactic and stellar rotation is investigated. Efforts were also made to improve the sensitivity and stability of torque measurements and understand the microscopic mechanism that causes the Scott effect.

Simplified model to describe the dissociative recombination of linear polyatomic ions of astrophysical interest

NASA Astrophysics Data System (ADS)

Fonseca Dos Santos, Samantha; Douguet, Nicolas; Kokoouline, Viatcheslav; Orel, Ann

2013-05-01

We will present theoretical results on the dissociative recombination (DR) of the linear polyatomic ions HCNH+, HCO+ and N2H+. Besides their astrophysical importance, they also share the characteristic that at low electronic impact energies their DR process happens via the indirect DR mechanism. We apply a general simplified model successfully implemented to treat the DR process of the highly symmetric non-linear molecules H3+, CH3+, H3O+ and NH4+ to calculated cross sections and DR rates for these ions. The model is based on multichannel quantum defect theory and accounts for all the main ingredients of indirect DR. New perspectives on dissociative recombination of HCO+ will also be discussed, including the possible role of HOC+ in storage ring experimental results. This work is supported by the DOE Office of Basic Energy Science and the National Science Foundation, Grant No's PHY-11-60611 and PHY-10-68785.

Monoatomic and cluster beam effect on ToF-SIMS spectra of self-assembled monolayers on gold

NASA Astrophysics Data System (ADS)

Tuccitto, N.; Torrisi, V.; Delfanti, I.; Licciardello, A.

2008-12-01

Self-assembled monolayers represent well-defined systems that is a good model surface to study the effect of primary ion beams used in secondary ion mass spectrometry. The effect of polyatomic primary beams on both aliphatic and aromatic self-assembled monolayers has been studied. In particular, we analysed the variation of the relative secondary ion yield of both substrate metal-cluster (Au n-) in comparison with the molecular ions (M -) and clusters (M xAu y-) by using Bi +, Bi 3+, Bi 5+ beams. Moreover, the differences in the secondary ion generation efficiency are discussed. The main effect of the cluster beams is related to an increased formation of low-mass fragments and to the enhancement of the substrate related gold-clusters. The results show that, at variance of many other cases, the static SIMS of self-assembled monolayers does not benefit of the use of polyatomic primary ions.

A systematic and feasible method for computing nuclear contributions to electrical properties of polyatomic molecules

NASA Astrophysics Data System (ADS)

Luis, Josep M.; Duran, Miquel; Andrés, José L.

1997-08-01

An analytic method to evaluate nuclear contributions to electrical properties of polyatomic molecules is presented. Such contributions control changes induced by an electric field on equilibrium geometry (nuclear relaxation contribution) and vibrational motion (vibrational contribution) of a molecular system. Expressions to compute the nuclear contributions have been derived from a power series expansion of the potential energy. These contributions to the electrical properties are given in terms of energy derivatives with respect to normal coordinates, electric field intensity or both. Only one calculation of such derivatives at the field-free equilibrium geometry is required. To show the useful efficiency of the analytical evaluation of electrical properties (the so-called AEEP method), results for calculations on water and pyridine at the SCF/TZ2P and the MP2/TZ2P levels of theory are reported. The results obtained are compared with previous theoretical calculations and with experimental values.

Optical Control of Internal Conversion in Pyrazine

NASA Astrophysics Data System (ADS)

Barry, Grant; Singha, Sima; Hu, Zhan; Seideman, Tamar; Gordon, Robert

2014-03-01

We apply quantum control schemes previously reserved for atoms and small molecules to more complex polyatomic molecules. Pyrazine was chosen as a model polyatomic molecule for its well-studied conical intersection seam between the S1 and S2 potential energy surfaces (PESs). Using shaped ultraviolet femtosecond laser pulses, we demonstrate optical control of the excited state dynamics of this molecule under collisionless conditions. This was achieved in a pump-probe experiment by employing a genetic algorithm programmed to suppress ionization of the pyrazine molecules at a preselected time. Our findings indicate that the optimized pulses localize the wave packet for times up to 1.5 ps at a location on the coupled S1/S2 PESs where ionization is energetically forbidden. Our approach is general and does not require knowledge of the molecular Hamiltonian. Funding provided by National Science Foundation grant no. CHE-0848198.

Polyatomic molecular Dirac-Hartree-Fock calculations with Gaussian basis sets

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.; Faegri, Knut, Jr.; Taylor, Peter R.

1990-01-01

Numerical methods have been used successfully in atomic Dirac-Hartree-Fock (DHF) calculations for many years. Some DHF calculations using numerical methods have been done on diatomic molecules, but while these serve a useful purpose for calibration, the computational effort in extending this approach to polyatomic molecules is prohibitive. An alternative more in line with traditional quantum chemistry is to use an analytical basis set expansion of the wave function. This approach fell into disrepute in the early 1980's due to problems with variational collapse and intruder states, but has recently been put on firm theoretical foundations. In particular, the problems of variational collapse are well understood, and prescriptions for avoiding the most serious failures have been developed. Consequently, it is now possible to develop reliable molecular programs using basis set methods. This paper describes such a program and reports results of test calculations to demonstrate the convergence and stability of the method.

Coherent Bichromatic Force Deflection of Molecules

NASA Astrophysics Data System (ADS)

Kozyryev, Ivan; Baum, Louis; Aldridge, Leland; Yu, Phelan; Eyler, Edward E.; Doyle, John M.

2018-02-01

We demonstrate the effect of the coherent optical bichromatic force on a molecule, the polar free radical strontium monohydroxide (SrOH). A dual-frequency retroreflected laser beam addressing the X˜2Σ+↔A˜2Π1 /2 electronic transition coherently imparts momentum onto a cryogenic beam of SrOH. This directional photon exchange creates a bichromatic force that transversely deflects the molecules. By adjusting the relative phase between the forward and counterpropagating laser beams we reverse the direction of the applied force. A momentum transfer of 70 ℏk is achieved with minimal loss of molecules to dark states. Modeling of the bichromatic force is performed via direct numerical solution of the time-dependent density matrix and is compared with experimental observations. Our results open the door to further coherent manipulation of molecular motion, including the efficient optical deceleration of diatomic and polyatomic molecules with complex level structures.

The Use of ICP-MS and IC-ICP-MS in Environmental and Exposure Assesssment

EPA Science Inventory

OVERVIEW: Application of collision/reaction cell interference reduction technology for the minimization of polyatomic interferences in environmental matrices. Improved risk assessments through the use of arsenic speciation approaches that estimate the bio-accessibility asso...

Ab initio potential-energy surfaces for complex, multichannel systems using modified novelty sampling and feedforward neural networks

NASA Astrophysics Data System (ADS)

Raff, L. M.; Malshe, M.; Hagan, M.; Doughan, D. I.; Rockley, M. G.; Komanduri, R.

2005-02-01

A neural network/trajectory approach is presented for the development of accurate potential-energy hypersurfaces that can be utilized to conduct ab initio molecular dynamics (AIMD) and Monte Carlo studies of gas-phase chemical reactions, nanometric cutting, and nanotribology, and of a variety of mechanical properties of importance in potential microelectromechanical systems applications. The method is sufficiently robust that it can be applied to a wide range of polyatomic systems. The overall method integrates ab initio electronic structure calculations with importance sampling techniques that permit the critical regions of configuration space to be determined. The computed ab initio energies and gradients are then accurately interpolated using neural networks (NN) rather than arbitrary parametrized analytical functional forms, moving interpolation or least-squares methods. The sampling method involves a tight integration of molecular dynamics calculations with neural networks that employ early stopping and regularization procedures to improve network performance and test for convergence. The procedure can be initiated using an empirical potential surface or direct dynamics. The accuracy and interpolation power of the method has been tested for two cases, the global potential surface for vinyl bromide undergoing unimolecular decomposition via four different reaction channels and nanometric cutting of silicon. The results show that the sampling methods permit the important regions of configuration space to be easily and rapidly identified, that convergence of the NN fit to the ab initio electronic structure database can be easily monitored, and that the interpolation accuracy of the NN fits is excellent, even for systems involving five atoms or more. The method permits a substantial computational speed and accuracy advantage over existing methods, is robust, and relatively easy to implement.

Matrix-enhanced secondary ion mass spectrometry: The Alchemist's solution?

NASA Astrophysics Data System (ADS)

Delcorte, Arnaud

2006-07-01

Because of the requirements of large molecule characterization and high-lateral resolution SIMS imaging, the possibility of improving molecular ion yields by the use of specific sample preparation procedures has recently generated a renewed interest in the static SIMS community. In comparison with polyatomic projectiles, however, signal enhancement by a matrix might appear to some as the alchemist's versus the scientist's solution to the current problems of organic SIMS. In this contribution, I would like to discuss critically the pros and cons of matrix-enhanced SIMS procedures, in the new framework that includes polyatomic ion bombardment. This discussion is based on a short review of the experimental and theoretical developments achieved in the last decade with respect to the three following approaches: (i) blending the analyte with a low-molecular weight organic matrix (MALDI-type preparation procedure); (ii) mixing alkali/noble metal salts with the analyte; (iii) evaporating a noble metal layer on the analyte sample surface (organic molecules, polymers).

Dual chain perturbation theory: A new equation of state for polyatomic molecules

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

Marshall, Bennett D., E-mail: bennett.d.marshall@exxonmobil.com

In the development of equations of state for polyatomic molecules, thermodynamic perturbation theory (TPT) is widely used to calculate the change in free energy due to chain formation. TPT is a simplification of a more general and exact multi-density cluster expansion for associating fluids. In TPT, all contributions to the cluster expansion which contain chain–chain interactions are neglected. That is, all inter-chain interactions are treated at the reference fluid level. This allows for the summation of the cluster theory in terms of reference system correlation functions only. The resulting theory has been shown to be accurate and has been widelymore » employed as the basis of many engineering equations of state. While highly successful, TPT has many handicaps which result from the neglect of chain–chain contributions. The subject of this document is to move beyond the limitations of TPT and include chain–chain contributions to the equation of state.« less

Multi-layer Lanczos iteration approach to calculations of vibrational energies and dipole transition intensities for polyatomic molecules

DOE PAGES

Yu, Hua-Gen

2015-01-28

We report a rigorous full dimensional quantum dynamics algorithm, the multi-layer Lanczos method, for computing vibrational energies and dipole transition intensities of polyatomic molecules without any dynamics approximation. The multi-layer Lanczos method is developed by using a few advanced techniques including the guided spectral transform Lanczos method, multi-layer Lanczos iteration approach, recursive residue generation method, and dipole-wavefunction contraction. The quantum molecular Hamiltonian at the total angular momentum J = 0 is represented in a set of orthogonal polyspherical coordinates so that the large amplitude motions of vibrations are naturally described. In particular, the algorithm is general and problem-independent. An applicationmore » is illustrated by calculating the infrared vibrational dipole transition spectrum of CH₄ based on the ab initio T8 potential energy surface of Schwenke and Partridge and the low-order truncated ab initio dipole moment surfaces of Yurchenko and co-workers. A comparison with experiments is made. The algorithm is also applicable for Raman polarizability active spectra.« less

The importance of Rydberg orbitals in dissociative ionization of small hydrocarbon molecules in intense laser fields.

PubMed

Jochim, Bethany; Siemering, R; Zohrabi, M; Voznyuk, O; Mahowald, J B; Schmitz, D G; Betsch, K J; Berry, Ben; Severt, T; Kling, Nora G; Burwitz, T G; Carnes, K D; Kling, M F; Ben-Itzhak, I; Wells, E; de Vivie-Riedle, R

2017-06-30

Much of our intuition about strong-field processes is built upon studies of diatomic molecules, which typically have electronic states that are relatively well separated in energy. In polyatomic molecules, however, the electronic states are closer together, leading to more complex interactions. A combined experimental and theoretical investigation of strong-field ionization followed by hydrogen elimination in the hydrocarbon series C 2 D 2 , C 2 D 4 and C 2 D 6 reveals that the photofragment angular distributions can only be understood when the field-dressed orbitals rather than the field-free orbitals are considered. Our measured angular distributions and intensity dependence show that these field-dressed orbitals can have strong Rydberg character for certain orientations of the molecule relative to the laser polarization and that they may contribute significantly to the hydrogen elimination dissociative ionization yield. These findings suggest that Rydberg contributions to field-dressed orbitals should be routinely considered when studying polyatomic molecules in intense laser fields.

Analysis of seven salad rocket (Eruca sativa) accessions: The relationships between sensory attributes and volatile and non-volatile compounds.

PubMed

Bell, Luke; Methven, Lisa; Signore, Angelo; Oruna-Concha, Maria Jose; Wagstaff, Carol

2017-03-01

Sensory and chemical analyses were performed on accessions of rocket (Eruca sativa) to determine phytochemical influences on sensory attributes. A trained panel was used to evaluate leaves, and chemical data were obtained for polyatomic ions, amino acids, sugars and organic acids. These chemical data (and data of glucosinolates, flavonols and headspace volatiles previously reported) were used in Principal Component Analysis (PCA) to determine variables statistically important to sensory traits. Significant differences were observed between samples for polyatomic ion and amino acid concentrations. PCA revealed strong, positive correlations between glucosinolates, isothiocyanates and sulfur compounds with bitterness, mustard, peppery, warming and initial heat mouthfeel traits. The ratio between glucosinolates and sugars inferred reduced perception of bitter aftereffects. We highlight the diversity of E. sativa accessions from a sensory and phytochemical standpoint, and the potential for breeders to create varieties that are nutritionally and sensorially superior to existing ones. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Dynamical tunneling versus fast diffusion for a non-convex Hamiltonian

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

Pittman, S. M.; Tannenbaum, E.; Heller, E. J.

This paper attempts to resolve the issue of the nature of the 0.01-0.1 cm{sup −1} peak splittings observed in high-resolution IR spectra of polyatomic molecules. One hypothesis is that these splittings are caused by dynamical tunneling, a quantum-mechanical phenomenon whereby energy flows between two disconnected regions of phase-space across dynamical barriers. However, a competing classical mechanism for energy flow is Arnol’d diffusion, which connects different regions of phase-space by a resonance network known as the Arnol’d web. The speed of diffusion is bounded by the Nekhoroshev theorem, which guarantees stability on exponentially long time scales if the Hamiltonian is steep.more » Here we consider a non-convex Hamiltonian that contains the characteristics of a molecular Hamiltonian, but does not satisfy the Nekhoroshev theorem. The diffusion along the Arnol’d web is expected to be fast for a non-convex Hamiltonian. While fast diffusion is an unlikely competitor for longtime energy flow in molecules, we show how dynamical tunneling dominates compared to fast diffusion in the nearly integrable regime for a non-convex Hamiltonian, as well as present a new kind of dynamical tunneling.« less

Modeling of carbon dioxide condensation in the high pressure flows using the statistical BGK approach

NASA Astrophysics Data System (ADS)

Kumar, Rakesh; Li, Zheng; Levin, Deborah A.

2011-05-01

In this work, we propose a new heat accommodation model to simulate freely expanding homogeneous condensation flows of gaseous carbon dioxide using a new approach, the statistical Bhatnagar-Gross-Krook method. The motivation for the present work comes from the earlier work of Li et al. [J. Phys. Chem. 114, 5276 (2010)] in which condensation models were proposed and used in the direct simulation Monte Carlo method to simulate the flow of carbon dioxide from supersonic expansions of small nozzles into near-vacuum conditions. Simulations conducted for stagnation pressures of one and three bar were compared with the measurements of gas and cluster number densities, cluster size, and carbon dioxide rotational temperature obtained by Ramos et al. [Phys. Rev. A 72, 3204 (2005)]. Due to the high computational cost of direct simulation Monte Carlo method, comparison between simulations and data could only be performed for these stagnation pressures, with good agreement obtained beyond the condensation onset point, in the farfield. As the stagnation pressure increases, the degree of condensation also increases; therefore, to improve the modeling of condensation onset, one must be able to simulate higher stagnation pressures. In simulations of an expanding flow of argon through a nozzle, Kumar et al. [AIAA J. 48, 1531 (2010)] found that the statistical Bhatnagar-Gross-Krook method provides the same accuracy as direct simulation Monte Carlo method, but, at one half of the computational cost. In this work, the statistical Bhatnagar-Gross-Krook method was modified to account for internal degrees of freedom for multi-species polyatomic gases. With the computational approach in hand, we developed and tested a new heat accommodation model for a polyatomic system to properly account for the heat release of condensation. We then developed condensation models in the framework of the statistical Bhatnagar-Gross-Krook method. Simulations were found to agree well with the experiment for all stagnation pressure cases (1-5 bar), validating the accuracy of the Bhatnagar-Gross-Krook based condensation model in capturing the physics of condensation.

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

NASA Astrophysics Data System (ADS)

Becker, Johanna Sabine

2002-12-01

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.

Line Shifts in Rotational Spectra of Polyatomic Chiral Molecules Caused by the Parity Violating Electroweak Interaction

NASA Astrophysics Data System (ADS)

Stohner, J.; Quack, M.

2009-06-01

Are findings in high-energy physics of any importance in molecular spectroscopy ? The answer is clearly `yes'. Energies of enantiomers were considered as exactly equal in an achiral environment, e.g. the gas phase. Today, however, it is well known that this is not valid. The violation of mirror-image symmetry (suggested theoretically and confirmed experimentally in 1956/57) was established in the field of nuclear, high-energy, and atomic physics since then, and it is also the cause for a non-zero energy difference between enantiomers. We expect today that the violation of mirror-image symmetry (parity violation) influences chemistry of chiral molecules as well as their spectroscopy. Progress has been made in the quantitative theoretical prediction of possible spectroscopic signatures of molecular parity violation. The experimental confirmation of parity violation in chiral molecules is, however, still open. Theoretical studies are helpful for the planning and important for a detailed analysis of rovibrational and tunneling spectra of chiral molecules. We report results on frequency shifts in rotational, vibrational and tunneling spectra of some selected chiral molecules which are studied in our group. If time permits, we shall also discuss critically some recent claims of experimental observations of molecular parity violation in condensed phase systems. T. D. Lee, C. N. Yang, Phys. Rev., 104, 254 (1956) C. S. Wu, E. Ambler, R. W. Hayward, D. D. Hoppes, R. P. Hudson, Phys. Rev., 105, 1413 (1957) M. Quack, Angew. Chem. Intl. Ed., 28, 571 (1989) Angew. Chem. Intl. Ed., 41, 4618 (2002) M. Quack, J. Stohner, Chimia, 59, 530 (2005) M. Quack, J. Stohner, M. Willeke, Ann Rev. Phys. Chem. 59, 741 (2008) M. Quack, J. Stohner, Phys. Rev. Lett., 84, 3807 (2000) M. Quack, J. Stohner, J. Chem. Phys., 119, 11228 (2003) J. Stohner, Int. J. Mass Spectrometry 233, 385 (2004) M. Gottselig, M. Quack, J. Stohner, M. Willeke, Int. J. Mass Spectrometry 233, 373 (2004) R. Berger, G. Laubender, M. Quack, A. Sieben, J. Stohner, M. Willeke, Angew. Chem. Intl. Ed., 44, 3623 (2005) J. Stohner, M. Quack, to be published

Electron molecular ion recombination: product excitation and fragmentation.

PubMed

Adams, Nigel G; Poterya, Viktoriya; Babcock, Lucia M

2006-01-01

Electron-ion dissociative recombination is an important ionization loss process in any ionized gas containing molecular ions. This includes the interstellar medium, circumstellar shells, cometary comae, planetary ionospheres, fusion plasma boundaries, combustion flames, laser plasmas and chemical deposition and etching plasmas. In addition to controlling the ionization density, the process generates many radical species, which can contribute to a parallel neutral chemistry. Techniques used to obtain rate data and product information (flowing afterglows and storage rings) are discussed and recent data are reviewed including diatomic to polyatomic ions and cluster ions. The data are divided into rate coefficients and cross sections, including their temperature/energy dependencies, and quantitative identification of neutral reaction products. The latter involve both ground and electronically excited states and including vibrational excitation. The data from the different techniques are compared and trends in the data are examined. The reactions are considered in terms of the basic mechanisms (direct and indirect processes including tunneling) and recent theoretical developments are discussed. Finally, new techniques are mentioned (for product identification; electrostatic storage rings, including single and double rings; Coulomb explosion) and new ways forward are suggested.

Fine-tuning molecular acoustic models: sensitivity of the predicted attenuation to the Lennard-Jones parameters

NASA Astrophysics Data System (ADS)

Petculescu, Andi G.; Lueptow, Richard M.

2005-01-01

In a previous paper [Y. Dain and R. M. Lueptow, J. Acoust. Soc. Am. 109, 1955 (2001)], a model of acoustic attenuation due to vibration-translation and vibration-vibration relaxation in multiple polyatomic gas mixtures was developed. In this paper, the model is improved by treating binary molecular collisions via fully pairwise vibrational transition probabilities. The sensitivity of the model to small variations in the Lennard-Jones parameters-collision diameter (σ) and potential depth (ɛ)-is investigated for nitrogen-water-methane mixtures. For a N2(98.97%)-H2O(338 ppm)-CH4(1%) test mixture, the transition probabilities and acoustic absorption curves are much more sensitive to σ than they are to ɛ. Additionally, when the 1% methane is replaced by nitrogen, the resulting mixture [N2(99.97%)-H2O(338 ppm)] becomes considerably more sensitive to changes of σwater. The current model minimizes the underprediction of the acoustic absorption peak magnitudes reported by S. G. Ejakov et al. [J. Acoust. Soc. Am. 113, 1871 (2003)]. .

Sudoku Puzzles as Chemistry Learning Tools

ERIC Educational Resources Information Center

Crute, Thomas D.; Myers, Stephanie A.

2007-01-01

A sudoku puzzle was designed that incorporated lists of chemistry terms like polyatomic ions, organic functional groups or strong nucleophiles that students need to learn. It was found that students enjoyed solving such puzzles and also such puzzles made the boring tasks of memorizing basic chemical terms an exciting one.

Method for Predicting Hypergolic Mixture Flammability Limits

DTIC Science & Technology

2017-02-01

liquid phase, in the gas phase, at the liquid / liquid interface and at the gas / liquid interface during hypergolic ignition and the interactions...of what happens in the liquid phase, in the gas phase, at the liquid / liquid interface and at the gas / liquid interface during hypergolic ignition...and the interactions of all these phases. The ignition happens in the gas -phase but products formed here and there (in the liquid phase or at

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

The effect of aged litter materials on polyatomic ion concentrations in fractionated suspended particulate matter from broiler house

USDA-ARS?s Scientific Manuscript database

Inorganic emissions from livestock production and subsequent deposition of these ions can be a major source of pollution, causing nitrogen enrichment, eutrophication, acidification of soils and surface waters, and aerosol formation. In the poultry house, ammonia and hydrogen sulfide emissions can a...

Stabilizing potentials in bound state analytic continuation methods for electronic resonances in polyatomic molecules

DOE PAGES

White, Alec F.; Head-Gordon, Martin; McCurdy, C. William

2017-01-30

The computation of Siegert energies by analytic continuation of bound state energies has recently been applied to shape resonances in polyatomic molecules by several authors. Here, we critically evaluate a recently proposed analytic continuation method based on low order (type III) Padé approximants as well as an analytic continuation method based on high order (type II) Padé approximants. We compare three classes of stabilizing potentials: Coulomb potentials, Gaussian potentials, and attenuated Coulomb potentials. These methods are applied to a model potential where the correct answer is known exactly and to the 2Π g shape resonance of N 2 - whichmore » has been studied extensively by other methods. Both the choice of stabilizing potential and method of analytic continuation prove to be important to the accuracy of the results. We then conclude that an attenuated Coulomb potential is the most effective of the three for bound state analytic continuation methods. With the proper potential, such methods show promise for algorithmic determination of the positions and widths of molecular shape resonances.« less

Variational treatment of electron-polyatomic-molecule scattering calculations using adaptive overset grids

NASA Astrophysics Data System (ADS)

Greenman, Loren; Lucchese, Robert R.; McCurdy, C. William

2017-11-01

The complex Kohn variational method for electron-polyatomic-molecule scattering is formulated using an overset-grid representation of the scattering wave function. The overset grid consists of a central grid and multiple dense atom-centered subgrids that allow the simultaneous spherical expansions of the wave function about multiple centers. Scattering boundary conditions are enforced by using a basis formed by the repeated application of the free-particle Green's function and potential Ĝ0+V ̂ on the overset grid in a Born-Arnoldi solution of the working equations. The theory is shown to be equivalent to a specific Padé approximant to the T matrix and has rapid convergence properties, in both the number of numerical basis functions employed and the number of partial waves employed in the spherical expansions. The method is demonstrated in calculations on methane and CF4 in the static-exchange approximation and compared in detail with calculations performed with the numerical Schwinger variational approach based on single-center expansions. An efficient procedure for operating with the free-particle Green's function and exchange operators (to which no approximation is made) is also described.

Stabilizing potentials in bound state analytic continuation methods for electronic resonances in polyatomic molecules

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

White, Alec F.; Head-Gordon, Martin; McCurdy, C. William

The computation of Siegert energies by analytic continuation of bound state energies has recently been applied to shape resonances in polyatomic molecules by several authors. Here, we critically evaluate a recently proposed analytic continuation method based on low order (type III) Padé approximants as well as an analytic continuation method based on high order (type II) Padé approximants. We compare three classes of stabilizing potentials: Coulomb potentials, Gaussian potentials, and attenuated Coulomb potentials. These methods are applied to a model potential where the correct answer is known exactly and to the 2Π g shape resonance of N 2 - whichmore » has been studied extensively by other methods. Both the choice of stabilizing potential and method of analytic continuation prove to be important to the accuracy of the results. We then conclude that an attenuated Coulomb potential is the most effective of the three for bound state analytic continuation methods. With the proper potential, such methods show promise for algorithmic determination of the positions and widths of molecular shape resonances.« less

Scattering matrix approach to the dissociative recombination of HCO{sup +} and N{sub 2}H{sup +}

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

Fonseca dos Santos, S.; Douguet, N.; Orel, A. E.

We present a theoretical study of the indirect dissociative recombination of linear polyatomic ions at low collisional energies. The approach is based on the computation of the scattering matrix just above the ionization threshold and enables the explicit determination of all diabatic electronic couplings responsible for dissociative recombination. In addition, we use the multi-channel quantum-defect theory to demonstrate the precision of the scattering matrix by reproducing accurately ab initio Rydberg state energies of the neutral molecule. We consider the molecular ions N{sub 2}H{sup +} and HCO{sup +} as benchmark systems of astrophysical interest and improve former theoretical studies, which hadmore » repeatedly produced smaller cross sections than experimentally measured. Specifically, we demonstrate the crucial role of the previously overlooked stretching modes for linear polyatomic ions with large permanent dipole moment. The theoretical cross sections for both ions agree well with experimental data over a wide energy range. Finally, we consider the potential role of the HOC{sup +} isomer in the experimental cross sections of HCO{sup +} at energies below 10 meV.« less

Ion dehydration controls adsorption at the micellar interface: hydrotropic ions.

PubMed

Lima, Filipe S; Andrade, Marcos F C; Mortara, Laura; Gustavo Dias, Luís; Cuccovia, Iolanda M; Chaimovich, Hernan

2017-11-22

The properties of ionic micelles depend on the nature of the counterion, and these effects become more evident as the ion adsorption at the interface increases. Prediction of the relative extent of ion adsorption is required for rational design of ionic micellar aggregates. Unlike the well understood adsorption of monatomic ions, the adsorption of polyatomic ions is not easily predicted. We combined experimental and computational methods to evaluate the affinity of hydrotropic ions, i.e., ions with polar and apolar regions, to the surface of positively charged micelles. We analyzed cationic micelles of dodecyltrimethylammonium and six hydrotropic counterions: methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, acetate, trifluoroacetate and benzoate. Our results demonstrated that the apolar region of hydrotropic ions had the largest influence on micellar properties. The dehydration of the apolar region of hydrotropic ions upon their adsorption at the micellar interface determined the ion adsorption extension, differently to what was expected based on Collins' law of matching affinities. These results may lead to more general models to describe the adsorption of ions, including polyatomic ions, at the micellar interface.

Direct simulation Monte Carlo modeling of relaxation processes in polyatomic gases

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

Pfeiffer, M., E-mail: mpfeiffer@irs.uni-stuttgart.de; Nizenkov, P., E-mail: nizenkov@irs.uni-stuttgart.de; Mirza, A., E-mail: mirza@irs.uni-stuttgart.de

2016-02-15

Relaxation processes of polyatomic molecules are modeled and implemented in an in-house Direct Simulation Monte Carlo code in order to enable the simulation of atmospheric entry maneuvers at Mars and Saturn’s Titan. The description of rotational and vibrational relaxation processes is derived from basic quantum-mechanics using a rigid rotator and a simple harmonic oscillator, respectively. Strategies regarding the vibrational relaxation process are investigated, where good agreement for the relaxation time according to the Landau-Teller expression is found for both methods, the established prohibiting double relaxation method and the new proposed multi-mode relaxation. Differences and applications areas of these two methodsmore » are discussed. Consequently, two numerical methods used for sampling of energy values from multi-dimensional distribution functions are compared. The proposed random-walk Metropolis algorithm enables the efficient treatment of multiple vibrational modes within a time step with reasonable computational effort. The implemented model is verified and validated by means of simple reservoir simulations and the comparison to experimental measurements of a hypersonic, carbon-dioxide flow around a flat-faced cylinder.« less

Direct simulation Monte Carlo modeling of relaxation processes in polyatomic gases

NASA Astrophysics Data System (ADS)

Pfeiffer, M.; Nizenkov, P.; Mirza, A.; Fasoulas, S.

2016-02-01

Relaxation processes of polyatomic molecules are modeled and implemented in an in-house Direct Simulation Monte Carlo code in order to enable the simulation of atmospheric entry maneuvers at Mars and Saturn's Titan. The description of rotational and vibrational relaxation processes is derived from basic quantum-mechanics using a rigid rotator and a simple harmonic oscillator, respectively. Strategies regarding the vibrational relaxation process are investigated, where good agreement for the relaxation time according to the Landau-Teller expression is found for both methods, the established prohibiting double relaxation method and the new proposed multi-mode relaxation. Differences and applications areas of these two methods are discussed. Consequently, two numerical methods used for sampling of energy values from multi-dimensional distribution functions are compared. The proposed random-walk Metropolis algorithm enables the efficient treatment of multiple vibrational modes within a time step with reasonable computational effort. The implemented model is verified and validated by means of simple reservoir simulations and the comparison to experimental measurements of a hypersonic, carbon-dioxide flow around a flat-faced cylinder.

Imaging a multidimensional multichannel potential energy surface: Photodetachment of H(-)(NH3) and NH4 (.).

PubMed

Hu, Qichi; Song, Hongwei; Johnson, Christopher J; Li, Jun; Guo, Hua; Continetti, Robert E

2016-06-28

Probes of the Born-Oppenheimer potential energy surfaces governing polyatomic molecules often rely on spectroscopy for the bound regions or collision experiments in the continuum. A combined spectroscopic and half-collision approach to image nuclear dynamics in a multidimensional and multichannel system is reported here. The Rydberg radical NH4 and the double Rydberg anion NH4 (-) represent a polyatomic system for benchmarking electronic structure and nine-dimensional quantum dynamics calculations. Photodetachment of the H(-)(NH3) ion-dipole complex and the NH4 (-) DRA probes different regions on the neutral NH4 PES. Photoelectron energy and angular distributions at photon energies of 1.17, 1.60, and 2.33 eV compare well with quantum dynamics. Photoelectron-photofragment coincidence experiments indicate dissociation of the nascent NH4 Rydberg radical occurs to H + NH3 with a peak kinetic energy of 0.13 eV, showing the ground state of NH4 to be unstable, decaying by tunneling-induced dissociation on a time scale beyond the present scope of multidimensional quantum dynamics.

Extension of the MIRS computer package for the modeling of molecular spectra: From effective to full ab initio ro-vibrational Hamiltonians in irreducible tensor form

NASA Astrophysics Data System (ADS)

Nikitin, A. V.; Rey, M.; Champion, J. P.; Tyuterev, Vl. G.

2012-07-01

The MIRS software for the modeling of ro-vibrational spectra of polyatomic molecules was considerably extended and improved. The original version [Nikitin AV, Champion JP, Tyuterev VlG. The MIRS computer package for modeling the rovibrational spectra of polyatomic molecules. J Quant Spectrosc Radiat Transf 2003;82:239-49.] was especially designed for separate or simultaneous treatments of complex band systems of polyatomic molecules. It was set up in the frame of effective polyad models by using algorithms based on advanced group theory algebra to take full account of symmetry properties. It has been successfully used for predictions and data fitting (positions and intensities) of numerous spectra of symmetric and spherical top molecules within the vibration extrapolation scheme. The new version offers more advanced possibilities for spectra calculations and modeling by getting rid of several previous limitations particularly for the size of polyads and the number of tensors involved. It allows dealing with overlapping polyads and includes more efficient and faster algorithms for the calculation of coefficients related to molecular symmetry properties (6C, 9C and 12C symbols for C3v, Td, and Oh point groups) and for better convergence of least-square-fit iterations as well. The new version is not limited to polyad effective models. It also allows direct predictions using full ab initio ro-vibrational normal mode Hamiltonians converted into the irreducible tensor form. Illustrative examples on CH3D, CH4, CH3Cl, CH3F and PH3 are reported reflecting the present status of data available. It is written in C++ for standard PC computer operating under Windows. The full package including on-line documentation and recent data are freely available at http://www.iao.ru/mirs/mirs.htm or http://xeon.univ-reims.fr/Mirs/ or http://icb.u-bourgogne.fr/OMR/SMA/SHTDS/MIRS.html and as supplementary data from the online version of the article.

Oxygen transport properties estimation by DSMC-CT simulations

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

Bruno, Domenico; Frezzotti, Aldo; Ghiroldi, Gian Pietro

Coupling DSMC simulations with classical trajectories calculations is emerging as a powerful tool to improve predictive capabilities of computational rarefied gas dynamics. The considerable increase of computational effort outlined in the early application of the method (Koura,1997) can be compensated by running simulations on massively parallel computers. In particular, GPU acceleration has been found quite effective in reducing computing time (Ferrigni,2012; Norman et al.,2013) of DSMC-CT simulations. The aim of the present work is to study rarefied Oxygen flows by modeling binary collisions through an accurate potential energy surface, obtained by molecular beams scattering (Aquilanti, et al.,1999). The accuracy ofmore » the method is assessed by calculating molecular Oxygen shear viscosity and heat conductivity following three different DSMC-CT simulation methods. In the first one, transport properties are obtained from DSMC-CT simulations of spontaneous fluctuation of an equilibrium state (Bruno et al, Phys. Fluids, 23, 093104, 2011). In the second method, the collision trajectory calculation is incorporated in a Monte Carlo integration procedure to evaluate the Taxman’s expressions for the transport properties of polyatomic gases (Taxman,1959). In the third, non-equilibrium zero and one-dimensional rarefied gas dynamic simulations are adopted and the transport properties are computed from the non-equilibrium fluxes of momentum and energy. The three methods provide close values of the transport properties, their estimated statistical error not exceeding 3%. The experimental values are slightly underestimated, the percentage deviation being, again, few percent.« less

Dynamic mapping of conical intersection seams: A general method for incorporating the geometric phase in adiabatic dynamics in polyatomic systems

NASA Astrophysics Data System (ADS)

Xie, Changjian; Malbon, Christopher L.; Yarkony, David R.; Guo, Hua

2017-07-01

The incorporation of the geometric phase in single-state adiabatic dynamics near a conical intersection (CI) seam has so far been restricted to molecular systems with high symmetry or simple model Hamiltonians. This is due to the fact that the ab initio determined derivative coupling (DC) in a multi-dimensional space is not curl-free, thus making its line integral path dependent. In a recent work [C. L. Malbon et al., J. Chem. Phys. 145, 234111 (2016)], we proposed a new and general approach based on an ab initio determined diabatic representation consisting of only two electronic states, in which the DC is completely removable, so that its line integral is path independent in the simply connected domains that exclude the CI seam. Then with the CIs included, the line integral of the single-valued DC can be used to construct the complex geometry-dependent phase needed to exactly eliminate the double-valued character of the real-valued adiabatic electronic wavefunction. This geometry-dependent phase gives rise to a vector potential which, when included in the adiabatic representation, rigorously accounts for the geometric phase in a system with an arbitrary locus of the CI seam and an arbitrary number of internal coordinates. In this work, we demonstrate this approach in a three-dimensional treatment of the tunneling facilitated dissociation of the S1 state of phenol, which is affected by a Cs symmetry allowed but otherwise accidental seam of CI. Here, since the space is three-dimensional rather than two-dimensional, the seam is a curve rather than a point. The nodal structure of the ground state vibronic wavefunction is shown to map out the seam of CI.

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

Study of Polyatomic Dynamics in the Atmosphere.

DTIC Science & Technology

1987-03-25

phere and the Shuttle ram glow. Ihij~pijj erif of th0 . repiir I ds’-vr ihes work carriled nio in the IAIfli V The~ prodi’ j "v of~ t~t electron beam...8217 diatomics-in -mole- Symposium on Molecular Spectroscopy, Ohio State University, Colum- bus , Ohio, June 1935.cules PES for Hj* is used the fundamental

Distortion of liquid film discharging from twin-fluid atomizer

NASA Astrophysics Data System (ADS)

Mehring, C.; Sirignano, W. A.

2001-11-01

The nonlinear distortion and disintegration of a thin liquid film exiting from a two-dimensional twin-fluid atomizer is analyzed numerically. Pulsed gas jets impacting on both sides of the discharging liquid film at the atomizer exit generate dilational and/or sinuous deformations of the film. Both liquid phase and gas phase are inviscid and incompressible. For the liquid phase the so-called long-wavelength approximation is employed yielding a system of unsteady one-dimensional equations for the planar film. Solution of Laplace's equation for the velocity potential yields the gas-phase velocity field on both sides of the liquid stream. Coupling between both phases is described through kinematic and dynamic boundary conditions at the phase interfaces, and includes the solution of the unsteady Bernoulli equation to determine the gas-phase pressure along the interfaces. Both gas- and liquid-phase equations are solved simultaneously. Solution of Laplace's equation for the gas streams is obtained by means of a boundary-element method. Numerical solutions for the liquid phase use the Lax-Wendroff method with Richtmyer splitting. Sheet distortion resulting from the stagnation pressure of the impacting gas jets and subsequent disturbance amplification due to Kelvin-Helmholtz effects are studied for various combinations of gas-pulse timing, gas-jet impact angles, gas-to-liquid-density ratio, liquid-phase Weber number and gas-jet-to-liquid-jet-momentum ratio. Dilational and sinuous oscillations of the liquid are examined and film pinch-off is predicted.

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.

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.

Simple setup for gas-phase H/D exchange mass spectrometry coupled to electron transfer dissociation and ion mobility for analysis of polypeptide structure on a liquid chromatographic time scale.

PubMed

Mistarz, Ulrik H; Brown, Jeffery M; Haselmann, Kim F; Rand, Kasper D

2014-12-02

Gas-phase hydrogen/deuterium exchange (HDX) is a fast and sensitive, yet unharnessed analytical approach for providing information on the structural properties of biomolecules, in a complementary manner to mass analysis. Here, we describe a simple setup for ND3-mediated millisecond gas-phase HDX inside a mass spectrometer immediately after ESI (gas-phase HDX-MS) and show utility for studying the primary and higher-order structure of peptides and proteins. HDX was achieved by passing N2-gas through a container filled with aqueous deuterated ammonia reagent (ND3/D2O) and admitting the saturated gas immediately upstream or downstream of the primary skimmer cone. The approach was implemented on three commercially available mass spectrometers and required no or minor fully reversible reconfiguration of gas-inlets of the ion source. Results from gas-phase HDX-MS of peptides using the aqueous ND3/D2O as HDX reagent indicate that labeling is facilitated exclusively through gaseous ND3, yielding similar results to the infusion of purified ND3-gas, while circumventing the complications associated with the use of hazardous purified gases. Comparison of the solution-phase- and gas-phase deuterium uptake of Leu-Enkephalin and Glu-Fibrinopeptide B, confirmed that this gas-phase HDX-MS approach allows for labeling of sites (heteroatom-bound non-amide hydrogens located on side-chains, N-terminus and C-terminus) not accessed by classical solution-phase HDX-MS. The simple setup is compatible with liquid chromatography and a chip-based automated nanoESI interface, allowing for online gas-phase HDX-MS analysis of peptides and proteins separated on a liquid chromatographic time scale at increased throughput. Furthermore, online gas-phase HDX-MS could be performed in tandem with ion mobility separation or electron transfer dissociation, thus enabling multiple orthogonal analyses of the structural properties of peptides and proteins in a single automated LC-MS workflow.

Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles.

PubMed

Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A

2014-07-23

We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.

Method and system for measuring multiphase flow using multiple pressure differentials

DOEpatents

Fincke, James R.

2001-01-01

An improved method and system for measuring a multiphase flow in a pressure flow meter. An extended throat venturi is used and pressure of the multiphase flow is measured at three or more positions in the venturi, which define two or more pressure differentials in the flow conduit. The differential pressures are then used to calculate the mass flow of the gas phase, the total mass flow, and the liquid phase. The method for determining the mass flow of the high void fraction fluid flow and the gas flow includes certain steps. The first step is calculating a gas density for the gas flow. The next two steps are finding a normalized gas mass flow rate through the venturi and computing a gas mass flow rate. The following step is estimating the gas velocity in the venturi tube throat. The next step is calculating the pressure drop experienced by the gas-phase due to work performed by the gas phase in accelerating the liquid phase between the upstream pressure measuring point and the pressure measuring point in the venturi throat. Another step is estimating the liquid velocity in the venturi throat using the calculated pressure drop experienced by the gas-phase due to work performed by the gas phase. Then the friction is computed between the liquid phase and a wall in the venturi tube. Finally, the total mass flow rate based on measured pressure in the venturi throat is calculated, and the mass flow rate of the liquid phase is calculated from the difference of the total mass flow rate and the gas mass flow rate.

The development of ensemble theory. A new glimpse at the history of statistical mechanics

NASA Astrophysics Data System (ADS)

Inaba, Hajime

2015-12-01

This paper investigates the history of statistical mechanics from the viewpoint of the development of the ensemble theory from 1871 to 1902. In 1871, Ludwig Boltzmann introduced a prototype model of an ensemble that represents a polyatomic gas. In 1879, James Clerk Maxwell defined an ensemble as copies of systems of the same energy. Inspired by H.W. Watson, he called his approach "statistical". Boltzmann and Maxwell regarded the ensemble theory as a much more general approach than the kinetic theory. In the 1880s, influenced by Hermann von Helmholtz, Boltzmann made use of ensembles to establish thermodynamic relations. In Elementary Principles in Statistical Mechanics of 1902, Josiah Willard Gibbs tried to get his ensemble theory to mirror thermodynamics, including thermodynamic operations in its scope. Thermodynamics played the role of a "blind guide". His theory of ensembles can be characterized as more mathematically oriented than Einstein's theory proposed in the same year. Mechanical, empirical, and statistical approaches to foundations of statistical mechanics are presented. Although it was formulated in classical terms, the ensemble theory provided an infrastructure still valuable in quantum statistics because of its generality.

Interaction Between the Broad-Lined Type Ic Supernova 2012ap and Carriers of Diffuse Interstellar Bands

NASA Technical Reports Server (NTRS)

Milisavljevic, Dan; Margutti, Raffaella; Crabtree, Kyle N.; Foster, Jonathan B.; Soderberg, Alicia M.; Fesen, Robert A.; Parrent, Jerod T.; Sanders, Nathan E.; Drout, Maria R.; Kamble, Atish;

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.

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.

Metal atom oxidation laser

DOEpatents

Jensen, R.J.; Rice, W.W.; Beattie, W.H.

1975-10-28

A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides.

Visualization of Potential Energy Function Using an Isoenergy Approach and 3D Prototyping

ERIC Educational Resources Information Center

Teplukhin, Alexander; Babikov, Dmitri

2015-01-01

In our three-dimensional world, one can plot, see, and comprehend a function of two variables at most, V(x,y). One cannot plot a function of three or more variables. For this reason, visualization of the potential energy function in its full dimensionality is impossible even for the smallest polyatomic molecules, such as triatomics. This creates…

Construction of Ligand Group Orbitals for Polyatomics and Transition-Metal Complexes Using an Intuitive Symmetry-Based Approach

ERIC Educational Resources Information Center

Johnson, Adam R.

2013-01-01

A molecular orbital (MO) diagram, especially its frontier orbitals, explains the bonding and reactivity for a chemical compound. It is therefore important for students to learn how to construct one. The traditional methods used to derive these diagrams rely on linear algebra techniques to combine ligand orbitals into symmetry-adapted linear…

Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

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

Soniat, Marielle; Rick, Steven W., E-mail: srick@uno.edu; Kumar, Revati

2015-07-28

The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is amore » hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.« less

Imaging a multidimensional multichannel potential energy surface: Photodetachment of H{sup −}(NH{sub 3}) and NH{sub 4}{sup −}

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

Hu, Qichi; Johnson, Christopher J.; Continetti, Robert E., E-mail: hguo@umn.edu, E-mail: rcontinetti@ucsd.edu

2016-06-28

Probes of the Born-Oppenheimer potential energy surfaces governing polyatomic molecules often rely on spectroscopy for the bound regions or collision experiments in the continuum. A combined spectroscopic and half-collision approach to image nuclear dynamics in a multidimensional and multichannel system is reported here. The Rydberg radical NH{sub 4} and the double Rydberg anion NH{sub 4}{sup −} represent a polyatomic system for benchmarking electronic structure and nine-dimensional quantum dynamics calculations. Photodetachment of the H{sup −}(NH{sub 3}) ion-dipole complex and the NH{sub 4}{sup −} DRA probes different regions on the neutral NH{sub 4} PES. Photoelectron energy and angular distributions at photon energiesmore » of 1.17, 1.60, and 2.33 eV compare well with quantum dynamics. Photoelectron-photofragment coincidence experiments indicate dissociation of the nascent NH{sub 4} Rydberg radical occurs to H + NH{sub 3} with a peak kinetic energy of 0.13 eV, showing the ground state of NH{sub 4} to be unstable, decaying by tunneling-induced dissociation on a time scale beyond the present scope of multidimensional quantum dynamics.« less

Proposal for Laser Cooling of Alkaline Earth Monoalkoxide Free Radicals

NASA Astrophysics Data System (ADS)

Baum, Louis; Kozyryev, Ivan; Matsuda, Kyle; Doyle, John M.

2016-05-01

Cold samples of polyatomic molecules will open new avenues in physics, chemistry, and quantum science. Non-diagonal Franck-Condon factors, technically challenging wavelengths, and the lack of strong electronic transitions inhibit direct laser cooling of nonlinear molecules. We identify a scheme for optical cycling in certain molecules with six or more atoms. Replacing hydrogen in alcohols with an alkaline earth metal (M) leads to alkaline earth monoalkoxide free radicals (MOR), which have favorable properties for laser cooling. M-O bond is very ionic, so the metal orbitals are slightly affected by the nature of R on the ligand. Diagonal Franck-Condon factors, laser accessible transitions, and a small hyperfine structure make MOR molecules suitable for laser cooling. We explore a scheme for optical cycling on the A - X transition of SrOCH3 . Molecules lost to dark vibrational states will be repumped on the B - X transition. Extension to larger species is possible through expansion of the R group since transitions involve the promotion of the metal-centered nonbonding valence electron. We will detail our estimations of the Franck-Condon factors, simulations of the cooling process and describe progress towards the Doppler cooling of MOR polyatomics.

Reduction of polyatomic interferences in ICP-MS by collision/reaction cell (CRC-ICP-MS) techniques

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

Eiden, Greg C; Barinaga, Charles J; Koppenaal, David W

2012-05-01

Polyatomic and other spectral interferences in plasma source mass spectrometry (PSMS) can be dramatically reduced using collision and reaction cells (CRC). These devices have been used for decades in fundamental studies of ion-molecule chemistry, but have only recently been applied to PSMS. Benefits of this approach as applied in inductively coupled plasma MS (ICP-MS) include interference reduction, isobar separation, and thermalization/focusing of ions. Novel ion-molecule chemistry schemes are now routinely designed and empirically evaluated with relative ease. These “chemical resolution” techniques can avert interferences requiring mass spectral resolutions of >600,000 (m/m). Purely physical ion beam processes, including collisional dampening andmore » collisional dissociation, are also employed to provide improved sensitivity, resolution, and spectral simplicity. CRC techniques are now firmly entrenched in current-day ICP-MS technology, enabling unprecedented flexibility and freedom from many spectral interferences. A significant body of applications has now been reported in the literature. CRC techniques are found to be most useful for specialized or difficult analytical needs and situations, and are employed in both single- and multi-element determination modes.« less

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

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.

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.

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.

Determination of Se at low concentration in coal by collision/reaction cell technology inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Henn, Alessandra S.; Rondan, Filipe S.; Mesko, Marcia F.; Mello, Paola A.; Perez, Magali; Armstrong, Joseph; Bullock, Liam A.; Parnell, John; Feldmann, Joerg; Flores, Erico M. M.

2018-05-01

A method is proposed for the determination of selenium at low concentration in coal by collision/reaction cell technology inductively coupled plasma mass spectrometry (CRC-ICP-MS). Samples were decomposed by high pressure microwave-assisted wet digestion (MAWD) using 250 mg of coal, a mixture of 5 mL of 14.4 mol L-1 HNO3 and 1 mL of 40% HF and 70 min of heating program (200 °C and 40 bar). Hydrogen gas used in the collision/reaction cell was investigated to minimize the argon-based interferences at m/z 77, 78 and 80. The rejection parameter (RPq) and the H2 gas flow rate were set to 0.45 and 4.8 mL min-1, respectively. The use of H2 in the cell resulted in other polyatomic interferences, such as 76Ge1H+, 79Br1H+ and 81Br1H+, which impaired Se determination using 77Se, 80Se and 82Se isotopes, thus Se determination was carried out by monitoring only 78Se isotope. Selenium was determined in certified reference materials of coal (NIST 1635 and SARM 20) and an agreement better than 95% was observed between the results obtained by CRC-ICP-MS and the certified values. Under optimized conditions, the instrumental limit of detection was 0.01 μg L-1 and the method limit of detection was 0.01 μg g-1, which was suitable for Se determination at very low concentration in coal.

The Helix Nebula Viewed in HCO+: Large-scale Mapping of the J = 1 → 0 Transition

NASA Astrophysics Data System (ADS)

Zeigler, N. R.; Zack, L. N.; Woolf, N. J.; Ziurys, L. M.

2013-11-01

The J = 1 → 0 transition of HCO+ at 89 GHz has been mapped across the Helix Nebula (NGC 7293) with 70'' spatial resolution (1.68 km s-1 velocity resolution) using the Arizona Radio Observatory 12 m telescope. This work is the first large-scale mapping project of a dense gas tracer (n(H2) ~ 105 cm-3) in old planetary nebulae. Observations of over 200 positions encompassing the classical optical image were conducted with a 3σ noise level of ~20 mK. HCO+ was detected at most positions, often exhibiting multiple velocity components indicative of complex kinematic structures in dense gas. The HCO+ spectra suggest that the Helix is composed of a bipolar, barrel-like structure with red- and blue-shifted halves, symmetric with respect to the central star and oriented ~10° east from the line of sight. A second bipolar, higher velocity outflow exists as well, situated along the direction of the Helix "plumes." The column density of HCO+ across the Helix is N tot ~ 1.5 × 1010-5.0 × 1011 cm-2, with an average value N ave ~ 1 × 1011 cm-2, corresponding to an abundance, relative to H2, of f ~ 1.4 × 10-8. This value is similar to that observed in young PN, and contradicts chemical models, which predict that the abundance of HCO+ decreases with nebular age. This study indicates that polyatomic molecules readily survive the ultraviolet field of the central white dwarf, and can be useful in tracing nebular morphology in the very late stages of stellar evolution.

Theoretical Understanding the Relations of Melting-point Determination Methods from Gibbs Thermodynamic Surface and Applications on Melting Curves of Lower Mantle Minerals

NASA Astrophysics Data System (ADS)

Yin, K.; Belonoshko, A. B.; Zhou, H.; Lu, X.

2016-12-01

The melting temperatures of materials in the interior of the Earth has significant implications in many areas of geophysics. The direct calculations of the melting point by atomic simulations would face substantial hysteresis problem. To overcome the hysteresis encountered in the atomic simulations there are a few different melting-point determination methods available nowadays, which are founded independently, such as the free energy method, the two-phase or coexistence method, and the Z method, etc. In this study, we provide a theoretical understanding the relations of these methods from a geometrical perspective based on a quantitative construction of the volume-entropy-energy thermodynamic surface, a model first proposed by J. Willard Gibbs in 1873. Then combining with an experimental data and/or a previous melting-point determination method, we apply this model to derive the high-pressure melting curves for several lower mantle minerals with less computational efforts relative to using previous methods only. Through this way, some polyatomic minerals at extreme pressures which are almost unsolvable before are calculated fully from first principles now.

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.

Metal atom oxidation laser

DOEpatents

Jensen, R.J.; Rice, W.W.; Beattie, W.H.

1975-10-28

A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides. (auth)

Vibrational Energy in Molecules and Nanoparticles: Applications to Energetic Materials

DTIC Science & Technology

2009-01-30

of vibrational energy in a polyatomic molecule, nitromethane . Work on water and amino acids partially supported by AFOSR are developmental in nature...have characterized the surface vibrations of HMX explosive and their interaction with polymer binders. We have introduced a major improvement in SFG...Vibrational energy in nitromethane and benzene E. Time resolved spectroscopy of chemistry in flash-heated nanoenergetic materials F. Complete

Trace element analysis of human urine collected after administration of Gd-based MRI contrast agents: characterizing spectral interferences using inorganic mass spectrometry

PubMed Central

Steuerwald, Amy J.; Parsons, Patrick J.; Arnason, John G.; Chen, Zhen; Peterson, C. Matthew; Louis, Germaine M. Buck

2013-01-01

Analysis of human urine is commonly used in biomonitoring studies to assess exposure to essential (e.g., Cu, Zn, Se) and non-essential (Pb, Cd, Pt) trace elements. These data are also used in epidemiological studies to evaluate potential associations between trace element exposure and various health outcomes within a population. Today most trace element analyses are typically performed using quadrupole-based inductively coupled plasma mass spectrometry (Q-ICP-MS). However, there is always the potential for spectral interferences with Q-ICP-MS instrumentation, especially when analyzing human specimens that may contain medications and other exogenous substances. Moreover, such xenobiotics may be unknown to the investigators. In a recent study focusing on environmental exposures and endometriosis: Endometriosis: Natural History, Diagnosis, and Outcomes (ENDO Study), urine specimens (n=619) were collected from participating women upon enrollment into the study or prior to surgery or pelvic magnetic resonance imaging (MRI), and analyzed for 21 trace elements by Q-ICP-MS. Here we report on some anomalous results observed for Se and Pt with elevated concentrations up to several orders of magnitude greater than what might be expected based on established reference intervals. Further investigations using Sector Field (SF-) ICP-MS instrumentation led to identification of doubly charged and polyatomic gadolinium (Gd) species traced to a Gd-based contrast agent that was administered to some subjects just prior to urine collection. Specifically, interferences from Gd2+ and several minor polyatomics were identified as interferences on all of the major isotopes of Se including 74Se, 76Se, 77Se, 78Se, 80Se, and 82Se. While trace amounts of Pt were present in the urine, a number of Gd-containing polyatomic species were also evident as major interferences on all isotopes of Pt (190Pt, 192Pt, 194Pt, 195Pt, 196Pt, and 198Pt), including Gd-chlorides, Gd-argides, and Gd-oxides. These observations underscore the importance of considering potential isobaric interferences when interpreting unusual trace element results for clinical specimens. PMID:27397951

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.

Microminiature gas chromatograph

DOEpatents

Yu, Conrad M.

1996-01-01

A microminiature gas chromatograph (.mu.GC) comprising a least one silicon wafer, a gas injector, a column, and a detector. The gas injector has a normally closed valve for introducing a mobile phase including a sample gas in a carrier gas. The valve is fully disposed in the silicon wafer(s). The column is a microcapillary in silicon crystal with a stationary phase and is mechanically connected to receive the mobile phase from the gas injector for the molecular separation of compounds in the sample gas. The detector is mechanically connected to the column for the analysis of the separated compounds of sample gas with electronic means, e.g., ion cell, field emitter and PIN diode.

A New Scaling Law of Resonance in Total Scattering Cross Section in Gases

NASA Astrophysics Data System (ADS)

Raju, Gorur Govinda

2009-10-01

Electrical discharges in gases continue to be an active area of research because of industrial applications such as power systems, environmental clean up, laser technology, semiconductor fabrication etc. A fundamental knowledge of electron-gas neutral interaction is indispensable and, the total scattering cross section is one of the quantities that have been measured extensively. The energy dependence of the total cross sections shows peaks or resonance processes that are operative in the collision process. These peaks and the energies at which they occur are shown to satisfy a broad relationship involving the polarizability and the dipole moment of the target particle. Data on 62 target particles belonging to the following species are analyzed. (Eq 1) Rare gas atoms (Eq 2) Di-atomic molecules with combinations of polar, non-polar, attaching, and non-attaching properties Poly-atomic molecules with combinations of polar, non-polar, attaching, and non-attaching properties. Methods of improving the newly identified scaling law and possible application have been identified. 1 INTRODUCTION: Data on electron-neutral interactions are one of the most fundamental in the study of gaseous electronics and an immense literature, both experimental and theoretical, has become available since about the year 1920. [1-5]. In view of the central role which these data play in all facets of gas discharges and plasma science, it is felt that a critical review of available data is timely, mainly for the community of high voltage engineers and industries connected with plasma science in general. The electron-neutral interaction, often referred to as scattering in the scientific literature, is quantified by using the quantity called the total scattering cross section (QT, m^2). In the literature on cross section, total cross section and total scattering cross section are terms used synonymously and we follow the same practice. A definition may be found in reference [1]. This paper concerns scaling of total cross section of gases at resonance energy and the electron energy at which resonance occurs. The meaning of resonance is briefly explained in the following section. Here, we use the term scaling to relate the two quantities mentioned, namely, the resonance energy and the total cross section at that energy. Consistent with the definition of scaling, if the law proposed holds, one of the two quantities mentioned above may be calculated if the other is known. Such a method is very useful in gas discharge modeling and calculation of breakdown voltages, as more fully explained in the later section of the paper. 2 DESCRIPTION OF RESONANCE: A brief description of resonance phenomena in several types of target particles, viz., atomic, poly atomic, polar, non-polar phenomena are presented. 3 PREVIOUS SCALING LAWS: A common representation of a given characteristic with as few adjustable parameters as possible is generally known as the scaling law. The Paschen curve for breakdown voltage is such a familiar scaling law. With reference to cross sections several attempts have been made to obtain a scaling law, with varying degree of success. If the cross section-energy curve is qualitatively similar without having sharp peaks and oscillations, moderately successful scaling laws may be devised. For example, the ionization cross section- energy curves for most gases follow a general pattern. Several published scaling laws are discussed. 4 A NEW SCALING LAW AND DISCUSSION: In this work the author has compiled the resonance details for more than 60 gasest hat include the range from simple atoms to complex molecules that are polyatomic, dipolar, electron-attaching and isomers. The target particles exhibit a number of distinct features, as far as their total cross section variation with electron energy is concerned as already explained.

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.

System for measuring multiphase flow using multiple pressure differentials

DOEpatents

Fincke, James R.

2003-01-01

An improved method and system for measuring a multi-phase flow in a pressure flow meter. An extended throat venturi is used and pressure of the multi-phase flow is measured at three or more positions in the venturi, which define two or more pressure differentials in the flow conduit. The differential pressures are then used to calculate the mass flow of the gas phase, the total mass flow, and the liquid phase. The system for determining the mass flow of the high void fraction fluid flow and the gas flow includes taking into account a pressure drop experienced by the gas phase due to work performed by the gas phase in accelerating the liquid phase.

Ionic Liquid Fuels for Chemical Propulsion

DTIC Science & Technology

2016-10-31

nucleophilicity in the ionic liquid is critical. Both gas -phase and condensed-phase (CPCM-GIL) density functional theory calculations support the...stability trends in dialkylimidazolium ionic liquids and could be used as a higher accuracy method than the gas -phase DFT approach for predicting thermal...stabilities of ionic liquids in general. One important finding from the comparison of the gas -phase basicities relative to the GIL condensed- phase

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.

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.

Comparing the catalytic oxidation of ethanol at the solid-gas and solid-liquid interfaces over size-controlled Pt nanoparticles: striking differences in kinetics and mechanism.

PubMed

Sapi, Andras; Liu, Fudong; Cai, Xiaojun; Thompson, Christopher M; Wang, Hailiang; An, Kwangjin; Krier, James M; Somorjai, Gabor A

2014-11-12

Pt nanoparticles with controlled size (2, 4, and 6 nm) are synthesized and tested in ethanol oxidation by molecular oxygen at 60 °C to acetaldehyde and carbon dioxide both in the gas and liquid phases. The turnover frequency of the reaction is ∼80 times faster, and the activation energy is ∼5 times higher at the gas-solid interface compared to the liquid-solid interface. The catalytic activity is highly dependent on the size of the Pt nanoparticles; however, the selectivity is not size sensitive. Acetaldehyde is the main product in both media, while twice as much carbon dioxide was observed in the gas phase compared to the liquid phase. Added water boosts the reaction in the liquid phase; however, it acts as an inhibitor in the gas phase. The more water vapor was added, the more carbon dioxide was formed in the gas phase, while the selectivity was not affected by the concentration of the water in the liquid phase. The differences in the reaction kinetics of the solid-gas and solid-liquid interfaces can be attributed to the molecular orientation deviation of the ethanol molecules on the Pt surface in the gas and liquid phases as evidenced by sum frequency generation vibrational spectroscopy.

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.

Microminiature gas chromatograph

DOEpatents

Yu, C.M.

1996-12-10

A microminiature gas chromatograph ({mu}GC) comprising a least one silicon wafer, a gas injector, a column, and a detector. The gas injector has a normally closed valve for introducing a mobile phase including a sample gas in a carrier gas. The valve is fully disposed in the silicon wafer(s). The column is a microcapillary in silicon crystal with a stationary phase and is mechanically connected to receive the mobile phase from the gas injector for the molecular separation of compounds in the sample gas. The detector is mechanically connected to the column for the analysis of the separated compounds of sample gas with electronic means, e.g., ion cell, field emitter and PIN diode. 7 figs.

Interference-free coherence dynamics of gas-phase molecules using spectral focusing.

PubMed

Wrzesinski, Paul J; Roy, Sukesh; Gord, James R

2012-10-08

Spectral focusing using broadband femtosecond pulses to achieve highly selective measurements has been employed for numerous applications in spectroscopy and microspectroscopy. In this work we highlight the use of spectral focusing for selective excitation and detection of gas-phase species. Furthermore, we demonstrate that spectral focusing, coupled with time-resolved measurements based upon probe delay, allows the observation of interference-free coherence dynamics of multiple molecules and gas-phase temperature making this technique ideal for gas-phase measurements of reacting flows and combustion processes.

Controlling the growth of multiple ordered heteromolecular phases by utilizing intermolecular repulsion

NASA Astrophysics Data System (ADS)

Henneke, Caroline; Felter, Janina; Schwarz, Daniel; Stefan Tautz, F.; Kumpf, Christian

2017-06-01

Metal/organic interfaces and their structural, electronic, spintronic and thermodynamic properties have been investigated intensively, aiming to improve and develop future electronic devices. In this context, heteromolecular phases add new design opportunities simply by combining different molecules. However, controlling the desired phases in such complex systems is a challenging task. Here, we report an effective way of steering the growth of a bimolecular system composed of adsorbate species with opposite intermolecular interactions--repulsive and attractive, respectively. The repulsive species forms a two-dimensional lattice gas, the density of which controls which crystalline phases are stable. Critical gas phase densities determine the constant-area phase diagram that describes our experimental observations, including eutectic regions with three coexisting phases. We anticipate the general validity of this type of phase diagram for binary systems containing two-dimensional gas phases, and also show that the density of the gas phase allows engineering of the interface structure.

Electron Interactions with Non-Linear Polyatomic Molecules and Their Radicals

DTIC Science & Technology

1993-12-01

developed which generates SCE quantities from molecular wave functions. This progress was realized in terms of some actual calculations on some molecules...section 4.A describes the basics of the Partial Differential Equation Theory; section 4.B describes the generalization to a finite element...Information Service (NTIS). At NTIS, it will be available to the general public, including foreign nations. This technical report has been reviewed and

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

Not Available

The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

Photodissociation Studies of Polyatomic Free Radicals

DTIC Science & Technology

1993-08-01

photofragment, that varies with vibrational level, and appears to have a strong J dependence. We are currently in the process of modelling these effects, as well...have also begun to study the photodissociation dynamics of thionyl halides, The photodissociation of thionyl chloride (C12SO) is of interest as a model ...concerted three-body fragmentation mechanism as the primary dissociation channel. A Franck- Condon/golden rule model elucidates the geometry prior to

Molecular-beam Studies of Primary Photochemical Processes

DOE R&D Accomplishments Database

Lee, Y. T.

1982-12-01

Application of the method of molecular-beam photofragmentation translational spectroscopy to the investigation of primary photochemical processes of polyatomic molecules is described. Examples will be given to illustrate how information concerning the energetics, dynamics, and mechanism of dissociation processes can be obtained from the precise measurements of angular and velocity distributions of products in an experiment in which a well-defined beam of molecules is crossed with a laser.

Correlation between molecular secondary ion yield and cluster ion sputtering for samples with different stopping powers

NASA Astrophysics Data System (ADS)

Heile, A.; Muhmann, C.; Lipinsky, D.; Arlinghaus, H. F.

2012-07-01

In static SIMS, the secondary ion yield, defined as detected ions per primary ion, can be increased by altering several primary ion parameters. For many years, no quantitative predictions could be made for the secondary ion yield enhancement of molecular ions. For thick samples of organic compounds, a power dependency of the secondary ion yield on the sputtering yield was shown. For this article, samples with thick molecular layers and (sub-)monolayers composed of various molecules were prepared on inorganic substrates such as silicon, silver, and gold, and subsequently analyzed. For primary ion bombardment, monoatomic (Ne+, Ar+, Ga+, Kr+, Xe+, Bi+) as well as polyatomic (Bin+, Bin++) primary ions were used within an energy range of 10-50 keV. The power dependency was found to hold true for the different samples; however, the exponent decreased with increasing stopping power. Based on these findings, a rule of thumb is proposed for the prediction of the lower limit of the secondary ion yield enhancement as a function of the primary ion species. Additionally, effects caused by the variation of the energy deposition are discussed, including the degree of molecular fragmentation and the non-linear increase of the secondary ion yield when polyatomic primary ions are used.

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

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.

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.

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.

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

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.

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.

Modeling of Liquid Steel/Slag/Argon Gas Multiphase Flow During Tundish Open Eye Formation in a Two-Strand Tundish

NASA Astrophysics Data System (ADS)

Chatterjee, Saikat; Li, Donghui; Chattopadhyay, Kinnor

2018-04-01

Multiphase flows are frequently encountered in metallurgical operations. One of the most effective ways to understand these processes is by flow modeling. The process of tundish open eye (TOE) formation involves three-phase interaction between liquid steel, slag, and argon gas. The two-phase interaction involving argon gas bubbles and liquid steel can be modeled relatively easily using the discrete phase modeling technique. However, the effect of an upper slag layer cannot be captured using this approach. The presence of an upper buoyant phase can have a major effect on the behavior of TOEs. Hence, a multiphase model, including three phases, viz. liquid steel, slag, and argon gas, in a two-strand slab caster tundish, was developed to study the formation and evolution of TOEs. The volume of fluid model was used to track the interphase between liquid steel and slag phases, while the discrete phase model was used to trace the movement of the argon gas bubbles in liquid steel. The variation in the TOE areas with different amounts of aspirated argon gas was examined in the presence of an overlying slag phase. The mathematical model predictions were compared against steel plant measurements.

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...

Entrapment of Hydrate-coated Gas Bubbles into Oil and Separation of Gas and Hydrate-film; Seafloor Experiments with ROV

NASA Astrophysics Data System (ADS)

Hiruta, A.; Matsumoto, R.

2015-12-01

We trapped gas bubbles emitted from the seafloor into oil-containing collector and observed an unique phenomena. Gas hydrate formation needs water for the crystal lattice; however, gas hydrates in some areas are associated with hydrophobic crude oil or asphalt. In order to understand gas hydrate growth in oil-bearing sediments, an experiment with cooking oil was made at gas hydrate stability condition. We collected venting gas bubbles into a collector with canola oil during ROV survey at a gas hydrate area in the eastern margin of the Sea of Japan. When the gas bubbles were trapped into collector with oil, gas phase appeared above the oil and gas hydrates, between oil and gas phase. At this study area within gas hydrate stability condition, control experiment with oil-free collector suggested that gas bubbles emitted from the seafloor were quickly covered with gas hydrate film. Therefore it is improbable that gas bubbles entered into the oil phase before hydrate skin formation. After the gas phase formation in oil-containing collector, the ROV floated outside of hydrate stability condition for gas hydrate dissociation and re-dived to the venting site. During the re-dive within hydrate stability condition, gas hydrate was not formed. The result suggests that moisture in the oil is not enough for hydrate formation. Therefore gas hydrates that appeared at the oil/gas phase boundary were already formed before bubbles enter into the oil. Hydrate film is the only possible origin. This observation suggests that hydrate film coating gas hydrate was broken at the sea water/oil boundary or inside oil. Further experiments may contribute for revealing kinetics of hydrate film and formation. This work was a part of METI (Ministry of Economy, Trade and Industry)'s project entitled "FY2014 Promoting research and development of methane hydrate". We also appreciate support of AIST (National Institute of Advanced Industrial Science and Technology).

Modelling Phase Transition Phenomena in Fluids

DTIC Science & Technology

2015-07-01

Sublimation line r @@I Triple point ? Vapourisation liner @@I Critical point -Fusion line Solid Liquid Gas Figure 1: Schematic of a phase diagram means that the...velocity field can be set zero, and only the balance of energy constitutes the Stefan model. In contrast to this the liquid - gas phase transitions...defined by requiring that the phase-transition line is crossed in a direction from solid to liquid or from liquid to gas (vapour) phases. The term T∗ δs is

DSMC simulation of two-phase plume flow with UV radiation

NASA Astrophysics Data System (ADS)

Li, Jie; Liu, Ying; Wang, Ning; Jin, Ling

2014-12-01

Rarefied gas-particle two-phase plume in which the phase of particles is liquid or solid flows from a solid propellant rocket of hypersonic vehicle flying at high altitudes, the aluminum oxide particulates not only impact the rarefied gas flow properties, but also make a great difference to plume radiation signature, so the radiation prediction of the rarefied gas-particle two-phase plume flow is very important for space target detection of hypersonic vehicles. Accordingly, this project aims to study the rarefied gas-particle two-phase flow and ultraviolet radiation (UV) characteristics. Considering a two-way interphase coupling of momentum and energy, the direct simulation Monte Carlo (DSMC) method is developed for particle phase change and the particle flow, including particulate collision, coalescence as well as separation, and a Monte Carlo ray trace model is implemented for the particulate UV radiation. A program for the numerical simulation of the gas-particle two-phase flow and radiation in which the gas flow nonequilibrium is strong is implemented as well. Ultraviolet radiation characteristics of the particle phase is studied based on the calculation of the flow field coupled with the radiation calculation, the radiation model for different size particles is analyzed, focusing on the effects of particle emission, absorption, scattering as well as the searchlight emission of the nozzle. A new approach may be proposed to describe the rarefied gas-particle two-phase plume flow and radiation transfer characteristics in this project.

Absolute measurements and certified reference material for iron isotopes using multiple-collector inductively coupled mass spectrometry.

PubMed

Zhou, Tao; Zhao, Motian; Wang, Jun; Lu, Hai

2008-01-01

Two enriched isotopes, 99.94 at.% 56Fe and 99.90 at.% 54Fe, were blended under gravimetric control to prepare ten synthetic isotope samples whose 56Fe isotope abundances ranged from 95% to 20%. For multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements typical polyatomic interferences were removed by using Ar and H2 as collision gas and operating the MC-ICP-MS system in soft mode. Thus high-precision measurements of the Fe isotope abundance ratios were accomplished. Based on the measurement of the synthetic isotope abundance ratios by MC-ICP-MS, the correction factor for mass discrimination was calculated and the results were in agreement with results from IRMM014. The precision of all ten correction factors was 0.044%, indicating a good linearity of the MC-ICP-MS method for different isotope abundance ratio values. An isotopic reference material was certified under the same conditions as the instrument was calibrated. The uncertainties of ten correction factors K were calculated and the final extended uncertainties of the isotopic certified Fe reference material were 5.8363(37) at.% 54Fe, 91.7621(51) at.% 56Fe, 2.1219(23) at.% 57Fe, and 0.2797(32) at.% 58Fe.

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.

Effect of measurement protocol on organic aerosol measurements of exhaust emissions from gasoline and diesel vehicles

NASA Astrophysics Data System (ADS)

Kim, Youngseob; Sartelet, Karine; Seigneur, Christian; Charron, Aurélie; Besombes, Jean-Luc; Jaffrezo, Jean-Luc; Marchand, Nicolas; Polo, Lucie

2016-09-01

Exhaust emissions of semi-volatile organic compounds (SVOC) from passenger vehicles are usually estimated only for the particle phase via the total particulate matter measurements. However, they also need to be estimated for the gas phase, as they are semi-volatile. To better estimate SVOC emission factors of passenger vehicles, a measurement campaign using a chassis dynamometer was conducted with different instruments: (1) a constant volume sampling (CVS) system in which emissions were diluted with filtered air and sampling was performed on filters and polyurethane foams (PUF) and (2) a Dekati Fine Particle Sampler (FPS) in which emissions were diluted with purified air and sampled with on-line instruments (PTR-ToF-MS, HR-ToF-AMS, MAAP, CPC). Significant differences in the concentrations of organic carbon (OC) measured by the instruments are observed. The differences can be explained by sampling artefacts, differences between (1) the time elapsed during sampling (in the case of filter and PUF sampling) and (2) the time elapsed from emission to measurement (in the case of on-line instruments), which vary from a few seconds to 15 min, and by the different dilution factors. To relate elapsed times and measured concentrations of OC, the condensation of SVOC between the gas and particle phases is simulated with a dynamic aerosol model. The simulation results allow us to understand the relation between elapsed times and concentrations in the gas and particle phases. They indicate that the characteristic times to reach thermodynamic equilibrium between gas and particle phases may be as long as 8 min. Therefore, if the elapsed time is less than this characteristic time to reach equilibrium, gas-phase SVOC are not at equilibrium with the particle phase and a larger fraction of emitted SVOC will be in the gas phase than estimated by equilibrium theory, leading to an underestimation of emitted OC if only the particle phase is considered or if the gas-phase SVOC are estimated by equilibrium theory. Current European emission inventories for passenger cars do not yet estimate gas-phase SVOC emissions, although they may represent 60% of total emitted SVOC (gas + particle phases).

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.

Heterogeneous reactivity of sea spray particles during the CalNex field campaign: Insight from single particle measurements and correlations with gas phase measurements

NASA Astrophysics Data System (ADS)

Gaston, C. J.; Riedel, T. P.; Thornton, J. A.; Wagner, N.; Brown, S. S.; Quinn, P.; Bates, T. S.; Prather, K. A.

2011-12-01

Sea spray particles are ubiquitous in marine environments. Heterogeneous reactions between sea spray particles and gas phase pollutants, such as HNO3(g), and N2O5(g), alter particle composition by displacing particulate phase halogens in sea spray and releasing these halogen species into the gas phase; these halogen-containing gas phase species play a significant role in tropospheric ozone production. Measurements of both gas phase and particle phase species on board the R/V Atlantis during the CalNEX 2010 field campaign provided an opportunity to examine the impact of heterogeneous reactivity of marine aerosols along the California coast. During the cruise, coastal measurements were made near the Santa Monica and Port of Los Angeles regions to monitor the chemical processing of marine aerosols. Sea spray particles were analyzed since these particles were the major chloride-containing particles detected. Real-time single particle measurements made using an aerosol time-of-flight mass spectrometer (ATOFMS) revealed the nocturnal processing of sea spray particles through the loss of particulate chloride and a simultaneous gain in particulate nitrate. Gas phase measurements are consistent with the particle phase observations: As N2O5(g) levels rose overnight, the production of ClNO2(g) coincided with the decrease in particulate chloride. These observations provide unique insight into heterogeneous reactivity from both a gas and particle phase perspective. Results from these measurements can be used to better constrain the rate of heterogeneous reactions on sea spray particles.

Superamphiphobic Silicon-Nanowire-Embedded Microsystem and In-Contact Flow Performance of Gas and Liquid Streams.

PubMed

Ko, Dong-Hyeon; Ren, Wurong; Kim, Jin-Oh; Wang, Jun; Wang, Hao; Sharma, Siddharth; Faustini, Marco; Kim, Dong-Pyo

2016-01-26

Gas and liquid streams are invariably separated either by a solid wall or by a membrane for heat or mass transfer between the gas and liquid streams. Without the separating wall, the gas phase is present as bubbles in liquid or, in a microsystem, as gas plugs between slugs of liquid. Continuous and direct contact between the two moving streams of gas and liquid is quite an efficient way of achieving heat or mass transfer between the two phases. Here, we report a silicon nanowire built-in microsystem in which a liquid stream flows in contact with an underlying gas stream. The upper liquid stream does not penetrate into the lower gas stream due to the superamphiphobic nature of the silicon nanowires built into the bottom wall, thereby preserving the integrity of continuous gas and liquid streams, although they are flowing in contact. Due to the superamphiphobic nature of silicon nanowires, the microsystem provides the best possible interfacial mass transfer known to date between flowing gas and liquid phases, which can achieve excellent chemical performance in two-phase organic syntheses.

Chemistry in the Dusty Coma of Comet Hale-Bopp

NASA Astrophysics Data System (ADS)

Boice, D. C.; Cochran, A. L.; Disanti, M. A.; Huebner, W. F.

1998-09-01

Recent progress on a multifluid, hydrodynamic model is presented for the dusty gas flow in the inner coma of comet Hale-Bopp at several heliocentric distances. The simulations are based on a 1-D neutral coma model with detailed photo and gas-phase chemistry and dust entrainment by the gas, a separate energy balance for the electrons, separate flow of the neutral gas, fast neutral atomic and molecular hydrogen, and dust entrainment with fragmentation. The model accounts for three sources of gas release: sublimation from surface ices, transport of gas from subsurface regions through the surface, and release of gas from dust in the coma. This permits a consistent study of the importance and strength of each possible source for a variety of gas-phase species. The simulations allow a study of the changes with heliocentric distance of features within a cometary coma, e.g., spatial distributions of gas-phase species and dust of various sizes and the velocity and temperature profiles. In particular, the model is used to probe spatial distributions of gas-phase species (e.g., CN, CH, C_3, C_2, HCN, HNC, CO) and dust, and the velocity and temperature structure to understand the complex gas-phase chemistry that occurs in the inner coma. Comparisons with observations are made where available to characterize the environment surrounding comet Hale-Bopp and to aid in assimilating a variety of diverse observations of this unique comet.

The effect of dry and wet deposition of condensable vapors on secondary organic aerosols concentrations over the continental US

NASA Astrophysics Data System (ADS)

Knote, C.; Hodzic, A.; Jimenez, J. L.

2015-01-01

The effect of dry and wet deposition of semi-volatile organic compounds (SVOCs) in the gas phase on the concentrations of secondary organic aerosol (SOA) is reassessed using recently derived water solubility information. The water solubility of SVOCs was implemented as a function of their volatility distribution within the WRF-Chem regional chemistry transport model, and simulations were carried out over the continental United States for the year 2010. Results show that including dry and wet removal of gas-phase SVOCs reduces annual average surface concentrations of anthropogenic and biogenic SOA by 48 and 63% respectively over the continental US. Dry deposition of gas-phase SVOCs is found to be more effective than wet deposition in reducing SOA concentrations (-40 vs. -8% for anthropogenics, and -52 vs. -11% for biogenics). Reductions for biogenic SOA are found to be higher due to the higher water solubility of biogenic SVOCs. The majority of the total mass of SVOC + SOA is actually deposited via the gas phase (61% for anthropogenics and 76% for biogenics). Results are sensitive to assumptions made in the dry deposition scheme, but gas-phase deposition of SVOCs remains crucial even under conservative estimates. Considering reactivity of gas-phase SVOCs in the dry deposition scheme was found to be negligible. Further sensitivity studies where we reduce the volatility of organic matter show that consideration of gas-phase SVOC removal still reduces average SOA concentrations by 31% on average. We consider this a lower bound for the effect of gas-phase SVOC removal on SOA concentrations. A saturation effect is observed for Henry's law constants above 108 M atm-1, suggesting an upper bound of reductions in surface level SOA concentrations by 60% through removal of gas-phase SVOCs. Other models that do not consider dry and wet removal of gas-phase SVOCs would hence overestimate SOA concentrations by roughly 50%. Assumptions about the water solubility of SVOCs made in some current modeling systems (H* = H* (CH3COOH); H* = 105 M atm-1; H* = H* (HNO3)) still lead to an overestimation of 35%/25%/10% compared to our best estimate.

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.

Numerical Simulation of Multiphase Flow in Nanoporous Organic Matter With Application to Coal and Gas Shale Systems

NASA Astrophysics Data System (ADS)

Song, Wenhui; Yao, Jun; Ma, Jingsheng; Sun, Hai; Li, Yang; Yang, Yongfei; Zhang, Lei

2018-02-01

Fluid flow in nanoscale organic pores is known to be affected by fluid transport mechanisms and properties within confined pore space. The flow of gas and water shows notably different characteristics compared with conventional continuum modeling approach. A pore network flow model is developed and implemented in this work. A 3-D organic pore network model is constructed from 3-D image that is reconstructed from 2-D shale SEM image of organic-rich sample. The 3-D pore network model is assumed to be gas-wet and to contain initially gas-filled pores only, and the flow model is concerned with drainage process. Gas flow considers a full range of gas transport mechanisms, including viscous flow, Knudsen diffusion, surface diffusion, ad/desorption, and gas PVT and viscosity using a modified van der Waals' EoS and a correlation for natural gas, respectively. The influences of slip length, contact angle, and gas adsorption layer on water flow are considered. Surface tension considers the pore size and temperature effects. Invasion percolation is applied to calculate gas-water relative permeability. The results indicate that the influences of pore pressure and temperature on water phase relative permeabilities are negligible while gas phase relative permeabilities are relatively larger in higher temperatures and lower pore pressures. Gas phase relative permeability increases while water phase relative permeability decreases with the shrinkage of pore size. This can be attributed to the fact that gas adsorption layer decreases the effective flow area of the water phase and surface diffusion capacity for adsorbed gas is enhanced in small pore size.

A fundamental study of gas formation and migration during leakage of stored carbon dioxide in subsurface formations

NASA Astrophysics Data System (ADS)

Sakaki, T.; Plampin, M. R.; Lassen, R. N.; Pawar, R. J.; Komatsu, M.; Jensen, K. H.; Illangasekare, T. H.

2011-12-01

Geologic sequestration of CO2 has received significant attention as a potential method for reducing the release of greenhouse gases into the atmosphere. Potential risk of leakage of the stored CO2 to the shallow zones of the subsurface is one of the critical issues that is needed to be addressed to design effective field storage systems. If a leak occurs, gaseous CO2 reaching shallow zones of the subsurface can potentially impact the surface and groundwater sources and vegetation. With a goal of developing models that can predict these impacts, a research study is underway to improve our understanding of the fundamental processes of gas-phase formation and multi-phase flow dynamics during CO2 migration in shallow porous media. The approach involves conducting a series of highly controlled experiments in soil columns and tanks to study the effects of soil properties, temperature, pressure gradients and heterogeneities on gas formation and migration. This paper presents the results from a set of column studies. A 3.6m long column was instrumented with 16 soil moisture sensors, 15 of which were capable of measuring electrical conductivity (EC) and temperature, eight water pressure, and two gas pressure sensors. The column was filled with test sands with known hydraulic and retention characteristics with predetermined packing configurations. Deionized water saturated with CO2 under ~0.3 kPa (roughly the same as the hydrostatic pressure at the bottom of the column) was injected at the bottom of the column using a peristaltic pump. Water and gas outflow at the top of the column were monitored continuously. The results, in general, showed that 1) gas phase formation can be triggered by multiple factors such as water pressure drop, temperature rise, and heterogeneity, 2) transition to gas phase tends to occur rather within a short period of time, 3) gas phase fraction was as high as ~40% so that gas flow was not via individual bubble movement but two-phase flow, 4) water outflow that was initially equal to the inflow rate increased when gas-phase started to form (i.e., water gets displaced), and 5) gas starts to flow upward after gas phase fraction stabilizes (i.e., buoyant force overcomes). These results suggest that the generation and migration processes of gas phase CO2 can be modelled as a traditional two-phase flow with source (when CO2 gas exsolved due to complex factors) as well as sink (when gas dissolved) terms. The experimental data will be used to develop and test the conceptual models that will guide the development of numerical simulators for applications involving CO2 storage and leakage.

Features of nanostructures sputtering

NASA Astrophysics Data System (ADS)

Kapustin, S. N.; Matveev, V. I.; Eseev, M. K.

2017-09-01

The research of ion sputtering of nanoparticles is interesting both from the fundamental point of view - for researching the interior structure of nanoobjects, and the economical one - nanostructures often play the role of functional supplements in composite materials under the radiation pressure. This process should be taken into account while creating objects decorated by nanoclusters during ion implantation. Polyatomic clusters obtained as a result of ion bombing could be used as nanodisperse catalysts or quantum points.

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

Zeigler, N. R.; Zack, L. N.; Ziurys, L. M.

The J = 1 → 0 transition of HCO{sup +} at 89 GHz has been mapped across the Helix Nebula (NGC 7293) with 70'' spatial resolution (1.68 km s{sup –1} velocity resolution) using the Arizona Radio Observatory 12 m telescope. This work is the first large-scale mapping project of a dense gas tracer (n(H{sub 2}) ∼ 10{sup 5} cm{sup –3}) in old planetary nebulae. Observations of over 200 positions encompassing the classical optical image were conducted with a 3σ noise level of ∼20 mK. HCO{sup +} was detected at most positions, often exhibiting multiple velocity components indicative of complex kinematicmore » structures in dense gas. The HCO{sup +} spectra suggest that the Helix is composed of a bipolar, barrel-like structure with red- and blue-shifted halves, symmetric with respect to the central star and oriented ∼10° east from the line of sight. A second bipolar, higher velocity outflow exists as well, situated along the direction of the Helix 'plumes'. The column density of HCO{sup +} across the Helix is N {sub tot} ∼ 1.5 × 10{sup 10}-5.0 × 10{sup 11} cm{sup –2}, with an average value N {sub ave} ∼ 1 × 10{sup 11} cm{sup –2}, corresponding to an abundance, relative to H{sub 2}, of f ∼ 1.4 × 10{sup –8}. This value is similar to that observed in young PN, and contradicts chemical models, which predict that the abundance of HCO{sup +} decreases with nebular age. This study indicates that polyatomic molecules readily survive the ultraviolet field of the central white dwarf, and can be useful in tracing nebular morphology in the very late stages of stellar evolution.« less

Diatomics-in-molecules description of the Rg-Hal2 rare gas-halogen van der Waals complexes with applications to He-Cl2

NASA Astrophysics Data System (ADS)

Grigorenko, B. L.; Nemukhin, A. V.; Buchachenko, A. A.; Stepanov, N. F.; Umanskii, S. Ya.

1997-03-01

The diatomics-in-molecules (DIM) technique is applied for a description of the low-lying states of the Rg-Hal2 van der Waals complexes correlating with the lowest states of constituent atoms Rg(1S)+Hal(2Pj)+Hal(2Pj). The important feature of this approach is the construction of polyatomic basis functions as products of the Hal2 diatomic eigenstates classified within the Hund "c" scheme and the atomic rare gas wave function. Necessary transformations to the other basis set representations are described, and finally all the matrix elements are expressed in terms of nonrelativistic adiabatic energies of Hal2 and Rg Hal fragments and spin-orbit splitting constant of the halogen atom. Our main concern is to test the DIM-based approximations of different levels taking the He-Cl2 system as an example. Namely, we have compared the results obtained within a hierarchy of approaches: (1) the simplest pairwise potential scheme as a far extreme of the DIM model, (2) the same as (1) but with the different components (Σ and Π) for He-Cl interaction, (3) the accurate DIM technique without spin-orbit terms, and (4) the highest level which takes into account all these contributions. The results have been compared to the other DIM like models as well. The shapes of two-dimensional potential surfaces for the ground (X) and excited (B) states of HeCl2, binding energies De with respect to He+Cl2, stretching and bending vibrational frequencies of the complex, binding energies D0, and spectral shifts for the B←X transition are discussed.

Direct evidence for the gas phase thermal polymerization of styrene. Determination of the initiation mechanism and structures of the early oligomers by ion mobility.

PubMed

Alsharaeh, Edreese H; Ibrahim, Yehia M; El-Shall, M Samy

2005-05-04

We present here direct evidence for the thermal self-initiated polymerization of styrene in the gas phase and establish that the initiation process proceeds via essentially the same mechanism (the Mayo mechanism) as in condensed phase polymerization. Furthermore, we provide structural identifications of the dimers and trimers formed in the gas phase.

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...

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...

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.

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.

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.

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.

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.

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.

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.

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

The solubility of gallium oxide in vapor and two-phase fluid filtration in hydrothermal systems

NASA Astrophysics Data System (ADS)

Bychkov, Andrew; Matveeva, Svetlana; Nekrasov, Stanislav

2010-05-01

The solubility of gallium and aluminum oxides in gas phase in the system Ga2O3 (Al2O3)-HCl-H2O was studied at 150-350°C and pressure up to saturated vapor. The concentration of gallium increases with the increasing of HCl pressure. The formulae of gallium gaseous specie was determined as GaOHCl2. The constant of gallium oxide solubility reaction was calculated at 150, 200, 250, 300 and 350°C. The concentration of aluminum in gas phase is insignificant in the same conditions. The possibility of gallium transportation in gas phase with small quantity of Al allow to divide this elements in hydrothermal processes with gas phase. The Ga/Al ratio in muscovite can be used as the indicator of gas phase separation and condensation. This indicator was not considered in the geochemical literature earlier. The separation of gas and liquid phases was determined in Akchatau (Kazahstan) and Spokoinoe (Russia) greisen W deposit by carbon isotope fractionation of carbon dioxide in fluid inclusion. The important feature of both ore mains is heterogenization and boiling of ore-forming fluids. Greisen ore bodies are formed as a result of strongly focused solution flow in the T-P gradient fields. It is possible to divide ore bodies of Akchatau in two types: muscovite and quartz. Muscovite type veins are thin and have small metasyntactic zone. Quartz type veins are localized in fault with large vertical extent (500 m) and content the large quantity of wolframite. These veins formed in condition of significant pressure decreasing from 2.5 to 0.5 kbar with fluid boiling. Gas and liquid phase separation specifies the vertical zonality of quartz type veins. The gas phase with the high gallium concentration is separated from a flow of liquid phase. Liquid phase react with the granites forming greisen metasomatites. Condensation of the gas phase in upper parts of massive produces the increasing of Ga/Al ratio in muscovite 3-5 times more, then in granites and bottom part of vein (from 2×10-4 to 8×10-4 mass ratio). The muscovite type veins has no separation between gas and liquid due to there thickness and small pressure gradient. There is no difference in Ga/Al ratio in muscovite from this veins. The Spokoinoe deposit is classified by mineralized dome type. The heterogenization of fluid occurs in H2O-CO2 system for water phase and carbon dioxide with temperature decreasing. Two-phase flow is separated in granite, forming greisen metosomatites. The Ga/Al ratio in rock increase up to 3 times to the upper part of metasomatitic zone. The Ga/Al ratio in muscovite can be applied for other hydrothermal systems for geochemical indicator of gas phase separation and condensation zone determination. This work is supported by RFBR project 10-05-00670 and 10-05-00320.

Desorption Induced by KEV Molecular and Cluster Projectiles.

NASA Astrophysics Data System (ADS)

Blain, Matthew Glenn

1990-01-01

A new experimental method has been developed for studying negative secondary ion (SI) emission from solid surfaces bombarded by polyatomic primary ions of 5 to 30 keV. The method is based on the time-of-flight (TOF) analysis of primary ions which are produced by either ^ {252}Cf fission fragment induced desorption or by extraction from a liquid metal ion source, and then accelerated into a field free region. The primary ions included organic monomer, dimer, and fragment ions of coronene and phenylalanine, (CsI)_ nCs ^{+} cluster ions, and Au _sp{n}{+} cluster ions. Secondary electrons, emitted from a target surface upon primary ion impact, are used to identify which primary ion has hit the surface. An event-by-event coincidence counting technique allows several secondary ion TOF spectra, correlated to several different primary ions, to be acquired simultaneously. Negative SI yields from organic (phenylalanine and dinitrostilbene), CsI, and Au surfaces have been measured for a number of different mono- and polyatomic primary ions. The results show, for example, yields ranging from 1 to 10% for phenylalanine (M-H) ^{ -}, 1 to 10% for I^{-} , and 1 to 5% for Au^{-} , with Cs_2I^ {+} and Cs_3I _sp{2}{+} clusters as projectiles. Yields for the same surfaces using Cs ^{+} primary ions are much less than 1%, indicating that SI yields are enhanced with clusters. A yield enhancement occurs when the SI yield per atom of a polyatomic projectile is greater than the SI yield of its monoatomic equivalent, at the same velocity. Thus, a (M-H) ^{-} yield increase of a factor of 50, when phenylalanine is bombarded with Cs_3I_sp{2} {+} instead of Cs^{+ }, represents a yield enhancement factor of 10. For the projectiles and samples studied, it was observed that the heavier the mass of the constituents of a projectile, the larger the enhancement effects, and that the largest yield enhancements (with CsI and Au _ n projectiles) occur for the organic target, phenylalanine. One possible explanation for the larger enhancements with organics, namely a thermal spike process, appears unlikely. Experiments with high and low melting point isomers of dinitrostilbene, bombarded with Cs _2I^{+} and Cs^{+} projectiles, showed larger Cs_2I^ {+} yield enhancements for the high melting point isomer.

Calculation of the Rate of Combustion of a Metallized Composite Solid Propellant with Allowance for the Size Distribution of Agglomerates

NASA Astrophysics Data System (ADS)

Poryazov, V. A.; Krainov, A. Yu.

2016-05-01

A physicomathematical model of combustion of a metallized composite solid propellant based on ammonium perchlorate has been presented. The model takes account of the thermal effect of decomposition of a condensed phase (c phase), convection, diffusion, the exothermal chemical reaction in a gas phase, the heating and combustion of aluminum particles in the gas flow, and the velocity lag of the particles behind the gas. The influence of the granulometric composition of aluminum particles escaping from the combustion surface on the linear rate of combustion has been investigated. It has been shown that information not only on the kinetics of chemical reactions in the gas phase, but also on the granulometric composition of aluminum particles escaping from the surface of the c phase into the gas, is of importance for determination of the linear rate of combustion.

A Computer Model for Analyzing Volatile Removal Assembly

NASA Technical Reports Server (NTRS)

Guo, Boyun

2010-01-01

A computer model simulates reactional gas/liquid two-phase flow processes in porous media. A typical process is the oxygen/wastewater flow in the Volatile Removal Assembly (VRA) in the Closed Environment Life Support System (CELSS) installed in the International Space Station (ISS). The volatile organics in the wastewater are combusted by oxygen gas to form clean water and carbon dioxide, which is solved in the water phase. The model predicts the oxygen gas concentration profile in the reactor, which is an indicator of reactor performance. In this innovation, a mathematical model is included in the computer model for calculating the mass transfer from the gas phase to the liquid phase. The amount of mass transfer depends on several factors, including gas-phase concentration, distribution, and reaction rate. For a given reactor dimension, these factors depend on pressure and temperature in the reactor and composition and flow rate of the influent.

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.

Spatial resolution of gas hydrate and permeability changes from ERT data in LARS simulating the Mallik gas hydrate production test

NASA Astrophysics Data System (ADS)

Priegnitz, Mike; Thaler, Jan; Spangenberg, Erik; Schicks, Judith M.; Abendroth, Sven

2014-05-01

The German gas hydrate project SUGAR studies innovative methods and approaches to be applied in the production of methane from hydrate-bearing reservoirs. To enable laboratory studies in pilot scale, a large reservoir simulator (LARS) was realized allowing for the formation and dissociation of gas hydrates under simulated in-situ conditions. LARS is equipped with a series of sensors. This includes a cylindrical electrical resistance tomography (ERT) array composed of 25 electrode rings featuring 15 electrodes each. The high-resolution ERT array is used to monitor the spatial distribution of the electrical resistivity during hydrate formation and dissociation experiments over time. As the present phases of poorly conducting sediment, well conducting pore fluid, non-conducting hydrates, and isolating free gas cover a wide range of electrical properties, ERT measurements enable us to monitor the spatial distribution of these phases during the experiments. In order to investigate the hydrate dissociation and the resulting fluid flow, we simulated a hydrate production test in LARS that was based on the Mallik gas hydrate production test (see abstract Heeschen et al., this volume). At first, a hydrate phase was produced from methane saturated saline water. During the two months of gas hydrate production we measured the electrical properties within the sediment sample every four hours. These data were used to establish a routine estimating both the local degrees of hydrate saturation and the resulting local permeabilities in the sediment's pore space from the measured resistivity data. The final gas hydrate saturation filled 89.5% of the total pore space. During hydrate dissociation, ERT data do not allow for a quantitative determination of free gas and remaining gas hydrates since both phases are electrically isolating. However, changes are resolved in the spatial distribution of the conducting liquid and the isolating phase with gas being the only mobile isolating phase. Hence, it is possible to detect areas in the sediment sample where free gas is released due to hydrate dissociation and displaces the liquid phase. Combined with measurements and numerical simulation of the total two-phase fluxes from the sediment sample (see abstract Abendroth et al., this volume), the LARS experiments allow for detailed information on the dissociation process during hydrate production. Here we present the workflow and first results estimating local hydrate saturations and permeabilities during hydrate formation and the movement of liquid and gas phases during hydrate dissociation, respectively.

Heterogeneous fuel for hybrid rocket

NASA Technical Reports Server (NTRS)

Stickler, David B. (Inventor)

1996-01-01

Heterogeneous fuel compositions suitable for use in hybrid rocket engines and solid-fuel ramjet engines, The compositions include mixtures of a continuous phase, which forms a solid matrix, and a dispersed phase permanently distributed therein. The dispersed phase or the matrix vaporizes (or melts) and disperses into the gas flow much more rapidly than the other, creating depressions, voids and bumps within and on the surface of the remaining bulk material that continuously roughen its surface, This effect substantially enhances heat transfer from the combusting gas flow to the fuel surface, producing a correspondingly high burning rate, The dispersed phase may include solid particles, entrained liquid droplets, or gas-phase voids having dimensions roughly similar to the displacement scale height of the gas-flow boundary layer generated during combustion.

Quantitative tomographic measurements of opaque multiphase flows

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

GEORGE,DARIN L.; TORCZYNSKI,JOHN R.; SHOLLENBERGER,KIM ANN

2000-03-01

An electrical-impedance tomography (EIT) system has been developed for quantitative measurements of radial phase distribution profiles in two-phase and three-phase vertical column flows. The EIT system is described along with the computer algorithm used for reconstructing phase volume fraction profiles. EIT measurements were validated by comparison with a gamma-densitometry tomography (GDT) system. The EIT system was used to accurately measure average solid volume fractions up to 0.05 in solid-liquid flows, and radial gas volume fraction profiles in gas-liquid flows with gas volume fractions up to 0.15. In both flows, average phase volume fractions and radial volume fraction profiles from GDTmore » and EIT were in good agreement. A minor modification to the formula used to relate conductivity data to phase volume fractions was found to improve agreement between the methods. GDT and EIT were then applied together to simultaneously measure the solid, liquid, and gas radial distributions within several vertical three-phase flows. For average solid volume fractions up to 0.30, the gas distribution for each gas flow rate was approximately independent of the amount of solids in the column. Measurements made with this EIT system demonstrate that EIT may be used successfully for noninvasive, quantitative measurements of dispersed multiphase flows.« less

Balancing Accuracy and Computational Efficiency for Ternary Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

White, M. D.

2011-12-01

Geologic accumulations of natural gas hydrates hold vast organic carbon reserves, which have the potential of meeting global energy needs for decades. Estimates of vast amounts of global natural gas hydrate deposits make them an attractive unconventional energy resource. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. Producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. The guest-molecule exchange technology releases CH4 by replacing it with a more thermodynamically stable molecule (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, liquid CO2, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulation of the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and phase transitions. This paper describes and demonstrates a numerical solution scheme for ternary hydrate systems that seeks a balance between accuracy and computational efficiency. This scheme uses a generalize cubic equation of state, functional forms for the hydrate equilibria and cage occupancies, variable switching scheme for phase transitions, and kinetic exchange of hydrate formers (i.e., CH4, CO2, and N2) between the mobile phases (i.e., aqueous, liquid CO2, and gas) and hydrate phase. Accuracy of the scheme will be evaluated by comparing property values and phase equilibria against experimental data. Computational efficiency of the scheme will be evaluated by comparing the base scheme against variants. The application of interest will the production of a natural gas hydrate deposit from a geologic formation, using the guest molecule exchange process; where, a mixture of CO2 and N2 are injected into the formation. During the guest-molecule exchange, CO2 and N2 will predominately replace CH4 in the large and small cages of the sI structure, respectively.

A Computationally Efficient Equation of State for Ternary Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

White, M. D.

2012-12-01

The potential energy resource of natural gas hydrates held in geologic accumulations, using lower volumetric estimates, is sufficient to meet the world demand for natural gas for nearly eight decades, at current rates of increase. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. The thermodynamic complexity of gas hydrate systems makes numerical simulation a particularly attractive research tool for understanding production strategies and experimental observations. Simply stated, producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. Alternatively, the guest-molecule exchange technology releases CH4 by replacing it with more thermodynamically stable molecules (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it potentially releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, nonaqueous liquid, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulations that predict the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and phase transitions. The phase equilibria for the ternary gas hydrate system within the gas hydrate stability range of composition, temperature and pressure, includes regions where the gas hydrate is in equilibrium with gas, nonaqueous liquid, or mixtures of gas and nonaqeuous liquid near the CO2-CH4-N2 mixture critical point. In these regions, solutions to cubic equations of state can be nonconvergent without accurate initial guesses. A hybrid tabular-cubic equation of state is described which avoids convergence issues, but conserves the characteristics and advantages of the cubic equation of state approaches to phase equilibria calculations. The application of interest will be the production of a natural gas hydrate deposit from a geologic formation, using the guest molecule exchange process; where, a mixture of CO2 and N2 are injected into the formation. During the guest-molecule exchange, CO2 and N2 will predominately replace CH4 in the large and small cages of the sI structure, respectively.

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.

Gas-Liquid Processing in Microchannels

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

TeGrotenhuis, Ward E.; Stenkamp, Victoria S.; Twitchell, Alvin

Processing gases and liquids together in microchannels having at least one dimension <1 mm has unique advantages for rapid heat and mass transfer. One approach for managing the two phases is to use porous structures as wicks within microchannels to segregate the liquid phase from the gas phase. Gas-liquid processing is accomplished by providing a gas flow path and inducing flow of the liquid phase through or along the wick under an induced pressure gradient. A variety of unit operations are enabled, including phase separation, partial condensation, absorption, desorption, and distillation. Results are reported of an investigation of microchannel phasemore » separation in a transparent, single-channel device. Next, heat exchange is integrated with the microchannel wick approach to create a partial condenser that also separates the condensate. Finally, the scale-up to a multi-channel phase separator is described.« less

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.

Research in Electronics - JSEP.

DTIC Science & Technology

1981-03-01

17. H . Helvajian and C. Wittig, "Collisional Quenching of HgBr(B 2 4i/2), Opt. Commun. 30, 189 (1979). 18. H . Reisler and C. Wittig, "Electronic...Luminescence Resulting from IR Multiple Photon Excitation, " in ’Photoselective Chemistry, Part I,’ J. Jortner ed., Wiley, 1981. 19. H . Helvajian , M...to Intramolecular V E coupling in IR Laser Excited Polyatomics, " J. Chem. Phys., in press. 22. H . Helvajian and C. Wittig, "Vibrational Quenching of

Hyperpolarized xenon NMR and MRI signal amplification by gas extraction

PubMed Central

Zhou, Xin; Graziani, Dominic; Pines, Alexander

2009-01-01

A method is reported for enhancing the sensitivity of NMR of dissolved xenon by detecting the signal after extraction to the gas phase. We demonstrate hyperpolarized xenon signal amplification by gas extraction (Hyper-SAGE) in both NMR spectra and magnetic resonance images with time-of-flight information. Hyper-SAGE takes advantage of a change in physical phase to increase the density of polarized gas in the detection coil. At equilibrium, the concentration of gas-phase xenon is ≈10 times higher than that of the dissolved-phase gas. After extraction the xenon density can be further increased by several orders of magnitude by compression and/or liquefaction. Additionally, being a remote detection technique, the Hyper-SAGE effect is further enhanced in situations where the sample of interest would occupy only a small proportion of the traditional NMR receiver. Coupled with targeted xenon biosensors, Hyper-SAGE offers another path to highly sensitive molecular imaging of specific cell markers by detection of exhaled xenon gas. PMID:19805177

In Situ Determination of Trace Elements in Fish Otoliths by Laser Ablation Double Focusing Sector Field Inductively Coupled Plasma Mass Spectrometry Using a Solution Standard Addition Calibration Method

NASA Astrophysics Data System (ADS)

Chen, Z.; Jones, C. M.

2002-05-01

Microchemistry of fish otoliths (fish ear bones) is a very useful tool for monitoring aquatic environments and fish migration. However, determination of the elemental composition in fish otolith by ICP-MS has been limited to either analysis of dissolved sample solution or measurement of limited number of trace elements by laser ablation (LA)- ICP-MS due to low sensitivity, lack of available calibration standards, and complexity of polyatomic molecular interference. In this study, a method was developed for in situ determination of trace elements in fish otoliths by laser ablation double focusing sector field ultra high sensitivity Finnigan Element 2 ICP-MS using a solution standard addition calibration method. Due to the lack of matrix-match solid calibration standards, sixteen trace elements (Na, Mg, P, Cr, Mn, Fe, Ni, Cu, Rb, Sr, Y, Cd, La, Ba, Pb and U) were determined using a solution standard calibration with Ca as an internal standard. Flexibility, easy preparation and stable signals are the advantages of using solution calibration standards. In order to resolve polyatomic molecular interferences, medium resolution (M/delta M > 4000) was used for some elements (Na, Mg, P, Cr, Mn, Fe, Ni, and Cu). Both external calibration and standard addition quantification strategies are compared and discussed. Precision, accuracy, and limits of detection are presented.

Exploring the dynamics of phase separation in colloid-polymer mixtures with long range attraction.

PubMed

Sabin, Juan; Bailey, Arthur E; Frisken, Barbara J

2016-06-28

We have studied the kinetics of phase separation and gel formation in a low-dispersity colloid - non-adsorbing polymer system with long range attraction using small-angle light scattering. This system exhibits two-phase and three-phase coexistence of gas, liquid and crystal phases when the strength of attraction is between 2 and 4kBT and gel phases when the strength of attraction is increased. For those samples that undergo macroscopic phase separation, whether to gas-crystal, gas-liquid or gas-liquid-crystal coexistence, we observe dynamic scaling of the structure factor and growth of a characteristic length scale that behaves as expected for phase separation in fluids. In samples that gel, the power law associated with the growth of the dominant length scale is not equal to 1/3, but appears to depend mainly on the strength of attraction, decreasing from 1/3 for samples near the coexistence region to 1/27 at 8kBT, over a wide range of colloid and polymer concentrations.

Aerosol-Phase Production of Nitrogen-Containing Oligomers After Uptake of Methylglyoxal and Cloud Processing

NASA Astrophysics Data System (ADS)

De Haan, D. O.; Riva, M.; Surratt, J. D.; Cazaunau, M.; Doussin, J. F.

2016-12-01

Minimal organic aerosol forms when aerosol particles are exposed to gas-phase methylglyoxal, but condensed phase laboratory studies of aerosol chemistry have suggested that methylglyoxal is a significant source of oligomerized aerosol material. In this study, various types of seed particles were exposed to gaseous methylglyoxal and then cloud-processed in the CESAM chamber. The gas phase was continuously probed by high-resolution PTR-MS during the experiments, and the particle phase WSOC was chemically characterized by high-resolution UPLC/ESI-DAD-QTOFMS. Uptake of methylglyoxal to dry particles caused optical rather than size changes, along with the release of imine products to the gas phase. High RH and cloud processing released some particle-bound methylglyoxal back to the gas phase but triggered an uptake of imine products. Analysis of the particle phase identified N-containing aldol condensation products derived from methylglyoxal, imine (produced from methylglyoxal and amine reactions), acetaldehyde (produced by methylglyoxal photolysis) and hydroxyacetone (produced by methylglyoxal disproportionation) monomers.

Finite Element Analysis Modeling of Chemical Vapor Deposition of Silicon Carbide

DTIC Science & Technology

2014-06-19

thesis primarily focuses on mass transport by gas -phase flow and diffusion , chemical reaction in gas phase and on solid surfaces, and thin film...chemical vapor deposition (CVD). This thesis primarily focuses on mass transport by gas -phase flow and diffusion , chemical reaction in gas phase and...9 Fluid Flow…………………………………………..…………………..…………….9 Thermodynamics………………………………………..………………….….…….11 Chemical Reaction and Diffusion

The effect of dry and wet deposition of condensable vapors on secondary organic aerosols concentrations over the continental US

DOE PAGES

Knote, C.; Hodzic, A.; Jimenez, J. L.

2015-01-06

The effect of dry and wet deposition of semi-volatile organic compounds (SVOCs) in the gas phase on the concentrations of secondary organic aerosol (SOA) is reassessed using recently derived water solubility information. The water solubility of SVOCs was implemented as a function of their volatility distribution within the WRF-Chem regional chemistry transport model, and simulations were carried out over the continental United States for the year 2010. Results show that including dry and wet removal of gas-phase SVOCs reduces annual average surface concentrations of anthropogenic and biogenic SOA by 48 and 63% respectively over the continental US. Dry deposition ofmore » gas-phase SVOCs is found to be more effective than wet deposition in reducing SOA concentrations (−40 vs. −8% for anthropogenics, and −52 vs. −11% for biogenics). Reductions for biogenic SOA are found to be higher due to the higher water solubility of biogenic SVOCs. The majority of the total mass of SVOC + SOA is actually deposited via the gas phase (61% for anthropogenics and 76% for biogenics). Results are sensitive to assumptions made in the dry deposition scheme, but gas-phase deposition of SVOCs remains crucial even under conservative estimates. Considering reactivity of gas-phase SVOCs in the dry deposition scheme was found to be negligible. Further sensitivity studies where we reduce the volatility of organic matter show that consideration of gas-phase SVOC removal still reduces average SOA concentrations by 31% on average. We consider this a lower bound for the effect of gas-phase SVOC removal on SOA concentrations. A saturation effect is observed for Henry's law constants above 10 8 M atm −1, suggesting an upper bound of reductions in surface level SOA concentrations by 60% through removal of gas-phase SVOCs. Other models that do not consider dry and wet removal of gas-phase SVOCs would hence overestimate SOA concentrations by roughly 50%. Assumptions about the water solubility of SVOCs made in some current modeling systems ( H * = H * (CH 3COOH); H * = 10 5 M atm −1; H * = H * (HNO 3)) still lead to an overestimation of 35%/25%/10% compared to our best estimate.« less

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 on the oligomers formed by gas-phase polymerization can be obtained using the mass-selected ion mobility technique where the measured collision cross-sections of the selected oligomer ions and collision-induced dissociation can provide fairly accurate structural identifications. The identification of the structures of the dimers and trimers formed in the gas-phase thermal polymerization of styrene confirms that the polymerization proceeds according to the Mayo mechanism. Similarly, the ion mobility technique has been utilized to confirm the formation of benzene cations by intracluster polymerization following the ionization of acetylene clusters. Finally, it has been shown that polymerization of styrene vapor on the surface of activated nanoparticles can lead to the incorporation of a variety of metal and metal oxide nanoparticles within polystyrene films. The ability to probe the reactivity and structure of the small growing oligomers in the gas phase can provide fundamental insight into mechanisms of polymerization that are difficult to obtain from condensed-phase studies. These experiments are also important for understanding the growth mechanisms of complex organics in flames, combustion processes, interstellar clouds, and solar nebula where gas-phase reactions, cluster polymerization, and surface catalysis on dust nanoparticles represent the major synthetic pathways. This research can lead to the discovery of novel initiation mechanisms and reaction pathways with applications in the synthesis of oligomers and nanocomposites with unique and improved properties.

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).

Modeling and Simulation of the Off-gas in an Electric Arc Furnace

NASA Astrophysics Data System (ADS)

Meier, Thomas; Gandt, Karima; Echterhof, Thomas; Pfeifer, Herbert

2017-12-01

The following paper describes an approach to process modeling and simulation of the gas phase in an electric arc furnace (EAF). The work presented represents the continuation of research by Logar, Dovžan, and Škrjanc on modeling the heat and mass transfer and the thermochemistry in an EAF. Due to the lack of off-gas measurements, Logar et al. modeled a simplified gas phase under consideration of five gas components and simplified chemical reactions. The off-gas is one of the main continuously measurable EAF process values and the off-gas flow represents a heat loss up to 30 pct of the entire EAF energy input. Therefore, gas phase modeling offers further development opportunities for future EAF optimization. This paper presents the enhancement of the previous EAF gas phase modeling by the consideration of additional gas components and a more detailed heat and mass transfer modeling. In order to avoid the increase of simulation time due to more complex modeling, the EAF model has been newly implemented to use an efficient numerical solver for ordinary differential equations. Compared to the original model, the chemical components H2, H2O, and CH4 are included in the gas phase and equilibrium reactions are implemented. The results show high levels of similarity between the measured operational data from an industrial scale EAF and the theoretical data from the simulation within a reasonable simulation time. In the future, the dynamic EAF model will be applicable for on- and offline optimizations, e.g., to analyze alternative input materials and mode of operations.

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 ...

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.

Interstellar Alcohols

NASA Technical Reports Server (NTRS)

Charnley, S. B.; Kress, M. E.; Tielens, A. G. G. M.; Millar, T. J.

1995-01-01

We have investigated the gas-phase chemistry in dense cores where ice mantles containing ethanol and other alcohols have been evaporated. Model calculations show that methanol, ethanol, propanol, and butanol drive a chemistry leading to the formation of several large ethers and esters. Of these molecules, methyl ethyl ether (CH3OC2H5) and diethyl ether (C2H5)2O attain the highest abundances and should be present in detectable quantities within cores rich in ethanol and methanol. Gas-phase reactions act to destroy evaporated ethanol and a low observed abundance of gas-phase C,H,OH does not rule out a high solid-phase abundance. Grain surface formation mechanisms and other possible gas-phase reactions driven by alcohols are discussed, as are observing strategies for the detection of these large interstellar molecules.

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.

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 ...

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.

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.

Theoretical gas to liquid shift of (15)N isotropic nuclear magnetic shielding in nitromethane using ab initio molecular dynamics and GIAO/GIPAW calculations.

PubMed

Gerber, Iann C; Jolibois, Franck

2015-05-14

Chemical shift requires the knowledge of both the sample and a reference magnetic shielding. In few cases as nitrogen (15N), the standard experimental reference corresponds to its liquid phase. Theoretical estimate of NMR magnetic shielding parameters of compounds in their liquid phase is then mandatory but usually replaced by an easily-get gas phase value, forbidding direct comparisons with experiments. We propose here to combine ab initio molecular dynamic simulations with the calculations of magnetic shielding using GIAO approach on extracted cluster's structures from MD. Using several computational strategies, we manage to accurately calculate 15N magnetic shielding of nitromethane in its liquid phase. Theoretical comparison between liquid and gas phase allows us to extrapolate an experimental value for the 15N magnetic shielding of nitromethane in gas phase between -121.8 and -120.8 ppm.

Microporous polymer films and methods of their production

DOEpatents

Aubert, James H.

1995-01-01

A process for producing thin microporous polymeric films for a variety of uses. The process utilizes a dense gas (liquified gas or supercritical fluid) selected to combine with a solvent-containing polymeric film so that the solvent is dissolved in the dense gas, the polymer is substantially insoluble in the dense gas, and two phases are formed. A microporous film is obtained by removal of a dense gas-solvent phase.

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.

Concentration, distribution and source apportionment of atmospheric polycyclic aromatic hydrocarbons in the southeast suburb of Beijing, China.

PubMed

Zhang, Shucai; Zhang, Wei; Wang, Kaiyan; Shen, Yating; Hu, Lianwu; Wang, Xuejun

2009-04-01

Total suspended particle samples and gas phase samples were collected at three representative sampling sites in the southeastern suburb of Beijing from March 2005 to January 2006. The samples were analyzed for 16 US EPA priority PAHs using GC/MS. Concentrations of Sigma PAHs in particle and gas phases were 0.21-1.18 x 10(3) ng m(-3) and 9.5 x 10(2) ng-1.03 x 10(5) ng m(-3), respectively. PAH concentrations displayed seasonal variation in the order of winter>spring>autumn>summer for particle phase, and winter>autumn>summer>spring for gas phase. Partial correlation analysis indicates that PAH concentrations in particle phase are negatively correlated with temperature and positively correlated with air pollution index of SO(2). No significant correlation is observed between gas phase PAHs and the auxiliary parameters. Sources of PAH are identified through principal component analysis, and source contributions are estimated through multiple linear regression. Major sources of atmospheric PAHs in the study area include coal combustion, coke industry, vehicular emission and natural gas combustion.

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

Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2018-02-01

Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

Solvation effects on alanine dipeptide: A MP2/cc-pVTZ//MP2/6-31G** study of (Phi, Psi) energy maps and conformers in the gas phase, ether, and water.

PubMed

Wang, Zhi-Xiang; Duan, Yong

2004-11-15

The effects of solvation on the conformations and energies of alanine dipeptide (AD) have been studied by ab initio calculations up to MP2/cc-pVTZ//MP2/6-31G**, utilizing the polarizable continuum model (PCM) to mimic solvation effects. The energy surfaces in the gas phase, ether, and water bear similar topological features carved by the steric hindrance, but the details differ significantly due to the solvent effects. The gas-phase energy map is qualitatively consistent with the Ramachandran plot showing seven energy minima. With respect to the gas-phase map, the significant changes of the aqueous map include (1) the expanded low-energy regions, (2) the emergence of an energy barrier between C5-beta and alpha(R)-beta(2) regions, (3) a clearly pronounced alpha(R) minimum, a new beta-conformer, and the disappearance of the gas-phase global minimum, and (4) the shift of the dominant region in LEII from the gas-phase C7(ax) region to the alpha(L) region. These changes bring the map in water to be much closer to the Ramachandran plot than the gas-phase map. The solvent effects on the geometries include the elongation of the exposed N-H and C=O bonds, the shortening of the buried HN--CO peptide bonds, and the enhanced planarity of the peptide bonds. The energy surface in ether has features similar to those both in the gas phase and in water. The free energy order computed in the gas phase and in ether is in good agreement with experimental studies that concluded that C5 and C7(eq) are the dominant species in both the gas phase and nonpolar solvents. The free energy order in water is consistent with the experimental observation that the dominant C7(eq) in the nonpolar solvent was largely replaced by P(II)-like (i.e., beta) and alpha(R) in the strong polar solvents. Based on calculations on AD + 4H(2)O and other AD-water clusters, we suggest that explicit water-AD interactions may distort C5 and beta (or alpha(R) and beta) to an intermediate conformation. Our analysis also shows that the PCM calculations at the MP2/cc-pVTZ//MP2/6-31G** level give good descriptions to the bulk solvent polarization effect. The results presented in this article should be of sufficient quality to characterize the peptide bonds in the gas phase and solvents. The energy surfaces may serve as the basis for developing of strategies enabling the inclusion of solvent polarization in the force field.

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.

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.

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

Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface.

PubMed

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2018-04-06

We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface-controlled by a crossover in how methane is supplied from the gas and liquid phases-which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

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 ...

Gaseous and particulate water-soluble organic and inorganic nitrogen in rural air in southern Scotland

NASA Astrophysics Data System (ADS)

González Benítez, Juan M.; Cape, J. Neil; Heal, Mathew R.

2010-04-01

Simultaneous daily measurements of water-soluble organic nitrogen (WSON), ammonium and nitrate were made between July and November 2008 at a rural location in south-east Scotland, using a 'Cofer' nebulizing sampler for the gas phase and collection on an open-face PTFE membrane for the particle phase. Average concentrations of NH 3 were 82 ± 17 nmol N m -3 (error is s.d. of triplicate samples), while oxidised N concentrations in the gas phase (from trapping NO 2 and HNO 3) were smaller, at 2.6 ± 2.2 nmol N m -3, and gas-phase WSON concentrations were 18 ± 11 nmol N m -3. The estimated collection efficiency of the nebulizing samplers for the gas phase was 88 (±8) % for NH 3, 37 (±16) % for NO 2 and 57 (±7) % for WSON; reported average concentrations have not been corrected for sampling efficiency. Concentrations in the particle phase were smaller, except for nitrate, at 21 ± 9, 10 ± 6 and 8 ± 9 nmol N m -3, respectively. The absence of correlation in either phase between WSON and either (NH 3 + NH 4+) or NO 3- concentrations suggests atmospheric WSON has diverse sources. During wet days, concentrations of gas and particle-phase inorganic N were lower than on dry days, whereas the converse was true for WSON. These data represent the first reports of simultaneous measurements of gas and particle phase water-soluble nitrogen compounds in rural air on a daily basis, and show that WSON occurs in both phases, contributing 20-25% of the total water-soluble nitrogen in air, in good agreement with earlier data on the contribution of WSON to total dissolved N in rainfall in the UK.

Effect of isothermal dilution on emission factors of organic carbon and n-alkanes in the particle and gas phases of diesel exhaust

NASA Astrophysics Data System (ADS)

Fujitani, Yuji; Saitoh, Katsumi; Fushimi, Akihiro; Takahashi, Katsuyuki; Hasegawa, Shuich; Tanabe, Kiyoshi; Kobayashi, Shinji; Furuyama, Akiko; Hirano, Seishiro; Takami, Akinori

2012-11-01

To investigate the effect of isothermal dilution (30 °C) on emission factors (EFs) of semivolatile and nonvolatile compounds of heavy-duty diesel exhaust, we measured EFs for particulate matter (PM), organic carbon (OC), and elemental carbon (EC) in the particle phase, and EFs for n-alkanes in both the particle phase and the gas phase of exhaust produced under high-idle engine operating conditions at dilution ratios (DRs) ranging from 8 to 1027. The EC EFs did not vary with DR, whereas the OC EFs in the particle phase determined at DR = 1027 were 13% of the EFs determined at DR = 8, owing to evaporation of organic compounds. Using partitioning theory and n-alkane EFs measured at DR = 14 and 238, we calculated the distributions of compounds between the particle and gas phases at DR = 1760, which corresponds to the DR for tailpipe emissions as they move from the tailpipe to the roadside atmosphere. The gas-phase EF of a compound with a vapor pressure of 10-7 Pa was 0.01 μg kg-1-fuel at DR = 14, and this value is 1/330 the value derived at DR = 1760. Our results suggest that the EFs of high-volatility compounds in the particle phase will be overestimated and that the EFs of low-volatility compounds in the gas phase will be underestimated if the estimates are derived from data obtained at the low DRs and they are applied to the real world. Therefore, extrapolation from EFs derived at low DR values to EFs at atmospherically relevant DRs will be a source of error in predictions of the concentrations of particulate matter and gas-phase precursors to secondary organic aerosols in air quality models.

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

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 .

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.

Thermodynamic considerations of the vapor phase reactions in III-nitride metal organic vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Sekiguchi, Kazuki; Shirakawa, Hiroki; Chokawa, Kenta; Araidai, Masaaki; Kangawa, Yoshihiro; Kakimoto, Koichi; Shiraishi, Kenji

2017-04-01

We analyzed the metal organic vapor phase epitaxial growth mechanism of the III-nitride semiconductors GaN, AlN, and InN by first-principles calculations and thermodynamic analyses. In these analyses, we investigated the decomposition processes of the group III source gases X(CH3)3 (X = Ga, Al, In) at finite temperatures and determined whether the (CH3)2GaNH2 adduct can be formed or not. The results of our calculations show that the (CH3)2GaNH2 adduct cannot be formed in the gas phase in GaN metal organic vapor phase epitaxy (MOVPE), whereas, in AlN MOVPE, the formation of the (CH3)2AlNH2 adduct in the gas phase is exclusive. In the case of GaN MOVPE, trimethylgallium (TMG, [Ga(CH3)3]) decomposition into Ga gas on the growth surface with the assistance of H2 carrier gas, instead of the formation of the (CH3)2GaNH2 adduct, occurs almost exclusively. Moreover, in the case of InN MOVPE, the formation of the (CH3)2InNH2 adduct does not occur and it is relatively easy to produce In gas even without H2 in the carrier gas.

Extinguishment of a Diffusion Flame Over a PMMA Cylinder by Depressurization in Reduced-Gravity

NASA Technical Reports Server (NTRS)

Goldmeer, Jeffrey Scott

1996-01-01

Extinction of a diffusion flame burning over horizontal PMMA (Polymethyl methacrylate) cylinders in low-gravity was examined experimentally and via numerical simulations. Low-gravity conditions were obtained using the NASA Lewis Research Center's reduced-gravity aircraft. The effects of velocity and pressure on the visible flame were examined. The flammability of the burning solid was examined as a function of pressure and the solid-phase centerline temperature. As the solid temperature increased, the extinction pressure decreased, and with a centerline temperature of 525 K, the flame was sustained to 0.1 atmospheres before extinguishing. The numerical simulation iteratively coupled a two-dimensional quasi-steady, gas-phase model with a transient solid-phase model which included conductive heat transfer and surface regression. This model employed an energy balance at the gas/solid interface that included the energy conducted by the gas-phase to the gas/solid interface, Arrhenius pyrolysis kinetics, surface radiation, and the energy conducted into the solid. The ratio of the solid and gas-phase conductive fluxes Phi was a boundary condition for the gas-phase model at the solid-surface. Initial simulations modeled conditions similar to the low-gravity experiments and predicted low-pressure extinction limits consistent with the experimental limits. Other simulations examined the effects of velocity, depressurization rate and Phi on extinction.

Dimerization and conformation-related free energy landscapes of dye-tagged amyloid-β12-28 linked to FRET experiments.

PubMed

Kulesza, Alexander; Daly, Steven; Dugourd, Philippe

2017-04-05

We have investigated the free energy landscape of Aβ-peptide dimer models in connection to gas-phase FRET experiments. We use a FRET-related distance coordinate and one conformation-related coordinate per monomer for accelerated structural exploration with well-tempered metadynamics in solvent and in vacuo. The free energy profiles indicate that FRET under equilibrium conditions should be significantly affected by the de-solvation upon the transfer of ions to the gas-phase. In contrast, a change in the protonation state is found to be less impacting once de-solvated. Comparing F19P and WT alloforms, for which we measure different FRET efficiencies in the gas-phase, we predict only the relevant structural differences in the solution populations, not under gas-phase equilibrium conditions. This finding supports the hypothesis that the gas-phase action-FRET measurement after ESI operates under non-equilibrium conditions, with a memory of the solution conditions - even for the dimer of this relatively short peptide. The structural differences in solution are rationalized in terms of conformational propensities around residue 19, which show a transition to a poly-proline type of pattern upon mutation to F19P - a difference that gets lost in the gas-phase.

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 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.

Derivation of a formula for the resonance integral for a nonorthogonal basis set

PubMed Central

Yim, Yung-Chang; Eyring, Henry

1981-01-01

In a self-consistent field calculation, a formula for the off-diagonal matrix elements of the core Hamiltonian is derived for a nonorthogonal basis set by a polyatomic approach. A set of parameters is then introduced for the repulsion integral formula of Mataga-Nishimoto to fit the experimental data. The matrix elements computed for the nonorthogonal basis set in the π-electron approximation are transformed to those for an orthogonal basis set by the Löwdin symmetrical orthogonalization. PMID:16593009

Microporous polymer films and methods of their production

DOEpatents

Aubert, J.H.

1995-06-06

A process is described for producing thin microporous polymeric films for a variety of uses. The process utilizes a dense gas (liquefied gas or supercritical fluid) selected to combine with a solvent-containing polymeric film so that the solvent is dissolved in the dense gas, the polymer is substantially insoluble in the dense gas, and two phases are formed. A microporous film is obtained by removal of a dense gas-solvent phase. 9 figs.

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

Passive landfill gas emission - Influence of atmospheric pressure and implications for the operation of methane-oxidising biofilters.

PubMed

Gebert, Julia; Groengroeft, Alexander

2006-01-01

A passively vented landfill site in Northern Germany was monitored for gas emission dynamics through high resolution measurements of landfill gas pressure, flow rate and composition as well as atmospheric pressure and temperature. Landfill gas emission could be directly related to atmospheric pressure changes on all scales as induced by the autooscillation of air, diurnal variations and the passage of pressure highs and lows. Gas flux reversed every 20 h on average, with 50% of emission phases lasting only 10h or less. During gas emission phases, methane loads fed to a connected methane oxidising biofiltration unit varied between near zero and 247 g CH4 h(-1)m(-3) filter material. Emission dynamics not only influenced the amount of methane fed to the biofilter but also the establishment of gas composition profiles within the biofilter, thus being of high relevance for biofilter operation. The duration of the gas emission phase emerged as most significant variable for the distribution of landfill gas components within the biofilter.

Gas network model allows full reservoir coupling

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

Methnani, M.M.

The gas-network flow model (Gasnet) developed for and added to an existing Qatar General Petroleum Corp. (OGPC) in-house reservoir simulator, allows improved modeling of the interaction among the reservoir, wells, and pipeline networks. Gasnet is a three-phase model that is modified to handle gas-condensate systems. The numerical solution is based on a control volume scheme that uses the concept of cells and junctions, whereby pressure and phase densities are defined in cells, while phase flows are defined at junction links. The model features common numerical equations for the reservoir, the well, and the pipeline components and an efficient state-variable solutionmore » method in which all primary variables including phase flows are solved directly. Both steady-state and transient flow events can be simulated with the same tool. Three test cases show how the model runs. One case simulates flow redistribution in a simple two-branch gas network. The second simulates a horizontal gas well in a waterflooded gas reservoir. The third involves an export gas pipeline coupled to a producing reservoir.« less

Under What Conditions Can Equilibrium Gas-Particle Partitioning Be Expected to Hold in the Atmosphere?

PubMed

Mai, Huajun; Shiraiwa, Manabu; Flagan, Richard C; Seinfeld, John H

2015-10-06

The prevailing treatment of secondary organic aerosol formation in atmospheric models is based on the assumption of instantaneous gas-particle equilibrium for the condensing species, yet compelling experimental evidence indicates that organic aerosols can exhibit the properties of highly viscous, semisolid particles, for which gas-particle equilibrium may be achieved slowly. The approach to gas-particle equilibrium partitioning is controlled by gas-phase diffusion, interfacial transport, and particle-phase diffusion. Here we evaluate the controlling processes and the time scale to achieve gas-particle equilibrium as a function of the volatility of the condensing species, its surface accommodation coefficient, and its particle-phase diffusivity. For particles in the size range of typical atmospheric organic aerosols (∼50-500 nm), the time scale to establish gas-particle equilibrium is generally governed either by interfacial accommodation or particle-phase diffusion. The rate of approach to equilibrium varies, depending on whether the bulk vapor concentration is constant, typical of an open system, or decreasing as a result of condensation into the particles, typical of a closed system.

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.

Amperometric detector for gas chromatography based on a silica sol-gel solid electrolyte.

PubMed

Steinecker, William H; Miecznikowski, Krzysztof; Kulesza, Pawel J; Sandlin, Zechariah D; Cox, James A

2017-11-01

An electrochemical cell comprising a silica sol-gel solid electrolyte, a working electrode that protrudes into a gas phase, and reference and counter electrodes that contact the solid electrolyte comprises an amperometric detector for gas chromatography. Under potentiostatic conditions, a current related to the concentration of an analyte in the gas phase is produced by its oxidation at the three-phase boundary among the sol-gel, working electrode, and the gas phase. The sol-gel is processed to contain an electrolyte that also serves as a humidistat to maintain a constant water activity even in the presence the gas chromatographic mobile phase. Response was demonstrated toward a diverse set of analytes, namely hydrogen, 1,2-ethandithiol, phenol, p-cresol, and thioanisole. Using flow injection amperometry of hydrogen with He as the carrier gas, 90% of the steady-state current was achieved in < 1s at a flow rate of 20mLmin -1 . A separation of 1,2-ethandithiol, phenol, p-cresol, and thioanisole at a 2.2mLmin -1 flow rate was achieved with respective detection limits (k = 3 criterion) of 4, 1, 3, and 70 ppmv when the working electrode potential was 800mV. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

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.

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 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

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.

Organic molecules, ions, and rare isotopologues in the remnant of the stellar-merger candidate, CK Vulpeculae (Nova 1670)

NASA Astrophysics Data System (ADS)

Kamiński, T.; Menten, K. M.; Tylenda, R.; Karakas, A.; Belloche, A.; Patel, N. A.

2017-11-01

Context. CK Vulpeculae (CK Vul) is an enigmatic star whose outburst was observed in 1670-72. A stellar-merger event was proposed to explain its ancient eruption. Aims: We aim to investigate the composition of the molecular gas recently discovered in the remnant of CK Vul. Deriving the chemical, elemental, and isotopic composition is crucial for identifying the nature of the object and obtaining clues on its progenitor(s). Methods: We observed millimeter and submillimeter-wave spectra of CK Vul using the IRAM 30 m and APEX telescopes. Radiative-transfer modeling of the observed molecular features was performed to yield isotopic ratios for various elements. Results: The spectra of CK Vul reveal a very rich molecular environment of low excitation (Tex ≲ 12 K). Atomic carbon and twenty-seven different molecules, including two ions, were identified. They range from simple diatomic to complex polyatomic species of up to seven atoms large. The chemical composition of the molecular gas is indicative of carbon and nitrogen-driven chemistry but oxides are also present. Additionally, the abundance of fluorine may be enhanced. The spectra are rich in isotopologues that are very rare in most known sources. All stable isotopes of C, N, O, Si, and S are observed and their isotopic ratios are derived. Conclusions: The composition of the remnant's molecular gas is most peculiar and gives rise to a very unique millimeter and submillimeter spectrum. The observation of ions and complex molecules suggests the presence of a photoionizing source but its nature (a central star or shocks) remains unknown. The elemental and isotopic composition of the gas cannot be easily reconciled with standard stellar nucleosynthesis but processing in hot CNO cycles and partial helium burning can explain most of the chemical peculiarities. The isotopic ratios of CK Vul are remarkably close to those of presolar "nova grains" but the link of Nova 1670 to objects responsible for these grains is unclear. The accuracy of isotopic ratios can be improved by future observations at higher angular resolutions and with realistic models of the kinematical structure of the remnant. The reduced spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/607/A78

In situ probing of doping- and stress-mediated phase transitions in a single-crystalline VO2 nanobeam by spatially resolved Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chang, Sung-Jin; Park, Jong Bae; Lee, Gaehang; Kim, Hae Jin; Lee, Jin-Bae; Bae, Tae-Sung; Han, Young-Kyu; Park, Tae Jung; Huh, Yun Suk; Hong, Woong-Ki

2014-06-01

We demonstrate an experimental in situ observation of the temperature-dependent evolution of doping- and stress-mediated structural phase transitions in an individual single-crystalline VO2 nanobeam on a Au-coated substrate under exposure to hydrogen gas using spatially resolved Raman spectroscopy. The nucleation temperature of the rutile R structural phase in the VO2 nanobeam upon heating under hydrogen gas was lower than that under air. The spatial structural phase evolution behavior along the length of the VO2 nanobeam under hydrogen gas upon heating was much more inhomogeneous than that along the length of the same nanobeam under air. The triclinic T phase of the VO2 nanobeam upon heating under hydrogen gas transformed to the R phase and this R phase was stabilized even at room temperature in air after sample cooling. In particular, after the VO2 nanobeam with the R phase was annealed at approximately 250 °C in air, it exhibited the monoclinic M1 phase (not the T phase) at room temperature during heating and cooling cycles. These results were attributed to the interplay between hydrogen doping and stress associated with nanobeam-substrate interactions. Our study has important implications for engineering metal-insulator transition properties and developing functional devices based on VO2 nanostructures through doping and stress.We demonstrate an experimental in situ observation of the temperature-dependent evolution of doping- and stress-mediated structural phase transitions in an individual single-crystalline VO2 nanobeam on a Au-coated substrate under exposure to hydrogen gas using spatially resolved Raman spectroscopy. The nucleation temperature of the rutile R structural phase in the VO2 nanobeam upon heating under hydrogen gas was lower than that under air. The spatial structural phase evolution behavior along the length of the VO2 nanobeam under hydrogen gas upon heating was much more inhomogeneous than that along the length of the same nanobeam under air. The triclinic T phase of the VO2 nanobeam upon heating under hydrogen gas transformed to the R phase and this R phase was stabilized even at room temperature in air after sample cooling. In particular, after the VO2 nanobeam with the R phase was annealed at approximately 250 °C in air, it exhibited the monoclinic M1 phase (not the T phase) at room temperature during heating and cooling cycles. These results were attributed to the interplay between hydrogen doping and stress associated with nanobeam-substrate interactions. Our study has important implications for engineering metal-insulator transition properties and developing functional devices based on VO2 nanostructures through doping and stress. Electronic supplementary information (ESI) available: Illustration, photograph, Raman data, and EDX spectra. See DOI: 10.1039/c4nr01118j

GAS- AND SOLID-PHASE PARTITIONING OF PCDDS/FS ON MSWI FLY ASH AND THE EFFECTS OF SAMPLING

EPA Science Inventory

Semi-volatile organic compounds (SOCs), including polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/Fs), are partitioned as gas-phase and particle-bound products of many industrial combustion processes. This gas/particle partitioning of SOCs has severe implications on both ...

A microfluidic device for open loop stripping of volatile organic compounds.

PubMed

Cvetković, Benjamin Z; Dittrich, Petra S

2013-03-01

The detection of volatile organic compounds is of great importance for assessing the quality of water. In this contribution, we describe a miniaturized stripping device that allows fast online detection of organic solvents in water. The core component is a glass microfluidic chip that facilitates the creation of an annular-flowing stream of water and nitrogen gas. Volatile compounds are transferred efficiently from the water into the gas phase along the microfluidic pathway at room temperature within less than 5 s. Before exiting the microchip, the liquid phase is separated from the enriched gas phase by incorporating side capillaries through which the hydrophilic water phase is withdrawn. The gas phase is conveniently collected at the outlet reservoir by tubing. Finally, a semiconductor gas sensor analyzes the concentration of (volatile) organic compounds in the nitrogen gas. The operation and use of the stripping device is demonstrated for the organic solvents THF, 1-propanol, toluene, ethylbenzene, benzaldehyde, and methanol. The mobile, inexpensive, and continuously operating system with liquid flow rates in the low range of microliters per minute can be connected to other detectors or implemented in chemical production line for process control.

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.

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

Time dependent chemistry in dense molecular clouds. I - Grain surface reactions, gas/grain interactions and infrared spectroscopy

NASA Technical Reports Server (NTRS)

Dhendecourt, L. B.; Allamandola, L. J.; Greenberg, J. M.

1985-01-01

For the fist time, a time-dependent model is described which includes the role of grains in the production of molecules in dense clouds including ion-molecule gas phase chemistry. The approach provides information regarding the coupling between the two phases. Although the coupling between the two chemistries is extremely strong, the two domains maintain their own identities. While H2O, CH4, and NH3 are made efficiently, with a high production rate on grains and released back to the gas phase, the gas phase is essentially responsible for the formation of CO, a very stable molecule which may or may not react on grains with atomic oxygen and may or may not form CO2.

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.

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.

Dispersed bubble reactor for enhanced gas-liquid-solids contact and mass transfer

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

Vimalchand, Pannalal; Liu, Guohai; Peng, WanWang

An apparatus to promote gas-liquid contact and facilitate enhanced mass transfer. The dispersed bubble reactor (DBR) operates in the dispersed bubble flow regime to selectively absorb gas phase constituents into the liquid phase. The dispersion is achieved by shearing the large inlet gas bubbles into fine bubbles with circulating liquid and additional pumped liquid solvent when necessary. The DBR is capable of handling precipitates that may form during absorption or fine catalysts that may be necessary to promote liquid phase reactions. The DBR can be configured with multistage counter current flow sections by inserting concentric cylindrical sections into the risermore » to facilitate annular flow. While the DBR can absorb CO.sub.2 in liquid solvents that may lead to precipitates at high loadings, it is equally capable of handling many different types of chemical processes involving solids (precipitates/catalysts) along with gas and liquid phases.« less

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

Rapid gas hydrate formation process

DOEpatents

Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.

2013-01-15

The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

Quantification of Semi-Volatile gas-phase Organic Compounds (SVOCs) & Organic Aerosol species and the role of SVOCs in Secondary Organic Aerosol formation

NASA Astrophysics Data System (ADS)

Khan, M. H.; Holzinger, R.

2013-12-01

A Thermal-Desorption Proton-Transfer-Reaction Mass-Spectrometer (TD-PTR-MS) with different sampling systems (multi-stage denuder for gas phase and impact on a collector for aerosol phase) has been deployed in summer 2013 during the Southern Oxidant and Aerosol Study (SOAS) at the SEARCH ground site, Centreville, Alabama for in-situ gas phase and aerosol measurements on an hourly time resolution. A bunch of DB-1 column (0.53 mm x 5.0 μm) is used in the denuder for capturing the bulk of SVOCs and a collection-thermal-desorption (CTD) cell is used for collecting aerosol particles. Several hundreds semivolatile organic compounds (SVOCs) in gas phase and aerosol phases have been detected. The high mass resolution capabilities of ~5000, low detection limit (<0.05 pptv for gas species, <0.01 ng m-3 for aerosol species) and good physical and chemical characterization of SVOCs with the TD-PTR-MS allows constraining both, the quantity and the chemical composition. The SEARCH site was highly impacted by Biogenic Volatile Organic Compounds (BVOCs) and occasionally influenced by anthropogenic pollution. BVOCs and their oxidation products are capable of partitioning into the particle phase, so their simultaneous quantification in both phases has been used to determine the gas/particle-phase partitioning. Our results show the expected diurnal variation based on the changes of air temperature for many species. The results from this study give valuable insights into sources and processing of Secondary Organic Aerosols (SOAs) that can be used to improve parameterization algorithms in regional and global climate models.

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.

Investigation of a measure of robustness in inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Makonnen, Yoseif; Beauchemin, Diane

2015-01-01

In industrial/commercial settings where operators often have minimal expertise in inductively coupled plasma (ICP) mass spectrometry (MS), there is a prevalent need for a response factor indicating robust plasma conditions, which is analogous to the Mg II/Mg I ratio in ICP optical emission spectrometry (OES), whereby a Mg II/Mg I ratio of 10 constitutes robust conditions. While minimizing the oxide ratio usually corresponds to robust conditions, there is no specific target value that is widely accepted as indicating robust conditions. Furthermore, tuning for low oxide ratios does not necessarily guarantee minimal matrix effects, as they really address polyatomic interferences. From experiments, conducted in parallel for both MS and OES, there were some element pairs of similar mass and very different ionization potential that were exploited for such a purpose, the rationale being that, if these elements were ionized to the same extent, then that could be indicative of a robust plasma. The Be II/Li I intensity ratio was directly related to the Mg II/Mg I ratio in OES. Moreover, the 9Be+/7Li+ ratio was inversely related to the CeO+/Ce+ and LaO+/La+ oxide ratios in MS. The effects of different matrices (i.e. 0.01-0.1 M Na) were also investigated and compared to a conventional argon plasma optimized for maximum sensitivity. The suppression effect of these matrices was significantly reduced, if not eliminated in the case of 0.01 M Na, when the 9Be+/7Li+ ratio was around 0.30 on the Varian 820 MS instrument. Moreover, a very similar ratio (0.28) increased robustness to the same extent on a completely different ICP-MS instrument (PerkinElmer NEXION). Much greater robustness was achieved using a mixed-gas plasma with nitrogen in the outer gas and either nitrogen or hydrogen as a sheathing gas, as the 9Be+/7Li+ ratio was then around 1.70. To the best of our knowledge, this is the first report on using a simple analyte intensity ratio, 9Be+/7Li+, to gauge plasma robustness.

In situ neutron diffraction study of deuterium gas absorption by AB5+y alloys used as negative electrode materials for Ni-MH batteries

NASA Astrophysics Data System (ADS)

Latroche, M.; Joubert, J.-M.; Guégan, A. Percheron; Isnard, O.

2004-07-01

LaNi5-type alloys store reversibly hydrogen and are used as negative electrode materials in Ni-MH batteries. Substitutions on La and Ni crystallographic sites have led to competitive materials with complex formulae Mm(Ni4.3-xMn0.4Al0.3Cox)1+y (Mm: mishmetal). Materials involving an unexpected metastable phase γ show the best cycle lives. This phase occurrence depends on the mishmetal composition, the cobalt rate and the over-stoichiometry. It is observed as a transitory phase only for charge in electrochemical process. To confirm the appearance of this phase during gas loading, in beam D2 gas absorption has been performed on two materials for which the γ phase is expected. Phase amounts and cell volumes have been measured by in situ neutron powder diffraction analysis under controlled gas pressure as a function of the state of charge.

Measurements and predictions of a liquid spray from an air-assist nozzle

NASA Technical Reports Server (NTRS)

Bulzan, Daniel L.; Levy, Yeshayahou; Aggarwal, Suresh K.; Chitre, Susheel

1991-01-01

Droplet size and gas velocity were measured in a water spray using a two-component Phase/Doppler Particle Analyzer. A complete set of measurements was obtained at axial locations from 5 to 50 cm downstream of the nozzle. The nozzle used was a simple axisymmetric air-assist nozzle. The sprays produced, using the atomizer, were extremely fine. Sauter mean diameters were less than 20 microns at all locations. Measurements were obtained for droplets ranging from 1 to 50 microns. The gas phase was seeded with micron sized droplets, and droplets having diameters of 1.4 microns and less were used to represent gas-phase properties. Measurements were compared with predictions from a multi-phase computer model. Initial conditions for the model were taken from measurements at 5 cm downstream. Predictions for both the gas phase and the droplets showed relatively good agreement with the measurements.

Alcohol Oxidation at Platinum–Gas and Platinum–Liquid Interfaces: The Effect of Platinum Nanoparticle Size, Water Coadsorption, and Alcohol Concentration

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

Tatsumi, Hironori; Liu, Fudong; Han, Hui-Ling

Platinum nanoparticles size range from 1 to 8 nm deposited on mesoporous silica MCF-17 catalyzed alcohol oxidations were studied in the gas and liquid phases. Among methanol, ethanol, 2- propanol and 2-butanol reactions, the turnover frequency increased with Pt nanoparticle size for all the alcohols utilized. The activation energies for the oxidations were almost same among all alcohol species, but higher in the gas phase than those in the liquid phase. Water coadsorption poisoned the reaction in the gas phase, while it increased the reaction turnover rates in the liquid phase. Sum frequency generation (SFG) vibrational spectroscopy studies and DFTmore » calculations revealed that the alcohol molecules pack horizontally on the metal surface in low concentrations and stand up in high concentrations, which affect the dissociation of β-hydrogen of the alcohols as the critical step in alcohol oxidations.« less

Alcohol Oxidation at Platinum–Gas and Platinum–Liquid Interfaces: The Effect of Platinum Nanoparticle Size, Water Coadsorption, and Alcohol Concentration

DOE PAGES

Tatsumi, Hironori; Liu, Fudong; Han, Hui-Ling; ...

2017-03-21

Platinum nanoparticles size range from 1 to 8 nm deposited on mesoporous silica MCF-17 catalyzed alcohol oxidations were studied in the gas and liquid phases. Among methanol, ethanol, 2- propanol and 2-butanol reactions, the turnover frequency increased with Pt nanoparticle size for all the alcohols utilized. The activation energies for the oxidations were almost same among all alcohol species, but higher in the gas phase than those in the liquid phase. Water coadsorption poisoned the reaction in the gas phase, while it increased the reaction turnover rates in the liquid phase. Sum frequency generation (SFG) vibrational spectroscopy studies and DFTmore » calculations revealed that the alcohol molecules pack horizontally on the metal surface in low concentrations and stand up in high concentrations, which affect the dissociation of β-hydrogen of the alcohols as the critical step in alcohol oxidations.« less

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.

Modeling biogenic gas bubbles formation and migration in coarse sand

NASA Astrophysics Data System (ADS)

Ye, S.

2011-12-01

Shujun Ye Department of Hydrosciences, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210093, China; sjye@nju.edu.cn Brent E. Sleep Department of Civil Engineering, University of Toronto, Toronto, ON, M5S 1A4 CANADA; sleep@ecf.utoronto.ca Methane gas generation in porous media was investigated in an anaerobic two-dimensional sand-filled cell. Inoculation of the lower portion of the cell with a methanogenic culture and addition of methanol to the bottom of the cell led to biomass growth and formation of a gas phase. The formation, migration, distribution and saturation of gases in the cell were visualized by the charge-coupled device (CCD) camera. Gas generated at the bottom of the cell in the biologically active zone moved upwards in discrete fingers, so that gas phase saturations (gas-filled fraction of void space) in the biologically active zone at the bottom of the cell did not exceed 40-50%, while gas accumulation at the top of the cell produced gas phase saturations as high as 80%. Macroscopic invasion percolation (MIP) at near pore scale[Glass, et al., 2001; Kueper and McWhorter, 1992]was used to model gas bubbles growth in porous media. The nonwetting phase migration pathway can be yielded directly by MIP. MIP was adopted to simulate the expansion, fragmentation, and mobilization of gas clusters in the cell. The production of gas, and gas phash saturations were simulated by a continuum model - compositional simulator (COMPSIM) [Sleep and Sykes, 1993]. So a combination of a continuum model and a MIP model was used to simulate the formation, fragmentation and migration of biogenic gas bubbles. Key words: biogenic gas; two dimensional; porous media; MIP; COMPSIM

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.

Surface charge-induced EDL interaction on the contact angle of surface nanobubbles.

PubMed

Jing, Dalei; Li, Dayong; Pan, Yunlu; Bhushan, Bharat

2016-11-01

The contact angle (CA) of surface nanobubbles is believed to affect the stability of nanobubbles and fluid drag in micro/nanofluidic systems. The CA of nanobubbles is dependent on size and is believed to be affected by the surface charge-induced electrical double layer (EDL). However, neither of these of attributes are well understood. In this paper, by introducing an EDL-induced electrostatic wetting tension, a theoretical model is first established to study the effect of EDLs formed near the solid-liquid interface and the liquid-nanobubble interface on the gas phase CA of nanobubbles. The size-dependence of this EDL interaction is studied as well. Next, by using atomic force microscopy (AFM), the effect of the EDL on nanobubbles' gas phase CA is studied with variable electrical potential at the solid-liquid interface, which is adjusted by an applied voltage. Both the theoretical and the experimental results show that the EDLs formed near the solid-liquid interface and the liquid-nanobubble interface lead to a reduction of gas phase CA of the surface nanobubbles because of an electrostatic wetting tension on the nanobubble due to the attractive electrostatic interaction between the liquid and nanobubble within the EDL, which is in the nanobubbles' outward direction. An EDL with a larger zeta potential magnitude leads to a larger gas phase CA reduction. Furthermore, the effect of EDL on the nanobubbles' gas phase CA shows a significant size-dependence considering the size dependence of the electrostatic wetting tension. The gas phase CA reduction due to the EDL decreases with increasing nanobubble height and increases with the nanobubble's increasing curvature radius, indicating that a surface charge-induced EDL could possibly explain the size dependence of the gas phase CA of nanobubbles.

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

Gas/solid particulate phthalic esters (PAEs) in Masson pine (Pinus massoniana L.) needles and rhizosphere surface soils.

PubMed

Wang, Wen-xin; Fan, Chinbay Q

2014-07-15

Phthalic acid esters (PAEs) are used in many branches of industry and are produced in huge amounts throughout the world. An investigation on particulate- and gas-phase distribution of PAEs has been conducted between January 2011 and December 2012 in Nanjing (China). Masson pine (Pinus massoniana L.) needles and rhizosphere surface soils were sampled from urban to suburban/remote sites, to investigate the pine needle/soil distribution of PAEs. The results showed that the average total PAE concentration (gas+particle) was 97.0ngm(-3). The six PAE congeners considered predominantly existed in the gas phase and the average contribution of gas phase to total PAEs ranged from 75.0% to 89.1%. The PAE concentrations in rhizosphere soils and pine needles were positively correlated with their particulate- and gas-phase concentrations, respectively, which suggested that surface soils accumulated PAEs mainly through gravity deposition of particles and pine needle stomata absorbed PAEs mainly from the gas phase. The gas/particle partitioning (KP) and soil-pine needle ratio (Rs/n) were determined. Experimentally determined KP values correlated well with the subcooled liquid vapor pressures (PL). A set of interesting relationships of logRs/n-logKP-logPL was employed to explain the experimental findings of PAEs deposition to surface soils and to needles. This data set offered a unique perspective into the influence that Rs/n played in KP and correlated with PL. Copyright © 2014 Elsevier B.V. All rights reserved.

The Pathophysiology of Decompression Sickness and the Effects of Doppler Detectable Bubbles.

DTIC Science & Technology

1980-12-18

Doppler Ultrasound and a calibrated 6 1 Venous Gas Embol i Scale. C. Electronic Counting of Doppler Bubble Signals 72 £ III. Pulmonary Embolism Studies...IA. Background 75 B. Right Ventricular Systolic Pressure following Gas 81 Embolization and Venous Gas Phase Content IC. Effects of Pulmonary Gas... Embolism on the Development 9 of Limb-Bend Decompression Sickness 1 IV. Gas Phase Formation in Highly Perfused Tissues IA. Renal 9 B. Cerebral 9 1 I I V

Exhaust plume impingement of chemically reacting gas-particle flows

NASA Technical Reports Server (NTRS)

Smith, S. D.; Penny, M. M.; Greenwood, T. F.; Roberts, B. B.

1975-01-01

A series of computer codes has been developed to predict gas-particle flows and resulting impingement forces, moments and heating rates to surfaces immersed in the flow. The gas-particle flow solution is coupled via heat transfer and drag between the phases with chemical effects included in the gas phase. The flow solution and impingement calculations are discussed. Analytical results are compared with test data obtained to evaluate gas-particle effects on the Space Shuttle thermal protection system during the staging maneuver.

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.

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.

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.

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.

MULTIGRAIN: a smoothed particle hydrodynamic algorithm for multiple small dust grains and gas

NASA Astrophysics Data System (ADS)

Hutchison, Mark; Price, Daniel J.; Laibe, Guillaume

2018-05-01

We present a new algorithm, MULTIGRAIN, for modelling the dynamics of an entire population of small dust grains immersed in gas, typical of conditions that are found in molecular clouds and protoplanetary discs. The MULTIGRAIN method is more accurate than single-phase simulations because the gas experiences a backreaction from each dust phase and communicates this change to the other phases, thereby indirectly coupling the dust phases together. The MULTIGRAIN method is fast, explicit and low storage, requiring only an array of dust fractions and their derivatives defined for each resolution element.

Calculation of Linear Stability of a Stratified Gas-Liquid Flow in an Inclined Plane Channel

NASA Astrophysics Data System (ADS)

Trifonov, Yu. Ya.

2018-01-01

Linear stability of liquid and gas counterflows in an inclined channel is considered. The full Navier-Stokes equations for both phases are linearized, and the dynamics of periodic disturbances is determined by means of solving a spectral problem in wide ranges of Reynolds numbers for the liquid and vapor velocity. Two unstable modes are found in the examined ranges: surface mode (corresponding to the Kapitsa waves at small velocities of the gas) and shear mode in the gas phase. The wave length and the phase velocity of neutral disturbances of both modes are calculated as functions of the Reynolds number for the liquid. It is shown that these dependences for the surface mode are significantly affected by the gas velocity.

Bioelectronic sniffer for nicotine using enzyme inhibition.

PubMed

Mitsubayashi, Kohji; Nakayama, Kazumi; Taniguchi, Midori; Saito, Hirokazu; Otsuka, Kimio; Kudo, Hiroyuki

2006-07-28

A novel bioelectronic sniffer for nicotine in the gas phase was developed with enzyme inhibition principle to butyrylcholinesterase activity. The bioelectronic devices for nicotine in the gas and liquid phases were constructed using a Clark-type dissolved oxygen electrode and a membrane immobilized butyrylcholinesterase and choline oxidase. After the assessment of the sensor performances to choline and butyrylcholine as pre-examinations, the characteristics of the biosensor and bio-sniffer for nicotine were evaluated in the liquid and gas phases, respectively. The sensor signal of the bio-devices with 300 micromol l(-1) of butyrylcholine decreased quickly following application of nicotine and reached to the steady-state current, thus relating the concentration of nicotine in the liquid and gas phases. The biosensor was used to measure nicotine solution from 10 to 300 micromol l(-1). In the gas-phase experiment, the current signal of the bio-sniffer was also found to be linearly to the nicotine concentration over the range of 10.0-1000 ppb including 75.0 ppb as threshold limit value (TLV) by American Conference of Governmental Industrial Hygienists (ACGIH).

Monoterpene oxidation in an oxidative flow reactor: SOA yields and the relationship between bulk gas-phase properties and organic aerosol growth

NASA Astrophysics Data System (ADS)

Friedman, B.; Link, M.; Farmer, D.

2016-12-01

We use an oxidative flow reactor (OFR) to determine the secondary organic aerosol (SOA) yields of five monoterpenes (alpha-pinene, beta-pinene, limonene, sabinene, and terpinolene) at a range of OH exposures. These OH exposures correspond to aging timescales of a few hours to seven days. We further determine how SOA yields of beta-pinene and alpha-pinene vary as a function of seed particle type (organic vs. inorganic) and seed particle mass concentration. We hypothesize that the monoterpene structure largely accounts for the observed variance in SOA yields for the different monoterpenes. We also use high-resolution time-of-flight chemical ionization mass spectrometry to calculate the bulk gas-phase properties (O:C and H:C) of the monoterpene oxidation systems as a function of oxidant concentrations. Bulk gas-phase properties can be compared to the SOA yields to assess the capability of the precursor gas-phase species to inform the SOA yields of each monoterpene oxidation system. We find that the extent of oxygenated precursor gas-phase species corresponds to SOA yield.

Gas driven displacement in a Hele-Shaw cell with chemical reaction

NASA Astrophysics Data System (ADS)

White, Andrew; Ward, Thomas

2011-11-01

Injecting a less viscous fluid into a more viscous fluid produces instabilities in the form of fingering which grow radially from the less viscous injection point (Saffman & Taylor, Proc. R. Soc. Lon. A, 1958). For two non-reacting fluids in a radial Hele-Shaw cell the ability of the gas phase to penetrate the liquid phase is largely dependent on the gap height, liquid viscosity and gas pressure. In contrast combining two reactive fluids such as aqueous calcium hydroxide and carbon dioxide, which form a precipitate, presents a more complex but technically relevant system. As the two species react calcium carbonate precipitates and increases the aqueous phase visocosity. This change in viscosity may have a significant impact on how the gas phase penetrates the liquid phase. Experimental are performed in a radial Hele-Shaw cell with gap heights O(10-100) microns by loading a single drop of aqueous calcium hydroxide and injecting carbon dioxide into the drop. The calcium hydroxide concentration, carbon dioxide pressure and gap height are varied and images of the gas penetration are analyzed to determine residual film thickness and bursting times.

The H+n-C5H12/n-C6H14→H2(v',j')+C5H11/C6H13 reactions: State-to-state dynamics and models of energy disposal

NASA Astrophysics Data System (ADS)

Picconatto, Carl A.; Srivastava, Abneesh; Valentini, James J.

2001-03-01

The rovibrational state distributions for the H2 product of the H+n-C5H12/n-C6H14→H2+C5H11/C6H13 reactions at 1.6 eV collision energy are reported. The results are compared to measurements made on the kinematically and energetically similar H+RH→H2+R (RH=CH4, C2H6, and C3H8) reactions as well as the atom-diatom reactions H+HX→H2+X(HX=HCl, HBr). For the title reactions, as for all the comparison reactions, the product appears in few of the energetically accessible states. This is interpreted as the result of a kinematic constraint on the product translational energy. Characteristic of the H+RH reactions we have previously studied, the title reactions show increasing rotational excitation of the H2 product with increasing vibrational excitation of it, a correlation that gets stronger as the size of the alkane increases. Trends and variations in the product energy disposal are analyzed and explained by a localized reaction model. This model predicates a truncation of the opacity function due to competing reactive sites in the polyatomic alkane reactant, and a relaxation of the otherwise tight coupling of energy and angular momentum conservation, because the polyatomic alkyl radical product is a sink for angular momentum.

Simulation of homogeneous condensation of small polyatomic systems in high pressure supersonic nozzle flows using Bhatnagar-Gross-Krook model

NASA Astrophysics Data System (ADS)

Kumar, Rakesh; Levin, Deborah A.

2011-03-01

In the present work, we have simulated the homogeneous condensation of carbon dioxide and ethanol using the Bhatnagar-Gross-Krook based approach. In an earlier work of Gallagher-Rogers et al. [J. Thermophys. Heat Transfer 22, 695 (2008)], it was found that it was not possible to simulate condensation experiments of Wegener et al. [Phys. Fluids 15, 1869 (1972)] using the direct simulation Monte Carlo method. Therefore, in this work, we have used the statistical Bhatnagar-Gross-Krook approach, which was found to be numerically more efficient than direct simulation Monte Carlo method in our previous studies [Kumar et al., AIAA J. 48, 1531 (2010)], to model homogeneous condensation of two small polyatomic systems, carbon dioxide and ethanol. A new weighting scheme is developed in the Bhatnagar-Gross-Krook framework to reduce the computational load associated with the study of homogeneous condensation flows. The solutions obtained by the use of the new scheme are compared with those obtained by the baseline Bhatnagar-Gross-Krook condensation model (without the species weighting scheme) for the condensing flow of carbon dioxide in the stagnation pressure range of 1-5 bars. Use of the new weighting scheme in the present work makes the simulation of homogeneous condensation of ethanol possible. We obtain good agreement between our simulated predictions for homogeneous condensation of ethanol and experiments in terms of the point of condensation onset and the distribution of mass fraction of ethanol condensed along the nozzle centerline.

Analysis of twenty five impurities in uranium matrix by ICP-MS with iron measurement optimized by using reaction collision cell, cold plasma or medium resolution.

PubMed

Quemet, Alexandre; Brennetot, Rene; Chevalier, Emilie; Prian, Edwina; Laridon, Anne-Laure; Mariet, Clarisse; Fichet, Pascal; Laszak, Ivan; Goutelard, Florence

2012-09-15

An analytical procedure was developed to determine the concentration of 25 impurities (Li, Be, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ag, Cd, In, Sm, Eu, Gd, Dy, W, Pb, Bi and Th) in a uranium matrix using the quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS). The dissolution of U(3)O(8) powder was made with a mixture of hydrochloric acid and nitric acid. Then, a selective separation of uranium using the UTEVA column was used before measurement by Q-ICP-MS. The procedure developed was verified using the Certified Reference Material "Morille". The analytical results agree well except for 5 elements where values are underestimated (Li, Be, In, Pb and Bi). Among the list of impurities, iron was particularly investigated because it is well known that this element possesses a polyatomic interference that increases the detection limit. A comparison between iron detection limits obtained with different methods was performed. Iron polyatomic interference was at least reduced, or at best entirely resolved in some cases, by using the cold plasma or the collision/reaction cell with several gases (He, NH(3) and CH(4)). High-resolution ICP-MS was used to compare the results obtained. A detection limit as low as 8 ng L(-1) was achieved. Copyright © 2012 Elsevier B.V. All rights reserved.

Identification and Quantification of Pesticides in Environmental Waters With Solid Phase Microextraction and Analysis Using Field-Portable Gas Chromatography-Mass Spectrometry

DTIC Science & Technology

2004-06-10

Microextraction and Analysis using Field-Portable Gas Chromatography-Mass Spectrometry Name of Candidate: CPT Michael J. Nack...and Analysis using Field-Portable Gas Chromatography-Mass Spectrometry Beyond brief excerpts is with the permission of the copyright owner, and...Pesticides in Environmental Waters with Solid Phase Microextraction and Analysis using Field-Portable Gas Chromatography-Mass Spectrometry

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) measurement of liquid-phase ROS.

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 Molecular Complexity of the Diffuse and Translucent Gas and PhotoDissociation Regions

NASA Astrophysics Data System (ADS)

McCarthy, Michael

This proposal requests funds to continue a laboratory program in close coordination with radio astronomical observations dedicated to the study of highly reactive polyatomic molecular ions in low density regions and photo-dissociation regions (PDRs). In doing so, the proposed studies will advance our understanding of the chemistry beyond light ions that have been observed so successfully in these regions with Herschel and recently extended with SOFIA, and thereby critically address a significant but unresolved question in molecular astronomy: Are larger molecules formed in a bottom-up or top-down chemistry? The rotational spectra of most new molecular ions will be detected in the laboratory in a resonant microwave cavity, followed either by microwave/millimeterwave double resonance or millimeter/THz absorption to better characterize their spectrum in bands covered by the heterodyne receivers HIFI on Herschel and GREAT on SOFIA. In collaboration with radioastronomer colleagues, we will search for the new ions in the published survey of the PDR region of the Orion Bar and archival data of other PDRs observed with the IRAM 30 m telescope; retrieve and analyze archival data from Herschel; and undertake searches for some of the new ions in PDRs and low density regions with SOFIA. This work will also have a strong bearing on proposed Early Release Science (ERS) observations of dense PDRs with the James Webb Space Telescope (JWST). The laboratory effort will build on previous work on molecular ions , specifically detection of the rotational spectra of a number of positive ions of astronomical interest such as H2NCO+, CCCH+, the cis- and trans isomers of HOSO+, HNCOH+, and H2CC(H)CNH+. We will focus our efforts on positive ions derived from closed-shell neutral molecules, radicals, and carbenes whose rotational spectra have been observed in our laboratory, and nearly all of which have also been identified in galactic molecular clouds. Examples of the ions we seek include polyatomic ions such as CN+, HCCCN+, HNCO+, c-C3H2+, etc. Collaborations with leading theoretical groups to accurately predict spectroscopic constants of the new ions will enhance the proposed laboratory investigations. Instrumental refinement will also be undertaken with particular emphasis on construction of a new cryogenically cooled ( 6 K) buffer gas cell. This ultra-sensitive instrument will possess a system temperature that is nearly 50 times lower than our most sensitive cavity spectrometer, and one close to the fundamental limit set by modern technology, thereby greatly enhancing our ability to detect elusive molecular ions that are produced in very low steady state concentrations. The essential capabilities of this instrument have already been demonstrated in collaborative investigations. Our laboratory program is well aligned with NASA's overall mission, because we seek to understand the role of the chemical bond on a cosmic scale and to provide a firm chemical foundation by which more complicated questions of biological origins can be addressed. The work here also provides much basic information to aid subsequent astronomical searches, particularly in the infrared. Finally, our research program is an excellent vehicle for integrating research and education. It provides exposure to quite diverse areas of science in a setting which encourages student initiative and independent investigation.

Characterization of Gas Chromatographic Liquid Phases Using McReynolds Constants. An Experiment for Instrumental Analysis Laboratory.

ERIC Educational Resources Information Center

Erskine, Steven R.; And Others

1986-01-01

Describes a laboratory experiment that is designed to aid in the understanding of the fundamental process involved in gas chromatographic separations. Introduces the Kovats retention index system for use by chemistry students to establish criteria for the optimal selection of gas chromatographic stationary phases. (TW)

Transient Catalytic Combustor Model With Detailed Gas and Surface Chemistry

NASA Technical Reports Server (NTRS)

Struk, Peter M.; Dietrich, Daniel L.; Mellish, Benjamin P.; Miller, Fletcher J.; Tien, James S.

2005-01-01

In this work, we numerically investigate the transient combustion of a premixed gas mixture in a narrow, perfectly-insulated, catalytic channel which can represent an interior channel of a catalytic monolith. The model assumes a quasi-steady gas-phase and a transient, thermally thin solid phase. The gas phase is one-dimensional, but it does account for heat and mass transfer in a direction perpendicular to the flow via appropriate heat and mass transfer coefficients. The model neglects axial conduction in both the gas and in the solid. The model includes both detailed gas-phase reactions and catalytic surface reactions. The reactants modeled so far include lean mixtures of dry CO and CO/H2 mixtures, with pure oxygen as the oxidizer. The results include transient computations of light-off and system response to inlet condition variations. In some cases, the model predicts two different steady-state solutions depending on whether the channel is initially hot or cold. Additionally, the model suggests that the catalytic ignition of CO/O2 mixtures is extremely sensitive to small variations of inlet equivalence ratios and parts per million levels of H2.

Study of a Multi-phase Hybrid Heat Exchanger-Reaction (HEX Reactor): Part 1 - Experimental Characterization

DTIC Science & Technology

2014-01-01

considerably higher frictional losses than if the liquid and gas phases were simply injected at the inlet as in references [11,12]. Although the...individual channel face opposite directions to form a tor- tuous network of crisscrossing passageways. Fluid streams direc - ted along the upper and...gravity SP single-phase TP two-phase c corrugated section e equivalent g gas phase h hydraulic l liquid phase pp port-to-port N. Niedbalski et al

TOGA: A TOUGH code for modeling three-phase, multi-component, and non-isothermal processes involved in CO 2-based Enhanced Oil Recovery

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

Pan, Lehua; Oldenburg, Curtis M.

TOGA is a numerical reservoir simulator for modeling non-isothermal flow and transport of water, CO 2, multicomponent oil, and related gas components for applications including CO 2-enhanced oil recovery (CO 2-EOR) and geologic carbon sequestration in depleted oil and gas reservoirs. TOGA uses an approach based on the Peng-Robinson equation of state (PR-EOS) to calculate the thermophysical properties of the gas and oil phases including the gas/oil components dissolved in the aqueous phase, and uses a mixing model to estimate the thermophysical properties of the aqueous phase. The phase behavior (e.g., occurrence and disappearance of the three phases, gas +more » oil + aqueous) and the partitioning of non-aqueous components (e.g., CO 2, CH 4, and n-oil components) between coexisting phases are modeled using K-values derived from assumptions of equal-fugacity that have been demonstrated to be very accurate as shown by comparison to measured data. Models for saturated (water) vapor pressure and water solubility (in the oil phase) are used to calculate the partitioning of the water (H 2O) component between the gas and oil phases. All components (e.g., CO 2, H 2O, and n hydrocarbon components) are allowed to be present in all phases (aqueous, gaseous, and oil). TOGA uses a multiphase version of Darcy’s Law to model flow and transport through porous media of mixtures with up to three phases over a range of pressures and temperatures appropriate to hydrocarbon recovery and geologic carbon sequestration systems. Transport of the gaseous and dissolved components is by advection and Fickian molecular diffusion. New methods for phase partitioning and thermophysical property modeling in TOGA have been validated against experimental data published in the literature for describing phase partitioning and phase behavior. Flow and transport has been verified by testing against related TOUGH2 EOS modules and CMG. The code has also been validated against a CO 2-EOR experimental core flood involving flow of three phases and 12 components. Results of simulations of a hypothetical 3D CO 2-EOR problem involving three phases and multiple components are presented to demonstrate the field-scale capabilities of the new code. This user guide provides instructions for use and sample problems for verification and demonstration.« less

The Iran Sanctions Act (ISA)

DTIC Science & Technology

2008-08-26

its partners, Gazprom of Russia and Petronas of Malaysia to develop phases 2 and 3 of the 25-phase South Pars gas field. The EU pledged to increase...would not be penalized. Total and Petronas subsequently negotiated to develop a liquified natural gas (LNG) export capability at Phase 11 of South

The Iran Sanctions Act (ISA)

DTIC Science & Technology

2009-04-14

of Russia and Petronas of Malaysia to develop phases 2 and 3 of the 25-phase South Pars gas field. The EU pledged to increase cooperation with the...and Petronas , the original South Pars investors, pulled out of a deal to develop a liquified natural gas (LNG) export capability at Phase 11 of South

ADVANCED COMBUSTION SYSTEMS FOR STATIONARY GAS TURBINE ENGINES: VOLUME I. REVIEW AND PRELIMINARY EVALUATION

EPA Science Inventory

The reports describe an exploratory development program to identify, evaluate, and demonstrate dry techniques for significantly reducing NOx from thermal and fuel-bound sources in stationary gas turbine engines. Volume 1 covers Phase I of the four-phase effort. In Phase I, duty c...

The Two-Phase Flow Separator Experiment Breadboard Model: Reduced Gravity Aircraft Results

NASA Technical Reports Server (NTRS)

Rame, E; Sharp, L. M.; Chahine, G.; Kamotani, Y.; Gotti, D.; Owens, J.; Gilkey, K.; Pham, N.

2015-01-01

Life support systems in space depend on the ability to effectively separate gas from liquid. Passive cyclonic phase separators use the centripetal acceleration of a rotating gas-liquid mixture to carry out phase separation. The gas migrates to the center, while gas-free liquid may be withdrawn from one of the end plates. We have designed, constructed and tested a breadboard that accommodates the test sections of two independent principal investigators and satisfies their respective requirements, including flow rates, pressure and video diagnostics. The breadboard was flown in the NASA low-gravity airplane in order to test the system performance and design under reduced gravity conditions.

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.

Low Reynolds Number Droplet Combustion In CO2 Enriched Atmospheres In Microgravity

NASA Technical Reports Server (NTRS)

Hicks, M. C.

2003-01-01

The effect of radiative feedback from the gas phase in micro-gravity combustion processes has been of increasing concern because of the implications in the selection and evaluation of appropriate fire suppressants. The use of CO2, an optically thick gas in the infrared region of the electromagnetic spectrum, has garnered widespread acceptance as an effective fire suppressant for most ground based applications. Since buoyant forces often dominate the flow field in 1-g environments the temperature field between the flame front and the fuel surface is not significantly affected by gas phase radiative absorption and re-emission as these hot gases are quickly swept downstream. However, in reduced gravity environments where buoyant-driven convective flows are negligible and where low-speed forced convective flows may be present at levels where gas phase radiation becomes important, then changes in environment that enhance gas phase radiative effects need to be better understood. This is particularly true in assessments of flammability limits and selection of appropriate fire suppressants for future space applications. In recognition of this, a ground-based investigation has been established that uses a droplet combustion configuration to systematically study the effects of enhanced gas phase radiation on droplet burn rates, flame structure, and radiative output from the flame zone.

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

Torrefaction of empty fruit bunches under biomass combustion gas atmosphere.

PubMed

Uemura, Yoshimitsu; Sellappah, Varsheta; Trinh, Thanh Hoai; Hassan, Suhaimi; Tanoue, Ken-Ichiro

2017-11-01

Torrefaction of oil palm empty fruit bunches (EFB) under combustion gas atmosphere was conducted in a batch reactor at 473, 523 and 573K in order to investigate the effect of real combustion gas on torrefaction behavior. The solid mass yield of torrefaction in combustion gas was smaller than that of torrefaction in nitrogen. This may be attributed to the decomposition enhancement effect by oxygen and carbon dioxide in combustion gas. Under combustion gas atmosphere, the solid yield for torrefaction of EFB became smaller as the temperature increased. The representative products of combustion gas torrefaction were carbon dioxide and carbon monoxide (gas phase) and water, phenol and acetic acid (liquid phase). By comparing torrefaction in combustion gas with torrefaction in nitrogen gas, it was found that combustion gas can be utilized as torrefaction gas to save energy and inert gas. Copyright © 2017 Elsevier Ltd. All rights reserved.

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, inaccuracies in the description of imidazole ring flip rotamerism were identified.

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.

Enzymatic oxidation of ethanol in the gaseous phase.

PubMed

Barzana, E; Karel, M; Klibanov, A M

1989-11-01

The enzymatic conversion of gaseous substrates represents a novel concept in bioprocessing. A critical parameter in such systems is the water activity, A(w) The present article reports the effect of A(w) on the catalytic performance of alcohol oxidase acting on ethanol vapors. Enzyme activity in the gas-phase reaction increases several orders of magnitude, whereas the thermostability decreases drastically when A(w) is increased from 0.11 to 0.97. The enzyme is active on gaseous substrates even at hydration levels below the monolayer coverage. Enhanced thermostability at lower hydrations results in an increase in the optimum temperature of the gas-phase reaction catalyzed by alcohol oxidase. The apparent activation energy decreases as A(w) increases, approaching the value obtained for the enzyme in aqueous solution. The formation of a pread-sorbed ethanol phase on the surface of the support is not a prerequisite for the reaction, suggesting that the reaction occurs by direct interaction of the gaseous substrate with the enzyme. The gas-phase reaction follows Michaelis-Menten kinetics, with a K(m) value almost 100 times lower than that in aqueous solution. Based on vapor-liquid equilibrium data and observed K(m) values, it is postulated that during the gas-phase reaction the ethanol on the enzyme establishes an equilibrium with the ethanol vapor similar to that between ethanol in water and ethanol in the gas phase.

A Computational Fluid Dynamic Model for a Novel Flash Ironmaking Process

NASA Astrophysics Data System (ADS)

Perez-Fontes, Silvia E.; Sohn, Hong Yong; Olivas-Martinez, Miguel

A computational fluid dynamic model for a novel flash ironmaking process based on the direct gaseous reduction of iron oxide concentrates is presented. The model solves the three-dimensional governing equations including both gas-phase and gas-solid reaction kinetics. The turbulence-chemistry interaction in the gas-phase is modeled by the eddy dissipation concept incorporating chemical kinetics. The particle cloud model is used to track the particle phase in a Lagrangian framework. A nucleation and growth kinetics rate expression is adopted to calculate the reduction rate of magnetite concentrate particles. Benchmark experiments reported in the literature for a nonreacting swirling gas jet and a nonpremixed hydrogen jet flame were simulated for validation. The model predictions showed good agreement with measurements in terms of gas velocity, gas temperature and species concentrations. The relevance of the computational model for the analysis of a bench reactor operation and the design of an industrial-pilot plant is discussed.

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.

Study of the radiated energy loss during massive gas injection mitigated disruptions on EAST

NASA Astrophysics Data System (ADS)

Duan, Y. M.; Hao, Z. K.; Hu, L. Q.; Wang, L.; Xu, P.; Xu, L. Q.; Zhuang, H. D.; EAST Team

2015-08-01

The MGI mitigated disruption experiments were carried out on EAST with a new fast gas controlling valve in 2012. Different amounts of noble gas He or mixed gas of 99% He + 1% Ar are injected into plasma in current flat-top phase and current ramp-down phase separately. The initial results of MGI experiments are described. The MGI system and the radiation measurement system are briefly introduced. The characteristics of radiation distribution and radiation energy loss are analyzed. About 50% of the stored thermal energy Wdia is dissipated by radiation during the entire disruption process and the impurities of C and Li from the PFC play important roles to radiative energy loss. The amount of the gas can affect the pre-TQ phase. Strong poloidal asymmetry of radiation begins to appear in the CQ phase, which is possibly caused by the plasma configuration changes as a result of VDE. No toroidal radiation asymmetry is observed presently.

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.

Multi-phase-fluid discrimination with local fibre-optical probes: III. Three-phase flows

NASA Astrophysics Data System (ADS)

Fordham, E. J.; Ramos, R. T.; Holmes, A.; Simonian, S.; Huang, S.-M.; Lenn, C. P.

1999-12-01

Local fibre-optical sensors (or `local probes') for immiscible-fluid discrimination are demonstrated in three-phase (oil/water/gas) flows. The probes are made from standard silica fibres with plane oblique facets polished at the fibre tip, with surface treatment for wettability control. They use total internal reflection to distinguish among drops, bubbles and other regions of fluid in multi-phase flows, on the basis of refractive-index contrast. Dual probes, using two sensors each with a quasi-binary output, are used to determine profiles of three-phase volume fraction in a flow of kerosene, water and air in a pipe. The individual sensors used discriminate oil from `not-oil' and gas from liquid; their logical combination discriminates among the three phases. Companion papers deal with the sensor designs used and quantitative results achieved in the simpler two-phase cases of liquid/liquid flows and gas/liquid flows.

Nitro-polycyclic aromatic hydrocarbon concentrations and sources in urban and suburban atmospheres of the Mid-Atlantic region

NASA Astrophysics Data System (ADS)

Bamford, Holly A.; Baker, Joel E.

Gas and particle phase concentrations of 26 nitro-PAHs were quantified in ambient air collected in downtown Baltimore, MD, an urban region, and in Fort Meade, MD, a suburban area 20 km south-southeast of Baltimore, during January and July 2001. Total (gas+particle) concentrations for individual nitro-PAH compounds varied by as much as five times from sample to sample within each month. 2-Nitrofluoranthene and 9-nitroanthracene were the most abundant of the nitro-PAHs quantitatively analyzed in the air at both sites, accounting for approximately half of the total nitro-PAH concentrations during January and July. Concentrations at Baltimore were on average two to three times higher than those measured at the Fort Meade site. Concentrations for most nitro-PAHs were higher in January than in July, suggesting a reduction in photodecay of nitro-PAHs during January promoted the accumulation of nitro-PAHs. Concentrations of nitro-PAHs produced from gas-phase reactions were significantly correlated with concentrations of oxides of nitrogen (NO x) measured simultaneously at the Fort Meade site. 3-Nitrophenanthrene and 4-nitrophenanthrene were negatively correlated with NO x and were the only nitro-PAHs correlated with O 3, suggesting a different formation mechanism for these compounds compared to the other nitro-PAHs found in this study. The relative contribution of gas-phase reactions and primary emission sources of nitro-PAHs were evaluated using source specific concentration ratios of 2-nitrofluoranthene and 1-nitropyrene (2-NF/1-NP). The mean ratios of 2-NF/1-NP at both sites were statistically higher in July than January, indicating gas-phase reactions were an important source of 2-nitrofluoranthene in the summer. However, in January, gas-phase reactions were reduced, the NO 3-initiated reaction in particular, and primary emissions may significantly contribute to ambient nitro-PAH levels. The two dominant gas-phase production pathways of nitro-PAHs from the OH and NO 3-initiated reactions were investigated using concentration ratios of 2-nitrofluoranthene and 2-nitropyrene (2-NF/2-NP). At both sites, 2-NF/2-NP ratios indicated that the daytime OH-initiated reaction was the dominant gas-phase formation pathway. The estimated contributions of nitro-PAHs produced through gas-phase reactions via the OH pathway during July were >45% and during January were >83% at both Fort Meade and Baltimore.

Feeding the fire: tracing the mass-loading of 107 K galactic outflows with O VI absorption

NASA Astrophysics Data System (ADS)

Chisholm, J.; Bordoloi, R.; Rigby, J. R.; Bayliss, M.

2018-02-01

Galactic outflows regulate the amount of gas galaxies convert into stars. However, it is difficult to measure the mass outflows remove because they span a large range of temperatures and phases. Here, we study the rest-frame ultraviolet spectrum of a lensed galaxy at z ˜ 2.9 with prominent interstellar absorption lines from O I, tracing neutral gas, up to O VI, tracing transitional phase gas. The O VI profile mimics weak low-ionization profiles at low velocities, and strong saturated profiles at high velocities. These trends indicate that O VI gas is co-spatial with the low-ionization gas. Further, at velocities blueward of -200 km s-1 the column density of the low-ionization outflow rapidly drops while the O VI column density rises, suggesting that O VI is created as the low-ionization gas is destroyed. Photoionization models do not reproduce the observed O VI, but adequately match the low-ionization gas, indicating that the phases have different formation mechanisms. Photoionized outflows are more massive than O VI outflows for most of the observed velocities, although the O VI mass outflow rate exceeds the photoionized outflow at velocities above the galaxy's escape velocity. Therefore, most gas capable of escaping the galaxy is in a hot outflow phase. We suggest that the O VI absorption is a temporary by-product of conduction transferring mass from the photoionized phase to an unobserved hot wind, and discuss how this mass-loading impacts the observed circum-galactic medium.

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.

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.

Hollow fiber gas-liquid membrane contactors for acid gas capture: a review.

PubMed

Mansourizadeh, A; Ismail, A F

2009-11-15

Membrane contactors using microporous membranes for acid gas removal have been extensively reviewed and discussed. The microporous membrane acts as a fixed interface between the gas and the liquid phase without dispersing one phase into another that offers a flexible modular and energy efficient device. The gas absorption process can offer a high selectivity and a high driving force for transport even at low concentrations. Using hollow fiber gas-liquid membrane contactors is a promising alternative to conventional gas absorption systems for acid gas capture from gas streams. Important aspects of membrane contactor as an efficient energy devise for acid gas removal including liquid absorbents, membrane characteristics, combination of membrane and absorbent, mass transfer, membrane modules, model development, advantages and disadvantages were critically discussed. In addition, current status and future potential in research and development of gas-liquid membrane contactors for acid gas removal were also briefly discussed.

Heterogeneously Catalyzed Endothermic Fuel Cracking

DTIC Science & Technology

2016-08-28

Much of this literature is in the context of gas -to- liquids technology and industrial dehydrogenation processes. Based on the published measurements...certain zeolites. Comparisons of conversion, major product distributions and molecular weight growth processes in the gas -phase pyrolysis of model...thereby maximizing the extent of cooling, (b) increase catalyst activity for fuel decomposition, but inhibit gas -phase molecular weight growth

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

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.

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.

Modeling Ignition of HMX with the Gibbs Formulation

NASA Astrophysics Data System (ADS)

Lee, Kibaek; Stewart, D. Scott

2017-06-01

We present a HMX model with the Gibbs formulation in which stress tensor and temperature are assumed to be in local equilibrium, but phase/chemical changes are not assumed to be in equilibrium. We assume multi-components for HMX including beta- and delta-phase, liquid, and gas phase of HMX and its gas products. Isotropic small strain solid model, modified Fried Howard liquid EOS, and ideal gas EOS are used for its relevant component. Phase/chemical changes are characterized as reactions and are in individual reaction rate. Maxwell-Stefan model is used for diffusion. Excited gas products in the local domain lead unreacted HMX solid to the ignition event. Density of the mixture, stress, strain, displacement, mass fractions, and temperature are considered in 1D domain with time histories. Office of Naval Research and Air Force Office of Scientific Research.

Probing the Gaseous Structure of a β-Hairpin Peptide with H/D Exchange and Electron Capture Dissociation

NASA Astrophysics Data System (ADS)

Straus, Rita N.; Jockusch, Rebecca A.

2017-02-01

An improved understanding of the extent to which native protein structure is retained upon transfer to the gas phase promises to enhance biological mass spectrometry, potentially streamlining workflows and providing fundamental insights into hydration effects. Here, we investigate the gaseous conformation of a model β-hairpin peptide using gas-phase hydrogen-deuterium (H/D) exchange with subsequent electron capture dissociation (ECD). Global gas-phase H/D exchange levels, and residue-specific exchange levels derived from ECD data, are compared among the wild type 16-residue peptide GB1p and several variants. High protection from H/D exchange observed for GB1p, but not for a truncated version, is consistent with the retention of secondary structure of GB1p in the gas phase or its refolding into some other compact structure. Four alanine mutants that destabilize the hairpin in solution show levels of protection similar to that of GB1p, suggesting collapse or (re)folding of these peptides upon transfer to the gas phase. These results offer a starting point from which to understand how a key secondary structural element, the β-hairpin, is affected by transfer to the gas phase. This work also demonstrates the utility of a much-needed addition to the tool set that is currently available for the investigation of the gaseous conformation of biomolecules, which can be employed in the future to better characterize gaseous proteins and protein complexes.

Heterogeneity-enhanced gas phase formation in shallow aquifers during leakage of CO2-saturated water from geologic sequestration sites

NASA Astrophysics Data System (ADS)

Plampin, Michael R.; Lassen, Rune N.; Sakaki, Toshihiro; Porter, Mark L.; Pawar, Rajesh J.; Jensen, Karsten H.; Illangasekare, Tissa H.

2014-12-01

A primary concern for geologic carbon storage is the potential for leakage of stored carbon dioxide (CO2) into the shallow subsurface where it could degrade the quality of groundwater and surface water. In order to predict and mitigate the potentially negative impacts of CO2 leakage, it is important to understand the physical processes that CO2 will undergo as it moves through naturally heterogeneous porous media formations. Previous studies have shown that heterogeneity can enhance the evolution of gas phase CO2 in some cases, but the conditions under which this occurs have not yet been quantitatively defined, nor tested through laboratory experiments. This study quantitatively investigates the effects of geologic heterogeneity on the process of gas phase CO2 evolution in shallow aquifers through an extensive set of experiments conducted in a column that was packed with layers of various test sands. Soil moisture sensors were utilized to observe the formation of gas phase near the porous media interfaces. Results indicate that the conditions under which heterogeneity controls gas phase evolution can be successfully predicted through analysis of simple parameters, including the dissolved CO2 concentration in the flowing water, the distance between the heterogeneity and the leakage location, and some fundamental properties of the porous media. Results also show that interfaces where a less permeable material overlies a more permeable material affect gas phase evolution more significantly than interfaces with the opposite layering.

Probing the Gaseous Structure of a β-Hairpin Peptide with H/D Exchange and Electron Capture Dissociation.

PubMed

Straus, Rita N; Jockusch, Rebecca A

2017-02-01

An improved understanding of the extent to which native protein structure is retained upon transfer to the gas phase promises to enhance biological mass spectrometry, potentially streamlining workflows and providing fundamental insights into hydration effects. Here, we investigate the gaseous conformation of a model β-hairpin peptide using gas-phase hydrogen-deuterium (H/D) exchange with subsequent electron capture dissociation (ECD). Global gas-phase H/D exchange levels, and residue-specific exchange levels derived from ECD data, are compared among the wild type 16-residue peptide GB1p and several variants. High protection from H/D exchange observed for GB1p, but not for a truncated version, is consistent with the retention of secondary structure of GB1p in the gas phase or its refolding into some other compact structure. Four alanine mutants that destabilize the hairpin in solution show levels of protection similar to that of GB1p, suggesting collapse or (re)folding of these peptides upon transfer to the gas phase. These results offer a starting point from which to understand how a key secondary structural element, the β-hairpin, is affected by transfer to the gas phase. This work also demonstrates the utility of a much-needed addition to the tool set that is currently available for the investigation of the gaseous conformation of biomolecules, which can be employed in the future to better characterize gaseous proteins and protein complexes. Graphical Abstract ᅟ.

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...

Dramatically stabilizing multiprotein complex structure in the absence of bulk water using tuned Hofmeister salts.

PubMed

Han, Linjie; Hyung, Suk-Joon; Ruotolo, Brandon T

2013-01-01

The role that water plays in the salt-based stabilization of proteins is central to our understanding of protein biophysics. Ion hydration and the ability of ions to alter water surface tension are typically invoked, along with direct ion-protein binding, to describe Hofmeister stabilization phenomena observed for proteins experimentally, but the relative influence of these forces has been extraordinarily difficult to measure directly. Recently, we have used gas-phase measurements of proteins and large multiprotein complexes, using a combination of innovative ion mobility (IM) and mass spectrometry (MS) techniques, to assess the ability of bound cations and anions to stabilize protein ions in the absence of the solvation forces described above. Our previous work has studied a broad set of 12 anions bound to a range of proteins and protein complexes, and while primarily motivated by the analytical challenges surrounding the gas-phase measurement of solution-phase relevant protein structures, our work has also lead to a detailed physical mechanism of anion-protein complex stabilization in the absence of bulk solvent. Our more-recent work has screened a similarly-broad set of cations for their ability to stabilize gas-phase protein structure, and we have discovered surprising differences between the operative mechanisms for cations and anions in gas-phase protein stabilization. In both cases, cations and anions affect protein stabilization in the absence of solvent in a manner that is generally reversed relative to their ability to stabilize the same proteins in solution. In addition, our evidence suggests that the relative solution-phase binding affinity of the anions and cations studied here is preserved in our gas-phase measurements, allowing us to study the influence of such interactions in detail. In this report, we collect and summarize such gas-phase measurements to distill a generalized picture of salt-based protein stabilization in the absence of bulk water. Further, we communicate our most recent efforts to study the combined effects of stabilizing cations and anions on gas-phase proteins, and identify those salts that bear anion/cation pairs having the strongest stabilizing influence on protein structures

DNS study of speed of sound in two-phase flows with phase change

NASA Astrophysics Data System (ADS)

Fu, Kai; Deng, Xiaolong

2017-11-01

Heat transfer through pipe flow is important for the safety of thermal power plants. Normally it is considered incompressible. However, in some conditions compressibility effects could deteriorate the heat transfer efficiency and even result in pipe rupture, especially when there is obvious phase change, due to the much lower sound speed in liquid-gas mixture flows. Based on the stratified multiphase flow model (Chang and Liou, JCP 2007), we present a new approach to simulate the sound speed in 3-D compressible two-phase dispersed flows, in which each face is divided into gas-gas, gas-liquid, and liquid-liquid parts via reconstruction by volume fraction, and fluxes are calculated correspondingly. Applying it to well-distributed air-water bubbly flows, comparing with the experiment measurements in air water mixture (Karplus, JASA 1957), the effects of adiabaticity, viscosity, and isothermality are examined. Under viscous and isothermal condition, the simulation results match the experimental ones very well, showing the DNS study with current method is an effective way for the sound speed of complex two-phase dispersed flows. Including the two-phase Riemann solver with phase change (Fechter et al., JCP 2017), more complex problems can be numerically studied.

Liquid Crystals in Chromatography

NASA Astrophysics Data System (ADS)

Witkiewicz, Zygfryd

The following sections are included: * INTRODUCTION * LIQUID CRYSTALS SUITABLE FOR GAS CHROMATOGRAPHY * Monomeric Liquid Crystal Stationary Phases * Polymeric Liquid Crystal Stationary Phases * Polymeric Liquid Crystal Stationary Phases * Conventional Analytical Columns * Capillary Columns * FACTORS AFFECTING THE CHROMATOGRAPHIC SEPARATIONS ON LIQUID CRYSTAL STATIONARY PHASES * Kind of Mesophase of the Liquid Crystal * Molecular Structure of the Liquid Crystals and of the Chromatographed Substances * Substrate on which the Liquid Crystal is Deposited * ANALYTICAL APPLICATIONS OF LIQUID CRYSTAL STATIONARY PHASES IN GAS CHROMATOGRAPHY * Separation of Isomers of Benzene and Naphthalene Derivatives * Separation of Alkane and Alkene Isomers * Separation of Mixtures of Benzene and Aliphatic Hydrocarbon Derivatives Containing Heteroatoms * Separation of Polynuclear Hydrocarbons * INVESTIGATION OF THE PROPERTIES OF LIQUID CRYSTALS BY GAS CHROMATOGRAPHY * APPLICATION OF LIQUID CRYSTALS IN LIQUID CHROMATOGRAPHY * Column Chromatography * Thin-Layer Chromatography * APPLICATION OF LIQUID CRYSTAL STATIONARY PHASES IN SUPERCRITICAL FLUID CHROMATOGRAPHY * FINAL REMARKS * References

ITFITS model for vibration--translation energy partitioning in atom-- polyatomic molecule collisions

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

Shobatake, K.; Rice, S.A.; Lee, Y.T.

1973-09-01

A model for vibration-translation energy partitioning in the collinear collision of an atom and an axially symmetric polyatonaic molecule is proposed. The model is based on an extension of the ideas of Mahan and Heidrich, Wilson, and Rapp. Comparison of energy transfers computed from classical trajesctory calculations and the model proposed indicate good agreement when the mass of the free atom is small relative to the mass of the bound atom it strikes. The agreement is less satisfactory when that mass ratio becomes large. (auth)

Electron Interactions with Non-Linear Polyatomic Molecules and their Radicals and Ions

DTIC Science & Technology

1991-06-01

is the usual antisymmetrization operator to ensure Pauli principle. In the expansion (4.1.2), we have neglected the correlation functions of the (N...Kochem, K M Scheuerlein, K Jung and H Ehrhardt, J. Phys. B19, 3625 (1986). [27]. A Jain, Ph.D. thesis (Queen’s University, Belfast) 1983. [2S]. D M...Winstead and V McLoy, Phys. Rev. A42, 5357 (1990). [52]. R Muiller, K Jung , K H Kochem, W Sohn and H Ehrhardt, J. Phys. B 18, 3971 (1985). [53]. L

Sequential Excitation Preparation of Molecular Energy Levels with Special Structural and Chemical Properties.

DTIC Science & Technology

1986-01-06

D.E. Reisner, and P.H. Vaccaro, pp. 393-404 in Lasers as Reactants and Probes in Chemistry, (eds. W.M. Jackson and A.B. Harvey) Howard University Press...as Reactants and Probes in Chemistry, Howard University (May 1982). 4. J.L. Kinsey, "An Outsider’s View of the Spectroscopy of Polyatomic Systems...Kinsey, C. Kittrell, D.E. Reisner, and P.H. Vaccaro, pp. 393-404 in Lasers as Reactants and Probes in Chemistry (eds. W.M. Jackson and A.B. Harvey), Howard

Pore-scale mechanisms of gas flow in tight sand reservoirs

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

Silin, D.; Kneafsey, T.J.; Ajo-Franklin, J.B.

2010-11-30

Tight gas sands are unconventional hydrocarbon energy resource storing large volume of natural gas. Microscopy and 3D imaging of reservoir samples at different scales and resolutions provide insights into the coaredo not significantly smaller in size than conventional sandstones, the extremely dense grain packing makes the pore space tortuous, and the porosity is small. In some cases the inter-granular void space is presented by micron-scale slits, whose geometry requires imaging at submicron resolutions. Maximal Inscribed Spheres computations simulate different scenarios of capillary-equilibrium two-phase fluid displacement. For tight sands, the simulations predict an unusually low wetting fluid saturation threshold, at whichmore » the non-wetting phase becomes disconnected. Flow simulations in combination with Maximal Inscribed Spheres computations evaluate relative permeability curves. The computations show that at the threshold saturation, when the nonwetting fluid becomes disconnected, the flow of both fluids is practically blocked. The nonwetting phase is immobile due to the disconnectedness, while the permeability to the wetting phase remains essentially equal to zero due to the pore space geometry. This observation explains the Permeability Jail, which was defined earlier by others. The gas is trapped by capillarity, and the brine is immobile due to the dynamic effects. At the same time, in drainage, simulations predict that the mobility of at least one of the fluids is greater than zero at all saturations. A pore-scale model of gas condensate dropout predicts the rate to be proportional to the scalar product of the fluid velocity and pressure gradient. The narrowest constriction in the flow path is subject to the highest rate of condensation. The pore-scale model naturally upscales to the Panfilov's Darcy-scale model, which implies that the condensate dropout rate is proportional to the pressure gradient squared. Pressure gradient is the greatest near the matrix-fracture interface. The distinctive two-phase flow properties of tight sand imply that a small amount of gas condensate can seriously affect the recovery rate by blocking gas flow. Dry gas injection, pressure maintenance, or heating can help to preserve the mobility of gas phase. A small amount of water can increase the mobility of gas condensate.« less

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.

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.

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.

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.

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.

Chemical vapor deposition reactor. [providing uniform film thickness

NASA Technical Reports Server (NTRS)

Chern, S. S.; Maserjian, J. (Inventor)

1977-01-01

An improved chemical vapor deposition reactor is characterized by a vapor deposition chamber configured to substantially eliminate non-uniformities in films deposited on substrates by control of gas flow and removing gas phase reaction materials from the chamber. Uniformity in the thickness of films is produced by having reactive gases injected through multiple jets which are placed at uniformally distributed locations. Gas phase reaction materials are removed through an exhaust chimney which is positioned above the centrally located, heated pad or platform on which substrates are placed. A baffle is situated above the heated platform below the mouth of the chimney to prevent downdraft dispersion and scattering of gas phase reactant materials.

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.

Thermodynamic approach to the paradox of diamond formation with simultaneous graphite etching in the low pressure synthesis of diamond

NASA Astrophysics Data System (ADS)

Hwang, Nong M.; Yoon, Duk Y.

1996-03-01

In spite of the critical handicap from the thermodynamic point of view, the atomic hydrogen hypothesis is strongly supported by experimental observations of diamond deposition with simultaneous graphite etching. Thermodynamic analysis of the CH system showed that at ˜ 1500 K, carbon solubility in the gas phase is minimal and thus, the equilibrium fraction of solid carbon is maximal. Depending on whether gas phase nucleation takes place or not, the driving force is for deposition or for etching of solid carbon below ˜ 1500 K for the input gas of the typical mixture of 1% CH 499% H 2. The previous observation of etching of the graphite substrate is not expected unless solid carbon precipitated in the gas phase. By rigorous thermodynamic analysis of the previous experimental observations of diamond deposition with simultaneous graphite etching, we suggested that the previous implicit assumption that diamond deposits by an atomic unit should be the weakest point leading to the thermodynamic paradox. The experimental observations could be successfully explained without violating thermodynamics by assuming that the diamond phase had nucleated in the gas phase as fine clusters.

All-soft, battery-free, and wireless chemical sensing platform based on liquid metal for liquid- and gas-phase VOC detection.

PubMed

Kim, Min-Gu; Alrowais, Hommood; Kim, Choongsoon; Yeon, Pyungwoo; Ghovanloo, Maysam; Brand, Oliver

2017-06-27

Lightweight, flexible, stretchable, and wireless sensing platforms have gained significant attention for personal healthcare and environmental monitoring applications. This paper introduces an all-soft (flexible and stretchable), battery-free, and wireless chemical microsystem using gallium-based liquid metal (eutectic gallium-indium alloy, EGaIn) and poly(dimethylsiloxane) (PDMS), fabricated using an advanced liquid metal thin-line patterning technique based on soft lithography. Considering its flexible, stretchable, and lightweight characteristics, the proposed sensing platform is well suited for wearable sensing applications either on the skin or on clothing. Using the microfluidic sensing platform, detection of liquid-phase and gas-phase volatile organic compounds (VOC) is demonstrated using the same design, which gives an opportunity to have the sensor operate under different working conditions and environments. In the case of liquid-phase chemical sensing, the wireless sensing performance and microfluidic capacitance tunability for different dielectric liquids are evaluated using analytical, numerical, and experimental approaches. In the case of gas-phase chemical sensing, PDMS is used both as a substrate and a sensing material. The gas sensing performance is evaluated and compared to a silicon-based, solid-state gas sensor with a PDMS sensing film.

BASIN-CENTERED GAS SYSTEMS OF THE U.S.

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

Marin A. Popov; Vito F. Nuccio; Thaddeus S. Dyman

2000-11-01

The USGS is re-evaluating the resource potential of basin-centered gas accumulations in the U.S. because of changing perceptions of the geology of these accumulations, and the availability of new data since the USGS 1995 National Assessment of United States oil and gas resources (Gautier et al., 1996). To attain these objectives, this project used knowledge of basin-centered gas systems and procedures such as stratigraphic analysis, organic geochemistry, modeling of basin thermal dynamics, reservoir characterization, and pressure analysis. This project proceeded in two phases which had the following objectives: Phase I (4/1998 through 5/1999): Identify and describe the geologic and geographicmore » distribution of potential basin-centered gas systems, and Phase II (6/1999 through 11/2000): For selected systems, estimate the location of those basin-centered gas resources that are likely to be produced over the next 30 years. In Phase I, we characterize thirty-three (33) potential basin-centered gas systems (or accumulations) based on information published in the literature or acquired from internal computerized well and reservoir data files. These newly defined potential accumulations vary from low to high risk and may or may not survive the rigorous geologic scrutiny leading towards full assessment by the USGS. For logistical reasons, not all basins received the level of detail desired or required.« less

A Review and Evaluation of the Phase Equilibria, Liquid-Phase Heats of Mixing and Excess Volumes, and Gas-Phase PVT Measurements for Nitrogen+Methane

NASA Astrophysics Data System (ADS)

Kidnay, A. J.; Miller, R. C.; Sloan, E. D.; Hiza, M. J.

1985-07-01

The available experimental data for vapor-liquid equilibria, heat of mixing, change in volume on mixing for liquid mixtures, and gas-phase PVT measurements for nitrogen+methane have been reviewed and where possible evaluated for consistency. The derived properties chosen for analysis and correlation were liquid mixture excess Gibbs free energies, and Henry's constants.

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.

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)

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

White, D.B.

This paper reports on experiments to examine gas migration rates in drilling muds that were performed in a 15-m-long, 200-mm-ID inclinable flow loop where air injection simulates gas entry during a kick. These tests were conducted using a xanthum gum (a common polymer used in drilling fluids) solution to simulate drilling muds as the liquid phase and air as the gas phase. This work represents a significant extension of existing correlations for gas/liquid flows in large pipe diameters with non- Newtonian fluids. Bubbles rise faster in drilling muds than in water despite the increased viscosity. This surprising result is causedmore » by the change in the flow regime, with large slug-type bubbles forming at lower void fractions. The gas velocity is independent of void fraction, thus simplifying flow modeling. Results show that a gas influx will rise faster in a well than previously believed. This has major implications for kick simulation, with gas arriving at the surface earlier than would be expected and the gas outflow rate being higher than would have been predicted. A model of the two-phase gas flow in drilling mud, including the results of this work, has been incorporated into the joint Schlumberger Cambridge Research (SCR)/BP Intl. kick model.« less

Crustal fingering: solidification on a viscously unstable interface

NASA Astrophysics Data System (ADS)

Fu, Xiaojing; Jimenez-Martinez, Joaquin; Cueto-Felgueroso, Luis; Porter, Mark; Juanes, Ruben

2017-11-01

Motivated by the formation of gas hydrates in seafloor sediments, here we study the volumetric expansion of a less viscous gas pocket into a more viscous liquid when the gas-liquid interfaces readily solidify due to hydrate formation. We first present a high-pressure microfluidic experiment to study the depressurization-controlled expansion of a Xenon gas pocket in a water-filled Hele-Shaw cell. The evolution of the pocket is controlled by three processes: (1) volumetric expansion of the gas; (2) rupturing of existing hydrate films on the gas-liquid interface; and (3) formation of new hydrate films. These result in gas fingering leading to a complex labyrinth pattern. To reproduce these observations, we propose a phase-field model that describes the formation of hydrate shell on viscously unstable interfaces. We design the free energy of the three-phase system to rigorously account for interfacial effects, gas compressibility and phase transitions. We model the hydrate shell as a highly viscous fluid with shear-thinning rheology to reproduce shell-rupturing behavior. We present high-resolution numerical simulations of the model, which illustrate the emergence of complex crustal fingering patterns as a result of gas expansion dynamics modulated by hydrate growth at the interface.

The Evolutionary Connection Bewtween z~2-3 Submillimeter Galaxies and AGN as Probed by Molecular Gas Excitation

NASA Astrophysics Data System (ADS)

Sharon, Chelsea E.; Riechers, Dominik A.; Carilli, Chris Luke; Hodge, Jacqueline; Walter, Fabian

2016-01-01

Theoretical work has suggested that active galactic nuclei (AGN) play an important role in quenching star formation in massive galaxies. Direct evidence for AGN affecting the molecular ISM has so far been limited to detections of molecular outflows in low-redshift systems and extreme excitation regions which represent a tiny fraction of the total gas. Indirect evidence for AGN's impact on their host galaxies' cold gas phase may be provided by measurements of the gas excitation and dynamics. At z~2-3, the peak epoch of star formation and AGN activity, previous observations of the CO(1-0) line revealed that submillimeter galaxies (SMGs) have multi-phase molecular gas, including substantial reservoirs of cold-phase gas. However, the entirety of the molecular gas in AGN-host galaxies appears highly excited, potentially supporting an evolutionary connection between these two populations. I will present a new VLA sample that nearly doubles the number of CO(1-0) detections in z~2-3 SMGs and AGN-host galaxies that allows us to better compare the cold gas properties of these systems and further investigate evidence for the effects of AGN on the star-forming molecular gas.

The analysis of the flow with water injection in a centrifugal compressor stage using CFD simulation

NASA Astrophysics Data System (ADS)

Michal, Tomášek; Richard, Matas; Tomáš, Syka

2017-09-01

This text deals with the principle of direct cooling of the pressure gas in a centrifugal compressor based on evaporation of the additional fluid phase in a control domain. A decrease of the gas temperature is reached by taking the heat, which is required for evaporation of the fluid phase. The influence of additional fluid phase on the parameters of the multiphase flow is compared with the ideal gas simulation in the defined domain and with the same boundary conditions.

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.

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.

Visualisation by high resolution synchrotron X-ray phase contrast micro-tomography of gas films on submerged superhydrophobic leaves.

PubMed

Lauridsen, Torsten; Glavina, Kyriaki; Colmer, Timothy David; Winkel, Anders; Irvine, Sarah; Lefmann, Kim; Feidenhans'l, Robert; Pedersen, Ole

2014-10-01

Floods can completely submerge terrestrial plants but some wetland species can sustain O2 and CO2 exchange with the environment via gas films forming on superhydrophobic leaf surfaces. We used high resolution synchrotron X-ray phase contrast micro-tomography in a novel approach to visualise gas films on submerged leaves of common cordgrass (Spartina anglica). 3D tomograms enabled a hitherto unmatched level of detail regarding the micro-topography of leaf gas films. Gas films formed only on the superhydrophobic adaxial leaf side (water droplet contact angle, Φ=162°) but not on the abaxial side (Φ=135°). The adaxial side of the leaves of common cordgrass is plicate with a longitudinal system of parallel grooves and ridges and the vast majority of the gas film volume was found in large ∼180μm deep elongated triangular volumes in the grooves and these volumes were connected to each neighbouring groove via a fine network of gas tubules (∼1.7μm diameter) across the ridges. In addition to the gas film retained on the leaf exterior, the X-ray phase contrast micro-tomography also successfully distinguished gas spaces internally in the leaf tissues, and the tissue porosity (gas volume per unit tissue volume) ranged from 6.3% to 20.3% in tip and base leaf segments, respectively. We conclude that X-ray phase contrast micro-tomography is a powerful tool to obtain quantitative data of exterior gas features on biological samples because of the significant difference in electron density between air, biological tissues and water. Copyright © 2014 Elsevier Inc. All rights reserved.

Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface

NASA Astrophysics Data System (ADS)

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2018-04-01

We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface—controlled by a crossover in how methane is supplied from the gas and liquid phases—which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

Determination of the rate of crystal growth from the gas phase under conditions of turbulent free convection

NASA Astrophysics Data System (ADS)

Alad'Ev, S. I.

1987-04-01

Crystal growth in vertical and horizontal cylindrical vials, with the substrate and the source serving as the vial ends, is investigated analytically, assuming that the medium consists of a binary mixture of an active and an inert gas. The active gas is made up of the gaseous products of reactions taking place at the substrate and at the source. It is shown that turbulent free convection leads to an increase in crystal growth rate. All other conditions being equal, crystal growth in vertical vials is greater than that in horizontal ones; in both cases crystal growth rate increases with the vial radius, temperature gradient in the gas phase, and gas phase density. The results are compared with experimental data on the growth of Ge crystals in the Ge-GeI4 system.

Implications of Low Volatility SOA and Gas-Phase Fragmentation Reactions on SOA Loadings and their Spatial and Temporal Evolution in the Atmosphere

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

Shrivastava, ManishKumar B.; Zelenyuk, Alla; Imre, Dan

2013-04-27

Recent laboratory and field measurements by a number of groups show that secondary organic aerosol (SOA) evaporates orders of magnitude slower than traditional models assume. In addition, chemical transport models using volatility basis set (VBS) SOA schemes neglect gas-phase fragmentation reactions, which are known to be extremely important. In this work, we present modeling studies to investigate the implications of non-evaporating SOA and gas-phase fragmentation reactions. Using the 3-D chemical transport model, WRF-Chem, we show that previous parameterizations, which neglect fragmentation during multi-generational gas-phase chemistry of semi-volatile/inter-mediate volatility organics ("aging SIVOC"), significantly over-predict SOA as compared to aircraft measurements downwindmore » of Mexico City. In sharp contrast, the revised models, which include gas-phase fragmentation, show much better agreement with measurements downwind of Mexico City. We also demonstrate complex differences in spatial SOA distributions when we transform SOA to non-volatile secondary organic aerosol (NVSOA) to account for experimental observations. Using a simple box model, we show that for same amount of SOA precursors, earlier models that do not employ multi-generation gas-phase chemistry of precursors ("non-aging SIVOC"), produce orders of magnitude lower SOA than "aging SIVOC" parameterizations both with and without fragmentation. In addition, traditional absorptive partitioning models predict almost complete SOA evaporation at farther downwind locations for both "non-aging SIVOC" and "aging SIVOC" with fragmentation. In contrast, in our revised approach, SOA transformed to NVSOA implies significantly higher background concentrations as it remains in particle phase even under highly dilute conditions. This work has significant implications on understanding the role of multi-generational chemistry and NVSOA formation on SOA evolution in the atmosphere.« less

Relative impact of short-term emissions controls on gas and particle-phase oxidative potential during the 2015 China Victory Day Parade in Beijing, China

NASA Astrophysics Data System (ADS)

Huang, Wei; Fang, Dongqing; Shang, Jing; Li, Zhengqiang; Zhang, Yang; Huo, Peng; Liu, Zhaoying; Schauer, James J.; Zhang, Yuanxun

2018-06-01

A field observation focusing on reactive oxygen species (ROS) was conducted before, during, and after the 2015 China Victory Day Parade to understand the influence of short-term emissions controls on atmospheric oxidative activity. The hourly average concentrations of PM2.5, SO2, NO, NO2, CO, O3, as well as gas and particle-phase ROS, were measured using a series of online instruments. PM2.5 concentrations during control days were significantly lower than non-control days, which directly lead to the "Parade Blue", yet reductions of most gaseous pollutants except SO2 were not so obvious as PM. Similarly, the control measures also led to a great loss of particle-phase ROS throughout the control period, while the reduction of ROS in gas phase was not obvious until the more stringent measures implemented since September 1. Furthermore, only weak positive correlations were observed among ROS and some other measured species, indicating ROS concentrations were affected by a number of comprehensive factors that single marker could not capture. Meanwhile, meteorological condition and regional transportation were also shown to be the minor factors affecting atmospheric oxidizing capacity. The results of this observation mainly revealed the control measures were conducive to reducing particle-related ROS. However, the reduction of gas-phase ROS activity was less effective given the menu of controls employed for the 2015 China Victory Day Parade. Therefore, short-term emissions controls only aimed to PM reduction and visibility improvement will produce the blue sky but will not equivalently reduce the gas-phase ROS. Supplemental control measures will be needed to further reduce gas-phase ROS concentrations.

Generation and delivery device for ozone gas

NASA Technical Reports Server (NTRS)

Andrews, Craig C. (Inventor); Murphy, Oliver J. (Inventor)

2002-01-01

The present invention provides an ozone generation and delivery system that lends itself to small scale applications and requires very low maintenance. The system preferably includes an anode reservoir and a cathode phase separator each having a hydrophobic membrane to allow phase separation of produced gases from water. The hydrogen gas, ozone gas and water containing ozone may be delivered under pressure.

Review on occurrence and behavior of PCDD/Fs and dl-PCBs in atmosphere of East Asia

NASA Astrophysics Data System (ADS)

Trinh, Minh Man; Chang, Moo Been

2018-05-01

This paper reviews the data from studies mainly published after 2000 to provide the current understanding of the physicochemical properties, atmospheric occurrence, gas/particle partitioning, fate and temporal trends in atmospheric matrix of PCDD/Fs and dl-PCBs of East Asia. Ambient PCDD/Fs and dl-PCBs concentrations in East Asia are found to be tens to hundreds times higher than that measured in Europe and North America. After strict regulations on PCDD/Fs and dl-PCBs emissions are enacted, the concentrations of these compounds decrease dramatically in Eastern Asian countries. In general, most of PCDD/Fs distribute in particle phase while dl-PCBs majorly exist in gas phase. Three main factors including physicochemical properties of the compounds, properties of particle and atmospheric condition affect the gas/particle partitioning of PCDD/Fs and dl-PCBs. The accuracy of absorption and adsorption models on predicting gas/particle partitioning of PCDD/Fs and dl-PCBs is evaluated. Gas-phase compounds are mostly removed from the atmosphere via reactions with OH radicals while those in particle phase are majorly removed by wet/dry deposition processes. The effects of removing processes and long-range transport on gas/particle partitioning are also discussed.

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 conversion between the most stable monosilanes.

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.

Gas and Particle Oxidation Products from Ozone Aging of Airborne Diesel Particles

NASA Astrophysics Data System (ADS)

Holmen, B. A.; Chen, Z.

2005-12-01

Diesel exhaust emissions contain fine particulate matter (PM2.5) composed of carbon-based particles with adsorbed compounds, including water soluble and insoluble substances. Many nonpolar organic compounds associated with diesel particulate matter (DPM) are known to be mutagenic and carcinogenic. In the presence of ozone, these DPM compounds can be transformed into polar species that are more toxic and poorly characterized. Understanding the gas and particle reaction products from DPM aging in the presence of tropospheric ozone is important for air quality, climate change and aerosol health effects. Aging experiments were conducted in a flow reactor to identify gas and particle-phase reaction products of DPM exposed to ambient levels of ozone. Diesel bus exhaust particles were collected on filters and then exposed to 0.1 - 0.5 ppm O3 for 0 to 72 h. Gaseous polar organic products formed during the aging experiments were collected on Tenax TA adsorbent coated with PFBHA derivatization agent. A thermal desorption gas chromatography mass spectrometry (TD/GC/MS) method was developed to determine gas-phase and particle-phase organic compounds. PFBHA and BSTFA derivatization agents converted polar species into less polar analogues prior to analysis. Preliminary results indicate that DPM hydrocarbons react with O3 to form many gas-phase polar products containing C=O (carbonyl) and COOH (carboxy) functional groups. Particle-phase PAH and alkane concentrations decreased significantly depending on time of exposure.

Separation mechanism of chiral impurities, ephedrine and pseudoephedrine, found in amphetamine-type substances using achiral modifiers in the gas phase.

PubMed

Holness, Howard K; Jamal, Adeel; Mebel, Alexander; Almirall, José R

2012-11-01

A new mechanism is proposed that describes the gas-phase separation of chiral molecules found in amphetamine-type substances (ATS) by the use of high-resolution ion mobility spectrometry (IMS). Straight-chain achiral alcohols of increasing carbon chain length, from methanol to n-octanol, are used as drift gas modifiers in IMS to highlight the mechanism proposed for gas-phase separations of these chiral molecules. The results suggest the possibility of using these achiral modifiers to separate the chiral molecules (R,S) and (S,R)-ephedrine and (S,S) and (R,R)-pseudoephedrine which contain an internal hydroxyl group at the first chiral center and an amino group at the other chiral center. Ionization was achieved with an electrospray source, the ions were introduced into an IMS with a resolving power of 80, and the resulting ion clusters were characterized with a coupled quadrupole mass spectrometer detector. A complementary computational study conducted at the density functional B3LYP/6-31g level of theory for the electronic structure of the analyte-modifier clusters was also performed, and showed either "bridged" or "independent" binding. The combined experimental and simulation data support the proposed mechanism for gas-phase chiral separations using achiral modifiers in the gas phase, thus enhancing the potential to conduct fast chiral separations with relative ease and efficiency.

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.

BIOMASS-FUELED, SMALL-SCALE, INTEGRATED-GASIFIER, GAS-TURBINE POWER PLANT: PROGRESS REPORT ON THE PHASE 2 DEVELOPMENT

EPA Science Inventory

The paper reports the latest efforts to complete development of Phase 2 of a three-phase effort to develop a family of small-scale (1 to 20 MWe) biomass-fueled power plants. The concept envisioned is an air-blown pressurized fluidized-bed gasifier followed by a dry hot gas clean...

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.

Evaluation of toxicity of trichloroethylene for plants

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

Ryu, S.B.; Davis, L.C.; Dana, J.

1996-12-31

Trichloroethylene (TCE) exposure of several species of plants was studied. Although earlier studies indicated that the root systems of plants could tolerate an aqueous phase concentration of 1 mM for a day, toxicity to whole plants was observed at somewhat lower levels in the gas phase in this study. The tested species included pumpkin (Cucurbita maxima), tomato (Lycopersicon esculentum), sweet potato (Dioscoria batata), tobacco (Nicotiana tabacum), soybean (Glycine max L. Merr), and alfalfa (Medicago sativa). Damage was observable as wilting or failure of the gravitropic response of shoots at levels above about 0.2 mM in the gas phase, which correspondsmore » to 0.5 mM in the aqueous phase. Plants were usually killed quickly at gas phase concentrations above 0.4 mM.« less

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.

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 accepted patterns, and the author believes that the present work provides more accurate insight into the modelling of liquid circulation in bubble columns. The characteristic bubbly flow at low gas velocity in a two-phase system is suppressed in the three-phase system. The degree of mixing within the system is found to be dependent on flow regime, liquid circulation and the ratio of solid phase physical properties.

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.

Effects of H3O+, OH-, \\text{O}_{2}^{-} , \\text{NO}_{\\text{x}}^{-} and NO x for Escherichia coli inactivation in atmospheric pressure DC corona discharges

NASA Astrophysics Data System (ADS)

Sekimoto, Kanako; Gonda, Rena; Takayama, Mitsuo

2015-08-01

The effects of ionic and neutral species such as H3O+, OH-, \\text{O}2- , \\text{NO}x- (x = 2, 3), and NO x on Escherichia coli (E. coli) inactivation in gas and liquid phases was investigated using atmospheric pressure DC corona discharges with point-to-plane electrodes. The above chemical species as well as OH and O3 were selectively irradiated onto E. coli suspensions on agar plates using a needle angle of 45° with respect to the plates, airflow, and a grid plate. Irradiation with the positive ion H3O+ did not inactivate E. coli, while the negative ions OH-/\\text{O}2- resulted in bactericidal inactivation, in both gas and liquid phases. In contrast, the negative ions \\text{NO}x- and neutral species NO x in the gas phase had quite strong bactericidal effects on E. coli compared to those species in the liquid phase. These results suggest that liquid-phase HNO3, formed primarily via the reaction of gas-phase \\text{NO}x- and NO x with H2O in agar, has only a weak inactivation effect on E. coli. Furthermore, using naphthylethylenediamine spectrophotometry, the threshold amount of gas-phase \\text{NO}x- and NO x for E. coli inactivation was determined to be  ≈1.3   ×   10-9 mol mm-1.

The hydrology of northern peatlands as affected by biogenic gas: Current developments and research needs

USGS Publications Warehouse

Rosenberry, D.O.; Glaser, P.H.; Siegel, D.I.

2006-01-01

Recent research indicates that accumulation and release of biogenic gas from northern peatlands may substantially affect future climate. Sudden release of free-phase gas bubbles into the atmosphere may preclude the conversion of methane to carbon dioxide in the uppermost oxic layer of the peat, resulting in greater contribution of methane to the atmosphere than is currently estimated. The hydrology of these peatlands also affects and is affected by this process, especially when gas is released suddenly and episodically. Indirect hydrological evidence indicates that ebullitive gas releases are relatively frequent in some peatlands and time-averaged rates may be significantly greater than diffusive releases. Estimates of free-phase gas contained in peat have ranged from 0 to nearly 20% of the peat volume. Abrupt changes in the volume of gas may alter hydraulic gradients and movement of water and solutes in peat, which in turn could alter composition and fluxes of the gas. Peat surfaces also move vertically and horizontally in response to accumulation and release of free-phase gas. Future research should address the distribution, temporal variability, and relative significance of ebullition in peatlands and the consequent hydrological responses to these gas-emission events. Copyright ?? 2006 John Wiley & Sons, Ltd.

Measurements of gas and particle polycyclic aromatic hydrocarbons (PAHs) in air at urban, rural and near-roadway sites

NASA Astrophysics Data System (ADS)

Pratt, G. C.; Herbrandson, C.; Krause, M. J.; Schmitt, C.; Lippert, C. J.; McMahon, C. R.; Ellickson, K. M.

2018-04-01

We measured polycyclic aromatic hydrocarbons (PAHs) in gas and particle phases over two years using high volume samplers equipped with quartz fiber filters and XAD-4 at a rural site, an urban site, and a site adjacent to a heavily trafficked roadway. Overall results were generally as expected, in that concentrations increased from rural to urban to near-roadway sites, and PAHs with high vapor pressures (liquid subcooled, PoL) and low octanol-air partition coefficients (Koa) were mainly in the gas phase, while those with low PoL and high Koa were predominantly in the particle phase. Intermediate PAHs existed in both phases with the phase distribution following a seasonal pattern of higher gas phase concentrations in summer due to temperature effects. The overall pattern of phase distribution was consistent with PAH properties and ambient conditions and was similar at all three sites. The particle-bound fraction (ϕ) was well-described empirically by nonlinear regressions with log Koa and log PoL as predictors. Adsorption and absorption models underestimated the particle-bound fraction for most PAHs. The dual aerosol-air/soot-air model generally represented the gas-particle partitioning better than the other models across all PAHs, but there was a tendency to underestimate the range in the particle-bound fraction seen in measurements. There was a statistically insignificant tendency for higher PAHs in the particle phase at the near roadway site, and one piece of evidence that PAHs may be enriched on ultrafine particles at the near roadway site. Understanding the phase and particle size distributions of PAHs in highly polluted, high exposure microenvironments near traffic sources will help shed light on potential health effects.

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

Kinetics of a gas adsorption compressor

NASA Technical Reports Server (NTRS)

Chan, C. K.; Tward, E.; Elleman, D. D.

1984-01-01

Chan (1981) has suggested that a process based on gas adsorption could be used as a means to drive a Joule-Thomson (J-T) device. The resulting system has several advantages. It is heat powered, it has no sealing, there are no mechanical moving parts, and no active control is required. In the present investigation, a two-phase model is used to analyze the transients of a gas adsorption compressor. The modeling of the adsorption process is based on a consideration of complete thermal and mechanical equilibrium between the gaseous phase and the adsorbed gas phase. The experimental arrangement for two sets of kinetic tests is discussed, and data regarding the experimental results are presented in graphs. For a theoretical study, a two-phase model was developed to predict the transient behavior of the compressor. A computer code was written to solve the governing equations with the aid of a standard forward marching predictor-corrector method.

Development of Monopole Interaction Models for Ionic Compounds. Part I: Estimation of Aqueous Henry's Law Constants for Ions and Gas Phase pKa Values for Acidic Compounds.

PubMed

Hilal, S H; Saravanaraj, A N; Carreira, L A

2014-02-01

The SPARC (SPARC Performs Automated Reasoning in Chemistry) physicochemical mechanistic models for neutral compounds have been extended to estimate Henry's Law Constant (HLC) for charged species by incorporating ionic electrostatic interaction models. Combinations of absolute aqueous pKa values, relative pKa values in the gas phase, and aqueous HLC for neutral compounds have been used to develop monopole interaction models that quantify the energy differences upon moving an ionic solute molecule from the gas phase to the liquid phase. Inter-molecular interaction energies were factored into mechanistic contributions of monopoles with polarizability, dipole, H-bonding, and resonance. The monopole ionic models were validated by a wide range of measured gas phase pKa data for 450 acidic compounds. The RMS deviation error and R(2) for the OH, SH, CO2 H, CH3 and NR2 acidic reaction centers (C) were 16.9 kcal/mol and 0.87, respectively. The calculated HLCs of ions were compared to the HLCs of 142 ions calculated by quantum mechanics. Effects of inter-molecular interaction of the monopoles with polarizability, dipole, H-bonding, and resonance on acidity of the solutes in the gas phase are discussed. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards building a robust computational framework to simulate multi-physics problems - a solution technique for three-phase (gas-liquid-solid) interactions

NASA Astrophysics Data System (ADS)

Zhang, Lucy

In this talk, we show a robust numerical framework to model and simulate gas-liquid-solid three-phase flows. The overall algorithm adopts a non-boundary-fitted approach that avoids frequent mesh-updating procedures by defining independent meshes and explicit interfacial points to represent each phase. In this framework, we couple the immersed finite element method (IFEM) and the connectivity-free front tracking (CFFT) method that model fluid-solid and gas-liquid interactions, respectively, for the three-phase models. The CFFT is used here to simulate gas-liquid multi-fluid flows that uses explicit interfacial points to represent the gas-liquid interface and for its easy handling of interface topology changes. Instead of defining different levels simultaneously as used in level sets, an indicator function naturally couples the two methods together to represent and track each of the three phases. Several 2-D and 3-D testing cases are performed to demonstrate the robustness and capability of the coupled numerical framework in dealing with complex three-phase problems, in particular free surfaces interacting with deformable solids. The solution technique offers accuracy and stability, which provides a means to simulate various engineering applications. The author would like to acknowledge the supports from NIH/DHHS R01-2R01DC005642-10A1 and the National Natural Science Foundation of China (NSFC) 11550110185.

A new, double-inversion mechanism of the F- + CH3Cl SN2 reaction in aqueous solution.

PubMed

Liu, Peng; Wang, Dunyou; Xu, Yulong

2016-11-23

Atomic-level, bimolecular nucleophilic substitution reaction mechanisms have been studied mostly in the gas phase, but the gas-phase results cannot be expected to reliably describe condensed-phase chemistry. As a novel, double-inversion mechanism has just been found for the F - + CH 3 Cl S N 2 reaction in the gas phase [Nat. Commun., 2015, 6, 5972], here, using multi-level quantum mechanics methods combined with the molecular mechanics method, we discovered a new, double-inversion mechanism for this reaction in aqueous solution. However, the structures of the stationary points along the reaction path show significant differences from those in the gas phase due to the strong influence of solvent and solute interactions, especially due to the hydrogen bonds formed between the solute and the solvent. More importantly, the relationship between the two double-inversion transition states is not clear in the gas phase, but, here we revealed a novel intermediate complex serving as a "connecting link" between the two transition states of the abstraction-induced inversion and the Walden-inversion mechanisms. A detailed reaction path was constructed to show the atomic-level evolution of this novel double reaction mechanism in aqueous solution. The potentials of mean force were calculated and the obtained Walden-inversion barrier height agrees well with the available experimental value.

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.

Modified sedimentation-dispersion model for solids in a three-phase slurry column

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

Smith, D.N.; Ruether, J.A.; Shah, Y.T.

1986-03-01

Solids distribution data for a three-phase, batch-fluidized slurry bubble column (SBC) are presented, using air as the gas phase, pure liquids and solutions as the liquid phase, and glass beads and carborundum catalyst powder as the solid phase. Solids distribution data for the three-phase SBC operated in a continuous mode of operation are also presented, using nitrogen as the gas phase, water as the liquid phase, and glass beads as the solid phase. A new model to provide a reasonable approach to predict solids concentration distributions for systems containing polydispersed solids is presented. The model is a modification of standardmore » sedimentation-dispersion model published earlier. Empirical correlations for prediction of hindered settling velocity and solids dispersion coefficient for systems containing polydispersed solids are presented. A new method of evaluating critical gas velocity (CGV) from concentrations of the sample withdrawn at the same port of the SBC is presented. Also presented is a new mapping for CGV which separates the two regimes in the SBC, namely, incomplete fluidization and complete fluidization.« less

Improving estimates of subsurface gas transport in unsaturated fractured media using experimental Xe diffusion data and numerical methods

NASA Astrophysics Data System (ADS)

Ortiz, J. P.; Ortega, A. D.; Harp, D. R.; Boukhalfa, H.; Stauffer, P. H.

2017-12-01

Gas transport in unsaturated fractured media plays an important role in a variety of applications, including detection of underground nuclear explosions, transport from volatile contaminant plumes, shallow CO2 leakage from carbon sequestration sites, and methane leaks from hydraulic fracturing operations. Gas breakthrough times are highly sensitive to uncertainties associated with a variety of hydrogeologic parameters, including: rock type, fracture aperture, matrix permeability, porosity, and saturation. Furthermore, a couple simplifying assumptions are typically employed when representing fracture flow and transport. Aqueous phase transport is typically considered insignificant compared to gas phase transport in unsaturated fracture flow regimes, and an assumption of instantaneous dissolution/volatilization of radionuclide gas is commonly used to reduce computational expense. We conduct this research using a twofold approach that combines laboratory gas experimentation and numerical modeling to verify and refine these simplifying assumptions in our current models of gas transport. Using a gas diffusion cell, we are able to measure air pressure transmission through fractured tuff core samples while also measuring Xe gas breakthrough measured using a mass spectrometer. We can thus create synthetic barometric fluctuations akin to those observed in field tests and measure the associated gas flow through the fracture and matrix pore space for varying degrees of fluid saturation. We then attempt to reproduce the experimental results using numerical models in PLFOTRAN and FEHM codes to better understand the importance of different parameters and assumptions on gas transport. Our numerical approaches represent both single-phase gas flow with immobile water, as well as full multi-phase transport in order to test the validity of assuming immobile pore water. Our approaches also include the ability to simulate the reaction equilibrium kinetics of dissolution/volatilization in order to identify when the assumption of instantaneous equilibrium is reasonable. These efforts will aid us in our application of such models to larger, field-scale tests and improve our ability to predict gas breakthrough times.

Evidence for a palaeo-oil column and alteration of residual oil in a gas-condensate field: Integrated oil inclusion and experimental results

NASA Astrophysics Data System (ADS)

Bourdet, Julien; Burruss, Robert C.; Chou, I.-Ming; Kempton, Richard; Liu, Keyu; Hung, Nguyen Viet

2014-10-01

In the Phuong Dong gas condensate field, Cuu Long Basin, Vietnam, hydrocarbon inclusions in quartz trapped a variety of petroleum fluids in the gas zone. Based on the attributes of the oil inclusion assemblages (fluorescence colour of the oil, bubble size, presence of bitumen), the presence of a palaeo-oil column is inferred prior to migration of gas into the reservoir. When a palaeo-oil column is displaced by gas, a residual volume fraction of oil remains in pores. If the gas does not completely mix with the oil, molecular partitioning between the residual oil and the new gas charge may change the composition and properties of the residual oil (gas stripping or gas washing). To simulate this phenomenon in the laboratory, we sealed small amounts of crude oil (42 and 30 °API) and excess pure gas (methane, ethane, or propane) in fused silica capillary capsules (FSCCs), with and without water. These mixtures were characterized with the same methods used to characterize the fluid inclusions, heating and cooling stage microscopy, fluorescence spectroscopy, synchrotron FT-IR, and Raman spectroscopy. At room temperature, mixtures of ethane and propane with the 30 °API oil formed a new immiscible fluorescent liquid phase with colour that is visually more blue than the initial oil. The fluorescence of the original oil phase shifted to yellow or disappeared with formation of semi-solid residues. The blue-shift of the fluorescence of the immiscible phases and strong CH stretching bands in FT-IR spectra are consistent with stripping of hydrocarbon molecules from the oil. In experiments in FSCCs with water solid residues are common. At elevated temperature, reproducing geologic reservoir conditions, the fluorescence changes and therefore the molecular fractionation are enhanced. However, the precipitation of solid residues is responsible of more complex changes. Mixing experiments with the 42 °API oil do not form a new immiscible hydrocarbon liquid although the fluorescence displays a similar yellow shift when gas is added. Solid residues rarely form in mixtures with 42 °API oil. FT-IR spectra suggest that the decrease of fluorescence intensity of the original oil at short wavelengths to be due to the partitioning of low molecular weight aromatic molecules into the vapour phase and/or the new immiscible liquid phase. The decrease of fluorescence intensity at long wavelengths appears to be due to loss of high molecular weight aromatics during precipitation of solid residues by desorption of aromatics and resins from asphaltenes. Desorption of low molecular weight aromatics and resins from asphaltenes during precipitation can also increase the fluorescence intensity at short wavelengths of the residual oil. Water clearly affects the precipitation of semi-solid residues from the oil phase of the lowest API gravity oil. The change of hydrocarbon phase(s) in UV-visible fluorescence and FT-IR enclosed within the FSCCs were compared with the fluorescence patterns of natural fluid inclusions at Phuong Dong gas condensate field. The experimental results support the concept of gas-washing of residual oil and are consistent with the oil inclusion attributes from the current gas zone at Phuong Dong field. The hydrocarbon charge history of the fractured granite reservoir is interpreted to result from the trapping of residual oil after drainage of a palaeo-oil column by gas.

Numerical investigation of influence on heat transfer characteristics to pneumatically conveyed dense phase flow by selecting models and boundary conditions

NASA Astrophysics Data System (ADS)

Zheng, Y.; Liu, Q.; Li, Y.

2012-03-01

Solids moving with a gas stream in a pipeline can be found in many industrial processes, such as power generation, chemical, pharmaceutical, food and commodity transfer processes. A mass flow rate of the solids is important characteristic that is often required to be measured (and controlled) to achieve efficient utilization of energy and raw materials in pneumatic conveying systems. The methods of measuring the mass flow rate of solids in a pneumatic pipeline can be divided into direct and indirect (inferential) measurements. A thermal solids' mass flow-meter, in principle, should ideally provide a direct measurement of solids flow rate, regardless of inhomogeneities in solids' distribution and environmental impacts. One key issue in developing a thermal solids' mass flow-meter is to characterize the heat transfer between the hot pipe wall and the gas-solids dense phase flow. The Eulerian continuum modeling with gas-solid two phases is the most common method for pneumatic transport. To model a gas-solid dense phase flow passing through a heated region, the gas phase is described as a continuous phase and the particles as the second phase. This study aims to describe the heat transfer characteristics between the hot wall and the gas-solids dense phase flow in pneumatic pipelines by modeling a turbulence gas-solid plug passing through the heated region which involves several actual and crucial issues: selections of interphase exchange coefficient, near-wall region functions and different wall surface temperatures. A sensitivity analysis was discussed to identify the influence on the heat transfer characteristics by selecting different interphase exchange coefficient models and different boundary conditions. Simulation results suggest that sensitivity analysis in the choice of models is very significant. The simulation results appear to show that a combination of choosing the Syamlal-O'Brien interphase exchange coefficient model and the standard k-ɛ model along with the standard wall function model might be the best approach, by which, the simulation data seems to be closest to the experimental results.

FLUID: A numerical interpolation procedure for obtaining thermodynamic and transport properties of fluids

NASA Technical Reports Server (NTRS)

Fessler, T. E.

1977-01-01

A computer program subroutine, FLUID, was developed to calculate thermodynamic and transport properties of pure fluid substances. It provides for determining the thermodynamic state from assigned values for temperature-density, pressure-density, temperature-pressure, pressure-entropy, or pressure-enthalpy. Liquid or two-phase (liquid-gas) conditions are considered as well as the gas phase. A van der Waals model is used to obtain approximate state values; these values are then corrected for real gas effects by model-correction factors obtained from tables based on experimental data. Saturation conditions, specific heat, entropy, and enthalpy data are included in the tables for each gas. Since these tables are external to the FLUID subroutine itself, FLUID can implement any gas for which a set of tables has been generated. (A setup phase is used to establish pointers dynamically to the tables for a specific gas.) Data-table preparation is described. FLUID is available in both SFTRAN and FORTRAN

Methods for recovering a solvent from a fluid volume and methods of removing at least one compound from a nonpolar solvent

DOEpatents

Ginosar, Daniel M.; Wendt, Daniel S.; Petkovic, Lucia M.

2014-06-10

A method of removing a nonpolar solvent from a fluid volume that includes at least one nonpolar compound, such as a fat, an oil or a triglyceride, is provided. The method comprises contacting a fluid volume with an expanding gas to expand the nonpolar solvent and form a gas-expanded solvent. The gas-expanded solvent may have a substantially reduced density in comparison to the at least one nonpolar compound and/or a substantially reduced capacity to solubilize the nonpolar compound, causing the nonpolar compounds to separate from the gas-expanded nonpolar solvent into a separate liquid phase. The liquid phase including the at least one nonpolar compound may be separated from the gas-expanded solvent using conventional techniques. After separation of the liquid phase, at least one of the temperature and pressure may be reduced to separate the nonpolar solvent from the expanding gas such that the nonpolar solvent may be recovered and reused.

Gas-liquid two-phase flow pattern identification by ultrasonic echoes reflected from the inner wall of a pipe

NASA Astrophysics Data System (ADS)

Liang, Fachun; Zheng, Hongfeng; Yu, Hao; Sun, Yuan

2016-03-01

A novel ultrasonic pulse echo method is proposed for flow pattern identification in a horizontal pipe with gas-liquid two-phase flow. A trace of echoes reflected from the pipe’s internal wall rather than the gas-liquid interface is used for flow pattern identification. Experiments were conducted in a horizontal air-water two-phase flow loop. Two ultrasonic transducers with central frequency of 5 MHz were mounted at the top and bottom of the pipe respectively. The experimental results show that the ultrasonic reflection coefficient of the wall-gas interface is much larger than that of the wall-liquid interface due to the large difference in the acoustic impedance of gas and liquid. The stratified flow, annular flow and slug flow can be successfully recognized using the attenuation ratio of the echoes. Compared with the conventional ultrasonic echo measurement method, echoes reflected from the inner surface of a pipe wall are independent of gas-liquid interface fluctuation, sound speed, and gas and liquid superficial velocities, which makes the method presented a promising technique in field practice.

FIELD TRAPPING OF SUBSURFACE VAPOR PHASE PETROLEUM HYDROCARBONS

EPA Science Inventory

Soil gas samples from intact soil cores were collected on adsorbents at a field site, then thermally desorbed and analyzed by laboratory gas chromatography (GC). ertical concentration profiles of predominant vapor phase petroleum hydrocarbons under ambient conditions were obtaine...

Buoyancy Driven Shear Flows of Bubble Suspensions

NASA Technical Reports Server (NTRS)

Koch, D. L.; Hill, R. J.; Chellppannair, T.; Zenit, R.; Zenit, R.; Spelt, P. D. M.

1999-01-01

In this work the gas volume fraction and the root-mean-squared fluid velocity are measured in buoyancy driven shear flows of bubble suspensions in a tall, inclined, rectangular channel. The experiments are performed under conditions where We << 1a nd Re >> 1, for which comparisons are made with kinetic theory and numerical simulations. Here Re = gamma(a(exp 2)/nu is the Reynolds number and We = rho(gamma(exp 2))a(exp 3)/sigma is the Weber number; gamma is the shear rate, a is the bubble radius, nu is the kinematic viscosity of the liquid, rho is the density of the liquid, and sigma is the surface tension of the gas/liquid interface. Kang et al. calculated the bubble phase pressure and velocity variance of sheared bubble suspensions under conditions where the bubbles are spherical and the liquid phase velocity field can be approximated using potential flow theory, i.e. We= 0 and Re >> 1. Such conditions can be achieved in an experiment using gas bubbles, with a radius of O(0.5mm), in water. The theory requires that there be no average relative motion of the gas and liquid phases, hence the motivation for an experimental program in microgravity. The necessity of performing preliminary, Earth based experiments, however, requires performing experiments where the gas phase rises in the liquid, which significantly complicates the comparison of experiments with theory. Rather than comparing experimental results with theory for a uniform, homogeneous shear flow, experiments can be compared directly with solutions of the averaged equations of motion for bubble suspensions. This requires accounting for the significant lift force acting on the gas phase when the bubbles rise parallel to the average velocity of the sheared suspension. Shear flows can be produced in which the bubble phase pressure gradient, arising from shear induced collisions amongst the bubbles, balances a body force (centrifugal or gravitational) on the gas phase. A steady, non-uniform gas volume fraction can be measured, from which the bubble phase pressure gradient can be obtained and compared to theory and numerical simulations. The presence of bounding walls further complicates the experiments, since the detailed interactions of the bubbles with bounding walls is not well understood, especially in the presence of gravity, where the momentum and energy exchange depends on the inclination of the wall.

Laboratory investigations of Titan haze formation: In situ measurement of gas and particle composition

NASA Astrophysics Data System (ADS)

Hörst, Sarah M.; Yoon, Y. Heidi; Ugelow, Melissa S.; Parker, Alex H.; Li, Rui; de Gouw, Joost A.; Tolbert, Margaret A.

2018-02-01

Prior to the arrival of the Cassini-Huygens spacecraft, aerosol production in Titan's atmosphere was believed to begin in the stratosphere where chemical processes are predominantly initiated by far ultraviolet (FUV) radiation. However, measurements taken by the Cassini Ultraviolet Imaging Spectrograph (UVIS) and Cassini Plasma Spectrometer (CAPS) indicate that haze formation initiates in the thermosphere where there is a greater flux of extreme ultraviolet (EUV) photons and energetic particles available to initiate chemical reactions, including the destruction of N2. The discovery of previously unpredicted nitrogen species in measurements of Titan's atmosphere by the Cassini Ion and Neutral Mass Spectrometer (INMS) indicates that nitrogen participates in the chemistry to a much greater extent than was appreciated before Cassini. The degree of nitrogen incorporation in the haze particles is important for understanding the diversity of molecules that may be present in Titan's atmosphere and on its surface. We have conducted a series of Titan atmosphere simulation experiments using either spark discharge (Tesla coil) or FUV photons (deuterium lamp) to initiate chemistry in CH4/N2 gas mixtures ranging from 0.01% CH4/99.99% N2 to 10% CH4/90% N2. We obtained in situ real-time measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) to measure the particle composition as a function of particle size and a proton-transfer ion-trap mass spectrometer (PIT-MS) to measure the composition of gas phase products. These two techniques allow us to investigate the effect of energy source and initial CH4 concentration on the degree of nitrogen incorporation in both the gas and solid phase products. The results presented here confirm that FUV photons produce not only solid phase nitrogen bearing products but also gas phase nitrogen species. We find that in both the gas and solid phase, nitrogen is found in nitriles rather than amines and that both the gas phase and solid phase products are composed primarily of molecules with a low degree of aromaticity. The UV experiments reproduce the absolute abundances measured in Titan's stratosphere for a number of gas phase species including C4H2, C6H6, HCN, CH3CN, HC3N, and C2H5CN.

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.

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 nitrogen in mixed gas injection into methane hydrate reservoirs has been far more successful at producing methane than pure carbon dioxide injections. These results also provide a test for the validity of equilibrium thermodynamics in transport-dominated mixed hydrate systems that can be validated by laboratory-scale flow-through experiments.

Atmospheric origins of perchlorate on Mars and in the Atacama

NASA Astrophysics Data System (ADS)

Catling, D. C.; Claire, M. W.; Zahnle, K. J.; Quinn, R. C.; Clark, B. C.; Hecht, M. H.; Kounaves, S.

2010-01-01

Isotopic studies indicate that natural perchlorate is produced on Earth in arid environments by the oxidation of chlorine species through pathways involving ozone or its photochemical products. With this analogy, we propose that the arid environment on Mars may have given rise to perchlorate through the action of atmospheric oxidants. A variety of hypothetical pathways can be proposed including photochemical reactions, electrostatic discharge, and gas-solid reactions. Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we made a preliminary study of the means to produce Atacama perchlorate to help shed light on the origin of Martian perchlorate. We investigated gas phase pathways using a 1-D photochemical model. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. The feasibility of gas phase production for the Atacama provides justification for future investigations of gas phase photochemistry as a possible source for Martian perchlorate.

Simultaneous imaging of fuel vapor mass fraction and gas-phase temperature inside gasoline sprays using two-line excitation tracer planar laser-induced fluorescence.

PubMed

Zigan, Lars; Trost, Johannes; Leipertz, Alfred

2016-02-20

This paper reports for the first time, to the best of our knowledge, on the simultaneous imaging of the gas-phase temperature and fuel vapor mass fraction distribution in a direct-injection spark-ignition (DISI) spray under engine-relevant conditions using tracer planar laser-induced fluorescence (TPLIF). For measurements in the spray, the fluorescence tracer 3-pentanone is added to the nonfluorescent surrogate fuel iso-octane, which is excited quasi-simultaneously by two different excimer lasers for two-line excitation LIF. The gas-phase temperature of the mixture of fuel vapor and surrounding gas and the fuel vapor mass fraction can be calculated from the two LIF signals. The measurements are conducted in a high-temperature, high-pressure injection chamber. The fluorescence calibration of the tracer was executed in a flow cell and extended significantly compared to the existing database. A detailed error analysis for both calibration and measurement is provided. Simultaneous single-shot gas-phase temperature and fuel vapor mass fraction fields are processed for the assessment of cyclic spray fluctuations.

Generation and delivery device for ozone gas and ozone dissolved in water

NASA Technical Reports Server (NTRS)

Andrews, Craig C. (Inventor); Murphy, Oliver J. (Inventor)

2004-01-01

The present invention provides an ozone generation and delivery system that lends itself to small scale applications and requires very low maintenance. The system preferably includes an anode reservoir and a cathode phase separator each having a hydrophobic membrane to allow phase separation of produced gases from water. The hydrogen gas, ozone gas and water containing ozone may be delivered under pressure.

MODELING AEROSOL FORMATION FROM ALPHA-PINENE + NOX IN THE PRESENCE OF NATURAL SUNLIGHT USING GAS PHASE KINETICS AND GAS-PARTICLE PARTITIONING THEORY. (R826771)

EPA Science Inventory

A kinetic mechanism was used to link and model the gas-phase reactions and
aerosol accumulation resulting from src="/ncer/pubs/images/alpha.gif">-pinene reactions in the presence of sunlight,
ozone (O₃), and oxides of nitrogen
(NO