Second law of thermodynamics in volume diffusion hydrodynamics in multicomponent gas mixtures

NASA Astrophysics Data System (ADS)

Dadzie, S. Kokou

2012-10-01

We presented the thermodynamic structure of a new continuum flow model for multicomponent gas mixtures. The continuum model is based on a volume diffusion concept involving specific species. It is independent of the observer's reference frame and enables a straightforward tracking of a selected species within a mixture composed of a large number of constituents. A method to derive the second law and constitutive equations accompanying the model is presented. Using the configuration of a rotating fluid we illustrated an example of non-classical flow physics predicted by new contributions in the entropy and constitutive equations.

Derivation of a reference dose for a complex petroleum hydrocarbon mixture

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

Ryer-Powder, J.E.; LaPirre, A.; Scofield, R.

1997-12-31

Petroleum hydrocarbon mixtures pose a challenge in assessing potential health effects associated with environmental exposures through impacted media. Two components of risk assessment that must be addressed when evaluating these mixtures are toxicity and environmental fate. In this paper, we focus on issues regarding toxicity. Specifically, we have developed a methodology to derive a reference dose (RfD) for a complex petroleum hydrocarbon mixture referred to as diluent. Diluent is a solvent used in the production of crude oil and is composed of hydrocarbons in the middle distillate range. Two conservative approaches to developing a reference dose for diluent are presented.more » Both involve separating the diluent into carbon number ranges (e.g., diluent consists of hydrocarbons containing between 5 carbons and greater than 21 carbons, so, the mixture can be divided into mixtures of hydrocarbons having 5 carbons, 6-11 carbons, etcetera) and assigning each range a representative RfD. In the first approach, the representative RfD for each range is that of one specific chemical within the range (e.g., the reference dose for the C{sub 5}-C{sub 8} carbon range is that of n-hexane). In the second approach, the RfD dose for each range is that of a mixture of chemicals representative of each carbon number range (e.g., the RfD for the C{sub 6} to C{sub 11} carbon range is that of mineral spirits). The RfD for each carbon range is then multiplied by the percent of diluent in the corresponding range and the products are added to arrive at a final RfD. The RfD for diluent using the first approach is estimated at 2 mg/kg-day and that using the second approach is estimated at 1 mg/kg-day.« less

Continuous electrophoretic purification of individual analytes from multicomponent mixtures.

PubMed

McLaren, David G; Chen, David D Y

2004-04-15

Individual analytes can be isolated from multicomponent mixtures and collected in the outlet vial by carrying out electrophoretic purification through a capillary column. Desired analytes are allowed to migrate continuously through the column under the electric field while undesired analytes are confined to the inlet vial by application of a hydrodynamic counter pressure. Using pressure ramping and buffer replenishment techniques, 18% of the total amount present in a bulk sample can be purified when the resolution to the adjacent peak is approximately 3. With a higher resolution, the yield could be further improved. Additionally, by periodically introducing fresh buffer into the sample, changes in pH and conductivity can be mediated, allowing higher purity (>or=99.5%) to be preserved in the collected fractions. With an additional reversed cycle of flow counterbalanced capillary electrophoresis, any individual component in a sample mixture can be purified providing it can be separated in an electrophoresis system.

Consensus sediment quality guidelines for polycyclic aromatic hydrocarbon mixtures

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

Swartz, R.C.

1999-04-01

Sediment quality guidelines (SQGs) for polycyclic aromatic hydrocarbons (PAHs) have been derived from a variety of laboratory, field, and theoretical foundations. They include the screening level concentration, effects ranges-low and -median, equilibrium partitioning concentrations, apparent effects threshold, {Sigma}PAH model, and threshold and probable effects levels. The resolution of controversial differences among the PAH SQGs lies in an understanding of the effects of mixtures. Polycyclic aromatic hydrocarbons virtually always occur in field-collected sediment as a complex mixture of covarying compounds. When expressed as a mixture concentration, that is, total PAH (TPAH), the guidelines form three clusters that were intended in theirmore » original derivations to represent threshold (TEC = 290 {micro}g/g organic carbon [OC]), median (MEC = 1,800 {micro}g/g OC), and extreme (EEC = 10,000 {micro}g/g OC) effects concentrations. The TEC/MEC/EEC consensus guidelines provide a unifying synthesis of other SQGs, reflect causal rather than correlative effects, account for mixtures, and predict sediment toxicity and benthic community perturbations at sites of PAH contamination. The TEC offers the most useful SQG because PAH mixtures are unlikely to cause adverse effects on benthic ecosystems below the TEC.« less

Development and validation of chemometrics-assisted spectrophotometric and liquid chromatographic methods for the simultaneous determination of two multicomponent mixtures containing bronchodilator drugs.

PubMed

El-Gindy, Alaa; Emara, Samy; Shaaban, Heba

2007-02-19

Three methods are developed for the determination of two multicomponent mixtures containing guaiphenesine (GU) with salbutamol sulfate (SL), methylparaben (MP) and propylparaben (PP) [mixture 1]; and acephylline piperazine (AC) with bromhexine hydrochloride (BX), methylparaben (MP) and propylparaben (PP) [mixture 2]. The resolution of the two multicomponent mixtures has been accomplished by using numerical spectrophotometric methods such as partial least squares (PLS-1) and principal component regression (PCR) applied to UV absorption spectra of the two mixtures. In addition HPLC method was developed using a RP 18 column at ambient temperature with mobile phase consisting of acetonitrile-0.05 M potassium dihydrogen phosphate, pH 4.3 (60:40, v/v), with UV detection at 243 nm for mixture 1, and mobile phase consisting of acetonitrile-0.05 M potassium dihydrogen phosphate, pH 3 (50:50, v/v), with UV detection at 245 nm for mixture 2. The methods were validated in terms of accuracy, specificity, precision and linearity in the range of 20-60 microg ml(-1) for GU, 1-3 microg ml(-1) for SL, 20-80 microg ml(-1) for AC, 0.2-1.8 microgml(-1) for PP and 1-5 microg ml(-1) for BX and MP. The proposed methods were successfully applied for the determination of the two multicomponent combinations in laboratory prepared mixtures and commercial syrups.

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2010 CFR

2010-07-01

... Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Averageboiling point * (degrees F) Criteria Reactivityfactor 1 80-205 Alkanes... + Dry Point) / 2 (b) Aromatic Hydrocarbon Solvents ...

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2011 CFR

2011-07-01

... Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Averageboiling point * (degrees F) Criteria Reactivityfactor 1 80-205 Alkanes... + Dry Point) / 2 (b) Aromatic Hydrocarbon Solvents ...

Effect of Substrate Wetting on the Morphology and Dynamics of Phase Separating Multi-Component Mixture

NASA Astrophysics Data System (ADS)

Goyal, Abheeti; Toschi, Federico; van der Schoot, Paul

2017-11-01

We study the morphological evolution and dynamics of phase separation of multi-component mixture in thin film constrained by a substrate. Specifically, we have explored the surface-directed spinodal decomposition of multicomponent mixture numerically by Free Energy Lattice Boltzmann (LB) simulations. The distinguishing feature of this model over the Shan-Chen (SC) model is that we have explicit and independent control over the free energy functional and EoS of the system. This vastly expands the ambit of physical systems that can be realistically simulated by LB simulations. We investigate the effect of composition, film thickness and substrate wetting on the phase morphology and the mechanism of growth in the vicinity of the substrate. The phase morphology and averaged size in the vicinity of the substrate fluctuate greatly due to the wetting of the substrate in both the parallel and perpendicular directions. Additionally, we also describe how the model presented here can be extended to include an arbitrary number of fluid components.

Viscosity of nonelectrolyte liquid mixtures. III Binary mixtures of methyl methacrylate with hydrocarbons, haloalkanes, and alkylamines

NASA Astrophysics Data System (ADS)

Oswal, S. L.; Patel, B. M.; Shah, H. R.; Oswal, P.

1994-07-01

Measurements of the viscosity η and the density ϱ are reported for 14 binary mixtures of methyl methacrylate (MMA) with hydrocarbons, haloalkanes, and alkylamines at 303.15 K. The viscosity data have been correlated with equations of Grunberg and Nissan, of McAllister, and of Auslaender. Furthermore, excess viscosity Δ In η and excess Gibbs energy of activation ΔG* E of viscous flow have been calculated and have been used to predict molecular interactions occurring in present binary mixtures. The results show the existence of specific interactions in MMA + aromatic hydrocarbons, MMA + haloalkanes, and MMA + primary amines.

Mathematical Model of Nonstationary Separation Processes Proceeding in the Cascade of Gas Centrifuges in the Process of Separation of Multicomponent Isotope Mixtures

NASA Astrophysics Data System (ADS)

Orlov, A. A.; Ushakov, A. A.; Sovach, V. P.

2017-03-01

We have developed and realized on software a mathematical model of the nonstationary separation processes proceeding in the cascades of gas centrifuges in the process of separation of multicomponent isotope mixtures. With the use of this model the parameters of the separation process of germanium isotopes have been calculated. It has been shown that the model adequately describes the nonstationary processes in the cascade and is suitable for calculating their parameters in the process of separation of multicomponent isotope mixtures.

Reproducible surface-enhanced Raman quantification of biomarkers in multicomponent mixtures.

PubMed

De Luca, Anna Chiara; Reader-Harris, Peter; Mazilu, Michael; Mariggiò, Stefania; Corda, Daniela; Di Falco, Andrea

2014-03-25

Direct and quantitative detection of unlabeled glycerophosphoinositol (GroPIns), an abundant cytosolic phosphoinositide derivative, would allow rapid evaluation of several malignant cell transformations. Here we report label-free analysis of GroPIns via surface-enhanced Raman spectroscopy (SERS) with a sensitivity of 200 nM, well below its apparent concentration in cells. Crucially, our SERS substrates, based on lithographically defined gold nanofeatures, can be used to predict accurately the GroPIns concentration even in multicomponent mixtures, avoiding the preliminary separation of individual compounds. Our results represent a critical step toward the creation of SERS-based biosensor for rapid, label-free, and reproducible detection of specific molecules, overcoming limits of current experimental methods.

Prebiotic hydrocarbon synthesis in impacting reduced astrophysical icy mixtures

DOE PAGES

Koziol, Lucas; Goldman, Nir

2015-04-21

We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extendedmore » structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Lastly, our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials.« less

Prebiotic hydrocarbon synthesis in impacting reduced astrophysical icy mixtures

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

Koziol, Lucas; Goldman, Nir

We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extendedmore » structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Lastly, our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials.« less

Sedimentation dynamics and equilibrium profiles in multicomponent mixtures of colloidal particles.

PubMed

Spruijt, E; Biesheuvel, P M

2014-02-19

In this paper we give a general theoretical framework that describes the sedimentation of multicomponent mixtures of particles with sizes ranging from molecules to macroscopic bodies. Both equilibrium sedimentation profiles and the dynamic process of settling, or its converse, creaming, are modeled. Equilibrium profiles are found to be in perfect agreement with experiments. Our model reconciles two apparently contradicting points of view about buoyancy, thereby resolving a long-lived paradox about the correct choice of the buoyant density. On the one hand, the buoyancy force follows necessarily from the suspension density, as it relates to the hydrostatic pressure gradient. On the other hand, sedimentation profiles of colloidal suspensions can be calculated directly using the fluid density as apparent buoyant density in colloidal systems in sedimentation-diffusion equilibrium (SDE) as a result of balancing gravitational and thermodynamic forces. Surprisingly, this balance also holds in multicomponent mixtures. This analysis resolves the ongoing debate of the correct choice of buoyant density (fluid or suspension): both approaches can be used in their own domain. We present calculations of equilibrium sedimentation profiles and dynamic sedimentation that show the consequences of these insights. In bidisperse mixtures of colloids, particles with a lower mass density than the homogeneous suspension will first cream and then settle, whereas particles with a suspension-matched mass density form transient, bimodal particle distributions during sedimentation, which disappear when equilibrium is reached. In all these cases, the centers of the distributions of the particles with the lowest mass density of the two, regardless of their actual mass, will be located in equilibrium above the so-called isopycnic point, a natural consequence of their hard-sphere interactions. We include these interactions using the Boublik-Mansoori-Carnahan-Starling-Leland (BMCSL) equation of

Evaluating the aquatic toxicity of complex organic chemical mixtures: lessons learned from polycyclic aromatic hydrocarbon and petroleum hydrocarbon case studies.

PubMed

Landrum, Peter F; Chapman, Peter M; Neff, Jerry; Page, David S

2012-04-01

Experimental designs for evaluating complex mixture toxicity in aquatic environments can be highly variable and, if not appropriate, can produce and have produced data that are difficult or impossible to interpret accurately. We build on and synthesize recent critical reviews of mixture toxicity using lessons learned from 4 case studies, ranging from binary to more complex mixtures of primarily polycyclic aromatic hydrocarbons and petroleum hydrocarbons, to provide guidance for evaluating the aquatic toxicity of complex mixtures of organic chemicals. Two fundamental requirements include establishing a dose-response relationship and determining the causative agent (or agents) of any observed toxicity. Meeting these 2 requirements involves ensuring appropriate exposure conditions and measurement endpoints, considering modifying factors (e.g., test conditions, test organism life stages and feeding behavior, chemical transformations, mixture dilutions, sorbing phases), and correctly interpreting dose-response relationships. Specific recommendations are provided. Copyright © 2011 SETAC.

FLAME SUPPRESSION AND LUBRICANT INTERACTION OF HYDROCARBON MIXTURES FOR HOUSEHOLD REFRIGERATOR/FREEZERS

EPA Science Inventory

The paper discusses the flame suppression and lubricant interaction of hydrocarbon (HC) mixtures for household refrigerator/freezers (R/Fs). The work focuses on blending the minimum amount of a fluoroiodocarbon (FIC) with previously optimized R/F-tested HC mixtures to reduce thei...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 5 2011-07-01 2011-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Boiling range (degrees F) Criteria Reactivityfactor 21 280-290 Aromatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 5 2010-07-01 2010-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Boiling range (degrees F) Criteria Reactivityfactor 21 280-290 Aromatic...

Development of a Novel Leak-Free Constant-Pressure Cylinder for Certified Reference Materials of Liquid Hydrocarbon Mixtures.

PubMed

Kim, Yong Doo; Kang, Ji Hwan; Bae, Hyun Kil; Kang, Namgoo; Oh, Sang Hyub; Lee, Jin-Hong; Woo, Jin Chun; Lee, Sangil

2017-11-21

Liquid hydrocarbon mixtures such as liquefied petroleum gas and liquefied natural gas are becoming integral parts of the world's energy system. Certified reference materials (CRMs) of liquid hydrocarbon mixtures are necessary to allow assessment of the accuracy and traceability of the compositions of such materials. A piston-type constant-pressure cylinder (PCPC) comprising chambers for a pressurizing gas (helium) and liquid (hydrocarbons) separated by a piston can be used to develop accurate and traceable liquid hydrocarbon mixture CRMs. The development of accurate CRMs relies on the maintenance of their composition. However, a PCPC might allow hydrocarbons to leak owing to the imperfect seal of the piston. In this study, a novel leak-free bellows-type constant-pressure cylinder (BCPC) is designed and evaluated by comparison with PCPCs. Liquid hydrocarbon mixtures consisting of ethane, propane, propene, isobutane, n-butane, 1-butene, and isopentane were prepared in both types of constant pressure cylinders and then monitored to check leakages between the gas and liquid chambers. Overall, notable leakage occurred from and into both chambers in the PCPCs, whereas no leakage occurred in the BCPCs in the three months after their gravimetric preparation. The BCPCs maintained no leakage even 10 months after their preparation, whereas the PCPCs showed significantly increasing leakage during the same period.

Multicomponent membranes

DOEpatents

Kulprathipanja, Santi; Kulkarni, Sudhir S.; Funk, Edward W.

1988-01-01

A multicomponent membrane which may be used for separating various components which are present in a fluid feed mixture comprises a mixture of a plasticizer such as a glycol and an organic polymer cast upon a porous organic polymer support. The membrane may be prepared by casting an emulsion or a solution of the plasticizer and polymer on the porous support, evaporating the solvent and recovering the membrane after curing.

MULTISUBSTRATE BIODEGRADATION KINETICS FOR BINARY AND COMPLEX MIXTURES OF POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

Biodegradation kinetics were studied for binary and complex mixtures of nine polycyclic aromatic hydrocarbons (PAHs): naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 2-ethylnaphthalene, phenanthrene, anthracene, pyrene, fluorene and fluoranthene. Discrepancies between the ...

A study of nonflammable ArCO 2-hydrocarbon gas mixtures for limited streamer tubes

NASA Astrophysics Data System (ADS)

Cartwright, S.; Schneekloth, U.; Alpat, B.; Artemi, C.; Battiston, R.; Bilei, G.; Italiani, M.; Pauluzzi, M.; Servoli, L.; Messner, R.; Wyss, J.; Zdarko, R.; Johnson, J.

1989-04-01

The gas mixtures generally used until now in limited streamer tube detectors (Ar+C 4H 10 or Ar+CO 2+C 5H 12) are very flammable when leaked into air. The safety issues are therefore very relevant for large-volume underground experiments. We have found a set of completely safe (i.e. nonflammable) ternary mixtures of the kind Ar + hydrocarbon + CO 2 containing less than ˜ 5% of Ar and less than ˜ 10% of hydrocarbon. We tested C 4H 10, C 5H 12 and C 6H 14 as quenching agents. The main characteristics of the various mixtures have been measured: singles (untriggered) counting rate versus high voltage and with different dead times, and average charge. The stability of these mixtures is good, and their spurious streamer activity is compared with the standard binary or ternary mixture. We studied in particular the combination Ar(2.5%) + C 4H 10(9.5%) + CO 2(88%). All the data suggest that this or a similar gas mixture can successfully replace standard flammable mixtures both in tracking devices and hadron calorimeters.

Methods of automatic nucleotide-sequence analysis. Multicomponent spectrophotometric analysis of mixtures of nucleic acid components by a least-squares procedure

PubMed Central

Lee, Sheila; McMullen, D.; Brown, G. L.; Stokes, A. R.

1965-01-01

1. A theoretical analysis of the errors in multicomponent spectrophotometric analysis of nucleoside mixtures, by a least-squares procedure, has been made to obtain an expression for the error coefficient, relating the error in calculated concentration to the error in extinction measurements. 2. The error coefficients, which depend only on the `library' of spectra used to fit the experimental curves, have been computed for a number of `libraries' containing the following nucleosides found in s-RNA: adenosine, guanosine, cytidine, uridine, 5-ribosyluracil, 7-methylguanosine, 6-dimethylaminopurine riboside, 6-methylaminopurine riboside and thymine riboside. 3. The error coefficients have been used to determine the best conditions for maximum accuracy in the determination of the compositions of nucleoside mixtures. 4. Experimental determinations of the compositions of nucleoside mixtures have been made and the errors found to be consistent with those predicted by the theoretical analysis. 5. It has been demonstrated that, with certain precautions, the multicomponent spectrophotometric method described is suitable as a basis for automatic nucleotide-composition analysis of oligonucleotides containing nine nucleotides. Used in conjunction with continuous chromatography and flow chemical techniques, this method can be applied to the study of the sequence of s-RNA. PMID:14346087

Multicomponent Separation Potential. Generalization of the Dirac Theory

NASA Astrophysics Data System (ADS)

Palkin, V. A.; Gadel‧shin, V. M.; Aleksandrov, O. E.; Seleznev, V. D.

2014-05-01

Formulas for the separation potential and the separative power have been obtained in the present work by generalizing the classical theory of Dirac, with the observance of his two axioms, to the case of a multicomponent mixture without considering a concrete cascade scheme. The resulting expressions are general characteristics of a separation process, since they are applicable to any separation methods and are independentof the form of the components in the mixture. They can be used in constructing actual cascades for separation of multicomponent mixtures and in determining the indices of their effi ciency.

On-Line Measurement of Heat of Combustion of Gaseous Hydrocarbon Fuel Mixtures

NASA Technical Reports Server (NTRS)

Sprinkle, Danny R.; Chaturvedi, Sushil K.; Kheireddine, Ali

1996-01-01

A method for the on-line measurement of the heat of combustion of gaseous hydrocarbon fuel mixtures has been developed and tested. The method involves combustion of a test gas with a measured quantity of air to achieve a preset concentration of oxygen in the combustion products. This method involves using a controller which maintains the fuel (gas) volumetric flow rate at a level consistent with the desired oxygen concentration in the combustion products. The heat of combustion is determined form a known correlation with the fuel flow rate. An on-line computer accesses the fuel flow data and displays the heat of combustion measurement at desired time intervals. This technique appears to be especially applicable for measuring heats of combustion of hydrocarbon mixtures of unknown composition such as natural gas.

Testing the accuracy of correlations for multicomponent mass transport of adsorbed gases in metal-organic frameworks: diffusion of H2/CH4 mixtures in CuBTC.

PubMed

Keskin, Seda; Liu, Jinchen; Johnson, J Karl; Sholl, David S

2008-08-05

Mass transport of chemical mixtures in nanoporous materials is important in applications such as membrane separations, but measuring diffusion of mixtures experimentally is challenging. Methods that can predict multicomponent diffusion coefficients from single-component data can be extremely useful if these methods are known to be accurate. We present the first test of a method of this kind for molecules adsorbed in a metal-organic framework (MOF). Specifically, we examine the method proposed by Skoulidas, Sholl, and Krishna (SSK) ( Langmuir, 2003, 19, 7977) by comparing predictions made with this method to molecular simulations of mixture transport of H 2/CH 4 mixtures in CuBTC. These calculations provide the first direct information on mixture transport of any species in a MOF. The predictions of the SSK approach are in good agreement with our direct simulations of binary diffusion, suggesting that this approach may be a powerful one for examining multicomponent diffusion in MOFs. We also use our molecular simulation data to test the ideal adsorbed solution theory method for predicting binary adsorption isotherms and a method for predicting mixture self-diffusion coefficients.

"Self-Shaping" of Multicomponent Drops.

PubMed

Cholakova, Diana; Valkova, Zhulieta; Tcholakova, Slavka; Denkov, Nikolai; Smoukov, Stoyan K

2017-06-13

In our recent study we showed that single-component emulsion drops, stabilized by proper surfactants, can spontaneously break symmetry and transform into various polygonal shapes during cooling [ Denkov Nature 2015 , 528 , 392 - 395 ]. This process involves the formation of a plastic rotator phase of self-assembled oil molecules beneath the drop surface. The plastic phase spontaneously forms a frame of plastic rods at the oil drop perimeter which supports the polygonal shapes. However, most of the common substances used in industry appear as mixtures of molecules rather than pure substances. Here we present a systematic study of the ability of multicomponent emulsion drops to deform upon cooling. The observed trends can be summarized as follows: (1) The general drop-shape evolution for multicomponent drops during cooling is the same as with single-component drops; however, some additional shapes are observed. (2) Preservation of the particle shape upon freezing is possible for alkane mixtures with chain length difference Δn ≤ 4; for greater Δn, phase separation within the droplet is observed. (3) Multicomponent particles prepared from alkanes with Δn ≤ 4 plastify upon cooling due to the formation of a bulk rotator phase within the particles. (4) If a compound, which cannot induce self-shaping when pure, is mixed with a certain amount of a compound which induces self-shaping, then drops prepared from this mixture can also self-shape upon cooling. (5) Self-emulsification phenomena are also observed for multicomponent drops. In addition to the three recently reported mechanisms of self-emulsification [ Tcholakova Nat. Commun. 2017 , ( 8 ), 15012 ], a new (fourth) mechanism is observed upon freezing for alkane mixtures with Δn > 4. It involves disintegration of the particles due to a phase separation of alkanes upon freezing.

Emergence of life from multicomponent mixtures of chemicals: the case for experiments with cycling physicochemical gradients.

PubMed

Spitzer, Jan

2013-04-01

The emergence of life from planetary multicomponent mixtures of chemicals is arguably the most complicated and least understood natural phenomenon. The fact that living cells are non-equilibrium systems suggests that life can emerge only from non-equilibrium chemical systems. From an astrobiological standpoint, non-equilibrium chemical systems arise naturally when solar irradiation strikes rotating surfaces of habitable planets: the resulting cycling physicochemical gradients persistently drive planetary chemistries toward "embryonic" living systems and an eventual emergence of life. To better understand the factors that lead to the emergence of life, I argue for cycling non-equilibrium experiments with multicomponent chemical systems designed to represent the evolving chemistry of Hadean Earth ("prebiotic soups"). Specifically, I suggest experimentation with chemical engineering simulators of Hadean Earth to observe and analyze (i) the appearances and phase separations of surface active and polymeric materials as precursors of the first "cell envelopes" (membranes) and (ii) the accumulations, commingling, and co-reactivity of chemicals from atmospheric, oceanic, and terrestrial locations.

Temperature- and pressure-dependent absorption cross sections of gaseous hydrocarbons at 3.39 µm

NASA Astrophysics Data System (ADS)

Klingbeil, A. E.; Jeffries, J. B.; Hanson, R. K.

2006-07-01

The pressure- and temperature-dependent absorption cross sections of several neat hydrocarbons and multi-component fuels are measured using a 3.39 µm helium-neon laser. Absorption cross section measurements are reported for methane, ethylene, propane, n-heptane, iso-octane, n-decane, n-dodecane, JP-10, gasoline and jet-A with an estimated uncertainty of less than 3.5%. The experimental conditions range from 298 to 673 K and from 500 to 2000 Torr with nitrogen as the bath gas. An apparatus is designed to facilitate these measurements, and specific care is taken to ensure the compositional accuracy of the hydrocarbon/N2 mixtures. The absorption cross sections of the smallest hydrocarbons, methane and ethylene, vary with temperature and pressure. The cross sections of larger hydrocarbons show negligible dependence on pressure and only a weak dependence on temperature. The reported data increase the range of conditions and the number of hydrocarbons for which cross section measurements are available at the HeNe laser wavelength.

Efficient and robust relaxation procedures for multi-component mixtures including phase transition

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

Han, Ee, E-mail: eehan@math.uni-bremen.de; Hantke, Maren, E-mail: maren.hantke@ovgu.de; Müller, Siegfried, E-mail: mueller@igpm.rwth-aachen.de

We consider a thermodynamic consistent multi-component model in multi-dimensions that is a generalization of the classical two-phase flow model of Baer and Nunziato. The exchange of mass, momentum and energy between the phases is described by additional source terms. Typically these terms are handled by relaxation procedures. Available relaxation procedures suffer from efficiency and robustness resulting in very costly computations that in general only allow for one-dimensional computations. Therefore we focus on the development of new efficient and robust numerical methods for relaxation processes. We derive exact procedures to determine mechanical and thermal equilibrium states. Further we introduce a novelmore » iterative method to treat the mass transfer for a three component mixture. All new procedures can be extended to an arbitrary number of inert ideal gases. We prove existence, uniqueness and physical admissibility of the resulting states and convergence of our new procedures. Efficiency and robustness of the procedures are verified by means of numerical computations in one and two space dimensions. - Highlights: • We develop novel relaxation procedures for a generalized, thermodynamically consistent Baer–Nunziato type model. • Exact procedures for mechanical and thermal relaxation procedures avoid artificial parameters. • Existence, uniqueness and physical admissibility of the equilibrium states are proven for special mixtures. • A novel iterative method for mass transfer is introduced for a three component mixture providing a unique and admissible equilibrium state.« less

Process and catalyst for converting synthesis gas to liquid hydrocarbon mixture

DOEpatents

Rao, V. Udaya S.; Gormley, Robert J.

1987-01-01

Synthesis gas containing CO and H.sub.2 is converted to a high-octane hydrocarbon liquid in the gasoline boiling point range by bringing the gas into contact with a heterogeneous catalyst including, in physical mixture, a zeolite molecular sieve, cobalt at 6-20% by weight, and thoria at 0.5-3.9% by weight. The contacting occurs at a temperature of 250.degree.-300.degree. C., and a pressure of 10-30 atmospheres. The conditions can be selected to form a major portion of the hydrocarbon product in the gasoline boiling range with a research octane of more than 80 and less than 10% by weight aromatics.

Coupling Oxygen Consumption with Hydrocarbon Oxidation in Bacterial Multicomponent Monooxygenases.

PubMed

Wang, Weixue; Liang, Alexandria D; Lippard, Stephen J

2015-09-15

A fundamental goal in catalysis is the coupling of multiple reactions to yield a desired product. Enzymes have evolved elegant approaches to address this grand challenge. A salient example is the biological conversion of methane to methanol catalyzed by soluble methane monooxygenase (sMMO), a member of the bacterial multicomponent monooxygenase (BMM) superfamily. sMMO is a dynamic protein complex of three components: a hydroxylase, a reductase, and a regulatory protein. The active site, a carboxylate-rich non-heme diiron center, is buried inside the 251 kDa hydroxylase component. The enzyme processes four substrates: O2, protons, electrons, and methane. To couple O2 activation to methane oxidation, timely control of substrate access to the active site is critical. Recent studies of sMMO, as well as its homologues in the BMM superfamily, have begun to unravel the mechanism. The emerging and unifying picture reveals that each substrate gains access to the active site along a specific pathway through the hydroxylase. Electrons and protons are delivered via a three-amino-acid pore located adjacent to the diiron center; O2 migrates via a series of hydrophobic cavities; and hydrocarbon substrates reach the active site through a channel or linked set of cavities. The gating of these pathways mediates entry of each substrate to the diiron active site in a timed sequence and is coordinated by dynamic interactions with the other component proteins. The result is coupling of dioxygen consumption with hydrocarbon oxidation, avoiding unproductive oxidation of the reductant rather than the desired hydrocarbon. To initiate catalysis, the reductase delivers two electrons to the diiron(III) center by binding over the pore of the hydroxylase. The regulatory component then displaces the reductase, docking onto the same surface of the hydroxylase. Formation of the hydroxylase-regulatory component complex (i) induces conformational changes of pore residues that may bring protons to the

Spontaneous ignition delay characteristics of hydrocarbon fuel-air mixtures

NASA Technical Reports Server (NTRS)

Lefebvre, A. H.; Freeman, W. G.; Cowell, L. H.

1986-01-01

The influence of pressure on the autoignition characteristics of homogeneous mixtures of hydrocarbon fuels in air is examined. Autoignition delay times are measured for propane, ethylene, methane, and acetylene in a continuous flow apparatus featuring a multi-point fuel injector. Results are presented for mixture temperatures from 670K to 1020K, pressures from 1 to 10 atmospheres, equivalence ratios from 0.2 to 0.7, and velocities from 5 to 30 m/s. Delay time is related to pressure, temperature, and fuel concentration by global reaction theory. The results show variations in global activation energy from 25 to 38 kcal/kg-mol, pressure exponents from 0.66 to 1.21, and fuel concentration exponents from 0.19 to 0.75 for the fuels studied. These results are generally in good agreement with previous studies carried out under similar conditions.

An improved molecular dynamics algorithm to study thermodiffusion in binary hydrocarbon mixtures

NASA Astrophysics Data System (ADS)

Antoun, Sylvie; Saghir, M. Ziad; Srinivasan, Seshasai

2018-03-01

In multicomponent liquid mixtures, the diffusion flow of chemical species can be induced by temperature gradients, which leads to a separation of the constituent components. This cross effect between temperature and concentration is known as thermodiffusion or the Ludwig-Soret effect. The performance of boundary driven non-equilibrium molecular dynamics along with the enhanced heat exchange (eHEX) algorithm was studied by assessing the thermodiffusion process in n-pentane/n-decane (nC5-nC10) binary mixtures. The eHEX algorithm consists of an extended version of the HEX algorithm with an improved energy conservation property. In addition to this, the transferable potentials for phase equilibria-united atom force field were employed in all molecular dynamics (MD) simulations to precisely model the molecular interactions in the fluid. The Soret coefficients of the n-pentane/n-decane (nC5-nC10) mixture for three different compositions (at 300.15 K and 0.1 MPa) were calculated and compared with the experimental data and other MD results available in the literature. Results of our newly employed MD algorithm showed great agreement with experimental data and a better accuracy compared to other MD procedures.

Phase equilibria computations of multicomponent mixtures at specified internal energy and volume

NASA Astrophysics Data System (ADS)

Myint, Philip C.; Nichols, Albert L., III; Springer, H. Keo

2017-06-01

Hydrodynamic simulation codes for high-energy density science applications often use internal energy and volume as their working variables. As a result, the codes must determine the thermodynamic state that corresponds to the specified energy and volume by finding the global maximum in entropy. This task is referred to as the isoenergetic-isochoric flash. Solving it for multicomponent mixtures is difficult because one must find not only the temperature and pressure consistent with the energy and volume, but also the number of phases present and the composition of the phases. The few studies on isoenergetic-isochoric flash that currently exist all require the evaluation of many derivatives that can be tedious to implement. We present an alternative approach that is based on a derivative-free method: particle swarm optimization. The global entropy maximum is found by running several instances of particle swarm optimization over different sets of randomly selected points in the search space. For verification, we compare the predicted temperature and pressure to results from the related, but simpler problem of isothermal-isobaric flash. All of our examples involve the equation of state we have recently developed for multiphase mixtures of the energetic materials HMX, RDX, and TNT. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Surface-slip equations for multicomponent nonequilibrium air flow

NASA Technical Reports Server (NTRS)

Gupta, R. N.; Scott, C. D.; Moss, J. N.

1985-01-01

Equations are presented for the surface-slip (or jump) values of species concentration, pressure, velocity, and temperature in the low-Reynolds number, high-altitude flight regime of a space vehicle. The equations are obtained from closed form solutions of the mass, momentum, and energy flux equations using the Chapman-Enskog velocity distribution function. This function represents a solution of the Boltzmann equation in the Navier-Stokes approximation. The analysis, obtained for nonequilibrium multicomponent air flow, includes the finite-rate surface catalytic recombination and changes in the internal energy during reflection from the surface. Expressions for the various slip quantities were obtained in a form which can be employed in flowfield computations. A consistent set of equations is provided for multicomponent, binary, and single species mixtures. Expression is also provided for the finite-rate, species-concentration boundary condition for a multicomponent mixture in absence of slip.

Surface-slip equations for multicomponent, nonequilibrium air flow

NASA Technical Reports Server (NTRS)

Gupta, Roop N.; Scott, Carl D.; Moss, James N.; Goglia, Gene

1985-01-01

Equations are presented for the surface slip (or jump) values of species concentration, pressure, velocity, and temperature in the low-Reynolds-number, high-altitude flight regime of a space vehicle. These are obtained from closed-form solutions of the mass, momentum, and energy flux equations using the Chapman-Enskog velocity distribution function. This function represents a solution of the Boltzmann equation in the Navier-Stokes approximation. The analysis, obtained for nonequilibrium multicomponent air flow, includes the finite-rate surface catalytic recombination and changes in the internal energy during reflection from the surface. Expressions for the various slip quantities have been obtained in a form which can readily be employed in flow-field computations. A consistent set of equations is provided for multicomponent, binary, and single species mixtures. Expression is also provided for the finite-rate species-concentration boundary condition for a multicomponent mixture in absence of slip.

Removal of polycyclic aromatic hydrocarbons in soil spiked with model mixtures of petroleum hydrocarbons and heterocycles using biosurfactants from Rhodococcus ruber IEGM 231.

PubMed

Ivshina, Irina; Kostina, Ludmila; Krivoruchko, Anastasiya; Kuyukina, Maria; Peshkur, Tatyana; Anderson, Peter; Cunningham, Colin

2016-07-15

Removal of polycyclic aromatic hydrocarbons (PAHs) in soil using biosurfactants (BS) produced by Rhodococcus ruber IEGM 231 was studied in soil columns spiked with model mixtures of major petroleum constituents. A crystalline mixture of single PAHs (0.63g/kg), a crystalline mixture of PAHs (0.63g/kg) and polycyclic aromatic sulfur heterocycles (PASHs), and an artificially synthesized non-aqueous phase liquid (NAPL) containing PAHs (3.00g/kg) dissolved in alkanes C10-C19 were used for spiking. Percentage of PAH removal with BS varied from 16 to 69%. Washing activities of BS were 2.5 times greater than those of synthetic surfactant Tween 60 in NAPL-spiked soil and similar to Tween 60 in crystalline-spiked soil. At the same time, amounts of removed PAHs were equal and consisted of 0.3-0.5g/kg dry soil regardless the chemical pattern of a model mixture of petroleum hydrocarbons and heterocycles used for spiking. UV spectra for soil before and after BS treatment were obtained and their applicability for differentiated analysis of PAH and PASH concentration changes in remediated soil was shown. The ratios A254nm/A288nm revealed that BS increased biotreatability of PAH-contaminated soils. Copyright © 2016 Elsevier B.V. All rights reserved.

TMVOC-MP: a parallel numerical simulator for Three-PhaseNon-isothermal Flows of Multicomponent Hydrocarbon Mixtures inporous/fractured media

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

Zhang, Keni; Yamamoto, Hajime; Pruess, Karsten

2008-02-15

TMVOC-MP is a massively parallel version of the TMVOC code (Pruess and Battistelli, 2002), a numerical simulator for three-phase non-isothermal flow of water, gas, and a multicomponent mixture of volatile organic chemicals (VOCs) in multidimensional heterogeneous porous/fractured media. TMVOC-MP was developed by introducing massively parallel computing techniques into TMVOC. It retains the physical process model of TMVOC, designed for applications to contamination problems that involve hydrocarbon fuels or organic solvents in saturated and unsaturated zones. TMVOC-MP can model contaminant behavior under 'natural' environmental conditions, as well as for engineered systems, such as soil vapor extraction, groundwater pumping, or steam-assisted sourcemore » remediation. With its sophisticated parallel computing techniques, TMVOC-MP can handle much larger problems than TMVOC, and can be much more computationally efficient. TMVOC-MP models multiphase fluid systems containing variable proportions of water, non-condensible gases (NCGs), and water-soluble volatile organic chemicals (VOCs). The user can specify the number and nature of NCGs and VOCs. There are no intrinsic limitations to the number of NCGs or VOCs, although the arrays for fluid components are currently dimensioned as 20, accommodating water plus 19 components that may be either NCGs or VOCs. Among them, NCG arrays are dimensioned as 10. The user may select NCGs from a data bank provided in the software. The currently available choices include O{sub 2}, N{sub 2}, CO{sub 2}, CH{sub 4}, ethane, ethylene, acetylene, and air (a pseudo-component treated with properties averaged from N{sub 2} and O{sub 2}). Thermophysical property data of VOCs can be selected from a chemical data bank, included with TMVOC-MP, that provides parameters for 26 commonly encountered chemicals. Users also can input their own data for other fluids. The fluid components may partition (volatilize and/or dissolve) among gas, aqueous, and

A continuum theory for multicomponent chromatography modeling.

PubMed

Pfister, David; Morbidelli, Massimo; Nicoud, Roger-Marc

2016-05-13

A continuum theory is proposed for modeling multicomponent chromatographic systems under linear conditions. The model is based on the description of complex mixtures, possibly involving tens or hundreds of solutes, by a continuum. The present approach is shown to be very efficient when dealing with a large number of similar components presenting close elution behaviors and whose individual analytical characterization is impossible. Moreover, approximating complex mixtures by continuous distributions of solutes reduces the required number of model parameters to the few ones specific to the characterization of the selected continuous distributions. Therefore, in the frame of the continuum theory, the simulation of large multicomponent systems gets simplified and the computational effectiveness of the chromatographic model is thus dramatically improved. Copyright © 2016 Elsevier B.V. All rights reserved.

[Biodegradability of the components of natural hydrocarbon mixtures previously submitted to landfarming].

PubMed

Pucci, G N; Pucci, O H

2003-01-01

The complex composition of the crude oil and the hydrocarbons that integrate the waste of the different stages of the oil industry turn this product a mixture that presents different difficulties for its elimination by biological methods. The objective of this paper was to study the biodegradation potential of autochthonous bacterial communities on hydrocarbons obtained from four polluted places and subjected to landfarming biorremediation system during a decade. The results showed a marked difference in biodegradability of the three main fractions of crude oil, aliphatic, aromatic, and polar fractions, obtained by column chromatography. All fractions were used as carbon source and energy. There were variations in the production of biomass among the different fractions as well as in the kinetics of biodegradation, according to the composition of each fraction.

Identification of unresolved complex mixtures (UCMs) of hydrocarbons in commercial fish oil supplements.

PubMed

Reid, Anna-Jean M; Budge, Suzanne M

2015-01-01

Heightened awareness of the health benefits of fish oil consumption has led to a great increase in the number of fish oil supplements available to the consumer. Therefore manufacturers are continually looking for ways to distinguish their products from those of competitors. Minimally refined or virgin fish oils provide a unique feature; however, petroleum hydrocarbon contamination from oil spills is a reality in the world's oceans. The question arises whether oil produced from fish species caught in these polluted areas is free of petroleum hydrocarbons, with particular interest in unresolved complex mixtures (UCMs). This study investigates the presence of UCMs in commercially available fish oil supplements advertised as being virgin, as well as refined. Weathered petroleum hydrocarbons in the form of a UCM were found at 523 µg g(-1) in a virgin Alaskan salmon oil supplement. Supplements that were refined were free of this contamination. Fish used in the production of fish oil supplements appear to have accumulated petrogenic hydrocarbons in their tissues which were not removed by minimal oil refining. Further study is required to determine if there are any health implications associated with long-term consumption of these contaminated supplements. © 2014 Society of Chemical Industry.

HYDROCARBON SPILL EXPOSURE ASSESSMENT MODELING

EPA Science Inventory

Hydrocarbon spills impact drinking water supplies at down gradient locations. onventional finite difference and finite element models of multiphase, multicomponent flow have extreme requirements for both computer time and site data. ite data and the intent of the modeling often d...

Enrichment of light hydrocarbon mixture

DOEpatents

Yang, Dali [Los Alamos, NM; Devlin, David [Santa Fe, NM; Barbero, Robert S [Santa Cruz, NM; Carrera, Martin E [Naperville, IL; Colling, Craig W [Warrenville, IL

2011-11-29

Light hydrocarbon enrichment is accomplished using a vertically oriented distillation column having a plurality of vertically oriented, nonselective micro/mesoporous hollow fibers. Vapor having, for example, both propylene and propane is sent upward through the distillation column in between the hollow fibers. Vapor exits neat the top of the column and is condensed to form a liquid phase that is directed back downward through the lumen of the hollow fibers. As vapor continues to ascend and liquid continues to countercurrently descend, the liquid at the bottom of the column becomes enriched in a higher boiling point, light hydrocarbon (propane, for example) and the vapor at the top becomes enriched in a lower boiling point light hydrocarbon (propylene, for example). The hollow fiber becomes wetted with liquid during the process.

Enrichment of light hydrocarbon mixture

DOEpatents

Yang,; Dali, [Los Alamos, NM; Devlin, David [Santa Fe, NM; Barbero, Robert S [Santa Cruz, NM; Carrera, Martin E [Naperville, IL; Colling, Craig W [Warrenville, IL

2010-08-10

Light hydrocarbon enrichment is accomplished using a vertically oriented distillation column having a plurality of vertically oriented, nonselective micro/mesoporous hollow fibers. Vapor having, for example, both propylene and propane is sent upward through the distillation column in between the hollow fibers. Vapor exits neat the top of the column and is condensed to form a liquid phase that is directed back downward through the lumen of the hollow fibers. As vapor continues to ascend and liquid continues to countercurrently descend, the liquid at the bottom of the column becomes enriched in a higher boiling point, light hydrocarbon (propane, for example) and the vapor at the top becomes enriched in a lower boiling point light hydrocarbon (propylene, for example). The hollow fiber becomes wetted with liquid during the process.

Biodegradation pattern of hydrocarbons from a fuel oil-type complex residue by an emulsifier-producing microbial consortium.

PubMed

Nievas, M L; Commendatore, M G; Esteves, J L; Bucalá, V

2008-06-15

The biodegradation of a hazardous waste (bilge waste), a fuel oil-type complex residue from normal ship operations, was studied in a batch bioreactor using a microbial consortium in seawater medium. Experiments with initial concentrations of 0.18 and 0.53% (v/v) of bilge waste were carried out. In order to study the biodegradation kinetics, the mass of n-alkanes, resolved hydrocarbons and unresolved complex mixture (UCM) hydrocarbons were assessed by gas chromatography (GC). Emulsification was detected in both experiments, possibly linked to the n-alkanes depletion, with differences in emulsification start times and extents according to the initial hydrocarbon concentration. Both facts influenced the hydrocarbon biodegradation kinetics. A sequential biodegradation of n-alkanes and UMC was found for the higher hydrocarbon content. Being the former growth associated, while UCM biodegradation was a non-growing process showing enzymatic-type biodegradation kinetics. For the lower hydrocarbon concentration, simultaneous biodegradation of n-alkanes and UMC were found before emulsification. Nevertheless, certain UCM biodegradation was observed after the medium emulsification. According to the observed kinetics, three main types of hydrocarbons (n-alkanes, biodegradable UCM and recalcitrant UCM) were found adequate to represent the multicomponent substrate (bilge waste) for future modelling of the biodegradation process.

Final report on EURAMET.QM-S6/1195: Bilateral comparison of liquefied hydrocarbon mixtures in constant pressure (piston) cylinders

NASA Astrophysics Data System (ADS)

Brown, Andrew S.; Downey, Michael L.; Milton, Martin J. T.; van der Veen, Adriaan M. H.; Zalewska, Ewelina T.; Li, Jianrong

2013-01-01

Traceable liquid hydrocarbon mixtures are required in order to underpin measurements of the composition and other physical properties of LPG (liquefied petroleum gas) and LNG (liquefied natural gas), thus meeting the needs of an increasingly large European industrial market. The development of traceable liquid hydrocarbon standards by National Measurement Institutes (NMIs) was still at a relatively early stage at the time this comparison was proposed in 2011. NPL and VSL, who were the only NMIs active in this area, had developed methods for the preparation and analysis of such standards in constant pressure (piston) cylinders, but neither laboratory had Calibration and Measurement Capabilities (CMCs) for these mixtures. This report presents the results of EURAMET 1195, the first comparison of liquid hydrocarbon mixtures between NMIs, which assessed the preparation and analytical capabilities of NPL and VSL for these mixtures. The comparison operated between August 2011 and January 2012. Each laboratory prepared a liquid hydrocarbon standard with nominally the same composition and these standards were exchanged for analysis. The results of the comparison show a good agreement between the laboratories' results and the comparison reference values for the six components with amount fractions greater than 1.0 cmol/mol (propane, propene, iso-butene, n-butane, iso-butane and 1-butene). Measurement of the three components with lower amount fractions (1,3-butadiene, iso-pentane and n-pentane) proved more challenging. In all but one case, the differences from the comparison reference values for these three components were greater than the expanded measurement uncertainty. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by EURAMET, according to the provisions of the CIPM Mutual

Development of a Relative Potency Factor (Rpf) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures (External Review Draft)

EPA Science Inventory

EPA is conducting a peer review and public comment of the scientific basis supporting the human health hazard and dose-response assessment of polycyclic aromatic hydrocarbon (PAH) mixtures that when finalized will appear on the Integrated Risk Information System (IRIS) database. ...

Effect of volatile hydrocarbon fractions on mobility and earthworm uptake of polycyclic aromatic hydrocarbons from soils and soil/lampblack mixtures.

PubMed

Bogan, Bill W; Beardsley, Kate E; Sullivan, Wendy R; Hayes, Thomas D; Soni, Bhupendra K

2005-01-01

Studies were conducted to examine the mobility and bioavailability to earthworms (Eisenia fetida) of priority pollutant polycyclic aromatic hydrocarbons (PAH) in a suite of 11 soils and soil/lampblack mixtures obtained from former manufactured-gas plant sites. Contaminant mobility was assessed using XAD4 resins encapsulated in dialysis tubing, which were exposed to slurried soils for 15 d. These experiments showed that mobility of PAH in the different soils strongly correlated to the levels of volatile hydrocarbons (namely, gasoline- and diesel-range organics [GRO and DRO]) that existed in the soils as co-contaminants. Actual PAH bioavailability (as measured by earthworm PAH concentrations) also appeared to depend on GRO + DRO levels, although this was most evident at high levels of these contaminants. These findings are discussed in view of the effects of dieselrange organics on oil viscosity, assuming that the hydrocarbon contaminants in these soils exist in the form of distinct adsorbed oil phases. This study, therefore, extends correlations between carrier-oil viscosity and dissolved solute bioavailability, previously observed in a number of other in vitro and whole-organism tests (and in bacterial mutagenicity studies in soil), to multicellular organisms inhabiting contaminated-soil systems.

BIOTRANSFORMATION OF MIXTURES OF CHLORINATED ALIPHATIC HYDROCARBONS BY AN ACETATE-GROWN METHANOGENIC ENRICHMENT CULTURE. (R825549C053)

EPA Science Inventory

Biotransformation of chlorinated aliphatic hydrocarbons under anaerobic conditions has received considerable attention due to the prevalence of these compounds as groundwater contaminants. However, information concerning the impact of mixtures of chlorinated compounds on their...

Metal-Polycyclic Aromatic Hydrocarbon Mixture Toxicity in Hyalella azteca. 1. Response Surfaces and Isoboles To Measure Non-additive Mixture Toxicity and Ecological Risk.

PubMed

Gauthier, Patrick T; Norwood, Warren P; Prepas, Ellie E; Pyle, Greg G

2015-10-06

Mixtures of metals and polycyclic aromatic hydrocarbons (PAHs) occur ubiquitously in aquatic environments, yet relatively little is known regarding their potential to produce non-additive toxicity (i.e., antagonism or potentiation). A review of the lethality of metal-PAH mixtures in aquatic biota revealed that more-than-additive lethality is as common as strictly additive effects. Approaches to ecological risk assessment do not consider non-additive toxicity of metal-PAH mixtures. Forty-eight-hour water-only binary mixture toxicity experiments were conducted to determine the additive toxic nature of mixtures of Cu, Cd, V, or Ni with phenanthrene (PHE) or phenanthrenequinone (PHQ) using the aquatic amphipod Hyalella azteca. In cases where more-than-additive toxicity was observed, we calculated the possible mortality rates at Canada's environmental water quality guideline concentrations. We used a three-dimensional response surface isobole model-based approach to compare the observed co-toxicity in juvenile amphipods to predicted outcomes based on concentration addition or effects addition mixtures models. More-than-additive lethality was observed for all Cu-PHE, Cu-PHQ, and several Cd-PHE, Cd-PHQ, and Ni-PHE mixtures. Our analysis predicts Cu-PHE, Cu-PHQ, Cd-PHE, and Cd-PHQ mixtures at the Canadian Water Quality Guideline concentrations would produce 7.5%, 3.7%, 4.4% and 1.4% mortality, respectively.

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 6 2014-07-01 2014-07-01 false Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2B Table 2B to Subpart E of Part 59—Reactivity Factors for Aliphatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 6 2014-07-01 2014-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2C Table 2C to Subpart E of Part 59—Reactivity Factors for Aromatic...

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 6 2013-07-01 2013-07-01 false Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2B Table 2B to Subpart E of Part 59—Reactivity Factors for Aliphatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 6 2013-07-01 2013-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2C Table 2C to Subpart E of Part 59—Reactivity Factors for Aromatic...

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 6 2012-07-01 2012-07-01 false Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2B Table 2B to Subpart E of Part 59—Reactivity Factors for Aliphatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 6 2012-07-01 2012-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2C Table 2C to Subpart E of Part 59—Reactivity Factors for Aromatic...

Validation of a numerical method for interface-resolving simulation of multicomponent gas-liquid mass transfer and evaluation of multicomponent diffusion models

NASA Astrophysics Data System (ADS)

Woo, Mino; Wörner, Martin; Tischer, Steffen; Deutschmann, Olaf

2018-03-01

The multicomponent model and the effective diffusivity model are well established diffusion models for numerical simulation of single-phase flows consisting of several components but are seldom used for two-phase flows so far. In this paper, a specific numerical model for interfacial mass transfer by means of a continuous single-field concentration formulation is combined with the multicomponent model and effective diffusivity model and is validated for multicomponent mass transfer. For this purpose, several test cases for one-dimensional physical or reactive mass transfer of ternary mixtures are considered. The numerical results are compared with analytical or numerical solutions of the Maxell-Stefan equations and/or experimental data. The composition-dependent elements of the diffusivity matrix of the multicomponent and effective diffusivity model are found to substantially differ for non-dilute conditions. The species mole fraction or concentration profiles computed with both diffusion models are, however, for all test cases very similar and in good agreement with the analytical/numerical solutions or measurements. For practical computations, the effective diffusivity model is recommended due to its simplicity and lower computational costs.

Passive dosing of polycyclic aromatic hydrocarbon (PAH) mixtures to terrestrial springtails: linking mixture toxicity to chemical activities, equilibrium lipid concentrations, and toxic units.

PubMed

Schmidt, Stine N; Holmstrup, Martin; Smith, Kilian E C; Mayer, Philipp

2013-07-02

A 7-day mixture toxicity experiment with the terrestrial springtail Folsomia candida was conducted, and the effects were linked to three different mixture exposure parameters. Passive dosing from silicone was applied to tightly control exposure levels and compositions of 12 mixture treatments, containing the polycyclic aromatic hydrocarbons (PAHs) naphthalene, phenanthrene, and pyrene. Springtail lethality was then linked to sum chemical activities (∑a), sum equilibrium lipid concentrations (∑C(lipid eq.)), and sum toxic units (∑TU). In each case, the effects of all 12 mixture treatments could be fitted to one sigmoidal exposure-response relationship. The effective lethal chemical activity (La50) of 0.027 was well within the expected range for baseline toxicity of 0.01-0.1. Linking the effects to the lipid-based exposure parameter yielded an effective lethal concentration (LC(lipid eq 50)) of 133 mmol kg(-1) lipid in good correspondence with the lethal membrane burden for baseline toxicity (40-160 mmol kg(-1) lipid). Finally, the effective lethal toxic unit (LTU50) of 1.20 was rather close to the expected value of 1. Altogether, passive dosing provided tightly controlled mixture exposure in terms of both level and composition, while ∑a, ∑C(lipid eq.), and ∑TU allowed baseline toxicity to be linked to mixture exposure.

Development of a Relative Potency Factor (RPF) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures (Interagency Science Consultation Draft)

EPA Science Inventory

On February 26, 2010, the draft Development of a Relative Potency Factor (RPF) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures document and the charge to external peer reviewers were released for external peer review and public comment. The draft document and t...

Prediction of vapour-liquid and vapour-liquid-liquid equilibria of nitrogen-hydrocarbon mixtures used in J-T refrigerators

NASA Astrophysics Data System (ADS)

Narayanan, Vineed; Venkatarathnam, G.

2018-03-01

Nitrogen-hydrocarbon mixtures are widely used as refrigerants in J-T refrigerators operating with mixtures, as well as in natural gas liquefiers. The Peng-Robinson equation of state has traditionally been used to simulate the above cryogenic process. Multi parameter Helmholtz energy equations are now preferred for determining the properties of natural gas. They have, however, been used only to predict vapour-liquid equilibria, and not vapour-liquid-liquid equilibria that can occur in mixtures used in cryogenic mixed refrigerant processes. In this paper the vapour-liquid equilibrium of binary mixtures of nitrogen-methane, nitrogen-ethane, nitrogen-propane, nitrogen-isobutane and three component mixtures of nitrogen-methane-ethane and nitrogen-methane-propane have been studied with the Peng-Robinson and the Helmholtz energy equations of state of NIST REFPROP and compared with experimental data available in the literature.

Polynuclear aromatic hydrocarbons for fullerene synthesis in flames

DOEpatents

Alford, J. Michael; Diener, Michael D.

2006-12-19

This invention provides improved methods for combustion synthesis of carbon nanomaterials, including fullerenes, employing multiple-ring aromatic hydrocarbon fuels selected for high carbon conversion to extractable fullerenes. The multiple-ring aromatic hydrocarbon fuels include those that contain polynuclear aromatic hydrocarbons. More specifically, multiple-ring aromatic hydrocarbon fuels contain a substantial amount of indene, methylnapthalenes or mixtures thereof. Coal tar and petroleum distillate fractions provide low cost hydrocarbon fuels containing polynuclear aromatic hydrocarbons, including without limitation, indene, methylnapthalenes or mixtures thereof.

Method for removing chlorine compounds from hydrocarbon mixtures

DOEpatents

Janoski, Edward J.; Hollstein, Elmer J.

1985-12-31

A process for removing halide ions from a hydrocarbon feedstream containing halogenated hydrocarbons wherein the contaminated feedstock is contacted with a solution of a suitable oxidizing acid containing a lanthanide oxide, the acid being present in a concentration of at least about 50 weight percent for a time sufficient to remove substantially all of the halide ion from the hydrocarbon feedstock.

Method for removing chlorine compounds from hydrocarbon mixtures

DOEpatents

Janoski, E.J.; Hollstein, E.J.

1984-09-29

A process for removing halide ions from a hydrocarbon feedstream containing halogenated hydrocarbons wherein the contaminated feedstock is contacted with a solution of a suitable oxidizing acid containing a lanthanide oxide, the acid being present in a concentration of at least about 50 weight percent for a time sufficient to remove substantially all of the halide ion from the hydrocarbon feedstock.

EXPOSURE ASSESSMENT MODELING FOR HYDROCARBON SPILLS INTO THE SUBSURFACE

EPA Science Inventory

Hydrocarbons which enter the subsurface through spills or leaks may create serious, long-lived ground-water contamination problems. onventional finite difference and finite element models of multiphase, multicomponent flow often have extreme requirements for both computer time an...

Bioremediation of Mixtures of High Molecular Weight Polycyclic Aromatic Hydrocarbons

NASA Astrophysics Data System (ADS)

Xu, H.; Wu, J.; Shi, X.; Sun, Y.

2014-12-01

Although bioremediation has been considered as one of the most promising means to remove polycyclic aromatic hydrocarbons (PAHs) from polluted environments, the efficacy of PAHs bioremediation still remains challenged, especially for high molecular weight PAHs (HMW PAHs) and their mixtures. This study was focused on (a) isolation and characterization of pure strain and mixed microbial communities able to degrade HMW PAHs and (b) further evaluation of the ability of the isolated microbes to degrade HMW PAHs mixtures in the absence and presence of indigenous flora. Fluoranthene, benzo[b]fluoranthene and pyrene were selected as the representative HMW PAHs in this study. A pure bacterial strain, identified as Herbaspirillum chlorophenolicum FA1, was isolated from activated sludge. A mixed bacterial community designated as consortium-4 was isolated from petroleum contaminated soils, containing Pseudomonas sp. FbP1、Enterobacter sp. FbP2、Hydrogenophaga sp. FbP3 and Luteolibacter pohnpeiensis. FbP4. To our knowledge, this is the first study to demonstrate that bacterial strains of Herbaspirillum chlorophenolicum FA1 and Luteolibacter pohnpeiensis. FbP4 can also degrade fluoranthene, benzo[b]fluoranthene and pyrene. Experiment results showed that both strain FA1 and consortium-4 could degrade fluoranthene, benzo[b]fluoranthene and pyrene within a wide range of temperature, pH and initial PAHs concentration. Degradation of HMW PAHs mixtures (binary and ternary) demonstrated the interactive effects that can alter the rate and extent of biodegradation within a mixture. The presence of indigenous flora was found to either increase or decrease the degradation of HMW PAHs, suggesting possible synergistic or competition effects. Biodegradation kinetics of HMW PAHs for sole substrates, binary and ternary systems was evaluated, with the purpose to better characterize and compare the biodegradation process of individual HMW PAH and mixtures of HMW PAHs. Results of this study

Photoactivation and toxicity of mixtures of polycyclic aromatic hydrocarbon compounds in marine sediment

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

Swartz, R.C.; Ferraro, S.P.; Lamberson, J.O.

1997-10-01

The direct toxicity and photoinduced toxicity of sediment-associated acenaphthene, phenanthrene, fluoranthene, and pyrene were determined for the marine amphipod Rhepoxynius abronius. The four polycyclic aromatic hydrocarbons (PAHs) were spiked into sediment in a concentration series of either single compounds or as approximately equitoxic mixtures of all four compounds. Standard 10-d sediment toxicity tests were conducted under fluorescent lighting. After 10 d, survivors were exposed for 1 h to ultraviolet (UV) radiation in the absence of sediment and then tested for their ability to bury in uncontaminated sediment. The 10-d median lethal concentrations (LC50s) were 2.31 mg acenaphthene/g organic carbon (OC),more » 2.22 mg phenanthrene/g OC, 3.31 mg fluoranthene/g OC, and 2.81 mg pyrene/g OC. These LC50s were used to calculate the sum of toxic units ({Sigma}TU) of the four PAHs in the approximately equitoxic mixtures. The {Sigma}TU LC50 was then calculated for the mixture treatments. If the toxicologic interaction of a mixture of contaminants is additive, {Sigma}TU LC50 = 1.0. The observed LC50 (1.55 {Sigma}TU) was slightly, but significantly, greater than unity, indicating that the interaction of PAHs in the mixture was less than additive. Exposure to UV radiation enhanced the toxic effects of fluoranthene and pyrene, but did not affect the toxicity of acenaphthene and phenanthrene. Effects of UV radiation on the toxicity of the mixture of four PAHs could be explained by the photoactivation of fluoranthene and pyrene alone. These results are consistent with predictions based on photophysical properties of PAH compounds.« less

Changes in Brain Monoamines Underlie Behavioural Disruptions after Zebrafish Diet Exposure to Polycyclic Aromatic Hydrocarbons Environmental Mixtures

PubMed Central

Vignet, Caroline; Trenkel, Verena M.; Vouillarmet, Annick; Bricca, Giampiero; Bégout, Marie-Laure; Cousin, Xavier

2017-01-01

Zebrafish were exposed through diet to two environmentally relevant polycyclic aromatic hydrocarbons (PAHs) mixtures of contrasted compositions, one of pyrolytic (PY) origin and one from light crude oil (LO). Monoamine concentrations were quantified in the brains of the fish after six month of exposure. A significant decrease in noradrenaline (NA) was observed in fish exposed to both mixtures, while a decrease in serotonin (5HT) and dopamine (DA) was observed only in LO-exposed fish. A decrease in metabolites of 5HT and DA was observed in fish exposed to both mixtures. Several behavioural disruptions were observed that depended on mixtures, and parallels were made with changes in monoamine concentrations. Indeed, we observed an increase in anxiety in fish exposed to both mixtures, which could be related to the decrease in 5HT and/or NA, while disruptions of daily activity rhythms were observed in LO fish, which could be related to the decrease in DA. Taken together, these results showed that (i) chronic exposures to PAHs mixtures disrupted brain monoamine contents, which could underlie behavioural disruptions, and that (ii) the biological responses depended on mixture compositions. PMID:28273853

Ozone Modulation/Membrane Introduction Mass Spectrometry for Analysis of Hydrocarbon Pollutants in Air

NASA Astrophysics Data System (ADS)

Atkinson, D. B.

2001-12-01

mixtures was also observed. Despite this problem, the hydrocarbon signal response can be calibrated and the method can be used for quantitative analysis of volatile hydrocarbon compounds in air samples. This methodology should augment the efficiency of the MIMS approach in online and onsite monitoring of VOC emissions. Bier, M.R., and R.G. Cooks, Membrane Interface for Selective Introduction of Volatile Compounds Directly into The Ionization Chamber of a Mass Spectrometer, Anal. Chem., 59 (4), 597, 1987. Cisper, M.E., C.G. Gill, L.E. Townsend, and P.H. Hemberger, On-Line Detection of Volatile Organic Compounds in Air at Parts-per-Trillion Levels by Membrane Introduction Mass Spectrometry, Anal. Chem., 67 (8), 1413-1417, 1995. Ketola, R.A., M. Ojala, and J. Heikkonen, A Non-linear Asymmetric Error Function-based Least Mean Square Approach for the Analysis of Multicomponent Mass Spectra Measured by Membrane Inlet Mass Spectrometry, Rapid Commun. Mass Spectrom., 13 (8), 654, 1999. Kotiaho, T., and R.G. Cooks, Membrane Introduction Mass Spectrometry in Environmental Analysis, in: J.J. Breen, M. J. Dellarco, (Eds), Pollution in Industrial processes, 126 pp., ACS Symp. Ser., Washington, D.C. 508, 1992.

Problems in Catalytic Oxidation of Hydrocarbons and Detailed Simulation of Combustion Processes

NASA Astrophysics Data System (ADS)

Xin, Yuxuan

This dissertation research consists of two parts, with Part I on the kinetics of catalytic oxidation of hydrocarbons and Part II on aspects on the detailed simulation of combustion processes. In Part I, the catalytic oxidation of C1--C3 hydrocarbons, namely methane, ethane, propane and ethylene, was investigated for lean hydrocarbon-air mixtures over an unsupported Pd-based catalyst, from 600 to 800 K and under atmospheric pressure. In Chapter 2, the experimental facility of wire microcalorimetry and simulation configuration were described in details. In Chapter 3 and 4, the oxidation rate of C1--C 3 hydrocarbons is demonstrated to be determined by the dissociative adsorption of hydrocarbons. A detailed surface kinetics model is proposed with deriving the rate coefficient of hydrocarbon dissociative adsorption from the wire microcalorimetry data. In Part II, four fundamental studies were conducted through detailed combustion simulations. In Chapter 5, self-accelerating hydrogen-air flames are studied via two-dimensional detailed numerical simulation (DNS). The increase in the global flame velocity is shown to be caused by the increase of flame surface area, and the fractal structure of the flame front is demonstrated by the box-counting method. In Chapter 6, skeletal reaction models for butane combustion are derived by using directed relation graph (DRG) and DRG-aided sensitivity analysis (DRGASA), and uncertainty minimization by polynomial chaos expansion (MUM-PCE) mothodes. The dependence of model uncertainty is subjected to the completeness of the model. In Chapter 7, a systematic strategy is proposed to reduce the cost of the multicomponent diffusion model by accurately accounting for the species whose diffusivity is important to the global responses of the combustion systems, and approximating those of less importance by the mixture-averaged model. The reduced model is validated in an n-heptane mechanism with 88 species. In Chapter 8, the influence of Soret

Detailed finite element method modeling of evaporating multi-component droplets

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

Diddens, Christian, E-mail: C.Diddens@tue.nl

The evaporation of sessile multi-component droplets is modeled with an axisymmetic finite element method. The model comprises the coupled processes of mixture evaporation, multi-component flow with composition-dependent fluid properties and thermal effects. Based on representative examples of water–glycerol and water–ethanol droplets, regular and chaotic examples of solutal Marangoni flows are discussed. Furthermore, the relevance of the substrate thickness for the evaporative cooling of volatile binary mixture droplets is pointed out. It is shown how the evaporation of the more volatile component can drastically decrease the interface temperature, so that ambient vapor of the less volatile component condenses on the droplet.more » Finally, results of this model are compared with corresponding results of a lubrication theory model, showing that the application of lubrication theory can cause considerable errors even for moderate contact angles of 40°. - Graphical abstract:.« less

Membrane separation of hydrocarbons

DOEpatents

Funk, Edward W.; Kulkarni, Sudhir S.; Chang, Y. Alice

1986-01-01

Mixtures of heavy oils and light hydrocarbons may be separated by passing the mixture over a polymeric membrane which comprises a polymer capable of maintaining its integrity in the presence of hydrocarbon compounds at temperature ranging from about ambient to about 100.degree. C. and pressures ranging from about 50 to about 1000 psi. The membranes which possess pore sizes ranging from about 10 to about 500 Angstroms are cast from a solvent solution and recovered.

Estimation of performance of a J-T refrigerators operating with nitrogen-hydrocarbon mixtures and a coiled tubes-in-tube heat exchanger

NASA Astrophysics Data System (ADS)

Satya Meher, R.; Venkatarathnam, G.

2018-06-01

The exergy efficiency of Joule-Thomson (J-T) refrigerators operating with mixtures (MRC systems) strongly depends on the choice of refrigerant mixture and the performance of the heat exchanger used. Helically coiled, multiple tubes-in-tube heat exchangers with an effectiveness of over 96% are widely used in these types of systems. All the current studies focus only on the different heat transfer correlations and the uncertainty in predicting performance of the heat exchanger alone. The main focus of this work is to estimate the uncertainty in cooling capacity when the homogenous model is used by comparing the theoretical and experimental studies. The comparisons have been extended to some two-phase models present in the literature as well. Experiments have been carried out on a J-T refrigerator at a fixed heat load of 10 W with different nitrogen-hydrocarbon mixtures in the evaporator temperature range of 100-120 K. Different heat transfer models have been used to predict the temperature profiles as well as the cooling capacity of the refrigerator. The results show that the homogenous two-phase flow model is probably the most suitable model for rating the cooling capacity of a J-T refrigerator operating with nitrogen-hydrocarbon mixtures.

Tolman lengths and rigidity constants of multicomponent fluids: Fundamental theory and numerical examples

NASA Astrophysics Data System (ADS)

Aasen, Ailo; Blokhuis, Edgar M.; Wilhelmsen, Øivind

2018-05-01

The curvature dependence of the surface tension can be described by the Tolman length (first-order correction) and the rigidity constants (second-order corrections) through the Helfrich expansion. We present and explain the general theory for this dependence for multicomponent fluids and calculate the Tolman length and rigidity constants for a hexane-heptane mixture by use of square gradient theory. We show that the Tolman length of multicomponent fluids is independent of the choice of dividing surface and present simple formulae that capture the change in the rigidity constants for different choices of dividing surface. For multicomponent fluids, the Tolman length, the rigidity constants, and the accuracy of the Helfrich expansion depend on the choice of path in composition and pressure space along which droplets and bubbles are considered. For the hexane-heptane mixture, we find that the most accurate choice of path is the direction of constant liquid-phase composition. For this path, the Tolman length and rigidity constants are nearly linear in the mole fraction of the liquid phase, and the Helfrich expansion represents the surface tension of hexane-heptane droplets and bubbles within 0.1% down to radii of 3 nm. The presented framework is applicable to a wide range of fluid mixtures and can be used to accurately represent the surface tension of nanoscopic bubbles and droplets.

Multi-Component Diffusion with Application To Computational Aerothermodynamics

NASA Technical Reports Server (NTRS)

Sutton, Kenneth; Gnoffo, Peter A.

1998-01-01

The accuracy and complexity of solving multicomponent gaseous diffusion using the detailed multicomponent equations, the Stefan-Maxwell equations, and two commonly used approximate equations have been examined in a two part study. Part I examined the equations in a basic study with specified inputs in which the results are applicable for many applications. Part II addressed the application of the equations in the Langley Aerothermodynamic Upwind Relaxation Algorithm (LAURA) computational code for high-speed entries in Earth's atmosphere. The results showed that the presented iterative scheme for solving the Stefan-Maxwell equations is an accurate and effective method as compared with solutions of the detailed equations. In general, good accuracy with the approximate equations cannot be guaranteed for a species or all species in a multi-component mixture. 'Corrected' forms of the approximate equations that ensured the diffusion mass fluxes sum to zero, as required, were more accurate than the uncorrected forms. Good accuracy, as compared with the Stefan- Maxwell results, were obtained with the 'corrected' approximate equations in defining the heating rates for the three Earth entries considered in Part II.

Myocardium Segmentation From DE MRI Using Multicomponent Gaussian Mixture Model and Coupled Level Set.

PubMed

Liu, Jie; Zhuang, Xiahai; Wu, Lianming; An, Dongaolei; Xu, Jianrong; Peters, Terry; Gu, Lixu

2017-11-01

Objective: In this paper, we propose a fully automatic framework for myocardium segmentation of delayed-enhancement (DE) MRI images without relying on prior patient-specific information. Methods: We employ a multicomponent Gaussian mixture model to deal with the intensity heterogeneity of myocardium caused by the infarcts. To differentiate the myocardium from other tissues with similar intensities, while at the same time maintain spatial continuity, we introduce a coupled level set (CLS) to regularize the posterior probability. The CLS, as a spatial regularization, can be adapted to the image characteristics dynamically. We also introduce an image intensity gradient based term into the CLS, adding an extra force to the posterior probability based framework, to improve the accuracy of myocardium boundary delineation. The prebuilt atlases are propagated to the target image to initialize the framework. Results: The proposed method was tested on datasets of 22 clinical cases, and achieved Dice similarity coefficients of 87.43 ± 5.62% (endocardium), 90.53 ± 3.20% (epicardium) and 73.58 ± 5.58% (myocardium), which have outperformed three variants of the classic segmentation methods. Conclusion: The results can provide a benchmark for the myocardial segmentation in the literature. Significance: DE MRI provides an important tool to assess the viability of myocardium. The accurate segmentation of myocardium, which is a prerequisite for further quantitative analysis of myocardial infarction (MI) region, can provide important support for the diagnosis and treatment management for MI patients. Objective: In this paper, we propose a fully automatic framework for myocardium segmentation of delayed-enhancement (DE) MRI images without relying on prior patient-specific information. Methods: We employ a multicomponent Gaussian mixture model to deal with the intensity heterogeneity of myocardium caused by the infarcts. To differentiate the myocardium from other tissues with

THE PENALIZED OPTIMAL EXPERIMENTAL DESIGN: THE PRECISE ESTIMATION OF AN INTERACTION THRESHOLD IN A MIXTURE OF EIGHTEEN POLYHALOGENATED AROMATIC HYDROCARBONS.

EPA Science Inventory

Crofton et al. (EHP, 2005) conducted a study of 18 polyhalogenated aromatic hydrocarbons (PHAHs) on serum total thyroxine (T4). Young female Long-Evans rats were dosed with the 18 single agents or a fixed-ratio mixture, and serum total T4 was measured via radioimmunoassay. The i...

Laboratory Analysis Of Water, Hydrocarbon And Ammonia Ice Mixtures Exposed To High-energy Electron Irradiation

NASA Astrophysics Data System (ADS)

Hand, Kevin P.; Carlson, R. W.; Tsapin, A. I.

2006-09-01

Irradiation of low temperature ices in the laboratory provides insight into processes that may be occurring on icy bodies in the solar system. Here we report on results from high-energy (10keV) electron irradiation of thin ice films at 1e-8 torr and 70-120K. Mixtures include water with CO2, C3H8, C3H6, C4H10 (butane and isobutane), C4H8,(1-butene and cis/trans-2-butene), and NH3. During irradiation of H2O + alkane films at 80K, CO2 and CH4 production is observed and both species are retained in the ice, possibly trapped in clathrates. The -CH3 infrared bands initially present are seen to decrease with increasing dose. Bands associated with -CH2- persist, indicating polymerization of the initial short-chain hydrocarbons. In alkenes a similar evolution toward polymerization is observed, however the first step appears to be the destruction of the C=C bond. Upon warming of the film, mass spectra data compliment the mid-infrared data and indicate the production of H2CO, however glycolic acid is not explicitly seen in the mass spectra. When warmed to 300K, residues remained for all irradiated films except that of the H2O + CO2 mixtures. Residues were analyzed with Matrix Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI). Results show the production of large aliphatic, very refractory, hydrocarbons (with m/z up to 2500). Mid-infrared spectra of the residues indicate carbonyls and alcohols, likely due to polymerized aldehydes and carboxylic acids. Films of H2O + C3H8 + NH3 at 70K show the production of OCN- (cyanate ion), formamide, along with other possible amides and hydrocarbons. HPLC results indicate the production of racemic alanine. Finally, results of abiotic experiments are compared to results from the irradiation of bacterial spores in ice. The application to Europa and Enceladus is discussed.

Numerical investigation of spray ignition of a multi-component fuel surrogate

NASA Astrophysics Data System (ADS)

Backer, Lara; Narayanaswamy, Krithika; Pepiot, Perrine

2014-11-01

Simulating turbulent spray ignition, an important process in engine combustion, is challenging, since it combines the complexity of multi-scale, multiphase turbulent flow modeling with the need for an accurate description of chemical kinetics. In this work, we use direct numerical simulation to investigate the role of the evaporation model on the ignition characteristics of a multi-component fuel surrogate, injected as droplets in a turbulent environment. The fuel is represented as a mixture of several components, each one being representative of a different chemical class. A reduced kinetic scheme for the mixture is extracted from a well-validated detailed chemical mechanism, and integrated into the multiphase turbulent reactive flow solver NGA. Comparisons are made between a single-component evaporation model, in which the evaporating gas has the same composition as the liquid droplet, and a multi-component model, where component segregation does occur. In particular, the corresponding production of radical species, which are characteristic of the ignition of individual fuel components, is thoroughly analyzed.

Finite time thermodynamics and the quasi-stability of closed-systems of natural hydrocarbon mixtures

NASA Astrophysics Data System (ADS)

Planche, H.

1996-11-01

The isothermal pyrolysis at 372°C, between 400 and 500 bars, of a paraffinic liquid hydrocarbon (natural physical conditions: 195°C, 1000 bars) has been performed over 3 months in order to observe composition changes and to calculate the total Gibbs energy of the fluid hydrocarbon mixture G(t). The approach of a G minimum corresponding to a reversible equilibrium of the composition has been detected. This is consistent with the observation of a significant C 11+ paraffin neo-formation flux after 2 months pyrolysis, and the overall stabilization trend for the fluid composition. The calculated stable composition of the saturates family is consistent with the one asymptotically reached after 1000 h of pyrolysis. This stable composition contains significant amounts of C 6+ paraffins. Assuming the functionality of G in the time-composition space to be conserved when changing temperature from pyrolysis back to the initial fluid natural condition, the stable composition extrapolated at 195°C is that of a liquid hydrocarbon, very close to the natural oil used in the pyrolysis experiments. The observed concentration of most of molecular components of mature oils would thus be controlled by the effective equilibrium of a reversible chemical network. The reversibility of the oil saturates to gas + aromatics conversion is most probably the reason why C 11+ paraffins may survive for as long as 100 Ma in the range 300 to 350°C as literature shows for hyper-mature rock extracts.

Dissipative hydrodynamics for multi-component systems

NASA Astrophysics Data System (ADS)

El, Andrej; Bouras, Ioannis; Wesp, Christian; Xu, Zhe; Greiner, Carsten

2012-11-01

Second-order dissipative hydrodynamic equations for each component of a multi-component system are derived using the entropy principle. Comparison of the solutions with kinetic transport results demonstrates validity of the obtained equations. We demonstrate how the shear viscosity of the total system can be calculated in terms of the involved cross-sections and partial densities. The presence of the inter-species interactions leads to a characteristic time dependence of the shear viscosity of the mixture, which also means that the shear viscosity of a mixture cannot be calculated using the Green-Kubo formalism the way it has been done recently. This finding is of interest for understanding of the shear viscosity of a quark-gluon plasma extracted from comparisons of hydrodynamic simulations with experimental results from RHIC and LHC.

21 CFR 178.3530 - Isoparaffinic petroleum hydrocarbons, synthetic.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Isoparaffinic petroleum hydrocarbons, synthetic... hydrocarbons, synthetic. Isoparaffinic petroleum hydrocarbons, synthetic, may be safely used in the production... isoparaffinic petroleum hydrocarbons, produced by synthesis from petroleum gases consist of a mixture of liquid...

21 CFR 178.3530 - Isoparaffinic petroleum hydrocarbons, synthetic.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Isoparaffinic petroleum hydrocarbons, synthetic... hydrocarbons, synthetic. Isoparaffinic petroleum hydrocarbons, synthetic, may be safely used in the production... isoparaffinic petroleum hydrocarbons, produced by synthesis from petroleum gases consist of a mixture of liquid...

Formation of hydrocarbons under upper mantle conditions: experimental view

NASA Astrophysics Data System (ADS)

Kolesnikov, Anton; Kutcherov, Vladimir G.

2010-05-01

Main postulates of the theory of abiogenic abyssal origin of petroleum have been developed in the last 50 years in Russia and Ukraine. According to this theory, hydrocarbon compounds were generated in the mantle and migrated through the deep faults into the Earth's crust. There they formed oil and gas deposits in any kinds of rocks and in any kind of their structural positions. Until recently the main obstacle to accept the theory was the lack of reliable and reproducible experimental data confirming the possibility of the synthesis of complex hydrocarbon systems under the mantle conditions. The results received in the last decade by different groups of researchers from Russia, U.S.A. and China have confirmed the possibility of generation of hydrocarbons from inorganic materials, highly distributed in the Earth's mantle, under thermobaric conditions of 70-250 km: 2 - 5 GPa and 1000-1500 K. Experiments made in the CONAC chamber at pressures of 3-5 GPa and temperatures of 1000-1500 K by Kutcherov et al. [1, 2] have demonstrated that the mixtures of hydrocarbons with composition similar to natural hydrocarbon systems have been received as a result of chemical reactions between CaCO3, FeO and H2O. Methane formation from the same compounds was registered after heating up to 600-1500 K at pressures of 4-11 GPa in diamond anvil cells [4, 5, 6]. Influence of oxidation state of carbon donor and cooling rate of the fluid synthesized at high pressure were studied using different types of high pressure equipments. It was shown that composition of the final hydrocarbon mixture depends on these parameters. Experimental investigations of transformation of methane and ethane at 2-5 GPa and 1000-1500 K [3] confirmed thermodynamic stability of heavy hydrocarbons in the upper mantle and showed the possibility of hydrocarbon chain growth even at oxidative environment. For development of the theory of abiogenic abyssal origin of petroleum it is necessary to arrange a set of new

Modeling the exposure functions of atmospheric polycyclic aromatic hydrocarbon mixtures in occupational environments.

PubMed

Petit, Pascal; Maître, Anne; Persoons, Renaud; Bicout, Dominique J

2017-04-15

The health risk assessment associated with polycyclic aromatic hydrocarbon (PAH) mixtures faces three main issues: the lack of knowledge regarding occupational exposure mixtures, the accurate chemical characterization and the estimation of cancer risks. To describe industries in which PAH exposures are encountered and construct working context-exposure function matrices, to enable the estimation of both the PAH expected exposure level and chemical characteristic profile of workers based on their occupational sector and activity. Overall, 1729 PAH samplings from the Exporisq-HAP database (E-HAP) were used. An approach was developed to (i) organize E-HAP in terms of the most detailed unit of description of a job and (ii) structure and subdivide the organized E-HAP into groups of detailed industry units, with each group described by the distribution of concentrations of gaseous and particulate PAHs, which would result in working context-exposure function matrices. PAH exposures were described using two scales: phase (total particulate and gaseous PAH distribution concentrations) and congener (16 congener PAH distribution concentrations). Nine industrial sectors were organized according to the exposure durations, short-term, mid-term and long-term into 5, 36 and 47 detailed industry units, which were structured, respectively, into 2, 4, and 7 groups for the phase scale and 2, 3, and 6 groups for the congener scale, corresponding to as much distinct distribution of concentrations of several PAHs. For the congener scale, which included groups that used products derived from coal, the correlations between the PAHs were strong; for groups that used products derived from petroleum, all PAHs in the mixtures were poorly correlated with each other. The current findings provide insights into both the PAH emissions generated by various industrial processes and their associated occupational exposures and may be further used to develop risk assessment analyses of cancers

Efficient Reservoir Simulation with Cubic Plus Association and Cross-Association Equation of State for Multicomponent Three-Phase Compressible Flow with Applications in CO2 Storage and Methane Leakage

NASA Astrophysics Data System (ADS)

Moortgat, J.

2017-12-01

We present novel simulation tools to model multiphase multicomponent flow and transport in porous media for mixtures that contain non-polar hydrocarbons, self-associating polar water, and cross-associating molecules like methane, ethane, unsaturated hydrocarbons, CO2 and H2S. Such mixtures often occur when CO2 is injected and stored in saline aquifers, or when methane is leaking into groundwater. To accurately predict the species transfer between aqueous, gaseous and oleic phases, and the subsequent change in phase properties, the self- and cross-associating behavior of molecules needs to be taken into account, particularly at the typical temperatures and pressures in deep formations. The Cubic-Plus-Association equation-of-state (EOS) has been demonstrated to be highly accurate for such problems but its excessive computational cost has prevented widespread use in reservoir simulators. We discuss the thermodynamical framework and develop sophisticated numerical algorithms that allow reservoir simulations with efficiencies comparable to a simple cubic EOS. This approach improves our predictive powers for highly nonlinear fluid behavior related to geological carbon sequestration, such as density driven flow and natural convection (solubility trapping), evaporation of water into the CO2-rich gas phase, and competitive dissolution-evaporation when CO2 is injected in, e.g., methane saturated aquifers. Several examples demonstrate the accuracy and robustness of this EOS framework for complex applications.

Method and apparatus for detecting gem-polyhalogenated hydrocarbons

DOEpatents

Anderson, deceased, William G.; Anderson, legal representative, Johanna S.

1990-01-01

A method and optrode for detecting gem polyhalogenated hydrocarbons in a sample fluid based on a single phase Fujiwara reaction as provided. The method comprises contacting a reaction mixture with a sample fluid which contains the gem-polyhalogenated hydrocarbons. The reaction mixture comprises an aqueous solution of pyridine or derivative thereof and a hindered nitrogen base. Upon contact a fluorescent and/or chromgenic reaction product forms whose fluorescence and/or absorbance is related to the concentration of gem-polyhalogenated hydrocarbons in the sample fluid.

Acute photo-induced toxicity and toxicokinetics of single compounds and mixtures of polycyclic aromatic hydrocarbons in zebrafish.

PubMed

Willis, Alison M; Oris, James T

2014-09-01

The present study examined photo-induced toxicity and toxicokinetics for acute exposure to selected polycyclic aromatic hydrocarbons (PAHs) in zebrafish. Photo-enhanced toxicity from co-exposure to ultraviolet (UV) radiation and PAHs enhanced the toxicity and exhibited toxic effects at PAH concentrations orders of magnitude below effects observed in the absence of UV. Because environmental exposure to PAHs is usually in the form of complex mixtures, the present study examined the photo-induced toxicity of both single compounds and mixtures of PAHs. In a sensitive larval life stage of zebrafish, acute photo-induced median lethal concentrations (LC50s) were derived for 4 PAHs (anthracene, pyrene, carbazole, and phenanthrene) to examine the hypothesis that phototoxic (anthracene and pyrene) and nonphototoxic (carbazole and phenanthrene) pathways of mixtures could be predicted from single exposures. Anthracene and pyrene were phototoxic as predicted; however, carbazole exhibited moderate photo-induced toxicity and phenanthrene exhibited weak photo-induced toxicity. The toxicity of each chemical alone was used to compare the toxicity of mixtures in binary, tertiary, and quaternary combinations of these PAHs, and a predictive model for environmental mixtures was generated. The results indicated that the acute toxicity of PAH mixtures was additive in phototoxic scenarios, regardless of the magnitude of photo-enhancement. Based on PAH concentrations found in water and circumstances of high UV dose to aquatic systems, there exists potential risk of photo-induced toxicity to aquatic organisms. © 2014 SETAC.

Finite-deformation phase-field chemomechanics for multiphase, multicomponent solids

NASA Astrophysics Data System (ADS)

Svendsen, Bob; Shanthraj, Pratheek; Raabe, Dierk

2018-03-01

The purpose of this work is the development of a framework for the formulation of geometrically non-linear inelastic chemomechanical models for a mixture of multiple chemical components diffusing among multiple transforming solid phases. The focus here is on general model formulation. No specific model or application is pursued in this work. To this end, basic balance and constitutive relations from non-equilibrium thermodynamics and continuum mixture theory are combined with a phase-field-based description of multicomponent solid phases and their interfaces. Solid phase modeling is based in particular on a chemomechanical free energy and stress relaxation via the evolution of phase-specific concentration fields, order-parameter fields (e.g., related to chemical ordering, structural ordering, or defects), and local internal variables. At the mixture level, differences or contrasts in phase composition and phase local deformation in phase interface regions are treated as mixture internal variables. In this context, various phase interface models are considered. In the equilibrium limit, phase contrasts in composition and local deformation in the phase interface region are determined via bulk energy minimization. On the chemical side, the equilibrium limit of the current model formulation reduces to a multicomponent, multiphase, generalization of existing two-phase binary alloy interface equilibrium conditions (e.g., KKS). On the mechanical side, the equilibrium limit of one interface model considered represents a multiphase generalization of Reuss-Sachs conditions from mechanical homogenization theory. Analogously, other interface models considered represent generalizations of interface equilibrium conditions consistent with laminate and sharp-interface theory. In the last part of the work, selected existing models are formulated within the current framework as special cases and discussed in detail.

Sorption characteristic of coal as regards of gas mixtures emitted in the process of the self-heating of coal

NASA Astrophysics Data System (ADS)

Wojtacha-Rychter, Karolina; Smoliński, Adam

2017-10-01

One of the most challenging tasks in the coal mining sector is the detection of endogenous fire risks. Under field conditions, the distance between the points where samples for the analyses are collected and the actual place where coal self-heating takes place may be quite remote. Coal is a natural sorbent with a diverse character of pore structures which are surrounded by fractures and cleavage planes constituting ideal spaces for the flow and adsorption of gases. The gases (methane, ethane, ethylene, propane, propylene, acetylene, carbon dioxide, carbon monoxide, hydrogen) released from the source of fire migrate through the seam and may be subject to adsorption, or they may cause the desorption of gases accumulated in coal. Therefore, the values of reference sample concentrations may be overstated or understated, respectively. The objective of this experimental study was to investigate the adsorption phenomena accompanying the flow of a multi-component gas mixture through a coal bed which may occur in situ. The research was conducted by means of a method based on a series of calorimetric/chromatographic measurements taken to determine the amount of gases released during coal heating at various temperatures under laboratory conditions. Based on the results obtained in the course of the experiments, it was concluded that the amount of gas adsorbed in the seam depends on the type of coal and the gas. Within the multi-component gas mixture, hydrocarbons demonstrated the largest sorption capacity, especially as concerns propylene.

Metal-Polycyclic Aromatic Hydrocarbon Mixture Toxicity in Hyalella azteca. 2. Metal Accumulation and Oxidative Stress as Interactive Co-toxic Mechanisms.

PubMed

Gauthier, Patrick T; Norwood, Warren P; Prepas, Ellie E; Pyle, Greg G

2015-10-06

Mixtures of metals and polycyclic aromatic hydrocarbons (PAHs) are commonly found in aquatic environments. Emerging reports have identified that more-than-additive mortality is common in metal-PAH mixtures. Individual aspects of PAH toxicity suggest they may alter the accumulation of metals and enhance metal-derived reactive oxygen species (ROS). Redox-active metals (e.g., Cu and Ni) are also capable of enhancing the redox cycling of PAHs. Accordingly, we explored the mutual effects redox-active metals and PAHs have on oxidative stress, and the potential for PAHs to alter the accumulation and/or homeostasis of metals in juvenile Hyalella azteca. Amphipods were exposed to binary mixtures of Cu, Cd, Ni, or V, with either phenanthrene (PHE) or phenanthrenequinone (PHQ). Mixture of Cu with either PAH produced striking more-than-additive mortality, whereas all other mixtures amounted to strictly additive mortality following 18-h exposures. We found no evidence to suggest that interactive effects on ROS production were involved in the more-than-additive mortality of Cu-PHE and Cu-PHQ mixtures. However, PHQ increased the tissue concentration of Cu in juvenile H. azteca, providing a potential mechanism for the observed more-than-additive mortality.

Equivalence of Brownian dynamics and dynamic Monte Carlo simulations in multicomponent colloidal suspensions.

PubMed

Cuetos, Alejandro; Patti, Alessandro

2015-08-01

We propose a simple but powerful theoretical framework to quantitatively compare Brownian dynamics (BD) and dynamic Monte Carlo (DMC) simulations of multicomponent colloidal suspensions. By extending our previous study focusing on monodisperse systems of rodlike colloids, here we generalize the formalism described there to multicomponent colloidal mixtures and validate it by investigating the dynamics in isotropic and liquid crystalline phases containing spherical and rodlike particles. In order to investigate the dynamics of multicomponent colloidal systems by DMC simulations, it is key to determine the elementary time step of each species and establish a unique timescale. This is crucial to consistently study the dynamics of colloidal particles with different geometry. By analyzing the mean-square displacement, the orientation autocorrelation functions, and the self part of the van Hove correlation functions, we show that DMC simulation is a very convenient and reliable technique to describe the stochastic dynamics of any multicomponent colloidal system. Our theoretical formalism can be easily extended to any colloidal system containing size and/or shape polydisperse particles.

Cuticular Hydrocarbons: Species and Population-Level Discrimination in Termites

Treesearch

Michael I. Haverty; Marion Page; Barbara L. Thorne; Pierre Escoubas

1991-01-01

Hydrocarbons in the cuticle of insects are essential in protecting them from desiccation. The vast variety of hydrocarbons synthesized by insects and the apparent species-specificity of cuticular hydrocarbon mixtures make them excellent taxonomic characters for separating species within termite genera. Hydrocarbon phenotypes of dampwood termites, Zootermopsis...

Scaled Particle Theory for Multicomponent Hard Sphere Fluids Confined in Random Porous Media.

PubMed

Chen, W; Zhao, S L; Holovko, M; Chen, X S; Dong, W

2016-06-23

The formulation of scaled particle theory (SPT) is presented for a quite general model of fluids confined in a random porous media, i.e., a multicomponent hard sphere (HS) fluid in a multicomponent hard sphere or a multicomponent overlapping hard sphere (OHS) matrix. The analytical expressions for pressure, Helmholtz free energy, and chemical potential are derived. The thermodynamic consistency of the proposed theory is established. Moreover, we show that there is an isomorphism between the SPT for a multicomponent system and that for a one-component system. Results from grand canonical ensemble Monte Carlo simulations are also presented for a binary HS mixture in a one-component HS or a one-component OHS matrix. The accuracy of various variants derived from the basic SPT formulation is appraised against the simulation results. Scaled particle theory, initially formulated for a bulk HS fluid, has not only provided an analytical tool for calculating thermodynamic properties of HS fluid but also helped to gain very useful insight for elaborating other theoretical approaches such as the fundamental measure theory (FMT). We expect that the general SPT for multicomponent systems developed in this work can contribute to the study of confined fluids in a similar way.

Improved predictive model for n-decane kinetics across species, as a component of hydrocarbon mixtures.

PubMed

Merrill, E A; Gearhart, J M; Sterner, T R; Robinson, P J

2008-07-01

n-Decane is considered a major component of various fuels and industrial solvents. These hydrocarbon products are complex mixtures of hundreds of components, including straight-chain alkanes, branched chain alkanes, cycloalkanes, diaromatics, and naphthalenes. Human exposures to the jet fuel, JP-8, or to industrial solvents in vapor, aerosol, and liquid forms all have the potential to produce health effects, including immune suppression and/or neurological deficits. A physiologically based pharmacokinetic (PBPK) model has previously been developed for n-decane, in which partition coefficients (PC), fitted to 4-h exposure kinetic data, were used in preference to measured values. The greatest discrepancy between fitted and measured values was for fat, where PC values were changed from 250-328 (measured) to 25 (fitted). Such a large change in a critical parameter, without any physiological basis, greatly impedes the model's extrapolative abilities, as well as its applicability for assessing the interactions of n-decane or similar alkanes with other compounds in a mixture model. Due to these limitations, the model was revised. Our approach emphasized the use of experimentally determined PCs because many tissues had not approached steady-state concentrations by the end of the 4-h exposures. Diffusion limitation was used to describe n-decane kinetics for the brain, perirenal fat, skin, and liver. Flow limitation was used to describe the remaining rapidly and slowly perfused tissues. As expected from the high lipophilicity of this semivolatile compound (log K(ow) = 5.25), sensitivity analyses showed that parameters describing fat uptake were next to blood:air partitioning and pulmonary ventilation as critical in determining overall systemic circulation and uptake in other tissues. In our revised model, partitioning into fat took multiple days to reach steady state, which differed considerably from the previous model that assumed steady-state conditions in fat at 4 h post

Membrane separation of hydrocarbons

DOEpatents

Chang, Y. Alice; Kulkarni, Sudhir S.; Funk, Edward W.

1986-01-01

Mixtures of heavy oils and light hydrocarbons may be separated by passing the mixture through a polymeric membrane. The membrane which is utilized to effect the separation comprises a polymer which is capable of maintaining its integrity in the presence of hydrocarbon compounds and which has been modified by being subjected to the action of a sulfonating agent. Sulfonating agents which may be employed will include fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, etc., the surface or bulk modified polymer will contain a degree of sulfonation ranging from about 15 to about 50%. The separation process is effected at temperatures ranging from about ambient to about 100.degree. C. and pressures ranging from about 50 to about 1000 psig.

QSAR prediction of additive and non-additive mixture toxicities of antibiotics and pesticide.

PubMed

Qin, Li-Tang; Chen, Yu-Han; Zhang, Xin; Mo, Ling-Yun; Zeng, Hong-Hu; Liang, Yan-Peng

2018-05-01

Antibiotics and pesticides may exist as a mixture in real environment. The combined effect of mixture can either be additive or non-additive (synergism and antagonism). However, no effective predictive approach exists on predicting the synergistic and antagonistic toxicities of mixtures. In this study, we developed a quantitative structure-activity relationship (QSAR) model for the toxicities (half effect concentration, EC 50 ) of 45 binary and multi-component mixtures composed of two antibiotics and four pesticides. The acute toxicities of single compound and mixtures toward Aliivibrio fischeri were tested. A genetic algorithm was used to obtain the optimized model with three theoretical descriptors. Various internal and external validation techniques indicated that the coefficient of determination of 0.9366 and root mean square error of 0.1345 for the QSAR model predicted that 45 mixture toxicities presented additive, synergistic, and antagonistic effects. Compared with the traditional concentration additive and independent action models, the QSAR model exhibited an advantage in predicting mixture toxicity. Thus, the presented approach may be able to fill the gaps in predicting non-additive toxicities of binary and multi-component mixtures. Copyright © 2018 Elsevier Ltd. All rights reserved.

Emulsifier of Arthrobacter RAG-1: specificity of hydrocarbon substrate.

PubMed Central

Rosenberg, E; Perry, A; Gibson, D T; Gutnick, D L

1979-01-01

The purified extracellular emulsifying factor produced by Arthrobacter RAG-1 (EF-RAG) emulsified light petroleum oil, diesel oil, and a variety of crude oils and gas oils. Although kerosine and gasoline were emulsified poorly by EF-RAG, they were converted into good substrates for emulsification by addition of aromatic compounds, such as 2-methylnaphthalene. Neither aromatic nor aliphatic fractions of crude oil were emulsified by EF-RAG; however, mixtures containing both fractions were emulsified. Pure aliphatic or aromatic hydrocarbons were emulsified poorly by EF-RAG. Binary mixtures containing an aliphatic and an aromatic hydrocarbon, however, were excellent substrates for EF-RAG-induced emulsification. Of a variety of alkylcyclohexane and alkylbenzene derivatives tested, only hexyl- or heptylbenzene and octyl- or decylcyclohexane were effectively emulsified by EF-RAG. These data indicate that for EF-RAG to induce emulsification of hydrocarbons in water, the hydrocarbon substrate must contain both aliphatic and cyclic components. With binary mixtures of methylnaphthalene and hexadecane, maximum emulsion was obtained with 25% hexadecane. PMID:453821

Recovery of nitrogen and light hydrocarbons from polyalkene purge gas

DOEpatents

Zwilling, Daniel Patrick; Golden, Timothy Christoph; Weist, Jr., Edward Landis; Ludwig, Keith Alan

2003-06-10

A method for the separation of a gas mixture comprises (a) obtaining a feed gas mixture comprising nitrogen and at least one hydrocarbon having two to six carbon atoms; (b) introducing the feed gas mixture at a temperature of about 60.degree. F. to about 105.degree. F. into an adsorbent bed containing adsorbent material which selectively adsorbs the hydrocarbon, and withdrawing from the adsorbent bed an effluent gas enriched in nitrogen; (c) discontinuing the flow of the feed gas mixture into the adsorbent bed and depressurizing the adsorbent bed by withdrawing depressurization gas therefrom; (d) purging the adsorbent bed by introducing a purge gas into the bed and withdrawing therefrom an effluent gas comprising the hydrocarbon, wherein the purge gas contains nitrogen at a concentration higher than that of the nitrogen in the feed gas mixture; (e) pressurizing the adsorbent bed by introducing pressurization gas into the bed; and (f) repeating (b) through (e) in a cyclic manner.

Conversion of oligomeric starch, cellulose, hydrolysates or sugars to hydrocarbons

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

Silks, Louis A; Sutton, Andrew; Kim, Jin Kyung

Embodiments of the present invention are directed to the conversion of a source material (e.g., a depolymerized oligosaccharide mixture, a monomeric sugar, a hydrolysate, or a mixture of monomeric sugars) to intermediate molecules containing 7 to 26 contiguous carbon atoms. These intermediates may also be converted to saturated hydrocarbons. Such saturated hydrocarbons are useful as, for example, fuels.

Novel anisole mixture and gasoline containing the same

DOEpatents

Singerman, Gary M.

1982-01-26

A novel anisole mixture containing anisole and a mixture of alkyl anisoles and liquid hydrocarbon fuels containing said novel anisole mixture in an amount sufficient to increase the octane number of said liquid fuel composition.

Noble gas and hydrocarbon tracers in multiphase unconventional hydrocarbon systems: Toward integrated advanced reservoir simulators

NASA Astrophysics Data System (ADS)

Darrah, T.; Moortgat, J.; Poreda, R. J.; Muehlenbachs, K.; Whyte, C. J.

2015-12-01

Although hydrocarbon production from unconventional energy resources has increased dramatically in the last decade, total unconventional oil and gas recovery from black shales is still less than 25% and 9% of the totals in place, respectively. Further, the majority of increased hydrocarbon production results from increasing the lengths of laterals, the number of hydraulic fracturing stages, and the volume of consumptive water usage. These strategies all reduce the economic efficiency of hydrocarbon extraction. The poor recovery statistics result from an insufficient understanding of some of the key physical processes in complex, organic-rich, low porosity formations (e.g., phase behavior, fluid-rock interactions, and flow mechanisms at nano-scale confinement and the role of natural fractures and faults as conduits for flow). Noble gases and other hydrocarbon tracers are capably of recording subsurface fluid-rock interactions on a variety of geological scales (micro-, meso-, to macro-scale) and provide analogs for the movement of hydrocarbons in the subsurface. As such geochemical data enrich the input for the numerical modeling of multi-phase (e.g., oil, gas, and brine) fluid flow in highly heterogeneous, low permeability formations Herein we will present a combination of noble gas (He, Ne, Ar, Kr, and Xe abundances and isotope ratios) and molecular and isotopic hydrocarbon data from a geographically and geologically diverse set of unconventional hydrocarbon reservoirs in North America. Specifically, we will include data from the Marcellus, Utica, Barnett, Eagle Ford, formations and the Illinois basin. Our presentation will include geochemical and geological interpretation and our perspective on the first steps toward building an advanced reservoir simulator for tracer transport in multicomponent multiphase compositional flow (presented separately, in Moortgat et al., 2015).

Biodegradation of hydrocarbon mixtures in surface waters at environmentally relevant levels - Effect of inoculum origin on kinetics and sequence of degradation.

PubMed

Birch, Heidi; Hammershøj, Rikke; Comber, Mike; Mayer, Philipp

2017-10-01

Biodegradation is a dominant removal process for many organic pollutants, and biodegradation tests serve as tools for assessing their environmental fate within regulatory risk assessment. In simulation tests, the inoculum is not standardized, varying in microbial quantity and quality, thereby potentially impacting the observed biodegradation kinetics. In this study we investigated the effect of inoculum origin on the biodegradation kinetics of hydrocarbons for five inocula from surface waters varying in urbanization and thus expected pre-exposure to petroleum hydrocarbons. A new biodegradation method for testing mixtures of hydrophobic chemicals at trace concentrations was demonstrated: Aqueous solutions containing 9 hydrocarbons were generated by passive dosing and diluted with surface water resulting in test systems containing native microorganisms exposed to test substances at ng-μg/L levels. Automated Headspace Solid Phase Microextraction coupled to GC-MS was applied directly to these test systems to determine substrate depletion relative to abiotic controls. Lag phases were generally less than 8 days. First order rate constants were within one order of magnitude for each hydrocarbon in four of the five waters but lower in water from a rural lake. The sequence of degradation between the 9 hydrocarbons showed similar patterns in the five waters indicating the potential for using selected hydrocarbons for benchmarking between biodegradation tests. Degradation half-times were shorter than or within one order of magnitude of BioHCwin predictions for 8 of 9 hydrocarbons. These results showed that location choice is important for biodegradation kinetics and can provide a relevant input to aquatic exposure and fate models. Copyright © 2017 Elsevier Ltd. All rights reserved.

Transport properties of nonelectrolyte liquid mixtures—VI. Viscosimetric study of binary mixtures of hexafluorobenzene with aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Dymond, J. H.; Robertson, J.

1985-01-01

Viscosity coefficients for binary mixtures of hexafluorobenzene with benzene, toluene, para-xylene, and mesitylene have been measured along the saturation line at temperatures from 15 to 120°C using specially designed capillary viscometers. Densities were measured using a pyknometer and volume-change apparatus. Deviations of the viscosities from a rectilinear dependence on mole fraction are consistent with enhanced interactions between unlike species, which increase with increasing number of methyl groups on the aromatic hydrocarbon and decrease with increasing temperature. The application of the Grunberg and Nissan equation, the Hildebrand equation, and energy of activation theories to these results is examined.

Detailed Investigation of Separation Performance of a MMM for Removal of Higher Hydrocarbons under Varying Operating Conditions

PubMed Central

Mushardt, Heike; Müller, Marcus; Shishatskiy, Sergey; Wind, Jan; Brinkmann, Torsten

2016-01-01

Mixed-matrix membranes (MMMs) are promising candidates to improve the competitiveness of membrane technology against energy-intensive conventional technologies. In this work, MMM composed of poly(octylmethylsiloxane) (POMS) and activated carbon (AC) were investigated with respect to separation of higher hydrocarbons (C3+) from permanent gas streams. Membranes were prepared as thin film composite membranes on a technical scale and characterized via scanning electron microscopy (SEM) and permeation measurements with binary mixtures of n-C4H10/CH4 under varying operating conditions (feed and permeate pressure, temperature, feed gas composition) to study the influence on separation performance. SEM showed good contact and absence of defects. Lower permeances but higher selectivities were found for MMM compared to pure POMS membrane. Best results were obtained at high average fugacity and activity of n-C4H10 with the highest selectivity estimated to be 36.4 at n-C4H10 permeance of 12 mN3/(m2·h·bar). Results were complemented by permeation of a multi-component mixture resembling a natural gas application, demonstrating the superior performance of MMM. PMID:26927194

A simple thermodynamic model useful for calculating gas solubilities in water/brine/hydrocarbon mixtures from 0 to 250 C and 1 to 150 bars

NASA Astrophysics Data System (ADS)

Perez, R. J.; Shevalier, M.; Hutcheon, I.

2004-05-01

Gas solubility is of considerable interest, not only for the theoretical understanding of vapor-liquid equilibria, but also due to extensive applications in combined geochemical, engineering, and environmental problems, such as greenhouse gas sequestration. Reliable models for gas solubility calculations in salt waters and hydrocarbons are also valuable when evaluating fluid inclusions saturated with gas components. We have modeled the solubility of methane, ethane, hydrogen, carbon dioxide, hydrogen sulfide, and five other gases in a water-brine-hydrocarbon system by solving a non-linear system of equations composed by modified Henry's Law Constants (HLC), gas fugacities, and assuming binary mixtures. HLCs are a function of pressure, temperature, brine salinity, and hydrocarbon density. Experimental data of vapor pressures and mutual solubilities of binary mixtures provide the basis for the calibration of the proposed model. It is demonstrated that, by using the Setchenow equation, only a relatively simple modification of the pure water model is required to assess the solubility of gases in brine solutions. Henry's Law constants for gases in hydrocarbons are derived using regular solution theory and Ostwald coefficients available from the literature. We present a set of two-parameter polynomial expressions, which allow simple computation and formulation of the model. Our calculations show that solubility predictions using modified HLCs are acceptable within 0 to 250 C, 1 to 150 bars, salinity up to 5 molar, and gas concentrations up to 4 molar. Our model is currently being used in the IEA Weyburn CO2 monitoring and storage project.

General Model for Multicomponent Ablation Thermochemistry

NASA Technical Reports Server (NTRS)

Milos, Frank S.; Marschall, Jochen; Rasky, Daniel J. (Technical Monitor)

1994-01-01

A previous paper (AIAA 94-2042) presented equations and numerical procedures for modeling the thermochemical ablation and pyrolysis of thermal protection materials which contain multiple surface species. This work describes modifications and enhancements to the Multicomponent Ablation Thermochemistry (MAT) theory and code for application to the general case which includes surface area constraints, rate limited surface reactions, and non-thermochemical mass loss (failure). Detailed results and comparisons with data are presented for the Shuttle Orbiter reinforced carbon-carbon oxidation protection system which contains a mixture of sodium silicate (Na2SiO3), silica (SiO2), silicon carbide (SiC), and carbon (C).

Methods for dispersing hydrocarbons using autoclaved bacteria

DOEpatents

Tyndall, Richard L.

1996-01-01

A method of dispersing a hydrocarbon includes the steps: providing a bacterium selected from the following group: ATCC 85527, ATCC 75529, and ATCC 55638, a mutant of any one of these bacteria possessing all the identifying characteristics of any one of these bacteria, and mixtures thereof; autoclaving the bacterium to derive a dispersant solution therefrom; and contacting the dispersant solution with a hydrocarbon to disperse the hydrocarbon. Moreover, a method for preparing a dispersant solution includes the following steps: providing a bacterium selected from the following group: ATCC 75527, ATCC 75529, and ATCC 55638, a mutant of any one of these bacteria possessing all the identifying characteristics of any one of these bacteria, and mixtures thereof; and autoclaving the bacterium to derive a dispersant solution therefrom.

Methods for dispersing hydrocarbons using autoclaved bacteria

DOEpatents

Tyndall, R.L.

1996-11-26

A method of dispersing a hydrocarbon includes the following steps: providing a bacterium selected from the following group: ATCC 85527, ATCC 75529, and ATCC 55638, a mutant of any one of these bacteria possessing all the identifying characteristics of any one of these bacteria, and mixtures; autoclaving the bacterium to derive a dispersant solution; and contacting the dispersant solution with a hydrocarbon to disperse the hydrocarbon. Moreover, a method for preparing a dispersant solution includes the following steps: providing a bacterium selected from the following group: ATCC 75527, ATCC 75529, and ATCC 55638, a mutant of any one of these bacteria possessing all the identifying characteristics of any one of these bacteria, and mixtures; and autoclaving the bacterium to derive a dispersant solution.

Dielectric constant of liquid alkanes and hydrocarbon mixtures

NASA Technical Reports Server (NTRS)

Sen, A. D.; Anicich, V. G.; Arakelian, T.

1992-01-01

The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

[Theoretical modeling and experimental research on direct compaction characteristics of multi-component pharmaceutical powders based on the Kawakita equation].

PubMed

Si, Guo-Ning; Chen, Lan; Li, Bao-Guo

2014-04-01

Base on the Kawakita powder compression equation, a general theoretical model for predicting the compression characteristics of multi-components pharmaceutical powders with different mass ratios was developed. The uniaxial flat-face compression tests of powder lactose, starch and microcrystalline cellulose were carried out, separately. Therefore, the Kawakita equation parameters of the powder materials were obtained. The uniaxial flat-face compression tests of the powder mixtures of lactose, starch, microcrystalline cellulose and sodium stearyl fumarate with five mass ratios were conducted, through which, the correlation between mixture density and loading pressure and the Kawakita equation curves were obtained. Finally, the theoretical prediction values were compared with experimental results. The analysis showed that the errors in predicting mixture densities were less than 5.0% and the errors of Kawakita vertical coordinate were within 4.6%, which indicated that the theoretical model could be used to predict the direct compaction characteristics of multi-component pharmaceutical powders.

High performance direct absorption spectroscopy of pure and binary mixture hydrocarbon gases in the 6-11 μm range

NASA Astrophysics Data System (ADS)

Heinrich, Robert; Popescu, Alexandru; Hangauer, Andreas; Strzoda, Rainer; Höfling, Sven

2017-08-01

The availability of accurate and fast hydrocarbon analyzers, capable of real-time operation while enabling feedback-loops, would lead to a paradigm change in the petro-chemical industry. Primarily gas chromatographs measure the composition of hydrocarbon process streams. Due to sophisticated gas sampling, these analyzers are limited in response time. As hydrocarbons absorb in the mid-infrared spectral range, the employment of fast spectroscopic systems is highly attractive due to significantly reduced maintenance costs and the capability to setup real-time process control. New developments in mid-infrared laser systems pave the way for the development of high-performance analyzers provided that accurate spectral models are available for multi-species detection. In order to overcome current deficiencies in the availability of spectroscopic data, we developed a laser-based setup covering the 6-11 μm wavelength range. The presented system is designated as laboratory reference system. Its spectral accuracy is at least 6.6× 10^{-3} cm^{-1} with a precision of 3× 10^{-3} cm^{-1}. With a "per point" minimum detectable absorption of 1.3× 10^{-3} cm^{-1} Hz^{{-}{1/2}} it allows us to perform systematic measurements of hydrocarbon spectra of the first 7 alkanes under conditions which are not tabulated in spectroscopic database. We exemplify the system performance with measured direct absorption spectra of methane, propane, iso-butane, and a mixture of methane and propane.

Tube radial distribution phenomenon with a two-phase separation solution of a fluorocarbon and hydrocarbon organic solvent mixture in a capillary tube and metal compounds separation.

PubMed

Kitaguchi, Koichi; Hanamura, Naoya; Murata, Masaharu; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2014-01-01

A fluorocarbon and hydrocarbon organic solvent mixture is known as a temperature-induced phase-separation solution. When a mixed solution of tetradecafluorohexane as a fluorocarbon organic solvent and hexane as a hydrocarbon organic solvent (e.g., 71:29 volume ratio) was delivered in a capillary tube that was controlled at 10°C, the tube radial distribution phenomenon (TRDP) of the solvents was clearly observed through fluorescence images of the dye, perylene, dissolved in the mixed solution. The homogeneous mixed solution (single phase) changed to a heterogeneous solution (two phases) with inner tetradecafluorohexane and outer hexane phases in the tube under laminar flow conditions, generating the dynamic liquid-liquid interface. We also tried to apply TRDP to a separation technique for metal compounds. A model analyte mixture, copper(II) and hematin, was separated through the capillary tube, and detected with a chemiluminescence detector in this order within 4 min.

Petroleum Hydrocarbon Mixture Toxicity and a Trait Based Approach to Soil Invertebrate Species for Site Specific Risk Assessments.

PubMed

Gainer, Amy; Cousins, Mark; Hogan, Natacha; Siciliano, Steven D

2018-05-05

Although petroleum hydrocarbons (PHCs) released to the environment typically occur as mixtures, PHC remediation guidelines often reflect individual substance toxicity. It is well documented that groups of aliphatic PHCs act via the same mechanism of action, nonpolar narcosis and, theoretically, concentration addition mixture toxicity principles apply. To assess this theory, ten standardized acute and chronic soil invertebrate toxicity tests on a range of organisms (Eisenia fetida, Lumbricus terrestris, Enchytraeus crypticus, Folsomia candida, Oppia nitens and Hypoaspis aculeifer) were conducted with a refined PHC binary mixture. Reference models for concentration addition and independent action were applied to the mixture toxicity data with consideration of synergism, antagonism and dose level toxicity. Both concentration addition and independent action, without further interactions, provided the best fit with observed response to the mixture. Individual fraction effective concentration values were predicted from optimized, fitted reference models. Concentration addition provided a better estimate than independent action of individual fraction effective concentrations based on comparison with available literature and species trends observed in toxic responses to the mixture. Interspecies differences in standardized laboratory soil invertebrate species responses to PHC contaminated soil was reflected in unique traits. Diets that included soil, large body size, permeable cuticle, low lipid content, lack of ability to molt and no maternal transfer were traits linked to a sensitive survival response to PHC contaminated soil in laboratory tests. Traits linked to sensitive reproduction response in organisms tested were long life spans with small clutch sizes. By deriving single fraction toxicity endpoints considerate of mixtures, we reduce resources and time required in conducting site specific risk assessments for the protection of soil organism's exposure pathway. This

Biofiltration of gasoline and diesel aliphatic hydrocarbons.

PubMed

Halecky, Martin; Rousova, Jana; Paca, Jan; Kozliak, Evguenii; Seames, Wayne; Jones, Kim

2015-02-01

The ability of a biofilm to switch between the mixtures of mostly aromatic and aliphatic hydrocarbons was investigated to assess biofiltration efficiency and potential substrate interactions. A switch from gasoline, which consisted of both aliphatic and aromatic hydrocarbons, to a mixture of volatile diesel n-alkanes resulted in a significant increase in biofiltration efficiency, despite the lack of readily biodegradable aromatic hydrocarbons in the diesel mixture. This improved biofilter performance was shown to be the result of the presence of larger size (C₉-C(12)) linear alkanes in diesel, which turned out to be more degradable than their shorter-chain (C₆-C₈) homologues in gasoline. The evidence obtained from both biofiltration-based and independent microbiological tests indicated that the rate was limited by biochemical reactions, with the inhibition of shorter chain alkane biodegradation by their larger size homologues as corroborated by a significant substrate specialization along the biofilter bed. These observations were explained by the lack of specific enzymes designed for the oxidation of short-chain alkanes as opposed to their longer carbon chain homologues.

The origin of aliphatic hydrocarbons in olive oil.

PubMed

Pineda, Manuel; Rojas, María; Gálvez-Valdivieso, Gregorio; Aguilar, Miguel

2017-11-01

There are many substances that can interfere with olive oil quality. Some of them are well characterized, but many others have an unknown origin. Saturated hydrocarbons make an extraordinary complex family of numerous molecules, some of them present naturally in vegetable oils. When major natural saturated hydrocarbons are analyzed by standard chromatographic methods, this complex mixture of saturated hydrocarbons appears as a hump in the chromatogram and is commonly named as unresolved complex mixture (UCM), whose origin remains unknown. In this work we studied the occurrence and the origin of aliphatic saturated hydrocarbons in olive oil. Hydrocarbons were analyzed in olive oil and along the industrial process of oil extraction. We also analyzed n-alkanes and the UCM fraction of hydrocarbons in leaf, fruit and oil from different varieties and different locations, and we also analyzed the soils at these locations. We conclude that the hydrocarbons present in olive oil do not necessarily have their origin in a contamination during olive oil elaboration; they seem to have a natural origin, as a result of olive tree metabolism and/or as the result of an intake and accumulation by the olive tree directly from the environment during its entire life cycle. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Reservoir simulation with the cubic plus (cross-) association equation of state for water, CO2, hydrocarbons, and tracers

NASA Astrophysics Data System (ADS)

Moortgat, Joachim

2018-04-01

This work presents an efficient reservoir simulation framework for multicomponent, multiphase, compressible flow, based on the cubic-plus-association (CPA) equation of state (EOS). CPA is an accurate EOS for mixtures that contain non-polar hydrocarbons, self-associating polar water, and cross-associating molecules like methane, ethane, unsaturated hydrocarbons, CO2, and H2S. While CPA is accurate, its mathematical formulation is highly non-linear, resulting in excessive computational costs that have made the EOS unfeasible for large scale reservoir simulations. This work presents algorithms that overcome these bottlenecks and achieve an efficiency comparable to the much simpler cubic EOS approach. The main applications that require such accurate phase behavior modeling are 1) the study of methane leakage from high-pressure production wells and its potential impact on groundwater resources, 2) modeling of geological CO2 sequestration in brine aquifers when one is interested in more than the CO2 and H2O components, e.g. methane, other light hydrocarbons, and various tracers, and 3) enhanced oil recovery by CO2 injection in reservoirs that have previously been waterflooded or contain connate water. We present numerical examples of all those scenarios, extensive validation of the CPA EOS with experimental data, and analyses of the efficiency of our proposed numerical schemes. The accuracy, efficiency, and robustness of the presented phase split computations pave the way to more widespread adoption of CPA in reservoir simulators.

Boiling of multicomponent working fluids used in refrigeration and cryogenic systems

NASA Astrophysics Data System (ADS)

Mogorychny, V. I.; Dolzhikov, A. S.

2017-11-01

Working fluids based on mixtures are widely used in cryogenic and refrigeration engineering. One of the main elements of low-temperature units is a recuperative heat exchanger where the return flow cools the direct (cold regeneration is carrying out) resulting in continuous boiling and condensation of the multicomponent working fluid in the channels. The temperature difference between the inlet and outlet of the heat exchanger can be more than 100K, which leads to a strong change in thermophysical properties along its length. In addition, the fraction of the liquid and vapor phases in the flow varies very much, which affects the observed flow regimes in the heat exchanger channels. At the moment there are not so many experimental data and analytical correlations that would allow to estimate the heat transfer coefficient during the flow of a two-phase mixture flow at low temperatures. The work is devoted to the study of the boiling process of multicomponent working fluids used in refrigeration and cryogenic engineering. The description of the method of determination of heat transfer coefficient during boiling of mixtures in horizontal heated channel is given as well as the design of the experimental stand allowing to make such measurements. This stand is designed on the basis of a refrigeration unit operating on the Joule-Thomson throttle cycle and makes it possible to measure the heat transfer coefficient with a good accuracy. Also, the calculated values of the heat transfer coefficient, obtained with the use of various correlations, are compared with the existing experimental data. Knowing of the heat transfer coefficient will be very useful in the design of heat exchangers for low-temperature units operating on a mixture refrigerant.

Embryotoxic effects of benzo[a]pyrene, chrysene and 7,12-dimethylbenz[a]-anthracene in petroleum hydrocarbon mixtures in mallard ducks

USGS Publications Warehouse

Hoffman, D.J.; Gay, M.L.

1981-01-01

Studies with different avian species have revealed that surface applications of microliter amounts of some crude and fuel oils that coat less than 70% of the egg surface result in considerable reduction in hatching with teratogenicity and stunted growth. Other stUdies have shown that the embryo toxicity is dependent on the aromatic hydrocarbon content, further suggesting that the toxicity is due to causes other than asphyxia. In the present study the effects of three polycyclic aromatic hydrocarbons identified in petroleum were examined on mallard (Anas platyrhynchos) embryo development. Addition of benzo[a]pyrene (BaP), chrysene, or 7,7 2-dimethylbenz[ a]anthracene (DMBA) to a synthetic petroleum hydrocarbon mixture of known composition and relatively low embryotoxicity resulted in embryo toxicity that was enhanced or equal to that of crude oil when 10 :I was applied externally to eggs at 72 h of development. The order of ability to enhance embryo toxicity was DMBA > BaP > chrysene. The temporal pattern of embryonic death was similar to that reported after exposure to crude oil, with additional mortality occurring after outgrowth of the chorioallantois. Retarded growth, as reflected by embryonic body weight, crown-rump length, and bill length, was accompanied by teratogenicity. Abnormal embryos exhibited extreme stunting; eye, brain, and bill defects; and incomplete ossification. Gas chromatographic-mass spectral analysis of externally treated eggs showed the passage of aromatic hydrocarbons including chrysene through the shell and shell membranes to the developing embryos. These findings suggest that the presence of polycyclic aromatic hydrocarbons in petroleum, including BaP, chrysene, and DMBA, significantly enhances the overall embryotoxicity in avian species.

From Trioleoyl glycerol to extra virgin olive oil through multicomponent triacylglycerol mixtures: Crystallization and polymorphic transformation examined with differential scanning calorimetry and X-ray diffration techniques.

PubMed

Bayés-García, L; Calvet, T; Cuevas-Diarte, M A; Ueno, S

2017-09-01

The polymorphic crystallization and transformation behavior of extra virgin olive oil (EVOO) was examined by using differential scanning calorimetry (DSC) and X-ray diffraction with both laboratory-scale (XRD) and synchrotron radiation source (SR-XRD). The complex behavior observed was studied by previously analyzing mixtures composed by its main 2 to 6 triacylglycerol (TAG) components. Thus, component TAGs were successively added to simulate EVOO composition, until reaching a 6 TAGs mixture, composed by trioleoyl glycerol (OOO), 1-palmitoyl-2,3-dioleoyl glycerol (POO), 1,2-dioleoyl-3-linoleoyl glycerol (OOL), 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol (POL), 1,2-dipalmitoyl-3-oleoyl glycerol (PPO) and 1-stearoyl-2,3-dioleoyl glycerol (SOO). Molten samples were cooled from 25°C to -80°C at a controlled rate of 2°C/min and subsequently heated at the same rate. The polymorphic behavior observed in multicomponent TAG mixtures was interpreted by considering three main groups of TAGs with different molecular structures: triunsaturated OOO and OOL, saturated-unsaturated-unsaturated POO, POL and SOO, and saturated-saturated-unsaturated PPO. As confirmed by our previous work, TAGs belonging to the same structural group displayed a highly similar polymorphic behavior. EVOO exhibited two different β'-2L polymorphic forms (β' 2 -2L and β' 1 -2L), which transformed into β'-3L when heated. Equivalent polymorphic pathways were detected when the same experimental conditions were applied to the 6 TAG components mixture. Hence, minor components may not exert a strong influence in this case. Copyright © 2017 Elsevier Ltd. All rights reserved.

Embryotoxic and teratogenic effects of petroleum hydrocarbons in mallards (Anas platyrhynchos)

USGS Publications Warehouse

Hoffman, D.J.

1979-01-01

Egg surface applications of microliter quantities of crude and refined oils of high aromatic content are embryotoxic to mallards (Anas platyrhynchos) and other avian species; applications of aliphatic hydrocarbons have virtually no effect. Mallard eggs at 72 h of development were exposed to a mixture of aromatic hydrocarbons or to aromatic compounds representative to those present in crude oil to assess their toxicity. The class composition of the mixture was similar to that of South Louisiana crude oil, an American Petroleum Institute reference oil. Application of 20 microliter of the mixture reduced embryonic survival by nearly 70%. The temporal pattern of embryonic death was similar to that after exposure to South Louisiana crude oil. Embryonic growth was stunted, as reflected by weight, crown-rump length, and bill length, and there was a significant increase in the incidence of abnormal survivors. When individual classes of aromatic hydrocarbons were tested, tetracyclics caused some embryonic death at the concentrations in the mixture. When classes were tested in all possible combinations of two, no combination appeared to be as toxic as the entire mixture. Addition of the tetracyclic compound chrysene to the aromatic mixture considerably enhanced embryotoxicity, but could not completely account for the toxicity of the crude oil. The presence of additional unidentified polycyclic aromatic hydrocarbons as well as methylated derivatives of polycyclic aromatic compounds such as chrysene may further account for the embryotoxicity of the crude oil.

Method and apparatus for synthesizing hydrocarbons

DOEpatents

Colmenares, C.A.; Somorjai, G.A.; Maj, J.J.

1983-06-21

A method and apparatus for synthesizing a mixture of hydrocarbons having five carbons or less is disclosed. An equal molar ratio of CO and H/sub 2/ gases is caused to pass through a ThO/sub 2/ catalyst having a surface area of about 80 to 125 m/sup 2//g. The catalyst further includes Na present as a substitutional cation in an amount of about 5 to 10 atom %. At a temperature of about 340 to 360/sup 0/C, and at pressures of about 20 to 50 atm, CH/sub 3/OH is produced in an amount of about 90 wt % of the total hydrocarbon mixture, and comprised 1 mole % of the effluent gas.

Numerical modeling of temperature and species distributions in hydrocarbon reservoirs

NASA Astrophysics Data System (ADS)

Bolton, Edward W.; Firoozabadi, Abbas

2014-01-01

We examine bulk fluid motion and diffusion of multicomponent hydrocarbon species in porous media in the context of nonequilibrium thermodynamics, with particular focus on the phenomenology induced by horizontal thermal gradients at the upper and lower horizontal boundaries. The problem is formulated with respect to the barycentric (mass-averaged) frame of reference. Thermally induced convection, with fully time-dependent temperature distributions, can lead to nearly constant hydrocarbon composition, with minor unmixing due to thermal gradients near the horizontal boundaries. Alternately, the composition can be vertically segregated due to gravitational effects. Independent and essentially steady solutions have been found to depend on how the compositions are initialized in space and may have implications for reservoir history. We also examine injection (to represent filling) and extraction (to represent leakage) of hydrocarbons at independent points and find a large distortion of the gas-oil contact for low permeability.

A generalized procedure for the prediction of multicomponent adsorption equilibria

DOE PAGES

Ladshaw, Austin; Yiacoumi, Sotira; Tsouris, Costas

2015-04-07

Prediction of multicomponent adsorption equilibria has been investigated for several decades. While there are theories available to predict the adsorption behavior of ideal mixtures, there are few purely predictive theories to account for nonidealities in real systems. Most models available for dealing with nonidealities contain interaction parameters that must be obtained through correlation with binary-mixture data. However, as the number of components in a system grows, the number of parameters needed to be obtained increases exponentially. Here, a generalized procedure is proposed, as an extension of the predictive real adsorbed solution theory, for determining the parameters of any activity model,more » for any number of components, without correlation. This procedure is then combined with the adsorbed solution theory to predict the adsorption behavior of mixtures. As this method can be applied to any isotherm model and any activity model, it is referred to as the generalized predictive adsorbed solution theory.« less

Method and apparatus for low temperature destruction of halogenated hydrocarbons

DOEpatents

Reagen, William Kevin; Janikowski, Stuart Kevin

1999-01-01

A method and apparatus for decomposing halogenated hydrocarbons are provided. The halogenated hydrocarbon is mixed with solvating agents and maintained in a predetermined atmosphere and at a predetermined temperature. The mixture is contacted with recyclable reactive material for chemically reacting with the recyclable material to create dehalogenated hydrocarbons and halogenated inorganic compounds. A feature of the invention is that the process enables low temperature destruction of halogenated hydrocarbons.

Construction of Joule Thomson inversion curves for mixtures using equation of state

NASA Astrophysics Data System (ADS)

Patankar, A. S.; Atrey, M. D.

2017-02-01

The Joule-Thomson effect is at the heart of Joule-Thomson cryocoolers and gas liquefaction cycles. The effective harnessing of this phenomenon necessitates the knowledge of Joule-Thomson coefficient and the inversion curve. When the working fluid is a mixture, (in mix refrigerant Joule-Thomson cryocooler, MRJT) the phase diagrams, equations of state and inversion curves of multi-component systems become important. The lowest temperature attainable by such a cryocooler depends on the inversion characteristics of the mixture used. In this work the construction of differential Joule-Thomson inversion curves of mixtures using Redlich-Kwong, Soave-Redlich-Kwong and Peng-Robinson equations of state is investigated assuming single phase. It is demonstrated that inversion curves constructed for pure fluids can be improved by choosing an appropriate value of acentric factor. Inversion curves are used to predict maximum inversion temperatures of multicomponent systems. An application where this information is critical is a two-stage J-T cryocooler using a mixture as the working fluid, especially for the second stage. The pre-cooling temperature that the first stage is required to generate depends on the maximum inversion temperature of the second stage working fluid.

Catalytic bismetallative multicomponent coupling reactions: scope, applications, and mechanisms

PubMed Central

Cho, Hee Yeon

2014-01-01

Catalytic reactions have played an indispensable role in organic chemistry for the last several decades. In particular, catalytic multicomponent reactions have attracted a lot of attention due to their efficiency and expediency towards complex molecule synthesis. The presence of bismetallic reagents (e.g. B–B, Si–Si, B–Si, Si–Sn, etc.) in this process renders the products enriched with various functional groups and multiple stereocenters. For this reason, catalytic bismetallative coupling is considered an effective method to generate the functional and stereochemical complexity of simple hydrocarbon substrates. This review highlights key developments of transition-metal catalyzed bismetallative reactions involving multiple π components. Specifically, it will highlight the scope, synthetic applications, and proposed mechanistic pathways of this process. PMID:24736839

Impact of multi-component diffusion in turbulent combustion using direct numerical simulations

DOE PAGES

Bruno, Claudio; Sankaran, Vaidyanathan; Kolla, Hemanth; ...

2015-08-28

This study presents the results of DNS of a partially premixed turbulent syngas/air flame at atmospheric pressure. The objective was to assess the importance and possible effects of molecular transport on flame behavior and structure. To this purpose DNS were performed at with two proprietary DNS codes and with three different molecular diffusion transport models: fully multi-component, mixture averaged, and imposing the Lewis number of all species to be unity.

Process for recovering hydrocarbons from hydrocarbon-containing biomass

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

Dzadzic, P.M.; Price, M.C.; Shih, C.J.

1982-07-06

A process is disclosed for enzymatically converting whole plant biomass containing hydrocarbon-containing laticifers to soluble sugars and recovering hydrocarbons in increased yields. The process comprises hydrolyzing whole plant cellulosic material in the presence of enzymes, particularly cellulase, hemicellulase, and pectinase, to produce a hydrocarbon product and recovering from the hydrolysis products a major proportion of the cellulase, hemicellulase and pectinase enzymes for reuse. At least some portion of the required make-up of cellulase, hemicellulase and pectinase enzymes is produced in a two-stage operation wherein, in the first stage, a portion of the output sugar solution is used to grow enzymemore » secreting microorganisms selected from the group consisting of cellulase-secreting microorganisms, hemicellulase-secreting microorganisms, pectinase-secreting microorganisms, and mixtures thereof, and in the second stage, cellulase, hemicellulase and pectinase enzyme formation is induced in the microorganism-containing culture medium by the addition of an appropriate inducer such as biomass. The cellulase, hemicellulase and pectinase enzymes are then recycled for use in the hydrolysis reaction.« less

Process for recovering hydrocarbons from a diatomite-type ore

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

Davis, B.W.

1983-02-15

A process for recovering hydrocarbons from a diatomite-type ore which comprises contacting the diatomite ore with a C/sub 4/-C/sub 10/ alcohol and thereafter contacting the diatomite ore-alcohol mixture with an aqueous alkaline solution to separate a hydrocarbon-alcohol phase and an alkaline aqueous phase containing the stripped diatomite ore. Thereafter, the alcohol is distilled off from the hydrocarbon phase and recycled back into the initial process.

Spatially resolved multicomponent gels

NASA Astrophysics Data System (ADS)

Draper, Emily R.; Eden, Edward G. B.; McDonald, Tom O.; Adams, Dave J.

2015-10-01

Multicomponent supramolecular systems could be used to prepare exciting new functional materials, but it is often challenging to control the assembly across multiple length scales. Here we report a simple approach to forming patterned, spatially resolved multicomponent supramolecular hydrogels. A multicomponent gel is first formed from two low-molecular-weight gelators and consists of two types of fibre, each formed by only one gelator. One type of fibre in this ‘self-sorted network’ is then removed selectively by a light-triggered gel-to-sol transition. We show that the remaining network has the same mechanical properties as it would have done if it initially formed alone. The selective irradiation of sections of the gel through a mask leads to the formation of patterned multicomponent networks, in which either one or two networks can be present at a particular position with a high degree of spatial control.

Alfven wave dispersion behavior in single- and multicomponent plasmas

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

Rahbarnia, K.; Grulke, O.; Klinger, T.

Dispersion relations of driven Alfven waves (AWs) are measured in single- and multicomponent plasmas consisting of mixtures of argon, helium, and oxygen in a magnetized linear cylindrical plasma device VINETA [C. Franck, O. Grulke, and T. Klinger, Phys. Plasmas 9, 3254 (2002)]. The decomposition of the measured three-dimensional magnetic field fluctuations and the corresponding parallel current pattern reveals that the wave field is a superposition of L- and R-wave components. The dispersion relation measurements agree well with calculations based on a multifluid Hall-magnetohydrodynamic model if the plasma resistivity is correctly taken into account.

Evaluation of Measurement Instrument Criterion Validity in Finite Mixture Settings

ERIC Educational Resources Information Center

Raykov, Tenko; Marcoulides, George A.; Li, Tenglong

2016-01-01

A method for evaluating the validity of multicomponent measurement instruments in heterogeneous populations is discussed. The procedure can be used for point and interval estimation of criterion validity of linear composites in populations representing mixtures of an unknown number of latent classes. The approach permits also the evaluation of…

Wave Velocities in Hydrocarbons and Hydrocarbon Saturated - Applications to Eor Monitoring.

NASA Astrophysics Data System (ADS)

Wang, Zhijing

In order to effectively utilize many new seismic technologies and interpret the results, acoustic properties of both reservoir fluids and rocks must be well understood. It is the main purpose of this dissertation to investigate acoustic wave velocities in different hydrocarbons and hydrocarbon saturated rocks under various reservoir conditions. The investigation consists of six laboratory experiments, followed by a series of theoretical and application analyses. All the experiments involve acoustic velocity measurements in hydrocarbons and rocks with different hydrocarbons, using the ultrasonic pulse-transmission methods, at elevated temperatures and pressures. In the experiments, wave velocities are measured versus both temperature and pressure in 50 hydrocarbons. The relations among the acoustic velocity, temperature, pressure, API gravity, and the molecular weight of the hydrocarbons are studied, and empirical equations are established which allow one to calculate the acoustic velocities in hydrocarbons with known API gravities. Wave velocities in hydrocarbon mixtures are related to the composition and the velocities in the components. The experimental results are also analyzed in terms of various existing theories and models of the liquid state. Wave velocities are also measured in various rocks saturated with different hydrocarbons. The compressional wave velocities in rocks saturated with pure hydrocarbons increase with increasing the carbon number of the hydrocarbons. They decrease markedly in all the heavy hydrocarbon saturated rocks as temperature increases. Such velocity decreases set the petrophysical basis for in-situ seismic monitoring thermal enhanced oil recovery processes. The effects of carbon dioxide flooding and different pore fluids on wave velocities in rocks are also investigated. It is highly possible that there exist reflections of seismic waves at the light-heavy oil saturation interfaces in-situ. It is also possible to use seismic methods

A framework for the use of single-chemical transcriptomics data in predicting the hazards associated with complex mixtures of polycyclic aromatic hydrocarbons.

PubMed

Labib, Sarah; Williams, Andrew; Kuo, Byron; Yauk, Carole L; White, Paul A; Halappanavar, Sabina

2017-07-01

The assumption of additivity applied in the risk assessment of environmental mixtures containing carcinogenic polycyclic aromatic hydrocarbons (PAHs) was investigated using transcriptomics. MutaTMMouse were gavaged for 28 days with three doses of eight individual PAHs, two defined mixtures of PAHs, or coal tar, an environmentally ubiquitous complex mixture of PAHs. Microarrays were used to identify differentially expressed genes (DEGs) in lung tissue collected 3 days post-exposure. Cancer-related pathways perturbed by the individual or mixtures of PAHs were identified, and dose-response modeling of the DEGs was conducted to calculate gene/pathway benchmark doses (BMDs). Individual PAH-induced pathway perturbations (the median gene expression changes for all genes in a pathway relative to controls) and pathway BMDs were applied to models of additivity [i.e., concentration addition (CA), generalized concentration addition (GCA), and independent action (IA)] to generate predicted pathway-specific dose-response curves for each PAH mixture. The predicted and observed pathway dose-response curves were compared to assess the sensitivity of different additivity models. Transcriptomics-based additivity calculation showed that IA accurately predicted the pathway perturbations induced by all mixtures of PAHs. CA did not support the additivity assumption for the defined mixtures; however, GCA improved the CA predictions. Moreover, pathway BMDs derived for coal tar were comparable to BMDs derived from previously published coal tar-induced mouse lung tumor incidence data. These results suggest that in the absence of tumor incidence data, individual chemical-induced transcriptomics changes associated with cancer can be used to investigate the assumption of additivity and to predict the carcinogenic potential of a mixture.

Effects of currently used pesticides and their mixtures on the function of thyroid hormone and aryl hydrocarbon receptor in cell culture

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

Ghisari, Mandana; Long, Manhai; Tabbo, Agnese

Evidence suggest that exposure to pesticides can interfere with the endocrine system by multiple mechanisms. The endocrine disrupting potential of currently used pesticides in Denmark was analyzed as single compounds and in an equimolar mixture of 5 selected pesticides. The pesticides were previously analyzed for effects on the function of estrogen and androgen receptors, the aromatase enzyme and steroidogenesis in vitro. In this study, the effect on thyroid hormone (TH) function and aryl hydrocarbon receptor (AhR) transactivity was assessed using GH3 cell proliferation assay (T-screen) and AhR responsive luciferase reporter gene bioassay, respectively. Thirteen pesticides were analyzed as follows: 2-methyl-4-chlorophenoxyaceticmore » acid, terbuthylazine, iodosulfuron-methyl-sodium, mesosulfuron-methyl, metsulfuron-methyl, chlormequat chloride, bitertanol, propiconazole, prothioconazole, mancozeb and its metabolite ethylene thiourea, cypermethrin, tau-fluvalinate, and malathion (currently banned in DK). In the T-screen, prothioconazole, malathion, tau-fluvalinate, cypermethrin, terbuthylazine and mancozeb significantly stimulated and bitertanol and propiconazole slightly reduced the GH3 cell proliferation. In the presence of triiodothyronine (T3), prothioconazole, tau-fluvalinate, propiconazole, cypermethrin and bitertanol significantly antagonized the T3-induced GH3 cell proliferation. Eleven of the tested pesticides agonized the AhR function, and bitertanol and prothioconazole inhibited the basal AhR activity. Bitertanol, propiconazole, prothioconazole and cypermethrin antagonized the TCDD-induced AhR transactivation at the highest tested concentration. The 5-component mixture had inducing effect but the combined effect could not be predicted due to the presence of bitertanol eliciting inhibitory effect. Upon removal of bitertanol from the mixture, the remaining four pesticides acted additively. In conclusion, our data suggest that pesticides currently used in

Quantitative analysis of multi-component gas mixture based on AOTF-NIR spectroscopy

NASA Astrophysics Data System (ADS)

Hao, Huimin; Zhang, Yong; Liu, Junhua

2007-12-01

Near Infrared (NIR) spectroscopy analysis technology has attracted many eyes and has wide application in many domains in recent years because of its remarkable advantages. But the NIR spectrometer can only be used for liquid and solid analysis by now. In this paper, a new quantitative analysis method of gas mixture by using new generation NIR spectrometer is explored. To collect the NIR spectra of gas mixtures, a vacuumable gas cell was designed and assembled to Luminar 5030-731 Acousto-Optic Tunable Filter (AOTF)-NIR spectrometer. Standard gas samples of methane (CH 4), ethane (C IIH 6) and propane (C 3H 8) are diluted with super pure nitrogen via precision volumetric gas flow controllers to obtain gas mixture samples of different concentrations dynamically. The gas mixtures were injected into the gas cell and the spectra of wavelength between 1100nm-2300nm were collected. The feature components extracted from gas mixture spectra by using Partial Least Squares (PLS) were used as the inputs of the Support Vector Regress Machine (SVR) to establish the quantitative analysis model. The effectiveness of the model is tested by the samples of predicting set. The prediction Root Mean Square Error (RMSE) of CH 4, C IIH 6 and C 3H 8 is respectively 1.27%, 0.89%, and 1.20% when the concentrations of component gas are over 0.5%. It shows that the AOTF-NIR spectrometer with gas cell can be used for gas mixture analysis. PLS combining with SVR has a good performance in NIR spectroscopy analysis. This paper provides the bases for extending the application of NIR spectroscopy analysis to gas detection.

Biological enhancement of hydrocarbon extraction

DOEpatents

Brigmon, Robin L [North Augusta, SC; Berry, Christopher J [Aiken, SC

2009-01-06

A method of microbial enhanced oil recovery for recovering oil from an oil-bearing rock formation is provided. The methodology uses a consortium of bacteria including a mixture of surfactant producing bacteria and non-surfactant enzyme producing bacteria which may release hydrocarbons from bitumen containing sands. The described bioprocess can work with existing petroleum recovery protocols. The consortium microorganisms are also useful for treatment of above oil sands, ground waste tailings, subsurface oil recovery, and similar materials to enhance remediation and/or recovery of additional hydrocarbons from the materials.

Temperature-dependent mid-IR absorption spectra of gaseous hydrocarbons

NASA Astrophysics Data System (ADS)

Klingbeil, Adam E.; Jeffries, Jay B.; Hanson, Ronald K.

2007-10-01

Quantitative mid-IR absorption spectra (2500 3400 cm-1) for 12 pure hydrocarbon compounds are measured at temperatures ranging from 25 to 500 °C using an FTIR spectrometer. The hydrocarbons studied are n-pentane, n-heptane, n-dodecane, 2,2,4-trimethyl-pentane (iso-octane), 2-methyl-butane, 2-methyl-pentane, 2,4,4-trimethyl-1-pentene, 2-methyl-2-butene, propene, toluene, m-xylene, and ethylbenzene. Room-temperature measurements of neat hydrocarbon vapor were made with an instrument resolution of both 0.1 and 1 cm-1 (FWHM) to confirm that the high-resolution setting was required only to resolve the propene absorption spectrum while the spectra of the other hydrocarbons could be resolved with 1 cm-1 resolution. High-resolution (0.1 cm-1), room-temperature measurements of neat hydrocarbons were made at low pressure (˜1 Torr, 133 Pa) and compared to measurements of hydrocarbon/N2 mixtures at atmospheric pressure to verify that no pressure broadening could be observed over this pressure range. The temperature was varied between 25 and 500 °C for atmospheric-pressure measurements of hydrocarbon/N2 mixtures (Xhydrocarbon˜0.06 1.5%) and it was found that the absorption cross section shows simple temperature-dependent behavior for a fixed wavelength over this temperature range. Comparisons with previous FTIR data over a limited temperature range and with high-resolution laser absorption data over a wide temperature range show good agreement.

Going Beyond, Going Further: Chemical Properties of Commonly Available Hydrocarbons.

ERIC Educational Resources Information Center

Perina, Ivo

1985-01-01

Background information, procedures used, and safety considerations are provided for experiments using natural gas. They include: (1) exploding a mixture of natural gas and oxygen; (2) testing for unsaturated hydrocarbons in natural gas; (3) substituting higher saturated hydrocarbons contained in kerosene with bromine; and (4) the pyrolysis of…

Toxic effects of unresolved complex mixtures of aromatic hydrocarbons accumulated by mussels, Mytilus edulis, from contaminated field sites.

PubMed

Donkin, Peter; Smith, Emma L; Rowland, Steven J

2003-11-01

Exposure of marine mussels (Mytilus edulis) to an unresolved complex mixture (UCM) of aromatic hydrocarbons isolated from a crude oil has been shown to reduce their feeding rate by 40%. The present study was undertaken to determine whether UCMs bioaccumulated by mussels in the field are also toxic. The feeding rate of mussels derived from polluted sites increased when they were placed in clean water, pointing to a loss of toxic agents from the tissues. At the end of the depuration period, water in which mussels from an oil-polluted site had been held contained a UCM. Steam-distillation extracts of the tissues of mussels taken from several polluted sites were shown to be highly toxic to the feeding activity of juvenile mussels. The tissues of mussels from these sites contained UCMs. Nontoxic steam distillates from clean mussels did not. Steam-distillation extracts of mussels from an oil-polluted site were fractionated by normal-phase high-performance liquid chromatography. A fraction, largely comprising a "monoaromatic" UCM, reduced the feeding rate of juvenile mussels by 70%. Two later-eluting fractions containing aromatic UCMs also produced smaller depressions in feeding rate. These results support our contention that some aromatic UCM hydrocarbons constitute a forgotten pollutant burden in the marine environment.

Coal-water mixture fuel burner

DOEpatents

Brown, T.D.; Reehl, D.P.; Walbert, G.F.

1985-04-29

The present invention represents an improvement over the prior art by providing a rotating cup burner arrangement for use with a coal-water mixture fuel which applies a thin, uniform sheet of fuel onto the inner surface of the rotating cup, inhibits the collection of unburned fuel on the inner surface of the cup, reduces the slurry to a collection of fine particles upon discharge from the rotating cup, and further atomizes the fuel as it enters the combustion chamber by subjecting it to the high shear force of a high velocity air flow. Accordingly, it is an object of the present invention to provide for improved combustion of a coal-water mixture fuel. It is another object of the present invention to provide an arrangement for introducing a coal-water mixture fuel into a combustion chamber in a manner which provides improved flame control and stability, more efficient combustion of the hydrocarbon fuel, and continuous, reliable burner operation. Yet another object of the present invention is to provide for the continuous, sustained combustion of a coal-water mixture fuel without the need for a secondary combustion source such as natural gas or a liquid hydrocarbon fuel. Still another object of the present invention is to provide a burner arrangement capable of accommodating a coal-water mixture fuel having a wide range of rheological and combustion characteristics in providing for its efficient combustion. 7 figs.

Pyrolysis process for producing condensed stabilized hydrocarbons utilizing a beneficially reactive gas

DOEpatents

Durai-Swamy, Kandaswamy

1982-01-01

In a process for recovery of values contained in solid carbonaceous material, the solid carbonaceous material is comminuted and then subjected to pyrolysis, in the presence of a carbon containing solid particulate source of heat and a beneficially reactive transport gas in a transport flash pyrolysis reactor, to form a pyrolysis product stream. The pyrolysis product stream contains a gaseous mixture and particulate solids. The solids are separated from the gaseous mixture to form a substantially solids-free gaseous stream which comprises volatilized hydrocarbon free radicals newly formed by pyrolysis. Preferably the solid particulate source of heat is formed by oxidizing part of the separated particulate solids. The beneficially reactive transport gas inhibits the reactivity of the char product and the carbon-containing solid particulate source of heat. Condensed stabilized hydrocarbons are obtained by quenching the gaseous mixture stream with a quench fluid which contains a capping agent for stabilizing and terminating newly formed volatilized hydrocarbon free radicals. The capping agent is partially depleted of hydrogen by the stabilization and termination reaction. Hydrocarbons of four or more carbon atoms in the gaseous mixture stream are condensed. A liquid stream containing the stabilized liquid product is then treated or separated into various fractions. A liquid containing the hydrogen depleted capping agent is hydrogenated to form a regenerated capping agent. At least a portion of the regenerated capping agent is recycled to the quench zone as the quench fluid. In another embodiment capping agent is produced by the process, separated from the liquid product mixture, and recycled.

Rogue waves in the multicomponent Mel'nikov system and multicomponent Schrödinger-Boussinesq system

NASA Astrophysics Data System (ADS)

Sun, Baonan; Lian, Zhan

2018-02-01

By virtue of the bilinear method and the KP hierarchy reduction technique, exact explicit rational solutions of the multicomponent Mel'nikov equation and the multicomponent Schrödinger-Boussinesq equation are constructed, which contain multicomponent short waves and single-component long wave. For the multicomponent Mel'nikov equation, the fundamental rational solutions possess two different behaviours: lump and rogue wave. It is shown that the fundamental (simplest) rogue waves are line localised waves which arise from the constant background with a line profile and then disappear into the constant background again. The fundamental line rogue waves can be classified into three: bright, intermediate and dark line rogue waves. Two subclasses of non-fundamental rogue waves, i.e., multirogue waves and higher-order rogue waves are discussed. The multirogue waves describe interaction of several fundamental line rogue waves, in which interesting wave patterns appear in the intermediate time. Higher-order rogue waves exhibit dynamic behaviours that the wave structures start from lump and then retreat back to it. Moreover, by taking the parameter constraints further, general higher-order rogue wave solutions for the multicomponent Schrödinger-Boussinesq system are generated.

Process for hydrogenation of hydrocarbon tars

DOEpatents

Dolbear, Geoffrey E.

1978-07-18

Hydrocarbon tars of high asphaltene content such as tars obtained from pyrolysis of coal are dissolved in a solvent formed from the hydrogenation of the coal tars, and the resultant mixture hydrogenated in the presence of a catalyst at a pressure from about 1500 to 5000 psig at a temperature from about 500.degree. F to about the critical temperature of the solvent to form a light hydrocarbon as a solvent for the tars. Hydrogen content is at least three times the amount of hydrogen consumed.

Multicomponent Gas Storage in Organic Cage Molecules

DOE PAGES

Zhang, Fei; He, Yadong; Huang, Jingsong; ...

2017-05-18

Porous liquids are a promising new class of materials featuring nanoscale cavity units dispersed in liquids that are suitable for applications such as gas storage and separation. In this work, we use molecular dynamics simulations to examine the multicomponent gas storage in a porous liquid consisting of crown-ether-substituted cage molecules dissolved in a 15-crown-5 solvent. We compute the storage of three prototypical small molecules including CO 2, CH 4, and N 2 and their binary mixtures in individual cage molecules. For porous liquids in equilibrium with a binary 1:1 gas mixture bath with partial gas pressure of 27.5 bar, amore » cage molecule shows a selectivity of 4.3 and 13.1 for the CO 2/CH 4 and CO 2/N 2 pairs, respectively. We provide a molecular perspective of how gas molecules are stored in the cage molecule and how the storage of one type of gas molecule is affected by other types of gas molecules. Finally, our results clarify the molecular mechanisms behind the selectivity of such cage molecules toward different gases.« less

Columnar to Nematic Mesophase Transition: Binary Mixtures of Copper Soaps with Hydrocarbons

NASA Astrophysics Data System (ADS)

Seghrouchni, R.; Skoulios, A.

1995-09-01

Copper (II) soaps are known to produce columnar mesophases at high temperatures. The polar groups of the soap molecules are stacked over one another within columns surrounded by the paraffin chains in a disordered conformation and laterally arranged according to a two-dimensional hexagonal lattice. Upon addition of a hydrocarbon, the mesophases swell homogeneously. The hydrocarbon molecules locate themselves among the disordered chains of the soap molecules, the columnar cores remain perfectly unchanged, keeping a constant intra-columnar stacking period, and the hexagonal lattice expands in proportion to the amount of hydrocarbon added to the system. Beyond a certain degree of swelling, the columnar mesophases suddenly turn into a nematic mesophase through a first-order phase transition. The structural elements that align parallel to the nematic director are the very same molecular columns that are involved in the columnar mesophases. The columnar to nematic mesophase transition was studied systematically as a function of the molecular size of the soaps and hydrocarbons used as diluents and discussed on a molecular level, emphasizing such aspects as the persistence length of the paraffin chains and the location of the solvent molecules among the columns.

The virial coefficients of hard hypersphere binary mixtures

NASA Astrophysics Data System (ADS)

Enciso, E.; Almarza, N. G.; Gonzalez, M. A.; Bermejo, F. J.

The third, fourth and fifth virial coefficients of hard hypersphere binary mixtures with dimensionality d = 4, 5 have been calculated for size ratios R ≥0.1, R ı σ22 / σ11 , where σ ii is the diameter of component i . The composition independent partial virial coefficients have been evaluated by Monte Carlo integration of the corresponding Mayer modified star diagrams. The results are compared with the predictions of Santos, S., Yuste, S. B., and Lopez de Haro, M., 1999, Molec. Phys ., 96 , 1 of the equation of state of a multicomponent mixture of hard hyperspheres, and the good agreement gives strong support to the validity of that recipe.

Exploring hydrocarbon-bearing shale formations with multi-component seismic technology and evaluating direct shear modes produced by vertical-force sources

NASA Astrophysics Data System (ADS)

Alkan, Engin

It is essential to understand natural fracture systems embedded in shale-gas reservoirs and the stress fields that influence how induced fractures form in targeted shale units. Multicomponent seismic technology and elastic seismic stratigraphy allow geologic formations to be better images through analysis of different S-wave modes as well as the P-wave mode. Significant amounts of energy produced by P-wave sources radiate through the Earth as downgoing SV-wave energy. A vertical-force source is an effective source for direct SV radiation and provides a pure shear-wave mode (SV-SV) that should reveal crucial information about geologic surfaces located in anisotropic media. SV-SV shear wave modes should carry important information about petrophysical characteristics of hydrocarbon systems that cannot be obtained using other elastic-wave modes. Regardless of the difficulties of extracting good-quality SV-SV signal, direct shear waves as well as direct P and converted S energy should be accounted for in 3C seismic studies. Acquisition of full-azimuth seismic data and sampling data at small intervals over long offsets are required for detailed anisotropy analysis. If 3C3D data can be acquired with improved signal-to-noise ratio, more uniform illumination of targets, increased lateral resolution, more accurate amplitude attributes, and better multiple attenuation, such data will have strong interest by the industry. The objectives of this research are: (1) determine the feasibility of extracting direct SV-SV common-mid-point sections from 3-C seismic surveys, (2) improve the exploration for stratigraphic traps by developing systematic relationship between petrophysical properties and combinations of P and S wave modes, (3) create compelling examples illustrating how hydrocarbon-bearing reservoirs in low-permeable rocks (particularly anisotropic shale formations) can be better characterized using different Swave modes (P-SV, SV-SV) in addition to the conventional P

Oxygen sensor for monitoring gas mixtures containing hydrocarbons

DOEpatents

Ruka, Roswell J.; Basel, Richard A.

1996-01-01

A gas sensor measures O.sub.2 content of a reformable monitored gas containing hydrocarbons H.sub.2 O and/or CO.sub.2, preferably in association with an electrochemical power generation system. The gas sensor has a housing communicating with the monitored gas environment and carries the monitored gas through an integral catalytic hydrocarbon reforming chamber containing a reforming catalyst, and over a solid electrolyte electrochemical cell used for sensing purposes. The electrochemical cell includes a solid electrolyte between a sensor electrode that is exposed to the monitored gas, and a reference electrode that is isolated in the housing from the monitored gas and is exposed to a reference gas environment. A heating element is also provided in heat transfer communication with the gas sensor. A circuit that can include controls operable to adjust operations via valves or the like is connected between the sensor electrode and the reference electrode to process the electrical signal developed by the electrochemical cell. The electrical signal varies as a measure of the equilibrium oxygen partial pressure of the monitored gas. Signal noise is effectively reduced by maintaining a constant temperature in the area of the electrochemical cell and providing a monitored gas at chemical equilibria when contacting the electrochemical cell. The output gas from the electrochemical cell of the sensor is fed back into the conduits of the power generating system.

Oxygen sensor for monitoring gas mixtures containing hydrocarbons

DOEpatents

Ruka, R.J.; Basel, R.A.

1996-03-12

A gas sensor measures O{sub 2} content of a reformable monitored gas containing hydrocarbons, H{sub 2}O and/or CO{sub 2}, preferably in association with an electrochemical power generation system. The gas sensor has a housing communicating with the monitored gas environment and carries the monitored gas through an integral catalytic hydrocarbon reforming chamber containing a reforming catalyst, and over a solid electrolyte electrochemical cell used for sensing purposes. The electrochemical cell includes a solid electrolyte between a sensor electrode that is exposed to the monitored gas, and a reference electrode that is isolated in the housing from the monitored gas and is exposed to a reference gas environment. A heating element is also provided in heat transfer communication with the gas sensor. A circuit that can include controls operable to adjust operations via valves or the like is connected between the sensor electrode and the reference electrode to process the electrical signal developed by the electrochemical cell. The electrical signal varies as a measure of the equilibrium oxygen partial pressure of the monitored gas. Signal noise is effectively reduced by maintaining a constant temperature in the area of the electrochemical cell and providing a monitored gas at chemical equilibria when contacting the electrochemical cell. The output gas from the electrochemical cell of the sensor is fed back into the conduits of the power generating system. 4 figs.

Hepatic gene expression in rainbow trout (Oncorhynchus mykiss) exposed to different hydrocarbon mixtures.

PubMed

Hook, Sharon E; Lampi, Mark A; Febbo, Eric J; Ward, Jeff A; Parkerton, Thomas F

2010-09-01

Traditional biomarkers for hydrocarbon exposure are not induced by all petroleum substances. The objective of this study was to determine if exposure to a crude oil and different refined oils would generate a common hydrocarbon-specific response in gene expression profiles that could be used as generic biomarkers of hydrocarbon exposure. Juvenile rainbow trout (Oncorhynchus mykiss) were exposed to the water accommodated fraction (WAF) of either kerosene, gas oil, heavy fuel oil, or crude oil for 96 h. Tissue was collected for RNA extraction and microarray analysis. Exposure to each WAF resulted in a different list of differentially regulated genes, with few genes in common across treatments. Exposure to crude oil WAF changed the expression of genes including cytochrome P4501A (CYP1A) and glutathione-S-transferase (GST) with known roles in detoxification pathways. These gene expression profiles were compared to others from previous experiments that used a diverse suite of toxicants. Clustering algorithms successfully identified gene expression profiles resulting from hydrocarbon exposure. These preliminary analyses highlight the difficulties of using single genes as diagnostic of petroleum hydrocarbon exposures. Further work is needed to determine if multivariate transcriptomic-based biomarkers may be a more effective tool than single gene studies for exposure monitoring of different oils. Copyright 2010 SETAC.

Process for converting light alkanes to higher hydrocarbons

DOEpatents

Noceti, Richard P.; Taylor, Charles E.

1988-01-01

A process is disclosed for the production of aromatic-rich, gasoline boiling range hydrocarbons from the lower alkanes, particularly from methane. The process is carried out in two stages. In the first, alkane is reacted with oxygen and hydrogen chloride over an oxyhydrochlorination catalyst such as copper chloride with minor proportions of potassium chloride and rare earth chloride. This produces an intermediate gaseous mixture containing water and chlorinated alkanes. The chlorinated alkanes are contacted with a crystalline aluminosilicate catalyst in the hydrogen or metal promoted form to produce gasoline range hydrocarbons with a high proportion of aromatics and a small percentage of light hydrocarbons (C.sub.2 -C.sub.4). The light hydrocarbons can be recycled for further processing over the oxyhydrochlorination catalyst.

Analysis of Multicomponent Adsorption Close to a Dew Point.

PubMed

Shapiro; Stenby

1998-10-15

We develop the potential theory of multicomponent adsorption close to a dew point. The approach is based on an asymptotic adsorption equation (AAE) which is valid in a vicinity of the dew point. By this equation the thickness of the liquid film is expressed through thermodynamic characteristics of the bulk phase. The AAE makes it possible to study adsorption in the regions of both the normal and the retrograde condensation. A simple correlation of the Kelvin radius for capillary condensation and the thickness of the adsorbed film is established. Numerical testing shows good agreement between the AAE and the direct calculations, even if the mixture is not close to a dew point. Copyright 1998 Academic Press.

Lateral Organization of Lipids in Multi-component Liposomes

NASA Astrophysics Data System (ADS)

Ramachandran, Sanoop; Laradji, Mohamed; Sunil Kumar, P. B.

2009-04-01

Inspite of the fluid nature and low elastic modulus, membranes play a crucial role in maintaining the structural integrity of the cell. Recent experiments have challenged the passive nature of the membrane as proposed by the classical fluid mosaic model. Experiments indicate that biomembranes of eukaryotic cells may be laterally organized into small nanoscopic domains, called rafts, which are rich in sphingomyelin and cholesterol. It is largely believed that this in-plane organization is essential for a variety of physiological functions such as signaling, recruitment of specific proteins and endocytosis. However, elucidation of the fundamental issues including the mechanisms leading to the formation of lipid rafts, their stability, and their size remain difficult. This has reiterated the importance of understanding the equilibrium phase behavior and the kinetics of fluid multicomponent lipid membranes before attempts are made to find the effects of more complex mechanisms that may be involved in the formation and stability of lipid rafts. Current increase in interest in the domain formation in multicomponent membranes also stems from the experiments demonstrating fluid-fluid coexistence in mixtures of lipids and cholesterol and the success of several computational models in predicting their behavior. Here we review time dependent Ginzburg Landau model, dynamical triangulation Monte Carlo, and dissipative particle dynamics which are some of the methods that are commonly employed.

On thermal conductivity of gas mixtures containing hydrogen

NASA Astrophysics Data System (ADS)

Zhukov, Victor P.; Pätz, Markus

2017-06-01

A brief review of formulas used for the thermal conductivity of gas mixtures in CFD simulations of rocket combustion chambers is carried out in the present work. In most cases, the transport properties of mixtures are calculated from the properties of individual components using special mixing rules. The analysis of different mixing rules starts from basic equations and ends by very complex semi-empirical expressions. The formulas for the thermal conductivity are taken for the analysis from the works on modelling of rocket combustion chambers. \\hbox {H}_2{-}\\hbox {O}_2 mixtures are chosen for the evaluation of the accuracy of the considered mixing rules. The analysis shows that two of them, of Mathur et al. (Mol Phys 12(6):569-579, 1967), and of Mason and Saxena (Phys Fluids 1(5):361-369, 1958), have better agreement with the experimental data than other equations for the thermal conductivity of multicomponent gas mixtures.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-09-06

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-03-08

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Heterogeneous OH oxidation of motor oil particles causes selective depletion of branched and less cyclic hydrocarbons.

PubMed

Isaacman, Gabriel; Chan, Arthur W H; Nah, Theodora; Worton, David R; Ruehl, Chris R; Wilson, Kevin R; Goldstein, Allen H

2012-10-02

Motor oil serves as a useful model system for atmospheric oxidation of hydrocarbon mixtures typical of anthropogenic atmospheric particulate matter, but its complexity often prevents comprehensive chemical speciation. In this work we fully characterize this formerly "unresolved complex mixture" at the molecular level using recently developed soft ionization gas chromatography techniques. Nucleated motor oil particles are oxidized in a flow tube reactor to investigate the relative reaction rates of observed hydrocarbon classes: alkanes, cycloalkanes, bicycloalkanes, tricycloalkanes, and steranes. Oxidation of hydrocarbons in a complex aerosol is found to be efficient, with approximately three-quarters (0.72 ± 0.06) of OH collisions yielding a reaction. Reaction rates of individual hydrocarbons are structurally dependent: compared to normal alkanes, reaction rates increased by 20-50% with branching, while rates decreased ∼20% per nonaromatic ring present. These differences in rates are expected to alter particle composition as a function of oxidation, with depletion of branched and enrichment of cyclic hydrocarbons. Due to this expected shift toward ring-opening reactions heterogeneous oxidation of the unreacted hydrocarbon mixture is less likely to proceed through fragmentation pathways in more oxidized particles. Based on the observed oxidation-induced changes in composition, isomer-resolved analysis has potential utility for determining the photochemical age of atmospheric particulate matter with respect to heterogeneous oxidation.

Profiling refined hydrocarbon fuels using polar components

USGS Publications Warehouse

Rostad, C.E.; Hostettler, F.D.

2007-01-01

Identification of a fuel released into the environment can be difficult due to biodegradation or weathering. Negative electrospray ionization/mass spectrometry was used to screen for unique polar components in a wide variety of commercial hydrocarbon products and mixtures. These fuels produced unique and relatively simple spectra. When applied to hydrocarbon samples from a large, long-term fuel spill in a relatively cool climate in which the alkane, isoprenoid, and alkylcyclohexane portions had begun to biodegrade or weather, the polar components in these samples had changed little over time. This technique provided rapid fuel identification on hydrocarbons released into the environment, without sample preparation, fractionation, or chromatography. Copyright ?? Taylor & Francis Group, LLC.

A solid-state NMR method to determine domain sizes in multi-component polymer formulations

NASA Astrophysics Data System (ADS)

Schlagnitweit, Judith; Tang, Mingxue; Baias, Maria; Richardson, Sara; Schantz, Staffan; Emsley, Lyndon

2015-12-01

Polymer domain sizes are related to many of the physical properties of polymers. Here we present a solid-state NMR experiment that is capable of measuring domain sizes in multi-component mixtures. The method combines selective excitation of carbon magnetization to isolate a specific component with proton spin diffusion to report on domain size. We demonstrate the method in the context of controlled release formulations, which represents one of today's challenges in pharmaceutical science. We show that we can measure domain sizes of interest in the different components of industrial pharmaceutical formulations at natural isotopic abundance containing various (modified) cellulose derivatives, such as microcrystalline cellulose matrixes that are film-coated with a mixture of ethyl cellulose (EC) and hydroxypropyl cellulose (HPC).

Catalysts for synthesizing various short chain hydrocarbons

DOEpatents

Colmenares, Carlos

1991-01-01

Method and apparatus (10), including novel photocatalysts, are disclosed for the synthesis of various short chain hydrocarbons. Light-transparent SiO.sub.2 aerogels doped with photochemically active uranyl ions (18) are fluidized in a fluidized-bed reactor (12) having a transparent window (16), by hydrogen and CO, C.sub.2 H.sub.4 or C.sub.2 H.sub.6 gas mixtures (20), and exposed to radiation (34) from a light source (32) external to the reactor (12), to produce the short chain hydrocarbons (36).

Surface tensions of solutions containing dicarboxylic acid mixtures

NASA Astrophysics Data System (ADS)

Lee, Jae Young; Hildemann, Lynn M.

2014-06-01

Organic solutes tend to lower the surface tension of cloud condensation nuclei, allowing them to more readily activate. The surface tension of various dicarboxylic acid aerosol mixtures was measured at 20 °C using the Wilhelmy plate method. At lower concentrations, the surface tension of a solution with equi-molar mixtures of dicarboxylic acids closely followed that of a solution with the most surface-active organic component alone. Measurements of surface tension for these mixtures were lower than predictions using Henning's model and the modified Szyszkowski equation, by ˜1-2%. The calculated maximum surface excess (Γmax) and inverse Langmuir adsorption coefficient (β) from the modified Szyszkowski equation were both larger than measured values for 6 of the 7 mixtures tested. Accounting for the reduction in surface tension in the Köhler equation reduced the critical saturation ratio for these multi-component mixtures - changes were negligible for dry diameters of 0.1 and 0.5 μm, but a reduction from 1.0068 to 1.0063 was seen for the 4-dicarboxylic acid mixture with a dry diameter of 0.05 μm.

Mechanism reduction for multicomponent surrogates: A case study using toluene reference fuels

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

Niemeyer, Kyle E.; Sung, Chih-Jen

Strategies and recommendations for performing skeletal reductions of multicomponent surrogate fuels are presented, through the generation and validation of skeletal mechanisms for a three-component toluene reference fuel. Using the directed relation graph with error propagation and sensitivity analysis method followed by a further unimportant reaction elimination stage, skeletal mechanisms valid over comprehensive and high-temperature ranges of conditions were developed at varying levels of detail. These skeletal mechanisms were generated based on autoignition simulations, and validation using ignition delay predictions showed good agreement with the detailed mechanism in the target range of conditions. When validated using phenomena other than autoignition, suchmore » as perfectly stirred reactor and laminar flame propagation, tight error control or more restrictions on the reduction during the sensitivity analysis stage were needed to ensure good agreement. In addition, tight error limits were needed for close prediction of ignition delay when varying the mixture composition away from that used for the reduction. In homogeneous compression-ignition engine simulations, the skeletal mechanisms closely matched the point of ignition and accurately predicted species profiles for lean to stoichiometric conditions. Furthermore, the efficacy of generating a multicomponent skeletal mechanism was compared to combining skeletal mechanisms produced separately for neat fuel components; using the same error limits, the latter resulted in a larger skeletal mechanism size that also lacked important cross reactions between fuel components. Based on the present results, general guidelines for reducing detailed mechanisms for multicomponent fuels are discussed.« less

Mechanism reduction for multicomponent surrogates: A case study using toluene reference fuels

DOE PAGES

Niemeyer, Kyle E.; Sung, Chih-Jen

2014-11-01

Strategies and recommendations for performing skeletal reductions of multicomponent surrogate fuels are presented, through the generation and validation of skeletal mechanisms for a three-component toluene reference fuel. Using the directed relation graph with error propagation and sensitivity analysis method followed by a further unimportant reaction elimination stage, skeletal mechanisms valid over comprehensive and high-temperature ranges of conditions were developed at varying levels of detail. These skeletal mechanisms were generated based on autoignition simulations, and validation using ignition delay predictions showed good agreement with the detailed mechanism in the target range of conditions. When validated using phenomena other than autoignition, suchmore » as perfectly stirred reactor and laminar flame propagation, tight error control or more restrictions on the reduction during the sensitivity analysis stage were needed to ensure good agreement. In addition, tight error limits were needed for close prediction of ignition delay when varying the mixture composition away from that used for the reduction. In homogeneous compression-ignition engine simulations, the skeletal mechanisms closely matched the point of ignition and accurately predicted species profiles for lean to stoichiometric conditions. Furthermore, the efficacy of generating a multicomponent skeletal mechanism was compared to combining skeletal mechanisms produced separately for neat fuel components; using the same error limits, the latter resulted in a larger skeletal mechanism size that also lacked important cross reactions between fuel components. Based on the present results, general guidelines for reducing detailed mechanisms for multicomponent fuels are discussed.« less

Multicomponent Implant Releasing Dexamethasone

NASA Astrophysics Data System (ADS)

Nikkola, L.; Vapalahti, K.; Ashammakhi, N.

2008-02-01

Several inflammatory conditions are usually treated with corticosteroids. There are various problems like side effects with traditional applications of steroids, e.g. topical, or systemic routes. Local drug delivery systems have been studied and developed to gain more efficient administration with fewer side effects. Earlier, we reported on developing Dexamethasone (DX) releasing biodegradable fibers. However, their drug release properties were not satisfactory in terms of onset of drug release. Thus, we assessed the development of multicomponent (MC) implant to enhance earlier drug release from such biodegradable fibers. Poly (lactide-co-glycolide) (PLGA) and 2 wt-% and 8 wt-% DX were compounded and extruded with twin-screw extruder to form of fibers. Some of the fibers were sterilized to obtain a change in drug release properties. Four different fiber classes were studied: 2 wt-%, 8 wt-%, sterilized 2 wt-%, and sterilized 8 wt-%. 3×4 different DX-releasing fibers were then heat-pressed to form one multicomponent rod. Half of the rods where sterilized. Drug release was measured from initial fibers and multicomponent rods using a UV/VIS spectrometer. Shear strength and changes in viscosity were also measured. Drug release studies showed that drug release commenced earlier from multicomponent rods than from component fibers. Drug release from multicomponent rods lasted from day 30 to day 70. The release period of sterilized rods extended from day 23 to day 57. When compared to the original component fibers, the drug release from MC rods commenced earlier. The initial shear strength of MC rods was 135 MPa and decreased to 105 MPa during four weeks of immersion in phosphate buffer solution. Accordingly, heat pressing has a positive effect on drug release. After four weeks in hydrolysis, no disintegration was observed.

Statistical mechanics of binary mixture adsorption in metal-organic frameworks in the osmotic ensemble.

PubMed

Dunne, Lawrence J; Manos, George

2018-03-13

Although crucial for designing separation processes little is known experimentally about multi-component adsorption isotherms in comparison with pure single components. Very few binary mixture adsorption isotherms are to be found in the literature and information about isotherms over a wide range of gas-phase composition and mechanical pressures and temperature is lacking. Here, we present a quasi-one-dimensional statistical mechanical model of binary mixture adsorption in metal-organic frameworks (MOFs) treated exactly by a transfer matrix method in the osmotic ensemble. The experimental parameter space may be very complex and investigations into multi-component mixture adsorption may be guided by theoretical insights. The approach successfully models breathing structural transitions induced by adsorption giving a good account of the shape of adsorption isotherms of CO 2 and CH 4 adsorption in MIL-53(Al). Binary mixture isotherms and co-adsorption-phase diagrams are also calculated and found to give a good description of the experimental trends in these properties and because of the wide model parameter range which reproduces this behaviour suggests that this is generic to MOFs. Finally, a study is made of the influence of mechanical pressure on the shape of CO 2 and CH 4 adsorption isotherms in MIL-53(Al). Quite modest mechanical pressures can induce significant changes to isotherm shapes in MOFs with implications for binary mixture separation processes.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

Statistical mechanics of binary mixture adsorption in metal-organic frameworks in the osmotic ensemble

NASA Astrophysics Data System (ADS)

Dunne, Lawrence J.; Manos, George

2018-03-01

Although crucial for designing separation processes little is known experimentally about multi-component adsorption isotherms in comparison with pure single components. Very few binary mixture adsorption isotherms are to be found in the literature and information about isotherms over a wide range of gas-phase composition and mechanical pressures and temperature is lacking. Here, we present a quasi-one-dimensional statistical mechanical model of binary mixture adsorption in metal-organic frameworks (MOFs) treated exactly by a transfer matrix method in the osmotic ensemble. The experimental parameter space may be very complex and investigations into multi-component mixture adsorption may be guided by theoretical insights. The approach successfully models breathing structural transitions induced by adsorption giving a good account of the shape of adsorption isotherms of CO2 and CH4 adsorption in MIL-53(Al). Binary mixture isotherms and co-adsorption-phase diagrams are also calculated and found to give a good description of the experimental trends in these properties and because of the wide model parameter range which reproduces this behaviour suggests that this is generic to MOFs. Finally, a study is made of the influence of mechanical pressure on the shape of CO2 and CH4 adsorption isotherms in MIL-53(Al). Quite modest mechanical pressures can induce significant changes to isotherm shapes in MOFs with implications for binary mixture separation processes. This article is part of the theme issue `Modern theoretical chemistry'.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

NASA Astrophysics Data System (ADS)

Pfrang, C.; Shiraiwa, M.; Pöschl, U.

2011-04-01

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles representative of atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant time scales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

NASA Astrophysics Data System (ADS)

Pfrang, C.; Shiraiwa, M.; Pöschl, U.

2011-07-01

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Detonability of hydrocarbon fuels in air

NASA Technical Reports Server (NTRS)

Beeson, H. D.; Mcclenagan, R. D.; Bishop, C. V.; Benz, F. J.; Pitz, W. J.; Westbrook, C. K.; Lee, J. H. S.

1991-01-01

Studies were conducted of the detonation of gas-phase mixtures of n-hexane and JP-4, with oxidizers as varied as air and pure oxygen, measuring detonation velocities and cell sizes as a function of stoichiometry and diluent concentration. The induction length of a one-dimensional Zeldovich-von Neumann-Doering detonation was calculated on the basis of a theoretical model that employed the reaction kinetics of the hydrocarbon fuels used. Critical energy and critical tube diameter are compared for a relative measure of the heavy hydrocarbon fuels studied; detonation sensitivity appears to increase slightly with increasing carbon number.

Secondhand Smoke-Prevalent Polycyclic Aromatic Hydrocarbon Binary Mixture-Induced Specific Mitogenic and Pro-inflammatory Cell Signaling Events in Lung Epithelial Cells

PubMed Central

Osgood, Ross S.; Upham, Brad L.; Bushel, Pierre R.; Velmurugan, Kalpana; Xiong, Ka-Na

2017-01-01

Abstract Low molecular weight polycyclic aromatic hydrocarbons (LMW PAHs; < 206.3 g/mol) are prevalent and ubiquitous environmental contaminants, presenting a human health concern, and have not been as thoroughly studied as the high MW PAHs. LMW PAHs exert their pulmonary effects, in part, through P38-dependent and -independent mechanisms involving cell-cell communication and the production of pro-inflammatory mediators known to contribute to lung disease. Specifically, we determined the effects of two representative LMW PAHs, 1-methylanthracene (1-MeA) and fluoranthene (Flthn), individually and as a binary PAH mixture on the dysregulation of gap junctional intercellular communication (GJIC) and connexin 43 (Cx43), activation of mitogen activated protein kinases (MAPK), and induction of inflammatory mediators in a mouse non-tumorigenic alveolar type II cell line (C10). Both 1-MeA, Flthn, and the binary PAH mixture of 1-MeA and Flthn dysregulated GJIC in a dose and time-dependent manner, reduced Cx43 protein, and activated the following MAPKs: P38, ERK1/2, and JNK. Inhibition of P38 MAPK prevented PAH-induced dysregulation of GJIC, whereas inhibiting ERK and JNK did not prevent these PAHs from dysregulating GJIC indicating a P38-dependent mechanism. A toxicogenomic approach revealed significant P38-dependent and -independent pathways involved in inflammation, steroid synthesis, metabolism, and oxidative responses. Genes in these pathways were significantly altered by the binary PAH mixture when compared with 1-MeA and Flthn alone suggesting interactive effects. Exposure to the binary PAH mixture induced the production and release of cytokines and metalloproteinases from the C10 cells. Our findings with a binary mixture of PAHs suggest that combinations of LMW PAHs may elicit synergistic or additive inflammatory responses which warrant further investigation and confirmation. PMID:28329830

Activation of hydrocarbons and the octane number

NASA Technical Reports Server (NTRS)

Peschard, Marcel

1939-01-01

This report presents an examination of the history of research on engine knocking and the various types of fuels used in the investigations of this phenomenon. According to this report, the spontaneous ignition of hydrocarbons doped with oxygen follows the logarithmic law within a certain temperature range, but not above 920 degrees K. Having extended the scope of investigations to prove hydrocarbons, the curves of the mixtures burned by air should then be established by progressive replacement of pure iso-octane with heptane. Pentane was also examined in this report.

The Solidification of Multicomponent Alloys

PubMed Central

Boettinger, William J.

2017-01-01

Various topics taken from the author’s research portfolio that involve multicomponent alloy solidification are reviewed. Topics include: ternary eutectic solidification and Scheil-Gulliver paths in ternary systems. A case study of the solidification of commercial 2219 aluminum alloy is described. Also described are modifications of the Scheil-Gulliver analysis to treat dendrite tip kinetics and solid diffusion for multicomponent alloys. PMID:28819348

Quantification of petroleum-type hydrocarbons in avian tissue

USGS Publications Warehouse

Gay, M.L.; Belisle, A.A.; Patton, J.F.

1980-01-01

Methods were developed for the analysis of 16 hydrocarbons in avian tissue. Mechanical extraction with pentane was followed by clean-up on Florisil and Silicar. Residues were determined by gas—liquid chromatography and gas—liquid, chromatography—mass spectrometry. The method was applied to the analysis of liver, kidney, fat, and brain tissue of mallard ducks (Anas platyrhynchos) fed a mixture of hydrocarbons. Measurable concentrations of all compounds analyzed were present in all tissues except brain. Highest concentrations were in fat.

In-situ process for recovering hydrocarbons from a diatomite-type formation

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

Davis, B.W.

1984-12-04

An in-situ process for recovering hydrocarbons from a diatomite-type formation which comprises contacting the diatomite formation with a C/sub 4/-C/sub 10/ alcohol and thereafter displacing the hydrocarbon-alcohol mixture with an aqueous alkaline solution towards a production well. The aqueous alkaline solution can be displaced with additional solution or another suitable medium such as a connate water drive.

Insight into unresolved complex mixtures of aromatic hydrocarbons in heavy oil via two-dimensional gas chromatography coupled with time-of-flight mass spectrometry analysis.

PubMed

Weng, Na; Wan, Shan; Wang, Huitong; Zhang, Shuichang; Zhu, Guangyou; Liu, Jingfu; Cai, Di; Yang, Yunxu

2015-06-12

The aromatic hydrocarbon fractions of five crude oils representing a natural sequence of increasing degree of biodegradation from the Liaohe Basin, NE, China, were analyzed using conventional gas chromatography-mass spectrometry (GC-MS) and comprehensive two-dimensional gas chromatography (GC×GC). Because of the limited peak capability and low resolution, compounds in the aromatic fraction of a heavily biodegraded crude oil that were analyzed by GC-MS appeared as unresolved complex mixtures (UCMs) or GC "humps". They could be separated based on their polarity by GC×GC. UCMs are composed mainly of aromatic biomarkers and aromatic hydrocarbons with branched alkanes or cycloalkanes substituents. The quantitative results achieved by GC×GC-FID were shown that monoaromatic hydrocarbons account for the largest number and mass of UCMs in the aromatic hydrocarbon fraction of heavily biodegraded crude oil, at 45% by mass. The number and mass of diaromatic hydrocarbons ranks second at 33% by mass, followed by the aromatic biomarker compounds, triaromatic, tetraaromatic, and pentaaromatic hydrocarbons, that account for 10%, 6%, 1.5%, and 0.01% of all aromatic compounds by mass, respectively. In the heavily biodegraded oil, compounds with monocyclic cycloalkane substituents account for the largest proportion of mono- and diaromatic hydrocarbons, respectively. The C4-substituted compounds account for the largest proportion of naphthalenes and the C3-substituted compounds account for the largest proportion of phenanthrenes, which is very different from non-biodegraded, slightly biodegraded, and moderately biodegraded crude oil. It is inferred that compounds of monoaromatic, diaromatic and triaromatic hydrocarbons are affected by biodegradation, that compounds with C1-, C2-substituents are affected by the increase in degree of biodegradation, and that their relative content decreased, whereas compounds with C3-substituents or more were affected slightly or unaffected, and their

On Boiling of Crude Oil under Elevated Pressure

NASA Astrophysics Data System (ADS)

Pimenova, Anastasiya V.; Goldobin, Denis S.

2016-02-01

We construct a thermodynamic model for theoretical calculation of the boiling process of multicomponent mixtures of hydrocarbons (e.g., crude oil). The model governs kinetics of the mixture composition in the course of the distillation process along with the boiling temperature increase. The model heavily relies on the theory of dilute solutions of gases in liquids. Importantly, our results are applicable for modelling the process under elevated pressure (while the empiric models for oil cracking are not scalable to the case of extreme pressure), such as in an oil field heated by lava intrusions.

Thermophysical Properties of Fluid Latent Heat Storage Material using Urea-Water Mixture

NASA Astrophysics Data System (ADS)

Hokamura, Taku; Ohkubo, Hidetoshi; Ashizawa, Kiyonori

This study is concerned with the measurement of thermophysical properties of a urea-water mixture with the aim of adopting the mixture as a latent heat storage material for air-conditioning systems. The urea-water mixture is made of natural substances and has a good fluidity. The urea concentration in the mixture was controlled by measuring the refractive index of the mixture. Being a multi-component substance, a urea-water solution has a liquid-solid co-existent phase on a phase-diagram. Therefore, the liquidus temperature was measured to establish a relationship between the fraction of the solid-phase and temperature. Furthermore, apparent values of specific heat and coefficient of viscosity were measured in the two-phase region where the solid phase is ice. The apparent specific heat and coefficient of viscosity were measure by using an adiabatic calorimeter and a stirring torque meter respectively. The results revealed that the urea-water mixture can probably be used as a latent heat storage material of good fluidity.

Comparative analysis of metagenomes from three methanogenic hydrocarbon-degrading enrichment cultures with 41 environmental samples.

PubMed

Tan, Boonfei; Fowler, S Jane; Abu Laban, Nidal; Dong, Xiaoli; Sensen, Christoph W; Foght, Julia; Gieg, Lisa M

2015-09-01

Methanogenic hydrocarbon metabolism is a key process in subsurface oil reservoirs and hydrocarbon-contaminated environments and thus warrants greater understanding to improve current technologies for fossil fuel extraction and bioremediation. In this study, three hydrocarbon-degrading methanogenic cultures established from two geographically distinct environments and incubated with different hydrocarbon substrates (added as single hydrocarbons or as mixtures) were subjected to metagenomic and 16S rRNA gene pyrosequencing to test whether these differences affect the genetic potential and composition of the communities. Enrichment of different putative hydrocarbon-degrading bacteria in each culture appeared to be substrate dependent, though all cultures contained both acetate- and H2-utilizing methanogens. Despite differing hydrocarbon substrates and inoculum sources, all three cultures harbored genes for hydrocarbon activation by fumarate addition (bssA, assA, nmsA) and carboxylation (abcA, ancA), along with those for associated downstream pathways (bbs, bcr, bam), though the cultures incubated with hydrocarbon mixtures contained a broader diversity of fumarate addition genes. A comparative metagenomic analysis of the three cultures showed that they were functionally redundant despite their enrichment backgrounds, sharing multiple features associated with syntrophic hydrocarbon conversion to methane. In addition, a comparative analysis of the culture metagenomes with those of 41 environmental samples (containing varying proportions of methanogens) showed that the three cultures were functionally most similar to each other but distinct from other environments, including hydrocarbon-impacted environments (for example, oil sands tailings ponds and oil-affected marine sediments). This study provides a basis for understanding key functions and environmental selection in methanogenic hydrocarbon-associated communities.

Studies of Particle Packings in Mixtures of Pharmaceutical Excipients

NASA Astrophysics Data System (ADS)

Bentham, Craig; Dutt, Meenakshi; Hancock, Bruno; Elliott, James

2005-03-01

Pharmaceutical powder blends used to generate tablets are complex multicomponent mixtures of the drug powder and excipients which facilitate the delivery of the required drug. The individual constituents of these blends can be noncohesive and cohesive powders. We study the geometric and mechanical characteristics of idealized mixtures of excipient particle packings, for a small but representative number of dry noncohesive particles, generated via gravitational compaction followed by uniaxial compaction. We discuss particle packings in 2- and 3- component mixtures of microcrystalline cellulose (MCC) & lactose and MCC, starch & lactose, respectively. We have computed the evolution of the force and stress distributions in monodisperse and polydisperse mixtures comprised of equal parts of each excipient; comparisons are made with results for particles packings of pure blends of MCC and lactose. We also compute the stress-strain relations for these mixtures. In order to obtain insight into details of the particle packings, we calculate the coordination number, packing fraction, radial distribution functions and contact angle distributions for the various mixtures. The numerical experiments have been performed on spheroidal idealizations of the excipient grains using Discrete Element Method simulations (Dutt et al., 2004 to be published).

Turbulent Burning Velocities of Two-Component Fuel Mixtures of Methane, Propane and Hydrogen

NASA Astrophysics Data System (ADS)

Kido, Hiroyuki; Nakahara, Masaya; Hashimoto, Jun; Barat, Dilmurat

In order to clarify the turbulent burning velocity of multi-component fuel mixtures, both lean and rich two-component fuel mixtures, in which methane, propane and hydrogen were used as fuels, were prepared while maintaining the laminar burning velocity approximately constant. A distinct difference in the measured turbulent burning velocity at the same turbulence intensity is observed for two-component fuel mixtures having different addition rates of fuel, even the laminar burning velocities are approximately the same. The burning velocities of lean mixtures change almost constantly as the rate of addition changes, whereas the burning velocities of the rich mixtures show no such tendency. This trend can be explained qualitatively based on the mean local burning velocity, which is estimated by taking into account the preferential diffusion effect for each fuel component. In addition, a model of turbulent burning velocity proposed for single-component fuel mixtures may be applied to two-component fuel mixtures by considering the estimated mean local burning velocity of each fuel.

Catalysts and process for liquid hydrocarbon fuel production

DOEpatents

White, Mark G.; Ranaweera, Samantha A.; Henry, William P.

2016-08-02

The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality distillates, gasoline components, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel supported bimetallic ion complex catalyst for conversion, and provides methods of preparing such novel catalysts and use of the novel catalysts in the process and system of the invention.

Method for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, Gregory A.; Thomas, Charles P.

1995-01-01

A system for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste).

Method for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, G.A.; Thomas, C.P.

1995-10-03

A system is described for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste). 4 figs.

Apparatus for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, G.A.; Thomas, C.P.

1996-02-13

A system is described for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste). 4 figs.

Apparatus for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, Gregory A.; Thomas, Charles P.

1996-01-01

A system for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste).

Biodegradation of individual and multiple chlorinated aliphatic hydrocarbons by methane-oxidizing cultures.

PubMed Central

Chang, H L; Alvarez-Cohen, L

1996-01-01

The microbial degradation of chlorinated and nonchlorinated methanes, ethanes, and ethanes by a mixed methane-oxidizing culture grown under chemostat and batch conditions is evaluated and compared with that by two pure methanotrophic strains: CAC1 (isolated from the mixed culture) and Methylosinus trichosporium OB3b. With the exception of 1,1-dichloroethylene, the transformation capacity (Tc) for each chlorinated aliphatic hydrocarbon was generally found to be in inverse proportion to its chlorine content within each aliphatic group (i.e., methanes, ethanes, and ethenes), whereas similar trends were not observed for degradation rate constants. Tc trends were similar for all methane-oxidizing cultures tested. None of the cultures were able to degrade the fully chlorinated aliphatics such as perchloroethylene and carbon tetrachloride. Of the four cultures tested, the chemostat-grown mixed culture exhibited the highest Tc for trichloroethylene, cis-1,2-dichloroethylene, tetrachloroethane, 1,1,1-trichloroethane, and 1,2-dichloroethane, whereas the pure batch-grown OB3b culture exhibited the highest Tc for all other compounds tested. The product toxicity of chlorinated aliphatic hydrocarbons in a mixture containing multiple compounds was cumulative and predictable when using parameters measured from the degradation of individual compounds. The Tc for each chlorinated aliphatic hydrocarbon in a mixture (Tcmix) and the total Tc for the mixture (sigma Tcmix) are functions of the individual Tc, the initial substrate concentration (S0), and the first-order rate constant (k/Ks) of each compound in the mixture, indicating the importance of identifying the properties and compositions of all potentially degradable compounds in a contaminant mixture. PMID:8795228

Viscosities of nonelectrolyte liquid mixtures. II. Binary and quaternary systems of some n-alkanes

NASA Astrophysics Data System (ADS)

Wakefield, D. L.; Marsh, K. N.; Zwolinski, B. J.

1988-01-01

This paper is the second in a series of viscosity and density studies on multicomponent mixtures of n-alkanes from 303 to 338 K. Reported here are the results of binary mixtures of n-tetracosane + n-octane as well as quaternary mixtures of n-tetracosane + n-octane + n-decane + n-hexane at 318.16, 328.16, and 338.16 K. Viscosities were determined using a standard U-tube Ostwald viscometer, and densities were determined using a flask-type pycnometer. Empirical relations tested include the Grunberg and Nissan equation and the method of corresponding states. In addition, comparisons were made regarding the behavior of this quaternary system and homologous binary mixtures of n-hexadecane + n-octane and n-tetracosane + n-octane at the same temperatures.

Laser ultrasonic multi-component imaging

DOEpatents

Williams, Thomas K [Federal Way, WA; Telschow, Kenneth [Des Moines, WA

2011-01-25

Techniques for ultrasonic determination of the interfacial relationship of multi-component systems are discussed. In implementations, a laser energy source may be used to excite a multi-component system including a first component and a second component at least in partial contact with the first component. Vibrations resulting from the excitation may be detected for correlation with a resonance pattern indicating if discontinuity exists at the interface of the first and second components.

Coherent Raman scattering with incoherent light for a multiply resonant mixture: Theory

NASA Astrophysics Data System (ADS)

Kirkwood, Jason C.; Ulness, Darin J.; Stimson, Michael J.; Albrecht, A. C.

1998-02-01

The theory for coherent Raman scattering (CRS) with broadband incoherent light is presented for a multiply resonant, multicomponent mixture of molecules that exhibits simultaneous multiple resonances with the frequencies of the driving fields. All possible pairwise hyperpolarizability contributions to the signal intensity are included in the theoretical treatment-(resonant-resonant, resonant-nonresonant, and nonresonant-nonresonant correlations between chromophores) and it is shown how the different types of correlations manifest themselves as differently behaved components of the signal intensity. The Raman resonances are modeled as Lorentzians in the frequency domain, as is the spectral density of the incoherent light. The analytic results for this multiply resonant mixture are presented and applied to a specific binary mixture. These analytic results will be used to recover frequencies and dephasing times in a series of experiments on multiply resonant mixtures.

Secondhand Smoke-Prevalent Polycyclic Aromatic Hydrocarbon Binary Mixture-Induced Specific Mitogenic and Pro-inflammatory Cell Signaling Events in Lung Epithelial Cells.

PubMed

Osgood, Ross S; Upham, Brad L; Bushel, Pierre R; Velmurugan, Kalpana; Xiong, Ka-Na; Bauer, Alison K

2017-05-01

Low molecular weight polycyclic aromatic hydrocarbons (LMW PAHs; < 206.3 g/mol) are prevalent and ubiquitous environmental contaminants, presenting a human health concern, and have not been as thoroughly studied as the high MW PAHs. LMW PAHs exert their pulmonary effects, in part, through P38-dependent and -independent mechanisms involving cell-cell communication and the production of pro-inflammatory mediators known to contribute to lung disease. Specifically, we determined the effects of two representative LMW PAHs, 1-methylanthracene (1-MeA) and fluoranthene (Flthn), individually and as a binary PAH mixture on the dysregulation of gap junctional intercellular communication (GJIC) and connexin 43 (Cx43), activation of mitogen activated protein kinases (MAPK), and induction of inflammatory mediators in a mouse non-tumorigenic alveolar type II cell line (C10). Both 1-MeA, Flthn, and the binary PAH mixture of 1-MeA and Flthn dysregulated GJIC in a dose and time-dependent manner, reduced Cx43 protein, and activated the following MAPKs: P38, ERK1/2, and JNK. Inhibition of P38 MAPK prevented PAH-induced dysregulation of GJIC, whereas inhibiting ERK and JNK did not prevent these PAHs from dysregulating GJIC indicating a P38-dependent mechanism. A toxicogenomic approach revealed significant P38-dependent and -independent pathways involved in inflammation, steroid synthesis, metabolism, and oxidative responses. Genes in these pathways were significantly altered by the binary PAH mixture when compared with 1-MeA and Flthn alone suggesting interactive effects. Exposure to the binary PAH mixture induced the production and release of cytokines and metalloproteinases from the C10 cells. Our findings with a binary mixture of PAHs suggest that combinations of LMW PAHs may elicit synergistic or additive inflammatory responses which warrant further investigation and confirmation. © The Author 2017. Published by Oxford University Press on behalf of the Society of Toxicology

Quantum turbulence in cold multicomponent matter

NASA Astrophysics Data System (ADS)

Pshenichnyuk, Ivan A.

2018-02-01

Quantum vortices are pivotal for understanding of phenomena in quantum hydrodynamics. Vortices were observed in different physical systems like trapped dilute Bose-Einstein condensates, liquid helium, exciton-polariton condensates and other types of systems. Foreign particles attached to the vortices often serve for a visualization of the vortex shape and kinematics in superfluid experiments. Fascinating discoveries were made in the field of cold quantum mixtures, where vortices created in one component may interact with the other component. This works raise the fundamental question of the interaction between quantum vortices and matter. The generalized nonlinear Schrodinger equation based formalism is applied here to model three different processes involving the interaction of quantum vortices with foreign particles: propagation of a fast classical particle in a superfluid under the influence of sound waves, scattering of a single fermion by a quantized vortex line and dynamics of vortex pairs doped with heavy bosonic matter. The obtained results allow to to clarify the details of recent experiments and acquire a better understanding of the multicomponent quantum turbulence.

Applicability of Separation Potentials to Determining the Parameters of Cascade Efficiency in Enrichment of Ternary Mixtures

NASA Astrophysics Data System (ADS)

Palkin, V. A.; Igoshin, I. S.

2017-01-01

The separation potentials suggested by various researchers for separating multicomponent isotopic mixtures are considered. An estimation of their applicability to determining the parameters of the efficiency of enrichment of a ternary mixture in a cascade with an optimum scheme of connection of stages made up of elements with three takeoffs is carried out. The separation potential most precisely characterizing the separative power and other efficiency parameters of stages and cascade schemes has been selected based on the results of the estimation made.

Measurement of viscosity of gaseous mixtures at atmospheric pressure

NASA Technical Reports Server (NTRS)

Singh, J. J.; Mall, G. H.; Chegini, H.

1986-01-01

Coefficients of viscosity of various types of gas mixtures, including simulated natural-gas samples, have been measured at atmospheric pressure and room temperature using a modified capillary tube method. Pressure drops across the straight capillary tube section of a thermal mass flowmeter were measured for small, well-defined, volume flow rates for the test gases and for standard air. In this configuration, the flowmeter provides the volumetric flow rates as well as a well-characterized capillary section for differential pressure measurements across it. The coefficients of viscosity of the test gases were calculated using the reported value of 185.6 micro P for the viscosity of air. The coefficients of viscosity for the test mixtures were also calculated using Wilke's approximation of the Chapman-Enskog (C-E) theory. The experimental and calculated values for binary mixtures are in agreement within the reported accuracy of Wilke's approximation of the C-E theory. However, the agreement for multicomponent mixtures is less satisfactory, possible because of the limitations of Wilkes's approximation of the classical dilute-gas state model.

Basic Considerations in the Combustion of Hydrocarbon Fuels with Air

NASA Technical Reports Server (NTRS)

Barnett, Henry C; Hibbard, Robert R

1957-01-01

Basic combustion research is collected, collated, and interpreted as it applies to flight propulsion. The following fundamental processes are treated in separate chapters: atomization and evaporation of liquid fuels, flow and mixing processes in combustion chambers, ignition and flammability of hydrocarbon fuels, laminar flame propagation, turbulent flames, flame stabilization, diffusion flames, oscillations in combustors, and smoke and coke formation in the combustion of hydrocarbon-air mixtures. Theoretical background, basic experimental data, and practical significance to flight propulsion are presented.

Synergy and other ineffective mixture risk definitions.

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

Hertzberg, R.; MacDonell, M.; Environmental Assessment

2002-04-08

A substantial effort has been spent over the past few decades to label toxicologic interaction outcomes as synergistic, antagonistic, or additive. Although useful in influencing the emotions of the public and the press, these labels have contributed fairly little to our understanding of joint toxic action. Part of the difficulty is that their underlying toxicological concepts are only defined for two chemical mixtures, while most environmental and occupational exposures are to mixtures of many more chemicals. Furthermore, the mathematical characterizations of synergism and antagonism are inextricably linked to the prevailing definition of 'no interaction,' instead of some intrinsic toxicological property.more » For example, the US EPA has selected dose addition as the no-interaction definition for mixture risk assessment, so that synergism would represent toxic effects that exceed those predicted from dose addition. For now, labels such as synergism are useful to regulatory agencies, both for qualitative indications of public health risk as well as numerical decision tools for mixture risk characterization. Efforts to quantify interaction designations for use in risk assessment formulas, however, are highly simplified and carry large uncertainties. Several research directions, such as pharmacokinetic measurements and models, and toxicogenomics, should promote significant improvements by providing multi-component data that will allow biologically based mathematical models of joint toxicity to replace these pairwise interaction labels in mixture risk assessment procedures.« less

A new method for multicomponent activity coefficients of electrolytes in aqueous atmospheric aerosols

NASA Astrophysics Data System (ADS)

Zaveri, Rahul A.; Easter, Richard C.; Wexler, Anthony S.

2005-01-01

Three-dimensional models of atmospheric inorganic aerosols need accurate and computationally efficient parameterizations of activity coefficients of various electrolytes in multicomponent aqueous solutions. In this paper, we extend the Taylor's series expansion mixing rule used by C. Wagner in 1952 for estimating activity coefficients in dilute alloy solutions to aqueous electrolyte solutions at any concentration. The resulting method, called the multicomponent Taylor expansion method (MTEM), estimates the mean activity coefficient of an electrolyte in a multicomponent solution on the basis of its values in binary solutions of all the electrolytes present in the mixture at the solution water activity aw, assuming aw is equal to the ambient relative humidity. MTEM is applied here for atmospheric aerosol systems containing H+, NH4+, Na+, Ca2+, SO42-, HSO4-, NO3-, and Cl- ions. The aerosol water content is calculated using the Zdanovskii-Stokes-Robinson (ZSR) method. For self-consistency, most of the MTEM and ZSR parameters are derived using the comprehensive Pitzer-Simonson-Clegg model at 298.15 K and are valid for an aw range of 0.2-0.97. Because CaSO4 is sparingly soluble, it is treated as a solid in the model over the entire aw range. MTEM is evaluated for several multicomponent systems representing various continental and marine aerosols and is contrasted against the mixing rule of C. L. Kusik and H. P. Meissner and of L. A. Bromley and the newer approach of S. Metzger and colleagues. Predictions of MTEM are found to be generally within a factor of 0.8-1.25 of the comprehensive Pitzer-Simonson-Clegg model and are shown to be significantly more accurate than predictions of the other three methods. MTEM also yields a noniterative solution of the bisulfate ion dissociation in sulfate-rich systems: a major computational advantage over other ionic-strength-based methods that require an iterative solution. CPU time requirements of MTEM relative to other methods for

Investigation of simultaneous biosorption of copper(II) and chromium(VI) on dried Chlorella vulgaris from binary metal mixtures: Application of multicomponent adsorption isotherms

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

Aksu, Z.; Acikel, U.; Kutsal, T.

1999-02-01

Although the biosorption of single metal ions to various kinds of microorganisms has been extensively studied and the adsorption isotherms have been developed for only the single metal ion situation, very little attention has been given to the bioremoval and expression of adsorption isotherms of multimetal ions systems. In this study the simultaneous biosorption of copper(II) and chromium(VI) to Chlorella vulgaris from a binary metal mixture was studied and compared with the single metal ion situation in a batch stirred system. The effects of pH and single- and dual-metal ion concentrations on the equilibrium uptakes were investigated. In previous studiesmore » the optimum biosorption pH had been determined as 4.0 for copper(II) and as 2.0 for chromium(VI). Multimetal ion biosorption studies were performed at these two pH values. It was observed that the equilibrium uptakes of copper(II) or chromium(VI) ions were changed due to the biosorption pH and the presence of other metal ions. Adsorption isotherms were developed for both single- and dual-metal ions systems at these two pH values, and expressed by the mono- and multicomponent Langmuir and Freundlich adsorption models. Model parameters were estimated by nonlinear regression. It was seen that the adsorption equilibrium data fitted very well to the competitive Freundlich model in the concentration ranges studied.« less

TURBULENT FLAME REACTOR STUDIES OF CHLORINATED HYDROCARBON DESTRUCTION EFFICIENCY

EPA Science Inventory

Four mixtures of C₁ and C₂ chlorinated hydrocarbons, diluted in heptane, were burned in a Turbulent Flame Reactor (TFR) under high and low oxygen conditions. Emissions of undestroyed feed, stable organic by-products, carbon monoxide, carbon dioxide and oxyg...

Medicines, shaken and stirred: a critical review on the ecotoxicology of pharmaceutical mixtures

PubMed Central

Backhaus, Thomas

2014-01-01

Analytical monitoring surveys routinely confirm that organisms in the environment are exposed to complex multi-component pharmaceutical mixtures. We are hence tasked with the challenge to take this into consideration when investigating the ecotoxicology of pharmaceuticals. This review first provides a brief overview of the fundamental approaches for mixture toxicity assessment, which is then followed by a critical review on the empirical evidence that is currently at hand on the ecotoxicology of pharmaceutical mixtures. It is concluded that, while the classical concepts of concentration addition and independent action (response addition) provide a robust scientific footing, several knowledge gaps remain. This includes, in particular, the need for more and better empirical data on the effects of pharmaceutical mixtures on soil organisms as well as marine flora and fauna, and exploring the quantitative consequences of toxicokinetic, toxicodynamic and ecological interactions. Increased focus should be put on investigating the ecotoxicology of pharmaceutical mixtures in environmentally realistic settings. PMID:25405972

Catalysts and process for liquid hydrocarbon fuel production

DOEpatents

White, Mark G; Liu, Shetian

2014-12-09

The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality gasoline components, aromatic compounds, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion, as well as a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst, and provides for use of the novel catalysts in the process and system of the invention.

Dynamics of coarsening in multicomponent lipid vesicles with non-uniform mechanical properties

NASA Astrophysics Data System (ADS)

Funkhouser, Chloe M.; Solis, Francisco J.; Thornton, K.

2014-04-01

Multicomponent lipid vesicles are commonly used as a model system for the complex plasma membrane. One phenomenon that is studied using such model systems is phase separation. Vesicles composed of simple lipid mixtures can phase-separate into liquid-ordered and liquid-disordered phases, and since these phases can have different mechanical properties, this separation can lead to changes in the shape of the vesicle. In this work, we investigate the dynamics of phase separation in multicomponent lipid vesicles, using a model that couples composition to mechanical properties such as bending rigidity and spontaneous curvature. The model allows the vesicle surface to deform while conserving surface area and composition. For vesicles initialized as spheres, we study the effects of phase fraction and spontaneous curvature. We additionally initialize two systems with elongated, spheroidal shapes. Dynamic behavior is contrasted in systems where only one phase has a spontaneous curvature similar to the overall vesicle surface curvature and systems where the spontaneous curvatures of both phases are similar to the overall curvature. The bending energy contribution is typically found to slow the dynamics by stabilizing configurations with multiple domains. Such multiple-domain configurations are found more often in vesicles with spheroidal shapes than in nearly spherical vesicles.

Multicomponent density functional theory embedding formulation.

PubMed

Culpitt, Tanner; Brorsen, Kurt R; Pak, Michael V; Hammes-Schiffer, Sharon

2016-07-28

Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density is separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF(-) molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent systems.

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-04-07

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: and for olefinic hydrocarbons: where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Gas adsorption and gas mixture separations using mixed-ligand MOF material

DOEpatents

Hupp, Joseph T [Northfield, IL; Mulfort, Karen L [Chicago, IL; Snurr, Randall Q [Evanston, IL; Bae, Youn-Sang [Evanston, IL

2011-01-04

A method of separating a mixture of carbon dioxiode and hydrocarbon gas using a mixed-ligand, metal-organic framework (MOF) material having metal ions coordinated to carboxylate ligands and pyridyl ligands.

Some Results from Studies of Microwave Discharges in Liquid Heavy Hydrocarbons

NASA Astrophysics Data System (ADS)

Averin, K. A.; Lebedev, Yu. A.; Shakhatov, V. A.

2018-01-01

Some results from studies of microwave discharges in heavy hydrocarbons are presented. Microwave energy was introduced into liquid hydrocarbon via a coaxial line. The pressure above the liquid surface was equal to the atmospheric pressure. The discharge was ignited in a mixture of argon and hydrocarbon vapor. Argon was supplied through a channel in the central conductor of the coaxial line. The emission spectra of discharges in different liquid hydrocarbons were studied. It is shown that the emission spectra mainly consist of sequences of Swan bands, while radiation of other plasma components is on the noise level. Spectra of plasma emission are presented for discharges in liquid n-heptane, nefras, and C-9 oil used to produce chemical fibers. The rotational (gas) and vibrational temperatures are determined by processing the observed spectra.

Origin of gasoline-range hydrocarbons and their migration by solution in carbon dioxide in Norton basin, Alaska.

USGS Publications Warehouse

Kvenvolden, K.A.; Claypool, G.E.

1980-01-01

Carbon dioxide from a submarine seep in Norton Sound carries a minor component of gas- and gasoline-range hydrocarbons. The molecular and isotopic compositions of the hydrocarbon gases and the presence of gasoline-range hydrocarbons indicate that these molecules are derived from thermal alteration of marine and/or nonmarine organic matter buried within Norton basin. The gasoline-range hydrocarbon distribution suggests that the hydrocarbon mixture is an immature petroleum-like condensate of lower temperature origin than normal crude oil. The submarine seep provides a natural example in support of a carbon dioxide solution transport mechanism thought to be operative in the migration of hydrocarbons in certain reservoirs.-Authors

Method and apparatus for synthesizing hydrocarbons

DOEpatents

Colmenares, C.A.; Somorjai, G.A.; Maj, J.J.

1985-04-16

A method and apparatus for synthesizing a mixture of aliphatic alcohols having five carbons or less is disclosed. An equal molar ratio of CO and H/sub 2/ gases is caused to pass through a ThO/sub 2/ catalyst having a surface area of about 80 to 125 m/sup 2//g. The catalyst further optionally includes Na ions present as substitutional cations in an amount of about 5 to 10 atom %. At a temperature of about 570 to 630/sup 0/K, and at pressures of about 20 to 50 atm, methanol and isobutanol are the predominant products and are produced in amounts of about 90 wt % of the total hydrocarbon mixture. 6 figs.

[Research on the method of interference correction for nondispersive infrared multi-component gas analysis].

PubMed

Sun, You-Wen; Liu, Wen-Qing; Wang, Shi-Mei; Huang, Shu-Hua; Yu, Xiao-Man

2011-10-01

A method of interference correction for nondispersive infrared multi-component gas analysis was described. According to the successive integral gas absorption models and methods, the influence of temperature and air pressure on the integral line strengths and linetype was considered, and based on Lorentz detuning linetypes, the absorption cross sections and response coefficients of H2O, CO2, CO, and NO on each filter channel were obtained. The four dimension linear regression equations for interference correction were established by response coefficients, the absorption cross interference was corrected by solving the multi-dimensional linear regression equations, and after interference correction, the pure absorbance signal on each filter channel was only controlled by the corresponding target gas concentration. When the sample cell was filled with gas mixture with a certain concentration proportion of CO, NO and CO2, the pure absorbance after interference correction was used for concentration inversion, the inversion concentration error for CO2 is 2.0%, the inversion concentration error for CO is 1.6%, and the inversion concentration error for NO is 1.7%. Both the theory and experiment prove that the interference correction method proposed for NDIR multi-component gas analysis is feasible.

Corrosion of aluminum alloys by chlorinated hydrocarbon/methanol mixtures

NASA Technical Reports Server (NTRS)

De Forest, W. S.

1967-01-01

Laboratory investigations show that water-free mixtures of Freon MF /trichlorofluoromethane/ and methanol vigorously attack aluminum alloys which contain significant amounts of copper. Freon MF alone did not attack the aluminum alloys at room temperature. Pure methanol had only a slight corrosive effect on the alloy.

Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

NASA Technical Reports Server (NTRS)

Jachimowski, C. J.; Wilson, C. H.

1980-01-01

The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.

Detonation velocity in poorly mixed gas mixtures

NASA Astrophysics Data System (ADS)

Prokhorov, E. S.

2017-10-01

The technique for computation of the average velocity of plane detonation wave front in poorly mixed mixture of gaseous hydrocarbon fuel and oxygen is proposed. Here it is assumed that along the direction of detonation propagation the chemical composition of the mixture has periodic fluctuations caused, for example, by layered stratification of gas charge. The technique is based on the analysis of functional dependence of ideal (Chapman-Jouget) detonation velocity on mole fraction (with respect to molar concentration) of the fuel. It is shown that the average velocity of detonation can be significantly (by more than 10%) less than the velocity of ideal detonation. The dependence that permits to estimate the degree of mixing of gas mixture basing on the measurements of average detonation velocity is established.

Multicomponent density functional theory embedding formulation

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

Culpitt, Tanner; Brorsen, Kurt R.; Pak, Michael V.

Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density ismore » separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF{sup −} molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent

Modeling viscosity and diffusion of plasma mixtures across coupling regimes

NASA Astrophysics Data System (ADS)

Arnault, Philippe

2014-10-01

Viscosity and diffusion of plasma for pure elements and multicomponent mixtures are modeled from the high-temperature low-density weakly coupled regime to the low-temperature high-density strongly coupled regime. Thanks to an atom in jellium modeling, the effect of electron screening on the ion-ion interaction is incorporated through a self-consistent definition of the ionization. This defines an effective One Component Plasma, or an effective Binary Ionic Mixture, that is representative of the strength of the interaction. For the viscosity and the interdiffusion of mixtures, approximate kinetic expressions are supplemented by mixing laws applied to the excess viscosity and self-diffusion of pure elements. The comparisons with classical and quantum molecular dynamics results reveal deviations in the range 20--40% on average with almost no predictions further than a factor of 2 over many decades of variation. Applications in the inertial confinement fusion context could help in predicting the growth of hydrodynamic instabilities.

Evaluation of the performance and response of the bacharach TLV sniffer and H-Nu photoionization gas analyzer to common hydrocarbon solvents.

PubMed

Chelton, C F; Zakraysek, N; Lautner, G M; Confer, R G

1983-10-01

Two direct reading instruments, the H-Nu PI 101 photoionization analyzer and the J.W. Bacharach TLV Sniffer, were evaluated under laboratory conditions to determine their performance characteristics when challenged by vapors of common hydrocarbon solvent mixtures. Each instrument was evaluated against the manufacturer's recommended test solvent for rise time, fall time, noise, span drift, zero drift, position sensitivity, battery life, and recharge time. The precision, accuracy, and operating linear range were also determined for the test solvents and some petroleum solvent mixtures which are common refinery products. For these latter mixtures, correction factors are presented which allow for an improved estimate of ambient concentrations when monitoring with each of these instruments. All tests except operating humidity range were performed by challenging each instrument with a known concentration of hydrocarbon generated by evaporating calculated liquid volumes into a static chamber. Humidity tests were performed using a dynamic dilution apparatus generating a fixed concentration of hydrocarbon while relative humidity was varied. Concentrations in both systems were verified by gas injection into gas chromatograph. Each instrument performed well when challenged by manufacturers' recommended test solvents. Humidity was shown to influence each instrument's readings. Also, the instruments were shown to have application as monitors of airborne concentrations of common hydrocarbon solvent mixtures.

RELATIONSHIPS BETWEEN LABORATORY AND PILOT-SCALE COMBUSTION OF SOME CHLORINATED HYDROCARBONS

EPA Science Inventory

Factors governing the occurence of trace amounts of residual organic substance emmissions (ROSEs) in full-scale incierators are not fully understood. Pilot-scale spray combustion expereiments involving some liquid chlorinated hydrocarbons (CHCs) and their dilute mixtures with hy...

Low-Temperature Catalytic Process To Produce Hydrocarbons From Sugars

DOEpatents

Cortright, Randy D.; Dumesic, James A.

2005-11-15

Disclosed is a method of producing hydrogen from oxygenated hydrocarbon reactants, such as methanol, glycerol, sugars (e.g. glucose and xylose), or sugar alcohols (e.g. sorbitol). The method takes place in the condensed liquid phase. The method includes the steps of reacting water and a water-soluble oxygenated hydrocarbon in the presence of a metal-containing catalyst. The catalyst contains a metal selected from the group consisting of Group VIIIB transitional metals, alloys thereof, and mixtures thereof. The disclosed method can be run at lower temperatures than those used in the conventional steam reforming of alkanes.

Hydrocarbon fingerprinting for application in forensic geology: Review with case studies

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

Bruce, L.G.; Schmidt, G.W.

1994-11-01

Forensic geology, the application of the science to the law, has required detailed classification, identification, and fingerprinting of hydrocarbons. Currently, the best overall tool for this is a chromatogram derived from capillary column gas chromatography (GC). Just as hardness and cleavage identify rock minerals and x-ray angles help identify clay minerals, retention time on a chromatogram can help identify key hydrocarbons, such as normal paraffins. N-paraffin ranges can be used to classify hydrocarbon mixtures such as gasoline, diesel fuel, or crude oil. Refined and crude petroleum may be distinguished on a chromatogram by the range of n-paraffins in a mixture,more » the shape of the n-paraffin envelope, the presence of absence of olefins, and the presence and relative abundance of certain hydrocarbon additives. Crude oils tend to have a wide range of n-paraffins whose envelope is asymmetric and includes a tail of heavier hydrocarbons. Refined products have a more limited n-paraffin range. With some notable exceptions, such as gasoline, the envelope of most refined products is bell shaped. Olefins are an artifact of the refining process and are not present in crudes. Methylcyclohexane is relatively abundant in gasolines. Isooctane and aromatics are more abundant in premium gasolines than in condensates and crudes. Fuel additives such as tetraethyl lead, methyl tertiary butyl ether, ethyl tertiary butyl alcohol, and ethanol do not exist in crudes. This paper uses case histories to illustrate fingerprinting techniques. Case one matches the fingerprint of a plume to a specific source. Case two eliminates casing-head condensate as the source of a plume and tags processed natural-gas liquids as the probable source. Case three illustrates how other organic compounds may be mistakenly identified as hydrocarbon contamination, and case four differentiates refined products.« less

HETEROGENEOUS PHOTOCATALYTIC DECOMPOSITION OF POLY- AROMATIC HYDROCARBONS OVER TITANIUM DIOXIDE

EPA Science Inventory

The photocatalytic degradation of a mixture of 16 polyaromatic hydrocarbons (PAHs) was investigated in aqueous suspensions of high surface area TiO₂ illuminated with 310–380 nm ultraviolet light. Triethylamine was utilized for extraction of PAH compounds from motor oil...

Biodegradation and environmental behavior of biodiesel mixtures in the sea: An initial study.

PubMed

DeMello, Jared A; Carmichael, Catherine A; Peacock, Emily E; Nelson, Robert K; Samuel Arey, J; Reddy, Christopher M

2007-07-01

Biodiesel, a mixture of fatty acid methyl esters (FAMEs) derived from animal fats or vegetable oils, is rapidly moving towards the mainstream as an alternative source of energy. However, the behavior of biodiesel, or blends of biodiesel with fossil diesel, in the marine environment have yet to be fully understood. Hence, we performed a series of initial laboratory experiments and simple calculations to evaluate the microbial and environmental fate of FAMEs. Aerobic seawater microcosms spiked with biodiesel or mixtures of biodiesel and fossil diesel revealed that the FAMEs were degraded at roughly the same rate as n-alkanes, and more rapidly than other hydrocarbon components. The residues extracted from these different microcosms became indistinguishable within weeks. Preliminary results from physical-chemical calculations suggest that FAMEs in biodiesel mixtures will not affect the evaporation rates of spilled petroleum hydrocarbons but may stabilize oil droplets in the water column and thereby facilitate transport.

Anthracene + Pyrene Solid Mixtures: Eutectic and Azeotropic Character

PubMed Central

Rice, James W.; Fu, Jinxia; Suuberg, Eric M.

2010-01-01

To better characterize the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the anthracene (1) + pyrene (2) system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at 404 K at x1 = 0.22. A model based on eutectic formation can be used to predict the enthalpy of fusion associated with the mixture. For mixtures that contain x1 < 0.90, the enthalpy of fusion is near that of pure pyrene. This and X-ray diffraction results indicate that mixtures of anthracene and pyrene have pyrene-like crystal structures and energetics until the composition nears that of pure anthracene. Solid-vapor equilibrium studies show that mixtures of anthracene and pyrene form solid azeotropes at x1 of 0.03 and 0.14. Additionally, mixtures at x1 = 0.99 sublime at the vapor pressure of pure anthracene, suggesting that anthracene behavior is not significantly influenced by x2 = 0.01 in the crystal structure. PMID:21116474

Bonding and structure in dense multi-component molecular mixtures

DOE PAGES

Meyer, Edmund R.; Ticknor, Christopher; Bethkenhagen, Mandy; ...

2015-10-30

We have performed finite-temperature density functional theory molecular dynamics simulations on dense methane, ammonia, and water mixtures (CH 4:NH 3:H 2O) for various compositions and temperatures (2000 K ≤ T ≤ 10000 K) that span a set of possible conditions in the interiors of ice-giant exoplanets. The equation-of-state, pair distribution functions, and bond autocorrelation functions (BACF) were used to probe the structure and dynamics of these complex fluids. In particular, an improvement to the choice of the cutoff in the BACF was developed that allowed analysis refinements for density and temperature effects. We note the relative changes in the naturemore » of these systems engendered by variations in the concentration ratios. As a result, a basic tenet emerges from all these comparisons that varying the relative amounts of the three heavy components (C,N,O) can effect considerable changes in the nature of the fluid and may in turn have ramifications for the structure and composition of various planetary layers.« less

Antioxidant-Based Eutectics of Irbesartan: Viable Multicomponent Forms for the Management of Hypertension.

PubMed

Haneef, Jamshed; Chadha, Renu

2018-04-01

The present research work highlights the development of multicomponent solid form of the antihypertensive drug irbesartan (IRB) to improve its biopharmaceutical attributes. Mechanochemical synthesis of a new solid form of IRB with coformers having antioxidant properties (syringic acid, nicotinic acid, and ascorbic acid) resulted into three eutectic mixtures (EMs). Formation of eutectic was ascertained by differential scanning calorimetry whereas exact stoichiometry (50/50% w/w) was established by phase diagram and Tamman's triangle. The strong homomeric interaction between individual components and steric hindrances is responsible for the eutectic formation. EMs exhibited superior apparent solubility (five- to nine fold) and significant enhancement in intrinsic dissolution rate (two- to three fold) as compared to the plain drug. In vivo pharmacokinetic and in vivo pharmacodynamic studies revealed a significant improvement in the biopharmaceutical performance of EMs. Marked protection against oxidative stress was observed in EMs over plain drug by controlling the level/activity of plasma H 2 O 2 and antioxidant enzymes (superoxide dismutase and catalase) in the kidney matrix of dexamethasone (Dexa)-induced hypertensive rats. Thus, these solid forms of IRB can serve as viable multicomponent forms to be translated into product development for better therapeutic efficacy in the management of hypertension.

Composition and Temperature Dependence of Shear Viscosity of Hydrocarbon Mixtures

DTIC Science & Technology

1980-07-01

HNN- XTHDCPD Binary System IX. VTF Eq. Parameters for Shear Viscosities Using Constant B Parameter X. Results of Fits to Master Viscosity Eqs. (43...T(K) for 5 C10 Hydrocarbons I Fig. 2a. log n versus 103/T(K) for HNNi I Fig. 2b. log n versus 103/T(K) for XTHDCPD Fig. 3. Isothem of log n versus X...CD for CO-MO Binary System Fig. 4. Isotherm of log n versus XNBC for NBC-DMO Binary System ( ~Fig. 5. Isotherm of log n versus XfINN for HNN- XTHDCPD

Polycyclic aromatic hydrocarbons as skin carcinogens: Comparison of benzo[a]pyrene, dibenzo[def,p]chrysene and three environmental mixtures in the FVB/N mouse

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

Siddens, Lisbeth K.; Larkin, Andrew; Superfund Research Center, Oregon State University

2012-11-01

The polycyclic aromatic hydrocarbon (PAH), benzo[a]pyrene (BaP), was compared to dibenzo[def,p]chrysene (DBC) and combinations of three environmental PAH mixtures (coal tar, diesel particulate and cigarette smoke condensate) using a two stage, FVB/N mouse skin tumor model. DBC (4 nmol) was most potent, reaching 100% tumor incidence with a shorter latency to tumor formation, less than 20 weeks of 12-O-tetradecanoylphorbol-13-acetate (TPA) promotion compared to all other treatments. Multiplicity was 4 times greater than BaP (400 nmol). Both PAHs produced primarily papillomas followed by squamous cell carcinoma and carcinoma in situ. Diesel particulate extract (1 mg SRM 1650b; mix 1) did notmore » differ from toluene controls and failed to elicit a carcinogenic response. Addition of coal tar extract (1 mg SRM 1597a; mix 2) produced a response similar to BaP. Further addition of 2 mg of cigarette smoke condensate (mix 3) did not alter the response with mix 2. PAH-DNA adducts measured in epidermis 12 h post initiation and analyzed by {sup 32}P post‐labeling, did not correlate with tumor incidence. PAH‐dependent alteration in transcriptome of skin 12 h post initiation was assessed by microarray. Principal component analysis (sum of all treatments) of the 922 significantly altered genes (p < 0.05), showed DBC and BaP to cluster distinct from PAH mixtures and each other. BaP and mixtures up-regulated phase 1 and phase 2 metabolizing enzymes while DBC did not. The carcinogenicity with DBC and two of the mixtures was much greater than would be predicted based on published Relative Potency Factors (RPFs). -- Highlights: ► Dibenzo[def,p]chrysene (DBC), 3 PAH mixtures, benzo[a]pyrene (BaP) were compared. ► DBC and 2 PAH mixtures were more potent than Relative Potency Factor estimates. ► Transcriptome profiles 12 hours post initiation were analyzed by microarray. ► Principle components analysis of alterations revealed treatment-based clustering. ► DBC gave a

Signal processing with a summing operational amplifier in multicomponent potentiometric titrations.

PubMed

Parczewski, A

1987-06-01

It has been proved that application of two indicator electrodes connected to the ordinary titration apparatus through an auxiliary electronic device (a summing operational amplifier) significantly extends the scope of multicomponent potentiometric titrations in which the analytes are determined simultaneously from a single titration curve. For each analyte there is a corresponding potential jump on the titration curve. By application of the proposed auxiliary device, the sum of the electrode potentials is measured. The device also enables the relative sizes of the potential jumps at the end-points on the titration curve to be varied. The advantages of the proposed signal processing are exemplified by complexometric potentiometric titrations of Fe(III) and Cu(II) in mixtures, with a platinum electrode and a copper ion-selective electrode as the indicator electrodes.

L-cysteine-derived ambidextrous gelators of aromatic solvents and ethanol/water mixtures.

PubMed

Pal, Amrita; Dey, Joykrishna

2013-02-19

A series of L-cysteine-derived double hydrocarbon chain amphiphilic gelators L-(3-alkyl-carbamoylsulfanyl)-2-(3-alkylurido)propionic acid with different hydrocarbon chain lengths (C6-C16) was designed and synthesized. These gelators efficiently gelate only aromatic solvents. The gelation ability increased with the increase of chain length up to C14, but then it dropped with further increase of chain length. The C12 and C14 derivatives also gelled ethanol/water mixtures. The gels were characterized by a number of methods, including FT-IR, NMR, and XRD spectroscopy, electron microscopy, and rheology. The amphiphiles were observed to form either flat lamellar or ribbonlike aggregates in aromatic solvents as well as in ethanol/water mixtures. The gelation in all the solvents employed was observed to be thermoreversible. The gel-to-sol transition temperature as well as mechanical strength of the organogels were observed to increase with the hydrocarbon chain length. Both types of gels of C8-C16 amphiphiles have gel-to-sol transition temperatures above the physiological temperature (310 K). FT-IR and variable temperature (1)H NMR measurements suggested that van der Waals interactions have major contribution in the gelation process. The gel-to-sol transition temperature and mechanical strength of the organogels in ethanol/water mixtures was observed to be higher than those of benzene organogel.

Spontaneous ignition characteristics of gaseous hydrocarbon-air mixtures

NASA Technical Reports Server (NTRS)

Freeman, G.; Lefebvre, A. H.

1984-01-01

Experiments are conducted to determine the spontaneous ignition delay times of gaseous propane, kerosine vapor, and n-heptane vapor in mixtures with air, and oxygen-enriched air, at atmospheric pressure. Over a range of equivalence ratios from 0.2 to 0.8 it is found that ignition delay times are sensibly independent of fuel concentration. However, the results indicate a strong dependence of delay times on oxygen concentration. The experimental data for kerosine and propane demonstrate very close agreement with the results obtained previously by Mullins and Lezberg respectively.

Identification and Quantification of Six-Ring C26H16 Cata-Condensed Polycyclic Aromatic Hydrocarbons in a Complex Mixture of Polycyclic Aromatic Hydrocarbons from Coal Tar

PubMed Central

Oña-Ruales, Jorge O.; Sharma, Arun K.; Wise, Stephen A.

2015-01-01

We applied a combination of normal-phase liquid chromatography (NPLC) with ultraviolet-visible spectroscopy and gas chromatography with mass spectrometry (GC/MS) for the fractionation, identification, and quantification of six ring C26H16 cata-condensed polycyclic aromatic hydrocarbons, PAHs, in the Standard Reference Material 1597a, Complex Mixture of PAHs from Coal Tar. For the characterization analysis, we calculated the GC retention indices of 17 C26H16 PAH authentic reference standards using the Rxi-PAH and DB-5 GC columns. Then, we used NPLC with ultraviolet-visible spectroscopy to isolate the fractions containing the C26H16 PAHs, and subsequently, we used GC/MS to establish the identity and quantity of the C26H16 PAHs using authentic reference standards. Following this procedure, 12 C26H16 cata-condensed PAHs benzo[c]pentaphene, dibenzo[f,k]tetraphene, benzo[h]pentaphene, dibenzo[a,l]tetracene, dibenzo[c,k]tetraphene, naphtho[2,3-c]tetraphene, dibenzo[a,c]tetracene, benzo[b]picene, dibenzo[a,j]tetracene, naphtho[2,1-a]tetracene, dibenzo[c,p]chrysene, and dibenzo[a,f]tetraphene were identified and quantified for the first time, and benzo[c]picene was quantified for the first time in an environmental combustion sample. PMID:26449848

Atmospheric emissions from the Deepwater Horizon spill constrain air-water partitioning, hydrocarbon fate, and leak rate

NASA Astrophysics Data System (ADS)

Ryerson, T. B.; Aikin, K. C.; Angevine, W. M.; Atlas, E. L.; Blake, D. R.; Brock, C. A.; Fehsenfeld, F. C.; Gao, R.-S.; de Gouw, J. A.; Fahey, D. W.; Holloway, J. S.; Lack, D. A.; Lueb, R. A.; Meinardi, S.; Middlebrook, A. M.; Murphy, D. M.; Neuman, J. A.; Nowak, J. B.; Parrish, D. D.; Peischl, J.; Perring, A. E.; Pollack, I. B.; Ravishankara, A. R.; Roberts, J. M.; Schwarz, J. P.; Spackman, J. R.; Stark, H.; Warneke, C.; Watts, L. A.

2011-04-01

The fate of deepwater releases of gas and oil mixtures is initially determined by solubility and volatility of individual hydrocarbon species; these attributes determine partitioning between air and water. Quantifying this partitioning is necessary to constrain simulations of gas and oil transport, to predict marine bioavailability of different fractions of the gas-oil mixture, and to develop a comprehensive picture of the fate of leaked hydrocarbons in the marine environment. Analysis of airborne atmospheric data shows massive amounts (˜258,000 kg/day) of hydrocarbons evaporating promptly from the Deepwater Horizon spill; these data collected during two research flights constrain air-water partitioning, thus bioavailability and fate, of the leaked fluid. This analysis quantifies the fraction of surfacing hydrocarbons that dissolves in the water column (˜33% by mass), the fraction that does not dissolve, and the fraction that evaporates promptly after surfacing (˜14% by mass). We do not quantify the leaked fraction lacking a surface expression; therefore, calculation of atmospheric mass fluxes provides a lower limit to the total hydrocarbon leak rate of 32,600 to 47,700 barrels of fluid per day, depending on reservoir fluid composition information. This study demonstrates a new approach for rapid-response airborne assessment of future oil spills.

Identification and quantification of seven fused aromatic rings C26H14 peri-condensed benzenoid polycyclic aromatic hydrocarbons in a complex mixture of polycyclic aromatic hydrocarbons from coal tar.

PubMed

Oña-Ruales, Jorge O; Ruiz-Morales, Yosadara; Wise, Stephen A

2016-04-15

A methodology for the characterization of groups of polycyclic aromatic hydrocarbons (PAHs) using a combination of normal phase liquid chromatography with ultraviolet-visible spectroscopy (NPLC/UV-vis) and gas chromatography with mass spectrometry (GC/MS) was used for the identification and quantification of seven fused aromatic rings C26H14 peri-condensed benzenoid polycyclic aromatic hydrocarbons, PAHs, in standard reference material (SRM) 1597a, complex mixture of PAHs from coal tar. The NPLC/UV-vis isolated the fractions based on the number of aromatic carbons and the GC/MS allowed the identification and quantification of five of the nine C26H14 PAH isomers; naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[b,pqr]perylene, naphtho[8,1,2-bcd]perylene, and dibenzo[cd,lm]perylene using a retention time comparison with authentic reference standards. For the other four benzenoid isomers with no available reference standards the following two approaches were used. First, the annellation theory was used to achieve the potential identification of benzo[qr]naphtho[3,2,1,8-defg]chrysene, and second, the elution distribution in the GC fractions was used to support the potential identification of benzo[qr]naphtho[3,2,1,8-defg]chrysene and to reach the tentative identifications of dibenzo[a,ghi]perylene, naphtho[7,8,1,2,3-pqrst]pentaphene, and anthra[2,1,9,8-opqra]naphthacene. It is the first time that naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[b,pqr]perylene, naphtho[8,1,2-bcd]perylene, and dibenzo[cd,lm]perylene are quantified, and the first time that benzo[qr]naphtho[3,2,1,8-defg]chrysene is potentially identified, in any sample, in any context. Copyright © 2016 Elsevier B.V. All rights reserved.

Multicomponent Droplet Evaporation on Chemical Micro-Patterned Surfaces

PubMed Central

He, Minghao; Liao, Dong; Qiu, Huihe

2017-01-01

The evaporation and dynamics of a multicomponent droplet on a heated chemical patterned surface were presented. Comparing to the evaporation process of a multicomponent droplet on a homogenous surface, it is found that the chemical patterned surface can not only enhance evaporation by elongating the contact line, but also change the evaporation process from three regimes for the homogenous surface including constant contact line (CCL) regime, constant contact angle (CCA) regime and mix mode (MM) to two regimes, i.e. constant contact line (CCL) and moving contact line (MCL) regimes. The mechanism of contact line stepwise movement in MCL regimes in the microscopic range is investigated in detail. In addition, an improved local force model on the contact line was employed for analyzing the critical receding contact angles on homogenous and patterned surfaces. The analysis results agree well for both surfaces, and confirm that the transition from CCL to MCL regimes indicated droplet composition changes from multicomponent to monocomponent, providing an important metric to predict and control the dynamic behavior and composition of a multicomponent droplet using a patterned surface. PMID:28157229

PHOTOACTIVATION AND TOXICITY OF MIXTURES OF POLYCYCLIC AROMATIC HYDROCARBON COMPOUNDS IN MARINE SEDIMENT

EPA Science Inventory

The direct toxicity and photoinduced toxicity of sediment-associated acenaphthene, phenanthrene, fluoranthene, and pyrene were determined for the marine amphipod Rhepoxynius abronius. The four polycyclic aromatic hydrocarbons (PAHs) were spiked into sediment in a concentration se...

Cage Occupation of Light Hydrocarbons in Gas Hydrate Crystals

NASA Astrophysics Data System (ADS)

Kida, M.; Watanabe, M.; Konno, Y.; Yoneda, J.; Jin, Y.; Nagao, J.

2016-12-01

Naturally occurring gas hydrates in marine or permafrost environments can trap methane and heavier hydrocarbons within its host lattice structure built up with hydrogen-bonded water molecules. Naturally occurring gas hydrates have been expected as new natural gas resources. It is important to reveal the distribution of guest hydrocarbons in host hydrate framework from viewpoint of assessment of gas capacity. In this study, we assessed cage occupancies of guest hydrocarbons in host hydrate framework of synthetic and natural gas hydrates using solid-state 13C NMR technique. As synthetic samples, gas hydrates formed from gas mixtures including C1 to C5 were investigated. As a natural sample, the pore-space gas hydrate sample recovered from the eastern Nankai Trough area during the 2012 JOGMEC/JAPEX Pressure coring operation was studied. As a result, it revealed that all heavier hydrocarbons than ethane are preferentially incorporated into the larger cage cavities in hydrate frameworks. We performed this study as a part of a Japanese National hydrate research program (MH21, funded by METI).

A general mixture equation of state for double bonding carboxylic acids with ≥2 association sites

NASA Astrophysics Data System (ADS)

Marshall, Bennett D.

2018-05-01

In this paper, we obtain the first general multi-component solution to Wertheim's thermodynamic perturbation theory for the case that molecules can participate in cyclic double bonds. In contrast to previous authors, we do not restrict double bonding molecules to a 2-site association scheme. Each molecule in a multi-component mixture can have an arbitrary number of donor and acceptor association sites. The one restriction on the theory is that molecules can have at most one pair of double bonding sites. We also incorporate the effect of hydrogen bond cooperativity in cyclic double bonds. We then apply this new association theory to 2-site and 3-site models for carboxylic acids within the polar perturbed chain statistical associating fluid theory equation of state. We demonstrate the accuracy of the approach by comparison to both pure and multi-component phase equilibria data. It is demonstrated that the 3-site association model gives substantially a different hydrogen bonding structure than a 2-site approach. We also demonstrate that inclusion of hydrogen bond cooperativity has a substantial effect on a liquid phase hydrogen bonding structure.

Solubility modeling of refrigerant/lubricant mixtures

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

Michels, H.H.; Sienel, T.H.

1996-12-31

A general model for predicting the solubility properties of refrigerant/lubricant mixtures has been developed based on applicable theory for the excess Gibbs energy of non-ideal solutions. In our approach, flexible thermodynamic forms are chosen to describe the properties of both the gas and liquid phases of refrigerant/lubricant mixtures. After an extensive study of models for describing non-ideal liquid effects, the Wohl-suffix equations, which have been extensively utilized in the analysis of hydrocarbon mixtures, have been developed into a general form applicable to mixtures where one component is a POE lubricant. In the present study we have analyzed several POEs wheremore » structural and thermophysical property data were available. Data were also collected from several sources on the solubility of refrigerant/lubricant binary pairs. We have developed a computer code (NISC), based on the Wohl model, that predicts dew point or bubble point conditions over a wide range of composition and temperature. Our present analysis covers mixtures containing up to three refrigerant molecules and one lubricant. The present code can be used to analyze the properties of R-410a and R-407c in mixtures with a POE lubricant. Comparisons with other models, such as the Wilson or modified Wilson equations, indicate that the Wohl-suffix equations yield more reliable predictions for HFC/POE mixtures.« less

Optoelectronics sensors of hydrocarbons based on NDIR technique

NASA Astrophysics Data System (ADS)

Prokopiuk, Artur

2017-08-01

Saturated hydrocarbons are mainly nontoxic, but as extremely flammable gases forming explosive mixtures with air. The Lower Explosive Level (LEL) for methane is 4.4%, which is very dangerous in the mining industry. Methane is also an asphyxiant gas causing coma or death. Therefore, continuous monitoring of the hydrocarbons concentration is very important. Optoelectronic methods are very attractive for this application, especially nondispersive infrared (NDIR) technique. It enables a direct, fast, and selective measurement of different gas concentrations. NDIR sensors have many advantages, which make them very promising for use as hydrocarbon detectors. Despite a lot of benefits, common used NDIR sensors have some disadvantages. They need periodic calibration and have limited detection range, from 100ppm. These parameters can be improved thanks to modernization detection scheme and use of newest IR sources and detectors. During Analyses selected IR sources and detectors were taken into account. Absorption spectra of analyzed hyrdrocarbons were studied to minimize impact interfering gases like carbon dioxide and water.

Volatile hydrocarbons and fuel oxygenates: Chapter 12

USGS Publications Warehouse

Cozzarelli, Isabelle M.

2014-01-01

Petroleum hydrocarbons and fuel oxygenates are among the most commonly occurring and widely distributed contaminants in the environment. This chapter presents a summary of the sources, transport, fate, and remediation of volatile fuel hydrocarbons and fuel additives in the environment. Much research has focused on the transport and transformation processes of petroleum hydrocarbons and fuel oxygenates, such as benzene, toluene, ethylbenzene, and xylenes and methyl tert‐butyl ether, in groundwater following release from underground storage tanks. Natural attenuation from biodegradation limits the movement of these contaminants and has received considerable attention as an environmental restoration option. This chapter summarizes approaches to environmental restoration, including those that rely on natural attenuation, and also engineered or enhanced remediation. Researchers are increasingly combining several microbial and molecular-based methods to give a complete picture of biodegradation potential and occurrence at contaminated field sites. New insights into the fate of petroleum hydrocarbons and fuel additives have been gained by recent advances in analytical tools and approaches, including stable isotope fractionation, analysis of metabolic intermediates, and direct microbial evidence. However, development of long-term detailed monitoring programs is required to further develop conceptual models of natural attenuation and increase our understanding of the behavior of contaminant mixtures in the subsurface.

Thermodynamic study of (anthracene + benzo[a]pyrene) solid mixtures

PubMed Central

Rice, James W.; Suuberg, Eric M.

2010-01-01

To characterize better the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the {anthracene (1) + benzo[a]pyrene (2)} system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at x1 = 0.26. The eutectic mixture is an amorphous solid that lacks organized crystal structure and melts between T = (414 and 420) K. For mixtures that contain 0.10 < x1 < 0.90, the enthalpy of fusion is dominated by that of the eutectic. Solid-vapor equilibrium studies show that mixtures of anthracene and benzo[a]pyrene at x1 < 0.10 sublime at the vapor pressure of pure benzo[a]pyrene. These results suggest that the solid-vapor equilibrium of benzo[a]pyrene is not significantly influenced by moderate levels of anthracene in the crystal structure. PMID:20814451

Cultivation of a bacterial consortium with the potential to degrade total petroleum hydrocarbon using waste activated sludge.

PubMed

Sivakumar, S; Song, Y C; Kim, S H; Jang, S H

2015-11-01

Waste activated sludge was aerobically treated to demonstrate multiple uses such as cultivating an oil degrading bacterial consortium; studying the influence of a bulking agent (peat moss) and total petroleum hydrocarbon concentration on bacterial growth and producing a soil conditioner using waste activated sludge. After 30 days of incubation, the concentration of oil-degrading bacteria was 4.3 x 10(8) CFU g(-1) and 4.5 x 10(8) CFU g(-1) for 5 and 10 g of total petroleum hydrocarbon, respectively, in a mixture of waste activated sludge (1 kg) and peat moss (0.1 kg). This accounts for approximately 88.4 and 91.1%, respectively, of the total heterotrophic bacteria (total-HB). The addition of bulking agent enhanced total-HB population and total petroleum hydrocarbon-degrading bacterial population. Over 90% of total petroleum hydrocarbon degradation was achieved by the mixture of waste activated sludge, bulking agent and total petroleum hydrocarbon. The results of physico-chemical parameters of the compost (waste activated sludge with and without added peat moss compost) and a substantial reduction in E. coli showed that the use of this final product did not exhibit risk when used as soil conditioner. Finally, the present study demonstrated that cultivation of total petroleum hydrocarbon-degrading bacterial consortium and production of compost from waste activated sludge by aerobic treatment was feasible.

Production and delivery of a fluid mixture to an annular volume of a wellbore

DOEpatents

Hermes, Robert E [Los Alamos, NM; Bland, Ronald Gene [Houston, TX; Foley, Ron Lee [Magnolia, TX; Bloys, James B [Katy, TX; Gonzalez, Manuel E [Kingwood, NM; Daniel, John M [Germantown, TN; Robinson, Ian M [Guisborough, GB; Carpenter, Robert B [Tomball, TX

2012-01-24

The methods described herein generally relate to preparing and delivering a fluid mixture to a confined volume, specifically an annular volume located between two concentrically oriented casing strings within a hydrocarbon fluid producing well. The fluid mixtures disclosed herein are useful in controlling pressure in localized volumes. The fluid mixtures comprise at least one polymerizable monomer and at least one inhibitor. The processes and methods disclosed herein allow the fluid mixture to be stored, shipped and/or injected into localized volumes, for example, an annular volume defined by concentric well casing strings.

Effect of post injections on mixture preparation and unburned hydrocarbon emissions in a heavy-duty diesel engine

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

O'Connor, Jacqueline; Musculus, Mark P. B.; Pickett, Lyle M.

This work explores the mechanisms by which a post injection can reduce unburned hydrocarbon (UHC) emissions in heavy-duty diesel engines operating at low-temperature combustion conditions. Post injections, small, close-coupled injections of fuel after the main injection, have been shown to reduce UHC in the authors’ previous work. In this work, we analyze optical data from laser-induced fluorescence of both CH 2O and OH and use chemical reactor modeling to better understand the mechanism by which post injections reduce UHC emissions. The results indicate that post-injection efficacy, or the extent to which a post injection reduces UHC emissions, is a strongmore » function of the cylinder pressure variation during the post injection. However, the data and analysis indicate that the pressure and temperature rise from the post injection combustion cannot solely explain the UHC reduction measured by both engine-out and optical diagnostics. In conclusion, the fluid-mechanic, thermal, and chemical interaction of the post injection with the main-injection mixture is a key part of UHC reduction; the starting action of the post jet and the subsequent entrainment of surrounding gases are likely both important processes in reducing UHC with a post injection.« less

Effect of post injections on mixture preparation and unburned hydrocarbon emissions in a heavy-duty diesel engine

DOE PAGES

O'Connor, Jacqueline; Musculus, Mark P. B.; Pickett, Lyle M.

2016-05-30

This work explores the mechanisms by which a post injection can reduce unburned hydrocarbon (UHC) emissions in heavy-duty diesel engines operating at low-temperature combustion conditions. Post injections, small, close-coupled injections of fuel after the main injection, have been shown to reduce UHC in the authors’ previous work. In this work, we analyze optical data from laser-induced fluorescence of both CH 2O and OH and use chemical reactor modeling to better understand the mechanism by which post injections reduce UHC emissions. The results indicate that post-injection efficacy, or the extent to which a post injection reduces UHC emissions, is a strongmore » function of the cylinder pressure variation during the post injection. However, the data and analysis indicate that the pressure and temperature rise from the post injection combustion cannot solely explain the UHC reduction measured by both engine-out and optical diagnostics. In conclusion, the fluid-mechanic, thermal, and chemical interaction of the post injection with the main-injection mixture is a key part of UHC reduction; the starting action of the post jet and the subsequent entrainment of surrounding gases are likely both important processes in reducing UHC with a post injection.« less

Predicting Multicomponent Adsorption Isotherms in Open-Metal Site Materials Using Force Field Calculations Based on Energy Decomposed Density Functional Theory.

PubMed

Heinen, Jurn; Burtch, Nicholas C; Walton, Krista S; Fonseca Guerra, Célia; Dubbeldam, David

2016-12-12

For the design of adsorptive-separation units, knowledge is required of the multicomponent adsorption behavior. Ideal adsorbed solution theory (IAST) breaks down for olefin adsorption in open-metal site (OMS) materials due to non-ideal donor-acceptor interactions. Using a density-function-theory-based energy decomposition scheme, we develop a physically justifiable classical force field that incorporates the missing orbital interactions using an appropriate functional form. Our first-principles derived force field shows greatly improved quantitative agreement with the inflection points, initial uptake, saturation capacity, and enthalpies of adsorption obtained from our in-house adsorption experiments. While IAST fails to make accurate predictions, our improved force field model is able to correctly predict the multicomponent behavior. Our approach is also transferable to other OMS structures, allowing the accurate study of their separation performances for olefins/paraffins and further mixtures involving complex donor-acceptor interactions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

THE GENOTOXICITY OF PRIORITY POLYCYCLIC AROMATIC HYDROCARBONS IN COMPLEX MIXTURES

EPA Science Inventory

Risk assessment of complex environmental samples suffers from difficulty in identifying toxic components, inadequacy of available toxicity data, and a paucity of knowledge about the behavior of geno(toxic) substances in complex mixtures. Lack of information about the behavior of ...

Effects of hydrocarbon contamination on ozone generation with dielectric barrier discharges

NASA Astrophysics Data System (ADS)

Lopez, Jose L.; Vezzu, Guido; Freilich, Alfred; Paolini, Bernhard

2013-08-01

The increasing usage of the feed gases of lower grade liquid oxygen (LOX) containing higher levels of trace hydrocarbon impurities in dielectric barrier discharge (DBD) for ozone generation requires a better understanding of the kinetics of the by-product formation resulting from reactions involving these hydrocarbon impurities. As a case study of hydrocarbon impurities, the kinetics of CH4 conversion in DBDs and the subsequent HNO3 formation were investigated by means of gas-phase plasma diagnostics, supported by detailed process modeling, and extensive in-situ and ex-situ by-product analysis. The by-products formation in the plasma with the presence of CH4, were found to differ significantly in oxygen-fed generators as compared to generators fed with oxygen/nitrogen mixtures. The amount of HNO3 formed depends on the concentration of NOx formed in the plasma and the amount of CH4 that is converted, but not on the O3 concentration. In the present work we have investigated CH4 concentrations of up to 1.95 wt% of the feed gas. The rate of deterioration of the overall ozone generator performance was found to be affected by the concentration of nitrogen in the oxygen/nitrogen mixture.

Identification and quantification of homologous series of compound in complex mixtures: autocovariance study of GC/MS chromatograms.

PubMed

Pietrogrande, Maria Chiara; Zampolli, Maria Grazia; Dondi, Francesco

2006-04-15

The paper describes a method for determining homologous classes of compounds in a multicomponent complex chromatogram obtained under programming elution conditions. The method is based on the computation of the autocovariance function of the experimental chromatogram (EACVF). The EACVF plot, if properly interpreted, can be regarded as a "class chromatogram" i.e., a virtual chromatogram formed by peaks whose positions and heights allow identification and quantification of the different homologous series, even if they are embedded in a random complex chromatogram. Theoretical models were developed to describe complex chromatograms displaying random retention pattern, ordered sequences or a combination of them. On the basis of theoretical autocovariance function, the properties of the chromatogram can be experimentally evaluated, under well-defined conditions: in particular, the two components of the chromatogram, ordered and random, can be identified. Moreover, the total number of single components (SCs) and the separated number of the SCs belonging to the random and ordered components can be determined, when the two components display the same concentration. If the mixture contains several homologous series with common frequency and different phase values, the number and identity of the different homologous series as well as the number of SCs belonging to each of them can be evaluated. Moreover, the power of the EACVF method can be magnified by applying it to the single ion monitoring (SIM) signals to selectively detect specific compound classes in order to identify the different homologous series. By this way, a full "decoding" of the complex multicomponent chromatogram is achieved. The method was validated on synthetic mixtures containing known amount of SCs belonging to homologous series of hydrocarbon, alcohols, ketones, and aromatic compounds in addition to other not structurally related SCs. The method was applied to both the total ion monitoring (TIC) and the

Global optimization of multicomponent distillation configurations: 2. Enumeration based global minimization algorithm

DOE PAGES

Nallasivam, Ulaganathan; Shah, Vishesh H.; Shenvi, Anirudh A.; ...

2016-02-10

We present a general Global Minimization Algorithm (GMA) to identify basic or thermally coupled distillation configurations that require the least vapor duty under minimum reflux conditions for separating any ideal or near-ideal multicomponent mixture into a desired number of product streams. In this algorithm, global optimality is guaranteed by modeling the system using Underwood equations and reformulating the resulting constraints to bilinear inequalities. The speed of convergence to the globally optimal solution is increased by using appropriate feasibility and optimality based variable-range reduction techniques and by developing valid inequalities. As a result, the GMA can be coupled with already developedmore » techniques that enumerate basic and thermally coupled distillation configurations, to provide for the first time, a global optimization based rank-list of distillation configurations.« less

A review on multicomponent seismology: A potential seismic application for reservoir characterization

PubMed Central

Farfour, Mohammed; Yoon, Wang Jung

2015-01-01

Searching for hydrocarbon reserves in deep subsurface is the main concern of wide community of geophysicists and geoscientists in petroleum industry. Exploration seismology has substantially contributed to finding and developing giant fields worldwide. The technology has evolved from two to three-dimensional method, and later added a fourth dimension for reservoir monitoring. Continuous depletion of many old fields and the increasing world consumption of crude oil pushed to consistently search for techniques that help recover more reserves from old fields and find alternative fields in more complex and deeper formations either on land and in offshore. In such environments, conventional seismic with the compressional (P) wave alone proved to be insufficient. Multicomponent seismology came as a solution to most limitations encountered in P-wave imaging. That is, recording different components of the seismic wave field allowed geophysicists to map complex reservoirs and extract information that could not be extracted previously. The technology demonstrated its value in many fields and gained popularity in basins worldwide. In this review study, we give an overview about multicomponent seismology, its history, data acquisition, processing and interpretation as well as the state-of the-art of its applications. Recent examples from world basins are highlighted. The study concludes that despite the success achieved in many geographical areas such as deep offshore in the Gulf of Mexico, Western Canada Sedimentary Basin (WCSB), North Sea, Offshore Brazil, China and Australia, much work remains for the technology to gain similar acceptance in other areas such as Middle East, East Asia, West Africa and North Africa. However, with the tremendous advances reported in data recording, processing and interpretation, the situation may change. PMID:27222756

A review on multicomponent seismology: A potential seismic application for reservoir characterization.

PubMed

Farfour, Mohammed; Yoon, Wang Jung

2016-05-01

Searching for hydrocarbon reserves in deep subsurface is the main concern of wide community of geophysicists and geoscientists in petroleum industry. Exploration seismology has substantially contributed to finding and developing giant fields worldwide. The technology has evolved from two to three-dimensional method, and later added a fourth dimension for reservoir monitoring. Continuous depletion of many old fields and the increasing world consumption of crude oil pushed to consistently search for techniques that help recover more reserves from old fields and find alternative fields in more complex and deeper formations either on land and in offshore. In such environments, conventional seismic with the compressional (P) wave alone proved to be insufficient. Multicomponent seismology came as a solution to most limitations encountered in P-wave imaging. That is, recording different components of the seismic wave field allowed geophysicists to map complex reservoirs and extract information that could not be extracted previously. The technology demonstrated its value in many fields and gained popularity in basins worldwide. In this review study, we give an overview about multicomponent seismology, its history, data acquisition, processing and interpretation as well as the state-of the-art of its applications. Recent examples from world basins are highlighted. The study concludes that despite the success achieved in many geographical areas such as deep offshore in the Gulf of Mexico, Western Canada Sedimentary Basin (WCSB), North Sea, Offshore Brazil, China and Australia, much work remains for the technology to gain similar acceptance in other areas such as Middle East, East Asia, West Africa and North Africa. However, with the tremendous advances reported in data recording, processing and interpretation, the situation may change.

Apparatus for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2001-01-01

A hydrocarbon fuel reformer (200) is disclosed suitable for producing synthesis hydrogen gas from reactions with hydrocarbons fuels, oxygen, and steam. The reformer (200) comprises first and second tubes (208,218). The first tube (208) includes a first catalyst (214) and receives a first mixture of steam and a first fuel. The second tube (218) is annularly disposed about the first tube (208) and receives a second mixture of an oxygen-containing gas and a second fuel. In one embodiment, a third tube (224) is annularly disposed about the second tube (218) and receives a first reaction reformate from the first tube (208) and a second reaction reformate from the second tube (218). A catalyst reforming zone (260) annularly disposed about the third tube (224) may be provided to subject reformate constituents to a shift reaction. In another embodiment, a fractionator is provided to distill first and second fuels from a fuel supply source.

Apparatus for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2002-01-01

Hydrocarbon fuel reformer 100 suitable for producing synthesis hydrogen gas from reactions with hydrocarbons fuels, oxygen, and steam. A first tube 108 has a first tube inlet 110 and a first tube outlet 112. The first tube inlet 110 is adapted for receiving a first mixture including an oxygen-containing gas and a first fuel. A partially oxidized first reaction reformate is directed out of the first tube 108 into a mixing zone 114. A second tube 116 is annularly disposed about the first tube 108 and has a second tube inlet 118 and a second tube outlet 120. The second tube inlet 118 is adapted for receiving a second mixture including steam and a second fuel. A steam reformed second reaction reformate is directed out of the second tube 116 and into the mixing zone 114. From the mixing zone 114, the first and second reaction reformates may be directed into a catalytic reforming zone 144 containing a reforming catalyst 147.

Simultaneous multi-component seismic denoising and reconstruction via K-SVD

NASA Astrophysics Data System (ADS)

Hou, Sian; Zhang, Feng; Li, Xiangyang; Zhao, Qiang; Dai, Hengchang

2018-06-01

Data denoising and reconstruction play an increasingly significant role in seismic prospecting for their value in enhancing effective signals, dealing with surface obstacles and reducing acquisition costs. In this paper, we propose a novel method to denoise and reconstruct multicomponent seismic data simultaneously. This method lies within the framework of machine learning and the key points are defining a suitable weight function and a modified inner product operator. The purpose of these two processes are to perform missing data machine learning when the random noise deviation is unknown, and building a mathematical relationship for each component to incorporate all the information of multi-component data. Two examples, using synthetic and real multicomponent data, demonstrate that the new method is a feasible alternative for multi-component seismic data processing.

Kinetic Studies of the Cometabolism of 1,4-DIOXANE and Chlorinated Aliphatic Hydrocarbon Mixtures by Rhodococcus Rhodochrous Grown on Isobutane

NASA Astrophysics Data System (ADS)

Rolston, H. M.; Semprini, L.; Thankitkul, S.; Azizian, M.; Hyman, M. R.

2016-12-01

1,4-dioxane (1,4-D) is a frequently observed groundwater contaminant due to its use as a stabilizer in commercial solvent formulations. In situ bioremediation could potentially provide a large cost savings for treatment of mixtures of chlorinated aliphatic hydrocarbons (CAHs) that include 1,4-D. Aerobic cometabolism is a particularly attractive option, as microorganisms can be stimulated in situ using specific primary substrates. Results will be presented that show the model isobutane-metabolizing bacteria, Rhodococcus rhodochrous (ATCC 21198), has the ability to transform 14-D at high rates and transformation capacities to concentrations below the drinking water screening level of 0.67 µg L-1. Resting cell transformation tests showed 1,4-D and a broad range of CAHs can be cometabolized by ATCC 21198. The maximum transformation rate (kmax) and the half-substrate coefficient (Ks) were determined for isobutane (the growth substrate), 1,4-D, 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2-trichloroethane (1,1,2-TCA), 1,1-dichloroethane (1,1-DCA); 1,2-dichloroethane ((1,2-DCA) and 1,1-dichloroethene (1,1-DCE). Of the CAHs tested, 1,1-DCA had the highest kmax, approximately 25% of that for isobutane utilization, while 1,1,1-TCA had the lowest kmax, approximately 2% of isobutane's. 1,4-D was rapidly transformed and had a kmax 25% of that of isobutane. ATCC 21198 effectively transformed mixtures of 1,4-D, 1,1-DCE, 1,2-DCA and 1,1,1-TCA, both in the presence and absence isobutane. Model simulations were performed for the simultaneous cometabolism of 1,4-D and CAH mixtures by ATCC 21198, that included inhibition among the contaminants and isobutane , and terms for a limited transformation capacity. A good match to experimental observations was obtaining using the independently measured rate parameters. Results of model simulations will also be presented using a reactive transport model to evaluate conditions of in situ bioremediation using strain ATCC 21198.

BIODEGRADATION OF A PAH MIXTURE BY NATIVE SUBSURFACE MICROBIOTA. (R828770)

EPA Science Inventory

Laboratory microcosm studies were conducted to estimate biodegradation rates for a mixture of five polycyclic aromatic hydrocarbon compounds (PAHs). Static microcosms were assembled using soil samples from two locations collected at a No. 2 fuel oil-contaminated site in the At...

Investigation of antioxidant properties of metal ascorbates and their mixtures by voltammetry

NASA Astrophysics Data System (ADS)

Vtorushina, A. N.; Nikonova, E. D.

2015-04-01

The paper describes modern ways for selection of anti-radical substances. Molding of such components with a carbon-based material decreases the rate of its oxidative destruction. Addition of such a component to a carbon-based material decreases the rate of its oxidative destruction. The purpose of this study is to determine the antioxidant activity of ascorbates metals (Ca, Mg, Li, Co, Fe), used in the practice of medicine, as well as mixtures based on them together with well-known antioxidants. In this article we examine the effect of metals on the process of ascorbate oxygen electroreduction. From these ascorbates lithium and magnesium ascorbate showed the greatest activity toward cathode oxygen reduction process. Also mixtures with well-known examined antioxidants ascorbate (glucose, dihydroquercetin) were investigated at different concentrations of components. It is shown that the multicomponent mixtures exhibit lower activity than the individual drugs. Recommended the creation of drugs on the basis of ascorbate Mg and Li with not more than 3 number of components.

Gauge transformation and symmetries of the commutative multicomponent BKP hierarchy

NASA Astrophysics Data System (ADS)

Li, Chuanzhong

2016-01-01

In this paper, we defined a new multi-component B type Kadomtsev-Petviashvili (BKP) hierarchy that takes values in a commutative subalgebra of {gl}(N,{{C}}). After this, we give the gauge transformation of this commutative multicomponent BKP (CMBKP) hierarchy. Meanwhile, we construct a new constrained CMBKP hierarchy that contains some new integrable systems, including coupled KdV equations under a certain reduction. After this, the quantum torus symmetry and quantum torus constraint on the tau function of the commutative multi-component BKP hierarchy will be constructed.

Using chromatography – desorption method of manufacturing gas mixtures for analytical instruments calibration

NASA Astrophysics Data System (ADS)

Platonov, I. A.; Kolesnichenko, I. N.; Lange, P. K.

2018-05-01

In this paper, the chromatography desorption method of obtaining gas mixtures of known compositions stable for a time sufficient to calibrate analytical instruments is considered. The comparative analysis results of the preparation accuracy of gas mixtures with volatile organic compounds using diffusion, polyabarbotage and chromatography desorption methods are presented. It is shown that the application of chromatography desorption devices allows one to obtain gas mixtures that are stable for 10...60 hours in a dynamic condition. These gas mixtures contain volatile aliphatic and aromatic hydrocarbons with a concentration error of no more than 7%. It is shown that it is expedient to use such gas mixtures for analytical instruments calibration (chromatographs, spectrophotometers, etc.)

Catalysts for the production of hydrocarbons from carbon monoxide and water

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

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-01-01

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n+1).gtoreq.x.gtoreq.O and for olefinic hydrocarbons: 2n.gtoreq.x.gtoreq.O where n is the number of carbon atoms in the product and x ismore » the molar amount of water in the reaction mixture.« less

Decarboxylation of fatty acids with triruthenium dodecacarbonyl: Influence of the compound structure and analysis of the product mixtures

USDA-ARS?s Scientific Manuscript database

Recently, the decarboxylation of oleic acid (9(Z)-octadecenoic acid) catalyzed by triruthenium dodecacarbonyl, Ru3(CO)12, to give a mixture of heptadecenes with concomitant formation of other hydrocarbons, heptadecane and C17 alkylbenzenes, was reported. The product mixture, consisting of about 77% ...

Complementary π-π interactions induce multicomponent coassembly into functional fibrils.

PubMed

Ryan, Derek M; Doran, Todd M; Nilsson, Bradley L

2011-09-06

Noncovalent self-assembled materials inspired by amyloid architectures are useful for biomedical applications ranging from regenerative medicine to drug delivery. The selective coassembly of complementary monomeric units to provide ordered multicomponent fibrils is a possible strategy for enhancing the sophistication of these noncovalent materials. Herein we report that complementary π-π interactions can be exploited to promote the coassembly of phenylalanine (Phe) derivatives that possess complementary aromatic side-chain functionality. Specifically, equimolar mixtures of Fmoc-Phe and Fmoc-F(5)-Phe, which possess side-chain groups with complementary quadrupole electronics, readily coassemble to form two-component fibrils and hydrogels under conditions where Fmoc-Phe alone fails to self-assemble. In addition, it was found that equimolar mixtures of Fmoc-Phe with monohalogenated (F, Cl, and Br) Fmoc-Phe derivatives also coassembled into two-component fibrils. These results collectively indicate that face-to-face quadrupole stacking between benzyl side-chain groups does not account for the molecular recognition between Phe and halogenated Phe derivatives that promote cofibrillization but that coassembly is mediated by more subtle π-π effects arising from the halogenation of the benzyl side chain. The use of complementary π-π interactions to promote the coassembly of two distinct monomeric units into ordered two-component fibrils dramatically expands the repertoire of noncovalent interactions that can be used in the development of sophisticated noncovalent materials. © 2011 American Chemical Society

Hydrodynamic model for expansion and collisional relaxation of x-ray laser-excited multi-component nanoplasma

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

Saxena, Vikrant, E-mail: vikrant.saxena@desy.de; Hamburg Center for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg; Ziaja, Beata, E-mail: ziaja@mail.desy.de

The irradiation of an atomic cluster with a femtosecond x-ray free-electron laser pulse results in a nanoplasma formation. This typically occurs within a few hundred femtoseconds. By this time the x-ray pulse is over, and the direct photoinduced processes no longer contributing. All created electrons within the nanoplasma are thermalized. The nanoplasma thus formed is a mixture of atoms, electrons, and ions of various charges. While expanding, it is undergoing electron impact ionization and three-body recombination. Below we present a hydrodynamic model to describe the dynamics of such multi-component nanoplasmas. The model equations are derived by taking the moments ofmore » the corresponding Boltzmann kinetic equations. We include the equations obtained, together with the source terms due to electron impact ionization and three-body recombination, in our hydrodynamic solver. Model predictions for a test case, expanding spherical Ar nanoplasma, are obtained. With this model, we complete the two-step approach to simulate x-ray created nanoplasmas, enabling computationally efficient simulations of their picosecond dynamics. Moreover, the hydrodynamic framework including collisional processes can be easily extended for other source terms and then applied to follow relaxation of any finite non-isothermal multi-component nanoplasma with its components relaxed into local thermodynamic equilibrium.« less

Cumulative Effects of In Utero Administration of Mixtures of Reproductive Toxicants that Disrupt Common Target Tissues via Diverse Mechanisms of Toxicity

PubMed Central

Rider, Cynthia V.; Furr, Johnathan R.; Wilson, Vickie S.; Gray, L. Earl

2010-01-01

Although risk assessments are typically conducted on a chemical-by-chemical basis, the 1996 Food Quality Protection Act required the US Environmental Protection Agency to consider cumulative risk of chemicals that act via a common mechanism of toxicity. To this end, we are conducting studies with mixtures of chemicals to elucidate mechanisms of joint action at the systemic level with the end goal of providing a framework for assessing the cumulative effects of reproductive toxicants. Previous mixture studies conducted with antiandrogenic chemicals are reviewed briefly and two new studies are described in detail. In all binary mixture studies, rats were dosed during pregnancy with chemicals, singly or in pairs at dosage levels equivalent to approximately one half of the ED50 for hypospadias or epididymal agenesis. The binary mixtures included: androgen receptor (AR) antagonists (vinclozolin plus procymidone), phthalate esters (DBP plus BBP and DEHP plus DBP), a phthalate ester plus an AR antagonist (DBP plus procymidone), a mixed mechanism androgen signaling disruptor (linuron) plus BBP, and two chemicals which disrupt epididymal differentiation through entirely different toxicity pathways: DBP (AR pathway) plus 2,3,7,8 TCDD (AhR pathway). We also conducted multi-component mixture studies combining several “antiandrogens” together. In the first study, seven chemicals (four pesticides and three phthalates) that elicit antiandrogenic effects at two different sites in the androgen signaling pathway (i.e. AR antagonist or inhibition of androgen synthesis) were combined. In the second study, three additional phthalates were added to make a ten chemical mixture. In both the binary mixture studies and the multi-component mixture studies, chemicals that targeted male reproductive tract development displayed cumulative effects that exceeded predictions based upon a response addition model and most often were in accordance with predictions based upon dose addition models

Method for producing hydrocarbon fuels from heavy polynuclear hydrocarbons by use of molten metal halide catalyst

DOEpatents

Gorin, Everett

1979-01-01

In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst, thereafter separating at least a substantial portion of the carbonaceous material associated with the reaction mixture from the spent molten metal halide and thereafter regenerating the metal halide catalyst, an improvement comprising contacting the spent molten metal halide catalyst after removal of a major portion of the carbonaceous material therefrom with an additional quantity of hydrogen is disclosed.

Availability of polycyclic aromatic hydrocarbons to earthworms (Eisenia andrei, Oligochaeta) in field-polluted soils and soil-sediment mixtures.

PubMed

Jager, Tjalling; Baerselman, Rob; Dijkman, Ellen; de Groot, Arthur C; Hogendoorn, Elbert A; de Jong, Ad; Kruitbosch, Jantien A W; Peijnenburg, Willie J G M

2003-04-01

The bioavailability of polycyclic aromatic hydrocarbons (PAHs) for earthworms (Eisenia andrei) was experimentally determined in seven field-polluted soils and 15 soil-sediment mixtures. The pore-water concentration of most PAHs was higher than predicted. However, most of the compound was associated with dissolved organic carbon (DOC) and not directly available for uptake by earthworms. The apparent sorption could be reasonably predicted on the basis of interactions with DOC; however, the biota-soil accumulation factors (BSAFs) for earthworms were up to two orders of magnitude lower than predicted by equilibrium partitioning. The large variability between sites was not fully explained by differences in sorption. Experimental results indicate that the pool of freely dissolved PAHs in the pore water became partially depleted because of uptake by the earthworms and that bioaccumulation is thus also influenced by the kinetics of PAH desorption and mass transport. A pilot study with Lumbricus rubellus showed that steady-state body residues were well correlated to E. andrei. Current results show that depositing dredge spoil on land may lead to increased bioavailability of the lower-molecular-weight PAHs. However, risk assessment can conservatively rely on equilibrium partitioning, but accurate prediction requires quantification of the kinetics of bioavailability.

Method And Apparatus For Converting Hydrocarbon Fuel Into Hydrogen Gas And Carbon Dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2001-03-27

A hydrocarbon fuel reforming method is disclosed suitable for producing synthesis hydrogen gas from reactions with hydrocarbons fuels, oxygen, and steam. A first mixture of an oxygen-containing gas and a first fuel is directed into a first tube 108 to produce a first reaction reformate. A second mixture of steam and a second fuel is directed into a second tube 116 annularly disposed about the first tube 108 to produce a second reaction reformate. The first and second reaction reformates are then directed into a reforming zone 144 and subject to a catalytic reforming reaction. In another aspect of the method, a first fuel is combusted with an oxygen-containing gas in a first zone 108 to produce a reformate stream, while a second fuel under steam reforming in a second zone 116. Heat energy from the first zone 108 is transferred to the second zone 116.

Anthropogenic and biogenic hydrocarbons in soils and vegetation from the South Shetland Islands (Antarctica).

PubMed

Cabrerizo, Ana; Tejedo, Pablo; Dachs, Jordi; Benayas, Javier

2016-11-01

Two Antarctic expeditions (in 2009 and 2011) were carried out to assess the local and remote anthropogenic sources of aliphatic and aromatic hydrocarbons, as well as potential biogenic hydrocarbons. Polycyclic aromatic hydrocarbons (PAHs), n-alkanes, biomarkers such as phytane (Ph) and pristane (Pr), and the aliphatic unresolved complex mixture (UCM), were analysed in soil and vegetation samples collected at Deception, Livingston, Barrientos and Penguin Islands (South Shetland Islands, Antarctica). Overall, the patterns of n-alkanes in lichens, mosses and grass were dominated by odd-over-even carbon number alkanes. Mosses and vascular plants showed high abundances of n-C21 to n-C35, while lichens also showed high abundances of n-C17 and n-C19. The lipid content was an important factor controlling the concentrations of n-alkanes in Antarctic vegetation (r(2)=0.28-0.53, p-level<0.05). n-C12 to n-C35 n-alkanes were analysed in soils with a predominance of odd C number n-alkanes (n-C25, n-C27, n-C29, and n-C31), especially in the background soils not influenced by anthropogenic sources. The large values for the carbon predominance index (CPI) and the correlations between odd alkanes and some PAHs suggest the potential biogenic sources of these hydrocarbons in Antarctica. Unresolved complex mixture and CPI values ~1 detected at soils collected at intertidal areas and within the perimeter of Juan Carlos research station, further supported the evidence that even a small settlement (20 persons during the austral summer) can affect the loading of aliphatic and aromatic hydrocarbons in nearby soils. Nevertheless, the assessment of Pr/n-C17 and Ph/n-C18 ratios showed that hydrocarbon degradation is occurring in these soils. Copyright © 2016 Elsevier B.V. All rights reserved.

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

1985-11-06

A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Mixtures Research at NIEHS: An Evolving Program

PubMed Central

Rider, Cynthia V; Carlin, Danielle J; DeVito, Micheal J; Thompson, Claudia L; Walker, Nigel J

2014-01-01

The National Institute of Environmental Health Sciences (NIEHS) has a rich history in evaluating the toxicity of mixtures. The types of mixtures assessed by the Division of the National Toxicology Program (DNTP) and the extramural community (through the Division of Extramural Research and Training (DERT)) have included a broad range of chemicals and toxicants, with each study having a unique set of questions and design considerations. Some examples of the types of mixtures studied include: groundwater contaminants, pesticides/fertilizers, dioxin-like chemicals (assessing the toxic equivalency approach), drug combinations, air pollution, metals, polycyclic aromatic hydrocarbons, technical mixtures (e.g. pentachlorophenol, flame retardants), and mixed entities (e.g. herbals, asbestos). These endeavors have provided excellent data on the toxicity of specific mixtures and have been informative to the human health risk assessment process in general (e.g. providing data on low dose exposures to environmental chemicals). However, the mixtures research effort at NIEHS, to date, has been driven by test article nominations to the DNTP or by investigator-initiated research through DERT. Recently, the NIEHS has embarked upon an effort to coordinate mixtures research across both intramural and extramural divisions in order to maximize mixtures research results. A path forward for NIEHS mixtures research will be based on feedback from a Request for Information (RFI) designed to gather up-to-date views on the knowledge gaps and roadblocks to evaluating mixtures and performing cumulative risk assessment, and a workshop organized to bring together mixtures experts from risk assessment, exposure science, biology, epidemiology, and statistics. The future of mixtures research at NIEHS will include projects from nominations to DNTP, studies by extramural investigators, and collaborations across government agencies that address high-priority questions in the field of mixtures research

Performance Analysis of Joule-Thomson Cooler Supplied with Gas Mixtures

NASA Astrophysics Data System (ADS)

Piotrowska, A.; Chorowski, M.; Dorosz, P.

2017-02-01

Joule-Thomson (J-T) cryo-coolers working in closed cycles and supplied with gas mixtures are the subject of intensive research in different laboratories. The replacement of pure nitrogen by nitrogen-hydrocarbon mixtures allows to improve both thermodynamic parameters and economy of the refrigerators. It is possible to avoid high pressures in the heat exchanger and to use standard refrigeration compressor instead of gas bottles or high-pressure oil free compressor. Closed cycle and mixture filled Joule-Thomson cryogenic refrigerator providing 10-20 W of cooling power at temperature range 90-100 K has been designed and manufactured. Thermodynamic analysis including the optimization of the cryo-cooler mixture has been performed with ASPEN HYSYS software. The paper describes the design of the cryo-cooler and provides thermodynamic analysis of the system. The test results are presented and discussed.

Liquid-liquid equilibria of binary mixtures of a lipidic ionic liquid with hydrocarbons.

PubMed

Green, Blane D; Badini, Alexander J; O'Brien, Richard A; Davis, James H; West, Kevin N

2016-01-28

Although structurally diverse, many ionic liquids (ILs) are polar in nature due to the strong coulombic forces inherent in ionic compounds. However, the overall polarity of the IL can be tuned by incorporating significant nonpolar content into one or more of the constituent ions. In this work, the binary liquid-liquid equilibria of one such IL, 1-methyl-3-(Z-octadec-9-enyl)imidazolium bistriflimide, with several hydrocarbons (n-hexane, n-octane, n-decane, cyclohexane, methylcyclohexane, 1-octene) is measured over the temperature range 0-70 °C at ambient pressure using a combination of cloud point and gravimetric techniques. The phase behavior of the systems are similar in that they exhibit two phases: one that is 60-90 mole% hydrocarbon and a second phase that is nearly pure hydrocarbon. Each phase exhibits a weak dependence of composition on temperature (steep curve) above ∼10 °C, likely due to swelling and restructuring of the nonpolar nano-domains of the IL being limited by energetically unfavorable restructuring in the polar nano-domains. The solubility of the n-alkanes decreases with increasing size (molar volume), a trend that continues for the cyclic alkanes, for which upper critical solution temperatures are observed below 70 °C. 1-Octene is found to be more soluble than n-octane, attributable to a combination of its lower molar volume and slightly higher polarity. The COSMO-RS model is used to predict the T-x'-x'' diagrams and gives good qualitative agreement of the observed trends. This work presents the highest known solubility of n-alkanes in an IL to date and tuning the structure of the ionic liquid to maximize the size/shape trends observed may provide the basis for enhanced separations of nonpolar species.

[Exploration of one-step preparation of Ganoderma lucidum multicomponent microemulsion].

PubMed

He, Jun-Jie; Chen, Yan; Du, Meng; Cao, Wei; Yuan, Ling; Zheng, Li-Yan

2013-03-01

To explore one-step method for the preparation of Ganoderma lucidum multicomponent microemulsion, according to the dissolution characteristics of triterpenes and polysaccharides in Ganoderma lucidum, formulation of the microemulsion was optimized. The optimal blank microemulsion was used as a solvent to sonicate the Ganoderma lucidum powder to prepare the multicomponent microemulsion, besides, its physicochemical properties were compared with the microemulsion made by conventional method. The results showed that the multicomponent microemulsion was characterized as (43.32 +/- 6.82) nm in size, 0.173 +/- 0.025 in polydispersity index (PDI) and -(3.98 +/- 0.82) mV in zeta potential. The contents of Ganoderma lucidum triterpenes and polysaccharides were (5.95 +/- 0.32) and (7.58 +/- 0.44) mg x mL(-1), respectively. Sonicating Ganoderma lucidum powder by blank microemulsion could prepare the multicomponent microemulsion. Compared with the conventional method, this method is simple and low cost, which is suitable for industrial production.

Dispersive—diffusive transport of non-sorbed solute in multicomponent solutions

NASA Astrophysics Data System (ADS)

Hu, Qinhong; Brusseau, Mark L.

1995-10-01

The composition of fuels, mixed-solvent wastes and other contaminants that find their way into the subsurface are frequently chemically complex. The dispersion and diffusion characteristics of multicomponent solutions in soil have rarely been compared to equivalent single-solute systems. The purpose of this work was to examine the diffusive and dispersive transport of single- and multi-component solutions in homogeneous porous media. The miscible displacement technique was used to investigate the transport behavior of 14C-labelled 2,4-dichlorophenoxyacetic acid ( 2,4-D) in two materials for which sorption of 2,4-D was minimal. Comparison of breakthrough curves collected for 2,4-D in single- and multi-component solutions shows that there is little, if any, difference in transport behavior over a wide range of pore-water velocities (70, 7, 0.66 and 0.06 cm h -1). Thus, dispersivities measured with a non-sorbing single-solute solution should be applicable to multicomponent systems.

Multicomponent gas sorption Joule-Thomson refrigeration

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor); Petrick, S. Walter (Inventor); Bard, Steven (Inventor)

1991-01-01

The present invention relates to a cryogenic Joule-Thomson refrigeration capable of pumping multicomponent gases with a single stage sorption compressor system. Alternative methods of pumping a multicomponent gas with a single stage compressor are disclosed. In a first embodiment, the sorbent geometry is such that a void is defined near the output of the sorption compressor. When the sorbent is cooled, the sorbent primarily adsorbs the higher boiling point gas such that the lower boiling point gas passes through the sorbent to occupy the void. When the sorbent is heated, the higher boiling point gas is desorbed at high temperature and pressure and thereafter propels the lower boiling point gas out of the sorption compressor. A mixing chamber is provided to remix the constituent gases prior to expansion of the gas through a Joule-Thomson valve. Other methods of pumping a multicomponent gas are disclosed. For example, where the sorbent is porous and the low boiling point gas does not adsorb very well, the pores of the sorbent will act as a void space for the lower boiling point gas. Alternatively, a mixed sorbent may be used where a first sorbent component physically adsorbs the high boiling point gas and where the second sorbent component chemically absorbs the low boiling point gas.

A review of the neurotoxicity risk of selected hydrocarbon fuels.

PubMed

Ritchie, G D; Still, K R; Alexander, W K; Nordholm, A F; Wilson, C L; Rossi, J; Mattie, D R

2001-01-01

Over 1.3 million civilian and military personnel are occupationally exposed to hydrocarbon fuels, emphasizing gasoline, jet fuel, diesel fuel, or kerosene. These exposures may occur acutely or chronically to raw fuel, vapor, aerosol, or fuel combustion exhaust by dermal, respiratory inhalation, or oral ingestion routes, and commonly occur concurrently with exposure to other chemicals and stressors. Hydrocarbon fuels are complex mixtures of 150-260+ aliphatic and aromatic hydrocarbon compounds containing varying concentrations of potential neurotoxicants including benzene, n-hexane, toluene, xylenes, naphthalene, and certain n-C9-C12 fractions (n-propylbenzene, trimethylbenzene isomers). Due to their natural petroleum base, the chemical composition of different hydrocarbon fuels is not defined, and the fuels are classified according to broad performance criteria such as flash and boiling points, complicating toxicological comparisons. While hydrocarbon fuel exposures occur typically at concentrations below permissible exposure limits for their constituent chemicals, it is unknown whether additive or synergistic interactions may result in unpredicted neurotoxicity. The inclusion of up to six performance additives in existing fuel formulations presents additional neurotoxicity challenge. Additionally, exposures to hydrocarbon fuels, typically with minimal respiratory or dermal protection, range from weekly fueling of personal automobiles to waist-deep immersion of personnel in raw fuel during maintenance of aircraft fuel tanks. Occupational exposures may occur on a near daily basis for from several months to over 20 yr. A number of published studies have reported acute or persisting neurotoxic effects from acute, subchronic, or chronic exposure of humans or animals to hydrocarbon fuels, or to certain constituent chemicals of these fuels. This review summarizes human and animal studies of hydrocarbon fuel-induced neurotoxicity and neurobehavioral consequences. It is

Post-Shock Sampling of Shock-Heated Hydrocarbon Fuels

DTIC Science & Technology

2016-07-07

on the ability to measure key hydrocarbon fragments (e.g. ethylene , methane, and acetylene) over a wide range of temperatures and pressures. The...series of experiments was conducted to validate the sampling system results and explore the thermal decomposition of ethylene and methane. Initially, a...1% ethylene /0.1% methane/balance argon fuel mixture was shock-heated to ~960 K – a temperature low enough that no reaction would occur. GC analysis

Study utilization of extractable petroleum hydrocarbons biodegradation waste as the main material for making solid fuels

NASA Astrophysics Data System (ADS)

Hendrianie, Nuniek; Juliastuti, Sri Rachmania; Ar-rosyidah, Fanny Husna; Rochman, Hilal Abdur

2017-05-01

Nowadays the existence of energy sources of oil and was limited. Therefore, it was important to searching for new innovations of renewable energy sources by utilizing the waste into a source of energy. On the other hand, the process of extractable petroleum hydrocarbons biodegradation generated sludge that had calorific value and untapped. Because of the need for alternative sources of energy innovation with the concept of zero waste and the fuel potential from extractable petroleum hydrocarbons biodegradation waste, so it was necessary to study the use of extractable petroleum hydrocarbons biodegradation waste as the main material for making solid fuel. In addition, sawdust is a waste that had a great quantities and also had a high calorific value to be mixed with extractable petroleum hydrocarbons biodegradation waste. The purpose of this study was to determine the characteristics of the extractable petroleum hydrocarbons biodegradation waste and to determine the potential and a combination of a mixture of extractable petroleum hydrocarbons biodegradation waste and sawdust which has the best calorific value. The variables of this study was the composition of the waste and sawdust as follows 1:1; 1:3; and 3:1 (mass of sawdust : mass of waste) and time of sawdust carbonization was 10, 15 and 20 minutes. Sawdust was carbonized to get the high heating value. The characteristic of main material and fuel analysis performed with proximate analysis. While the calorific value analysis was performed with a bomb calorimeter. From the research, it was known that extractable petroleum hydrocarbons biodegradation waste had a moisture content of 3.06%; volatile matter 19.98%; ash content of 0.56%; fixed carbon content of 76.4% and a calorific value of 717 cal/gram. And a mixture that had the highest calorific value (4286.5 cal/gram) achieved in comparison sawdust : waste (3:1) by carbonization of sawdust for 20 minutes.

Surface-Sensitive and Bulk Studies on the Complexation and Photosensitized Degradation of Catechol by Iron(III) as a Model for Multicomponent Aerosol Systems

NASA Astrophysics Data System (ADS)

Al-abadleh, H. A.; Tofan-Lazar, J.; Situm, A.; Ruffolo, J.; Slikboer, S.

2013-12-01

Surface water plays a crucial role in facilitating or inhibiting surface reactions in atmospheric aerosols. Little is known about the role of surface water in the complexation of organic molecules to transition metals in multicomponent aerosol systems. We will show results from real time diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments for the in situ complexation of catechol to Fe(III) and its photosensitized degradation under dry and humid conditions. Catechol was chosen as a simple model for humic-like substances (HULIS) in aerosols and aged polyaromatic hydrocarbons (PAH). It has also been detected in secondary organic aerosols (SOA) formed from the reaction of hydroxyl radicals with benzene. Given the importance of the iron content in aerosols and its biogeochemistry, our studies were conducted using FeCl3. For comparison, these surface-sensitive studies were complemented with bulk aqueous ATR-FTIR, UV-vis, and HPLC measurements for structural, quantitative and qualitative information about complexes in the bulk, and potential degradation products. The implications of our studies on understanding interfacial and condensed phase chemistry relevant to multicomponent aerosols, water thin islands on buildings, and ocean surfaces containing transition metals will be discussed.

Virasoro symmetry of the constrained multicomponent Kadomtsev-Petviashvili hierarchy and its integrable discretization

NASA Astrophysics Data System (ADS)

Li, Chuanzhong; He, Jingsong

2016-06-01

We construct Virasoro-type additional symmetries of a kind of constrained multicomponent Kadomtsev-Petviashvili (KP) hierarchy and obtain the Virasoro flow equation for the eigenfunctions and adjoint eigenfunctions. We show that the algebraic structure of the Virasoro symmetry is retained under discretization from the constrained multicomponent KP hierarchy to the discrete constrained multicomponent KP hierarchy.

Auto-ignition of hydrocarbons behind reflected shock waves.

NASA Technical Reports Server (NTRS)

Vermeer, D. J.; Meyer, J. W.; Oppenheim, A. K.

1972-01-01

The paper reports on the study of auto-ignition of hydrocarbon-oxygen mixtures behind reflected shock waves. Because of their bearing on the problem of knock in internal combustion engines, n-heptane and iso-octane were chosen as the combustible species. Their stoichiometric mixtures with oxygen had to be diluted with 70% argon to reduce the influence of the boundary layer. Photographic records demonstrated the existence of two different modes of ignition, as has been previously established for the hydrogen-oxygen system. The pressure-temperature limits between these regions of mild and strong ignition were determined. From the same experimental tests, induction time data were obtained over the pressure range of 1-4 atm and the temperature interval of 1200-1700 K.

Equation of state of mixtures: density functional theory (DFT) simulations and experiments on Sandia's Z machine

NASA Astrophysics Data System (ADS)

Magyar, R. J.; Root, S.; Haill, T. A.; Schroen, D. G.; Mattsson, T. R.; Flicker, D. G.; Sandia National Laboratories Collaboration

2011-06-01

Mixtures of materials are expected to behave quite differently from their isolated constituents, particularly when the constituents atomic numbers differ significantly. To investigate the mixture behavior, we performed density functional theory (DFT) calculations on xenon/hydrogen, xenon/ethane, and platinum/hydrocarbon mixtures. In addition, we performed shock compression experiments on platinum-doped hydrocarbon foams up to 480 GPa using the Sandia Z-accelerator. Since the DFT simulations treat electrons and nuclei generically, simulations of pure and mix systems are expected to be of comparable accuracy. The DFT and experimental results are compared to hydrodynamic simulations using different mixing models in the equation of state. The role of de-mixing and the relative contributions of the enthalpy of mixing are explored. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a wholly owned subsidiary of the Lockheed Martin company, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Co-acclimation of bacterial communities under stresses of hydrocarbons with different structures

PubMed Central

Wang, Hui; Wang, Bin; Dong, Wenwen; Hu, Xiaoke

2016-01-01

Crude oil is a complex mixture of hydrocarbons with different structures; its components vary in bioavailability and toxicity. It is important to understand how bacterial communities response to different hydrocarbons and their co-acclimation in the process of degradation. In this study, microcosms with the addition of structurally different hydrocarbons were setup to investigate the successions of bacterial communities and the interactions between different bacterial taxa. Hydrocarbons were effectively degraded in all microcosms after 40 days. High-throughput sequencing offered a great quantity of data for analyzing successions of bacterial communities. The results indicated that the bacterial communities responded dramatically different to various hydrocarbons. KEGG database and PICRUSt were applied to predict functions of individual bacterial taxa and networks were constructed to analyze co-acclimations between functional bacterial groups. Almost all functional genes catalyzing degradation of different hydrocarbons were predicted in bacterial communities. Most of bacterial taxa were believed to conduct biodegradation processes via interactions with each other. This study addressed a few investigated area of bacterial community responses to structurally different organic pollutants and their co-acclimation and interactions in the process of biodegradation. The study could provide useful information to guide the bioremediation of crude oil pollution. PMID:27698451

The Kirkwood-Buff theory of solutions and the local composition of liquid mixtures.

PubMed

Shulgin, Ivan L; Ruckenstein, Eli

2006-06-29

The present paper is devoted to the local composition of liquid mixtures calculated in the framework of the Kirkwood-Buff theory of solutions. A new method is suggested to calculate the excess (or deficit) number of various molecules around a selected (central) molecule in binary and multicomponent liquid mixtures in terms of measurable macroscopic thermodynamic quantities, such as the derivatives of the chemical potentials with respect to concentrations, the isothermal compressibility, and the partial molar volumes. This method accounts for an inaccessible volume due to the presence of a central molecule and is applied to binary and ternary mixtures. For the ideal binary mixture it is shown that because of the difference in the volumes of the pure components there is an excess (or deficit) number of different molecules around a central molecule. The excess (or deficit) becomes zero when the components of the ideal binary mixture have the same volume. The new method is also applied to methanol + water and 2-propanol + water mixtures. In the case of the 2-propanol + water mixture, the new method, in contrast to the other ones, indicates that clusters dominated by 2-propanol disappear at high alcohol mole fractions, in agreement with experimental observations. Finally, it is shown that the application of the new procedure to the ternary mixture water/protein/cosolvent at infinite dilution of the protein led to almost the same results as the methods involving a reference state.

Enforcing realizability in explicit multi-component species transport

PubMed Central

McDermott, Randall J.; Floyd, Jason E.

2015-01-01

We propose a strategy to guarantee realizability of species mass fractions in explicit time integration of the partial differential equations governing fire dynamics, which is a multi-component transport problem (realizability requires all mass fractions are greater than or equal to zero and that the sum equals unity). For a mixture of n species, the conventional strategy is to solve for n − 1 species mass fractions and to obtain the nth (or “background”) species mass fraction from one minus the sum of the others. The numerical difficulties inherent in the background species approach are discussed and the potential for realizability violations is illustrated. The new strategy solves all n species transport equations and obtains density from the sum of the species mass densities. To guarantee realizability the species mass densities must remain positive (semidefinite). A scalar boundedness correction is proposed that is based on a minimal diffusion operator. The overall scheme is implemented in a publicly available large-eddy simulation code called the Fire Dynamics Simulator. A set of test cases is presented to verify that the new strategy enforces realizability, does not generate spurious mass, and maintains second-order accuracy for transport. PMID:26692634

Ultrafast photophysical studies of a multicomponent sunscreen: Oxybenzone-titanium dioxide mixtures

NASA Astrophysics Data System (ADS)

Baker, Lewis A.; Grosvenor, Lucy C.; Ashfold, Michael N. R.; Stavros, Vasilios G.

2016-11-01

Recent studies of the sunscreen constituent oxybenzone have suggested that the dominant mechanism underlying the efficient photoprotection it offers relies on an initial ultrafast enol → keto tautomerisation, followed by nonadiabatic transfer to the ground electronic state. Subsequent collisions with the solvent bath then reform the original enol-tautomer. Utilising femtosecond transient electronic absorption spectroscopy we explore the dissipation of electronic excitation energy in oxybenzone in the presence of titanium dioxide, a widely used, and complementary sunscreen component. We find the relaxation dynamics of this popular organic filter are unaltered by the presence of this favoured inorganic scatterer and the overall dynamics can be described by the additive contribution of the individual constituents. The combination of the two components provides broadband photoprotective properties justifying the widely used organic filter and inorganic scatterer mixtures in commercial sunscreen products.

Some aspects of multicomponent excess free energy models with subregular binaries

NASA Astrophysics Data System (ADS)

Cheng, Weiji; Ganguly, Jibamitra

1994-09-01

We have shown that two of the most commonly used multicomponent formulations of excess Gibbs free energy of mixing, those by WOHL (1946, 1953) and REDLICH and KISTER (1948), are formally equivalent if the binaries are constrained to have subregular properties, and also that other subregular multicomponent formulations developed in the mineralogical and geochemical literature are equivalent to, or higher order extensions of, these formulations. We have also presented a compact derivation of a multicomponent subregular solution leading to the same expression as derived by HELFFRICH and WOOD (1989). It is shown that Wohl's multicomponent formulation involves combination of binary excess free energies, which are calculated at compositions obtained by normal projection of the multicomponent composition onto the bounding binary joins, and is, thus, equivalent to the formulation developed by MUGGIANU et al. (1975). Finally, following the lead of HILLERT (1980), we have explored the limiting behavior of regular and subregular ternary solutions when a pair of components become energetically equivalent, and have, thus, derived an expression for calculating the ternary interaction parameter in a ternary solution from a knowledge of the properties of the bounding binaries, when one of these binaries is nearly ideal.

Reappraisal of hydrocarbon biomarkers in Archean rocks

PubMed Central

French, Katherine L.; Hallmann, Christian; Hope, Janet M.; Schoon, Petra L.; Zumberge, J. Alex; Hoshino, Yosuke; Peters, Carl A.; George, Simon C.; Love, Gordon D.; Brocks, Jochen J.; Buick, Roger; Summons, Roger E.

2015-01-01

Hopanes and steranes found in Archean rocks have been presented as key evidence supporting the early rise of oxygenic photosynthesis and eukaryotes, but the syngeneity of these hydrocarbon biomarkers is controversial. To resolve this debate, we performed a multilaboratory study of new cores from the Pilbara Craton, Australia, that were drilled and sampled using unprecedented hydrocarbon-clean protocols. Hopanes and steranes in rock extracts and hydropyrolysates from these new cores were typically at or below our femtogram detection limit, but when they were detectable, they had total hopane (<37.9 pg per gram of rock) and total sterane (<32.9 pg per gram of rock) concentrations comparable to those measured in blanks and negative control samples. In contrast, hopanes and steranes measured in the exteriors of conventionally drilled and curated rocks of stratigraphic equivalence reach concentrations of 389.5 pg per gram of rock and 1,039 pg per gram of rock, respectively. Polycyclic aromatic hydrocarbons and diamondoids, which exceed blank concentrations, exhibit individual concentrations up to 80 ng per gram of rock in rock extracts and up to 1,000 ng per gram of rock in hydropyrolysates from the ultraclean cores. These results demonstrate that previously studied Archean samples host mixtures of biomarker contaminants and indigenous overmature hydrocarbons. Therefore, existing lipid biomarker evidence cannot be invoked to support the emergence of oxygenic photosynthesis and eukaryotes by ∼2.7 billion years ago. Although suitable Proterozoic rocks exist, no currently known Archean strata lie within the appropriate thermal maturity window for syngenetic hydrocarbon biomarker preservation, so future exploration for Archean biomarkers should screen for rocks with milder thermal histories. PMID:25918387

Learning and discrimination of cuticular hydrocarbons in a social insect

PubMed Central

van Wilgenburg, Ellen; Felden, Antoine; Choe, Dong-Hwan; Sulc, Robert; Luo, Jun; Shea, Kenneth J.; Elgar, Mark A.; Tsutsui, Neil D.

2012-01-01

Social insect cuticular hydrocarbon (CHC) mixtures are among the most complex chemical cues known and are important in nest-mate, caste and species recognition. Despite our growing knowledge of the nature of these cues, we have very little insight into how social insects actually perceive and discriminate among these chemicals. In this study, we use the newly developed technique of differential olfactory conditioning to pure, custom-designed synthetic colony odours to analyse signal discrimination in Argentine ants, Linepithema humile. Our results show that tri-methyl alkanes are more easily learned than single-methyl or straight-chain alkanes. In addition, we reveal that Argentine ants can discriminate between hydrocarbons with different branching patterns and the same chain length, but not always between hydrocarbons with the same branching patterns but different chain length. Our data thus show that biochemical characteristics influence those compounds that ants can discriminate between, and which thus potentially play a role in chemical signalling and nest-mate recognition. PMID:21831880

Health effects of acid aerosols formed by atmospheric mixtures.

PubMed Central

Kleinman, M T; Phalen, R F; Mautz, W J; Mannix, R C; McClure, T R; Crocker, T T

1989-01-01

Under ambient conditions, sulfur and nitrogen oxides can react with photochemical products and airborne particles to form acidic vapors and aerosols. Inhalation toxicological studies were conducted, exposing laboratory animals, at rest and during exercise, to multicomponent atmospheric mixtures under conditions favorable to the formation of acidic reaction products. Effects of acid and ozone mixtures on early and late clearance of insoluble radioactive particles in the lungs of rats appeared to be dominated by the oxidant component (i.e., the mixture did cause effects that were significantly different from those of ozone alone). Histopathological evaluations showed that sulfuric acid particles alone did not cause inflammatory responses in centriacinar units of rat lung parenchyma (expressed in terms of percent lesion area) but did cause significant damage (cell killing followed by a wave of cell replication) in nasal respiratory epithelium, as measured by uptake of tritiated thymidine in the DNA of replicating cells. Mixtures of ozone and nitrogen dioxide, which form nitric acid, caused significant inflammatory responses in lung parenchyma (in excess of effects seen in rats exposed to ozone alone), but did not damage nasal epithelium. Mixtures containing acidic sulfate particles, ozone, and nitrogen dioxide damaged both lung parenchyma and nasal epithelia. In rats exposed at rest, the response of the lung appeared to be dominated by the oxidant gas-phase components, while responses in the nose were dominated by the acidic particles. In rats exposed at exercise, however, mixtures of ozone and sulfuric acid particles significantly (2.5-fold) elevated the degree of lung lesion formation over that seen in rats exposed to ozone alone under an identical exercise protocol. PMID:2707193

Solubility of polyethers in hydrocarbons at low temperatures. A model for potential genetic backbones on warm titans.

PubMed

McLendon, Christopher; Opalko, F Jeffrey; Illangkoon, Heshan I; Benner, Steven A

2015-03-01

Ethers are proposed here as the repeating backbone linking units in linear genetic biopolymers that might support Darwinian evolution in hydrocarbon oceans. Hydrocarbon oceans are found in our own solar system as methane mixtures on Titan. They may be found as mixtures of higher alkanes (propane, for example) on warmer hydrocarbon-rich planets in exosolar systems ("warm Titans"). We report studies on the solubility of several short polyethers in propane over its liquid range (from 85 to 231 K, or -188 °C to -42 °C). These show that polyethers are reasonably soluble in propane at temperatures down to ca. 200 K. However, their solubilities drop dramatically at still lower temperatures and become immeasurably low below 170 K, still well above the ∼ 95 K in Titan's oceans. Assuming that a liquid phase is essential for any living system, and genetic biopolymers must dissolve in that biosolvent to support Darwinism, these data suggest that we must look elsewhere to identify linear biopolymers that might support genetics in Titan's surface oceans. However, genetic molecules with polyether backbones may be suitable to support life in hydrocarbon oceans on warm Titans, where abundant organics and environments lacking corrosive water might make it easier for life to originate.

BIODEGRADATION OF A PAH MIXTURE BY NATIVE SUBSURFACE MICROBIOTA. (R828770C004)

EPA Science Inventory

Laboratory microcosm studies were conducted to estimate biodegradation rates for a mixture of five polycyclic aromatic hydrocarbon compounds (PAHs). Static microcosms were assembled using soil samples from two locations collected at a No. 2 fuel oil-contaminated site in the At...

CHANGES IN GENE EXPRESSION PROFILE FOLLOWING SHORT-TERM EXPOSURE TO AN ENVIRONMENTALLY RELEVANT MIXTURE OF PHAHS

EPA Science Inventory

Changes in gene expression profile following short-term exposure to an environmentally relevant mixture of PHAHs
Polyhalogenated aromatic hydrocarbons (PHAH) including, polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins (PCDDS) and polychlorinated dibenzofurans...

Diamond deposition in a hot-filament reactor using different hydrocarbon precursor gases

NASA Astrophysics Data System (ADS)

May, P. W.; Everitt, N. M.; Trevor, C. G.; Ashfold, M. N. R.; Rosser, K. N.

1993-07-01

A hot-filament reactor was used to deposit polycrystalline diamond films upon single-crystal Si substrates using hydrocarbon/H 2 gas mixtures. We studied the effect upon the deposition process and resulting film properties by varying the hydrocarbon gas from C 1H x to C 4H x alkanes. This was done maintaining a constant carbon-to-hydrogen ratio, but using a substantially lower-than- normal filament temperature (1500°C) in order to highlight differences in activation barriers and in the chemistry of the diamond-forming step. It was found that with increasing hydrocarbon chain length the deposition rate decreased, from a value of about 0.4 μm h -1 for methane/H 2 mixtures to less than 0.07 μm h -1 for butane/H 2. This was accompanied by an increase in the relative proportion of amorphous carbon to diamond present in the films. After one hour deposition the diamond grain size remained constant at about 20 nm, irrespective of the precursor gas. The measured Knoop hardness of the films also decreased when using process gases other than methane. We also studied the effect of changing the bond order in C 2H x precursor gases (ethane, ethene, ethyne) but found that this had no effect on either the deposition rate or the film quality.

Carbon deposition model for oxygen-hydrocarbon combustion, volume 1

NASA Technical Reports Server (NTRS)

Hernandez, R.; Ito, J. I.; Niiya, K. Y.

1987-01-01

Presented are details of the design, fabrication, and testing of subscale hardware used in the evaluation of carbon deposition characteristics of liquid oxygen and three hydrocarbon fuels for both main chamber and preburner/gas generator operating conditions. In main chamber conditions, the deposition of carbon on the combustion chamber wall was investigated at mixture ratios of 2.0 to 4.0 and at pressures of 1000 to 1500 psia. No carbon deposition on the chamber walls was detected at these main chamber mixture ratios. In preburner/gas generator operating conditions, the deposition of carbon on the turbine simulator tubes was evaluated at mixture ratios of 0.20 to 0.60 and at chamber pressures of 720 to 1650 psia. The results of the tests showed carbon deposition rate to be a strong function of mixture ratio and a weak function of chamber pressure. Further analyses evaluated the operational consequences of carbon deposition on preburner/gas generator performance. The report is in two volumes, of which this is Volume 1 covering the main body of the report plus Appendixes A through D.

Carbon Deposition Model for Oxygen-Hydrocarbon Combustion, Volume 2

NASA Technical Reports Server (NTRS)

Hernandez, R.; Ito, J. I.; Niiya, K. Y.

1987-01-01

Presented are details of the design, fabrication, and testing of subscale hardware used in the evaluation of carbon deposition characteristics of liquid oxygen and three hydrocarbon fuels for both main chamber and preburner/gas generator operating conditions. In main chamber conditions, the deposition of carbon on the combustion chamber wall was investigated at mixture ratios of 2.0 to 4.0 and at chamber pressures of 1000 to 1500 psia. No carbon deposition on chamber walls was detected at these main chamber mixture ratios. In preburner/gas generator operating conditions, the deposition of carbon on the turbine simulator tubes was evaluated at mixture ratios of 0.20 to 0.60 and at chamber pressures of 720 to 1650 psia. The results of the tests showed carbon deposition rate to be a strong function of mixture ratio and a weak function of chamber pressure. Further analyses evaluated the operational concequences of carbon deposition on preburner/gas generator performance. This is Volume 2 of the report, which contains data plots of all the test programs.

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

Agrawal, Rakesh

This project sought and successfully answered two big challenges facing the creation of low-energy, cost-effective, zeotropic multi-component distillation processes: first, identification of an efficient search space that includes all the useful distillation configurations and no undesired configurations; second, development of an algorithm to search the space efficiently and generate an array of low-energy options for industrial multi-component mixtures. Such mixtures are found in large-scale chemical and petroleum plants. Commercialization of our results was addressed by building a user interface allowing practical application of our methods for industrial problems by anyone with basic knowledge of distillation for a given problem. Wemore » also provided our algorithm to a major U.S. Chemical Company for use by the practitioners. The successful execution of this program has provided methods and algorithms at the disposal of process engineers to readily generate low-energy solutions for a large class of multicomponent distillation problems in a typical chemical and petrochemical plant. In a petrochemical complex, the distillation trains within crude oil processing, hydrotreating units containing alkylation, isomerization, reformer, LPG (liquefied petroleum gas) and NGL (natural gas liquids) processing units can benefit from our results. Effluents from naphtha crackers and ethane-propane crackers typically contain mixtures of methane, ethylene, ethane, propylene, propane, butane and heavier hydrocarbons. We have shown that our systematic search method with a more complete search space, along with the optimization algorithm, has a potential to yield low-energy distillation configurations for all such applications with energy savings up to 50%.« less

MIXTURES OF THYROID DISRUPTING CHEMICALS: TESTING ADDITIVITY OF HEPATIC INDUCERS AND THYROID PEROXIDASE INHIBITORS.

EPA Science Inventory

Humans are exposed to chemical mixtures via diet, occupation, and the environment. Previous data demonstrated that low doses of polycyclic halogenated aromatic hydrocarbons (PHAHs) acting through similar mechanisms result in an additive reduction of thyroxine (T4). If xenobioti...

Simulation of a hydrocarbon fueled scramjet exhaust

NASA Technical Reports Server (NTRS)

Leng, J.

1982-01-01

Exhaust nozzle flow fields for a fully integrated, hydrocarbon burning scramjet were calculated for flight conditions of M (undisturbed free stream) = 4 at 6.1 km altitude and M (undisturbed free stream) = 6 at 30.5 km altitude. Equilibrium flow, frozen flow, and finite rate chemistry effects are considered. All flow fields were calculated by method of characteristics. Finite rate chemistry results were evaluated by a one dimensional code (Bittker) using streamtube area distributions extracted from the equilibrium flow field, and compared to very slow artificial rate cases for the same streamtube area distribution. Several candidate substitute gas mixtures, designed to simulate the gas dynamics of the real engine exhaust flow, were examined. Two mixtures are found to give excellent simulations of the specified exhaust flow fields when evaluated by the same method of characteristics computer code.

Photochemical processes on Titan: Irradiation of mixtures of gases that simulate Titan's atmosphere

NASA Astrophysics Data System (ADS)

Tran, Buu N.; Joseph, Jeffrey C.; Force, Michael; Briggs, Robert G.; Vuitton, Veronique; Ferris, James P.

2005-09-01

Photochemical reaction pathways in Titan's atmosphere were investigated by irradiation of the individual components and the mixture containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene. The quantum yields for the loss of the reactants and the formation of products were determined. Photolysis of ethylene yields mainly saturated compounds (ethane, propane, and butane) while photolysis of acetylene yields the same saturated compounds as well as ethylene and diacetylene. Irradiation of cyanoacetylene yields mainly hydrogen cyanide and small amounts of acetonitrile. When an amount of methane corresponding to its mixing ratio on Titan was added to these mixtures the quantum yields for the loss of reactants decreased and the quantum yields for hydrocarbon formation increased indicative of a hydrogen atom abstraction from methane by the photochemically generated radicals. GC/MS analysis of the products formed by irradiation of mixtures of all these gases generated over 120 compounds which were mainly aliphatic hydrocarbons containing double and triple bonds along with much smaller amounts of aromatic compounds like benzene, toluene and phenylacetylene. The reaction pathways were investigated by the use of 13C acetylene in these gas mixtures. No polycyclic aromatic compounds were detected. Vapor pressures of these compounds under conditions present in Titan's atmosphere were calculated. The low molecular weight compounds likely to be present in the atmosphere and aerosols of Titan as a result of photochemical processes are proposed.

Sustainable Separations of C4‐Hydrocarbons by Using Microporous Materials

PubMed Central

Gehre, Mascha; Guo, Zhiyong; Rothenberg, Gadi

2017-01-01

Abstract Petrochemical refineries must separate hydrocarbon mixtures on a large scale for the production of fuels and chemicals. Typically, these hydrocarbons are separated by distillation, which is extremely energy intensive. This high energy cost can be mitigated by developing materials that can enable efficient adsorptive separation. In this critical review, the principles of adsorptive separation are outlined, and then the case for C4 separations by using zeolites and metal–organic frameworks (MOFs) is examined. By analyzing both experimental and theoretical studies, the challenges and opportunities in C4 separation are outlined, with a focus on the separation mechanisms and structure–selectivity correlations. Zeolites are commonly used as adsorbents and, in some cases, can separate C4 mixtures well. The pore sizes of eight‐membered‐ring zeolites, for example, are in the order of the kinetic diameters of C4 isomers. Although zeolites have the advantage of a rigid and highly stable structure, this is often difficult to functionalize. MOFs are attractive candidates for hydrocarbon separation because their pores can be tailored to optimize the adsorbate–adsorbent interactions. MOF‐5 and ZIF‐7 show promising results in separating all C4 isomers, but breakthrough experiments under industrial conditions are needed to confirm these results. Moreover, the flexibility of the MOF structures could hamper their application under industrial conditions. Adsorptive separation is a promising viable alternative and it is likely to play an increasingly important role in tomorrow's refineries. PMID:28621064

"Unresolved Complex Mixture" (UCM): A brief history of the term and moving beyond it.

PubMed

Farrington, John W; Quinn, James G

2015-07-15

The term "Unresolved Complex Mixture" (UCM) has been used extensively for decades to describe a gas chromatographic characteristic indicative of the presence of fossil fuel hydrocarbons (mainly petroleum hydrocarbons) in hydrocarbons isolated from aquatic samples. We chronicle the origin of the term. While it is still a useful characteristic for screening samples, more modern higher resolution two dimensional gas chromatography and gas chromatography coupled with advanced mass spectrometry techniques (Time-of-Flight or Fourier Transform-Ion Cyclotron Resonance) should be employed for analyses of petroleum contaminated samples. This will facilitate advances in understanding of the origins, fates and effects of petroleum compounds in aquatic environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

MODELING GALACTIC EXTINCTION WITH DUST AND 'REAL' POLYCYCLIC AROMATIC HYDROCARBONS

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

Mulas, Giacomo; Casu, Silvia; Cecchi-Pestellini, Cesare

We investigate the remarkable apparent variety of galactic extinction curves by modeling extinction profiles with core-mantle grains and a collection of single polycyclic aromatic hydrocarbons. Our aim is to translate a synthetic description of dust into physically well-grounded building blocks through the analysis of a statistically relevant sample of different extinction curves. All different flavors of observed extinction curves, ranging from the average galactic extinction curve to virtually 'bumpless' profiles, can be described by the present model. We prove that a mixture of a relatively small number (54 species in 4 charge states each) of polycyclic aromatic hydrocarbons can reproducemore » the features of the extinction curve in the ultraviolet, dismissing an old objection to the contribution of polycyclic aromatic hydrocarbons to the interstellar extinction curve. Despite the large number of free parameters (at most the 54 Multiplication-Sign 4 column densities of each species in each ionization state included in the molecular ensemble plus the 9 parameters defining the physical properties of classical particles), we can strongly constrain some physically relevant properties such as the total number of C atoms in all species and the mean charge of the mixture. Such properties are found to be largely independent of the adopted dust model whose variation provides effects that are orthogonal to those brought about by the molecular component. Finally, the fitting procedure, together with some physical sense, suggests (but does not require) the presence of an additional component of chemically different very small carbonaceous grains.« less

Sustainable Separations of C4 -Hydrocarbons by Using Microporous Materials.

PubMed

Gehre, Mascha; Guo, Zhiyong; Rothenberg, Gadi; Tanase, Stefania

2017-10-23

Petrochemical refineries must separate hydrocarbon mixtures on a large scale for the production of fuels and chemicals. Typically, these hydrocarbons are separated by distillation, which is extremely energy intensive. This high energy cost can be mitigated by developing materials that can enable efficient adsorptive separation. In this critical review, the principles of adsorptive separation are outlined, and then the case for C 4 separations by using zeolites and metal-organic frameworks (MOFs) is examined. By analyzing both experimental and theoretical studies, the challenges and opportunities in C 4 separation are outlined, with a focus on the separation mechanisms and structure-selectivity correlations. Zeolites are commonly used as adsorbents and, in some cases, can separate C 4 mixtures well. The pore sizes of eight-membered-ring zeolites, for example, are in the order of the kinetic diameters of C 4 isomers. Although zeolites have the advantage of a rigid and highly stable structure, this is often difficult to functionalize. MOFs are attractive candidates for hydrocarbon separation because their pores can be tailored to optimize the adsorbate-adsorbent interactions. MOF-5 and ZIF-7 show promising results in separating all C 4 isomers, but breakthrough experiments under industrial conditions are needed to confirm these results. Moreover, the flexibility of the MOF structures could hamper their application under industrial conditions. Adsorptive separation is a promising viable alternative and it is likely to play an increasingly important role in tomorrow's refineries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simultaneous determination of hydrocarbon renewable diesel, biodiesel and petroleum diesel contents in diesel fuel blends using near infrared (NIR) spectroscopy and chemometrics.

PubMed

Alves, Julio Cesar Laurentino; Poppi, Ronei Jesus

2013-11-07

Highly polluting fuels based on non-renewable resources such as fossil fuels need to be replaced with potentially less polluting renewable fuels derived from vegetable or animal biomass, these so-called biofuels, are a reality nowadays and many countries have started the challenge of increasing the use of different types of biofuels, such as ethanol and biodiesel (fatty acid alkyl esters), often mixed with petroleum derivatives, such as gasoline and diesel, respectively. The quantitative determination of these fuel blends using simple, fast and low cost methods based on near infrared (NIR) spectroscopy combined with chemometric methods has been reported. However, advanced biofuels based on a mixture of hydrocarbons or a single hydrocarbon molecule, such as farnesane (2,6,10-trimethyldodecane), a hydrocarbon renewable diesel, can also be used in mixtures with biodiesel and petroleum diesel fuel and the use of NIR spectroscopy for the quantitative determination of a ternary fuel blend of these two hydrocarbon-based fuels and biodiesel can be a useful tool for quality control. This work presents a development of an analytical method for the quantitative determination of hydrocarbon renewable diesel (farnesane), biodiesel and petroleum diesel fuel blends using NIR spectroscopy combined with chemometric methods, such as partial least squares (PLS) and support vector machines (SVM). This development leads to a more accurate, simpler, faster and cheaper method when compared to the standard reference method ASTM D6866 and with the main advantage of providing the individual quantification of two different biofuels in a mixture with petroleum diesel fuel. Using the developed PLS model the three fuel blend components were determined simultaneously with values of root mean square error of prediction (RMSEP) of 0.25%, 0.19% and 0.38% for hydrocarbon renewable diesel, biodiesel and petroleum diesel, respectively, the values obtained were in agreement with those suggested by

Infrared spectroscopy for the determination of hydrocarbon types in jet fuels

NASA Technical Reports Server (NTRS)

Buchar, C. S.

1981-01-01

The concentration of hydrocarbon types in conventional jet fuels and synfuels can be measured using a computerized infrared spectrophotometer. The computerized spectrophotometer is calibrated using a fuel of known aromatic and olefinic content. Once calibration is completed, other fuels can be rapidly analyzed using an analytical program built into the computer. The concentration of saturates can be calculated as 100 percent minus the sum of the aromatic and olefinic concentrations. The analysis of a number of jet fuels produced an average standard deviation of 1.76 percent for aromatic types and one of 3.99 percent for olefinic types. Other substances such as oils and organic mixtures can be analyzed for their hydrocarbon content.

Coal liquefaction process using pretreatment with a binary solvent mixture

DOEpatents

Miller, Robert N.

1986-01-01

An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300.degree. C. before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil.

Homogeneous reactions of hydrocarbons, silane, and chlorosilanes in radiofrequency plasmas at low pressures

NASA Technical Reports Server (NTRS)

Avni, R.; Carmi, U.; Inspektor, A.; Rosenthal, I.

1984-01-01

The ion-molecule and radical-molecule mechanisms are responsible for the dissociation of hydrocarbon, silane, and chlorosilane monomers and the formation of polymerized species, respectively, in an RF plasma discharge. In a plasma containing a mixture of monomer and argon the rate-determining step for both dissociation and polymerization is governed by an ion-molecule type of interaction. Adding hydrogen or ammonia to the monomer-argon mixture transforms the rate-determining step from an ion-molecule interaction to a radical-molecule interaction for both monomer dissociation and polymerization.

Validation of a mixture-averaged thermal diffusion model for premixed lean hydrogen flames

NASA Astrophysics Data System (ADS)

Schlup, Jason; Blanquart, Guillaume

2018-03-01

The mixture-averaged thermal diffusion model originally proposed by Chapman and Cowling is validated using multiple flame configurations. Simulations using detailed hydrogen chemistry are done on one-, two-, and three-dimensional flames. The analysis spans flat and stretched, steady and unsteady, and laminar and turbulent flames. Quantitative and qualitative results using the thermal diffusion model compare very well with the more complex multicomponent diffusion model. Comparisons are made using flame speeds, surface areas, species profiles, and chemical source terms. Once validated, this model is applied to three-dimensional laminar and turbulent flames. For these cases, thermal diffusion causes an increase in the propagation speed of the flames as well as increased product chemical source terms in regions of high positive curvature. The results illustrate the necessity for including thermal diffusion, and the accuracy and computational efficiency of the mixture-averaged thermal diffusion model.

Discrimination of complex mixtures by a colorimetric sensor array: coffee aromas.

PubMed

Suslick, Benjamin A; Feng, Liang; Suslick, Kenneth S

2010-03-01

The analysis of complex mixtures presents a difficult challenge even for modern analytical techniques, and the ability to discriminate among closely similar such mixtures often remains problematic. Coffee provides a readily available archetype of such highly multicomponent systems. The use of a low-cost, sensitive colorimetric sensor array for the detection and identification of coffee aromas is reported. The color changes of the sensor array were used as a digital representation of the array response and analyzed with standard statistical methods, including principal component analysis (PCA) and hierarchical clustering analysis (HCA). PCA revealed that the sensor array has exceptionally high dimensionality with 18 dimensions required to define 90% of the total variance. In quintuplicate runs of 10 commercial coffees and controls, no confusions or errors in classification by HCA were observed in 55 trials. In addition, the effects of temperature and time in the roasting of green coffee beans were readily observed and distinguishable with a resolution better than 10 degrees C and 5 min, respectively. Colorimetric sensor arrays demonstrate excellent potential for complex systems analysis in real-world applications and provide a novel method for discrimination among closely similar complex mixtures.

Discrimination of Complex Mixtures by a Colorimetric Sensor Array: Coffee Aromas

PubMed Central

Suslick, Benjamin A.; Feng, Liang; Suslick, Kenneth S.

2010-01-01

The analysis of complex mixtures presents a difficult challenge even for modern analytical techniques, and the ability to discriminate among closely similar such mixtures often remains problematic. Coffee provides a readily available archetype of such highly multicomponent systems. The use of a low-cost, sensitive colorimetric sensor array for the detection and identification of coffee aromas is reported. The color changes of the sensor array were used as a digital representation of the array response and analyzed with standard statistical methods, including principal component analysis (PCA) and hierarchical clustering analysis (HCA). PCA revealed that the sensor array has exceptionally high dimensionality with 18 dimensions required to define 90% of the total variance. In quintuplicate runs of 10 commercial coffees and controls, no confusions or errors in classification by HCA were observed in 55 trials. In addition, the effects of temperature and time in the roasting of green coffee beans were readily observed and distinguishable with a resolution better than 10 °C and 5 min, respectively. Colorimetric sensor arrays demonstrate excellent potential for complex systems analysis in real-world applications and provide a novel method for discrimination among closely similar complex mixtures. PMID:20143838

Sources and distribution of aliphatic and polyaromatic hydrocarbons in sediments from the Neuquen River, Argentine Patagonia.

PubMed

Monza, Liliana B; Loewy, Ruth M; Savini, Mónica C; Pechen de d'Angelo, Ana M

2013-01-01

Spatial distribution and probable sources of aliphatic and polyaromatic hydrocarbons (AHs, PAHs) were investigated in surface sediments collected along the bank of the Neuquen River, Argentina. Total concentrations of aliphatic hydrocarbons ranged between 0.41 and 125 μg/g dw. Six stations presented low values of resolved aliphatic hydrocarbons and the n-alkane distribution indexes applied suggested a clear biogenic source. These values can be considered the baseline levels of aliphatic hydrocarbons for the river sediments. This constitutes important information for the assessment of future impacts since a strong impulse in the exploitation of shale gas and shale oil in these zones is nowadays undergoing. For the other 11 stations, a mixture of aliphatic hydrocarbons of petrogenic and biogenic origin was observed. The spatial distribution reflects local inputs of these pollutants with a significant increase in concentrations in the lower course, where two major cities are located. The highest values of total aliphatic hydrocarbons were found in this sector which, in turn, was the only one where individual PAHs were detected.

Cumulative Exposure Assessment for Trace-Level Polycyclic Aromatic Hydrocarbons (PAHs) using Human Blood and Plasma Analysis

EPA Science Inventory

Humans experience chronic cumulative trace-level exposure to mixtures of volatile, semi-volatile, and non-volatile polycyclic aromatic hydrocarbons (PAHs) present in the environment as by-products of combustion processes. Certain PAHs are known or suspected human carcinogens and ...

Heat transfer during condensation of steam from steam-gas mixtures in the passive safety systems of nuclear power plants

NASA Astrophysics Data System (ADS)

Portnova, N. M.; Smirnov, Yu B.

2017-11-01

A theoretical model for calculation of heat transfer during condensation of multicomponent vapor-gas mixtures on vertical surfaces, based on film theory and heat and mass transfer analogy is proposed. Calculations were performed for the conditions implemented in experimental studies of heat transfer during condensation of steam-gas mixtures in the passive safety systems of PWR-type reactors of different designs. Calculated values of heat transfer coefficients for condensation of steam-air, steam-air-helium and steam-air-hydrogen mixtures at pressures of 0.2 to 0.6 MPa and of steam-nitrogen mixture at the pressures of 0.4 to 2.6 MPa were obtained. The composition of mixtures and vapor-to-surface temperature difference were varied within wide limits. Tube length ranged from 0.65 to 9.79m. The condensation of all steam-gas mixtures took place in a laminar-wave flow mode of condensate film and turbulent free convection in the diffusion boundary layer. The heat transfer coefficients obtained by calculation using the proposed model are in good agreement with the considered experimental data for both the binary and ternary mixtures.

Criteria for Modeling in LES of Multicomponent Fuel Flow

NASA Technical Reports Server (NTRS)

Bellan, Josette; Selle, Laurent

2009-01-01

A report presents a study addressing the question of which large-eddy simulation (LES) equations are appropriate for modeling the flow of evaporating drops of a multicomponent liquid in a gas (e.g., a spray of kerosene or diesel fuel in air). The LES equations are obtained from the direct numerical simulation (DNS) equations in which the solution is computed at all flow length scales, by applying a spatial low-pass filter. Thus, in LES the small scales are removed and replaced by terms that cannot be computed from the LES solution and instead must be modeled to retain the effect of the small scales into the equations. The mathematical form of these models is a subject of contemporary research. For a single-component liquid, there is only one LES formulation, but this study revealed that for a multicomponent liquid, there are two non-equivalent LES formulations for the conservation equations describing the composition of the vapor. Criteria were proposed for selecting the multicomponent LES formulation that gives the best accuracy and increased computational efficiency. These criteria were applied in examination of filtered DNS databases to compute the terms in the LES equations. The DNS databases are from mixing layers of diesel and kerosene fuels. The comparisons resulted in the selection of one of the multicomponent LES formulations as the most promising with respect to all criteria.

The Stingless Bee Melipona solani Deposits a Signature Mixture and Methyl Oleate to Mark Valuable Food Sources.

PubMed

Alavez-Rosas, David; Malo, Edi A; Guzmán, Miguel A; Sánchez-Guillén, Daniel; Villanueva-Gutiérrez, Rogel; Cruz-López, Leopoldo

2017-10-01

Stingless bees foraging for food improve recruitment by depositing chemical cues on valuable food sites or pheromone marks on vegetation. Using gas chromatography/mass spectrometry and bioassays, we showed that Melipona solani foragers leave a mixture composed mostly of long chain hydrocarbons from their abdominal cuticle plus methyl oleate from the labial gland as a scent mark on rich food sites. The composition of hydrocarbons was highly variable among individuals and varied in proportions, depending on the body part. A wide ratio of compounds present in different body parts of the bees elicited electroantennogram responses from foragers and these responses were dose dependent. Generally, in bioassays, these bees prefer to visit previously visited feeders and feeders marked with extracts from any body part of conspecifics. The mean number of visits to a feeder was enhanced when synthetic methyl oleate was added. We propose that this could be a case of multi-source odor marking, in which hydrocarbons, found in large abundance, act as a signature mixture with attraction enhanced through deposition of methyl oleate, which may indicate a rich food source.

Separation of C2 hydrocarbons from methane in a microporous metal-organic framework

NASA Astrophysics Data System (ADS)

Tang, Fu-Shun; Lin, Rui-Biao; Lin, Rong-Guang; Zhao, John Cong-Gui; Chen, Banglin

2018-02-01

The recovery of C2 hydrocarbons including acetylene, ethylene and ethane is challenging but important for natural gas upgrading. The separation of C2 hydrocarbons over methane was demonstrated here by using a microporous metal-organic framework [Zn3(OH)2(SDB)2] (H2SDB = 4,4'-sulfonyldibenzoic acid) consisting narrow one-dimensional pore channels. Gas sorption experiments revealed that this MOF material showed considerable uptake capacity for C2H2, C2H4 and C2H6 under ambient conditions, while its capacity for CH4 was very low. High selectivity from IAST calculations for C2H2/CH4, C2H4/CH4 and C2H6/CH4 binary mixtures demonstrated that this MOF material were promising for efficiently separating important separation of C2 hydrocarbons from methane in natural gas processing.

Molecular Analysis of Surfactant-Driven Microbial Population Shifts in Hydrocarbon-Contaminated Soil†

PubMed Central

Colores, Gregory M.; Macur, Richard E.; Ward, David M.; Inskeep, William P.

2000-01-01

We analyzed the impact of surfactant addition on hydrocarbon mineralization kinetics and the associated population shifts of hydrocarbon-degrading microorganisms in soil. A mixture of radiolabeled hexadecane and phenanthrene was added to batch soil vessels. Witconol SN70 (a nonionic, alcohol ethoxylate) was added in concentrations that bracketed the critical micelle concentration (CMC) in soil (CMC′) (determined to be 13 mg g−1). Addition of the surfactant at a concentration below the CMC′ (2 mg g−1) did not affect the mineralization rates of either hydrocarbon. However, when surfactant was added at a concentration approaching the CMC′ (10 mg g−1), hexadecane mineralization was delayed and phenanthrene mineralization was completely inhibited. Addition of surfactant at concentrations above the CMC′ (40 mg g−1) completely inhibited mineralization of both phenanthrene and hexadecane. Denaturing gradient gel electrophoresis of 16S rRNA gene segments showed that hydrocarbon amendment stimulated Rhodococcus and Nocardia populations that were displaced by Pseudomonas and Alcaligenes populations at elevated surfactant levels. Parallel cultivation studies revealed that the Rhodococcus population can utilize hexadecane and that the Pseudomonas and Alcaligenes populations can utilize both Witconol SN70 and hexadecane for growth. The results suggest that surfactant applications necessary to achieve the CMC alter the microbial populations responsible for hydrocarbon mineralization. PMID:10877792

Features of the propagation of laminar spherical flames initiated by a spark discharge in mixtures of methane, pentane, and hydrogen with air at atmospheric pressure

NASA Astrophysics Data System (ADS)

Rubtsov, N. M.; Seplyarskii, B. S.; Troshin, K. Ya.; Chernysh, V. I.; Tsvetkov, G. I.

2011-10-01

Using high-speed digital color cinematography, we studied the propagation of a laminar spherical flame in stoichiometric mixtures of hydrogen, methane, and pentane with air in the presence of additives at atmospheric pressure in constant-volume reactors, and derived quantitative data on the time of formation of a stable flame front. Cellular flames caused by gas-dynamic instability attributable to convective flows arising during the afterburning of gas were observed in hydrocarbon-air stoichiometric mixtures diluted with inert additives. It was found that the effect of additives of carbon dioxide and argon (>10%) and minor additives of CCl4 on the combustion of hydrocarbons, and of propylene on the combustion of hydrogen-rich mixtures, lead to periods of delay in the development of a laminar spherical flame; in addition, additives of propylene promote the combustion of hydrogen poor mixtures.

On a Thermodynamic Approach to Material Selection for Service in Aggressive Multi-Component Gaseous and/or Vapor Environments

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

Glazoff, Michael Vasily; Marschman, Steven Craig; Soelberg, Nicholas Ray

This report fulfills the M4 milestone, M4FT-15IN08020110 UNF Analysis Support, under Work Package Number FT-15IN080201. The issue of materials selection for many engineering applications represents an important problem, particularly in cases where material failure is possible as a result of corrosive environments. For example, 304 dual purpose or 316 stainless steel is used in the construction of many used nuclear fuel storage canisters. Deployed all over the world, these canisters are housed inside shielded enclosures and cooled passively by convective airflow. When located along seaboards or particular industrial areas, salt, other corrosive chemicals, and moisture can become entrained in themore » air that cools the canisters. It is important to develop an understanding of what impact, if any, that chemical environment will have on those canisters. In many cases of corrosion in aggressive gaseous environments, the material selection process is based on some general recommendations, anecdotal evidence, and/or the past experience of that particular project’s participants. For gaseous mixtures, the theoretical basis is practically limited to the construction of the so-called “Ellingham diagrams” for pure metals. These plots predict the equilibrium temperature between different individual metals, their respective oxides, and oxygen gas. Similar diagrams can be constructed for the reactions with sulfur, nitrogen, carbon, etc. In the generalization of this approach by Richardson and Jeffes, additional scales can be superimposed upon an Ellingham diagram that would correspond to different gaseous mixtures, e.g. CO/CO 2, or H 2/H 2O. However, while the general approach to predicting the stability of a multi-component heterogeneous alloy (e.g., steel or a superalloy) in a multi-component aggressive gaseous environment was developed in very general form, actual examples of its applications to concrete real-life problems are practically absent. This is related to

Hierarchy of Supercurrents in Multicomponent Atomic Josephson Vortices

NASA Astrophysics Data System (ADS)

Kaurov, Vitaliy

2009-03-01

We show that a quasi-1D long atomic Josephson junction [1,2] containing a mixture of BECs can sustain multi-component Josephson vortices (mJV). A new exact soliton solution is given to describe a stationary mJV in the general N-component case. Depending on system parameters (scattering lengths, tunneling strengths, and chemical potentials) Josephson supercurrents of different components form a hierarchy according to their intensity and proximity to phase slip. By tuning the parameters it is possible to turn off or on particular currents using the JV -- dark soliton interconversion effect [1,2]. Inside the mJV different components may circulate either in the same or opposite directions resulting in bulk super-counter-flow in the latter case. The weak tunneling limit can be described by a modified Sine-Gordon model. An approximate solution for mJV propagating along the junction is found for the two-component case. The degeneracy of stationary mJV with respect to co-flow or counter-flow configurations is lifted by the uniform motion of mJV. Which configuration is energetically preferable depends on the interspecies scattering length. [1] V. M. Kaurov and A. B. Kuklov, Phys. Rev. A 71, 011601(R) (2005). [2] V. M. Kaurov and A. B. Kuklov, Phys. Rev. A 73, 013627 (2006).

Coal liquefaction process using pretreatment with a binary solvent mixture

DOEpatents

Miller, R.N.

1986-10-14

An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300 C before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil. 1 fig.

A Weibull characterization for tensile fracture of multicomponent brittle fibers

NASA Technical Reports Server (NTRS)

Barrows, R. G.

1977-01-01

A statistical characterization for multicomponent brittle fibers in presented. The method, which is an extension of usual Weibull distribution procedures, statistically considers the components making up a fiber (e.g., substrate, sheath, and surface) as separate entities and taken together as in a fiber. Tensile data for silicon carbide fiber and for an experimental carbon-boron alloy fiber are evaluated in terms of the proposed multicomponent Weibull characterization.

Cascade multicomponent synthesis of indoles, pyrazoles, and pyridazinones by functionalization of alkenes.

PubMed

Matcha, Kiran; Antonchick, Andrey P

2014-10-27

The development of multicomponent reactions for indole synthesis is demanding and has hardly been explored. The present study describes the development of a novel multicomponent, cascade approach for indole synthesis. Various substituted indole derivatives were obtained from simple reagents, such as unfunctionalized alkenes, diazonium salts, and sodium triflinate, by using an established straightforward and regioselective method. The method is based on the radical trifluoromethylation of alkenes as an entry into Fischer indole synthesis. Besides indole synthesis, the application of the multicomponent cascade reaction to the synthesis of pyrazoles and pyridazinones is described. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrocarbons in recent sediment of the Monterey Bay National Marine Sanctuary

USGS Publications Warehouse

Kvenvolden, K.A.; Hostettler, F.D.; Rosenbauer, R.W.; Lorenson, T.D.; Castle, W.T.; Sugarman, S.

2002-01-01

A complex mixture of hydrocarbons is present in the recent sediment of the Monterey Bay National Marine Sanctuary. Eighteen samples from the continental shelf between San Francisco and Monterey contain aliphatic and aromatic hydrocarbons showing biological contributions from both marine and terrigenous sources, with the terrigenous indicators more pronounced near Monterey. Of particular interest, however, is a low-level background of petroleum-related compounds, including 28,30-bisnorhopane and 18??+??(H)-oleanane, which are characteristic of many crude oils from the Monterey Formation of California. Thus, the sediments are overprinted by a regional chemical signature which may be derived from eroded Monterey Formation rocks and from onshore and offshore seeps releasing petroleum from Monterey Formation source rocks. ?? 2002 Elsevier Science B.V. All rights reserved.

An isotherm-based thermodynamic model of multicomponent aqueous solutions, applicable over the entire concentration range.

PubMed

Dutcher, Cari S; Ge, Xinlei; Wexler, Anthony S; Clegg, Simon L

2013-04-18

In previous studies (Dutcher et al. J. Phys. Chem. C 2011, 115, 16474-16487; 2012, 116, 1850-1864), we derived equations for the Gibbs energy, solvent and solute activities, and solute concentrations in multicomponent liquid mixtures, based upon expressions for adsorption isotherms that include arbitrary numbers of hydration layers on each solute. In this work, the long-range electrostatic interactions that dominate in dilute solutions are added to the Gibbs energy expression, thus extending the range of concentrations for which the model can be used from pure liquid solute(s) to infinite dilution in the solvent, water. An equation for the conversion of the reference state for solute activity coefficients to infinite dilution in water has been derived. A number of simplifications are identified, notably the equivalence of the sorption site parameters r and the stoichiometric coefficients of the solutes, resulting in a reduction in the number of model parameters. Solute concentrations in mixtures conform to a modified Zdanovskii-Stokes-Robinson mixing rule, and solute activity coefficients to a modified McKay-Perring relation, when the effects of the long-range (Debye-Hückel) term in the equations are taken into account. Practical applications of the equations to osmotic and activity coefficients of pure aqueous electrolyte solutions and mixtures show both satisfactory accuracy from low to high concentrations, together with a thermodynamically reasonable extrapolation (beyond the range of measurements) to extreme concentration and to the pure liquid solute(s).

General Synthetic Strategy for Libraries of Supported Multicomponent Metal Nanoparticles.

PubMed

Yang, Hui; Bradley, Siobhan J; Wu, Xin; Chan, Andrew; Waterhouse, Geoffrey I N; Nann, Thomas; Zhang, Jian; Kruger, Paul E; Ma, Shengqian; Telfer, Shane G

2018-04-18

Nanoparticles comprising three or more different metals are challenging to prepare. General methods that tackle this challenge are highly sought after as multicomponent metal nanoparticles display favorable properties in applications such as catalysis, biomedicine, and imaging. Herein, we report a practical and versatile approach for the synthesis of nanoparticles composed of up to four different metals. This method relies on the thermal decomposition of nanostructured composite materials assembled from platinum nanoparticles, a metal-organic framework (ZIF-8), and a tannic acid coordination polymer. The controlled integration of multiple metal cations (Ni, Co, Cu, Mn, Fe, and/or Tb) into the tannic acid shell of the precursor material dictates the composition of the final multicomponent metal nanoparticles. Upon thermolysis, the platinum nanoparticles seed the growth of the multicomponent metal nanoparticles via coalescence with the metallic constituents of the tannic acid coordination polymer. The nanoparticles are supported in the walls of hollow nitrogen-doped porous carbon capsules created by the decomposition of the organic components of the precursor. The capsules prevent sintering and detachment of the nanoparticles, and their porosity allows for efficient mass transport. To demonstrate the utility of producing a broad library of supported multicomponent metal nanoparticles, we tested their electrocatalytic performance toward the hydrogen evolution reaction and oxygen evolution reaction. We discovered functional relationships between the composition of the nanoparticles and their electrochemical activity and identified the PtNiCu and PtNiCuFe nanoparticles as particularly efficient catalysts. This highlights how to generate diverse libraries of multicomponent metal nanoparticles that can be synthesized and subsequently screened to identify high-performance materials for target applications.

Catalysis and Multi-Component Reactions

NASA Astrophysics Data System (ADS)

Shibasaki, Masakatsu; Yus, Miguel; Bremner, Stacy; Comer, Eamon; Shore, Gjergji; Morin, Sylvie; Organ, Michael G.; van der Eycken, Erik; Merkul, Eugen; Dorsch, Dieter; Müller, Thomas J. J.; Ryabukhin, Sergey V.; Ostapchuk, Eugeniy N.; Plaskon, Andrey S.; Volochnyuk, Dmitriy M.; Shivanyuk, Alexander N.; Tolmachev, Andrey A.; Sheibani, Hassan; Babaie, Maryam; Behzadi, Soheila; Dabiri, Minoo; Bahramnejad, Mahboobeh; Bashiribod, Sahareh; Hekmatshoar, Rahim; Sadjadi, Sodeh; Khorasani, Mohammad; Polyakov, Anatoliy I.; Eryomina, Vera A.; Medvedeva, Lidiya A.; Tihonova, Nadezhda I.; Listratova, Anna V.; Voskressensky, Leonid G.; Merkul, Eugen; Dorsch, Dieter; Müller, Thomas J. J.; Sheibani, Hassan; Esfandiarpoor, Zeinab; Behzadi, Soheila; Titova, Julia A.; Fedorova, Olga V.; Ovchinnikova, Irina G.; Valova, Marina S.; Koryakova, Olga V.; Rusinov, Gennady L.; Charushin, Valery N.; Hekmatshoar, Rahim; Sadjadi, Sodeh

We have been studying the development of new asymmetric two-center catalysis using rare earth alkoxides and bifunctional sugar and related ligands. In The Fourth International Conference on Multi-Component Reactions and Related Chemistry (MCR 2009), new catalytic asymmetric reactions using catalysts 1 and 2 and catalytic asymmetric syntheses of ranirestat 3 and tamiflu 4 will be presented.

Nanoporous Boron Nitride as Exceptionally Thermally Stable Adsorbent: Role in Efficient Separation of Light Hydrocarbons.

PubMed

Saha, Dipendu; Orkoulas, Gerassimos; Yohannan, Samuel; Ho, Hoi Chun; Cakmak, Ercan; Chen, Jihua; Ozcan, Soydan

2017-04-26

In this work, nanoporous boron nitride sample was synthesized with a Brunauer-Emmett-Teller (BET) surface area of 1360 m 2 /g and particle size 5-7 μm. The boron nitride was characterized with X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electron microscopy (TEM and SEM). Thermogravimetric analysis (TGA) under nitrogen and air and subsequent analysis with XPS and XRD suggested that its structure is stable in air up to 800 °C and in nitrogen up to 1050 °C, which is higher than most of the common adsorbents reported so far. Nitrogen and hydrocarbon adsorption at 298 K and pressure up to 1 bar suggested that all hydrocarbon adsorption amounts were higher than that of nitrogen and the adsorbed amount of hydrocarbon increases with an increase in its molecular weight. The kinetics of adsorption data suggested that adsorption becomes slower with the increase in molecular weight of hydrocarbons. The equilibrium data suggested that that boron nitride is selective to paraffins in a paraffin-olefin mixture and hence may act as an "olefin generator". The ideal adsorbed solution theory (IAST)-based selectivity for CH 4 /N 2 , C 2 H 6 /CH 4 , and C 3 H 8 /C 3 H 6 was very high and probably higher than the majority of adsorbents reported in the literature. IAST-based calculations were also employed to simulate the binary mixture adsorption data for the gas pairs of CH 4 /N 2 , C 2 H 6 /CH 4 , C 2 H 6 /C 2 H 4 , and C 3 H 8 /C 3 H 6 . Finally, a simple mathematical model was employed to simulate the breakthrough behavior of the above-mentioned four gas pairs in a dynamic column experiment. The overall results suggest that nanoporous boron nitride can be used as a potential adsorbent for light hydrocarbon separation.

Production of saturated and unsaturated silahydrocarbon mixtures using rhodium catalyst, and to products produced thereby

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

Onopchenki, A.; Sabourin, E.T.

1986-02-25

This patent describes a process for the production of a mixture of saturated and unstaurated silahydrocarbons. This process contacts an admixture consisting of (A) at least one alpha-olefin containing from 2 to about 20 carbon atoms per molecule, and (B) at least one alkylsilane selected from the group consisting of (i) a dialkylsilane (ii) a trialkylsilane (iii) mixtures thereof, with a catalyst consisting of a homogeneous monomeric rhodium-containing catalyst having a basicity substantially equal to or less than that provided by a rhodium-containing catalyst having a triphenyl phosphine ligand or a heterogeneous rhodium-containing catalyst in a halogen-free inert solvent. Themore » process conducted at a temperature of from about 30/sup 0/ to about 200/sup 0/C., a weight ratio of olefin to alkylsilane of from about 0.5 to about 20 to one and a catalyst concentration of from about 1 x 10-/sup 5/ to about 1 x 10-/sup 2/ millimoles of catalyst per millimole alkylsilane, to produce a mixture containing saturated silane hydrocarbons and an unsaturated silahydrocarbon. Inclusive with the proviso that the molecular weight of the unsaturated silane hydrocarbon is above 300.« less

Compartmentalisation Strategies for Hydrocarbon-based Biota on Titan

NASA Astrophysics Data System (ADS)

Norman, Lucy; Skipper, N.; Fortes, A. D.; Crawford, I.

2012-05-01

The goal of our study is to determine the nature of compartimentalisation strategies for any organisms inhabiting the hydrocarbon polar lakes of Titan (the largest moon of Saturn). Titan is the only moon in the solar system with a substantial atmosphere; it has a remarkably earth- like ‘hydrological' cycle, with evidence for storm cloud activity, rainfall and river systems, often with subsequent drainage into lakes and seas at high latitudes (1, 2). However, at the low surface temperature of 94 K, the liquid involved is not water, but a mixture of methane, ethane and propane (3). Due to Titan's plethora of organic chemistries it has long been recognised that it may provide useful insights into the pre-biotic evolution of early Earth (4). Since receiving huge amounts of data via the Cassini-Huygens mission to the Saturnian system astrobiologists have speculated that exotic biota might currently inhabit this environment, consuming acetylene (snowed onto the surface as a result of atmospheric photochemistry) and hydrogen whilst excreting methane (5, 6). This consumption should lead to an anomalous hydrogen depletion near the surface; and evidence to suggest this depletion exists has been published (7). Nevertheless, many questions still remain concerning the possible physiological traits of biota in these environments, including whether cell- like structures can form in low temperature, low molecular weight hydrocarbons. Terrestrial cell membranes are vesicular structures composed primarily of a phospholipid bilayer with the hydrophilic head groups arranged around the periphery. Simplified analogues of these structures, called liposomes, plus vesicles prepared from other surfactant types e.g. polymers, are artificially prepared primarily for pharmaceutical reasons e.g. drug delivery. However, these types of model cell membrane are also thought to be akin to the first proto-cells that terrestrial life utilised (8). Recently reversed aggregate types, such as reverse

Hydrothermal synthesis of hydrocarbons at low temperature. Implications for sustaining a biosphere in Europa

NASA Astrophysics Data System (ADS)

Navarro-Gonzalez, Rafael; Montoya, Lilia; Davis, Wanda; McKay, Chris

Observational evidence from Earth-borne systems and space missions as well as theoretical arguments suggest that Jupiter's satellite Europa could be geologically active today and may possess an ocean of liquid water of about 100 km deep underneath the icy surface about 10 km thickness. The existence of an aqueous ocean is an important requirement for life, as we know it. However, a biosphere also depends of an adequate energy source to drive the most fundamental biological processes such as metabolism, growth, reproduction, etc. Methanogenesis associated with hydrothermal vents may potentially drive a biosphere in an European ocean. We report here on the production of a large variety of hydrocarbons in hydrothermal systems at low temperatures (150° C). The chemical composition of the hydrothermal vent gases was derived from a thermochemical model that assumes that Europa had a cometary (solar, less H) abundance at high temperatures characteristic of a vent. Specifically the following gas mixture was used: 45% CO2 , 45% CH4, and 10 % N2 . A 500 ml stainless steel reactor was filled with 200 ml triply distilled water and the gas mixture at 1 bar at 25° C. In some experiments 3 g of pyrite were added into the reaction vessel. The system was heated for 24 hrs in the temperature range from 100 to 375° C. At the completion of the experiment, the reaction was quenched to 25° C and the gas mixture was analyzed by GC-FTIR-MS techniques. In the absence of pyrite, methane is oxidized to carbon dioxide with the possible production of hydrogen. In contrast in the presence of pyrite, methane is converted into a suite of hydrocarbons from C2 to C7 containing all possible isomers. The production of these compounds was found at temperatures as low as 150° C. In order to get a better understanding of the chemical mechanism involved in the synthesis of hydrocarbons and explore the effect on the initial oxidation state of the carbon used, we performed additional experiments in

From supramolecular polymers to multi-component biomaterials.

PubMed

Goor, Olga J G M; Hendrikse, Simone I S; Dankers, Patricia Y W; Meijer, E W

2017-10-30

The most striking and general property of the biological fibrous architectures in the extracellular matrix (ECM) is the strong and directional interaction between biologically active protein subunits. These fibers display rich dynamic behavior without losing their architectural integrity. The complexity of the ECM taking care of many essential properties has inspired synthetic chemists to mimic these properties in artificial one-dimensional fibrous structures with the aim to arrive at multi-component biomaterials. Due to the dynamic character required for interaction with natural tissue, supramolecular biomaterials are promising candidates for regenerative medicine. Depending on the application area, and thereby the design criteria of these multi-component fibrous biomaterials, they are used as elastomeric materials or hydrogel systems. Elastomeric materials are designed to have load bearing properties whereas hydrogels are proposed to support in vitro cell culture. Although the chemical structures and systems designed and studied today are rather simple compared to the complexity of the ECM, the first examples of these functional supramolecular biomaterials reaching the clinic have been reported. The basic concept of many of these supramolecular biomaterials is based on their ability to adapt to cell behavior as a result of dynamic non-covalent interactions. In this review, we show the translation of one-dimensional supramolecular polymers into multi-component functional biomaterials for regenerative medicine applications.

Sensitivity of the immature rat uterotrophic assay to mixtures of estrogens.

PubMed Central

Tinwell, Helen; Ashby, John

2004-01-01

We have evaluated whether mixtures of estrogens, present in the mix at doses that are individually inactive in the immature rat uterotrophic assay, can give a uterotrophic response. Seven chemicals were evaluated: nonylphenol, bisphenol A (BPA), methoxychlor, genistein (GEN), estradiol, diethylstilbestrol, and ethinyl estradiol. Dose responses in the uterotrophic assay were constructed for each chemical. The first series of experiments involved evaluating binary mixtures of BPA and GEN at dose levels that gave moderate uterotrophic responses when tested individually. The mixtures generally showed an intermediate or reduced uterotrophic effect compared with when the components of the mixture were tested alone at the dose used in the mixture. The next series of experiments used a multicomponent (complex) mixture of all seven chemicals evaluated at doses that gave either weakly positive or inactive uterotrophic responses when tested individually in the assay. Doses that were nominally equi-uterotrophic ranged over approximately six orders of magnitude for the seven chemicals. Doses of agents that gave a weak uterotrophic response when tested individually gave a marginally enhanced positive response in the assay when tested combined as a mixture. Doses of agents that gave a negative uterotrophic response when tested individually gave a positive response when tested as a mixture. These data indicate that a variety of different estrogen receptor (ER) agonists, present individually at subeffective doses, can act simultaneously to evoke an ER-regulated response. However, translating these findings into the process of environmental hazard assessment will be difficult. The simple addition of the observed, or predicted, activities for the components of a mixture is confirmed here to be inappropriate and to overestimate the actual effect induced by the mixture. Equally, isobole analysis is only suitable for two- or three-component mixtures, and concentration addition requires

ANALYSES OF THE INTERACTIONS WITHIN BINARY MIXTURES OF CARCINOGENIC PAHS USING MORPHOLOGICAL CELL TRANSFORMATION OF C3H10T1/2CL8 CELLS

EPA Science Inventory

ANALYSES OF THE INTERACTIONS WITHIN BINARY MIXTURES OF CARCINOGENIC PAHS USING MORPHOLOGICAL CELL TRANSFORMATION OF C3HIOT1/2 CL8 CELLS.

Studies of defined mixtures of carcinogenic polycyclic aromatic hydrocarbons (PAH) have identified three major categories of interacti...

Selective separation of fluorinated compounds from complex organic mixtures by pyrolysis-comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry.

PubMed

Nakajima, Yoji; Arinami, Yuko; Yamamoto, Kiyoshi

2014-12-29

The usefulness of comprehensive two-dimensional gas chromatography (GC×GC) was demonstrated for the selective separation of fluorinated compounds from organic mixtures, such as kerosene/perfluorokerosene mixtures, pyrolysis products derived from polyethylene/ethylene-tetrafluoroethylene alternating copolymer mixture and poly[2-(perfluorohexyl)ethyl acrylate]. Perfluorocarbons were completely separated from hydrocarbons in the two-dimensional chromatogram. Fluorohydrocarbons in the pyrolysis products of polyethylene/ethylene-tetrafluoroethylene alternating copolymer mixture were selectively isolated from their hydrocarbon counterparts and regularly arranged according to their chain length and fluorine content in the two-dimensional chromatogram. A reliable structural analysis of the fluorohydrocarbons was achieved by combining effective GC×GC positional information with accurate mass spectral data obtained by high-resolution time-of-flight mass spectrometry (HRTOF-MS). 2-(Perfluorohexyl)ethyl acrylate monomer, dimer, and trimer as well as 2-(perfluorohexyl)ethyl alcohol in poly[2-(perfluorohexyl)ethyl acrylate] pyrolysis products were detected in the bottommost part of the two-dimensional chromatogram with separation from hydrocarbons possessing terminal structure information about the polymer, such as α-methylstyrene. Pyrolysis-GC×GC/HRTOF-MS appeared particularly suitable for the characterization of fluorinated polymer microstructures, such as monomer sequences and terminal groups. Copyright © 2014 Elsevier B.V. All rights reserved.

The use of gaseous fuels mixtures for SI engines propulsion

NASA Astrophysics Data System (ADS)

Flekiewicz, M.; Kubica, G.

2016-09-01

Paper presents results of SI engine tests, carried on for different gaseous fuels. Carried out analysis made it possible to define correlation between fuel composition and engine operating parameters. Tests covered various gaseous mixtures: of methane and hydrogen and LPG with DME featuring different shares. The first group, considered as low carbon content fuels can be characterized by low CO2 emissions. Flammability of hydrogen added in those mixtures realizes the function of combustion process activator. That is why hydrogen addition improves the energy conversion by about 3%. The second group of fuels is constituted by LPG and DME mixtures. DME mixes perfectly with LPG, and differently than in case of other hydrocarbon fuels consists also of oxygen makes the stoichiometric mixture less oxygen demanding. In case of this fuel an improvement in engine volumetric and overall engine efficiency has been noticed, when compared to LPG. For the 11% DME share in the mixture an improvement of 2% in the efficiency has been noticed. During the tests standard CNG/LPG feeding systems have been used, what underlines utility value of the research. The stand tests results have been followed by combustion process simulation including exhaust forming and charge exchange.

Method for simultaneous recovery of hydrogen from water and from hydrocarbons

DOEpatents

Willms, R. Scott

1996-01-01

Method for simultaneous recovery of hydrogen and hydrogen isotopes from water and from hydrocarbons. A palladium membrane, when utilized in cooperation with a nickel catalyst in a reactor, has been found to drive reactions such as water gas shift, steam reforming and methane cracking to substantial completion by removing the product hydrogen from the reacting mixture. In addition, ultrapure hydrogen is produced, thereby eliminating the need for an additional processing step.

Diagnostics of capacitively-coupled hydrocarbon plasmas for deposition of diamond-like carbon films using quadrupole mass spectrometry and Langmuir probe

NASA Astrophysics Data System (ADS)

Oda, Akinori; Fukai, Shun; Kousaka, Hiroyuki; Ohta, Takayuki

2015-09-01

Diamond-like carbon (DLC) films are the hydrogenated amorphous carbon films, which contains a mixture of sp2- and sp3-bonded carbon. The DLC films have been widely used for various applications, such as automotive, semiconductors, medical devices, since have excellent material properties in lower friction, higher chemical stability, higher hardness, higher wear resistance. Until now, numerous investigations on the DLC films using plasma assisted chemical vapor deposition have been done. For precise control of coating technique of DLC films, it is enormously important to clarify the fundamental properties in hydrocarbon plasmas, as a source of hydrocarbon ions and radicals. In this paper, the fundamental properties in a low pressure radio-frequency hydrocarbon (Ar/CH4 (1 %) gas mixture) plasmas have been diagnosed using a quadrupole mass spectrometer (HIDEN ANARYTICAL Ltd., EQP-300) and Langmuir probe system (HIDEN ANARYTICAL Ltd., ESPion). This work was partly supported by KAKENHI (No.26420247), and a ``Grant for Advanced Industrial Technology Development (No.11B06004d)'' in 2011 from the New Energy and Industrial Technology Development Organization (NEDO) of Japan.

Size matters in the water uptake and hygroscopic growth of atmospherically relevant multicomponent aerosol particles.

PubMed

Laskina, Olga; Morris, Holly S; Grandquist, Joshua R; Qin, Zhen; Stone, Elizabeth A; Tivanski, Alexei V; Grassian, Vicki H

2015-05-14

Understanding the interactions of water with atmospheric aerosols is crucial for determining the size, physical state, reactivity, and climate impacts of this important component of the Earth's atmosphere. Here we show that water uptake and hygroscopic growth of multicomponent, atmospherically relevant particles can be size dependent when comparing 100 nm versus ca. 6 μm sized particles. It was determined that particles composed of ammonium sulfate with succinic acid and of a mixture of chlorides typical of the marine environment show size-dependent hygroscopic behavior. Microscopic analysis of the distribution of components within the aerosol particles show that the size dependence is due to differences in the mixing state, that is, whether particles are homogeneously mixed or phase separated, for different sized particles. This morphology-dependent hygroscopicity has consequences for heterogeneous atmospheric chemistry as well as aerosol interactions with electromagnetic radiation and clouds.

Bioassays with terrestrial and aquatic species as monitoring tools of hydrocarbon degradation.

PubMed

Bori, Jaume; Vallès, Bettina; Ortega, Lina; Riva, Maria Carme

2016-09-01

In this study chemical analyses and ecotoxicity tests were applied for the assessment of a heavily hydrocarbon-contaminated soil prior and after the application of a remediation procedure that consisted in the stimulation of soil autochthonous populations of hydrocarbon degraders in static-ventilated biopiles. Terrestrial bioassays were applied in mixtures of test soils and artificial control soil and studied the survival and reproduction of Eisenia fetida and the avoidance response of E. fetida and Folsomia candida. Effects on aquatic organisms were studied by means of acute tests with Vibrio fischeri, Raphidocelis subcapitata, and Daphnia magna performed on aqueous elutriates from test soils. The bioremediation procedure led to a significant reduction in the concentration of hydrocarbons (from 34264 to 3074 mg kg(-1), i.e., 91 % decrease) and toxicity although bioassays were not able to report a percentage decrease of toxicity as high as the percentage reduction. Sublethal tests proved the most sensitive terrestrial bioassays and avoidance tests with earthworms and springtails showed potential as monitoring tools of hydrocarbon remediation due to their high sensitivity and short duration. The concentrations of hydrocarbons in water extracts from test soils were 130 and 100 μg L(-1) before and after remediation, respectively. Similarly to terrestrial tests, most aquatic bioassays detected a significant reduction in toxicity, which was almost negligible at the end of the treatment. D. magna survival was the most affected by soil elutriates although toxicity to the crustacean was associated to the salinity of the samples rather than to the concentration of hydrocarbons. Ecotoxicity tests with aqueous soil elutriates proved less relevant in the assessment of hydrocarbon-contaminated soils due to the low hydrosolubility of hydrocarbons and the influence of the physicochemical parameters of the aquatic medium.

Usage of air jigging for multi-component separation of construction and demolition waste.

PubMed

Ambrós, Weslei Monteiro; Sampaio, Carlos Hoffmann; Cazacliu, Bogdan Grigore; Miltzarek, Gerson Luis; Miranda, Leonardo R

2017-02-01

The use of air jigging for performing multi-component separation in the treatment of mixed construction and demolition waste was studied. Sorting tests were carried out with mixtures of equal bulk volume of concrete and brick in which fixed quantities of unwanted materials - gypsum, wood and paper - were added. Experimental results have demonstrated the possibility to use air jigging to carry out both the removal of low-density contaminants and the concrete concentration in only one process step. In relation to the removal of contaminants only, the overall performance of jigging process can be comparable with that of commercial air classifiers and automatic sorting systems. Also, the initial content of contaminants seems does not have a significant effect on the separation extent. These results are of particular importance for recycling plants processing as they represent an alternative to optimize the use of air jigs. Further investigation is needed in order to evaluate the practical feasibility of such method. Copyright © 2016 Elsevier Ltd. All rights reserved.

Transferrable monolithic multicomponent system for near-ultraviolet optoelectronics

NASA Astrophysics Data System (ADS)

Qin, Chuan; Gao, Xumin; Yuan, Jialei; Shi, Zheng; Jiang, Yuan; Liu, Yuhuai; Wang, Yongjin; Amano, Hiroshi

2018-05-01

A monolithic near-ultraviolet multicomponent system is implemented on a 0.8-mm-diameter suspended membrane by integrating a transmitter, waveguide, and receiver into a single chip. Two identical InGaN/Al0.10Ga0.90N multiple-quantum well (MQW) diodes are fabricated using the same process flow, which separately function as a transmitter and receiver. There is a spectral overlap between the emission and detection spectra of the MQW diodes. Therefore, the receiver can respond to changes in the emission of the transmitter. The multicomponent system is mechanically transferred from silicon, and the wire-bonded transmitter on glass experimentally demonstrates spatial light transmission at 200 Mbps using non-return-to-zero on–off keying modulation.

Multicomponent cognitive-behavioral group therapy with hypnosis for the treatment of fibromyalgia: long-term outcome.

PubMed

Castel, Antoni; Cascón, Rosalia; Padrol, Anna; Sala, José; Rull, Maria

2012-03-01

This study compared the efficacy of 2 psychological treatments for fibromyalgia with each other and with standard care. Ninety-three patients with fibromyalgia (FM) were randomly assigned to 1 of the 3 experimental conditions: 1) multicomponent cognitive-behavioral therapy (CBT); 2) multicomponent CBT with hypnosis; and 3) pharmacological treatment (standard care control group). The outcome measures of pain intensity, catastrophizing, psychological distress, functionality, and sleep disturbances were assessed before treatment, immediately after treatment, and at 3- and 6-month follow-up visits. CBT and CBT with hypnosis participants received the standard pharmacological management plus 14 weekly, 120-minute-long sessions of psychological treatment. All but 1 session followed a group format; the remaining session was individual. The analyses indicated that: 1) patients with FM who received multicomponent CBT alone or multicomponent CBT with hypnosis showed greater improvements than patients who received only standard care; and 2) adding hypnosis enhanced the effectiveness of multicomponent CBT. This study presents new evidence about the efficacy of multicomponent CBT for FM and about the additional effects of hypnosis as a complement to CBT. The relevance and implications of the obtained results are discussed. This article highlights the beneficial effects of adding hypnosis in a multicomponent cognitive-behavioral group treatment of fibromyalgia patients. Also, this research showed that by adding hypnosis the length of treatment did not increase. Copyright © 2012 American Pain Society. Published by Elsevier Inc. All rights reserved.

Formulation of electroclinic, ferroelectric and antiferroelectric liquid crystal mixtures suitable for display devices

NASA Astrophysics Data System (ADS)

Debnath, Asim; Goswami, Debarghya; Mandal, Pradip Kumar

2018-04-01

Most of the liquid crystal display (LCD) devices starting from simplest wrist watches or calculators to complex laptops or flat TV sets are based on nematics. Although a tremendous improvement in the quality of display as well as reduction of manufacturing cost has taken place over the years, there are many issues which the LC industry is trying hard to address. Ferroelectric liquid crystals (FLC) are of current interest in the LCD industry since among various other advantages FLC based displays have micro-second order switching compared to milli-second order switching in nematic based displays. To meet the market demand much effort has been made to optimize the physical parameters of FLCs, such as temperature range, spontaneous polarization (PS), helical pitch (p), switching time (τ), tilt angle (θ) and rotational viscosity (γ). Multicomponent mixtures are, therefore, formulated to optimize all the required properties for practical applications since no single FLC compound can satisfy the above requirements. To the best of our knowledge electroclinic, ferroelectric and antiferroelectric liquid crystal mixtures have been formulated first time by any Indian group which have properties suitable for FLC based display devices and at par with mixtures used in the industry.

Methods of reforming hydrocarbon fuels using hexaaluminate catalysts

DOEpatents

Gardner, Todd H [Morgantown, WV; Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV

2012-03-27

A metal substituted hexaaluminate catalyst for reforming hydrocarbon fuels to synthesis gas of the general formula AB.sub.yAl.sub.12-yO.sub.19-.delta., A being selected from alkali metals, alkaline earth metals and lanthanide metals or mixtures thereof. A dopant or surface modifier selected from a transitions metal, a spinel of an oxygen-ion conductor is incorporated. The dopant may be Ca, Cs, K, La, Sr, Ba, Li, Mg, Ce, Co, Fe, Ir, Rh, Ni, Ru, Cu, Pe, Os, Pd, Cr, Mn, W, Re, Sn, Gd, V, Ti, Ag, Au, and mixtures thereof. The oxygen-ion conductor may be a perovskite selected from M'RhO.sub.3, M'PtO.sub.3, M'PdO.sub.3, M'IrO.sub.3, M'RuO.sub.3 wherein M'=Mg, Sr, Ba, La, Ca; a spinel selected from MRh.sub.2O.sub.4, MPt.sub.2O.sub.4, MPd.sub.2O.sub.4, MIr.sub.2O.sub.4, MRu.sub.2O.sub.4 wherein M=Mg, Sr, Ba, La, Ca and mixtures thereof; a florite is selected from M''O.sub.2.

Removal of hydrocarbon from refinery tank bottom sludge employing microbial culture.

PubMed

Saikia, Rashmi Rekha; Deka, Suresh

2013-12-01

Accumulation of oily sludge is becoming a serious environmental threat, and there has not been much work reported for the removal of hydrocarbon from refinery tank bottom sludge. Effort has been made in this study to investigate the removal of hydrocarbon from refinery sludge by isolated biosurfactant-producing Pseudomonas aeruginosa RS29 strain and explore the biosurfactant for its composition and stability. Laboratory investigation was carried out with this strain to observe its efficacy of removing hydrocarbon from refinery sludge employing whole bacterial culture and culture supernatant to various concentrations of sand-sludge mixture. Removal of hydrocarbon was recorded after 20 days. Analysis of the produced biosurfactant was carried out to get the idea about its stability and composition. The strain could remove up to 85 ± 3 and 55 ± 4.5 % of hydrocarbon from refinery sludge when whole bacterial culture and culture supernatant were used, respectively. Maximum surface tension reduction (26.3 mN m(-1)) was achieved with the strain in just 24 h of time. Emulsification index (E24) was recorded as 100 and 80 % with crude oil and n-hexadecane, respectively. The biosurfactant was confirmed as rhamnolipid containing C8 and C10 fatty acid components and having more mono-rhamnolipid congeners than the di-rhamnolipid ones. The biosurfactant was stable up to 121 °C, pH 2-10, and up to a salinity value of 2-10 % w/v. To our knowledge, this is the first report showing the potentiality of a native strain from the northeast region of India for the efficient removal of hydrocarbon from refinery sludge.

Catalytic conversion of biomass-derived ethanol to liquid hydrocarbon blend-stock: Effect of light gas recirculation

DOE PAGES

Li, Zhenglong; Lepore, Andrew W.; Davison, Brian H.; ...

2016-01-01

Here, we describe a light gas recirculation (LGR) method to increase the liquid hydrocarbon yield with reduced aromatic content from catalytic conversion of ethanol to hydrocarbons. The previous liquid hydrocarbon yield is ~40% from one-pass ethanol conversion over V-ZSM-5 at 350 C and atmospheric pressure where the remaining ~60% yield is light gas hydrocarbons. In comparison, the liquid hydrocarbon yield increases to 80% when a simulated light gas hydrocarbon stream is co-fed at a rate of 0.053 mol g-1 h-1 with ethanol due to the conversion of most of the light olefins. The LGR also significantly improves the quality ofmore » the liquid hydrocarbon blend-stock by reducing aromatic content and overall benzene concentration. For 0.027 mol g-1 h-1 light gas mixture co-feeding, the average aromatic content in liquid hydrocarbons is 51.5% compared with 62.5% aromatic content in ethanol only experiment. Average benzene concentration decreases from 3.75% to 1.5% which is highly desirable since EPA limits benzene concentration in gasoline to 0.62%. As a result of low benzene concentration, the blend-wall for ethanol derived liquid hydrocarbons changes from ~18% to 43%. The remaining light paraffins and olefins can be further converted to valuable BTX products (94% BTX in the liquid) over Ga-ZSM-5 at 500 C. Thus, the LGR is an effective approach to convert ethanol to liquid hydrocarbons with higher liquid yield and low aromatic content, especially low benzene concentration, which could be blended with gasoline in a much higher ratio than ethanol or ethanol derived hydrocarbon blend-stock.« less

Catalytic conversion of biomass-derived ethanol to liquid hydrocarbon blend-stock: Effect of light gas recirculation

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

Li, Zhenglong; Lepore, Andrew W.; Davison, Brian H.

Here, we describe a light gas recirculation (LGR) method to increase the liquid hydrocarbon yield with reduced aromatic content from catalytic conversion of ethanol to hydrocarbons. The previous liquid hydrocarbon yield is ~40% from one-pass ethanol conversion over V-ZSM-5 at 350 C and atmospheric pressure where the remaining ~60% yield is light gas hydrocarbons. In comparison, the liquid hydrocarbon yield increases to 80% when a simulated light gas hydrocarbon stream is co-fed at a rate of 0.053 mol g-1 h-1 with ethanol due to the conversion of most of the light olefins. The LGR also significantly improves the quality ofmore » the liquid hydrocarbon blend-stock by reducing aromatic content and overall benzene concentration. For 0.027 mol g-1 h-1 light gas mixture co-feeding, the average aromatic content in liquid hydrocarbons is 51.5% compared with 62.5% aromatic content in ethanol only experiment. Average benzene concentration decreases from 3.75% to 1.5% which is highly desirable since EPA limits benzene concentration in gasoline to 0.62%. As a result of low benzene concentration, the blend-wall for ethanol derived liquid hydrocarbons changes from ~18% to 43%. The remaining light paraffins and olefins can be further converted to valuable BTX products (94% BTX in the liquid) over Ga-ZSM-5 at 500 C. Thus, the LGR is an effective approach to convert ethanol to liquid hydrocarbons with higher liquid yield and low aromatic content, especially low benzene concentration, which could be blended with gasoline in a much higher ratio than ethanol or ethanol derived hydrocarbon blend-stock.« less

An Experimental Investigation of Hypergolic Ignition Delay of Hydrogen Peroxide with Fuel Mixtures

NASA Technical Reports Server (NTRS)

Blevins, John A.; Gostowski, Rudy; Chianese, Silvio

2003-01-01

An experimental evaluation of decomposition and ignition delay of hydrogen peroxide at concentrations of 80% to 98% with combinations of hydrocarbon fuels, tertiary amines and transition metal chelates will be presented in the proposed paper. The results will be compared to hydrazine ignition delays with hydrogen peroxide and nitric acid mixtures using the same test apparatus.

A comparison of flame ionization and ozone chemiluminescence for the determination of atmospheric hydrocarbons.

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

Marley, N. A.; Gaffney, J. S.; Environmental Research

A reactive hydrocarbon analyzer has been constructed on the basis of chemiluminescence reaction with ozone. This detector is designed to operate at varying temperatures which take advantage of the different rates of reaction of the hydrocarbon classes with ozone to yield a measure of their atmospheric reactivity. When operated at high temperatures (170 C), all hydrocarbons will give a chemiluminescence signal. Reported here is a direct comparison of the ozone chemiluminescent detector (operated at a temperature of 170 C) with a flame ionization detector. This comparison was accomplished by connecting a capillary gas chromatograph to each of the two detectorsmore » by means of a switching valve. Twenty-seven compounds representing alkanes, alkenes, aromatics, and oxygenated hydrocarbons (aldehydes, ketones, alcohols, and ethers) were studied. For the compounds studied, analytical sensitivities were 10-1000 times better for the chemiluminescence detector. The results of this comparison indicate that the response of the chemiluminescent detector at 170 C correlates with a total carbon detector (flame ionization detection) and that total response is a measure of total carbon in the sample. The chemiluminescent system will be very useful for gas chromatographic detection of atmospheric hydrocarbons, particularly of oxygenates in complex mixtures.« less

Isocyanide-mediated multicomponent synthesis of C-oximinoamidines.

PubMed

Mercalli, Valentina; Meneghetti, Fiorella; Tron, Gian Cesare

2013-11-15

By capitalizing on the different reactivity of nitrile N-oxides with isocyanides and amine, α-oximinoamidines, a so far elusive class of compounds, have been synthesized in a straightforward way by reacting isocyanides, syn-chlorooximes, and amines in a multicomponent fashion.

Comparison of forcefields for molecular dynamics simulations of hydrocarbon phase diagrams

NASA Astrophysics Data System (ADS)

Pisarev, V. V.; Zakharov, S. A.

2018-01-01

Molecular dynamics calculations of vapor-liquid equilibrium of methane-n-butane mixture are performed. Three force-field models are tested: the TraPPE-UA united-atom forcefield, LOPLS-AA all-atom forcefield and a fully flexible version of the TraPPE-EH all-atom forcefield. All those forcefields reproduce well the composition of liquid phase in the mixture as a function of pressure at the 300 K isotherm, while significant discrepancies from experimental data are observed in the saturated vapor compositions with OPLS-AA and TraPPE-UA forcefields. The best agreement with the experimental phase diagram is found with TraPPE-EH forcefield which accurately reproduces compositions of both liquid and vapor phase. This forcefield can be recommended for simulation of two-phase hydrocarbon systems.

Method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2000-01-01

A method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide within a reformer 10 is disclosed. According to the method, a stream including an oxygen-containing gas is directed adjacent to a first vessel 18 and the oxygen-containing gas is heated. A stream including unburned fuel is introduced into the oxygen-containing gas stream to form a mixture including oxygen-containing gas and fuel. The mixture of oxygen-containing gas and unburned fuel is directed tangentially into a partial oxidation reaction zone 24 within the first vessel 18. The mixture of oxygen-containing gas and fuel is further directed through the partial oxidation reaction zone 24 to produce a heated reformate stream including hydrogen gas and carbon monoxide. Steam may also be mixed with the oxygen-containing gas and fuel, and the reformate stream from the partial oxidation reaction zone 24 directed into a steam reforming zone 26. High- and low-temperature shift reaction zones 64,76 may be employed for further fuel processing.

Apparatus for hydrocarbon extraction

DOEpatents

Bohnert, George W.; Verhulst, Galen G.

2013-03-19

Systems and methods for hydrocarbon extraction from hydrocarbon-containing material. Such systems and methods relate to extracting hydrocarbon from hydrocarbon-containing material employing a non-aqueous extractant. Additionally, such systems and methods relate to recovering and reusing non-aqueous extractant employed for extracting hydrocarbon from hydrocarbon-containing material.

Underground thermal generation of hydrocarbons from dry, southwestern coals

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

Vanderborgh, N.E.; Elliott, G.R.B.

1978-01-01

The LASL underground coal conversion concept produces intermediate-BTU fuel gas for nearby industries such as ''minemouth'' electric power plants, plus major byproducts in the form of liquid and gaseous hydrocarbons for feedstocks to chemical plants e.g., substitute natural gas (SNG) producers. The concept involves controlling the water influx and drying the coal, generating hydrocarbons, by pyrolysis and finally gasifying the residual char with O/sub 2//CO/sub 2/ or air/CO/sub 2/ mixtures to produce industrial fuel gases. Underground conversion can be frustrated by uncontrolled water in the coal bed. Moisture can (a) prevent combustion, (b) preclude fuel gas formation by lowering reactionmore » zone temperatures and creating kinetic problems, (c) ruin product gas quality by dropping temperatures into a thermodynamically unsatisfactory regime, (d) degrade an initially satisfactory fuel gas by consuming carbon monoxide, (e) waste large amounts of heat, and (f) isolate reaction zones so that the processing will bypass blocks of coal.« less

Method for producing nanocrystalline multicomponent and multiphase materials

DOEpatents

Eastman, Jeffrey A.; Rittner, Mindy N.; Youngdahl, Carl J.; Weertman, Julia R.

1998-01-01

A process for producing multi-component and multiphase nanophase materials is provided wherein a plurality of elements are vaporized in a controlled atmosphere, so as to facilitate thorough mixing, and then condensing and consolidating the elements. The invention also provides for a multicomponent and multiphase nanocrystalline material of specified elemental and phase composition having component grain sizes of between approximately 1 nm and 100 nm. This material is a single element in combination with a binary compound. In more specific embodiments, the single element in this material can be a transition metal element, a non-transition metal element, a semiconductor, or a semi-metal, and the binary compound in this material can be an intermetallic, an oxide, a nitride, a hydride, a chloride, or other compound.

Reduced chemical kinetic model of detonation combustion of one- and multi-fuel gaseous mixtures with air

NASA Astrophysics Data System (ADS)

Fomin, P. A.

2018-03-01

Two-step approximate models of chemical kinetics of detonation combustion of (i) one hydrocarbon fuel CnHm (for example, methane, propane, cyclohexane etc.) and (ii) multi-fuel gaseous mixtures (∑aiCniHmi) (for example, mixture of methane and propane, synthesis gas, benzene and kerosene) are presented for the first time. The models can be used for any stoichiometry, including fuel/fuels-rich mixtures, when reaction products contain molecules of carbon. Owing to the simplicity and high accuracy, the models can be used in multi-dimensional numerical calculations of detonation waves in corresponding gaseous mixtures. The models are in consistent with the second law of thermodynamics and Le Chatelier's principle. Constants of the models have a clear physical meaning. The models can be used for calculation thermodynamic parameters of the mixture in a state of chemical equilibrium.

Nestmate recognition in social wasps: manipulation of hydrocarbon profiles induces aggression in the European hornet

NASA Astrophysics Data System (ADS)

Ruther, Joachim; Sieben, Stefan; Schricker, Burkhard

2002-03-01

The influence of individual cuticular hydrocarbons on nestmate recognition in the European hornet, Vespa crabro L., was investigated. We observed the behavioural response of workers towards differently treated dead conspecifics in a bioassay. Dummies were extracted with dichloromethane and extracts were spiked with microgram amounts of synthetic hydrocarbons naturally occurring on the cuticle of V. crabro. These modified extracts were reapplied to extracted workers that were subsequently tested in the bioassay. Non-spiked nestmate dummies (negative control) and untreated non-nestmate dummies (positive control) were tested in control experiments. The addition of only heneicosane or a mixture of heneicosane, tricosane, and ( Z)-9-tricosene to the extracts led to a significant increase of agonistic behaviour in workers leaving the nest for foraging flights. Returning workers reacted much less aggressively than those leaving. This is one of the first behavioural proofs that manipulation of cuticular hydrocarbon profiles can be perceived by a social insect species. The results support the hypothesis that colony-specific cuticular hydrocarbon profiles are involved in the phenomenon of nestmate recognition among social insects.

Application of a High-Throughput Analyzer in Evaluating Solid Adsorbents for Post-Combustion Carbon Capture via Multicomponent Adsorption of CO2, N-2, and H2O

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

Mason, JA; McDonald, TM; Bae, TH

Despite the large number of metal-organic frameworks that have been studied in the context of post-combustion carbon capture, adsorption equilibria of gas mixtures including CO2, N-2, and H2O, which are the three biggest components of the flue gas emanating from a coal- or natural gas-fired power plant, have never been reported. Here, we disclose the design and validation of a high-throughput multicomponent adsorption instrument that can measure equilibrium adsorption isotherms for mixtures of gases at conditions that are representative of an actual flue gas from a power plant. This instrument is used to study 15 different metal-organic frameworks, zeolites, mesoporousmore » silicas, and activated carbons representative of the broad range of solid adsorbents that have received attention for CO2 capture. While the multicomponent results presented in this work provide many interesting fundamental insights, only adsorbents functionalized with alkylamines are shown to have any significant CO2 capacity in the presence of N-2 and H2O at equilibrium partial pressures similar to those expected in a carbon capture process. Most significantly, the amine-appended metal organic framework mmen-Mg-2(dobpdc) (mmen = N,N'-dimethylethylenediamine, dobpdc (4-) = 4,4'-dioxido-3,3'-biphenyldicarboxylate) exhibits a record CO2 capacity of 4.2 +/- 0.2 mmol/g (16 wt %) at 0.1 bar and 40 degrees C in the presence of a high partial pressure of H2O.« less

Application of a high-throughput analyzer in evaluating solid adsorbents for post-combustion carbon capture via multicomponent adsorption of CO2, N2, and H2O.

PubMed

Mason, Jarad A; McDonald, Thomas M; Bae, Tae-Hyun; Bachman, Jonathan E; Sumida, Kenji; Dutton, Justin J; Kaye, Steven S; Long, Jeffrey R

2015-04-15

Despite the large number of metal-organic frameworks that have been studied in the context of post-combustion carbon capture, adsorption equilibria of gas mixtures including CO2, N2, and H2O, which are the three biggest components of the flue gas emanating from a coal- or natural gas-fired power plant, have never been reported. Here, we disclose the design and validation of a high-throughput multicomponent adsorption instrument that can measure equilibrium adsorption isotherms for mixtures of gases at conditions that are representative of an actual flue gas from a power plant. This instrument is used to study 15 different metal-organic frameworks, zeolites, mesoporous silicas, and activated carbons representative of the broad range of solid adsorbents that have received attention for CO2 capture. While the multicomponent results presented in this work provide many interesting fundamental insights, only adsorbents functionalized with alkylamines are shown to have any significant CO2 capacity in the presence of N2 and H2O at equilibrium partial pressures similar to those expected in a carbon capture process. Most significantly, the amine-appended metal organic framework mmen-Mg2(dobpdc) (mmen = N,N'-dimethylethylenediamine, dobpdc (4-) = 4,4'-dioxido-3,3'-biphenyldicarboxylate) exhibits a record CO2 capacity of 4.2 ± 0.2 mmol/g (16 wt %) at 0.1 bar and 40 °C in the presence of a high partial pressure of H2O.

Cuticular hydrocarbons as a tool for the identification of insect species: Puparial cases from Sarcophagidae

PubMed Central

Braga, Marina Vianna; Pinto, Zeneida Teixeira; de Carvalho Queiroz, Margareth Maria; Matsumoto, Nana; Blomquist, Gary James

2013-01-01

The external surface of all insects is covered by a species-specific complex mixture of highly stable, very long chain cuticular hydrocarbons (CHCs). Gas chromatography coupled to mass spectrometry was used to identify CHCs from four species of Sarcophagidae, Peckia (Peckia) chrysostoma, Peckia (Pattonella) intermutans, Sarcophaga (Liopygia) ruficornis and Sarcodexia lambens. The identified CHCs were mostly a mixture of n-alkanes, monomethylalkanes and dimethylalkanes with linear chain lengths varying from 23 to 33 carbons. Only two alkenes were found in all four species. S. lambens had a composition of CHCs with linear chain lengths varying from C23 to C33, while the other three species linear chain lengths from 24 to 31 carbons. n-Heptacosane, n-nonacosane and 3-methylnonacosane, n-triacontane and n-hentriacontane occurred in all four species. The results show that these hydrocarbon profiles may be used for the taxonomic differentiation of insect species and are a useful additional tool for taxonomic classification, especially when only parts of the insect specimen are available. PMID:23932943

The role of NH3 and hydrocarbon mixtures in GaN pseudo-halide CVD: a quantum chemical study.

PubMed

Gadzhiev, Oleg B; Sennikov, Peter G; Petrov, Alexander I; Kachel, Krzysztof; Golka, Sebastian; Gogova, Daniela; Siche, Dietmar

2014-11-01

The prospects of a control for a novel gallium nitride pseudo-halide vapor phase epitaxy (PHVPE) with HCN were thoroughly analyzed for hydrocarbons-NH3-Ga gas phase on the basis of quantum chemical investigation with DFT (B3LYP, B3LYP with D3 empirical correction on dispersion interaction) and ab-initio (CASSCF, coupled clusters, and multireference configuration interaction including MRCI+Q) methods. The computational screening of reactions for different hydrocarbons (CH4, C2H6, C3H8, C2H4, and C2H2) as readily available carbon precursors for HCN formation, potential chemical transport agents, and for controlled carbon doping of deposited GaN was carried out with the B3LYP method in conjunction with basis sets up to aug-cc-pVTZ. The gas phase intermediates for the reactions in the Ga-hydrocarbon systems were predicted at different theory levels. The located π-complexes Ga…C2H2 and Ga…C2H4 were studied to determine a probable catalytic activity in reactions with NH3. A limited influence of the carbon-containing atmosphere was exhibited for the carbon doping of GaN crystal in the conventional GaN chemical vapor deposition (CVD) process with hydrocarbons injected in the gas phase. Our results provide a basis for experimental studies of GaN crystal growth with C2H4 and C2H2 as auxiliary carbon reagents for the Ga-NH3 and Ga-C-NH3 CVD systems and prerequisites for reactor design to enhance and control the PHVPE process through the HCN synthesis.

Mixture modeling of multi-component data sets with application to ion-probe zircon ages

NASA Astrophysics Data System (ADS)

Sambridge, M. S.; Compston, W.

1994-12-01

A method is presented for detecting multiple components in a population of analytical observations for zircon and other ages. The procedure uses an approach known as mixture modeling, in order to estimate the most likely ages, proportions and number of distinct components in a given data set. Particular attention is paid to estimating errors in the estimated ages and proportions. At each stage of the procedure several alternative numerical approaches are suggested, each having their own advantages in terms of efficency and accuracy. The methodology is tested on synthetic data sets simulating two or more mixed populations of zircon ages. In this case true ages and proportions of each population are known and compare well with the results of the new procedure. Two examples are presented of its use with sets of SHRIMP U-238 - Pb-206 zircon ages from Palaeozoic rocks. A published data set for altered zircons from bentonite at Meishucun, South China, previously treated as a single-component population after screening for gross alteration effects, can be resolved into two components by the new procedure and their ages, proportions and standard errors estimated. The older component, at 530 +/- 5 Ma (2 sigma), is our best current estimate for the age of the bentonite. Mixture modeling of a data set for unaltered zircons from a tonalite elsewhere defines the magmatic U-238 - Pb-206 age at high precision (2 sigma +/- 1.5 Ma), but one-quarter of the 41 analyses detect hidden and significantly older cores.

Coupling spectroscopic and chromatographic techniques for evaluation of the depositional history of hydrocarbons in a subtropical estuary.

PubMed

Martins, César C; Doumer, Marta E; Gallice, Wellington C; Dauner, Ana Lúcia L; Cabral, Ana Caroline; Cardoso, Fernanda D; Dolci, Natiely N; Camargo, Luana M; Ferreira, Paulo A L; Figueira, Rubens C L; Mangrich, Antonio S

2015-10-01

Spectroscopic and chromatographic techniques can be used together to evaluate hydrocarbon inputs to coastal environments such as the Paranaguá estuarine system (PES), located in the SW Atlantic, Brazil. Historical inputs of aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed using two sediment cores from the PES. The AHs were related to the presence of biogenic organic matter and degraded oil residues. The PAHs were associated with mixed sources. The highest hydrocarbon concentrations were related to oil spills, while relatively low levels could be attributed to the decrease in oil usage during the global oil crisis. The results of electron paramagnetic resonance were in agreement with the absolute AHs and PAHs concentrations measured by chromatographic techniques, while near-infrared spectroscopy results were consistent with unresolved complex mixture (UCM)/total n-alkanes ratios. These findings suggest that the use of a combination of techniques can increase the accuracy of assessment of contamination in sediments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Polycyclic aromatic hydrocarbons - Primitive pigment systems in the prebiotic environment

NASA Technical Reports Server (NTRS)

Deamer, D. W.

1992-01-01

The chemical evolution of meteoritic organics in the primitive earth is examined experimentally with attention given to the photochemical effects of hydrocarbon/water mixtures. Also addressed are the generation of amphiphilic products by photochemical reactions and the transduction of light energy into potentially useful forms. Polycyclic aromatic hydrocarbons (PAHs) absorb light and exist in carbonaceous chondrites; PAHs are therefore examined as primitive pigments by means of salt solutions with pyrene, fluoranthene, and pyrene derivatives with hexadecane. The hexadecane undergoes photochemical oxidation and yields long-chain amphiphiles with oxygen supplied by water, and acid pH shifts also occur. PAHs are also tested in lipid bilayer membranes to examine light-energy transduction. Protons are found to accumulate within the membrane-bounded volume to form proton gradients, and this reaction is theorized to be a good model of primitive photochemical reactions that related to the transduction of light energy into useable forms.

Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation-Experimental studies

NASA Astrophysics Data System (ADS)

Damle, Ashok S.

One of the most promising technologies for lightweight, compact, portable power generation is proton exchange membrane (PEM) fuel cells. PEM fuel cells, however, require a source of pure hydrogen. Steam reforming of hydrocarbons in an integrated membrane reactor has potential to provide pure hydrogen in a compact system. Continuous separation of product hydrogen from the reforming gas mixture is expected to increase the yield of hydrogen significantly as predicted by model simulations. In the laboratory-scale experimental studies reported here steam reforming of liquid hydrocarbon fuels, butane, methanol and Clearlite ® was conducted to produce pure hydrogen in a single step membrane reformer using commercially available Pd-Ag foil membranes and reforming/WGS catalysts. All of the experimental results demonstrated increase in hydrocarbon conversion due to hydrogen separation when compared with the hydrocarbon conversion without any hydrogen separation. Increase in hydrogen recovery was also shown to result in corresponding increase in hydrocarbon conversion in these studies demonstrating the basic concept. The experiments also provided insight into the effect of individual variables such as pressure, temperature, gas space velocity, and steam to carbon ratio. Steam reforming of butane was found to be limited by reaction kinetics for the experimental conditions used: catalysts used, average gas space velocity, and the reactor characteristics of surface area to volume ratio. Steam reforming of methanol in the presence of only WGS catalyst on the other hand indicated that the membrane reactor performance was limited by membrane permeation, especially at lower temperatures and lower feed pressures due to slower reconstitution of CO and H 2 into methane thus maintaining high hydrogen partial pressures in the reacting gas mixture. The limited amount of data collected with steam reforming of Clearlite ® indicated very good match between theoretical predictions and

Multisubstrate biodegradation kinetics of naphthalene, phenanthrene, and pyrene mixtures

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

Guha, S.; Peters, C.A.; Jaffe, P.R.

Biodegradation kinetics of naphthalene, phenanthrene and pyrene were studied in sole-substrate systems, and in binary and ternary mixtures to examine substrate interactions. The experiments were conducted in aerobic batch aqueous systems inoculated with a mixed culture that had been isolated from soils contaminated with polycyclic aromatic hydrocarbons (PAHs). Monod kinetic parameters and yield coefficients for the individual parameters and yield coefficients for the individual compounds were estimated from substrate depletion and CO{sub 2} evolution rate data in sole-substrate experiments. In all three binary mixture experiments, biodegradation kinetics were comparable to the sole-substrate kinetics. In the ternary mixture, biodegradation of naphthalenemore » was inhibited and the biodegradation rates of phenanthrene and pyrene were enhanced. A multisubstrate form of the Monod kinetic model was found to adequately predict substrate interactions in the binary and ternary mixtures using only the parameters derived from sole-substrate experiments. Numerical simulations of biomass growth kinetics explain the observed range of behaviors in PAH mixtures. In general, the biodegradation rates of the more degradable and abundant compounds are reduced due to competitive inhibition, but enhanced biodegradation of the more recalcitrant PAHs occurs due to simultaneous biomass growth on multiple substrates. In PAH-contaminated environments, substrate interactions may be very large due to additive effects from the large number of compounds present.« less

Process and apparatus for the production of hydrogen by steam reforming of hydrocarbon

DOEpatents

Sircar, Shivaji; Hufton, Jeffrey Raymond; Nataraj, Shankar

2000-01-01

In the steam reforming of hydrocarbon, particularly methane, under elevated temperature and pressure to produce hydrogen, a feed of steam and hydrocarbon is fed into a first reaction volume containing essentially only reforming catalyst to partially reform the feed. The balance of the feed and the reaction products of carbon dioxide and hydrogen are then fed into a second reaction volume containing a mixture of catalyst and adsorbent which removes the carbon dioxide from the reaction zone as it is formed. The process is conducted in a cycle which includes these reactions followed by countercurrent depressurization and purge of the adsorbent to regenerate it and repressurization of the reaction volumes preparatory to repeating the reaction-sorption phase of the cycle.

Electrical properties of methane hydrate + sediment mixtures

USGS Publications Warehouse

Du Frane, Wyatt L.; Stern, Laura A.; Constable, Steven; Weitemeyer, Karen A.; Smith, Megan M; Roberts, Jeffery J.

2015-01-01

Knowledge of the electrical properties of multicomponent systems with gas hydrate, sediments, and pore water is needed to help relate electromagnetic (EM) measurements to specific gas hydrate concentration and distribution patterns in nature. Toward this goal, we built a pressure cell capable of measuring in situ electrical properties of multicomponent systems such that the effects of individual components and mixing relations can be assessed. We first established the temperature-dependent electrical conductivity (σ) of pure, single-phase methane hydrate to be ~5 orders of magnitude lower than seawater, a substantial contrast that can help differentiate hydrate deposits from significantly more conductive water-saturated sediments in EM field surveys. Here we report σ measurements of two-component systems in which methane hydrate is mixed with variable amounts of quartz sand or glass beads. Sand by itself has low σ but is found to increase the overall σ of mixtures with well-connected methane hydrate. Alternatively, the overall σ decreases when sand concentrations are high enough to cause gas hydrate to be poorly connected, indicating that hydrate grains provide the primary conduction path. Our measurements suggest that impurities from sand induce chemical interactions and/or doping effects that result in higher electrical conductivity with lower temperature dependence. These results can be used in the modeling of massive or two-phase gas-hydrate-bearing systems devoid of conductive pore water. Further experiments that include a free water phase are the necessary next steps toward developing complex models relevant to most natural systems.

Dissipative effects in multi-component systems

NASA Astrophysics Data System (ADS)

El, Andrej; Bouras, Ioannis; Xu, Zhe; Greiner, Carsten

2013-05-01

Using a smooth initial condition of Glauber type in the kinetic transport algorithm BAMPS we investigate differences in behavior of a multi-component system and its one-component equivalent with the same η/s value. Flow harmonic coefficients v2 and v4 are shown to have very low sensitivity to the details of microscopic interactions in the system.

ReaxFF based molecular dynamics simulations of ignition front propagation in hydrocarbon/oxygen mixtures under high temperature and pressure conditions.

PubMed

Ashraf, Chowdhury; Jain, Abhishek; Xuan, Yuan; van Duin, Adri C T

2017-02-15

In this paper, we present the first atomistic-scale based method for calculating ignition front propagation speed and hypothesize that this quantity is related to laminar flame speed. This method is based on atomistic-level molecular dynamics (MD) simulations with the ReaxFF reactive force field. Results reported in this study are for supercritical (P = 55 MPa and T u = 1800 K) combustion of hydrocarbons as elevated pressure and temperature are required to accelerate the dynamics for reactive MD simulations. These simulations are performed for different types of hydrocarbons, including alkyne, alkane, and aromatic, and are able to successfully reproduce the experimental trend of reactivity of these hydrocarbons. Moreover, our results indicate that the ignition front propagation speed under supercritical conditions has a strong dependence on equivalence ratio, similar to experimentally measured flame speeds at lower temperatures and pressures which supports our hypothesis that ignition front speed is a related quantity to laminar flame speed. In addition, comparisons between results obtained from ReaxFF simulation and continuum simulations performed under similar conditions show good qualitative, and reasonable quantitative agreement. This demonstrates that ReaxFF based MD-simulations are a promising tool to study flame speed/ignition front speed in supercritical hydrocarbon combustion.

Process for the production of liquid hydrocarbons

DOEpatents

Bhatt, Bharat Lajjaram; Engel, Dirk Coenraad; Heydorn, Edward Clyde; Senden, Matthijis Maria Gerardus

2006-06-27

The present invention concerns a process for the preparation of liquid hydrocarbons which process comprises contacting synthesis gas with a slurry of solid catalyst particles and a liquid in a reactor vessel by introducing the synthesis gas at a low level into the slurry at conditions suitable for conversion of the synthesis gas into liquid hydrocarbons, the solid catalyst particles comprising a catalytic active metal selected from cobalt or iron on a porous refractory oxide carrier, preferably selected from silica, alumina, titania, zirconia or mixtures thereof, the catalyst being present in an amount between 10 and 40 vol. percent based on total slurry volume liquids and solids, and separating liquid material from the solid catalyst particles by using a filtration system comprising an asymmetric filtration medium (the selective side at the slurry side), in which filtration system the average pressure differential over the filtration medium is at least 0.1 bar, in which process the particle size distribution is such that at least a certain amount of the catalyst particles is smaller than the average pore size of the selective layer of the filtration medium. The invention also comprises an apparatus to carry out the process described above.

Method for producing nanocrystalline multicomponent and multiphase materials

DOEpatents

Eastman, J.A.; Rittner, M.N.; Youngdahl, C.J.; Weertman, J.R.

1998-03-17

A process for producing multi-component and multiphase nanophase materials is provided wherein a plurality of elements are vaporized in a controlled atmosphere, so as to facilitate thorough mixing, and then condensing and consolidating the elements. The invention also provides for a multicomponent and multiphase nanocrystalline material of specified elemental and phase composition having component grain sizes of between approximately 1 nm and 100 nm. This material is a single element in combination with a binary compound. In more specific embodiments, the single element in this material can be a transition metal element, a non-transition metal element, a semiconductor, or a semi-metal, and the binary compound in this material can be an intermetallic, an oxide, a nitride, a hydride, a chloride, or other compound. 6 figs.

Topological defects in mixtures of superconducting condensates with different charges

NASA Astrophysics Data System (ADS)

Garaud, Julien; Babaev, Egor

2014-06-01

We investigate the topological defects in phenomenological models describing mixtures of charged condensates with commensurate electric charges. Such situations are expected to appear for example in liquid metallic deuterium. This is modeled by a multicomponent Ginzburg-Landau theory where the condensates are coupled to the same gauge field by different coupling constants whose ratio is a rational number. We also briefly discuss the case where electric charges are incommensurate. Flux quantization and finiteness of the energy per unit length dictate that the different condensates have different winding and thus different number of (fractional) vortices. Competing attractive and repulsive interactions lead to molecule-like bound states between fractional vortices. Such bound states have finite energy and carry integer flux quanta. These can be characterized by the CP1 topological invariant that motivates their denomination as skyrmions.

Tunable integration of absorption-membrane-adsorption for efficiently separating low boiling gas mixtures near normal temperature

PubMed Central

Liu, Huang; Pan, Yong; Liu, Bei; Sun, Changyu; Guo, Ping; Gao, Xueteng; Yang, Lanying; Ma, Qinglan; Chen, Guangjin

2016-01-01

Separation of low boiling gas mixtures is widely concerned in process industries. Now their separations heavily rely upon energy-intensive cryogenic processes. Here, we report a pseudo-absorption process for separating low boiling gas mixtures near normal temperature. In this process, absorption-membrane-adsorption is integrated by suspending suitable porous ZIF material in suitable solvent and forming selectively permeable liquid membrane around ZIF particles. Green solvents like water and glycol were used to form ZIF-8 slurry and tune the permeability of liquid membrane surrounding ZIF-8 particles. We found glycol molecules form tighter membrane while water molecules form looser membrane because of the hydrophobicity of ZIF-8. When using mixing solvents composed of glycol and water, the permeability of liquid membrane becomes tunable. It is shown that ZIF-8/water slurry always manifests remarkable higher separation selectivity than solid ZIF-8 and it could be tuned to further enhance the capture of light hydrocarbons by adding suitable quantity of glycol to water. Because of its lower viscosity and higher sorption/desorption rate, tunable ZIF-8/water-glycol slurry could be readily used as liquid absorbent to separate different kinds of low boiling gas mixtures by applying a multistage separation process in one traditional absorption tower, especially for the capture of light hydrocarbons. PMID:26892255

Occupational exposure to aromatic hydrocarbons and polycyclic aromatic hydrocarbons at a coke plant.

PubMed

Bieniek, Grażyna; Łusiak, Agnieszka

2012-08-01

The objective of this study was to assess the external exposure to aromatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) of coke-oven workers and by-product workers at a coke plant in Poland. The content of benzene, toluene, xylene, and naphthalene in a gaseous phase and the content of dibenzo[a,h]anthracene, benz[a]anthracene, anthracene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benz[ghi]perylene, chrysene, and indeno[1,2,3-c,d]pyrene in a particulate phase of coke plant workers were measured in the workers mentioned above. A toxic equivalency factor BaP(eq) was used to estimate human health risk associated with respiratory exposure to PAHs. Time-weighted values of the exposure to AHs in the coke plant were as follows: benzene (range 0.01-2.71 mg m(-3)), toluene (0.01-1.73 mg m(-3)), xylene (0.01-0.78 mg m(-3)), naphthalene (6.0-6079 μg m(-3)), and the concentrations of hydrocarbons did not exceed the exposure limits. The results for particle-bound PAHs were equal to 1.96 μg m(-3) for B(a)P, 0.73 μg m(-3) for DBA, 3.23 μg m(-3) for BaA, 4.35 μg m(-3) for BbF, 3.02 μg m(-3) for BkF, 4.54 μg m(-3) for IND, 4.32 μg m(-3) for CHR, and 0.73 μg m(-3) for Ant. The results of personal air measurements (median values of the sum of nine carcinogenic PAHs) were 2.115 μg m(-3) (coke-oven workers, n = 207), 0.326 μg m(-3) (coke by-product workers, n = 33), and 0.653 μg m(-3) (total area workers, n = 38). The benzo[a]pyrene equivalent concentrations (BaP(eq)) of 10 PAHs were 1.33, 0.183, and 0.284 μg m(-3), respectively. We found out that coke plant workers are simultaneously exposed to a mixture of aromatic and polycyclic hydrocarbons present in the breathing zone air. Exposure levels are significantly influenced by job categories. Coke by-product workers are significantly more exposed to benzene, toluene, and xylene and less to PAHs. Coke-oven workers are mainly exposed to PAHs. Coke-oven workplaces (top side, coke side, and

Multicomponent Dark Matter in Radiative Seesaw Models

NASA Astrophysics Data System (ADS)

Aoki, Mayumi; Kaneko, Daiki; Kubo, Jisuke

2017-11-01

We discuss radiative seesaw models, in which an exact Z_2¥times Z_2' symmetry is imposed. Due to the exact Z_2¥times Z_2' symmetry, neutrino masses are generated at a two-loop level and at least two extra stable electrically neutral particles are predicted. We consider two models: one has a multi-component dark matter system and the other one has a dark radiation in addition to a dark matter. In the multi-component dark matter system, non-standard dark matter annihilation processes exist. We find that they play important roles in determining the relic abundance and also responsible for the monochromatic neutrino lines resulting from the dark matter annihilation process. In the model with the dark radiation, the structure of the Yukawa coupling is considerably constrained and gives an interesting relationship among cosmology, lepton flavor violating decay of the charged leptons and the decay of the inert Higgs bosons.

Analysis of the impregnation of ZnO:Mn2+ nanoparticles on cigarette filters for trapping polycyclic aromatic hydrocarbons (PAHs)

NASA Astrophysics Data System (ADS)

Estrada-Izquierdo, Irma; Sánchez-Espindola, Esther; Uribe-Hernández, Raúl; Ramón-Gallegos, Eva

2012-10-01

Each cigarette can generate 1149 ng of a mixture of 14 polycyclic aromatic hydrocarbons, of which there are a lot of information about its harmful effects on the environment and human health, they are considered mutagenic, teratogenic and carcinogenic. In this paper we tested ZnO:Mn2+ nanoparticles, attached to the filters of cigarettes. The first results showed that the filtration system was able to catch the Benzo(a)pyrene contained in cigarette smoke; but more tests are needed to quantify the efficiency with greater accuracy over other polycyclic aromatic hydrocarbons.

MICROWAVE-ACCELERATED MULTICOMPONENT REACTIONS UNDER SOLVENT-FREE CONDITIONS

EPA Science Inventory

The application of microwave-accelerated solventless synthetic protocols in multicomponent (MCC) reactions will be exemplified by several condensation and cyclization reactions including the rapid one-pot assembly of valuable heterocyclic compounds from in situ generated intermed...

Rapid correction of electron microprobe data for multicomponent metallic systems

NASA Technical Reports Server (NTRS)

Gupta, K. P.; Sivakumar, R.

1973-01-01

This paper describes an empirical relation for the correction of electron microprobe data for multicomponent metallic systems. It evaluates the empirical correction parameter, a for each element in a binary alloy system using a modification of Colby's MAGIC III computer program and outlines a simple and quick way of correcting the probe data. This technique has been tested on a number of multicomponent metallic systems and the agreement with the results using theoretical expressions is found to be excellent. Limitations and suitability of this relation are discussed and a model calculation is also presented in the Appendix.

Multilevel, multicomponent microarchitectures of vertically-aligned carbon nanotubes for diverse applications.

PubMed

Qu, Liangti; Vaia, Rich A; Dai, Liming

2011-02-22

A simple multiple contact transfer technique has been developed for controllable fabrication of multilevel, multicomponent microarchitectures of vertically aligned carbon nanotubes (VA-CNTs). Three dimensional (3-D) multicomponent micropatterns of aligned single-walled carbon nanotubes (SWNTs) and multiwalled carbon nanotubes (MWNTs) have been fabricated, which can be used to develop a newly designed touch sensor with reversible electrical responses for potential applications in electronic devices, as demonstrated in this study. The demonstrated dependence of light diffraction on structural transfiguration of the resultant CNT micropattern also indicates their potential for optical devices. Further introduction of various components with specific properties (e.g., ZnO nanorods) into the CNT micropatterns enabled us to tailor such surface characteristics as wettability and light response. Owing to the highly generic nature of the multiple contact transfer strategy, the methodology developed here could provide a general approach for interposing a large variety of multicomponent elements (e.g., nanotubes, nanorods/wires, photonic crystals, etc.) onto a single chip for multifunctional device applications.

[Study on high accuracy detection of multi-component gas in oil-immerse power transformer].

PubMed

Fan, Jie; Chen, Xiao; Huang, Qi-Feng; Zhou, Yu; Chen, Gang

2013-12-01

In order to solve the problem of low accuracy and mutual interference in multi-component gas detection, a kind of multi-component gas detection network with high accuracy was designed. A semiconductor laser with narrow bandwidth was utilized as light source and a novel long-path gas cell was also used in this system. By taking the single sine signal to modulate the spectrum of laser and using space division multiplexing (SDM) and time division multiplexing (TDM) technique, the detection of multi-component gas was achieved. The experiments indicate that the linearity relevance coefficient is 0. 99 and the measurement relative error is less than 4%. The system dynamic response time is less than 15 s, by filling a volume of multi-component gas into the gas cell gradually. The system has advantages of high accuracy and quick response, which can be used in the fault gas on-line monitoring for power transformers in real time.

The Physical Properties of a Lavage Mixture of Pulmonary Surfactant, Perfluorodecaline, and Methylprednisolone (Perfactant Lavage)

DTIC Science & Technology

2014-05-09

release: distribution unlimited Purpose: To characterize the physical properties of a lavage mixture of pulmonary surfactant, perfluorocarbon and...methylprednisolone. Background: Perfluorocarbons (PFCs) are compounds derived from hydrocarbons by the substitution of hydrogen atoms with fluorine...atoms. Perfluorocarbon liquids are colorless, odorless and biologically inert. They are highly dense, due to their molecular weight. Their low

Stability of hydrocarbon systems at thermobaric conditions corresponding to depth down to 50 km

NASA Astrophysics Data System (ADS)

Kutcherov, V.; Kolesnikov, A.; Mukhina, E.; Serovaiskii, A.

2017-12-01

Most of the theoretical models show that crude oil stability is limited by the depth of 6-8 km (`oil window'). Commercial discovery of crude oil deposits on the depth more than 10 km in the different petroleum basins worldwide casts doubt on the validity of the above-mentioned theoretical calculations. Therefore, the question at which depth complex hydrocarbon systems could be stable is important not only from fundamental research point of view but has a great practical application. To answer this question a hydrocarbon mixture was investigated under thermobaric conditions corresponding to the conditions of the Earth's lower crust. Experiments were conducted by means of Raman Mössbauer spectroscopy. The results obtained show that the complex hydrocarbon systems could be stable and remain their qualitative and quantitative composition at temperature 320-450 °C and pressure 0.7-1.4 GPa. The oxidizing resistance of hydrocarbon system was tested in the modelled the Earth's crust surrounding. The hydrocarbon system stability at the presence of Fe2O3 strongly confirms that the Earth's crust oxygen fugacity does not influence on petroleum composition. The data obtained broaden our knowledge about the possible range of depths for crude oil and natural gas deposits in the Earth's crust and give us the possibility to revise the depth of petroleum deposits occurrence.

Methane and other hydrocarbon gases in sediment from the southeastern North American continental margin

USGS Publications Warehouse

Kvenvolden, K.A.; Lorenson, T.D.

2000-01-01

Residual concentrations and distributions of hydrocarbon gases from methane to n-heptane were measured in sediments at seven sites on Ocean Drilling Program (ODP) Leg 164. Three sites were drilled at the Cape Fear Diapir of the Carolina Rise, and one site was drilled on the Blake Ridge Diapir. Methane concentrations at these sites result from microbial generation which is influenced by the amount of pore-water sulfate and possible methane oxidation. Methane hydrate was found at the Blake Ridge Diapir site. The other hydrocarbon gases at these sites are likely the produce of early microbial processes. Three sites were drilled on a transect of holes across the crest of the Blake Ridge. The base of the zone of gas-hydrate occurrence was penetrated at all three sites. Trends in hydrocarbon gas distributions suggest that methane is microbial in origin and that the hydrocarbon gas mixture is affected by diagenesis, outgassing, and, near the surface, by microbial oxidation. Methane hydrate was recovered at two of these three sites, although gas hydrate is likely present at all three sites. The method used here for determining amounts of residual hydrocarbon gases has its limitations and provides poor assessment of gas distributions, particularly in the stratigraphic interval below about ~ 100 mbsf. One advantage of the method, however, is that it yields sufficient quantities of gas for other studies such as isotopic determinations.

Improvement in device performance from a mixture of a liquid crystal and photosensitive acrylic prepolymer with the photoinduced vertical alignment method

PubMed Central

Ho, Czung-Yu; Lin, Fa-Hsin; Tao, Yu-Tai; Lee, Jiunn-Yih

2011-01-01

In a multicomponent nematic liquid crystal (NLC) mixture of a liquid crystal (negative-type NLC) and a photosensitive acrylic prepolymer, photopolymerization upon UV irradiation induces the separation of the LC and photosensitive acrylic prepolymer layers, thereby leading to a vertical arrangement of LC molecules. In this study, we propose a simple vertical alignment method for LC molecules, by adding a chiral smectic A (SmA∗) liquid crystal having homeotropic texture characteristics to an NLC mixture solution. Measurements of electro-optical properties revealed that the addition of the SmA∗ LC not only strengthened the anchoring force of the copolymer alignment film surface, but also significantly enhanced the contrast ratio (∼73%), response time and grayscale switching performance of the device. PMID:27877462

Method And Apparatus For Converting Hydrocarbon Fuel Into Hydrogen Gas And Carbon Dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2000-09-26

A method is disclosed for synthesizing hydrogen gas from hydrocarbon fuel. A first mixture of steam and a first fuel is directed into a first tube 208 to subject the first mixture to a first steam reforming reaction in the presence of a first catalyst 214. A stream of oxygen-containing gas is pre-heated by transferring heat energy from product gases. A second mixture of the pre-heated oxygen-containing gas and a second fuel is directed into a second tube 218 disposed about the first tube 208 to subject the second mixture to a partial oxidation reaction and to provide heat energy for transfer to the first tube 208. A first reaction reformate from the first tube 208 and a second reaction reformate from the second tube 218 are directed into a third tube 224 disposed about the second tube 218 to subject the first and second reaction reformates to a second steam reforming reaction, wherein heat energy is transferred to the third tube 224 from the second tube 218.

Separation of {sup 32}P-postlabeled DNA adducts of polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons by HPLC

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

King, L.C.; Gallagher, J.E.; Lewtas, J.

The {sup 32}P-postlabeling assay, thin-layer chromatography, and reverse-phase high-pressure liquid chromatography (HPLC) were used to separate DNA adducts formed from 10 polycyclic aromatic hydrocarbons (PAHs) and 6 nitrated polycyclic aromatic hydrocarbons (NO{sub 2}-PAHs). The PAHs included benzo[j]fluoranthene, benzo[k]fluoranthene, indeno[1,2,3-cd]pyrene, benzo[a]pyrene, chrysene, 6-methylchrysene, 5-methylchrysene, and benz[a]anthracene. The NO{sub 2}-PAHs included 1-nitropyrene, 2-nitrofluoranthene, 3-nitrofluoranthene, 1,6-dinitropyrene, 1,3-dinitropyrene, and 1,8-dinitropyrene. Separation of seven of the major PAH-DNA adducts was achieved by an initial PAH HPLC gradient system. The major NO{sub 2}-PAH-DNA adducts were not all separated from each other using the initial PAH HPLC gradient but were clearly separated from the PAH-DNA adducts. Amore » second NO{sub 2}-PAH HPLC gradient system was developed to separate NO{sub 2}-PAH-DNA adducts following one-dimensional TLC and HPLC analysis. HPLC profiles of NO{sub 2}-PAH-DNA adducts were compared using both adduct enhancement versions of the {sup 32}P-postlabeling assay to evaluate the use of this technique on HPLC to screen for the presence of NO{sub 2}-PAH-DNA adducts. To demonstrate the application of these separation methods to a complex mixture of DNA adducts, the chromatographic mobilities of the {sup 32}P-postlabeled DNA adduct standards (PAHs and NO{sub 2}-PAHs) were compared with those produced by a complex mixture of polycyclic organic matter (POM) extracted from diesel emission particles. The diesel-derived adducts did not elute with the identical retention time of any of the PAH or NO{sub 2}-PAH standards used in this study. HPLC analyses of the NO{sub 2}-PAH-derived adducts (butanol extracted) revealed the presence of multiple DNA adducts.« less

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

Hydrocarbon reforming catalyst material and configuration of the same

DOEpatents

Singh, Prabhakar; Shockling, Larry A.; George, Raymond A.; Basel, Richard A.

1996-01-01

A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in an electrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina, wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated, at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall.

Hydrocarbon reforming catalyst material and configuration of the same

DOEpatents

Singh, P.; Shockling, L.A.; George, R.A.; Basel, R.A.

1996-06-18

A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in an electrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina, wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated, at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall. 5 figs.

Digital holographic microscopy of phase separation in multicomponent lipid membranes

NASA Astrophysics Data System (ADS)

Farzam Rad, Vahideh; Moradi, Ali-Reza; Darudi, Ahmad; Tayebi, Lobat

2016-12-01

Lateral in-homogeneities in lipid compositions cause microdomains formation and change in the physical properties of biological membranes. With the presence of cholesterol and mixed species of lipids, phospholipid membranes segregate into lateral domains of liquid-ordered and liquid-disordered phases. Coupling of two-dimensional intralayer phase separations and interlayer liquid-crystalline ordering in multicomponent membranes has been previously demonstrated. By the use of digital holographic microscopy (DHMicroscopy), we quantitatively analyzed the volumetric dynamical behavior of such membranes. The specimens are lipid mixtures composed of sphingomyelin, cholesterol, and unsaturated phospholipid, 1,2-dioleoyl-sn-glycero-3-phosphocholine. DHMicroscopy in a transmission mode is an effective tool for quantitative visualization of phase objects. By deriving the associated phase changes, three-dimensional information on the morphology variation of lipid stacks at arbitrary time scales is obtained. Moreover, the thickness distribution of the object at demanded axial planes can be obtained by numerical focusing. Our results show that the volume evolution of lipid domains follows approximately the same universal growth law of previously reported area evolution. However, the thickness of the domains does not alter significantly by time; therefore, the volume evolution is mostly attributed to the changes in area dynamics. These results might be useful in the field of membrane-based functional materials.

Biosurfactant-producing strains in enhancing solubilization and biodegradation of petroleum hydrocarbons in groundwater.

PubMed

Liu, Hong; Wang, Hang; Chen, Xuehua; Liu, Na; Bao, Suriguge

2014-07-01

Three biosurfactant-producing strains designated as BS-1, BS-3, and BS-4 were screened out from crude oil-contaminated soil using a combination of surface tension measurement and oil spreading method. Thin layer chromatography and infrared analysis indicated that the biosurfactants produced by the three strains were lipopeptide, glycolipid, and phospholipid. The enhancement of solubilization and biodegradation of petroleum hydrocarbons in groundwater employing biosurfactant-producing strains was investigated. The three strain mixtures led to more solubilization of petroleum hydrocarbons in groundwater, and the solubilization rate was 10.5 mg l−1. The combination of biosurfactant-producing strains and petroleum-degrading strains exhibited a higher biodegradation efficiency of 85.4 % than the petroleum-degrading strains (71.2 %). Biodegradation was enhanced the greatest with biosurfactant-producing strains and petroleum-degrading strains in a ratio of 1:1. Fluorescence microscopy images illustrate that the oil dispersed into smaller droplets and emulsified in the presence of biosurfactant-producing strains, which attached to the oil. Thus, the biodegradation of petroleum hydrocarbons in groundwater was enhanced.

THE EFFECTS OF EQUIVALENCE RATIO ON THE FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND SOOT IN PREMIXED ETHANE FLAMES. (R825412)

EPA Science Inventory

Abstract

The formation of polycyclic aromatic hydrocarbons (PAH) and soot has been investigated in atmospheric-pressure, laminar, ethane/oxygen/argon premixed flames as a function of mixture equivalence ratio. Mole fraction profiles of major products, trace aromatics, ...

MICROWAVE-FACILITATED MULTICOMPONENT REACTIONS UNDER SOLVENT-FREE CONDITIONS

EPA Science Inventory

The application of microwave-expedited solvent-free synthetic protocols in multi-component (MCC) reactions will be exemplified by several condensation and cyclization reactions including the rapid one-pot assembly of heterocyclic compounds from in situ generated intermediates. R...

In situ measurements of the photochemical formation rates and optical properties of organic aerosols in CH4/CO2 mixtures.

NASA Astrophysics Data System (ADS)

Adamkovics, M.; Boering, K. A.

2003-12-01

The presence of photochemically-generated hazes has a significant impact on radiative transfer in planetary atmospheres. While the rates of particle formation have been inferred from photochemical or microphysical models constrained to match observations, these rates have not been determined experimentally. Thus, the fundamental kinetics of particle formation are not known and remain highly parameterized in planetary atmospheric models. We have developed instrumentation for measuring the formation rates and optical properties of organic aerosols produced by irradiating mixtures of precursor gases via in situ optical (633nm) scattering and online quadrupole mass spectrometry (1-200 amu). Results for the generation of particulate hydrocarbons from the irradiation of pure, gas-phase CH4 as well as CH4/CO2 mixtures with vacuum ultraviolet (120-160nm) light, along with simultaneous measurements of the evolution of higher gas-phase hydrocarbons will be presented.

Monochromatic multicomponent fluorescence sedimentation velocity for the study of high-affinity protein interactions

PubMed Central

Zhao, Huaying; Fu, Yan; Glasser, Carla; Andrade Alba, Eric J; Mayer, Mark L; Patterson, George; Schuck, Peter

2016-01-01

The dynamic assembly of multi-protein complexes underlies fundamental processes in cell biology. A mechanistic understanding of assemblies requires accurate measurement of their stoichiometry, affinity and cooperativity, and frequently consideration of multiple co-existing complexes. Sedimentation velocity analytical ultracentrifugation equipped with fluorescence detection (FDS-SV) allows the characterization of protein complexes free in solution with high size resolution, at concentrations in the nanomolar and picomolar range. Here, we extend the capabilities of FDS-SV with a single excitation wavelength from single-component to multi-component detection using photoswitchable fluorescent proteins (psFPs). We exploit their characteristic quantum yield of photo-switching to imprint spatio-temporal modulations onto the sedimentation signal that reveal different psFP-tagged protein components in the mixture. This novel approach facilitates studies of heterogeneous multi-protein complexes at orders of magnitude lower concentrations and for higher-affinity systems than previously possible. Using this technique we studied high-affinity interactions between the amino-terminal domains of GluA2 and GluA3 AMPA receptors. DOI: http://dx.doi.org/10.7554/eLife.17812.001 PMID:27436096

Design and evaluation of high performance rocket engine injectors for use with hydrocarbon fuels

NASA Technical Reports Server (NTRS)

Pavli, A. J.

1979-01-01

The feasibility of using a heavy hydrocarbon fuel as a rocket propellant is examined. A method of predicting performance of a heavy hydrocarbon in terms of vaporization effectiveness is described and compared to other fuels and to experimental test results. Experiments were done at a chamber pressure of 4137 KN/sq M (600 psia) with RP-1, JP-10, and liquefied natural gas as fuels, and liquid oxygen as the oxidizer. Combustion length effects were explored over a range of 21.6 cm (8 1/2 in) to 55.9 cm (22 in). Four injector types were tested, each over a range of mixture ratios. Further configuration modifications were obtained by reaming each injector several times to provide test data over a range of injector pressure drop.

Structure of highly asymmetric hard-sphere mixtures: an efficient closure of the Ornstein-Zernike equations.

PubMed

Amokrane, S; Ayadim, A; Malherbe, J G

2005-11-01

A simple modification of the reference hypernetted chain (RHNC) closure of the multicomponent Ornstein-Zernike equations with bridge functions taken from Rosenfeld's hard-sphere bridge functional is proposed. Its main effect is to remedy the major limitation of the RHNC closure in the case of highly asymmetric mixtures--the wide domain of packing fractions in which it has no solution. The modified closure is also much faster, while being of similar complexity. This is achieved with a limited loss of accuracy, mainly for the contact value of the big sphere correlation functions. Comparison with simulation shows that inside the RHNC no-solution domain, it provides a good description of the structure, while being clearly superior to all the other closures used so far to study highly asymmetric mixtures. The generic nature of this closure and its good accuracy combined with a reduced no-solution domain open up the possibility to study the phase diagram of complex fluids beyond the hard-sphere model.

Biofuel components change the ecology of bacterial volatile petroleum hydrocarbon degradation in aerobic sandy soil.

PubMed

Elazhari-Ali, Abdulmagid; Singh, Arvind K; Davenport, Russell J; Head, Ian M; Werner, David

2013-02-01

We tested the hypothesis that the biodegradation of volatile petroleum hydrocarbons (VPHs) in aerobic sandy soil is affected by the blending with 10 percent ethanol (E10) or 20 percent biodiesel (B20). When inorganic nutrients were scarce, competition between biofuel and VPH degraders temporarily slowed monoaromatic hydrocarbon degradation. Ethanol had a bigger impact than biodiesel, reflecting the relative ease of ethanol compared to methyl ester biodegradation. Denaturing gradient gel electrophoresis (DGGE) of bacterial 16S rRNA genes revealed that each fuel mixture selected for a distinct bacterial community, each dominated by Pseudomonas spp. Despite lasting impacts on soil bacterial ecology, the overall effects on VHP biodegradation were minor, and average biomass yields were comparable between fuel types, ranging from 0.40 ± 0.16 to 0.51 ± 0.22 g of biomass carbon per gram of fuel carbon degraded. Inorganic nutrient availability had a greater impact on petroleum hydrocarbon biodegradation than fuel composition. Copyright © 2012 Elsevier Ltd. All rights reserved.

Direct observation of the photodegradation of anthracene and pyrene adsorbed onto mangrove leaves.

PubMed

Wang, Ping; Wu, Tun-Hua; Zhang, Yong

2014-01-01

An established synchronous fluorimetry method was used for in situ investigation of the photodegradation of pyrene (PYR) and anthracene (ANT) adsorbed onto fresh leaves of the seedlings of two mangrove species, Aegiceras corniculatum (L.) Blanco (Ac) and Kandelia obovata (Ko) in multicomponent mixtures (mixture of the ANT and PYR). Experimental results indicated that photodegradation was the main transformation pathway for both ANT and PYR in multicomponent mixtures. The amount of the PAHs volatilizing from the leaf surfaces and entering the inner leaf tissues was negligible. Over a certain period of irradiation time, the photodegradation of both PYR and ANT adsorbed onto the leaves of Ac and Ko followed first-order kinetics, with faster rates being observed on Ac leaves. In addition, the photodegradation rate of PYR on the leaves of the mangrove species in multicomponent mixtures was much slower than that of adsorbed ANT. Compared with the PAHs adsorbed as single component, the photodegradation rate of ANT adsorbed in multicomponent mixtures was slower, while that of PYR was faster. Moreover, the photodegradation of PYR and ANT dissolved in water in multicomponent mixtures was investigated for comparison. The photodegradation rate on leaves was much slower than in water. Therefore, the physical-chemical properties of the substrate may strongly influence the photodegradation rate of adsorbed PAHs.

Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide

NASA Astrophysics Data System (ADS)

Juliá-Hernández, Francisco; Moragas, Toni; Cornella, Josep; Martin, Ruben

2017-05-01

Catalytic carbon-carbon bond formation has enabled the streamlining of synthetic routes when assembling complex molecules. It is particularly important when incorporating saturated hydrocarbons, which are common motifs in petrochemicals and biologically relevant molecules. However, cross-coupling methods that involve alkyl electrophiles result in catalytic bond formation only at specific and previously functionalized sites. Here we describe a catalytic method that is capable of promoting carboxylation reactions at remote and unfunctionalized aliphatic sites with carbon dioxide at atmospheric pressure. The reaction occurs via selective migration of the catalyst along the hydrocarbon side-chain with excellent regio- and chemoselectivity, representing a remarkable reactivity relay when compared with classical cross-coupling reactions. Our results demonstrate that site-selectivity can be switched and controlled, enabling the functionalization of less-reactive positions in the presence of a priori more reactive ones. Furthermore, we show that raw materials obtained in bulk from petroleum processing, such as alkanes and unrefined mixtures of olefins, can be used as substrates. This offers an opportunity to integrate a catalytic platform en route to valuable fatty acids by transforming petroleum-derived feedstocks directly.

Plasma chemistry of NO in complex gas mixtures excited with a surfatron launcher.

PubMed

Hueso, J L; González-Elipe, A R; Cotrino, J; Caballero, A

2005-06-09

The plasma chemistry of NO has been investigated in gas mixtures with oxygen and/or hydrocarbon and Ar as carrier gas. Surface wave discharges operating at microwave frequencies have been used for this study. The different plasma reactions have been analyzed for a pressure range between 30 and 75 Torr. Differences in product concentration and/or reaction yields smaller than 10% were found as a function of this parameter. The following gas mixtures have been considered for investigation: Ar/NO, Ar/NO/O2, Ar/NO/CH4, Ar/CH4/O2, Ar/NO/CH4/O2. It is found that NO decomposes into N2 and O2, whereas other products such as CO, H2, and H2O are also formed when CH4 and O2 are present in the reaction mixture. Depending on the working conditions, other minority products such as HCN, CO2, and C2 or higher hydrocarbons have been also detected. The reaction of an Ar/NO plasma with deposits of solid carbon has also been studied. The experiments have provided useful information with respect to the possible removal of soot particles by this type of plasma. It has been shown that carbon deposits are progressively burned off by interaction with the plasma, and practically 100% decomposition of NO was found. Plasma intermediate species have been studied by optical emission spectroscopy (OES). Bands and/or peaks due to N2*, NO*, OH*, C2*, CN*, CH*, or H* were detected with different relative intensities depending on the gas mixture. From the analysis of both the reaction products and efficiency and the type of intermediate species detected by OES, different plasma reactions and processes are proposed to describe the plasma chemistry of NO in each particular mixture of gases. The results obtained provide interesting insights about the plasma removal of NO in real gas exhausts.

Dissolution of multi-component LNAPL gasolines: The effects of weathering and composition

NASA Astrophysics Data System (ADS)

Lekmine, Greg; Bastow, Trevor P.; Johnston, Colin D.; Davis, Greg B.

2014-05-01

The composition of light non-aqueous phase liquid (LNAPL) gasoline and other petroleum products changes profoundly over their life once released into aquifers. However limited attention has been given to how such changes affect key parameters such as the activity coefficients which control partitioning of components of petroleum fuel into groundwater and are used to predict long-term risk from fuel releases. Laboratory experiments were conducted on a range of fresh, weathered and synthetic gasoline mixtures designed to mimic the expected changes in composition in an aquifer. Weathered gasoline created under controlled evaporation and water washing, and naturally weathered gasoline, were investigated. Equilibrium concentrations in water and molar fractions in the gasoline mixtures were compared with equilibrium concentrations predicted by Raoult's law assuming ideal behaviour of the solutions. The experiments carried out allowed the relative sensitivity of the activity coefficients of key risk drivers such as benzene, toluene, ethylbenzene and xylene (BTEX) compounds to be quantified with respect to the presence of other types of compounds and where the source LNAPL had undergone different types of weathering. Results differed for the mixtures examined but in some cases higher than predicted dissolved equilibrium concentrations showed non-ideal behaviour for toluene, benzene and xylenes. Comparison of the activity coefficients showed that the naturally weathered gasoline and a 50% evaporated unleaded gasoline present a similar range of values varying between 1.0 and 1.2, suggesting close to ideal partitioning between the LNAPL and water. The fresh and water-washed gasoline had higher values for the activity coefficient, from 1.2 to 1.4, indicating non-ideal partitioning. Results from synthetic mixtures demonstrated that these differences could be due to the different molar fractions of the nC5 and nC6 aliphatic hydrocarbons acting on the molecular interactions

Predicting Microstructure and Microsegregation in Multicomponent Aluminum Alloys

NASA Astrophysics Data System (ADS)

Yan, Xinyan; Ding, Ling; Chen, ShuangLin; Xie, Fanyou; Chu, M.; Chang, Y. Austin

Accurate predictions of microstructure and microsegregation in metallic alloys are highly important for applications such as alloy design and process optimization. Restricted assumptions concerning the phase diagram could easily lead to erroneous predictions. The best approach is to couple microsegregation modeling with phase diagram computations. A newly developed numerical model for the prediction of microstructure and microsegregation in multicomponent alloys during dendritic solidification was introduced. The micromodel is directly coupled with phase diagram calculations using a user-friendly and robust phase diagram calculation engine-PANDAT. Solid state back diffusion, undercooling and coarsening effects are included in this model, and the experimentally measured cooling curves are used as the inputs to carry out the calculations. This model has been used to predict the microstructure and microsegregation in two multicomponent aluminum alloys, 2219 and 7050. The calculated values were confirmed using results obtained from directional solidification.

Mixtures of Chemical Pollutants at European Legislation Safety Concentrations: How Safe Are They?

PubMed Central

Carvalho, Raquel N.; Arukwe, Augustine; Ait-Aissa, Selim; Bado-Nilles, Anne; Balzamo, Stefania; Baun, Anders; Belkin, Shimshon; Blaha, Ludek; Brion, François; Conti, Daniela; Creusot, Nicolas; Essig, Yona; Ferrero, Valentina E. V.; Flander-Putrle, Vesna; Fürhacker, Maria; Grillari-Voglauer, Regina; Hogstrand, Christer; Jonáš, Adam; Kharlyngdoh, Joubert B.; Loos, Robert; Lundebye, Anne-Katrine; Modig, Carina; Olsson, Per-Erik; Pillai, Smitha; Polak, Natasa; Potalivo, Monica; Sanchez, Wilfried; Schifferli, Andrea; Schirmer, Kristin; Sforzini, Susanna; Stürzenbaum, Stephen R.; Søfteland, Liv; Turk, Valentina; Viarengo, Aldo; Werner, Inge; Yagur-Kroll, Sharon; Zounková, Radka; Lettieri, Teresa

2014-01-01

The risk posed by complex chemical mixtures in the environment to wildlife and humans is increasingly debated, but has been rarely tested under environmentally relevant scenarios. To address this issue, two mixtures of 14 or 19 substances of concern (pesticides, pharmaceuticals, heavy metals, polyaromatic hydrocarbons, a surfactant, and a plasticizer), each present at its safety limit concentration imposed by the European legislation, were prepared and tested for their toxic effects. The effects of the mixtures were assessed in 35 bioassays, based on 11 organisms representing different trophic levels. A consortium of 16 laboratories was involved in performing the bioassays. The mixtures elicited quantifiable toxic effects on some of the test systems employed, including i) changes in marine microbial composition, ii) microalgae toxicity, iii) immobilization in the crustacean Daphnia magna, iv) fish embryo toxicity, v) impaired frog embryo development, and vi) increased expression on oxidative stress-linked reporter genes. Estrogenic activity close to regulatory safety limit concentrations was uncovered by receptor-binding assays. The results highlight the need of precautionary actions on the assessment of chemical mixtures even in cases where individual toxicants are present at seemingly harmless concentrations. PMID:24958932

Improving the hydrocarbon production via co-pyrolysis of bagasse with bio-plastic and dual-catalysts layout.

PubMed

Zhang, Huiyan; Likun, Peter Keliona Wani; Xiao, Rui

2018-03-15

Catalytic fast pyrolysis (CFP) of bagasse and bio-plastic (chicken feather keratin) and their mixtures were conducted to produce aromatic hydrocarbons over a HZSM-5, USY, and dual-catalysts layout. The effects of temperature, co-feeding ratios, feed-to-catalyst ratios and dual catalysts on hydrocarbon yields and selectivities were investigated. The results show a general improvement in the aromatic hydrocarbons yields in all cases compared to non-catalytic and pure biomass pyrolysis. The aromatic hydrocarbons increased by 10 fold with the increase of temperature from 400°C to 700°C. The aromatic yields increased 1.5 times at co-feeding, 2.0 greater at feed/HZSM-5 ratio of 1:6, 1.2 times at feed/USY ratio of 1:16, and 2.66 times at USY/HZSM-5 scenario. The selectivities towards benzene increased, at higher co-feeding ratios, while that of toluene shows an opposite trend. Xylenes selectivities were less sensitive to the changes of co-feeding ratios. In contrast, the USY catalyst only produced little amount of toluene and xylenes. The dual catalyst design (USY/HZSM-5) resulted in the highest aromatic yields, than other catalyst design scenarios. The pyrolysis temperature is a significant parameter for hydrocarbon production. Co-feeding bagasse and bio-plastic enhanced biomass conversion to aromatic compounds. For any type of zeolite catalyst, there was an optimum feed-to-catalyst ratio that generated maximum hydrocarbons. Dual catalyst layout shows a new opportunity for efficient conversion of biomass materials into hydrocarbons. Copyright © 2017 Elsevier B.V. All rights reserved.

A MIXTURE OF DIOXINS, FURANS, AND NON-ORTHO PCBS BASED UPON CONCENSUS TOXIC EQUIVLENCY FACTORS PRODUCES DIOXIN-LIKE REPRODUCTIVE EFFECTS

EPA Science Inventory

2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD; dioxin) and related polyhalogenated aromatic hydrocarbons (PHAHs) alter the reproductive development of laboratory animals. Therefore, we exposed animals to a mixture of dioxin and dioxin-like compounds including TCDD, 1,2,3,7,8-pentachl...

Multicomponent Fitness Training Improves Walking Economy in Older Adults.

PubMed

Valenti, Giulio; Bonomi, Alberto Giovanni; Westerterp, Klaas Roelof

2016-07-01

Walking economy declines with increasing age, possibly leading to mobility limitation in older adults. Multicomponent fitness training could delay the decline in walking economy. This study aimed to determine the effect of multicomponent fitness training on walking economy in older adults. Participants were untrained adults, age 50 to 83 yr (N = 26, 10 males, age = 63 ± 6 yr, BMI = 25.6 ± 2.1 kg·m, mean ± SD). A control group was also recruited (N = 16, 9 males, age = 66 ± 10 yr, BMI = 25.4 ± 3.0 kg·m), matching the intervention group for age, weight, body composition, and fitness. The intervention group followed a multicomponent fitness program of 1 h, twice per week during 1 yr. The control group did not take part in any physical training. Fat-free mass, walking economy, and maximal oxygen uptake (V˙O2max) were measured in both groups before and after the year. Walking economy was measured with indirect calorimetry as the lowest energy needed to displace 1 kg of body mass for 1 m while walking on a treadmill. The data were compared between the two groups with repeated-measures ANOVA. Thirty-two subjects completed all measurements. There was an interaction between the effects of time and group on V˙O2max (P < 0.05) and walking economy (P < 0.05), whereas fat-free mass did not change significantly (P = 0.06). V˙O2max decreased by 1.8 mL·kg·min in the control group and increased by 1.3 mL·kg·min in the intervention group. The lowest energy needed to walk increased by 0.12 J·kg·m in the control group and decreased in the intervention group by 0.13 J·kg·m. Multicomponent fitness training decreases walking cost in older adults, preserving walking economy. Thus, training programs could delay mobility limitation with increasing age.

Distribution of Hydrocarbon-Utilizing Microorganisms and Hydrocarbon Biodegradation Potentials in Alaskan Continental Shelf Areas

PubMed Central

Roubal, George; Atlas, Ronald M.

1978-01-01

Hydrocarbon-utilizing microorganisms were enumerated from Alaskan continental shelf areas by using plate counts and a new most-probable-number procedure based on mineralization of 14C-labeled hydrocarbons. Hydrocarbon utilizers were ubiquitously distributed, with no significant overall concentration differences between sampling regions or between surface water and sediment samples. There were, however, significant seasonal differences in numbers of hydrocarbon utilizers. Distribution of hydrocarbon utilizers within Cook Inlet was positively correlated with occurrence of hydrocarbons in the environment. Hydrocarbon biodegradation potentials were measured by using 14C-radiolabeled hydrocarbon-spiked crude oil. There was no significant correlation between numbers of hydrocarbon utilizers and hydrocarbon biodegradation potentials. The biodegradation potentials showed large seasonal variations in the Beaufort Sea, probably due to seasonal depletion of available nutrients. Non-nutrient-limited biodegradation potentials followed the order hexadecane > naphthalene ≫ pristane > benzanthracene. In Cook Inlet, biodegradation potentials for hexadecane and naphthalene were dependent on availability of inorganic nutrients. Biodegradation potentials for pristane and benzanthracene were restricted, probably by resistance to attack by available enzymes in the indigenous population. PMID:655706

Duration of the hydrocarbon fluid formation under thermobaric conditions of the Earth's upper mantle

NASA Astrophysics Data System (ADS)

Mukhina, Elena; Kolesnikov, Anton; Kutcherov, Vladimir

2016-04-01

Deep abiogenic formation of hydrocarbons is an inherent part of the Earth's global carbon cycle. It was experimentally confirmed that natural gas could be formed from inorganic carbon and hydrogen containing minerals at pressure and temperature corresponding to the Earth's upper mantle conditions. Reaction between calcite, wustite and water in the large volume device was studied in several works. It was previously proposed that reaction is possible only after 40 minutes of exposure at high pressure and temperature. In this work similar experiment at P = 60 kbar and T = 1200 K were carried out in "Toroid" type chamber with the 5 seconds duration of thermobaric exposure. Gas chromatographic analysis of the reaction products has shown the presence of hydrocarbon mixture comparable to 5 minutes and 6 hours exposure experiments. Based on this fact it is possible to conclude that the reaction of natural gas formation is instant at least at given thermobaric conditions. This experiment will help to better understand the process of deep hydrocarbon generation, particularly its kinetics.

Numerical analysis of multicomponent responses of surface-hole transient electromagnetic method

NASA Astrophysics Data System (ADS)

Meng, Qing-Xin; Hu, Xiang-Yun; Pan, He-Ping; Zhou, Feng

2017-03-01

We calculate the multicomponent responses of surface-hole transient electromagnetic method. The methods and models are unsuitable as geoelectric models of conductive surrounding rocks because they are based on regular local targets. We also propose a calculation and analysis scheme based on numerical simulations of the subsurface transient electromagnetic fields. In the modeling of the electromagnetic fields, the forward modeling simulations are performed by using the finite-difference time-domain method and the discrete image method, which combines the Gaver-Stehfest inverse Laplace transform with the Prony method to solve the initial electromagnetic fields. The precision in the iterative computations is ensured by using the transmission boundary conditions. For the response analysis, we customize geoelectric models consisting of near-borehole targets and conductive wall rocks and implement forward modeling simulations. The observed electric fields are converted into induced electromotive force responses using multicomponent observation devices. By comparing the transient electric fields and multicomponent responses under different conditions, we suggest that the multicomponent-induced electromotive force responses are related to the horizontal and vertical gradient variations of the transient electric field at different times. The characteristics of the response are determined by the varying the subsurface transient electromagnetic fields, i.e., diffusion, attenuation and distortion, under different conditions as well as the electromagnetic fields at the observation positions. The calculation and analysis scheme of the response consider the surrounding rocks and the anomalous field of the local targets. It therefore can account for the geological data better than conventional transient field response analysis of local targets.

(n, N) type maintenance policy for multi-component systems with failure interactions

NASA Astrophysics Data System (ADS)

Zhang, Zhuoqi; Wu, Su; Li, Binfeng; Lee, Seungchul

2015-04-01

This paper studies maintenance policies for multi-component systems in which failure interactions and opportunistic maintenance (OM) involve. This maintenance problem can be formulated as a Markov decision process (MDP). However, since an action set and state space in MDP exponentially expand as the number of components increase, traditional approaches are computationally intractable. To deal with curse of dimensionality, we decompose such a multi-component system into mutually influential single-component systems. Each single-component system is formulated as an MDP with the objective of minimising its long-run average maintenance cost. Under some reasonable assumptions, we prove the existence of the optimal (n, N) type policy for a single-component system. An algorithm to obtain the optimal (n, N) type policy is also proposed. Based on the proposed algorithm, we develop an iterative approximation algorithm to obtain an acceptable maintenance policy for a multi-component system. Numerical examples find that failure interactions and OM pose significant effects on a maintenance policy.

Shock wave induced condensation in fuel-rich gaseous and gas-particles mixtures

NASA Astrophysics Data System (ADS)

Fomin, P. A.

2018-03-01

The possibility of fuel vapor condensation in shock waves in fuel-rich (cyclohexane-oxygen) gaseous mixtures and explosion safety aspects of this effect are discussed. It is shown, that condensation process can essentially change the chemical composition of the gas. For example, the molar fraction of the oxidizer can increase in a few times. As a result, mixtures in which the initial concentration of fuel vapor exceeds the Upper Flammability Limit can, nevertheless, explode, if condensation shifts the composition of the mixture into the ignition region. The rate of the condensation process is estimated. This process can be fast enough to significantly change the chemical composition of the gas and shift it into the flammable range during the compression phase of blast waves, generated by explosions of fuel-vapor clouds or rapture of pressurized chemical reactors, with characteristic size of a few meters. It is shown that the presence of chemically inert microparticles in the gas mixtures under consideration increases the degree of supercooling and the mass of fuel vapors that have passed into the liquid and reduces the characteristic condensation time in comparison with the gas mixture without microparticles. The fuel vapor condensation should be taken into account in estimation the explosion hazard of chemical reactors, industrial and civil constructions, which may contain fuel-rich gaseous mixtures of heavy hydrocarbons with air.

Storage and recovery of methane-ethane mixtures in single shale pores

NASA Astrophysics Data System (ADS)

Wu, Haiyi; Qiao, Rui

2017-11-01

Natural gas production from shale formations has received extensive attention recently. While great progress has been made in understanding the adsorption and transport of single-component gas inside shales' nanopores, the adsorption and transport of multicomponent shale gas under reservoir conditions (CH4 and C2H6 mixture) has only begun to be studied. In this work, we use molecular simulations to compute the storage of CH4 and C2H6 mixtures in single nanopores and their subsequent recovery. We show that surface adsorption contributes greatly to the storage of CH4 and C2H6 inside the pores and C2H6 is enriched over CH4. The enrichment of C2H6 is enhanced as the pore is narrowed, but is weakened as the pressure increases. We show that the recovery of gas mixtures from the nanopores approximately follows the diffusive scaling law. The ratio of the production rates of C2H6 and CH4 is close to their initial mole ratio inside the pore despite that the mobility of pure C2H6 is much smaller than that of pure CH4 inside the pores. By using scale analysis, we show that the strong coupling between the transport of CH4 and C2H6 is responsible for the effective recovery of C2H6 from the nanopores.

Design and evaluation of high performance rocket engine injectors for use with hydrocarbon fuels

NASA Technical Reports Server (NTRS)

Pavli, A. J.

1979-01-01

An experimental program to determine the feasibility of using a heavy hydrocarbon fuel as a rocket propellant is reported herein. A method of predicting performance of a heavy hydrocarbon in terms of vaporization effectiveness is described and compared to other fuels and to experimental test results. The work was done at a chamber pressure of 4137 KN/sq M (600 psia) with RP-1, JP-10, and liquefied natural gas as fuels, and liquid oxygen as the oxidizer. Combustion length effects were explored over a range of 21.6 cm (8 1/2 in.) to 55.9 cm (22 in.). Four injector types were tested, each over a range of mixture ratios. Further configuration modifications were obtained by 'reaming' each injector several times to provide test data over a range of injector pressure drop.

Hydrocarbon contamination of coastal sediments from the Sfax area (Tunisia), Mediterranean Sea.

PubMed

Louati, A; Elleuch, B; Kallel, M; Saliot, A; Dagaut, J; Oudot, J

2001-06-01

The coastal area off the city of Sfax (730,000 inhabitants), well-known for fisheries and industrial activities, receives high inputs of organic matter mostly anthropogenic. Eighteen stations were selected in the vicinity of the direct discharge of industrial sewage effluents in the sea in order to study the spatial distribution of the organic contamination. Surface sediments sampled in the shallow shelf were analysed for hydrocarbons by Fourier transform infrared spectroscopy, gas chromatography and gas chromatography/mass spectrometry. Total hydrocarbon distributions revealed high contamination as compared to other coastal Mediterranean sites, with an average concentration of 1865 ppm/dry weight sediment. Gas chromatographic distribution patterns, values of unresolved mixture/n-alkane ratio and distributions of steranes and hopanes confirmed a petroleum contamination of the Arabian light crude oil type. Biogenic compounds were also identified with a series of short-chain carbon-numbered n-alkenes in the carbon range 16-24.

40 CFR 59.506 - How do I demonstrate compliance if I manufacture multi-component kits?

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 5 2010-07-01 2010-07-01 false How do I demonstrate compliance if I manufacture multi-component kits? 59.506 Section 59.506 Protection of Environment ENVIRONMENTAL PROTECTION... § 59.506 How do I demonstrate compliance if I manufacture multi-component kits? (a) If you manufacture...

Determination of hydrocarbons transported by urban runoff in sediments of São Gonçalo Channel (Pelotas - RS, Brazil).

PubMed

Sanches Filho, Pedro J; Böhm, Emerson M; Böhm, Giani M B; Montenegro, Gissele O; Silveira, Lucas A; Betemps, Glauco R

2017-01-30

A high concentration of hydrocarbons in the environment is indicative of pollution. To evaluate the effect of hydrocarbons transported by urban runoff, the present study analyzed total petroleum hydrocarbons (TPHs), aliphatic hydrocarbons (AHs), unresolved complex mixture (UCM), and n-alkanes of the sediments of the canal that cross the urban area of Pelotas, Rio Grande do Sul, Brazil. The carbon preference index (CPI), terrigenous/aquatic ratio (TAR), and pristane/phytane ratio were determined. The TPH content ranged from 177,043.7μg·kg -1 ±13.4% to 5,892,667.0μg·kg -1 ±5.9%. The total aliphatic content ranged from 116,268.8μg·kg -1 ±11.1% to 2,393,592.6μg·kg -1 ±7.7%, indicating chronic contamination of n-alkanes petrogenic and biogenic sources. The levels of hydrocarbons (TPH, AHs, and n-alkanes) were considered relatively high, confirming the effect of urban runoff on the drainage system of cities and their consequent effect on the estuarine region of Patos Lagoon and other water resources. Copyright © 2016 Elsevier Ltd. All rights reserved.

Apparatus for recovering gaseous hydrocarbons from hydrocarbon-containing solid hydrates

DOEpatents

Elliott, Guy R. B.; Barraclough, Bruce L.; Vanderborgh, Nicholas E.

1984-01-01

A method and apparatus are provided for producing gaseous hydrocarbons from formations comprising solid hydrocarbon hydrates located under either a body of land or a body of water. The vast natural resources of such hydrocarbon hydrates can thus now be economically mined. Relatively warm brine or water is brought down from an elevation above that of the hydrates through a portion of the apparatus and passes in contact with the hydrates, thus melting them. The liquid then continues up another portion of the apparatus, carrying entrained hydrocarbon vapors in the form of bubbles, which can easily be separated from the liquid. After a short startup procedure, the process and apparatus are substantially self-powered.

Electrostatic twisted modes in multi-component dusty plasmas

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

Ayub, M. K.; National Centre for Physics, Shahdra Valley Road, Quaid-i-Azam University Campus, Islamabad 44000; Pohang University of Sciences and Technology, Pohang, Gyeongbuk 790-784

Various electrostatic twisted modes are re-investigated with finite orbital angular momentum in an unmagnetized collisionless multi-component dusty plasma, consisting of positive/negative charged dust particles, ions, and electrons. For this purpose, hydrodynamical equations are employed to obtain paraxial equations in terms of density perturbations, while assuming the Gaussian and Laguerre-Gaussian (LG) beam solutions. Specifically, approximated solutions for potential problem are studied by using the paraxial approximation and expressed the electric field components in terms of LG functions. The energy fluxes associated with these modes are computed and corresponding expressions for orbital angular momenta are derived. Numerical analyses reveal that radial/angular modemore » numbers as well as dust number density and dust charging states strongly modify the LG potential profiles attributed to different electrostatic modes. Our results are important for understanding particle transport and energy transfer due to wave excitations in multi-component dusty plasmas.« less

A multicomponent exercise program for institutionalized older adults.

PubMed

Justine, Maria; Hamid, Tengku Aizan

2010-10-01

This study examined the effects of a multicomponent exercise program on depression and quality of life in institutionalized older adults. A quasi-experimental pretest-posttest design was used. Participants were recruited from a publicly funded shelter home in Seremban, Negeri Sembilan Malaysia. The experimental group consisted of 23 volunteers 60 or older who performed 60 minutes of supervised exercise three times per week for 12 weeks. The control group consisted of 20 volunteers who continued with a sedentary lifestyle. At 12 weeks, the exercise group demonstrated an improvement in quality of life by 10.74% (p > 0.05) but not depression (-1.6%, p > 0.05). The control group demonstrated a decrease in both quality of life by 11.26% (p > 0.05) and level of depression by 17.7% (p > 0.05). This study suggests a multicomponent exercise program is a feasible intervention to improve quality of life in institutionalized older adults. Copyright 2010, SLACK Incorporated.

Novel Reagents for Multi-Component Reactions

NASA Astrophysics Data System (ADS)

Wang, Yanguang; Basso, Andrea; Nenajdenko, Valentine G.; Gulevich, Anton V.; Krasavin, Mikhail; Bushkova, Ekaterina; Parchinsky, Vladislav; Banfi, Luca; Basso, Andrea; Cerulli, Valentina; Guanti, Giuseppe; Riva, Renata; Rozentsveig, Igor B.; Rozentsveig, Gulnur N.; Popov, Aleksandr V.; Serykh, Valeriy J.; Levkovskaya, Galina G.; Cao, Song; Shen, Li; Liu, Nianjin; Wu, Jingjing; Li, Lina; Qian, Xuhong; Chen, Xiaopeng; Wang, Hongbo; Feng, Jinwu; Wang, Yanguang; Lu, Ping; Heravi, Majid M.; Sadjadi, Samaheh; Kazemizadeh, Ali Reza; Ramazani, Ali; Kudyakova, Yulia S.; Goryaeva, Marina V.; Burgart, Yanina V.; Saloutin, Victor I.; Mossetti, Riccardo; Pirali, Tracey; Tron, Gian Cesare; Rozhkova, Yulia S.; Mayorova, Olga A.; Shklyaev, Yuriy V.; Zhdanko, Alexander G.; Nenajdenko, Valentine G.; Stryapunina, Olga G.; Plekhanova, Irina V.; Glushkov, Vladimir A.; Shklyaev, Yurii V.

Ketenimines are a class of versatile and highly reactive intermediates that can participate in a variety of organic reactions, such as nucleophilic additions, radical additions, [2 + 2] and [2 + 4] cycloadditions, and sigmatropic rearrangements. In this presentation, we report on a series of multi-component reactions that involve a ketenimine intermediate. These reactions could furnish diverse heterocyclic compounds, including functionalized iminocoumarin, iminodihydroqunolines, iminothiochromens, pyrrolines, isoquinolines, pyridines, β-lactams, imino-1,2-dihydrocoumarins, and benzimidazoles.

Direct Observation of the Photodegradation of Anthracene and Pyrene Adsorbed onto Mangrove Leaves

PubMed Central

Wang, Ping; Wu, Tun-Hua; Zhang, Yong

2014-01-01

An established synchronous fluorimetry method was used for in situ investigation of the photodegradation of pyrene (PYR) and anthracene (ANT) adsorbed onto fresh leaves of the seedlings of two mangrove species, Aegiceras corniculatum (L.) Blanco (Ac) and Kandelia obovata (Ko) in multicomponent mixtures (mixture of the ANT and PYR). Experimental results indicated that photodegradation was the main transformation pathway for both ANT and PYR in multicomponent mixtures. The amount of the PAHs volatilizing from the leaf surfaces and entering the inner leaf tissues was negligible. Over a certain period of irradiation time, the photodegradation of both PYR and ANT adsorbed onto the leaves of Ac and Ko followed first-order kinetics, with faster rates being observed on Ac leaves. In addition, the photodegradation rate of PYR on the leaves of the mangrove species in multicomponent mixtures was much slower than that of adsorbed ANT. Compared with the PAHs adsorbed as single component, the photodegradation rate of ANT adsorbed in multicomponent mixtures was slower, while that of PYR was faster. Moreover, the photodegradation of PYR and ANT dissolved in water in multicomponent mixtures was investigated for comparison. The photodegradation rate on leaves was much slower than in water. Therefore, the physical-chemical properties of the substrate may strongly influence the photodegradation rate of adsorbed PAHs. PMID:25144741

Investigation of the ignition of liquid hydrocarbon fuels with nanoadditives

NASA Astrophysics Data System (ADS)

Bakulin, V. N.; Velikodnyi, V. Yu.; Levin, Yu. K.; Popov, V. V.

2017-12-01

During our experimental studies we showed a high efficiency of the influence of nanoparticle additives on the stability of the ignition of hydrocarbon fuels and the stabilization of their combustion in a highfrequency high-voltage discharge. We detected the effects of a jet deceleration, an increase in the volume of the combustible mixture, and a reduction in the inflammation delay time. These effects have been estimated quantitatively by digitally processing the video frames of the ignition of a bubbled kerosene jet with 0.5% graphene nanoparticle additives and without these additives. This effect has been explained by the influence of electrodynamic processes.

Bioaccumulation of petroleum hydrocarbons in arctic amphipods in the oil development area of the Alaskan Beaufort Sea.

PubMed

Neff, Jerry M; Durell, Gregory S

2012-04-01

An objective of a multiyear monitoring program, sponsored by the US Department of the Interior, Bureau of Ocean Energy Management was to examine temporal and spatial changes in chemical and biological characteristics of the Arctic marine environment resulting from offshore oil exploration and development activities in the development area of the Alaskan Beaufort Sea. To determine if petroleum hydrocarbons from offshore oil operations are entering the Beaufort Sea food web, we measured concentrations of hydrocarbons in tissues of amphipods, Anonyx nugax, sediments, Northstar crude oil, and coastal peat, collected between 1999 and 2006 throughout the development area. Mean concentrations of polycyclic aromatic hydrocarbons (PAH), saturated hydrocarbons (SHC), and sterane and triterpane petroleum biomarkers (StTr) were not significantly different in amphipods near the Northstar oil production facility, before and after it came on line in 2001, and in amphipods from elsewhere in the study area. Forensic analysis of the profiles (relative composition and concentrations) of the 3 hydrocarbon classes revealed that hydrocarbon compositions were different in amphipods, surface sediments where the amphipods were collected, Northstar crude oil, and peat from the deltas of 4 North Slope rivers. Amphipods and sediments contained a mixture of petrogenic, pyrogenic, and biogenic PAH. The SHC in amphipods were dominated by pristane derived from zooplankton, indicating that the SHC were primarily from the amphipod diet of zooplankton detritus. The petroleum biomarker StTr profiles did not resemble those in Northstar crude oil. The forensic analysis revealed that hydrocarbons in amphipod tissues were not from oil production at Northstar. Hydrocarbons in amphipod tissues were primarily from their diet and from river runoff and coastal erosion of natural diagenic and fossil terrestrial materials, including seep oils, kerogens, and peat. Offshore oil and gas exploration and development

Hydrocarbons in Deep-Sea Sediments following the 2010 Deepwater Horizon Blowout in the Northeast Gulf of Mexico.

PubMed

Romero, Isabel C; Schwing, Patrick T; Brooks, Gregg R; Larson, Rebekka A; Hastings, David W; Ellis, Greg; Goddard, Ethan A; Hollander, David J

2015-01-01

The Deepwater Horizon (DWH) spill released 4.9 million barrels of oil into the Gulf of Mexico (GoM) over 87 days. Sediment and water sampling efforts were concentrated SW of the DWH and in coastal areas. Here we present geochemistry data from sediment cores collected in the aftermath of the DWH event from 1000-1500 m water depth in the DeSoto Canyon, NE of the DWH wellhead. Cores were analyzed at high-resolution (at 2 mm and 5 mm intervals) in order to evaluate the concentration, composition and input of hydrocarbons to the seafloor. Specifically, we analyzed total organic carbon (TOC), aliphatic, polycyclic aromatic hydrocarbon (PAHs), and biomarker (hopanes, steranes, diasteranes) compounds to elucidate possible sources and transport pathways for deposition of hydrocarbons. Results showed higher hydrocarbon concentrations during 2010-2011 compared to years prior to 2010. Hydrocarbon inputs in 2010-2011 were composed of a mixture of sources including terrestrial, planktonic, and weathered oil. Our results suggest that after the DWH event, both soluble and highly insoluble hydrocarbons were deposited at enhanced rates in the deep-sea. We proposed two distinct transport pathways of hydrocarbon deposition: 1) sinking of oil-particle aggregates (hydrocarbon-contaminated marine snow and/or suspended particulate material), and 2) advective transport and direct contact of the deep plume with the continental slope surface sediments between 1000-1200 m. Our findings underline the complexity of the depositional event observed in the aftermath of the DWH event in terms of multiple sources, variable concentrations, and spatial (depth-related) variability in the DeSoto Canyon, NE of the DWH wellhead.

Hydrocarbons in Deep-Sea Sediments following the 2010 Deepwater Horizon Blowout in the Northeast Gulf of Mexico

PubMed Central

Romero, Isabel C.; Schwing, Patrick T.; Brooks, Gregg R.; Larson, Rebekka A.; Hastings, David W.; Ellis, Greg; Goddard, Ethan A.; Hollander, David J.

2015-01-01

The Deepwater Horizon (DWH) spill released 4.9 million barrels of oil into the Gulf of Mexico (GoM) over 87 days. Sediment and water sampling efforts were concentrated SW of the DWH and in coastal areas. Here we present geochemistry data from sediment cores collected in the aftermath of the DWH event from 1000 – 1500 m water depth in the DeSoto Canyon, NE of the DWH wellhead. Cores were analyzed at high-resolution (at 2 mm and 5 mm intervals) in order to evaluate the concentration, composition and input of hydrocarbons to the seafloor. Specifically, we analyzed total organic carbon (TOC), aliphatic, polycyclic aromatic hydrocarbon (PAHs), and biomarker (hopanes, steranes, diasteranes) compounds to elucidate possible sources and transport pathways for deposition of hydrocarbons. Results showed higher hydrocarbon concentrations during 2010-2011 compared to years prior to 2010. Hydrocarbon inputs in 2010-2011 were composed of a mixture of sources including terrestrial, planktonic, and weathered oil. Our results suggest that after the DWH event, both soluble and highly insoluble hydrocarbons were deposited at enhanced rates in the deep-sea. We proposed two distinct transport pathways of hydrocarbon deposition: 1) sinking of oil-particle aggregates (hydrocarbon-contaminated marine snow and/or suspended particulate material), and 2) advective transport and direct contact of the deep plume with the continental slope surface sediments between 1000-1200 m. Our findings underline the complexity of the depositional event observed in the aftermath of the DWH event in terms of multiple sources, variable concentrations, and spatial (depth-related) variability in the DeSoto Canyon, NE of the DWH wellhead. PMID:26020923

Influence of hydrocarbon fuel structural constitution and flame temperature on soot formation in laminar diffusion flames

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

Gulder, O.L.

1989-11-01

A systematic study of soot formation along the centerlines of axisymmetric laminar diffusion flames of a large number of liquid hydrocarbons, hydrocarbon blends, and transportation fuels were made. Measurements of the attenuation of a laser beam across the flame diameter were used to obtain the soot volume fraction, assuming Rayleigh extinction. Two sets of hydrocarbon blends were designed such that the molecular fuel composition varied considerably but the temperature fields in the flames were kept practically constant. Thus it was possible to separate the effects of molecular structure and the flame temperature on soot formation. It was quantitatively shown thatmore » the smoke height is a lumped measure of fuel molecular constitution and hydrogen-to-carbon ratio. Hydrocarbon fuel molecular composition was characterized by six carbon atom types that can be obtained, for complex hydrocarbon mixtures like transportation fuels, from proton nuclear magnetic resonance (/sup 1/H NMR) measurements. Strong attenuation of the laser beam was observed at heights very close to the burner rim. Visible flame profiles along the flame length were shown to have good self-similarity. Kent's model for diffusion flames was modified to include the effects of differences in flame temperatures and molecular diffusivities between fuels. An analysis based on the present data provides an assessment of the degree of contribution of different carbon atom types to the maximum soot volume fractions.« less

TESTING FOR ADDITIVITY IN THE LOW DOSE REGION OF AN ENVIRONMENTALLY RELEVANT MIXTURE OF 18 OLYHALOGENATED AROMATIC HYDROCARBONS.

EPA Science Inventory

A common default assumption in risk assessment of chemical mixtures is that the chemicals combine additively in the low dose region. Under additivity, with information from single chemical dose-response data, the risk associated with the mixture can be estimated. The objective ...

Hydrodynamic theory of diffusion in two-temperature multicomponent plasmas

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

Ramshaw, J.D.; Chang, C.H.

Detailed numerical simulations of multicomponent plasmas require tractable expressions for species diffusion fluxes, which must be consistent with the given plasma current density J{sub q} to preserve local charge neutrality. The common situation in which J{sub q} = 0 is referred to as ambipolar diffusion. The use of formal kinetic theory in this context leads to results of formidable complexity. We derive simple tractable approximations for the diffusion fluxes in two-temperature multicomponent plasmas by means of a generalization of the hydrodynamical approach used by Maxwell, Stefan, Furry, and Williams. The resulting diffusion fluxes obey generalized Stefan-Maxwell equations that contain drivingmore » forces corresponding to ordinary, forced, pressure, and thermal diffusion. The ordinary diffusion fluxes are driven by gradients in pressure fractions rather than mole fractions. Simplifications due to the small electron mass are systematically exploited and lead to a general expression for the ambipolar electric field in the limit of infinite electrical conductivity. We present a self-consistent effective binary diffusion approximation for the diffusion fluxes. This approximation is well suited to numerical implementation and is currently in use in our LAVA computer code for simulating multicomponent thermal plasmas. Applications to date include a successful simulation of demixing effects in an argon-helium plasma jet, for which selected computational results are presented. Generalizations of the diffusion theory to finite electrical conductivity and nonzero magnetic field are currently in progress.« less

Efficient Ab initio Modeling of Random Multicomponent Alloys

DOE PAGES

Jiang, Chao; Uberuaga, Blas P.

2016-03-08

Here, we present in this Letter a novel small set of ordered structures (SSOS) method that allows extremely efficient ab initio modeling of random multi-component alloys. Using inverse II-III spinel oxides and equiatomic quinary bcc (so-called high entropy) alloys as examples, we also demonstrate that a SSOS can achieve the same accuracy as a large supercell or a well-converged cluster expansion, but with significantly reduced computational cost. In particular, because of this efficiency, a large number of quinary alloy compositions can be quickly screened, leading to the identification of several new possible high entropy alloy chemistries. Furthermore, the SSOS methodmore » developed here can be broadly useful for the rapid computational design of multi-component materials, especially those with a large number of alloying elements, a challenging problem for other approaches.« less

The Precise Measurement of Vapor-Liquid Equilibrium Properties of the CO2/Isopentane Binary Mixture, and Fitted Parameters for a Helmholtz Energy Mixture Model

NASA Astrophysics Data System (ADS)

Miyamoto, H.; Shoji, Y.; Akasaka, R.; Lemmon, E. W.

2017-10-01

Natural working fluid mixtures, including combinations of CO2, hydrocarbons, water, and ammonia, are expected to have applications in energy conversion processes such as heat pumps and organic Rankine cycles. However, the available literature data, much of which were published between 1975 and 1992, do not incorporate the recommendations of the Guide to the Expression of Uncertainty in Measurement. Therefore, new and more reliable thermodynamic property measurements obtained with state-of-the-art technology are required. The goal of the present study was to obtain accurate vapor-liquid equilibrium (VLE) properties for complex mixtures based on two different gases with significant variations in their boiling points. Precise VLE data were measured with a recirculation-type apparatus with a 380 cm3 equilibration cell and two windows allowing observation of the phase behavior. This cell was equipped with recirculating and expansion loops that were immersed in temperature-controlled liquid and air baths, respectively. Following equilibration, the composition of the sample in each loop was ascertained by gas chromatography. VLE data were acquired for CO2/ethanol and CO2/isopentane binary mixtures within the temperature range from 300 K to 330 K and at pressures up to 7 MPa. These data were used to fit interaction parameters in a Helmholtz energy mixture model. Comparisons were made with the available literature data and values calculated by thermodynamic property models.

Topical viscosity control for light hydrocarbon displacing fluids in petroleum recovery and in fracturing fluids for well stimulation

DOEpatents

Heller, John P.; Dandge, Dileep K.

1986-01-01

Solvent-type flooding fluids comprising light hydrocarbons in the range of ethane to hexane (and mixtures thereof) are used to displace crude oil in formations having temperatures of about 20 degrees to about 150 degrees Centigrade and pressures above about 650 psi, the light hydrocarbons having dissolved therein from about 0.05% to about 3% of an organotin compound of the formula R.sub.3 SnF where each R is independently an alkyl, aryl or alkyaryl group from 3 to 12 carbon atoms. Under the pressures and temperatures described, the organotin compounds become pentacoordinated and linked through the electronegative bridges, forming polymers within the light hydrocarbon flooding media to render them highly viscous. Under ambient conditions, the viscosity control agents will not readily be produced from the formation with either crude oil or water, since they are insoluble in the former and only sparingly soluble in the latter.

A novel bioremediation strategy for petroleum hydrocarbon pollutants using salt tolerant Corynebacterium variabile HRJ4 and biochar.

PubMed

Zhang, Hairong; Tang, Jingchun; Wang, Lin; Liu, Juncheng; Gurav, Ranjit Gajanan; Sun, Kejing

2016-09-01

The present work aimed to develop a novel strategy to bioremediate the petroleum hydrocarbon contaminants in the environment. Salt tolerant bacterium was isolated from Dagang oilfield, China and identified as Corynebacterium variabile HRJ4 based on 16S rRNA gene sequence analysis. The bacterium had a high salt tolerant capability and biochar was developed as carrier for the bacterium. The bacteria with biochar were most effective in degradation of n-alkanes (C16, C18, C19, C26, C28) and polycyclic aromatic hydrocarbons (NAP, PYR) mixture. The result demonstrated that immobilization of C. variabile HRJ4 with biochar showed higher degradation of total petroleum hydrocarbons (THPs) up to 78.9% after 7-day of incubation as compared to the free leaving bacteria. The approach of this study will be helpful in clean-up of petroleum-contamination in the environments through bioremediation process using eco-friendly and cost effective materials like biochar. Copyright © 2016. Published by Elsevier B.V.

Multicomponent self-assembly as a tool to harness new properties from peptides and proteins in material design.

PubMed

Okesola, Babatunde O; Mata, Alvaro

2018-05-21

Nature is enriched with a wide variety of complex, synergistic, and highly functional protein-based multicomponent assemblies. As such, nature has served as a source of inspiration for using multicomponent self-assembly as a platform to create highly ordered, complex, and dynamic protein and peptide-based nanostructures. Such an assembly system relies on the initial interaction of distinct individual building blocks leading to the formation of a complex that subsequently assembles into supramolecular architectures. This approach not only serves as a powerful platform for gaining insight into how proteins co-assemble in nature but also offers huge opportunities to harness new properties not inherent in the individual building blocks. In the past decades, various multicomponent self-assembly strategies have been used to extract synergistic properties from proteins and peptides. This review highlights the updates in the field of multicomponent self-assembly of proteins and peptides and summarizes various strategies, including covalent conjugation, ligand-receptor interactions, templated/directed assembly and non-specific co-assembly, for driving the self-assembly of multiple proteins and peptide-based building blocks into functional materials. In particular, we focus on peptide- or protein-containing multicomponent systems that, upon self-assembly, enable the emergence of new properties or phenomena. The ultimate goal of this review is to highlight the importance of multicomponent self-assembly in protein and peptide engineering, and to advocate its growth in the fields of materials science and nanotechnology.

Multicomponent Linguistic Awareness Intervention for At-Risk Kindergarteners

ERIC Educational Resources Information Center

Zoski, Jennifer L.; Erickson, Karen A.

2017-01-01

This study investigated the feasibility of multicomponent linguistic awareness intervention on early literacy skills in at-risk kindergarteners. Seventeen students, including native Spanish-speaking English language learners (n = 10) and native English speakers (n = 7), participated in a 6-week small-group therapy program, for a total of 12…

An Inexpensive, Single Use Carbon-Based Sensor for the Rapid and Early Detection of Hydrocarbon Leaks.

PubMed

Sebastian, H Bri; Mayall, Robert M; Pilonieta, Roberto J; Bryant, Steven L

2017-06-23

A novel fabrication process for a single use, low-cost organic solvent sensor has been developed. The process is simple, and the materials are readily available. Carbon nanomaterials are self-assembled at a water/hexane interface, where the hexane phase contains dissolved paraffin wax. Upon the controlled evaporation of hexane, the paraffin wax precipitates, trapping the carbon nanoparticles at the surface in a paraffin wax backbone, realizing a carbon-nanoparticle-decorated film. The film is hydrophobic and highly electrically conductive. When exposed to hydrocarbons or a mixture of hydrocarbons, the conductive carbon network deteriorates and an increase in film resistivity is monitored. The rate of change in resistivity is proportional to the concentration and composition of organic molecules in contact with the film.

Estimating the number of pure chemical components in a mixture by X-ray absorption spectroscopy.

PubMed

Manceau, Alain; Marcus, Matthew; Lenoir, Thomas

2014-09-01

Principal component analysis (PCA) is a multivariate data analysis approach commonly used in X-ray absorption spectroscopy to estimate the number of pure compounds in multicomponent mixtures. This approach seeks to describe a large number of multicomponent spectra as weighted sums of a smaller number of component spectra. These component spectra are in turn considered to be linear combinations of the spectra from the actual species present in the system from which the experimental spectra were taken. The dimension of the experimental dataset is given by the number of meaningful abstract components, as estimated by the cascade or variance of the eigenvalues (EVs), the factor indicator function (IND), or the F-test on reduced EVs. It is shown on synthetic and real spectral mixtures that the performance of the IND and F-test critically depends on the amount of noise in the data, and may result in considerable underestimation or overestimation of the number of components even for a signal-to-noise (s/n) ratio of the order of 80 (σ = 20) in a XANES dataset. For a given s/n ratio, the accuracy of the component recovery from a random mixture depends on the size of the dataset and number of components, which is not known in advance, and deteriorates for larger datasets because the analysis picks up more noise components. The scree plot of the EVs for the components yields one or two values close to the significant number of components, but the result can be ambiguous and its uncertainty is unknown. A new estimator, NSS-stat, which includes the experimental error to XANES data analysis, is introduced and tested. It is shown that NSS-stat produces superior results compared with the three traditional forms of PCA-based component-number estimation. A graphical user-friendly interface for the calculation of EVs, IND, F-test and NSS-stat from a XANES dataset has been developed under LabVIEW for Windows and is supplied in the supporting information. Its possible application to

Full 3-dimensional digital workflow for multicomponent dental appliances: A proof of concept.

PubMed

van der Meer, W Joerd; Vissink, Arjan; Ren, Yijin

2016-04-01

The authors used a 3-dimensional (3D) printer and a bending robot to produce a multicomponent dental appliance to assess whether 3D digital models of the dentition are applicable for a full digital workflow. The authors scanned a volunteer's dentition with an intraoral scanner (Lava Chairside Oral Scanner C.O.S., 3M). A digital impression was used to design 2 multicomponent orthodontic appliances. Biocompatible acrylic baseplates were produced with the aid of a 3D printer. The metal springs and clasps were produced by a bending robot. The fit of the 2 appliances was assessed by 2 experienced orthodontists. The authors assessed both orthodontic appliances with the volunteer's dentition and found the fit to be excellent. Clinicians can fully produce a multicomponent dental appliance consisting of both an acrylic baseplate and other parts, such as clasps, springs, or screws, using a digital workflow process without the need for a physical model of the patient's dentition. Plaster models can be superfluous for orthodontic treatment as digital models can be used in all phases of a full digital workflow in orthodontics. The arduous task of making a multicomponent dental appliance that involves bending wires can possibly be replaced by a computer, design software, a 3D printer, and a bending robot. Copyright © 2016 American Dental Association. Published by Elsevier Inc. All rights reserved.

Theory and Simulation of Multicomponent Osmotic Systems

PubMed Central

Karunaweera, Sadish; Gee, Moon Bae; Weerasinghe, Samantha; Smith, Paul E.

2012-01-01

Most cellular processes occur in systems containing a variety of components many of which are open to material exchange. However, computer simulations of biological systems are almost exclusively performed in systems closed to material exchange. In principle, the behavior of biomolecules in open and closed systems will be different. Here, we provide a rigorous framework for the analysis of experimental and simulation data concerning open and closed multicomponent systems using the Kirkwood-Buff (KB) theory of solutions. The results are illustrated using computer simulations for various concentrations of the solutes Gly, Gly2 and Gly3 in both open and closed systems, and in the absence or presence of NaCl as a cosolvent. In addition, KB theory is used to help rationalize the aggregation properties of the solutes. Here one observes that the picture of solute association described by the KB integrals, which are directly related to the solution thermodynamics, and that provided by more physical clustering approaches are different. It is argued that the combination of KB theory and simulation data provides a simple and powerful tool for the analysis of complex multicomponent open and closed systems. PMID:23329894

Multicomponent, Rare-Earth-Doped Thermal-Barrier Coatings

NASA Technical Reports Server (NTRS)

Miller, Robert A.; Zhu, Dongming

2005-01-01

Multicomponent, rare-earth-doped, perovskite-type thermal-barrier coating materials have been developed in an effort to obtain lower thermal conductivity, greater phase stability, and greater high-temperature capability, relative to those of the prior thermal-barrier coating material of choice, which is yttria-partially stabilized zirconia. As used here, "thermal-barrier coatings" (TBCs) denotes thin ceramic layers used to insulate air-cooled metallic components of heat engines (e.g., gas turbines) from hot gases. These layers are generally fabricated by plasma spraying or physical vapor deposition of the TBC materials onto the metal components. A TBC as deposited has some porosity, which is desirable in that it reduces the thermal conductivity below the intrinsic thermal conductivity of the fully dense form of the material. Undesirably, the thermal conductivity gradually increases because the porosity gradually decreases as a consequence of sintering during high-temperature service. Because of these and other considerations such as phase transformations, the maximum allowable service temperature for yttria-partially stabilized zirconia TBCs lies in the range of about 1,200 to 1,300 C. In contrast, the present multicomponent, rare-earth-doped, perovskite-type TBCs can withstand higher temperatures.

Apparatus and methods for hydrocarbon extraction

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

Bohnert, George W.; Verhulst, Galen G.

Systems and methods for hydrocarbon extraction from hydrocarbon-containing material. Such systems and methods relate to extracting hydrocarbon from hydrocarbon-containing material employing a non-aqueous extractant. Additionally, such systems and methods relate to recovering and reusing non-aqueous extractant employed for extracting hydrocarbon from hydrocarbon-containing material.

Research design issues for evaluating complex multicomponent interventions in neighborhoods and communities.

PubMed

Komro, Kelli A; Flay, Brian R; Biglan, Anthony; Wagenaar, Alexander C

2016-03-01

Major advances in population health will not occur unless we translate existing knowledge into effective multicomponent interventions, implement and maintain these in communities, and develop rigorous translational research and evaluation methods to ensure continual improvement and sustainability. We discuss challenges and offer approaches to evaluation that are key for translational research stages 3 to 5 to advance optimized adoption, implementation, and maintenance of effective and replicable multicomponent strategies. The major challenges we discuss concern (a) multiple contexts of evaluation/research, (b) complexity of packages of interventions, and (c) phases of evaluation/research questions. We suggest multiple alternative research designs that maintain rigor but accommodate these challenges and highlight the need for measurement systems. Longitudinal data collection and a standardized continuous measurement system are fundamental to the evaluation and refinement of complex multicomponent interventions. To be useful to T3-T5 translational research efforts in neighborhoods and communities, such a system would include assessments of the reach, implementation, effects on immediate outcomes, and effects of the comprehensive intervention package on more distal health outcomes.

Temperature Dependence of Dissociative Electron Attachment to Halogenated Hydrocarbons

NASA Astrophysics Data System (ADS)

Wang, Yicheng; Christophorou, Loucas G.

1996-10-01

Most of the gas mixtures currently in use for plasma processing of semiconductors involve halogenated hydrocarbons such as the strongly electronegative gases CCl4 and CFCl_3, the weakly electronegative gas CF_2Cl2 and the very weakly electronegative gases CHF3 and CF_4. Many dissociation processes are known to occur for these molecules. One of these dissociation reactions which is particularly effective for the strongly electronegative hydrocarbons is dissociative electron attachment. Even for weakly electron attaching gases, molecular dissociation via dissociative electron attachment at low energies can be an efficient dissociation process if the gas temperature is higher than ambient. Dissociative electron attachment is known to increase with increasing temperature above room temperature for many such compounds. In this paper, we report our measurements on the increases of the total electron attachment rate constant for CF_2Cl2 with increasing gas temperature from room temperature to about 600 K. -Research sponsored in part by the U.S. Air Force Wright Laboratory under contract F33615-96-C-2600 with the University of Tennessee. Also, Department of Physics, The University of Tennessee, Knoxville, TN.

Optimal Multicomponent Analysis Using the Generalized Standard Addition Method.

ERIC Educational Resources Information Center

Raymond, Margaret; And Others

1983-01-01

Describes an experiment on the simultaneous determination of chromium and magnesium by spectophotometry modified to include the Generalized Standard Addition Method computer program, a multivariate calibration method that provides optimal multicomponent analysis in the presence of interference and matrix effects. Provides instructions for…

Multicomponent Reactions in Ligation and Bioconjugation Chemistry.

PubMed

Reguera, Leslie; Méndez, Yanira; Humpierre, Ana R; Valdés, Oscar; Rivera, Daniel G

2018-05-25

Multicomponent reactions (MCRs) encompass an exciting class of chemical transformations that have proven success in almost all fields of synthetic organic chemistry. These convergent procedures incorporate three or more reactants into a final product in one pot, thus combining high levels of complexity and diversity generation with low synthetic cost. Striking applications of these processes are found in heterocycle, peptidomimetic, and natural product syntheses. However, their potential in the preparation of large macro- and biomolecular constructs has been realized just recently. This Account describes the most relevant results of our group in the utilization of MCRs for ligation/conjugation of biomolecules along with significant contributions from other laboratories that validate the utility of this special class of bioconjugation process. Thus, MCRs have proven to be efficient in the ligation of lipids to peptides and oligosaccharides as well as the ligation of steroids, carbohydrates, and fluorescent and affinity tags to peptides and proteins. In the field of glycolipids, we highlight the power of isocyanide-based MCRs with the one-pot double lipidation of glycan fragments functionalized as either the carboxylic acid or amine. In peptide chemistry, the versatility of the multicomponent ligation strategy is demonstrated in both solution-phase lipidation protocols and solid-phase procedures enabling the simultaneous lipidation and biotinylation of peptides. In addition, we show that MCRs are powerful methods for synchronized lipidation/labeling and macrocyclization of peptides, thus accomplishing in one step what usually requires long sequences. In the realm of protein bioconjugation, MCRs have also proven to be effective in labeling, site-selective modification, immobilization, and glycoconjugation processes. For example, we illustrate a successful application of multicomponent polysaccharide-protein conjugation with the preparation of multivalent

Non-stationary component extraction in noisy multicomponent signal using polynomial chirping Fourier transform.

PubMed

Lu, Wenlong; Xie, Junwei; Wang, Heming; Sheng, Chuan

2016-01-01

Inspired by track-before-detection technology in radar, a novel time-frequency transform, namely polynomial chirping Fourier transform (PCFT), is exploited to extract components from noisy multicomponent signal. The PCFT combines advantages of Fourier transform and polynomial chirplet transform to accumulate component energy along a polynomial chirping curve in the time-frequency plane. The particle swarm optimization algorithm is employed to search optimal polynomial parameters with which the PCFT will achieve a most concentrated energy ridge in the time-frequency plane for the target component. The component can be well separated in the polynomial chirping Fourier domain with a narrow-band filter and then reconstructed by inverse PCFT. Furthermore, an iterative procedure, involving parameter estimation, PCFT, filtering and recovery, is introduced to extract components from a noisy multicomponent signal successively. The Simulations and experiments show that the proposed method has better performance in component extraction from noisy multicomponent signal as well as provides more time-frequency details about the analyzed signal than conventional methods.

Nature and prevalence of non-additive toxic effects in industrially relevant mixtures of organic chemicals.

PubMed

Parvez, Shahid; Venkataraman, Chandra; Mukherji, Suparna

2009-06-01

The concentration addition (CA) and the independent action (IA) models are widely used for predicting mixture toxicity based on its composition and individual component dose-response profiles. However, the prediction based on these models may be inaccurate due to interaction among mixture components. In this work, the nature and prevalence of non-additive effects were explored for binary, ternary and quaternary mixtures composed of hydrophobic organic compounds (HOCs). The toxicity of each individual component and mixture was determined using the Vibrio fischeri bioluminescence inhibition assay. For each combination of chemicals specified by the 2(n) factorial design, the percent deviation of the predicted toxic effect from the measured value was used to characterize mixtures as synergistic (positive deviation) and antagonistic (negative deviation). An arbitrary classification scheme was proposed based on the magnitude of deviation (d) as: additive (< or =10%, class-I) and moderately (10< d < or =30 %, class-II), highly (30< d < or =50%, class-III) and very highly (>50%, class-IV) antagonistic/synergistic. Naphthalene, n-butanol, o-xylene, catechol and p-cresol led to synergism in mixtures while 1, 2, 4-trimethylbenzene and 1, 3-dimethylnaphthalene contributed to antagonism. Most of the mixtures depicted additive or antagonistic effect. Synergism was prominent in some of the mixtures, such as, pulp and paper, textile dyes, and a mixture composed of polynuclear aromatic hydrocarbons. The organic chemical industry mixture depicted the highest abundance of antagonism and least synergism. Mixture toxicity was found to depend on partition coefficient, molecular connectivity index and relative concentration of the components.

Radical and ion molecule mechanisms in the polymerization of hydrocarbons and chlorosilanes in RF plasmas at low pressures ( 1.0 torr)

NASA Technical Reports Server (NTRS)

Avni, R.; Carmi, U.; Inspektor, A.; Rosenthal, I.

1984-01-01

The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.

Application of ion chromatography to the study of hydrolysis of some halogenated hydrocarbons at ambient temperatures

NASA Technical Reports Server (NTRS)

Otterson, D. A.

1978-01-01

The application of ion chromatography to the study of very slow rates of hydrolysis of some halogenated hydrocarbons was investigated. The halide concentrations in the aqueous phase of mixtures of a carbonate buffer (pH = 10.3) and either chloroform (CHC13) or fluorotrichloromethane (CFC13) after aging for various lengths of time at room temperature, were determined by ion chromatography. Hydrolysis of CHC13 caused the C1(-) concentration to increase by about 1500 ppb per day. On the other hand neither the F(-) or C1(-) concentration in the CFC13 mixture increased by as much as 1 ppb per day. The magnitude of errors in the determination of halides prevented any firm conclusions regarding hydrolysis in this mixture. However, these results were used to show how ion chromatography could expedite identification of the hydrolyzing substance as well as investigations of hydrolysis mechanisms.

Production of low molecular weight hydrocarbons by volcanic eruptions on early Mars.

PubMed

Segura, Antígona; Navarro-González, Rafael

2005-10-01

Methane and other larger hydrocarbons have been proposed as possible greenhouse gases on early Mars. In this work we explore if volcanic processes may have been a source for such molecules based on theoretical and experimental considerations. Geologic evidence and numerical simulations indicate that explosive volcanism was widely distributed throughout Mars. Volcanic lightning is typically produced in such explosive volcanism. Therefore this geologic setting was studied to determine if lightning could be a source for hydrocarbons in volcanic plumes. Volcanic lightning was simulated by focusing a high-energy infrared laser beam inside of a Pyrex reactor that contained the proposed volcanic gas mixture composed of 64% CH(4), 24% H(2), 10% H(2)O and 2% N(2), according to an accretion model and the nitrogen content measured in Martian meteorites. The analysis of products was performed by gas chromatography coupled to infrared and mass spectroscopy. Eleven hydrocarbons were identified among the products, of which acetylene (C(2)H(2)) was the most abundant. A thermochemical model was used to determine which hydrocarbons could arise only from volcanic heat. In this case, acetylene and ethylene are formed at magmatic temperatures. Our results indicate that explosive volcanism may have injected into the atmosphere of early Mars approximately 6 x 10(12) g yr(-1) of acetylene, and approximately 2 x 10(12) g yr(-1) of 1,3-butadiyne, both produced by volcanic lightning, approximately 5 x 10(11) g yr(-1) of ethylene produced by volcanic heat, and 10(13) g yr(-1) of methane.