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Sample records for n-pentane n-hexane n-heptane

  1. A comparative study on the neurotoxicity of n-pentane, n-hexane, and n-heptane in the rat.

    PubMed Central

    Takeuchi, Y; Ono, Y; Hisanaga, N; Kitoh, J; Sugiura, Y

    1980-01-01

    The neurotoxicity of n-pentane, n-hexane, and n-heptane have been studied in Wistar strain male rats after exposure to 3000 ppm of n-pentane, n-hexane, or n-heptane for 12 hours a day for 16 weeks. The nerve conduction velocity and the distal latency were measured before the beginning of the exposure and after exposure for four, eight, 12, and 16 weeks. The experiment showed that n-hexane disturbed the conduction velocity of the motor nerve and the mixed nerve and prolonged the distal latency in the rat's tail, but that n-pentane and n-heptane did not. The light and electron microscopic examination showed that the peripheral nerve, the neuromuscular junction, and the muscle fibre of the rats exposed to n-hexane were severely impaired, but those of the rats exposed to n-pentane or n-heptane showed no particular changes even after 16 weeks of exposure. These results show that n-hexane is far more toxic to the peripheral nerve of the rat than n-pentane or n-heptane. It is necessary to study the neurotoxicity of other petroleum hydrocarbons, since some reports suggest that petroleum solvents might possibly contain neurotoxic hydrocarbons other than n-hexane. Images PMID:7426474

  2. Binary chromatographic data and estimation of adsorbent porosities. [data for system n-heptane/n-pentane

    NASA Technical Reports Server (NTRS)

    Meisch, A. J.

    1972-01-01

    Data for the system n-pentane/n-heptane on porous Chromosorb-102 adsorbent were obtained at 150, 175, and 200 C for mixtures containing zero to 100% n-pentane by weight. Prior results showing limitations on superposition of pure component data to predict multicomponent chromatograms were verified. The thermodynamic parameter MR0 was found to be a linear function of sample composition. A nonporous adsorbent failed to separate the system because of large input sample dispersions. A proposed automated data processing scheme involving magnetic tape recording of the detector signals and processing by a minicomputer was rejected because of resolution limitations of the available a/d converters. Preliminary data on porosity and pore size distributions of the adsorbents were obtained.

  3. Heats of n-hexane and n-heptane vapor adsorption onto polyhydroxyaluminum montmorillonite

    NASA Astrophysics Data System (ADS)

    Muminov, S. Z.; Khandamov, D. A.; Rakhimova, G. B.

    2011-01-01

    The differential isosteric heat of the adsorption of n-hexane and n-heptane vapors on dehydrated polyhydroxyaluminum montmorillonite was determined. Using the temperature dependence of the parameters of the adsorption equilibrium, it was established that substituting sodium ions for polyhydroxyaluminum cations leads to an increase in the volume of micropores and the adsorption heat of hydrocarbons, and the curves of the adsorption heats of C6H14 and C7H16 are of an extreme nature. The appearance of the maxima is associated with the interaction between and among the adsorbate molecules and active centers, due to consolidation in the process of filling micropore volumes.

  4. On the behavior of solutions of xenon in liquid n-alkanes: solubility of xenon in n-pentane and n-hexane.

    PubMed

    Bonifácio, Rui P M F; Martins, Luís F G; McCabe, Clare; Filipe, Eduardo J M

    2010-12-01

    The solubility of xenon in liquid n-pentane and n-hexane has been studied experimentally, theoretically, and by computer simulation. Measurements of the solubility are reported for xenon + n-pentane as a function of temperature from 254 to 305 K. The uncertainty in the experimental data is less than 0.15%. The thermodynamic functions of solvation such as the standard Gibbs energy, enthalpy, and entropy of solvation have been calculated from Henry's law coefficients for xenon + n-pentane solutions and also for xenon + n-hexane, which were reported in previous work. The results provide a further example of the similarity between the xenon + n-alkane interaction and the n-alkane + n-alkane interactions. Using the SAFT-VR approach we were able to quantitatively predict the experimental solubility for xenon in n-pentane and semiquantitatively that of xenon in n-hexane using simple Lorentz-Berthelot combining rules to describe the unlikely interaction. Henry's constants at infinite dilution for xenon + n-pentane and xenon + n-hexane were also calculated by Monte Carlo simulation using a united atom force field to describe the n-alkane and the Widom test particle insertion method. PMID:21067166

  5. The non-ideal behaviour of the interfacial tension of the n-heptane + perfluoro-n-hexane mixture: A computational study

    NASA Astrophysics Data System (ADS)

    Dominguez, Hector

    2015-05-01

    Computer simulations of the n-heptane + perfluoro-n-hexane system is used to understand the unusual behaviour of the horizontal inflection of the vapour-liquid interfacial tension experiments of alkanes-perfluoroalkanes mixtures. Simulations are conducted and good agreement with experiments is obtained. From the results a change in curvature to a nearly constant value in the tensions at high perfluoro-n-hexane compositions is identified. Dynamic, thermodynamic and structural properties are analysed in that region and peculiar tendencies of those properties are found which help us to understand the nature of the uncommon inflection in the isotherms.

  6. A model of reduced oxidation kinetics using constituents and species: Iso-octane and its mixtures with n-pentane, iso-hexane and n-heptane

    SciTech Connect

    Harstad, Kenneth; Bellan, Josette

    2010-11-15

    A previously described methodology for deriving a reduced kinetic mechanism for alkane oxidation and tested for n-heptane is here shown to be valid, in a slightly modified version, for iso-octane and its mixtures with n-pentane, iso-hexane and n-heptane. The model is still based on partitioning the species into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement in the species ensemble, and mathematically decomposing the heavy species into constituents which are radicals. For the same similarity variable found from examining the n-heptane LLNL mechanism in conjunction with CHEMKIN II, the appropriately scaled total constituent molar density still exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures in the cold ignition regime. When extended to larger initial temperatures than for cold ignition, the self-similar behavior becomes initial temperature dependent, which indicates that rather than using functional fits for the enthalpy generation due to the heavy species' oxidation, an ideal model based on tabular information extracted from the complete LLNL kinetics should be used instead. Similarly to n-heptane, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable, but here their slope variation is no longer fitted and instead, their rate equations are used with the ideal model to calculate them. As in the original model, the light species ensemble is partitioned into quasi-steady and unsteady species; the quasi-steady light species mole fractions are computed using the ideal model and the unsteady species are calculated as progress variables using rates extracted from the ideal model. Results are presented comparing the performance of the model with that of the LLNL mechanism using CHEMKIN II. The model reproduces excellently the temperature and species evolution versus time or versus the similarity variable, with the exception of very rich mixtures, where the predictions are still very good but the multivalued aspect of these functions at the end of oxidation is not captured in the reduction. The ignition time is predicted within percentages of the LLNL values over a wide range of equivalence ratios, initial pressures and initial temperatures. (author)

  7. Thermodynamics of acrylic esters containing binary liquid mixtures. I. Excess volumes and isentropic compressibilities of alkyl methacrylates + n-hexane, + n-heptane, + carbon tetrachloride, + chlorobenzene, and o-dichlorobenzene at 303.15 K

    NASA Astrophysics Data System (ADS)

    Sastry, N. V.; Dave, P. N.

    1996-11-01

    Excess volumes and isentropic compressibilities of 15 binary liquid mixtures containing methyl methacrylate (MMA). ethyl methacrylate (EMA), and butyl methacrylate (BM) and n-Hexane, n-heptane, carbon tetrachloride chlorobenzene and o-dichlorobenzene are derived from the measured densities and speeds of sound at 303.15 K. The dependence of the excess volumes and the isentropic compressibilities both on the alkyl chain length and on the nature of the solvent shots the dominance of dispersing interactions in the mixtures of aliphatic hydrocarbons and specific interactions im the chlorinated solvent mixtures. The speeds of sound of binary mixtures of MMA were found to be reasonably predicted by free length and collision factor theories. An attempt is also made to estimate the individual contributions of interactional. free volume and P * effects to the overall excess volumes of binary mixtures containing MMA. The results indicate that the three factors are equally responsible for the observed values.

  8. n-Heptane

    Integrated Risk Information System (IRIS)

    n - Heptane ; CASRN 142 - 82 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effec

  9. n-Hexane

    Integrated Risk Information System (IRIS)

    n - Hexane ; CASRN 110 - 54 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  10. n-Hexane

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 03 / 012 www.epa.gov / iris TOXICOLOGICAL REVIEW OF n - HEXANE ( CAS No . 110 - 54 - 3 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) November 2005 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This docum ent has been revie

  11. Does n-heptane cause peripheral neurotoxicity? A case report in a shoemaker.

    PubMed

    Valentini, F; Agnesi, R; Dal Vecchio, L; Bartolucci, G B; De Rosa, E

    1994-05-01

    Subjective and electrophysiological signs relating to the central and peripheral nervous systems developed in a shoemaker, a few months after beginning work at home. Signs of central nervous system involvement rapidly disappeared after the end of the exposure, whereas those of mild peripheral neuropathy lasted for several months. The glue used contained a variety of solvents including ethylacetate, cyclohexane, methylcyclohexane, methylethylketone and others; n-hexane was not detected, whereas, unusually, n-heptane was. This exposure was reproduced experimentally in the same work room and the solvent air level did not exceed the American Conference of Governmental Industrial Hygienists threshold values. A tentative conclusion is that the toxic effects on the peripheral nerve are likely to be due to n-heptane. PMID:8032028

  12. Separation of a 2-propanol/n-heptane mixture by liquid membrane perstraction

    SciTech Connect

    Papadopoulos, T.; Sirkar, K.K. )

    1993-04-01

    The effectiveness of perstraction separation of a 2 vol% 2-propanol-n-heptane mixture using dodecane as the strip liquid was studied using a hollow fiber contained liquid membrane permeator (HFCLMP). The liquid membranes used were pure water and 3 wt% water in sulfolane. Both liquid membranes yielded similar mass-transfer coefficients and 2-propanol removal rates. Pure water, however, exhibited 3 times higher selectivity for 2-propanol than 3 wt % water in sulfolane. Selectivities of 2-propanol over n-heptane as high as 447 were experimentally obtained. The observed fluxes and selectivities at 25C are close to those obtained in prevaporation of a 10% 2-propanol-n-hexane mixture through cellulose ester films at 60C. A first-order mathematical model was developed using partition coefficients that are functions of solute concentrations, and it predicts the observed behavior of the two systems relatively well.

  13. Structure of liquid n-hexane

    NASA Astrophysics Data System (ADS)

    Venturi, G.; Formisano, F.; Cuello, G. J.; Johnson, M. R.; Pellegrini, E.; Bafile, U.; Guarini, E.

    2009-07-01

    The structure of deuterated liquid n-hexane has been investigated at room temperature by neutron diffraction and molecular dynamics simulations. By carrying out a careful analysis of the measurements, experimental data were obtained in very good agreement with the simulated data. This allowed a thorough analysis of the simulation results aiming at the evaluation of the partial, intra-, and intermolecular components of the n-hexane structure. We finally compare the intramolecular differential cross sections calculated from the most probable n-hexane molecular configurations with the measured and simulated data.

  14. [Metabolism and toxicity of n-pentane and isopentane].

    PubMed

    Chiba, S; Oshida, S

    1991-04-01

    n-Pentane and isopentane have a wide range of use, for example, for cleaning precision machinery, extracting essence and oil, and as liquid fuel for now very popular disposable lighters. They are contained in liquefied petroleum gas and natural gas as trace constituents. In our present experiments, we studied the metabolism and toxicity of these n-pentane and isopentane metabolites. Male mice of ICR strain were exposed to about 5% n-pentane for one hour while the oxygen in the environmental air was maintained at about 20%. Then their blood and liver tissue were collected and analyzed by means of GC and GC-MS. The metabolites thus obtained were 2-pentanol, 3-pentanol and 2-pentanone. The same procedure was repeated with isopentane; 3-methyl-2-butanol, 2-methyl-2-butanol and 3-methyl-2-butanone were detected as the resultant metabolites. In the presence of the NADPH-generating system liver microsomes were made to react to the substrate of saturated n-pentane or isopentane aqueous solution at 37 degrees C for one hour. As a result, the same metabolites were produced as obtained in the exposure experiment. It was therefore suggested that n-pentane and isopentane were metabolized chiefly by liver microsomes. Male mice of ICR strain were fed with 80 mg/kg b.w. of phenobarbital for consecutive four days and exposed to n-pentane or isopentane for one hour. This resulted in an increase in the amount of 2-pentanol and 2-pentanone in the n-pentane inhalation and 2-methyl-2-butanol in the isopentane inhalation experiment. The toxicity of each metabolite was studied on cultured cells. The metabolites were individually mixed with HeLa S3 cell suspension, incubated for three days, and their concentration which inhibited the growth of cells by 50% (IGC 50) were compared. It was demonstrated as a result that the IGC 50 for any of the metabolites was lower than that for methanol, ethanol or acetone used as control. PMID:1920919

  15. Polyneuropathy due to n-hexane.

    PubMed

    Paulson, G W; Waylonis, G W

    1976-08-01

    In 25 years, at least eight of 50 total exposed employees in a small plant developed a mild neuropathy. Studies of urine or blood for lead, arsenic, mercury, cadmium, thallium, and antimony revealed no sign of toxic agents, but the atmosphere in one room contained toxic levels of n-hexane. The sourse was the glue used in the plant. Serum cholinesterase levels were reduced, offering a possible laboratory tests to alert clinicians to the possibility of n-hexane exposure. All patients recovered completely. Mechanical and administrative adjustments should prevent such industrial accidents. PMID:182098

  16. Effect of methanol on the biofiltration of n-hexane.

    PubMed

    Zehraoui, Abderrahman; Hassan, Ashraf Aly; Sorial, George A

    2012-06-15

    This study investigated the removal of recalcitrant compounds in the presence of a hydrophilic compound. n-Hexane is used as a model compound to represent hydrophobic compounds. Methanol has been introduced in mixture with n-hexane in order to increase the bioavailability of n-hexane in trickle-bed-air-biofilters (TBABs). The mixing ratios investigated were: 70% methanol:30% n-hexane, and 80% methanol:20% n-hexane by volume. n-Hexane loading rates (LRs) ranged from 0.9 to 13.2 g m(-3) h(-1). Methanol LRs varied from 4.6 to 64.5 g m(-3) h(-1) and from 2.3 to 45.2 g m(-3) h(-1) depending upon the mixing ratio used. Biofilter performance, effect of mixing ratios of methanol to n-hexane, removal profile along biofilter depth, COD/nitrogen consumption and CO(2) production were studied under continuous loading operation conditions. Results have shown that the degradation of n-hexane is significantly enhanced by the presence of methanol for n-hexane LRs less than 13.2 g m(-3) h(-1). For n-hexane LR greater than 13.2 g m(-3) h(-1), even though methanol had impacted n-hexane biodegradation, its removal efficiency was higher than our previous study for biodegradation of n-hexane alone, in presence of surfactant, or in presence of benzene. On the other hand, the degradation of methanol was not impacted by the presence of n-hexane. PMID:22516522

  17. Effect of methanol on the biofiltration of n-hexane.

    TOXLINE Toxicology Bibliographic Information

    Zehraoui A; Hassan AA; Sorial GA

    2012-06-15

    This study investigated the removal of recalcitrant compounds in the presence of a hydrophilic compound. n-Hexane is used as a model compound to represent hydrophobic compounds. Methanol has been introduced in mixture with n-hexane in order to increase the bioavailability of n-hexane in trickle-bed-air-biofilters (TBABs). The mixing ratios investigated were: 70% methanol:30% n-hexane, and 80% methanol:20% n-hexane by volume. n-Hexane loading rates (LRs) ranged from 0.9 to 13.2 g m(-3) h(-1). Methanol LRs varied from 4.6 to 64.5 g m(-3) h(-1) and from 2.3 to 45.2 g m(-3) h(-1) depending upon the mixing ratio used. Biofilter performance, effect of mixing ratios of methanol to n-hexane, removal profile along biofilter depth, COD/nitrogen consumption and CO(2) production were studied under continuous loading operation conditions. Results have shown that the degradation of n-hexane is significantly enhanced by the presence of methanol for n-hexane LRs less than 13.2 g m(-3) h(-1). For n-hexane LR greater than 13.2 g m(-3) h(-1), even though methanol had impacted n-hexane biodegradation, its removal efficiency was higher than our previous study for biodegradation of n-hexane alone, in presence of surfactant, or in presence of benzene. On the other hand, the degradation of methanol was not impacted by the presence of n-hexane.

  18. N-hexane neuropathy in offset printers.

    PubMed

    Chang, C M; Yu, C W; Fong, K Y; Leung, S Y; Tsin, T W; Yu, Y L; Cheung, T F; Chan, S Y

    1993-05-01

    In an offset printing factory with 56 workers, 20 (36%) developed symptomatic peripheral neuropathy due to exposure to n-hexane. Another 26 workers (46%) were found to have subclinical neuropathy. The initial change in the nerve conduction study was reduced amplitude of the sensory action potentials, followed by reduced amplitude of the motor action potentials, reduction in motor conduction velocities and increase in distal latencies. These changes indicate primary axonal degeneration with secondary demyelination. Sural nerve biopsy in a severe case showed giant axonal swellings due to accumulation of 10nm neurofilaments, myelin sheath attenuation and widening of nodal gaps. The development of neuropathy bore no direct relationship to the duration of exposure, hence factors such as individual susceptibility may be important. Optic neuropathy and CNS involvement were uncommon and autonomic neuropathy was not encountered. PMID:8505647

  19. Extinction and Autoignition of n-Heptane in Counterflow Configuration

    SciTech Connect

    Seiser, R.; Pitsch, H.; Seshadri, K.; Pitz, W.J.; Curran, H.J.

    2000-01-12

    A study is performed to elucidate the mechanisms of extinction and autoignition of n-heptane in strained laminar flows under nonpremixed conditions. A previously developed detailed mechanism made UP of 2540 reversible elementary reactions among 557 species is the starting point for the study. The detailed mechanism was previously used to calculate ignition delay times in homogeneous reactors, and concentration histories of a number of species in plug-flow and jet-stirred reactors. An intermediate mechanism made up of 1282 reversible elementary reactions among 282 species and a short mechanism made up of 770 reversible elementary reactions among 160 species are assembled from this detailed mechanism. Ignition delay times in an isochoric homogeneous reactor calculated using the intermediate and the short mechanism are found to agree well with those calculated using the detailed mechanism. The intermediate and the short mechanism are used to calculate extinction and autoignition of n-heptane in strained laminar flows. Steady laminar flow of two counter flowing Streams toward a stagnation plane is considered. One stream made up of prevaporized n-heptane and nitrogen is injected from the fuel boundary and the other stream made up of air and nitrogen is injected from the oxidizer boundary. Critical conditions of extinction and autoignition given by the strain rate, temperature and concentrations of the reactants at the boundaries, are calculated. The results are found to agree well with experiments. Sensitivity analysis is carried out to evaluate the influence of various elementary reactions on autoignition. At all values of the strain rate investigated here, high temperature chemical processes are found to control autoignition. In general, the influence of low temperature chemistry is found to increase with decreasing strain. A key finding of the present study is that strain has more influence on low temperature chemistry than the temperature of the reactants.

  20. Extended soot limits for rich n-heptane/air flames

    NASA Technical Reports Server (NTRS)

    Ryason, P. R.

    1977-01-01

    A rich n-heptane/air mixture was burned in a flat flame burner in an inert environment, and the soot limits of stable one-stage flames were measured. With a small thin metal plate placed on the flame to suppress soot-containing cusps on the flamelets, the richest soot-free flame burned was with a mixture for which the equivalence ratio was 2.25. Hydrogen yield was, however, low. Extremely rich soot-free two-stage flames could be obtained, but they were unstable.

  1. n-Hexane metabolism in occupationally exposed workers.

    PubMed Central

    Mutti, A; Falzoi, M; Lucertini, S; Arfini, G; Zignani, M; Lombardi, S; Franchini, I

    1984-01-01

    Lung uptake and excretion of n-hexane were studied in ten workers in a shoe factory. Simultaneous samples of inhaled and alveolar air were collected with the aid of a Rhan-Otis valve, personal samplers, and charcoal tubes. Alveolar excretion was monitored during a six hour postexposure period. Uptake was calculated from lung ventilation, the retention coefficient, and environmental concentrations. The amount of exhaled n-hexane was calculated from the decay curve. According to the experimental data, alveolar retention was about 25% of the inhaled n-hexane, corresponding to a lung uptake of about 17%. The postexposure alveolar excretion was about 10% of the total uptake. The main metabolites of n-hexane were identified and measured by capillary GC/MS in spot urine samples collected before, at the end, and 15 hours after the same working shift. Urinary concentrations were low, though related to n-hexane in the air. 2,5-Hexanedione in the end of shift samples gave the best estimate of overall exposure. About 3 mg/g creatinine of 2,5-hexanedione would correspond to about 50 ppm of n-hexane in the air (mean daily exposure). PMID:6498115

  2. Rich n-heptane and diesel combustion in porous media

    SciTech Connect

    Pastore, A.; Mastorakos, E.

    2010-04-15

    Rich n-heptane and diesel flames in two-layer porous media are experimentally investigated in the context of syngas production. The stable operating points of n-heptane reforming have been determined and the mole fractions of H{sub 2}, CO, CO{sub 2} and light hydrocarbons have been measured in the exhaust gas at an equivalence ratio of 2 for different thermal input values. The reformer performance has been assessed also from the point of view of the heat losses and the mixture homogeneity. The pre-vapouriser produces an approximately uniform vapour-air mixture upstream of the flame front. The range of flow rates for stable flames decreased with increasing equivalence ratio. Heat losses were about 10% of the thermal input at high firing rates. A 77.2% of the equilibrium H{sub 2} was achieved at a flame speed of 0.82 m/s. The same reactor with a different porous matrix for the reforming stage demonstrates diesel reforming to syngas with a conversion efficiency of 77.3% for a flame speed of 0.65 m/s. (author)

  3. Industrial application of catalytic systems for n-heptane isomerization.

    PubMed

    Alemn-Vzquez, Laura Olivia; Cano-Domnguez, Jos Luis; Torres-Garca, Enelio; Villagmez-Ibarra, Jos Roberto

    2011-01-01

    The ideal gasoline must have a high pump octane number, in the 86 to 94 range, and a low environmental impact. Alkanes, as a family, have much lower photochemical reactivities than aromatics or olefins, but only the highly branched alkanes have adequate octane numbers. The purpose of this work is to examine the possibilities of extending the technological alternative of paraffin isomerization to heavier feedstocks (i.e., n-heptane) using non-conventional catalytic systems which have been previously proposed in the literature: a Pt/sulfated zirconia catalyst and a molybdenum sub-oxide catalyst. Under the experimental conditions at which these catalysts have been evaluated, the molybdenum sub-oxide catalyst maintains a good activity and selectivity to isomerization after 24 h, while the Pt/sulfated zirconia catalyst shows a higher dimethylpentanes/methylhexanes ratio, probably due to a lower operating temperature, but also a high formation of cracking products, and presents signs of deactivation after 8 h. Though much remains to be done, the performance of these catalysts indicates that there are good perspectives for their industrial application in the isomerization of n-heptane and heavier alkanes. PMID:21760573

  4. The Burning of Large N-Heptane Droplets in Microgravity

    NASA Technical Reports Server (NTRS)

    Manzello, Samuel L.; Choi, Mun Young; Kazakov, Andrei; Dryer, Frederick L.; Dobashi, Ritsu; Hirano, Toshisuke; Ferkul, Paul (Technical Monitor)

    2000-01-01

    Experimental results are presented on the burning and sooting behavior of large n-heptane droplets in air at atmospheric pressure under microgravity conditions. The experiments were performed at the Japanese Microgravity Center (JAMIC) 10 sec dropshaft in Hokkaido, Japan. Soot volume fraction, burning rate, flame standoff and luminosity were measured for droplets of 2.6 mm and 2.9 mm in initial diameter. These are the largest droplets for which soot volume fraction measurements have ever been performed. Previous measurements of soot volume fractions for n-heptane droplets, confined to smaller droplet sizes of less than 1.8 mm, indicated that maximum soot volume fraction increased monotonically with initial droplet size. The new results demonstrate for the first time that sooting tendency is reduced for large droplets as it has been speculated previously but never confirmed experimentally. The lower soot volume fractions for the larger droplets were also accompanied by higher burning rates. The observed phenomenon is believed to be caused by the dimensional influence on radiative heat losses from the flame. Numerical calculations confirm that soot radiation affects the droplet burning behavior.

  5. A study on biological monitoring of n-hexane exposure.

    PubMed

    Iwata, M; Takeuchi, Y; Hisanaga, N; Ono, Y

    1983-01-01

    n-Hexane is one of the solvents widely used in industry and well known to be neurotoxic. Recently it was clearly revealed that n-hexane is metabolized in vivo and its metabolites are excreted in the urine. However, the relationship between the exposed dose of n-hexane and the metabolites in the urine has not yet been substantially determined. Therefore, in this investigation we intended to clarify the above relationship in order to establish its usefulness for biological monitoring of n-hexane exposure. The exposed dose was measured by means of a personal monitoring badge worn by workers in seven factories manufacturing vinyl sandals. The time-weighted average (TWA) concentration of n-hexane was 0.2-47.4 ppm. The n-hexane metabolites in the urine of 22 workers were measured with modified Perbellini's method [12] in the early morning (6:00-7:00 hrs) and at 17:00 hrs. 2,5-Dimethylfuran, 2,5-hexanedione and gamma-valerolactone were identified by gas chromatography and mass spectrometory. At 17:00 hrs the means +/- SD of the metabolites were 0.21 +/- 0.11 mg/l for 2,5-dimethylfuran, 1.13 +/- 0.71 mg/l for 2,5-hexanedione, and 2.04 +/- 2.31 mg/l for gamma-valerolactone. The metabolites were also found in the urine in the early morning. 2-Hexanol was not detected in the urine of any worker examined. A strong correlation between TWA concentration of n-hexane and 2,5-hexanedione in the urine was found at 17:00 hrs (r = 0.895, P less than 0.001). The results suggest that the urinary metabolites of n-hexane, especially 2,5-hexanedione, could be useful indicators for biological monitoring of n-hexane exposure. Furthermore the present study offers the advantage of a better estimate of n-hexane TWA. PMID:6852931

  6. Theoretical and experimental comparison of the Soret effect for binary mixtures of toluene and n-hexane, and benzene and n-heptane

    NASA Astrophysics Data System (ADS)

    Abbasi, Alireza; Ziad Saghir, M.; Kawaji, Masahiro

    2010-04-01

    Thermodiffusion along with molecular diffusion occurs in many engineering systems and in nature. Thermodiffusion has a great effect on concentration distribution in binary mixtures. A new approach to predicting the Soret coefficient in binary mixtures of linear chain and aromatic hydrocarbons using the thermodynamics of irreversible processes is presented. In particular, this approach is based on free volume theory, which explains the diffusivity in diffusion-limited systems. Free volume states that the transfer kinetics of molecules depends greatly on molecular size and shape. The proposed model, combined with Shukla and Firoozabadi's model, was applied to predict the Soret coefficient. The perturbed chain statistical associating fluid theory equation of state (PCSAFT-EoS) was used to calculate the related thermodynamic properties. Comparisons of the theoretical results with experimental data show good agreement.

  7. N-heptane adsorption and desorption in mesoporous materials

    NASA Astrophysics Data System (ADS)

    Zaleski, R.; Gorgol, M.; B?azewicz, A.; Kierys, A.; Goworek, J.

    2015-06-01

    Positron Annihilation Lifetime Spectroscopy (PALS) was used for an in situ monitoring of adsorption and desorption processes. The disordered and ordered porous silica as well as the porous polymer were used as adsorbents, while an adsorbate in all the cases was n-heptane. The lifetimes and particularly the intensities of the ortho-positronium(o-Ps) components depend strongly on the adsorbate pressure. The analysis of these dependencies allows us to identify several processes, which are taking place during sorption. At low pressure, an island-like growth of the first layers of the adsorbate on the silica, in a contrary to a swelling of the polymer, is observed. A size of the pores, which remain empty, is estimated at the subsequent stages of the adsorbate condensation and evaporation. The adsorbate thrusting into micropores is deduced at p/p0 > 0.6 whilst the mesopores are still not completely filled.

  8. Evoked potentials in chronic n-hexane intoxication

    SciTech Connect

    Huang, C.C.; Chu, N.S. )

    1989-07-01

    Somatosensory, brainstem auditory and pattern-reversal visual evoked potentials (SEP, BAEP and PVEP) were studied in 5 patients with n-hexane polyneuropathy to determine if the CNS was affected. In SEPs, the median central conduction (N13-to-N20) was normal but the tibial central conduction (N22-to-P40) was delayed. The central conduction time (I-to-V interval) of the BAEP was also prolonged. However, the P100 latency of the PVEP was normal. The present data indicate that the spinal cord and the brainstem are primarily affected in chronic n-hexane intoxication.

  9. A New Exploration of the Torsional Energy Surface of N-Pentane Using Molecular Modeling Software

    ERIC Educational Resources Information Center

    Galembeck, Sergio E.; Caramori, Giovanni F.; Romero, Jose Ricardo

    2005-01-01

    The torsional potential energy surface of a chemical compounds, the accessible conformations at a specified temperature and the transition states that connect these confirmations establishes many chemical properties such as dynamic behavior, reactivity and biological activity. A conformational search of n-pentane is presented using computational

  10. Nonpremixed n-heptane autoignition in unsteady counterflow

    SciTech Connect

    Liu, Shiling; Hewson, John C.; Chen, Jacqueline H.

    2006-06-15

    The effect of unsteady strain on n-heptane autoignition at elevated pressure is studied numerically with detailed chemistry and transport in the counterflow configuration. Specifically, fuel and air temperatures are chosen so that two-stage ignition occurs, as is typical, in the negative temperature-coefficient regime, and the strain perturbations are selected to rapidly rise and fall to mimic rapid turbulent strain-rate fluctuations. For these rapid fluctuations, the response of the mixing layer is unsteady. Small to moderate strain-rate fluctuations result in a small increase in the ignition delay. For sufficiently large strain rates such that the critical scalar dissipation rate is exceeded, the ignition delay is substantially greater. The latter delay results from both the time required for the dissipation rate to decay to below its critical value and the longer ignition delay time for systems with dissipation rates near the critical dissipation rate. For all magnitudes of strain-rate fluctuation, there is evidence that the second stage of the two-stage ignition is more sensitive to inhibition by higher dissipation rates. For sufficiently large dissipation rates, the heat losses force the second stage to the border between the low- and intermediate-temperature chemistries. (author)

  11. Transition region ignition characteristics of n-heptane fuel sprays

    NASA Technical Reports Server (NTRS)

    Danis, A. M.; Cernansky, N. P.; Namer, I.

    1985-01-01

    Ignition studies were perferred on monodisperse n-heptane sprays at atmospheric pressure over a range of equivalence ratios and droplet diameters. A capacitive discharge spark ignition system was used as the ignition source, providing independent control of spark energy and duration. Preliminary measurements were made to optimize spark duration and spark gap, optimum conditions being those at which the maximum frequency or probability of ignition was observed. The effect of spark duration on ignition frequency for several spark energies was determined for equivalence ratios of 0.5 and 1.0 and initial droplet diameters of 28 and 68 microns. Spark duration had little effect on ignition frequency over the entire 15 to 170 mu s range examined. Spark durations of 70 to 80 mu s were used for all subsequent work. The spark gap was optimized at equivalence ratios of 0.6, 0.8 and 1.0 and initial droplet diameters of 30, 40, 50, 60 and 70 microns by varying the electrode spacing from 0.5 to 5.0 mm while maintaining a constant spark energy. The optimum gap was determined to be 3.0 mm for nearly all conditions.

  12. Strategies for mechanism reduction for large hydrocarbons: n-heptane

    SciTech Connect

    Lu, Tianfeng; Law, Chung K.

    2008-07-15

    A 55-species reduced mechanism for n-heptane oxidation was derived from a 188-species skeletal mechanism, which was previously obtained from a detailed mechanism consisting of 561 species using a directed relation graph (DRG). This reduced mechanism was derived by first obtaining a skeletal mechanism with 78 species using DRG-aided sensitivity analysis. The unimportant reactions were eliminated by using the importance index defined in computational singular perturbation (CSP), with a newly posited restriction to treat each reversible reaction as a single reaction. An isomer lumping approach, also developed in the present study, then groups the isomers with similar thermal and diffusion properties so that the number of species transport equations is reduced. It was found that the intragroup mass fractions of the isomers can be approximated as constants in the present reduced mechanism, leading to a 68-species mechanism with 283 elementary reactions. Finally, 13 global quasi-steady-state species were identified using a CSP-based time-scale analysis, resulting in the 55-species reduced mechanism, with 283 elementary reactions lumped into 51 semiglobal steps. Validation of the reduced mechanism shows good agreement with the detailed mechanism for both ignition and extinction phenomena. The inadequacy of the detailed mechanism in predicting the experimental laminar flame speed is also demonstrated. (author)

  13. Changes in urinary n-hexane metabolites by co-exposure to various concentrations of methyl ethyl ketone and fixed n-hexane levels.

    PubMed

    Shibata, E; Huang, J; Ono, Y; Hisanaga, N; Iwata, M; Saito, I; Takeuchi, Y

    1990-01-01

    To make clear how the n-hexane metabolism is modified by co-exposure with MEK, rats were exposed to various concentrations of MEK mixed with a fixed concentration of n-hexane. Twenty-four male Wistar rats were divided into four equal groups. Each group was exposed for 8 h to 2000 ppm n-hexane, 2000 ppm n-hexane plus 200 ppm MEK, 2000 ppm n-hexane plus 630 ppm MEK and 2000 ppm n-hexane plus 2000 ppm MEK, respectively. Free metabolites and the sum of free and conjugated metabolites of n-hexane were analyzed by gas chromatography. The main metabolite was 2-hexanol during the exposure and 2,5-hexanedione (2,5-HD) after the exposure in any group. The main metabolites, 2-hexanol and 2,5 HD, decreased in inverse proportion to the co-exposed MEK concentrations. The results suggest that augmentation of n-hexane neurotoxicity by MEK co-exposure could not be explained only by 2,5-HD. In addition, 2,5-HD is recommended as an index for biological monitoring of n-hexane exposure. However, one should be careful to evaluate the exposed n-hexane concentration by urinary 2,5-HD, because n-hexane metabolism could be largely modified by co-exposure with MEK. PMID:2350238

  14. Selective optical detection of n-heptane/iso-octane vapors by polyimide lightguides

    NASA Astrophysics Data System (ADS)

    Podgorsek, R. P.; Franke, H.; Feger, C.

    1995-03-01

    The optical anisotropy of planar polyimide lightguides in an atmosphere of n-heptane / iso-octane is investigated in a transient experiment for pure and several mixed-vapor concentrations. The polymer sensor responds only to n-heptane and not to iso-octane vapors. However, the presence of the latter affects the dynamic behavior of the waveguide anisotropy, which can be fitted by a stretched exponential time dependence. The saturation values of the birefringence are an absolute measure for the n-heptane concentration and are not affected by the presence of the iso-octane vapors.

  15. n-hexane as a model for compressed simple liquids

    NASA Astrophysics Data System (ADS)

    Randzio, S. L.; Grolier, J.-P. E.; Quint, J. R.; Eatough, D. J.; Lewis, E. A.; Hansen, L. D.

    1994-05-01

    Isobaric thermal expansivities, ?p, of n-hexane have been measured by pressure-controlled scanning calorimetry from just above the saturation vapor pressure to 40 MPa at temperatures from 303 to 453 K and to 300 MPa at 503 K. These new data are combined with literature data to obtain a correlation equation for ?p valid from 240 to 503 K at pressures up to 700 MPa. Correlation equations are developed for the saturated vapor pressure, specific volume, and isobaric heat capacity of liquid n-hexane from 240 to 503 K. Calculated volumes, isobaric and isochoric specific heat capacities. isothermal compressibilities, and thermal coefficients of pressure are presented for the entire range of pressure and temperature. The pressure-temperature behavior of these quantities is discussed as a model behavior for simple liquids without strong intermolecular interactions.

  16. Whole-cell double oxidation of n-heptane.

    PubMed

    Mller, Christina A; Dennig, Alexander; Welters, Tim; Winkler, Till; Ruff, Anna Joelle; Hummel, Werner; Grger, Harald; Schwaneberg, Ulrich

    2014-12-10

    Biocascades allow one-pot synthesis of chemical building blocks omitting purification of reaction intermediates and expenses for downstream processing. Here we show the first whole cell double oxidation of n-heptane to produce chiral alcohols and heptanones. The concept of an artificial operon for co-expression of a monooxygenase from Bacillus megaterium (P450 BM3) and an alcohol dehydrogenase (RE-ADH) from Rhodococcus erythropolis is reported and compared to the widely used two-plasmid or Duet-vector expression systems. Both catalysts are co-expressed on a polycistronic constructs (single mRNA) that reduces recombinant DNA content and metabolic burden for the host cell, therefore increasing growth rate and expression level. Using the artificial operon system, the expression of P450 BM3 reached 81mgg(-1) cell dry weight. In addition, in situ cofactor regeneration through the P450 BM3/RE-ADH couple was enhanced by coupling to glucose oxidation by E. coli. Under optimized reaction conditions the artificial operon system displayed a product formation of 656mgL(-1) (5.7mM) of reaction products (heptanols+heptanones), which is 3-fold higher than the previously reported values for an in vitro oxidation cascade. In conjunction with the high product concentrations it was possible to obtain ee values of >99% for (S)-3-heptanol. Coexpression of a third alcohol dehydrogenase from Lactobacillus brevis (Lb-ADH) in the same host yielded complete oxidation of all heptanol isomers. Introduction of a second ADH enabled further to utilize both cofactors in the host cell (NADH and NADPH) which illustrates the simplicity and modular character of the whole cell oxidation concept employing an artificial operon system. PMID:24925696

  17. Neuropathy associated with chronic low level exposure to n-hexane

    SciTech Connect

    Ruff, R.L.; Petito, C.K.; Acheson, L.S.

    1981-05-01

    Concentrations of n-hexane greater than the threshold limit value (TLV) of 500 ppm are known to produce peripheral neuropathy. This report describes the case of a worker who developed peripheral neuropathy, with a histologic pattern characteristic of n-hexane toxicity, after chronic on-the-job exposure to n-hexane at concentrations less than 450 ppm. We suggest that the current TLV for n-hexane be reevaluated.

  18. Spectra and structure of binary azeotropes. II. Acetone- n-pentane

    NASA Astrophysics Data System (ADS)

    Jalilian, M. R.

    2007-01-01

    Acetone and n-pentane from an azeotrope with the mole ratio of 1:3, respectively. As the result of this azeotrope formation, some characteristic vibrational modes in FT-IR and chemical shifts in 1H NMR changes. The amount of these band and signal changes is an indication of the extend of interaction between two components and their orientation in unit structure of the cluster. FT-IR and 1H NMR spectra of pure substances and their azeotrope were recorded, spectral changes analyzed. Unit structure of azeotrope was deduced based on mole ratio, boiling point changes of pure components, and spectral changes in fundamental frequency and chemical shifts.

  19. Changes of n-hexane metabolites in urine of rats exposed to various concentrations of n-hexane and to its mixture with toluene or MEK.

    PubMed

    Iwata, M; Takeuchi, Y; Hisanaga, N; Ono, Y

    1983-01-01

    It is well known that n-hexane produces peripheral neuropathy, and 2,5-hexanedione, one of the metabolites of n-hexane, is thought to be the main causative agent. Recently, the metabolites of n-hexane in urine have been measured by gas chromatography, and 2,5-hexanedione was proved to be useful for the biological monitoring of n-hexane exposure. In the present experiment, we intended to clarify the change of n-hexane metabolites in the urine of rats exposed to various concentrations of n-hexane and to its mixture with toluene of MEK. In the first experiment, five separate groups of five rats each were exposed to 100, 500, 1000, or 3000 ppm of n-hexane, or fresh air respectively in an exposure chamber for 8 h a day. Urinary samples were gathered during exposure, 16, 24, and 40 h after exposure. Half of each sample was analyzed by gas chromatography after hydrolysis with acid and enzymes, and the other half was analyzed without hydrolysis. 2,5-Dimethylfuran, MBK, 2-hexanol, 2,5-hexanedione, and gamma-valerolactone could be identified as n-hexane metabolites in the urine. The main metabolites were 2-hexanol and 2,5-hexanedione. 2-Hexanol was mostly excreted during exposure, while most of the 2,5-hexanedione was excreted after the end of exposure. The amount of metabolites in the urine correlatively increased with the concentration of n-hexane from 100 to 1000 ppm, but the amount of metabolites scarcely increased when the concentration of n-hexane increased from 1000 to 3000 ppm.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:6654498

  20. The simulation of organic rankine cycle power plant with n-pentane working fluid

    NASA Astrophysics Data System (ADS)

    Nurhilal, Otong; Mulyana, Cukup; Suhendi, Nendi; Sapdiana, Didi

    2016-02-01

    In the steam power plant in Indonesia the dry steam from separator directly used to drive the turbin. Meanwhile, brine from the separator with low grade temperature reinjected to the earth. The brine with low grade temperature can be converted indirectly to electrical power by organic Rankine cycle (ORC) methods. In ORC power plant the steam are released from vaporization of organic working fluid by brine. The steam released are used to drive an turbine which in connected to generator to convert the mechanical energy into electric energy. The objective of this research is the simulation ORC power plant with n-pentane as organic working fluid. The result of the simulation for brine temperature around 165°C and the pressure 8.001 bar optained the net electric power around 1173 kW with the cycle thermal efficiency 14.61% and the flow rate of n-pentane around 15.51 kg/s. This result enable to applied in any geothermal source in Indonesia.

  1. Method for the simultaneous quantification of n-hexane metabolites: application to n-hexane metabolism determination.

    PubMed

    Soriano, T; Menndez, M; Sanz, P; Repetto, M

    1996-06-01

    1. The described analytical procedure permits the simultaneous determination of the main n-hexane metabolites in urine. 2-Hexanone, 2-hexanol, 2, 5-hexanediol and 2, 5-hexanedione, were chosen to dose the rats used in this study. All urine samples were collected and analysed on a daily basis, before and after acidic hydrolysis (pH 0.1) by GC/MS. 2-Hexanone, 2, 5-dimethylfurane, gamma-valerolactone and 2, 5-hexanedione were determined before hydrolysis: 2-hexanol and 2, 5-hexanediol, after hydrolysis; and 5-hydroxy-2-hexanone and 4, 5-dihydroxy-2-hexanone were calculated by the difference between gamma-valerolactone and 2, 5-hexanedione with and without hydrolysis, respectively. 2. A metabolic scheme was proposed reflecting the biotransformations undergone by the four compounds assayed. We consider 2, 5-dimethylfurane as a "true metabolite' because the quantities detected were always greater before hydrolysis. 3. It has been reported that human and rat n-hexane metabolism follow a similar pattern. Therefore, as a practical application and without increasing either sample or time requirements, the simultaneous quantification of the different metabolites and their excretion profile could provide better information about the metabolic situation of exposed workers than the determination of 2, 5-hexanedione alone. According to our experimental results, 4, 5-dihydroxy-2-hexanone itself would be a good toxicity indicator. PMID:8793533

  2. Calorimetric study on the state of water and 1-pentanol in the water/1-pentanol/AOT/n-heptane system

    SciTech Connect

    D'Aprano, A.; Lizzio, A.; Liveri, V.T.

    1988-04-07

    Molar enthalpies of solution of 1-pentanol in the AOT/n-heptane system as well as of water in 1-pentanol/n-heptane and in 1-pentanol/AOT/n-heptane systems have been measured at 25/sup 0/C. The results indicate that at infinite dilution, following a Poisson distribution, 1-pentanol molecules distribute between the AOT reversed micelles and the continuous organic phase, whereas at finite concentrations of 1-pentanol, reversed micelles and alcoholic aggregates coexist. It is also found that water added to 1-pentanol/AOT/n-heptane systems is incorporated in both AOT reversed micelles and alcoholic aggregates.

  3. In situ high-pressure and high-temperature experiments on n-heptane.

    PubMed

    Qiao, Erwei; Zheng, Haifei; Long, Changxing

    2012-02-01

    The Raman spectroscopy of n-heptane was investigated in a moissanite anvil cell at ambient temperatures and a diamond anvil cell under pressures of up to ~2000 MPa and at temperature range from 298 to 588 K. The results show that at room temperature the vibration modes, assigned to the symmetric and antisymmetric stretching of CH(3) and CH(2) stretching, shifted to higher frequency according to quasi-linearity with increasing pressure, and a liquid-solid phase transition occurred at near 1150 MPa. The high-temperature solidus line of n-heptane follows a quadratic function of P = 0.00737T(2) + 5.27977T - 1195.76556. Upon phase change, fitting the experimental data obtained in the temperature range of 183?412 K to the Clausius-Clapeyron equation allows one to define the thermodynamic parameters of n-heptane of dP/dT = 0.01474T + 5.27977. PMID:22449288

  4. [Effect of Cordyceps militaris on the damage of rats induced by n-hexane].

    PubMed

    Shen, Q; Chen, S

    2001-02-01

    Acutely inhaling n-hexane model was adopted to study the effect of Cordyceps militaris and the damage induced by n-hexane. The results showed that Cordyceps militaris was effective on the resisting lipid peroxidation. The results also showed that acutely inhaling n-hexane could lead to or enhance the damage reaction of oxygen free radicals, which could lead to injure of lipid peroxidation. That may be one of the mechanism of n-hexane toxicity effect on living things. PMID:11402725

  5. Absorption and recovery of n-hexane in aqueous solutions of fluorocarbon surfactants.

    PubMed

    Xiao, Xiao; Yan, Bo; Fu, Jiamo; Xiao, Xianming

    2015-11-01

    n-Hexane is widely used in industrial production as an organic solvent. As an industrial exhaust gas, the contribution of n-hexane to air pollution and damage to human health are attracting increasing attention. In the present study, aqueous solutions of two fluorocarbon surfactants (FSN100 and FSO100) were investigated for their properties of solubilization and dynamic absorption of n-hexane, as well as their capacity for regeneration and n-hexane recovery by thermal distillation. The results show that the two fluorocarbon surfactants enhance dissolution and absorption of n-hexane, and their effectiveness is closely related to their concentrations in solution. For low concentration solutions (0.01%-0.30%), the partition coefficient decreases dramatically and the saturation capacity increases significantly with increasing concentration, but the changes for both are more modest when the concentration is over 0.30%. The FSO100 solution presents a smaller partition coefficient and a greater saturation capacity than the FSN100 solution at the same concentration, indicating a stronger solubilization for n-hexane. Thermal distillation is a feasible method to recover n-hexane from these absorption solutions, and to regenerate them. With 90sec heating at 80-85C, the recovery of n-hexane ranges between 81% and 85%, and the regenerated absorption solution maintains its original performance during reuse. This study provides basic information on two fluorocarbon surfactants for application in the treatment of industrial n-hexane waste gases. PMID:26574100

  6. Spectra and structure of binary azeotropes II. Acetone-n-pentane.

    PubMed

    Jalilian, M R

    2007-01-01

    Acetone and n-pentane from an azeotrope with the mole ratio of 1:3, respectively. As the result of this azeotrope formation, some characteristic vibrational modes in FT-IR and chemical shifts in 1H NMR changes. The amount of these band and signal changes is an indication of the extend of interaction between two components and their orientation in unit structure of the cluster. FT-IR and 1H NMR spectra of pure substances and their azeotrope were recorded, spectral changes analyzed. Unit structure of azeotrope was deduced based on mole ratio, boiling point changes of pure components, and spectral changes in fundamental frequency and chemical shifts. PMID:16807080

  7. Ignition of n-heptane pool by heated stagnating oxidizing flow

    SciTech Connect

    Liu, Wei; Zhu, Delin; Wu, Ning; Law, Chung K.

    2010-02-15

    The ignition temperature of a liquid pool of n-heptane by heated oxidizer in a stagnation flow was experimentally determined for system pressures of 0.61-3 atm and pressure-weighted strain rates of 60-350 s{sup -1}. The surface of the liquid pool was maintained at a fixed location through continuous replenishment. The state of ignition was brought about, and monitored, by gradually increasing the oxidizer temperature. The strain rate was determined by seeding and measuring the oxidizer flow velocity using laser Doppler velocimetry (LDV). Computational simulation of the ignition event with detailed chemistry and transport was conducted by using a stagnation-flow code. The kinetic mechanisms utilized are a high-temperature n-heptane oxidation model, with 130 species and 955 reactions, and a reduced one of 58 species derived from a detailed mechanism of 561 species and 2539 reactions. The former mechanism yielded better agreement with the experimental measurements in general over the conditions examined. It was also found that the mole fraction of n-heptane at the interface changed only slightly with pressure and strain rate, and can be considered to have minimal effect on the ignition responses studies herein. A recently developed explosive mode analysis (EMA) was conducted to identify the controlling radicals and reactions in the non-premixed ignition of n-heptane. (author)

  8. A reactive molecular dynamics study of n-heptane pyrolysis at high temperature.

    PubMed

    Ding, Junxia; Zhang, Liang; Zhang, Yan; Han, Ke-Li

    2013-04-25

    n-Heptane is the most important straight chain paraffin in the fossil-fuel industry. In this work, pyrolysis of n-heptane at high temperature is investigated by a series of ReaxFF based reactive molecular dynamic simulations. The pyrolysis correlated intermediate reactions, important product/intermediate distributions, and corresponding kinetics behaviors are systematically analyzed at atomistic level. The results indicate that the entire pyrolysis process is radical-dominated. The unimolecular dissociation is the main pathway of n-heptane decomposition. Initiation of the decomposition is mainly through C-C bond fission. Central C-C bonds would dissociate prior to the terminal ones. Besides, the Rice-Kossiakoff theory is proved for the pyrolysis of n-heptane at the atomistic level. To give a better description of the pyrolysis behavior, some alkane related intermolecular reactions should be considered in the mechanism. The apparent activation energy extracted from the present simulations is 43.02-54.49 kcal/mol in the temperature range 2400-3000 K, which is reasonably consistent with the experimental results. PMID:23544797

  9. Ozone production by a dc corona discharge in air contaminated by n-heptane

    NASA Astrophysics Data System (ADS)

    Pekrek, S.

    2008-01-01

    Beneficial purposes of ozone such as elimination of odours, harmful bacteria and mildew can be used for transportation of food, fruits and vegetables with the aim to extend their storage life. To date the main technique used for this purpose in the transportation of these commodities, e.g. by trucks, was cooling. Here a combination of cooling together with the supply of ozone into containers with these commodities is considered. For these purposes we studied the effect of air contamination by n-heptane (part of automotive fuels) and humidity on ozone production by a dc hollow needle to mesh corona discharge. We found that, for both polarities of the needle electrode, addition of n-heptane to air (a) decreases ozone production; (b) causes discharge poisoning to occur at lower current than for air; (c) does not substantially influence the current for which the ozone production reaches the maximum. Finally the maximum ozone production for the discharge in air occurs for the same current as the maximum ozone production for the discharge contaminated by n-heptane. We also found that humidity decreases ozone production from air contaminated by n-heptane irrespective of the polarity of the coronating needle electrode. This dependence is stronger for the discharge with the needle biased positively.

  10. Catalytic steam cracking of n-heptane with special reference to the effect of calcined dolomite

    SciTech Connect

    Taralas, G.

    1996-07-01

    The catalyzed steam cracking of n-heptane was carried out using a fixed-bed reactor and different, commercially available limestone [CaCO{sub 3}], dolomites [CaMg(CO{sub 3}){sub 2}], and NiMo/{gamma}-Al{sub 2}O{sub 3} as the catalysts. The steam cracking of n-heptane was investigated by variation of water and n-heptane partial pressure and by the additions of hydrogen and carbon dioxide to the water vapor at a total pressure of 101.3 kPa. In the presence of calcined dolomite (1,073 K), the partial pressure of water vapor (p{sub H{sub 2}O} = 9.1 {minus} 34.2 kPa) enhances cracking efficiency, whereas hydrogen (p{sub H{sub 2}} {approx} 33 kPa) and carbon dioxide (CO{sub 2} = 39 vol %), when added to the cracking mixture (973 K), do suppress conversion of n-heptane.

  11. Quaternary liquid-liquid equilibrium of n-heptane-toluene-o-xylene-propylene carbonate

    SciTech Connect

    Salem, A.B.S.H.; Hamad, E.Z.; Al-Naafa, M.A. . Chemical Engineering Dept.)

    1994-03-01

    Liquid-liquid equilibrium data for the system n-heptane/toluene/o-xylene/propylene carbonate were obtained at 25 OC. Experimental tie line data were measured by gas chromatographic analysis. The UNIQUAC and NRTL models were used to predict the quaternary data from the corresponding ternary data. Agreement between the predictions and the experimental data was satisfactory.

  12. IRIS Toxicological Review and Summary Documents for N-Hexane (External Review Draft)

    EPA Science Inventory

    EPA's assessment of the noncancer health effects and carcinogenic potential of n-hexane was last prepared and added to the IRIS data base in 1990. The IRIS program is updating the IRIS assessment for n-hexane; this update will incorporate health effects information published sin...

  13. A model-free temperature-dependent conformational study of n-pentane in nematic liquid crystals

    NASA Astrophysics Data System (ADS)

    Burnell, E. Elliott; Weber, Adrian C. J.; Dong, Ronald Y.; Meerts, W. Leo; de Lange, Cornelis A.

    2015-01-01

    The proton NMR spectra of n-pentane orientationally ordered in two nematic liquid-crystal solvents are studied over a wide temperature range and analysed using covariance matrix adaptation evolutionary strategy. Since alkanes possess small electrostatic moments, their anisotropic intermolecular interactions are dominated by short-range size-and-shape effects. As we assumed for n-butane, the anisotropic energy parameters of each n-pentane conformer are taken to be proportional to those of ethane and propane, independent of temperature. The observed temperature dependence of the n-pentane dipolar couplings allows a model-free separation between conformer degrees of order and conformer probabilities, which cannot be achieved at a single temperature. In this way for n-pentane 13 anisotropic energy parameters (two for trans trans, tt, five for trans gauche, tg, and three for each of gauche+ gauche+, pp, and gauche+ gauche-, pm), the isotropic trans-gauche energy difference Etg and its temperature coefficient Etg ' are obtained. The value obtained for the extra energy associated with the proximity of the two methyl groups in the gauche+ gauche- conformers (the pentane effect) is sensitive to minute details of other assumptions and is thus fixed in the calculations. Conformer populations are affected by the environment. In particular, anisotropic interactions increase the trans probability in the ordered phase.

  14. A model-free temperature-dependent conformational study of n-pentane in nematic liquid crystals

    SciTech Connect

    Burnell, E. Elliott; Weber, Adrian C. J.; Dong, Ronald Y.; Meerts, W. Leo; Lange, Cornelis A. de

    2015-01-14

    The proton NMR spectra of n-pentane orientationally ordered in two nematic liquid-crystal solvents are studied over a wide temperature range and analysed using covariance matrix adaptation evolutionary strategy. Since alkanes possess small electrostatic moments, their anisotropic intermolecular interactions are dominated by short-range size-and-shape effects. As we assumed for n-butane, the anisotropic energy parameters of each n-pentane conformer are taken to be proportional to those of ethane and propane, independent of temperature. The observed temperature dependence of the n-pentane dipolar couplings allows a model-free separation between conformer degrees of order and conformer probabilities, which cannot be achieved at a single temperature. In this way for n-pentane 13 anisotropic energy parameters (two for trans trans, tt, five for trans gauche, tg, and three for each of gauche{sub +} gauche{sub +}, pp, and gauche{sub +} gauche{sub −}, pm), the isotropic trans-gauche energy difference E{sub tg} and its temperature coefficient E{sub tg}{sup ′} are obtained. The value obtained for the extra energy associated with the proximity of the two methyl groups in the gauche{sub +} gauche{sub −} conformers (the pentane effect) is sensitive to minute details of other assumptions and is thus fixed in the calculations. Conformer populations are affected by the environment. In particular, anisotropic interactions increase the trans probability in the ordered phase.

  15. 2,5-Hexanedione excretion after occupational exposure to n-hexane.

    PubMed Central

    Ahonen, I; Schimberg, R W

    1988-01-01

    The urinary excretion of the n-hexane metabolite 2,5-hexanedione (HD) was determined in four shoe factory workers during four workingdays that were preceded by four free days and followed by two free days. The correlation between excretion of HD and the n-hexane concentrations in the workroom air was evaluated. The air concentrations of n-hexane and those of acetone, toluene, and other organic solvents were monitored with charcoal tubes. All the urine from each worker was collected at freely chosen intervals during the experimental period and the following two free days. The samples were analysed by gas chromatography. The relative excretion of HD increased as the exposure to n-hexane increased, although it seemed that HD accumulated progressively in the body at the highest n-hexane concentrations and at higher total solvent concentrations. Images PMID:3342196

  16. Elasticity and phase behaviour of n-heptane and n-nonane in nanopores

    NASA Astrophysics Data System (ADS)

    Schappert, Klaus; Gemmel, Laura; Meisberger, Dennis; Pelster, Rolf

    2015-09-01

    Here we present an ultrasonic study on the elasticity of normal alkanes (n-heptane and n-nonane) in the nanopores of porous Vycor glass (average pore radius rP = 2.74 \\text{nm} ). Above the melting temperature we have found a non-zero shear modulus for both n-heptane and n-nonane, which is also typical for the rotator phases of bulk alkanes at temperatures below the melting temperature. This points to the formation of a special molecular order of the adsorbed alkanes. Furthermore, the alkanes undergo a continuous stiffening over a broad temperature range (of ? T > 60 \\text{K} for heptane or ? T > 120 \\text{K} for nonane). The results clearly indicate that nanoconfinement induces an extremely broad continuous transition of heptane and nonane into a crystalline low-temperature phase.

  17. Asymptotic analysis with reduced chemistry for the burning of n-heptane droplets

    NASA Technical Reports Server (NTRS)

    Card, J. M.; Williams, F. A.

    1992-01-01

    The method of rate-ratio asymptotics is used with reduced chemistry to analyze the flame structure and extinction of an isolated n-heptane droplet burning under quasisteady, spherically symmetrical conditions. The outer transport zones are described by the classical Burke-Schumann solution. The inner reaction zone consists of a thin layer, on the rich side of the flame, where the fuel is consumed, and on the lean side, a broader but still asymptotically thin oxidation layer, where H2 and CO are consumed. Special attention is given to differences in predictions of extinction conditions, caused by different chemical-kinetic approximations in the reduced chemistry, including fuel-chemistry effects through molecules containing more than one carbon atom. From the analysis, extinction diameters for n-heptane droplets are estimated for different pressures and ambient oxygen concentrations. The results show that extinction diameters are extremely sensitive to the number of radicals consumed in breaking down each fuel molecule.

  18. Free volumes evolution during desorption of n-heptane from silica with regular pore geometry. Positron annihilation study

    NASA Astrophysics Data System (ADS)

    Goworek, J.; Zaleski, R.; Buda, W.; Kierys, A.

    2010-06-01

    The mechanism of n-heptane evaporation from mesoporous MCM-41 silica was investigated by positron annihilation lifetime spectroscopy (PALS). Experiments were performed in situ during desorption of hydrocarbon under stepwise lowered pressure. Desorption is a quasicontinuous process that corresponds to emptying various types of free volumes in the silica/ n-heptane system, including mesopores. Insight into the kinetics of desorption was derived from the changes of PALS spectra associated with succeeding stages of pore emptying. For the investigated system emptying of pores and formation of bubbles in the n-heptane condensate present in regular pores were found to take place at various bulk saturating vapour pressure of the fluid.

  19. Volume properties of reverse micellar systems AOT/ n-heptane/DMSO-water

    NASA Astrophysics Data System (ADS)

    Sargsyan, A. R.; Shahinyan, G. A.; Markarian, S. A.

    2014-05-01

    The volume properties of reverse micellar systems bis(2-ethylhexyl) sulfosuccinate sodium salt/ n-heptane/dimethyl sulfoxide-water are studied via densitometry. The presence of dimethyl sulfoxide and the increase in its amount in a dimethyl sulfoxide-water mixed solvent raise the apparent volume of the polar phase. This increase is also observed when the degree of hydration of the polar core and the temperature are raised.

  20. An experimental study of the combined effects of n-hexane and methyl ethyl ketone.

    PubMed Central

    Takeuchi, Y; Ono, Y; Hisanaga, N; Iwata, M; Aoyama, M; Kitoh, J; Sugiura, Y

    1983-01-01

    This study was intended to determine whether or not methyl ethyl ketone (MEK) enhances the neurotoxicity of n-hexane at low concentration and after long term exposure. Separate groups of eight rats were exposed to 100 ppm n-hexane, 200 ppm MEK, 100 ppm n-hexane plus 200 ppm MEK, or fresh air in an exposure chamber for 12 hours a day for 24 weeks. The body weight, motor nerve conduction velocity (MCV), distal motor latency (DL), and mixed nerve conduction velocities (MNCVs) were measured before exposure and after four, eight, 12, 16, 20, and 24 weeks' exposure. One rat of each group was histopathologically examined after 24 weeks' exposure. Exposure of 100 ppm n-hexane did not significantly decrease the functions of the peripheral nerve throughout the experiment. Exposure to 200 ppm MEK significantly increased MCV and MNCVs and decreased DL after four weeks' exposure, but at this later stage no significant changes were found throughout the experiment by comparison with the controls. Mixed exposure to 100 ppm n-hexane plus 200 ppm MEK significantly decreased by comparison with the controls. On histopathological examination of the tail nerve, however, no changes were found in any of the exposed groups or the controls. These results suggest that MEK might enhance the neurotoxicity of n-hexane at a low concentration, and mixed exposures to n-hexane and MEK should be avoided. PMID:6830718

  1. Urinary excretion of the metabolites of n-hexane and its isomers during occupational exposure.

    PubMed Central

    Perbellini, L; Brugnone, F; Faggionato, G

    1981-01-01

    Environmental exposure to commercial hexane (n-hexane, 2-methylpentane, and 3-methylpentane) was tested in several work places in five shoe factories by taking three grap-air samples during the afternoon shift. Individual exposure ranges were 32-500 mg/m3 for n-hexane, 11-250 mg/m3 for 2-methylpentane, and 10-204 mg/m3 for 3-methylpentane. The metabolites of commercial hexane in the urine of 41 workers were measured at the end of the work shift. 2-Hexanol, 2,5-hexanedione, 2,5-dimethylfuran, and gamma-valerolactone were found as n-hexane metabolites and 2-methyl-2-pentanol and 3-methyl-2-pentanol as 2-methylpentane and 3-methylpentane metabolites. The presence of metabolites in the urine was correlated with occupational exposure to solvents. n-Hexane exposure was correlated more positively with 2-hexanol and 2,5-hexanedione than with 2,5-dimethylfuran and gamma-valerolactone. A good correlation was also found between total n-hexane metabolites and n-hexane exposure. 2-Methyl-2-pentanol and 3-methyl-2-pentanol were highly correlated with 2-methylpentane and 3-methylpentane exposure. The results suggest that the urinary excretion of hexane metabolites may be used for monitoring occupational exposure to n-hexane and its isomers. PMID:7470400

  2. Urinary excretion of the metabolites of n-hexane and its isomers during occupational exposure.

    PubMed

    Perbellini, L; Brugnone, F; Faggionato, G

    1981-02-01

    Environmental exposure to commercial hexane (n-hexane, 2-methylpentane, and 3-methylpentane) was tested in several work places in five shoe factories by taking three grap-air samples during the afternoon shift. Individual exposure ranges were 32-500 mg/m3 for n-hexane, 11-250 mg/m3 for 2-methylpentane, and 10-204 mg/m3 for 3-methylpentane. The metabolites of commercial hexane in the urine of 41 workers were measured at the end of the work shift. 2-Hexanol, 2,5-hexanedione, 2,5-dimethylfuran, and gamma-valerolactone were found as n-hexane metabolites and 2-methyl-2-pentanol and 3-methyl-2-pentanol as 2-methylpentane and 3-methylpentane metabolites. The presence of metabolites in the urine was correlated with occupational exposure to solvents. n-Hexane exposure was correlated more positively with 2-hexanol and 2,5-hexanedione than with 2,5-dimethylfuran and gamma-valerolactone. A good correlation was also found between total n-hexane metabolites and n-hexane exposure. 2-Methyl-2-pentanol and 3-methyl-2-pentanol were highly correlated with 2-methylpentane and 3-methylpentane exposure. The results suggest that the urinary excretion of hexane metabolites may be used for monitoring occupational exposure to n-hexane and its isomers. PMID:7470400

  3. 2H and 13C NMR studies of orientational order and actual amount of n-heptane molecule in liquid crystal phases of the 7CB-n-heptane system

    NASA Astrophysics Data System (ADS)

    Kumagai, Yoshihide; Ohashi, Ryutaro; Ida, Tomonori; Mizuno, Motohiro

    2015-10-01

    The orientational order of n-heptane molecules in the nematic phase and the smectic A (SmA) phase of the 4-heptyl-4?-cyanobiphenyl (7CB)-n-heptane binary system was investigated by 2H NMR spectroscopy. The increase in the mobility of the alkyl chain region corresponding to an increase in the amount of n-heptane enhanced the micro-segregation of the core and the alkyl chain region and contributed to the formation of the SmA phase for this system. The actual amount of n-heptane molecule adsorbed in the SmA phase was assessed by 2H and 13C NMR for the coexistence state of the isotropic liquid and the SmA phase.

  4. Biotransformation of n-hexane and methyl n-butyl ketone in guinea pigs and mice.

    PubMed

    Couri, D; Abdel-Rahman, M S; Hetland, L B

    1978-04-01

    Peripheral neuropathies caused by exposures to the industrial solvents n-hexane and MBK exhibit strinkingly similar characteristics. In in vivo studies, the metabolites of MBK and n-hexane identified in blood and urine of guinea pigs were 2-hexanol (partly as glucuronide in urine); and 2,5-hexanedione which was detected only in MBK treated groups. Phenobarbital pretreatment increased 2-hexanol urinary excretion in both solvent treatment groups. In in vitro studies, hepatic reduction of MBK required the cytosol fraction to form 2-hexanol; whereas the oxidation of MBK and n-hexane required the microsomal fraction to form 2,5-hexanedione and 2-hexanol, respectively. The in vivo and in vitro biotransformation of MBK and n-hexane to a common metabolite (2-hexanol) suggests that the neurotoxic action of these solvents may be metabolite related. PMID:645557

  5. Enhancements of methane, benzene, and n-pentane by oil and gas fields observed from the DC-3 aircraft campaign: A case study

    NASA Astrophysics Data System (ADS)

    Farris, Carolyn Michelle

    Observations in the boundary layer from the 1 June flight in Colorado of the 2012 Deep Convective Clouds and Chemistry campaign shows enhancements of n-pentane, methane, and benzene near oil and gas wells that are not correlated with enhancements in carbon monoxide. To further investigate the source of methane emissions, an i-pentane:n-pentane ratio is compared to surface measurements from the Denver-Julesberg Basin and found to be similar. Measurements of n-pentane, methane, benzene and CO are also shown with proximity to Denver to compare an urban signature with an oil and gas well emissions signature. Elevated n-pentane, methane, and benzene mixing ratios without enhancements in CO from the 1 June flight are considered to be strongly influenced by emissions from oil and natural gas fields located near the sampling locations.

  6. A numerical study of thermal and chemical effects in interactions of n-heptane flames with a single surface

    SciTech Connect

    Owston, Rebecca; Magi, Vinicio; Abraham, John

    2007-02-15

    The thermal and chemical effects of a one-dimensional, premixed flame quenching against a single surface are studied numerically. Fuels considered include n-heptane and molar-based mixtures of 95/5 and 70/30 percent n-heptane and hydrogen, respectively. A reduced gas-phase kinetic mechanism for n-heptane is employed. Wall boundary conditions investigated include both an adiabatic and an isothermal wall with temperatures ranging from 298 to 1200 K. The effects of equivalence ratio variations between 0.7 and 3 are investigated. The computations with n-heptane and n-heptane/hydrogen mixtures show that for wall temperatures greater than 400 K heat release rates have a higher value for the wall-interacting flame than for the freely propagating flame. It is also seen that the peak wall heat flux increases with increasing wall temperatures up to 1000 K. Chemical pathway analysis reveals the importance of radical recombination reactions at the surface to the heat release profiles of this study. The effect of H, O, and OH radical recombination near the inert wall is observed to lower the heat release spike on a 750 K isothermal boundary. The concentrations of intermediate hydrocarbons in the near-wall region are studied and related to unburned hydrocarbon formation in an engine cylinder. It is shown that a simple one-step global reaction rate expression for n-heptane fuel conversion cannot reproduce the flame-wall trends observed with the reduced n-heptane mechanism. (author)

  7. Experimental and modeling investigation of the low-temperature oxidation of n-heptane

    PubMed Central

    Herbinet, Olivier; Husson, Benoit; Serinyel, Zeynep; Cord, Maximilien; Warth, Valérie; Fournet, René; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Wang, Zhandong; Xie, Mingfeng; Cheng, Zhanjun; Qi, Fei

    2013-01-01

    The low-temperature oxidation of n-heptane, one of the reference species for the octane rating of gasoline, was investigated using a jet-stirred reactor and two methods of analysis: gas chromatography and synchrotron vacuum ultra-violet photo-ionization mass spectrometry (SVUV-PIMS) with direct sampling through a molecular jet. The second method allowed the identification of products, such as molecules with hydroperoxy functions, which are not stable enough to be detected using gas chromatography. Mole fractions of the reactants and reaction products were measured as a function of temperature (500-1100K), at a residence time of 2s, at a pressure of 800 torr (1.06 bar) and at stoichiometric conditions. The fuel was diluted in an inert gas (fuel inlet mole fraction of 0.005). Attention was paid to the formation of reaction products involved in the low temperature oxidation of n-heptane, such as olefins, cyclic ethers, aldehydes, ketones, species with two carbonyl groups (diones) and ketohydroperoxides. Diones and ketohydroperoxides are important intermediates in the low temperature oxidation of n-alkanes but their formation have rarely been reported. Significant amounts of organic acids (acetic and propanoic acids) were also observed at low temperature. The comparison of experimental data and profiles computed using an automatically generated detailed kinetic model is overall satisfactory. A route for the formation of acetic and propanoic acids was proposed. Quantum calculations were performed to refine the consumption routes of ketohydroperoxides towards diones. PMID:23712100

  8. The Cracking of N-Heptane in the Gas Phase State and in the HZSM-5 Zeolite: A Quantum Molecular Dynamics Study

    SciTech Connect

    Zaragoza, I P.; Santamaria, Ruben

    2002-10-10

    Quantum molecular dynamics is used to investigate the cracking of a representative hydrocarbon of the paraffin family (n-heptane), analyzing the effects of temperature in the fragmentation of n-heptane when this compound is in the gas phase and inside a typical industrial catalyst (zeolite HZSM-5). The hydrocarbon structural and electronic features in the two environments are determined and compared. The results substantiate current views and exhibit the basic aspects in the cracking of n-heptane.

  9. [Decrease in the n-hexane risk in shoe manufacturing industry].

    PubMed

    Agnesi, R; Valentini, F; Dal Vecchio, L

    1994-01-01

    In recent years the composition of the glues used in the shoe manufacturing industry in the "Riviera del Brenta" area (northern Italy) has changed considerably, with a gradual reduction of n-hexane. This fact emerged from a survey of 337 gluing stations in 105 shoe factories where 104 different commercial products containing organic solvents were found. The determining element in this change was the substitution of technical hexane with other refinery products which have a low n-hexane content (< 5%). There was a possible health risk due to n-hexane exposure in about only 10% of the gluing stations and in about 8% of commercial products, where mixtures of technical hexane are used. Ethyl acetate, cyclo-hexane, hexane isomers, methyl ethyl ketone, heptane and acetone are among the solvents most frequently used. This change means that assessment of glue composition will be necessary before beginning a health monitoring programme of the exposed population. PMID:7808346

  10. Rotator Phases of n-Heptane under High Pressure: Raman Scattering and X-ray Diffraction Studies

    SciTech Connect

    C Ma; Q Zhou; F Li; J Hao; J Shu; L Huang; F Huang; Q Cui

    2011-12-31

    We performed high-pressure Raman scattering and angle-dispersive synchrotron X-ray diffraction measurements on n-heptane at room temperature. It has been found that n-heptane undergoes a liquid to rotator phase III (R{sub III}) transition at 1.2 GPa and then transforms into another rotator phase R{sub IV} at about 3 GPa. As the pressure reaches 7.5 GPa, a transition from an orientationally disordered R{sub IV} phase to an ordered crystalline state starts and is completed around 14.5 GPa. Our results clearly present the high-pressure phase transition sequence (liquid-R{sub III}-R{sub IV}-crystal) of n-heptane, similar to that of normal alkanes.

  11. Effects of n-hexane and its metabolites on cloned voltage-operated neuronal potassium channels.

    PubMed

    Madeja, M; Binding, N; Musshoff, U; Witting, U; Speckmann, E J

    1997-01-01

    In order to study the mechanisms of acute n-hexane intoxication, the effects of n-hexane and its metabolites 2-hexanol, methyl-n-butyl ketone, 2,5-hexanediol and 2,5-hexanedione on the cloned voltage-operated potassium channels Kv1.1, Kv1.4, Kv2.1 and Kv3.4 were investigated with electrophysiological techniques in the expression system of Xenopus oocytes. n-Hexane had no effect at any channel, whereas some of its metabolites led to reductions of the potassium currents. The greatest effects obtained were caused by 2-hexanol at the Kv2.1 channel, resulting in reductions of 13% at 0 mV with a concentration of 500 mg/l and IC50 of ca. 3500 mg/l. The reduction appeared to be caused by a shift of the current-voltage relation to the right. Methyl-n-butyl ketone showed smaller effects, whereas 2,5-hexanedione and 2,5-hexandiol were nearly ineffective. Concerning the different potassium channels, the sensitivity to the metabolites differed. The metabolites showed greatest sensitivity towards the Kv2.1 channel and lowest sensitivity towards the Kv3.4 channel. Since the n-hexane metabolite concentrations in the brain during acute n-hexane intoxication are unknown, the relevance of the data is still unclear. The size of the effects and the currently available data on tissue concentration, however, make it more likely that the action of n-hexane and its metabolites on voltage-operated potassium channels is not a major mechanism for acute neurotoxicity. PMID:9101040

  12. Rate-ratio asymptotic analysis of autoignition of n-heptane in laminar nonpremixed flows

    SciTech Connect

    Seshadri, K.; Peters, N.; Paczko, G.

    2006-07-15

    A rate-ratio asymptotic analysis is carried out to elucidate the mechanisms of autoignition of n-heptane (C{sub 7}H{sub 16}) in laminar, nonpremixed flows. It has been previously established that autoignition of n-heptane takes place in three distinct regimes. These regimes are called the low-temperature regime, the intermediate-temperature regime, and the high-temperature regime. The present analysis considers the high-temperature regime. A reduced chemical-kinetic mechanism made up of two global steps is used in the analysis. The reduced mechanism is deduced from a skeletal mechanism made up of 16 elementary reactions. The skeletal mechanism is derived from a short mechanism made up of 30 elementary reactions. The short mechanism is deduced from a detailed mechanism made up of 56 elementary reactions. In the reduced mechanism, the first global step represents a sequence of fast reactions starting from the rate-limiting elementary reaction between n-heptane and HO{sub 2}. In this global step C{sub 7}H{sub 16} is consumed and hydrogen peroxide (H{sub 2}O{sub 2}) is formed. The second global step represents a sequence of fast reactions starting from the rate-limiting elementary reaction in which H{sub 2}O{sub 2} is consumed and OH is formed. A key aspect of the second global step is that the sequence of fast reactions gives rise to consumption of fuel only without net consumption of H{sub 2}O{sub 2}. This makes the chemical system autocatalytic. The unsteady flamelet equations are used to predict the onset of autoignition. In the flamelet equations a conserved scalar quantity, Z, is used as the independent variable. On the oxidizer side of the mixing layer Z=0, and on the fuel side Z=1. The practical case where the temperature of the oxidizer stream, T{sub 2}, is much greater than the temperature of the fuel stream is considered. Therefore autoignition is presumed to take place close to Z=0. Balance equations are written for C{sub 7}H{sub 16} and H{sub 2}O{sub 2}. It is postulated that autoignition will take place when the gradient of mass fraction fuel with respect to Z, evaluated at Z=0, is zero. The value of T{sub 2} when autoignition takes place is obtained as a function of the strain rate. These critical conditions of autoignition obtained from asymptotic analysis agree well with those calculated using the detailed mechanism and the skeletal mechanism. (author)

  13. Selective Oxidation of n-Hexane by Cu (II) Nanoclusters Supported on Nanocrystalline Zirconia Catalyst.

    PubMed

    Acharyya, Shankha Shubhra; Ghosh, Shilpi; Adak, Shubhadeep; Singh, Raghuvir; Saran, Sandeep; Bal, Rajaram

    2015-08-01

    Cu (II) nanoclusters supported on nanocrystalline zirconia catalyst (with size ~15 nm), was prepared by using cationic surfactant cetyltrimethylammonium in a hydrothermal synthesis method. The catalyst was characterized by XRD, XPS, TGA, SEM, TEM, FTIR and ICP-AES. The catalyst was found to be efficient in selective oxidation of n-hexane to 2-hexanol. An n-hexane conversion of 55%, with a 2-hexanol selectivity of 70% was achieved over this catalyst in liquid phase, without the use of any solvent. The catalyst can be reused several times without any significant activity loss. PMID:26369156

  14. Spray evaporation and dispersion of n-heptane droplets within premixed flame

    NASA Astrophysics Data System (ADS)

    Chrigui, Mouldi; Zghal, Ali; Sadiki, Amsini; Janicka, Johannes

    2010-10-01

    A detailed numerical simulation of n-heptane droplets was carried out on a stationary three-dimensional configuration with complex geometry. The investigations focused on spray evaporation and dispersion within a carrier phase that featured operating conditions similar to those found in industrial applications, i.e. elevated pressure and temperature. The simulations were carried out using the Eulerian-Lagrangian approach with two-way coupling. There were two cases. The first dealt with spray characteristics within the preheated carrier phase without considering combustion. The second investigated the influence of combustion on droplet characteristics. Both cases had the same boundary conditions. The numerical simulations used two models to compute the progress variable mean reaction rate that governs the combustion process, which is captured by the Bray-Moss-Libby model.

  15. Microgravity combustion of isolated n-decane and n-heptane droplets

    NASA Technical Reports Server (NTRS)

    Choi, Mun Y.; Dryer, Frederick L.; Card, John M.; Williams, Forman A.; Haggard, John B.; Borowski, Brian A.

    1992-01-01

    This paper presents recent experimental results on n-heptane droplet combustion from a 5.0 second Zero-Gravity Facility. For these experiments, droplet sizes from 1 mm to 1.75 mm were studied, oxygen mole fractions in nitrogen ranged from 12 to 21 percent, and the pressure was varied from 0.25 to 1 atm. Disruptive burning mechanisms were observed in some of the experiments conducted in air environments. However, this behavior was inhibited by reducing the oxygen concentration and/or the system pressure. The above results suggest that combinations of lower oxygen indices and reduced ambient pressures are important to reducing the effects of sooting on droplet vaporization-rates.

  16. Some Recent Observations on the Burning of Isolated N-Heptane and Alcohol Droplets

    NASA Technical Reports Server (NTRS)

    Dryer, F. L.; Kazakov, A.; Urban, B. D.

    2001-01-01

    In a joint program involving Prof. F.A. Williams of the University of California, San Diego and Dr. V. Nayagam of the National Center for Microgravity Research on Combustion and Fluid Dynamics, the combustion of liquid fuel droplets of n-heptane, n-decane, methanol, methanol-water, ethanol and ethanol-water having initial diameters between about 1 mm and 6 mm continues to be studied. The objectives of the work are to improve fundamental knowledge of droplet combustion dynamics for pure fuels and fuel-water mixtures through microgravity experiments and theoretical analyses. The Princeton contributions to the collaborative program supports the engineering design, data analysis, and data interpretation requirements for the study of initially single component, spherically symmetric, isolated droplet combustion studies through experiments and numerical modeling. The complementary UCSD contributions apply asymptotic theoretical analyses and are described in the published literature and in a companion communication in this conference. The combined program continues to focus on analyses of results obtained from Fiber Supported Droplet Combustion (FSDC) experiments (FSDC-2, STS- 94) conducted with the above fuels in shuttle cabin air and Droplet Combustion Experiment (DCE) data obtained for unsupported and fiber supported droplets of n-heptane in Helium-Oxygen mixtures and cabin air (STS-83, STS-94). The program is preparing for a second DCE experimental mission using methanol/methanol-water as fuels and helium-oxygen-nitrogen environments. DCE-2 is to be conducted aboard the International Space Station. Emphases of recent Princeton work are on the study of simple alcohols (methanol, ethanol) and alcohol/water mixtures as fuels, with time-dependent measurements of drop size, flame-standoff, liquid-phase composition, and finally, extinction. Ground based experiments have included bench-scale studies at Princeton and collaborative experimental studies in the 2.2 second drop tower at NASA-Glenn Research Center.

  17. Effect of saponins on n-hexane removal in biotrickling filters.

    PubMed

    Tu, Yanhong; Yang, Chunping; Cheng, Yan; Zeng, Guangming; Lu, Li; Wang, Lu

    2014-10-22

    Saponins was applied to enhance the removal of n-hexane in a biotrickling filter (BTF) in this study. Comparison experiments were carried out to examine the effect of saponins on n-hexane removal in two BTFs at various saponins concentrations, n-hexane loading rates (LRs) and gas empty bed contact times (EBCTs). Results show that the optimum concentration of saponins in nutrient feed was 50.0mgL(-1). When organic LR of n-hexane increased from 47.8 to 120.0gm(-3)h(-1), the removal efficiency (RE) for BTF1 (with saponins) and BTF2 (without saponins) decreased from 91.3% to 83.3% and from 62.8% to 56.8%, respectively. As gas EBCT decreased from 30.0 to 7.5s, the RE declined from 88.4% to 64.5% for BTF1 and from 61.4% to 38.3% for BTF2. Saponins could also decrease the biomass accumulation rate within the medium bed. These results could be referred in the design and operation of BTFs for hydrophobic VOC removal. PMID:25459827

  18. Communication: Molecular dynamics and 1H NMR of n-hexane in liquid crystals

    NASA Astrophysics Data System (ADS)

    Weber, Adrian C. J.; Burnell, E. Elliott; Meerts, W. Leo; de Lange, Cornelis A.; Dong, Ronald Y.; Muccioli, Luca; Pizzirusso, Antonio; Zannoni, Claudio

    2015-07-01

    The NMR spectrum of n-hexane orientationally ordered in the nematic liquid crystal ZLI-1132 is analysed using covariance matrix adaptation evolution strategy (CMA-ES). The spectrum contains over 150 000 transitions, with many sharp features appearing above a broad, underlying background signal that results from the plethora of overlapping transitions from the n-hexane as well as from the liquid crystal. The CMA-ES requires initial search ranges for NMR spectral parameters, notably the direct dipolar couplings. Several sets of such ranges were utilized, including three from MD simulations and others from the modified chord model that is specifically designed to predict hydrocarbon-chain dipolar couplings. In the end, only inaccurate dipolar couplings from an earlier study utilizing proton-proton double quantum 2D-NMR techniques on partially deuterated n-hexane provided the necessary estimates. The precise set of dipolar couplings obtained can now be used to investigate conformational averaging of n-hexane in a nematic environment.

  19. KINETICS AND SELECTIVITY OF DEEP CATALYTIC OXIDATION OF N-HEXANE AND BENZENE

    EPA Science Inventory

    Deep (complete) catalytic combustion (oxidation) of volatile organic compounds (VOCs) is emerging as an important emission control technique. A fundamental study was carried out for low-temperature deep oxidation of n-hexane and benzene over a 0.1% Pt, 3% Ni/gamma-Al2O3 catalyst....

  20. Oxidation of 1-butanol and a mixture of n-heptane/1-butanol in a motored engine

    SciTech Connect

    Zhang, Yu.; Boehman, Andre L.

    2010-10-15

    The oxidation of neat 1-butanol and a mixture of n-heptane and 1-butanol was studied in a modified CFR engine at an equivalence ratio of 0.25 and an intake temperature of 120 C. The engine compression ratio was gradually increased from the lowest point to the point where significant high temperature heat release was observed. Heat release analyses showed that no noticeable low temperature heat release behavior was observed from the oxidation of neat 1-butanol while the n-heptane/1-butanol mixture exhibited pronounced cool flame behavior. Species concentration profiles were obtained via GC-MS and GC-FID/TCD. Quantitative analyses of the reaction products from the oxidation of neat 1-butanol indicate that 1-butanol is consumed mainly through H-atom abstraction. Among the H-atom abstraction reactions, it is observed that the H-atom abstraction from the {alpha}-carbon of 1-butanol is particularly favored. The investigation on the oxidation of the mixture of n-heptane/1-butanol showed that the oxidation of 1-butanol is facilitated at low temperatures through the radical pool generated from the oxidation of n-heptane. (author)

  1. EFFECTS OF EQUIVALENCE RATIO ON SPECIES AND SOOT CONCENTRATIONS IN PREMIXED N-HEPTANE FLAMES. (R828193)

    EPA Science Inventory

    The micro-structure of laminar premixed, atmospheric-pressure, fuel-rich flames of n-heptane/oxygen/argon has been studied at two equivalence ratios (C/O = 0.63 and C/O = 0.67). A heated quartz microprobe coupled to an online gas chromatography/mass spectrometry (HP 5890 Serie...

  2. Characterization of n-Hexane sub-fraction of Bridelia micrantha (Berth) and its antimycobacterium activity

    PubMed Central

    2011-01-01

    Background Tuberculosis, caused by Mycobacterium tuberculosis (MTB), is the most notified disease in the world. Development of resistance to first line drugs by MTB is a public health concern. As a result, there is the search for new and novel sources of antimycobacterial drugs for example from medicinal plants. In this study we determined the in vitro antimycobacterial activity of n-Hexane sub-fraction from Bridelia micrantha (Berth) against MTB H37Ra and a clinical isolate resistant to all five first-line antituberculosis drugs. Methods The antimycobacterial activity of the n-Hexane sub-fraction of ethyl acetate fractions from acetone extracts of B. micrantha barks was evaluated using the resazurin microplate assay against two MTB isolates. Bioassay-guided fractionation of the ethyl acetate fraction was performed using 100% n-Hexane and Chloroform/Methanol (99:1) as solvents in order of increasing polarity by column chromatography and Resazurin microtiter plate assay for susceptibility tests. Results The n-Hexane fraction showed 20% inhibition of MTB H37Ra and almost 35% inhibition of an MTB isolate resistant to all first-line drugs at 10 ?g/mL. GC/MS analysis of the fraction resulted in the identification of twenty-four constituents representing 60.5% of the fraction. Some of the 24 compounds detected included Benzene, 1.3-bis (3-phenoxyphenoxy (13.51%), 2-pinen-4-one (10.03%), N(b)-benzyl-14-(carboxymethyl) (6.35%) and the least detected compound was linalool (0.2%). Conclusions The results show that the n-Hexane fraction of B. micrantha has antimycobacterial activity. PMID:21481267

  3. Shock-tube study of the autoignition of n-heptane/toluene/air mixtures at intermediate temperatures and high pressures

    SciTech Connect

    Herzler, J.; Fikri, M.; Hitzbleck, K.; Starke, R.; Schulz, C.; Roth, P.; Kalghatgi, G.T.

    2007-04-15

    The ignition delay times of mixtures containing 35% n-heptane and 65% toluene by liquid volume at room temperature (i.e., 28% n-heptane/72% toluene by mole fraction) were determined in a high-pressure shock tube in the temperature range 620{<=} T{<=}1180 K at pressures of about 10, 30, and 50 bar and equivalence ratios, {phi}, of 0.3 and 1.0. The equation {tau}/{mu}s=9.8 x 10{sup -3} exp (15,680 K/T)(p/bar){sup -0.883} represents the data for {phi}=0.3 in the temperature range between 980 and 1200 K. At lower temperatures no ignition was found at 10 bar within the maximum test time of 15 ms, whereas for 50 bar, a reduced activation energy was observed. A pressure coefficient of -1.06 was found for the data with {phi}=1.0. No common equation for the data at {phi}=1.0 could be found analogous to that for {phi}=0.3 because the ignition delay times show no Arrhenius-like behavior. A comparison with ignition delay times of n-heptane/air and toluene/air for {phi}=1.0 and 30 bar shows that the values of the mixture of the two components are between the values of the single substances. Furthermore, the results confirm the negative temperature coefficient behavior found for the mixtures at 30 and 50 bar, similar to n-heptane/air. A comparison for the other pressure and equivalence ratio values of this study was not possible because of the lack of data for pure toluene. These experimental data have been used in the development of a chemical kinetics model for toluene/n-heptane mixtures as described in a companion paper. (author)

  4. An Experimental Study of n-Heptane and JP-7 Extinction Limits in an Opposed Jet Burner

    NASA Technical Reports Server (NTRS)

    Convery, Janet L.; Pellett, Gerald L.; O'Brien, Walter F., Jr.; Wilson, Lloyd G.; Williams, John

    2005-01-01

    Propulsion engine combustor design and analysis requires experimentally verified data on the chemical kinetics of fuel. Among the important data is the combustion extinction limit as measured by observed maximum flame strain rate. The extinction limit relates to the ability to maintain a flame in a combustor during operation. Extinction limit data can be obtained for a given fuel by means of a laminar flame experiment using an opposed jet burner (OJB). Laminar extinction limit data can be applied to the turbulent application of a combustor via laminar flamelet modeling. The OJB consists of two axi-symmetric tubes (one for fuel and one for oxidizer), which produce a flat, disk-like counter-flow diffusion flame. This paper presents results of experiments to measure extinction limits for n-heptane and the military specification fuel JP-7, obtained from an OJB. JP-7 is an Air Force-developed fuel that continues to be important in the area of hypersonics. Because of its distinct properties it is currently the hydrocarbon fuel of choice for use in Scramjet engines. This study provides much-desired data for JP-7, for which very little information previously existed. The interest in n-heptane is twofold. First, there has been a significant amount of previous extinction limit study and resulting data with this fuel. Second, n-heptane (C7H16) is a pure substance, and therefore does not vary in composition as does JP-7, which is a mixture of several different hydrocarbons. These two facts allow for a baseline to be established by comparing the new OJB results to those previously taken. Additionally, the data set for n-heptane, which previously existed for mixtures up to 26 mole percent in nitrogen, is completed up to 100% n-heptane. The extinction limit data for the two fuels are compared, and complete experimental results are included.

  5. Urinary excretion of n-hexane metabolites. A comparative study in rat, rabbit and monkey.

    PubMed

    Perbellini, L; Amantini, M C; Brugnone, F; Frontali, N

    1982-09-01

    Exposure to n-hexane, a component of many industrial solvent mixtures, is known to cause polyneuropathy in man. The concentration of metabolites in urine following exposure may be useful in biological monitoring. In a comparative study experimental animals (rat, rabbit and monkey) were subjected to single inhalatory treatments of 6, 12 and 24 h with 5,000 ppm of pure n-hexane. At the end of the treatments and at intervals thereafter, urine, and in rats also blood, were collected and analyzed for n-hexane and its metabolites. While the urine of rats contained 2-hexanol, 3-hexanol, methyl n-butyl ketone, 2,5-dimethylfuran, y-valerolactone and 2,5-hexanedione, rabbit and monkey urine were found to contain only 2-hexanedione, rabbit and monkey urine were to contain only 2-hexanol, 3-hexanol, methyl n-butyl ketone and 2,5-hexanedione. Within 72 h of the end of exposure, the principal metabolite was 2,5-dimethylfuran in rats and 2-hexanol in rabbits and monkeys. In all three species the excretion rates of methyl n-butyl ketone, 3-hexanol and 2-hexanol peaked several hours earlier than 2,5-hexanedione (and gamma-valerolactone and 2,5-dimethylfuran in rats). In all species 2,5-hexanedione was still detectable in urine 60 h following exposure. n-Hexane metabolites in rat blood were 2-hexanol, methyl-n-butyl ketone, 2,5-dimethylfuran and 2,4-hexanedione. The first two, as well as n-hexane itself, were found in maximum concentration immediately after termination of exposure, while 2,5-dimethylfuran and 2,5-hexanedione, with the longer exposure times, peaked some hours later. The data from urine collected at the end of exposure were compared with those obtained in a parallel study in humans occupationally exposed to a mixture of hexane isomers. Humans chronically exposed to 10-140 ppm n-hexane had 2,5-hexanedione concentrations in urine ranging from 0.4 to 21.7 mg/l, i.e., in the same proportion as rats exposed once for 6 or 12 h to 5,000 ppm. PMID:7149986

  6. Increased microsomal metabolism of n-hexane in rat kidney and liver after inhalation of isopropanol.

    PubMed

    Zahlsen, K; Aarstad, K; Nilsen, O G

    1984-01-01

    Inhalation of 200, 2,000, and 8,000 ppm isopropanol for 2 weeks enhanced the in vitro metabolism of n-hexane in microsomal preparations. The formation of the preneurotoxic metabolite 2-hexanol increased 9, 80, and 198%, respectively, in the kidney and 9, 22, and 132% in the liver. The concentration of cytochrome P-450 was also increased in a dose-dependent way with increases of 14, 40, and 43%, respectively, in the kidney and 6, 12, and 18% in the liver. The present investigation demonstrates similar effects of isopropanol after inhalation on kidney and liver microsomal enzymes. In both organs isopropanol was shown to potentiate the formation of neurotoxic metabolites from n-hexane. However, cytochrome P-450 appears to be more easily induced in kidney than in liver. PMID:6595990

  7. Effect of Pressure on Absorption Spectra of Lycopene in n-Hexane and CS2 Solvents

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Liu, Wei-Long; Zheng, Zhi-Ren; Huo, Ming-Ming; Li, Ai-Hua; Yang, Bin

    2010-01-01

    The absorption spectra of lycopene in n-hexane and CS2 are measured under high pressure and the results are compared with ?-carotene. In the lower pressure range, the deviation from the linear dependence on the Bayliss parameter (BP) for ?-carotene is more visible than that for lycopene. With the further increase of the solvent BP, the 0-0 bands of lycopene and ?-carotene red shift at almost the same rate in n-hexane; however, the 0-0 band of lycopene red shifts slower than that of ?-carotene in CS2. The origins of these diversities are discussed taking into account the dispersion interactions and structures of solute and solvent molecules.

  8. Fluorescence vesicles by self-assembly of oligo(biphenylene vinylene) bolaamphiphiles in n-hexane

    NASA Astrophysics Data System (ADS)

    Hwang, In-Wook; Kim, Yong-Rok

    2013-09-01

    Self-assembly of an oligo(biphenylene vinylene); OBPV bolaamphiphile with two polar coils of significantly long poly(propylene oxide); PPO (n = 21) at each end generated a fluorescent vesicle in apolar n-hexane. The vesicle efficiently produced trans-stilbene-like OBPV excimer emissions, as evidenced by an intense, redshifted, structured fluorescence spectrum with a long decay time of 5.0 0.1 ns. An OBPV chromophore bound at both sides via a polar coil-to-coil interaction in apolar n-hexane was conducive to OBPV excimer emission, as evident from analysis of the spectroscopic data obtained from OBPVs with different PPO coil lengths (n = 13, 21, 34).

  9. Ignition characteristics of rich n-heptane fuel sprays in the transition region

    NASA Technical Reports Server (NTRS)

    Danis, A. M.; Cernansky, N. P.; Namer, I.

    1985-01-01

    Ignition studies were performed on monodisperse n-heptane sprays at atmospheric pressure over a range of equivalence ratios and droplet diameters. A capacitive discharge spark ignition system was used as the ignition source, providing independent control of spark energy and duration. Preliminary measurements were made to optimize spark duration and spark gap, optimum conditions being those at which the maximum frequency or probability of ignition was observed. Using the optimum electrode spacing and spark duration, the frequency of ignition was determined as a function of spark energy for three overall equivalence ratios (0.6, 0.8, and 1.0) and for initial droplet diameters of 25, 40, 50, 60, and 70 microns. An LDA system was used to determine the actual equivalence ratio at the spark gap, which varied from 1.5 to 4.7. The spark energy at which the frequency of ignition was 90 percent was defined as the minimum ignition energy. These data indicated that the ignitability of the sprays was enhanced as the equivalence ratio was increased, but was diminished as the droplet size was increased. The increase in minimum ignition energy with increasing droplet size and fixed equivalence ratio was nearly linear over the range of parameters studied. However, the effect became smaller with increasing equivalence ratio.

  10. Direct numerical simulation of ignition in turbulent n-heptane liquid-fuel spray jets

    SciTech Connect

    Wang, Y.; Rutland, C.J.

    2007-06-15

    Direct numerical simulation was used for fundamental studies of the ignition of turbulent n-heptane liquid-fuel spray jets. A chemistry mechanism with 33 species and 64 reactions was adopted to describe the chemical reactions. The Eulerian method is employed to solve the carrier-gas flow field and the Lagrangian method is used to track the liquid-fuel droplets. Two-way coupling interaction is considered through the exchange of mass, momentum, and energy between the carrier-gas fluid and the liquid-fuel spray. The initial carrier-gas temperature was 1500 K. Six cases were simulated with different droplet radii (from 10 to 30 {mu}m) and two initial velocities (100 and 150 m/s). From the simulations, it was found that evaporative cooling and turbulence mixing play important roles in the ignition of liquid-fuel spray jets. Ignition first occurs at the edges of the jets where the fuel mixture is lean, and the scalar dissipation rate and the vorticity magnitude are very low. For smaller droplets, ignition occurs later than for larger droplets due to increased evaporative cooling. Higher initial droplet velocity enhances turbulence mixing and evaporative cooling. For smaller droplets, higher initial droplet velocity causes the ignition to occur earlier, whereas for larger droplets, higher initial droplet velocity delays the ignition time. (author)

  11. Observations on a Slow Burning Regime for Hydrocarbon Droplets - N-Heptane/Air Results

    NASA Technical Reports Server (NTRS)

    Choi, Mun Y.; Dryer, Frederick L.; Haggard, John B., Jr.

    1991-01-01

    Experiments on n-heptane/airdroplet combustion under reduced gravity have served as a benchmark for much of the existing theoretical efforts on the modeling of sphero-synmmetric droplet burning. New experiments conducted in the NASA-Lewis Research Center 2.2 second droptower (at less than 10 exp -5 g) which emphasize the production of sphero-symmetry and low relative droplet/gas convection produce burning rates in air (for about 1 mm droplets) as much as 40-percent lower than the classical result (0.78 sq mm/s). The burning rate is proportional to the measured droplet/gas relative velocity, and the observed functional dependence is much larger than predicted by published convective correlations. New results clearly indicate that the droplet/laboratory velocity does not correspond to the relative droplet/gas velocity. Thus, the convective effects on droplet combustion is not properly characterized by droplet motion alone. Differences in the burning rates are speculated to result from the effects of the accumulated soot as well as the asymmetry (caused by convection) in the temperature and species distributions surrounding the droplet.

  12. Development of a reduced n-heptane oxidation mechanism for HCCI combustion modeling

    SciTech Connect

    Maroteaux, F.; Noel, L.

    2006-07-15

    Homogeneous charge compression ignition (HCCI) is one of the alternatives to reduce significantly engine emissions for future regulations. This new alternative combustion process is mainly controlled by chemical kinetics in comparison with the conventional combustion in internal combustion engines. The optimization of the engine over the complete engine operation range requires an accurate analysis of the combustion process under all operating conditions; detailed modeling of the HCCI process is an opportunity to realize the engine optimization at lower cost. The combination of CFD computations with detailed chemistry leads to excessive computation times, and is not achievable with current computer capabilities. In this paper, a reduced chemical model for n-heptane is described, in view of its implementation into a CFD simulation code. In the first part, the reduction process to get to the 61-step mechanism is detailed and then the 26-step mechanism is described; this further reduction is carried out under various conditions that include a range of interest in engine applications. The third part is dedicated to extensive validation work in reference to the original detailed mechanism and two reduced mechanisms published in the literature, focusing on the prediction of ignition delay times under constant as well as variable volume conditions. A good and accurate reproduction of both ignition delay times and heat release can be reached with the 26-step model. (author)

  13. Adsorption from n-heptane/benzene liquid mixture on acid leached bentonite powders

    NASA Astrophysics Data System (ADS)

    Sar?kaya, Yksel; Baykal, Mehmet; nal, M?erref; Yener, Nilgn

    2013-10-01

    In this study, adsorption excess isotherms of n-heptane/benzene liquid mixture on hydrochloric acid leached bentonite powders were determined. Adsorptions were conducted at 25 C for 48 h. Experimental results were evaluated with both Schay-Nagy (SN) and Everett (E) methods. Specific surface areas (SSN and SE) of the powders were calculated regarding monolayer adsorption capacity of the preferentially adsorbed benzene. Adsorption equilibrium constants (K ? 1) were obtained by the E-method. The SE and SSN values are closed to each other. SE-values were found much lower than the corresponding Brunauer, Emmett and Teller (BET)-values. This difference was discussed with respect to the interaction of adsorbed molecules with solid surface, their collision diameter, molar cross sectional surface area and orientation in dense monolayer. Even the maximum for the SE was not associated with the maxima for K and nanopore volume (V), their values changed approximately parallel to each other with respect to the HCl% by the leaching.

  14. Inhalation developmental toxicology studies: Teratology study of n-hexane in rats: Final report

    SciTech Connect

    Mast, T.J.

    1987-12-01

    The straight chain hydrocarbon, n-hexane, is a volatile, ubiquitous solvent used in industrial, academic, and smaller commercial environments. The significant opportunity for women of child-bearing age to be exposed to this chemical prompted the undertaking of a study to assess the developmental toxicity of n-hexane in an animal model. Timed-pregnant (30 animals per group) and virgin (10 animals per group) Sprague-Dawley rats were exposed to 0 (filtered air), 200, 1000, and 5000 ppM n-hexane (99.9% purity) vapor in inhalation chambers for 20 h/day for a period of 14 consecutive days. Sperm-positive females were exposed for 6 to 19 days of gestation (dg) and virgins were exposed concurrently for 14 consecutive days. The day of sperm detection was designated as 0 dg for mated females. Adult female body weights were monitored prior to, throughout the exposure period, and at sacrifice. Uterine, placental, and fetal body weights were obtained for gravid females at sacrifice. Implants were enumerated and their status recorded as live fetus, early or late resorption, or dead. Live fetuses were sexed and examined for gross, visceral, skeletal, and soft-tissue craniofacial defects. 16 refs., 3 figs., 7 tabs.

  15. Methodological investigations on the determination of n-hexane metabolites in urine.

    PubMed

    Fedtke, N; Bolt, H M

    1986-01-01

    Male Wistar rats were exposed to 1000 ppm n-hexane, and the excreted urinary metabolites were analyzed by capillary gas chromatography-mass spectrometry (GC-MS). 1-Hexanol, 2-hexanol, 3-hexanol, 2-hexanone, 2,5-hexanedione, 2,5-dimethyltetrahydrofuran, 2,5-dimethyl-2,3-dihydrofuran and gamma-valerolactone were identified by their retention times and their mass spectra. Quantitative gas chromatographic analyses were performed using an FID. Experiments on the hydrolysis of conjugated n-hexane metabolites revealed that enzymatic hydrolysis (in addition to acid hydrolysis) was not required, as treatment with HCl hydrolyzed conjugates sensitive to acid as well as conjugates sensitive to beta-glucuronidase. By incorporating acid hydrolysis only and by using C18-cartridges for sample extraction, a method was developed that allowed the determination of n-hexane metabolites with a sample preparation time of only 45 min. Assay precision was assessed by repeated analyses of the same urine sample. Coefficients of variation for the individual metabolites ranged from between 1.8 and 3.3. PMID:3949399

  16. Inhalation developmental toxicology studies: Teratology study of n-hexane in mice: Final report

    SciTech Connect

    Mast, T.J.; Decker, J.R.; Stoney, K.H.; Westerberg, R.B.; Evanoff, J.J.; Rommereim, R.L.; Weigel, R.J.

    1988-05-01

    Gestational exposure to n-hexane resulted in an increase in the number of resorbed fetuses for exposure groups relative to the control group; however, the increases were not directly correlated to exposure concentration. The differences were statistically significant for the 200-ppM with respect to total intrauterine death (early plus late resorptions), and with respect to late resorptions for the 5000-ppM group. A small, but statistically significant, reduction in female (but not male) fetal body weight relative to the control group was observed at the 5000-ppM exposure level. There were no exposure-related increases in any individual fetal malformation or variation, nor was there any increase in the incidence of combined malformations or variations. Gestational exposure of CD-1 mice to n-hexane vapors appeared to cause a degree of concentration-related developmental toxicity in the absence of overt maternal toxicity, but the test material was not found to be teratogenic. This developmental toxicity was manifested as an increase in the number of resorptions per litter for all exposure levels, and as a decrease in the uterine: extra-gestational weight gain ratio at the 5000-ppM exposure level. Because of the significant increase in the number of resorptions at the 200-ppM exposure level, a no observable effect level (NOEL) for developmental toxicity was not established for exposure of mice to 200, 1000 or 5000-ppM n-hexane vapors. 21 refs., 3 figs., 9 tabs.

  17. Influence of zeolite pore structure on product selectivities for protolysis and hydride transfer reactions in the cracking of n-pentane.

    PubMed

    Miyaji, Akimitsu; Iwase, Yasuyoshi; Nishitoba, Toshiki; Long, Nguyen Quang; Motokura, Ken; Baba, Toshihide

    2015-02-21

    The conversion of n-pentane was carried out to examine the effects of reaction conditions on changes in product selectivities at 823 K, using zeolites with 10- and 12-membered rings. We also investigated the influence of the pore structure of these zeolites on their catalytic activities for both protolysis and hydride transfer reactions. In the first half of this work, we examined the influence of acidic proton concentration and n-pentane pressure on the reaction rates for protolysis and hydride transfer reactions using ZSM-5 zeolites. The rates of hydride transfer reactions were more influenced by pentane pressure compared to protolysis reactions, and were proportional to the square of n-pentane pressure and the concentration of acidic protons. In the second half of this work, the influence of the zeolite pore structure on changes in product selectivities with n-pentane conversion and that on the rates of protolysis and the hydride transfer reactions were revealed using various zeolites with 10- and 12-membered rings. The catalytic activities of zeolites for the protolysis and hydride transfer reactions were influenced more by the spatial volume of the zeolite cavity than the acid strength of protons on the zeolite. PMID:25598271

  18. Experimental assessment of quasi-binary picture of thermotropics: Induced smectic A phase in 7CB-n-heptane system

    NASA Astrophysics Data System (ADS)

    Yamaoka, Yuuki; Taniguchi, Yuki; Yasuzuka, Syuma; Yamamura, Yasuhisa; Saito, Kazuya

    2011-07-01

    Quasi-binary (QB) picture of thermotropics, which regards a neat thermotropic liquid crystal as a binary system consisting of (semi)rigid core and molten alkyl chain, was assessed experimentally for the most famous (and representative) thermotropic mesogenic series nCB. By adding n-heptane as solvent, the smectic A phase was induced in 7CB-n-heptane system. Small angle x-ray diffraction showed that the QB picture holds not only in the phase behavior but also in the structure. It is suggested that the melting of 8CB and 9CB to isotropic liquid via smectic and nematic liquid crystals can be understood as a thermotropic-lyotropic crossover.

  19. Molecular Dynamics Simulations Reveal Inhomogeneity-Enhanced Stacking of Violanthrone-78-Based Polyaromatic Compounds in n-Heptane-Toluene Mixtures.

    PubMed

    Jian, Cuiying; Tang, Tian

    2015-07-01

    We elucidated the effect of inhomogeneity in solutes on the aggregation of our representative polyaromatic (PA) compounds through a series of molecular dynamics simulations. Two kinds of solutes, a single type of PA compounds and a mixture of four types of PA compounds, were simulated in toluene, n-heptane, and heptol (mixture of toluene and n-heptane). The geometries of the resultant aggregates were quantified using gyradius ratios. Our results revealed that in toluene, while a single type of PA compound can only form short-cylinder-like aggregates, by having a solute mixture, parallel stacking of PA cores is enhanced, leading to the formation of one-dimensional (1D) rod-like structure. The enhanced stacking is caused by collective arrangement of the PA molecules; i.e., PA compounds of different types appear in an alternating manner in the aggregate. In addition, while the aggregated geometries of a single type of PA compounds were found to be affected by the composition of the solvents, the existence of the 1D structure formed by mixture seems to be insensitive to the solvents. On the other hand, the longest range of stacking is achieved by having a small amount of toluene ("good" solvent) in n-heptane ("bad" solvent). PMID:26076902

  20. Kinetic modeling of autoignition of higher hydrocarbons: n-heptane, n-octane and iso-octane

    SciTech Connect

    Westbrook, C.K.; Pitz, W.J.

    1986-08-01

    In the present paper, the construction of reaction mechanisms for larger fuel molecules is described, drawing heavily on experience and trends established in previous studies of smaller fuel molecules. Sensitivity analysis shows which classes of reaction steps are likely to have the greatest influence on computed results and for which additional experimental information is needed. This process is illustrated for the cases of n-heptane, n-octane, and iso-octane. N-heptane and iso-octane are of interest since they are the reference fuels defining octane number, having octane numbers of 0 and 100, respectively. N-octane is included since it can be compared with n-heptane to illustrate the importance of fuel molecule size with the structure unchanged, and it can be compared with iso-octane to show the influence of molecular structure with molecular size unchanged. Computed results under shock tube and under internal combustion engine conditions will be described to demonstrate how initial pressure, temperature, fuel type, fuel structure, and other important parameters affect the rates of autoignition. These differences will be interpreted in terms of the detailed kinetic reaction mechanism, and strategies for modifying autoignition rates will be discussed. 27 refs., 4 figs., 1 tab.

  1. A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane

    NASA Technical Reports Server (NTRS)

    Harstad, Kenneth G.; Bellan, Josette

    2011-01-01

    The reduction of elementary or skeletal oxidation kinetics to a subgroup of tractable reactions for inclusion in turbulent combustion codes has been the subject of numerous studies. The skeletal mechanism is obtained from the elementary mechanism by removing from it reactions that are considered negligible for the intent of the specific study considered. As of now, there are many chemical reduction methodologies. A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement of the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL (Lawrence Livermore National Laboratory) skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately non-dimensionalized global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The reduced model is based on concepts consistent with those of Large Eddy Simulation (LES) in which functional forms are used to replace the small scales eliminated through filtering of the governing equations; in LES, these small scales are unimportant as far as the overwhelming part of dynamic energy is concerned. Here, the scales thought unimportant for recovering the thermodynamic energy are removed. The concept is tested by using tabular information from the LLNL skeletal mechanism in conjunction with CHEMKIN II utilized as surrogate ideal functions replacing the necessary functional forms. The test reveals that the similarity concept is indeed justified and that the combustion temperature is well predicted, but that the ignition time is over-predicted, a fact traced to neglecting a detailed description of the processes leading to the heavies chemical decomposition. To palliate this deficiency, functional modeling is incorporated into this conceptual reduction in addition to the modeling the evolution of the global constituent molar density, the enthalpy evolution of the heavies, the contribution to the reaction rate of the unsteady lights from other light species and from the heavies, the molar density evolution of oxygen and water, and the mole fractions of the quasisteady light species. The model is compact in that there are only nine species-related progress variables. Results are presented showing the performance of the model for predicting the temperature and species evolution. The model reproduces the ignition time over a wide range of equivalence ratios, initial pressure, and initial temperature.

  2. Formulation reproducing the ignition delays simulated by a detailed mechanism: Application to n-heptane combustion

    SciTech Connect

    Imbert, Bruno; Lafosse, Fabien; Catoire, Laurent; Paillard, Claude-Etienne; Khasainov, Boris

    2008-11-15

    This article is part of the project to model the kinetics of high-temperature combustions, occurring behind shock waves and in detonation waves. The ''conventional'' semi-empirical correlations of ignition delays have been reformulated, by keeping the Arrhenius equation form. It is shown how a polynomial with 3{sup N} coefficients (where N element of is the number of adjustable kinetic parameters, likely to be simultaneously chosen among the temperature T, the pressure P, the inert fraction X{sub Ar}, and the equivalence ratio {phi}) can reproduce the delays predicted by the Curran et al. [H.J. Curran, P. Gaffuri, W.J. Pitz, C.K. Westbrook, Combust. Flame 129 (2002) 253-280] detailed mechanism (565 species and 2538 reactions), over a wide range of conditions (comparable with the validity domain). The deviations between the simulated times and their fits (typically 1%) are definitely lower than the uncertainties related to the mechanism (at least 25%). In addition, using this new formalism to evaluate these durations is about 10{sup 6} times faster than simulating them with SENKIN (CHEMKIN III package) and only 10 times slower than using the classical correlations. The adaptation of the traditional method for predicting delays is interesting for modeling, because those performances are difficult to obtain simultaneously with other reduction methods (either purely mathematical, chemical, or even mixed). After a physical and mathematical justification of the proposed formalism, some of its potentialities for n-heptane combustion are presented. In particular, the trends of simulated delays and activation energies are shown for {sub T} {sub element} {sub of} {sub [1500} {sub K,1900} {sub K},} {sub P} {sub element} {sub of} {sub [10kPa,1MPa]}, X{sub Ar} element of [0,0.7], and {phi} element of {sub [0.25,4.0]}. (author)

  3. Some Recent Observations on the Burning of Isolated N-Heptane and Alcohol Droplets

    NASA Technical Reports Server (NTRS)

    Dryer, F. L.

    1999-01-01

    In a joint program involving Prof F.A. Williams of the University of California, San Diego and Dr. Vedha Nayagam of the National Center for Microgravity Research on Fluid and Combustion, the combustion of liquid fuel droplets having initial diameters between about 1 mm and 6 mm is being studied. The objectives of the work are to improve fundamental knowledge of droplet combustion dynamics through microgravity experiments and theoretical analyses. The Princeton contributions to the collaborative program supports the engineering design, data analysis, and data interpretation requirements for the study of initially single component, spherically symmetric, isolated droplet combustion studies through experiments and numerical modeling. The complementary UCSD contributions apply asymptotic theoretical analyses and are described in the published literature and in a companion communication in this volume. Emphases of the Princeton work are on the study of simple alcohols (methanol, ethanol), alcohol/water mixtures, and pure alkanes (n-heptane, n-decane) as fuels, with time dependent measurements of drop size, flame-stand-off, liquid-phase composition, and finally, extinction. Ground based experiments have included bench-scale studies at Princeton and collaborative experimental studies in the 2.2 and 5.18 second drop towers at NASA-Glenn Research Center. Spacelab studies have included fiber-supported droplet combustion (FSDC) experiments in the Glovebox facility with accompanying numerical analyses. Experiments include FSDC-1, performed on the USML-2 mission in October, 1995 (STS-73) and FSDC-2, on the second flight of the MSL-1 mission in July, 1997 (STS-94).

  4. Characterization and modeling of premixed turbulent n-heptane ames in the thin reaction zone regime

    NASA Astrophysics Data System (ADS)

    Savard, Bruno

    n-heptane/air premixed turbulent flames in the high-Karlovitz portion of the thin reaction zone regime are characterized and modeled in this thesis using Direct Numerical Simulations (DNS) with detailed chemistry. In order to perform these simulations, a time-integration scheme that can efficiently handle the stiffness of the equations solved is developed first. A first simulation with unity Lewis number is considered in order to assess the effect of turbulence on the flame in the absence of differential diffusion. A second simulation with non-unity Lewis numbers is considered to study how turbulence affects differential diffusion. In the absence of differential diffusion, minimal departure from the 1D unstretched flame structure (species vs. temperature profiles) is observed. In the non-unity Lewis number case, the flame structure lies between that of 1D unstretched flames with "laminar'' non-unity Lewis numbers and unity Lewis number. This is attributed to effective Lewis numbers resulting from intense turbulent mixing and a first model is proposed. The reaction zone is shown to be thin for both flames, yet large chemical source term fluctuations are observed. The fuel consumption rate is found to be only weakly correlated with stretch, although local extinctions in the non-unity Lewis number case are well correlated with high curvature. These results explain the apparent turbulent flame speeds. Other variables that better correlate with this fuel burning rate are identified through a coordinate transformation. It is shown that the unity Lewis number turbulent flames can be accurately described by a set of 1D (in progress variable space) flamelet equations parameterized by the dissipation rate of the progress variable. In the non-unity Lewis number flames, the flamelet equations suggest a dependence on a second parameter, the diffusion of the progress variable. A new tabulation approach is proposed for the simulation of such flames with these dimensionally-reduced manifolds.

  5. In vitro antioxidant activity and HPTLC determination of n-hexane extract of Emilia sonchifolia (L.)DC.

    PubMed Central

    Sophia, D.; Ragavendran, P.; Arulraj, C.; Gopalakrishnan, V. K.

    2011-01-01

    The free radical scavenging activities of n-hexane extract of the whole plant of Emilia sonchifolia was evaluated by employing various in vitro assay systems like DPPH radical scavenging activity, superoxide radical scavenging activity and hydrogen peroxide scavenging activity with IC50 values 180, 160 and 160 ?g/ml respectively. The results of the study indicate that the n-hexane extract of the whole plant of Emilia sonchifolia possess a significant scavenging effect with increasing concentrations probably due to its antioxidant potential. High performance thin layer chromatography (HPTLC) analysis in the n-hexane extract of Emilia sonchifolia showed the presence of terpenoids which probably may be responsible for the antioxidant activity. Thus, n-hexane extract of Emilia sonchifolia can be used potentially as a bioactive source of natural antioxidants due to the presence of terpenoids in it PMID:24826021

  6. In vitro antioxidant activity and HPTLC determination of n-hexane extract of Emilia sonchifolia (L.)DC.

    PubMed

    Sophia, D; Ragavendran, P; Arulraj, C; Gopalakrishnan, V K

    2011-09-01

    The free radical scavenging activities of n-hexane extract of the whole plant of Emilia sonchifolia was evaluated by employing various in vitro assay systems like DPPH radical scavenging activity, superoxide radical scavenging activity and hydrogen peroxide scavenging activity with IC50 values 180, 160 and 160 ?g/ml respectively. The results of the study indicate that the n-hexane extract of the whole plant of Emilia sonchifolia possess a significant scavenging effect with increasing concentrations probably due to its antioxidant potential. High performance thin layer chromatography (HPTLC) analysis in the n-hexane extract of Emilia sonchifolia showed the presence of terpenoids which probably may be responsible for the antioxidant activity. Thus, n-hexane extract of Emilia sonchifolia can be used potentially as a bioactive source of natural antioxidants due to the presence of terpenoids in it. PMID:24826021

  7. Molecular dynamics simulations of n-hexane at 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide interface.

    PubMed

    Lsal, Martin; Izk, Pavel

    2013-07-01

    Molecular dynamics simulations of n-hexane adsorbed onto the interface of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([bmim][Tf2N]) are performed at three n-hexane surface densities, ranged from 0.7 to 2.3 ?mol/m(2) at 300 K. For [bmim][Tf2N] room-temperature ionic liquid, we use a non-polarizable all-atom force field with the partial atomic charges based on ab initio calculations for the isolated ion pair. The net charges of the ions are 0.89e, which mimics the anion to cation charge transfer and polarization effects. The OPLS-AA force field is employed for modeling of n-hexane. The surface tension is computed using the mechanical route and its value decreases with increase of the n-hexane surface density. The [bmim][Tf2N]/n-hexane interface is analyzed using the intrinsic method, and the structural and dynamic properties of the interfacial, sub-interfacial, and central layers are computed. We determine the surface roughness, global and intrinsic density profiles, and orientation ordering of the molecules to describe the structure of the interface. We further compute the survival probability, normal and lateral self-diffusion coefficients, and re-orientation correlation functions to elucidate the effects of n-hexane on dynamics of the cations and anions in the layers. PMID:23822317

  8. Molecular dynamics simulations of n-hexane at 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide interface

    NASA Astrophysics Data System (ADS)

    Lsal, Martin; Izk, Pavel

    2013-07-01

    Molecular dynamics simulations of n-hexane adsorbed onto the interface of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([bmim][Tf2N]) are performed at three n-hexane surface densities, ranged from 0.7 to 2.3 ?mol/m2 at 300 K. For [bmim][Tf2N] room-temperature ionic liquid, we use a non-polarizable all-atom force field with the partial atomic charges based on ab initio calculations for the isolated ion pair. The net charges of the ions are 0.89e, which mimics the anion to cation charge transfer and polarization effects. The OPLS-AA force field is employed for modeling of n-hexane. The surface tension is computed using the mechanical route and its value decreases with increase of the n-hexane surface density. The [bmim][Tf2N]/n-hexane interface is analyzed using the intrinsic method, and the structural and dynamic properties of the interfacial, sub-interfacial, and central layers are computed. We determine the surface roughness, global and intrinsic density profiles, and orientation ordering of the molecules to describe the structure of the interface. We further compute the survival probability, normal and lateral self-diffusion coefficients, and re-orientation correlation functions to elucidate the effects of n-hexane on dynamics of the cations and anions in the layers.

  9. Molecular dynamics simulations of n-hexane at 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide interface

    SciTech Connect

    Lisal, Martin; Izak, Pavel

    2013-07-07

    Molecular dynamics simulations of n-hexane adsorbed onto the interface of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([bmim][Tf{sub 2}N]) are performed at three n-hexane surface densities, ranged from 0.7 to 2.3 {mu}mol/m{sup 2} at 300 K. For [bmim][Tf{sub 2}N] room-temperature ionic liquid, we use a non-polarizable all-atom force field with the partial atomic charges based on ab initio calculations for the isolated ion pair. The net charges of the ions are {+-}0.89e, which mimics the anion to cation charge transfer and polarization effects. The OPLS-AA force field is employed for modeling of n-hexane. The surface tension is computed using the mechanical route and its value decreases with increase of the n-hexane surface density. The [bmim][Tf{sub 2}N]/n-hexane interface is analyzed using the intrinsic method, and the structural and dynamic properties of the interfacial, sub-interfacial, and central layers are computed. We determine the surface roughness, global and intrinsic density profiles, and orientation ordering of the molecules to describe the structure of the interface. We further compute the survival probability, normal and lateral self-diffusion coefficients, and re-orientation correlation functions to elucidate the effects of n-hexane on dynamics of the cations and anions in the layers.

  10. N-hexane neuropathy with vertigo and cold allodynia in a silk screen printer: A case study.

    PubMed

    Pradhan, Sunil; Tandon, Ruchika

    2015-01-01

    N-hexane neuropathy is an occupational disease caused by exposure to n-hexane, which is used as a solvent in silk screen printing. Here, we describe a 35-year-old man, a silk screen printer by profession, who presented with dizziness, distal swelling of both lower limbs for 10 months and tingling and burning sensation in both feet for 9.5 months along with cold allodynia. The patient had normal results of a motor and sensory system examination, apart from an impaired temperature sense. Nerve conduction tests showed a conduction block in bilateral common peroneal nerves and absence of conduction in bilateral sural nerves. These symptoms resolved when further exposure to n-hexane was ceased but cold allodynia remained. Thus, cold allodynia and impaired temperature sense can be a manifestation of n-hexane neuropathy. Hence, abnormalities on nerve conduction studies can be detected in n-hexane neuropathy patients, even before clinical examination detects any such abnormalities. In the case of the patients presenting with sensory motor neuropathy, history of occupational exposure to n-hexane becomes important, as the sooner the disease is detected, the better the chances of recovery. PMID:26224503

  11. Combustion characteristics and influential factors of isooctane active-thermal atmosphere combustion assisted by two-stage reaction of n-heptane

    SciTech Connect

    Lu, Xingcai; Ji, Libin; Ma, Junjun; Zhou, Xiaoxin; Huang, Zhen

    2011-02-15

    This paper presents an experimental study on the isooctane active-thermal atmosphere combustion (ATAC) which is assisted by two-stage reaction of n-heptane. The active-thermal atmosphere is created by low- and high-temperature reactions of n-heptane which is injected at intake port, and isooctane is directly injected into combustion chamber near the top dead center. The effects of isooctane injection timing, active-thermal atmosphere intensity, overall equivalence ratio, and premixed ratio on combustion characteristics and emissions are investigated. The experimental results reveal that, the isooctane ignition and combustion can be classified to thermal atmosphere combustion, active atmosphere combustion, and active-thermal atmosphere combustion respectively according to the extent of n-heptane oxidation as well as effects of isooctane quenching and charge cooling. n-Heptane equivalence ratio, isooctane equivalence ratio and isooctane delivery advance angle are major control parameters. In one combustion cycle, the isooctane ignited and burned after those of n-heptane, and then this combustion phenomenon can also be named as dual-fuel sequential combustion (DFSC). The ignition timing of the overall combustion event is mainly determined by n-heptane equivalence ratio and can be controlled in flexibility by simultaneously adjusting isooctane equivalence ratio. The isooctane ignition regime, overall thermal efficiency, and NO{sub x} emissions show strong sensitivity to the fuel delivery advance angle between 20 CA BTDC and 25 CA BTDC. (author)

  12. Viscosities of nonelectrolyte liquid mixtures. II. Binary mixtures of n-hexane with alkanoates and bromoalkanoates

    NASA Astrophysics Data System (ADS)

    Oswal, S. L.; Dave, J. P.

    1992-11-01

    Viscosity measurements are reported for mixtures of ethyl ethanoate, ethyl propionate, ethyl butyrate, ethyl-2-bromopropionate, ethyl-3-bromopropionate, ethyl-2-bromobutyrate, and ethyl-4-bromobutyrate with n-hexane at 303.15 K. The viscosity data have been correlated with equations of Grunberg and Nissan, of McAllister, and of Auslaender. Furthermore, excess Gibbs energies of activation ?G * E of viscous flow have been calculated with Eyring's theory of absolute reaction rates and values of ?G * E for the present binary mixtures have been explained in terms of the dipole-dipole interaction in alkanoates and the intramolecular Br...O interaction in bromoalkanoates.

  13. Spectra and structure of binary azeotropes. III. Acetone- n-hexane

    NASA Astrophysics Data System (ADS)

    Jalilian, M. R.

    2007-04-01

    Acetone and n-hexane form an azeotrope with the mole ratio 2:1. As a result of this phenomenon, some characteristic vibrational modes in FT-IR and some chemical shifts in 1H NMR spectra changes. The amount of these changes is an indication of the extension of interaction between two components and their orientation in unit structure of the cluster. FT-IR and 1H NMR spectra of pure substances and their azeotrope were recorded and spectral changes analyzed. Based on mole ratio of constituents, boiling point depressions, spectral changes in fundamental frequencies, and chemical shifts, unit structure of the azeotrope were deduced.

  14. Spectra and structure of binary azeotropes. III. Acetone-n-hexane.

    PubMed

    Jalilian, M R

    2007-04-01

    Acetone and n-hexane form an azeotrope with the mole ratio 2:1. As a result of this phenomenon, some characteristic vibrational modes in FT-IR and some chemical shifts in 1H NMR spectra changes. The amount of these changes is an indication of the extension of interaction between two components and their orientation in unit structure of the cluster. FT-IR and 1H NMR spectra of pure substances and their azeotrope were recorded and spectral changes analyzed. Based on mole ratio of constituents, boiling point depressions, spectral changes in fundamental frequencies, and chemical shifts, unit structure of the azeotrope were deduced. PMID:16920003

  15. Cobalt pivalate complex as a catalyst for liquid phase oxidation of n-hexane

    NASA Astrophysics Data System (ADS)

    Moskovskaya, I. F.; Maerle, A. A.; Shvydkiy, N. V.; Romanovsky, B. V.; Ivanova, I. I.

    2015-09-01

    Catalytic properties of cobalt(II) pivalate complex as both individual and supported on mesoporous molecular sieves Si-KIT-6, Al-KIT-6, and Ce-KIT-6 were investigated in liquid-phase oxidation of n-hexane with molecular oxygen. This complex was shown to be an active and selective catalyst for the oxidation of n-C6H14 into C1-C4 carboxylic acids. The activity of Co(II) pivalate remains practically unchanged on heterogenizing the complex on molecular sieve supports. At the same time, its selectivity and resistance towards an oxidative degradation are slightly increased.

  16. Adsorption of n-hexane and intermediate molecular weight aromatic hydrocarbons on LaY zeolite

    SciTech Connect

    Ruthven, D.M.; Kaul, B.K.

    1996-06-01

    Experimental equilibrium isotherms, Henry`s law constants, and heats of sorption are reported for n-hexane, benzene, toluene, p-xylene, mesitylene, naphthalene, trimethylbenzene (TMP), and hexamethylbenzene (HMB) in La-exchanged zeolite Y (Si/Al = 1.8). Henry`s law constants and energies of adsorption are substantially smaller than those for NaX zeolite, reflecting the absence of accessible cations in LaY. These data provide a basis for the estimation of adsorbed phase concentrations of the relevant hydrocarbons on REY cracking catalysts under reaction conditions.

  17. Ignition of turbulent swirling n-heptane spray flames using single and multiple sparks

    SciTech Connect

    Marchionea, T.; Ahmeda, S.F.; Mastorakos, E.

    2009-01-15

    This paper examines ignition processes of an n-heptane spray in a flow typical of a liquid-fuelled burner. The spray is created by a hollow-cone pressure atomiser placed in the centre of a bluff body, around which swirling air induces a strong recirculation zone. Ignition was achieved by single small sparks of short duration (2 mm; 0.5 ms), located at various places inside the flow so as to identify the most ignitable regions, or larger sparks of longer duration (5 mm; 8 ms) repeated at 100 Hz, located close to the combustion chamber enclosure so as to mimic the placement and characteristics of a gas turbine combustor surface igniter. The air and droplet velocities, the droplet diameter, and the total (i.e. liquid plus vapour) equivalence ratio were measured in inert flow by phase Doppler anemometry and sampling respectively. Fast camera imaging suggested that successful ignition events were associated with flamelets that propagated back towards the spray nozzle. Measurements of ignition probability with the single spark showed that localised ignition inside the spray is more likely to result in successful flame establishment when the spark is located in a region of negative velocity, relatively small droplet Sauter mean diameter, and mean equivalence ratio within the flammability limits. Ignition with the single spark was not possible at the location where the multiple spark experiments were performed. For those, the multiple spark sequence lasted approximately 1 to 5 s. It was found that a long spark sequence increases the ignition efficiency, which reached a maximum of 100% at the axial distance where the recirculation zone had maximum width. Ignition was not feasible with the spark downstream of about two burner diameters. Visualisation showed that small flame kernels emanate very often from the spark, which can be stretched as far as 20 mm from the electrodes by the turbulent velocity fluctuations. These kernels survive very little time. Successful overall ignition occurs at a random time from the spark initiation and, as in the case of the single spark, success is associated with kernels that move without getting extinguished towards the bluff body. The results demonstrate that the energy deposited by multiple sparks and spark stretching in a turbulent flow can have a spatially far-reaching effect to initiate combustion. (author)

  18. Normalized fluctuations, H2O vs n-hexane: Site-correlated percolation

    NASA Astrophysics Data System (ADS)

    Koga, Yoshikata; Westh, Peter; Sawamura, Seiji; Taniguchi, Yoshihiro

    1996-08-01

    Entropy, volume and the cross fluctuations were normalized to the average volume of a coarse grain with a fixed number of molecules, within which the local and instantaneous value of interest is evaluated. Comparisons were made between liquid H2O and n-hexane in the range from -10 C to 120 C and from 0.1 MPa to 500 MPa. The difference between H2O and n-hexane in temperature and pressure dependencies of these normalized fluctuations was explained in terms of the site-correlated percolation theory for H2O. In particular, the temperature increase was confirmed to reduce the hydrogen bond probability, while the pressure appeared to have little effect on the hydrogen bond probability. According to the Le Chatelier principle, however, the putative formation of ``ice-like'' patches at low temperatures due to the site-correlated percolation requirement is retarded by pressure increases. Thus, only in the limited region of low pressure (<300 MPa) and temperature (<60 C), the fluctuating ice-like patches are considered to persist.

  19. Hydraulic transport across hydrophilic and hydrophobic nanopores: Flow experiments with water and n -hexane

    NASA Astrophysics Data System (ADS)

    Gruener, Simon; Wallacher, Dirk; Greulich, Stefanie; Busch, Mark; Huber, Patrick

    2016-01-01

    We experimentally explore pressure-driven flow of water and n -hexane across nanoporous silica (Vycor glass monoliths with 7- or 10-nm pore diameters, respectively) as a function of temperature and surface functionalization (native and silanized glass surfaces). Hydraulic flow rates are measured by applying hydrostatic pressures via inert gases (argon and helium, pressurized up to 70 bar) on the upstream side in a capacitor-based membrane permeability setup. For the native, hydrophilic silica walls, the measured hydraulic permeabilities can be quantitatively accounted for by bulk fluidity provided we assume a sticking boundary layer, i.e., a negative velocity slip length of molecular dimensions. The thickness of this boundary layer is discussed with regard to previous capillarity-driven flow experiments (spontaneous imbibition) and with regard to velocity slippage at the pore walls resulting from dissolved gas. Water flow across the silanized, hydrophobic nanopores is blocked up to a hydrostatic pressure of at least 70 bar. The absence of a sticking boundary layer quantitatively accounts for an enhanced n -hexane permeability in the hydrophobic compared to the hydrophilic nanopores.

  20. n-Hexane hydro-isomerization over promoted Pd/HZSM-5 catalysts

    NASA Astrophysics Data System (ADS)

    Thoa Dao, Thi Kim; Loc Luu, Cam

    2015-09-01

    A series of Pd/HZSM-5 catalysts modified by various metallic species, including Co, Ni, Fe, Re, and Cu, was prepared by sequential impregnation. Contents of Pd and second metals in modified catalysts were 0.8 and 1.0 wt%, respectively. Physico-chemical characteristics of catalysts were investigated by nitrogen physi-sorption (BET), x-ray diffraction (XRD), transmission electron microscopy (TEM), ammonia temperature programmed desorption (NH3-TPD), temperature programmed reduction (TPR) and hydrogen pulse chemisorption (HPC). Coke formation was studied by the method of thermogravimetric analysis (TGA). The activities of catalysts in n-hexane isomerization were studied in a micro-flow reactor under atmospheric pressure at 250 C, and molar ratio of H2: n-hexane of 5.92. It was found that Co, Ni, Fe, and Re additives exhibited geometric and electronic effects toward Pd/HZSM-5 catalyst, leading to an enhancement of its activity and stability. On the contrary, Cu additive caused Pd/HZSM-5 to become poorer in activity and stability.

  1. Performance and bacterial population composition of an n-hexane degrading biofilter working under fluctuating conditions.

    PubMed

    Valenzuela-Reyes, Edgardo; Casas-Flores, Sergio; Isordia-Jasso, Isabel; Arriaga, Sonia

    2014-09-01

    In this work, several conditions of pH and inlet load (IL) were applied to a scale laboratory biofilter treating n-hexane vapors during 143 days. During the first 79 days of operation (period 1, P1), the system was fed with neutral pH mineral medium (MM) and the IL was progressively decreased from 177 to 16 g m(-3) h(-1). A maximum elimination capacity (EC) of 30 g m(-3) h(-1) was obtained at an IL of 176.9 ± 9.8 g m(-3) h(-1). During the following 64 days (period 2, P2), acidic conditions were induced by feeding the biofilter with acidic buffer solution and pH 4 MM in order to evaluate the effect of bacterial community changes on EC. Within the acidic period, a maximum EC of 54 g m(-3) h(-1) (IL 132.3 ± 13 g m(-3) h(-1)) was achieved. Sequence analysis of 16S rDNA genes amplified from the consortium revealed the presence of Sphingobacteria, Actinobacteria, and α-, β- and γ-Proteobacteria. An Actinobacteria of the Mycobacterium genus had presence throughout the whole experiment of biofiltration showing resistance to fluctuating pH and IL conditions. Batch tests confirm the bacterial predominance and a negligible contribution of fungi in the degradation of n-hexane. PMID:25099371

  2. Hydraulic transport across hydrophilic and hydrophobic nanopores: Flow experiments with water and n-hexane.

    PubMed

    Gruener, Simon; Wallacher, Dirk; Greulich, Stefanie; Busch, Mark; Huber, Patrick

    2016-01-01

    We experimentally explore pressure-driven flow of water and n-hexane across nanoporous silica (Vycor glass monoliths with 7- or 10-nm pore diameters, respectively) as a function of temperature and surface functionalization (native and silanized glass surfaces). Hydraulic flow rates are measured by applying hydrostatic pressures via inert gases (argon and helium, pressurized up to 70 bar) on the upstream side in a capacitor-based membrane permeability setup. For the native, hydrophilic silica walls, the measured hydraulic permeabilities can be quantitatively accounted for by bulk fluidity provided we assume a sticking boundary layer, i.e., a negative velocity slip length of molecular dimensions. The thickness of this boundary layer is discussed with regard to previous capillarity-driven flow experiments (spontaneous imbibition) and with regard to velocity slippage at the pore walls resulting from dissolved gas. Water flow across the silanized, hydrophobic nanopores is blocked up to a hydrostatic pressure of at least 70 bar. The absence of a sticking boundary layer quantitatively accounts for an enhanced n-hexane permeability in the hydrophobic compared to the hydrophilic nanopores. PMID:26871150

  3. Effects of anionic surfactant on n-hexane removal in biofilters.

    PubMed

    Cheng, Yan; He, Huijun; Yang, Chunping; Yan, Zhou; Zeng, Guangming; Qian, Hui

    2016-05-01

    The biodegradability of three anion surfactants by biofilm microorganisms and the toxicity of the most readily biodegradable surfactant to biofilm microorganisms were examined using batch experiments, and the optimal concentration of SDS for enhanced removal of hexane was investigated using two biotrickling filters (BTFs) for comparison. Results showed that SDS could be biodegraded by microorganisms, and its toxicity to microorganisms within the experimental range was negligible. The best concentration of SDS in biofiltration of n-hexane was 0.1 CMC and the elimination capacity (EC) of 50.4 g m(-3) h(-1) was achieved at a fixed loading rate (LR) of 72 g m(-3) h(-1). When an inlet concentration of n-hexane increased from 600 to 850 mg m(-3), the removal efficiency (RE) decreased from 67% to 41% by BTF2 (with SDS) and from 52% to 42% by BTF1 (without SDS). SDS could enhance hexane removal from 43% (BTF1) to 60% (BTF2) at gas empty-bed residence time (EBRT) of 7.5 s and an inlet concentration of 200 mg m(-3). PMID:26907592

  4. Experimental study and chemical analysis of n-heptane homogeneous charge compression ignition combustion with port injection of reaction inhibitors

    SciTech Connect

    Lue, Xingcai; Ji, Libin; Zu, Linlin; Hou, Yuchun; Huang, Cheng; Huang, Zhen

    2007-05-15

    The control of ignition timing in the homogeneous charge compression ignition (HCCI) of n-heptane by port injection of reaction inhibitors was studied in a single-cylinder engine. Four suppression additives, methanol, ethanol, isopropanol, and methyl tert-butyl ether (MTBE), were used in the experiments. The effectiveness of inhibition of HCCI combustion with various additives was compared under the same equivalence ratio of total fuel and partial equivalence ratio of n-heptane. The experimental results show that the suppression effectiveness increases in the order MTBE < isopropanol << ethanol < methanol. But ethanol is the best additive when the operating ranges, indicated thermal efficiency, and emissions are considered. For ethanol/n-heptane HCCI combustion, partial combustion may be observed when the mole ratio of ethanol to that of total fuel is larger than 0.20; misfires occur when the mole ratio of ethanol to that of total fuel larger than 0.25. Moreover, CO emissions strongly depend on the maximum combustion temperature, while HC emissions are mainly dominated by the mole ratio of ethanol to that of total fuel. To obtain chemical mechanistic informations relevant to the ignition behavior, detailed chemical kinetic analysis was conducted. The simulated results also confirmed the retarding of the ignition timing by ethanol addition. In addition, it can be found from the simulation that HCHO, CO, and C{sub 2}H{sub 5}OH could not be oxidized completely and are maintained at high levels if the partial combustion or misfire occurs (for example, for leaner fuel/air mixture). (author)

  5. On the characterization of NaDEHP/n-heptane nonaqueous reverse micelles: the effect of the polar solvent.

    PubMed

    Quintana, Silvina S; Dario Falcone, R; Silber, Juana J; Moyano, Fernando; Mariano Correa, N

    2015-03-14

    The behavior of two polar solvents, ethylene glycol (EG) and dimethylformamide (DMF), entrapped in sodium bis-(2-ethylhexyl) phosphate (NaDEHP)/n-heptane reverse micelles (RMs) was investigated using dynamic light scattering (DLS), molecular probe absorption and FT-IR spectroscopy. DLS results reveal the formation of RMs containing EG and DMF as a polar component. To the best of our knowledge this is the first report where both polar solvents are entrapped by the NaDEHP surfactant to effectively create RMs. We use the solvatochromism behavior of the molecular probe, 1-methyl-8-oxyquinolinum betaine (QB), and FT-IR spectroscopy to investigate the physicochemical properties of the non-aqueous RMs. Our results demonstrate that the NaDEHP surfactant interacts through hydrogen bonds with EG at the EG/NaDEHP interface and this interaction is responsible for destroying the bulk structure of pure solvent EG when entrapped in NaDEHP RMs. On the other hand, when DMF is incorporated inside the RMs the bulk structure of DMF is destroyed upon encapsulation by the Na-DMF interaction at the DMF/NaDEHP interface. Our results are completely different than the one observed for DMF/n-heptane/AOT. Our results show how the physicochemical properties, such as micropolarity, microviscosity and hydrogen bond interaction, of nonaqueous NaDEHP/n-heptane RMs interfaces can be dramatically changed by simply using different non-aqueous polar solvents. Thus, these results can be very useful to employ these novel RMs as nanoreactors since the dimensions of the RMs are around 10 to 20 nm. PMID:25684091

  6. Determination of low concentrations of aromatic hydrocarbons in multicomponent mixtures with iso-octane and n-heptane

    NASA Astrophysics Data System (ADS)

    Vesnin, V. L.; Muradov, V. G.

    2011-11-01

    We have experimentally studied the absorption spectra of hydrocarbon mixtures based on n-heptane and isooctane with small (1%-2%) additions of aromatic hydrocarbons (benzene, toluene, xylene). The study was conducted in the region of the first overtones of the vibrational spectra for the hydrocarbon groups CH3, CH2, CH. We show that four-component modeling of the absorption spectrum of the hydrocarbon mixture and minimization of the deviation of the model spectrum from the experimental spectrum allow us to separately determine the content of the aromatic additives for concentrations from 1%.

  7. Simulation of auto-ignition of iso-octane and n-heptane in an internal combustion engine

    SciTech Connect

    Basevich, V.Ya.; Belyaev, A.A.; Brandshteter, V.

    1994-05-01

    A detailed kinetic mechanism is proposed for the oxidation of iso-octane, n-heptane, and mixtures of them in air (number of particles 43, number of reactions 284), which satisfactorily describes the distinctive features of low-temperature and high-temperature oxidation at an initial temperature of 1200 K, pressure of 15-40 absolute atmospheres or higher, and a fuel excess ratio of 0.5-2. The abbreviated mechanisms obtained to describe the auto-ignition of fuel with an octane number of 90 involve 27 particles (38 reactions) and 18 particles (22 reactions).

  8. The oxidation of n-butane and n-heptane in a CFR engine; Isomerization reactions and delay of autoignition

    SciTech Connect

    Sahetchian, K.A.; Blin, N.; Rigny, R.; Seydi, A. ); Murat, M. )

    1990-03-01

    During the oxidation of {ital n}-butane in a flow system and also in a motored CFR engine (600 rpm) hydrogen peroxide, primary and secondary butylhydroperoxides, and peracetic acid are formed. In the CFR engine these peroxides appear only when the compression ratio is larger than 10:1 ({ital T}{sub max} = 650 K). No autoignition has been observed. A comparison of {ital n}-butane and {ital n}-heptane oxidation is presented. Isomerization reactions,which are correlated with the alkane structure and the octane number, account for the differences in the experimental results.

  9. Position specificity in n-hexane hydroxylation by two forms of cytochrome P-450 in rat liver microsomes.

    PubMed

    Morohashi, K; Sadano, H; Okada, Y; Omura, T

    1983-02-01

    The hydroxylation of n-hexane by rat liver microsomes was studied and the contribution of different molecular species of cytochrome P-450 to the hydroxylation reaction was examined. In the case of untreated rats, the products of NADPH-dependent n-hexane hydroxylation were 1-, 2-, and 3-hexanols, and the major one was 2-hexanol. Phenobarbital (PB) treatment of animals resulted in a significant increase of the hydroxylation activity. The formation of 2- and 3-hexanols was much more significantly increased than that of 1-hexanol. On the other hand, 3-methylcholanthrene (MC) treatment stimulated the formation of 3-hexanol and the formation of the other two isomeric alcohols was rather decreased. These observations suggested the position specificities of the PB-inducible form (P-450(PB)) and MC-inducible form (P-450(MC)) of cytochrome P-450 in the hydroxylation of n-hexane. Inhibition experiments using antibodies specific to P-450(PB) and P-450(MC) also indicated that P-450(PB) was more active in the hydroxylation at the 2-position whereas P-450(MC) was more specific for the 3-position. NADPH-dependent n-hexane hydroxylation systems were reconstituted by the use of purified NADPH-cytochrome P-450 reductase and P-450(PB) or P-450(MC), and the activities of the reconstituted systems supported the proposed position specificities of these two forms of cytochrome P-450 in n-hexane hydroxylation. PMID:6404899

  10. Metabolism of n-hexane by rat liver and extrahepatic tissues and the effect of cytochrome P-450 inducers.

    PubMed

    Crosbie, S J; Blain, P G; Williams, F M

    1997-03-01

    1. The in vitro metabolism of n-hexane was studied in rat liver, lung, brain and skeletal muscle microsomes and in microsomes prepared from cell lines expressing human cytochrome P-450 2E1 or 2B6. The hydroxylated metabolites of n-hexane were quantified by gas chromatography-mass spectometry. 2. Rat liver and extensor digitorum longus (EDL, fast-twitch skeletal muscle) microsomes and the CYP 2B6 microsomes produced the pre-neurotoxic metabolite of n-hexane, 2-hexanol as a major metabolite in contrast to the other rat tissues examined. 3. Inhibition of 2- and 3-hexanol production from n-hexane by rat lung microsomes using metyrapone, an inhibitor of cytochrome P-450 2B1 activity, resulted in almost complete inhibition of lung microsomal activity. 4. Production of all three hexanols was significantly increased with phenobarbital-induced rat liver microsomes, with a 10-fold increase in 2- and 3-hexanol production. A slight increase in 2-hexanol production with phenobarbital-induced rat EDL and brain microsomes was observed. No increase in n-hexane metabolism was noted following induction with beta-naphthoflavone or with ethanol. PMID:9088965

  11. Changes of n-hexane neurotoxicity and its urinary metabolites by long-term co-exposure with MEK or toluene.

    PubMed

    Iwata, M; Takeuchi, Y; Hisanaga, N; Ono, Y

    1984-01-01

    It is well known that the neurotoxicity of n-hexane may be modified upon co-exposure with other organic solvents. In order to elucidate this mechanism further, rats were exposed to 500ppm n-hexane, 500ppm n-hexane plus 500ppm methyl ethyl ketone (MEK), 500ppm n-hexane plus 500ppm toluene, or air only for 8h per day for 33 weeks. The body weight, motor nerve conduction velocity (MCV) and distal latency (DL) were determined before exposure and after 4, 8, 12, 16, 20, 24, 29, and 33 weeks of exposure. From each group one rat was histologically examined after 33 weeks of exposure. To establish a relationship between the n-hexane neurotoxicity and changes in biotransformation, urinary metabolites (2-hexanol, methyl n-butyl ketone (MBK), 2,5-hexanedione, 2,5-dimethylfuran, and gamma-valerolactone) were measured by gas chromatography on the first exposure day, and after 1, 2, 4, 8, 12, 16, 20, 24, 29, and 33 weeks of exposure. The total amounts of metabolites of n-hexane in the urine significantly decreased upon co-exposure of n-hexane, with MEK as well as with toluene, in comparison with those of animals exposed to n-hexane alone. 2,5-Hexanedione, which is considered the ultimate neurotoxic metabolite of n-hexane, also decreased. Electrophysiological and histological studies did not reveal statistically significant differences between any two groups among the four groups. It is considered that the present results might explain the combined effects of n-hexane and toluene which decrease n-hexane neurotoxicity, but do not explain those of n-hexane and MEK. Therefore, other mechanisms of the combined effects of n-hexane and MEK should be studied. PMID:6511097

  12. Exploring the effect of fluid dynamics and kinetic mechanisms on n-heptane autoignition in transient jets

    SciTech Connect

    Viggiano, Annarita

    2010-02-15

    The influence of physical parameters and of flow patterns on the prediction of n-heptane ignition dynamic in transient reacting n-heptane jets, in high pressure environment under laminar conditions, has been explored by using different kinetic mechanisms. Some preliminary transient laminar flamelet computations have been performed, thus showing that the sensitivity of the ignition time to strain rate depends on the kinetic mechanism used. Therefore, the structure of the reacting jet, in particular the localization of ignition spots, is investigated. The results show that, if the initial temperature of the reacting mixture is out of the intermediate range (800-1000 K) towards lower values, the fluid dynamics has an essential role. In this case, the ignition delay time is almost insensitive to the specific kinetic mechanism adopted, conversely it is severely shortened by increasing the streamwise velocity. The burning spot is located in the core of fuel roll-up, where low values of scalar dissipation rate occur. Nevertheless, the most reactive mixture fraction conditions are well predicted by chemical kinetics, as they are in good agreement with those computed for the one-dimensional diffusion layer. When the initial temperature of fuel and air is increased in the intermediate range, ignition is strongly dependent on the kinetic mechanism used. In these cases, the choice of an accurate chemical scheme is fundamental in order to obtain reliable results. (author)

  13. Asymptotic analysis for the burning of n-heptane droplets using a four-step reduced mechanism

    NASA Technical Reports Server (NTRS)

    Card, J. M.

    1993-01-01

    A four-step reduced mechanism is obtained from a minimal chemical-kinetic description, where the effects of the elementary rates are treated as parameters in the expressions for the global rates. This mechanism is used to analyze the extinction characteristics of a single n-heptane droplet burning under quasi-steady, spherically symmetrical conditions. The reaction layer consists of a merged inner zone, on the fuel-rich side of the flame, where fuel and H atoms are consumed thereby producing H2 and CO along with H2O and CO2, and an oxygen-consumption zone, on the fuel-lean side, where H2 and CO are oxidized to produce additional H2O and CO2 along with H radicals. For the inner zone, a parameter mu is identified which describes the ratio of the thickness of a fuel-consumption layer to that of an H-recombination layer. Analytical solutions for the rate of scalar dissipation at extinction are obtained in the limiting cases of mu tending to 0 and mu tending to infinity. From the results of the analysis, extinction diameters for n-heptane droplets are estimated for different pressures and ambient oxygen concentrations.

  14. Plasma-enhanced chemical vapor deposition of n-heptane and methyl methacrylate for potential cell alignment applications.

    PubMed

    Steinbach, Annina; Tautzenberger, Andrea; Schaller, Andreas; Kalytta-Mewes, Andreas; Tränkle, Sebastian; Ignatius, Anita; Volkmer, Dirk

    2012-10-24

    Plasma-enhanced chemical vapor deposited polymers (plasma polymers) are promising candidates for biomaterials applications. In the present study, plasma deposition as a fast and easily scalable method was adapted to deposit coatings from n-heptane and methyl methacrylate monomers onto glass substrates. Linear patterns with line and groove widths between 1.25 and 160 μm were introduced by degrative UV-lithography for cell alignment. Differential interference contrast optical microscopy, profilometry and atomic force microscopy revealed that the patterned surfaces had a smooth, homogeneous appearance and a pattern height of 8 and 45 nm for plasma deposited n-heptane and methyl methacrylate, respectively. UV-lithography increased the oxygen content on the surface drastically as shown by X-ray photoelectron spectroscopy. After immersion in simulated body fluid for 21 days, the pattern was still intact, and the ester groups were also maintained for the most part as shown by infrared spectroscopy. To test the coatings' potential applicability for biomaterial surfaces in a preliminary experiment, we cultured murine preosteoblastic MC3T3-E1 cells on these coatings. Light and electron microscopically, a normal spindle-shaped and aligned cell morphology was observed. At the mRNA level, cells showed no signs of diminished proliferation or elevated expression of apoptosis markers. In conclusion, plasma-enhanced chemical vapor deposited polymers can be patterned with a fast and feasible method and might be suitable materials to guide cell alignment. PMID:22992135

  15. Measurement of the urinary metabolites of N-hexane, cyclohexane and their isomers by gas chromatography.

    PubMed

    Perbellini, L; Brugnone, F; Silvestri, R; Gaffuri, E

    1981-01-01

    A gas chromatographic method for analyzing the urinary metabolites of n-hexane (2-hexanol, 2,5-hexanedione, 2,5-dimethylfuran and gamma-valerolactone), of 2-methylpentane (2-methyl-2-pentanol), of 3-methylpentane (3-methyl-2-pentanol), and of cyclohexane (cyclohexanol) was developed. Processing of urine and the gas chromatographic conditions are described. The recovery rate of all hexane metabolites, except 2,5-dimethylfuran, ranged between 92 and 100%. The variation coefficient of metabolites determination was between 1.5 and 5%, apart from 2.5-dimethylfuran determination for which the variation coefficient was 15%. The detection limits ranged between 0.2 and 0.7 mg/l and between 0.05 and 0.1 mg/l when a packed or capillary column was used. Results obtained from a packed and capillary column are discussed. PMID:7216504

  16. Complex formation between excited-state saturated amines and water in n-hexane solution

    SciTech Connect

    Halpern, A.M.; Ruggles, C.J.; Zhang, X.K.

    1987-06-10

    Fluorescence spectra and decay curves of dilute solutions (<3 x 10/sup -4/ M) of triethylamine (TEA), tri-n-propylamine (TPA), and 1,4-diazabicyclo(2.2.2)octane (DABCO) in H/sub 2/O- and D/sub 2/O-saturated n-hexane reveal the presence of a complex formed between the electronically excited amine and water. The decay curves, measured between 273 and 323 K (and at 280 and 360 nm; 300 and 400 nm for DABCO), conform to the standard monomer-excimer photokinetic scheme and are analyzed accordingly. These results indicate that the binding energy of the excited TEA-H/sub 2/O complex (B*) is ca. 7.8 kcal/mol, which is larger than that of the ground-state TEA hydrate. B* for the TPA and DABCO-H/sub 2/O complexes is estimated to be ca. 10 and 8.8 kcal/mol, respectively. Stationary-state measurements are consistent with these assignments. The activation energy for the diffusion of water in n-hexane (assumed to be monomeric) appears to be very small (<1 kcal/mol). The decay constants of the three complexes studied are ca. 3.4 x 10/sup 7/ s/sup -1/ for amine-H/sub 2/O and 2.9 x 10/sup 7/ s/sup -1/ for the amine-D/sub 2/O systems. Intrinsic fluorescence quantum efficiencies of the amine-H/sub 2/O complexes are 0.17, 0.23, and 0.28 for TEA, TPA, and DABCO, respectively, at 303 K. A Foerster cycle analysis of the dry and H/sub 2/O-saturated fluorescence spectra of TEA, when taking the ground-state hydrate into account indicates that the repulsion energy of the post-fluorescence (TEA-H/sub 2/O) complex is ca. 10 kcal/mol.

  17. Effect of adamantane-containing additives on the isomerization of n-heptane in the ionic liquid trimethylammonium hydrochloride-aluminum chloride

    NASA Astrophysics Data System (ADS)

    Vasina, T. V.; Kustov, L. M.; Novakov, I. A.; Orlinson, B. S.

    2013-01-01

    We study the effect of adamantane-containing additives on the process of isomerization of n-heptane in the ionic liquid trimethylammonium hydrochloride-aluminum chloride (1 : 2 mol). It is shown that introducing 1-cyanomethyl-3-cyanoadamantane (5.0 wt %) into the reaction mixture slows conversion and lowers the yield of iso-products by a factor of more than 1.5, while adding adamantylpolyimide (0.5-5.0 wt %) substantially accelerates the isomerization of n-heptane and increases the yield of iso-products. In addition, this reaction proceeds under mild conditions at 40C in the absence of hydrogen and precious metals.

  18. Kinetic modeling of n-hexane oxyfunctionalization by hydrogen peroxide on titanium silicalites of MEL structure (TS-2)

    SciTech Connect

    Gallot, J.E.; Fu, H.; Kapoor, M.P.

    1996-07-01

    The authors present mathematical models of catalytic oxyfunctionalization of n-hexane over titanium silicalites. The model showed second-order reaction rates with respect to H{sub 2}O{sub 2} concentration in the aqueous phase. 56 refs., 7 figs., 3 tabs.

  19. Calculation of the density of solutions (sunflower oil + n-hexane) over a wide range of temperatures and pressure

    NASA Astrophysics Data System (ADS)

    Safarov, M. M.; Abdukhamidova, Z.

    1995-09-01

    We present the results from an experimental investigation of the density of the sunflower oil system as a function of the mass concentration of n-hexane in the ranges of temperatures T=290 520 K and pressures P=0.101 98.1 MPa. A method of hydrostatic weighing was used to measure the density of the solutions under study.

  20. Novel platinum/KL catalysts for the aromatization of N-hexane

    NASA Astrophysics Data System (ADS)

    Jacobs, Gary

    A number of studies were conducted to understand the underlying reasons for the uniqueness of Pt/KL for its high activity and selectivity for benzene production. Catalytic screening of basic supported Pt catalysts revealed that aromatization passes through dehydrogenated intermediates, including hexenes. Pt/KL was found to more efficiently convert hexenes to benzene than nonmicroporous basic supported Pt catalysts. The role of L-zeolite was found to protect the Pt clusters from bimolecular pathways leading to the deposition of coke on the surface of the Pt. Sulfur deactivates Pt/KL by agglomeration of Pt clusters and the formation of Pt-S, breaking up Pt ensembles required for aromatization. The role of morphology of Pt inside the L-zeolite channels was found to play an important role on catalytic stability. Series of catalysts were prepared by incipient wetness and vapor phase impregnation and characterized by a variety of techniques, including H2 chemisorption, EXAFS, FTIR of adsorbed CO, MCP ring opening, and TEM and tested by both pulse and flow mode n-hexane reaction. While both catalysts exhibited small Pt clusters inside the channels of the L-zeolite, the IWI had a fraction near the surface region large enough to block channels. Under reaction, the IWI catalysts deactivated to about half the initial activity. However, VPI had Pt clusters small enough to reside in the lobes of the ellipsoid cages of the channels; these catalysts were remarkably stable. Addition of a small amount of thulium to KL was found to aid in dispersing the Pt. Using TPO, thulium was found to act a sulfur getter. Electronic modification to Pt by exchanging the zeolite cation from potassium to lithium was studied by shape resonance XANES, microcalorimetry, and pulse neopentane hydrogenolysis. Addition of lithium resulted in a shift of the Fermi level of Pt away from the antibonding state of Pt-H, strengthening the chemisorption bond. Increased hydrogenolysis rates were observed for both neopentane and n-hexane aromatization experiments at the expense of aromatization. Finally, regeneration of Pt/KL catalysts was studied for sulfur poisoned catalysts. While air effectively burned off coke deposits, sintering of Pt resulted. An oxychlorination treatment effectively redispersed the Pt.

  1. A molecular ``phase ordering'' phase transition leading to a modulated aperiodic composite in n-heptane/urea

    NASA Astrophysics Data System (ADS)

    Mariette, C.; Huard, M.; Rabiller, P.; Nichols, Shane M.; Ecolivet, C.; Janssen, Ted; Alquist, Keith E.; Hollingsworth, Mark D.; Toudic, B.

    2012-03-01

    n-Heptane/urea is an aperiodic inclusion compound in which the ratio of host and guest repeats along the channel axis is very close to unity and is found to have a constant value (0.981) from 280 K to 90 K. Below 280 K, two phase transitions are observed. The first (Tc1 = 145 K) is a ferroelastic phase transition that generates superstructure reflections for the host while leaving the guest with 1D order. The second (Tc2 = 130 K) is a "phase ordering" transition to a four-dimensional structure (P2111(0??)) with pronounced host-guest intermodulation and a temperature dependent phase shift between guests in adjacent channels.

  2. A molecular ;phase ordering; phase transition leading to a modulated aperiodic composite in n-heptane/urea

    SciTech Connect

    Mariette, C.; Huard, M.; Rabiller, P.; Nichols, Shane M.; Ecolivet, C.; Janssen, Ted; Alquist, III, Keith E.; Hollingsworth, Mark D.; Toudic, B.

    2012-07-11

    n-Heptane/urea is an aperiodic inclusion compound in which the ratio of host and guest repeats along the channel axis is very close to unity and is found to have a constant value (0.981) from 280 K to 90 K. Below 280 K, two phase transitions are observed. The first (T{sub c1} = 145 K) is a ferroelastic phase transition that generates superstructure reflections for the host while leaving the guest with 1D order. The second (T{sub c2} = 130 K) is a 'phase ordering' transition to a four-dimensional structure (P2{sub 1}11(0{beta}{gamma})) with pronounced host-guest intermodulation and a temperature dependent phase shift between guests in adjacent channels.

  3. Lift-off stability of n-heptane jet diffusion flames in homogeneous environments of fuel and air

    SciTech Connect

    Samuel, P.; Karim, G.A.

    1995-12-31

    The lift off of jet diffusion flames of a liquid fuel in coflowing streams of air was established experimentally for a range of jet discharge and stream velocities. The improvement in the lift off stability of the flame due to the presence of a small concentration of an auxiliary gaseous fuel in the surrounding air was established. Liquid n-heptane was the jet fuel while methane, ethylene, propane and hydrogen were employed individually as the auxiliary fuels. It is shown that the lift off distance and the corresponding ignition delay of the jet flame can be correlated for all the observations made in terms of derived dimensionless grouping of the main parameters varied.

  4. NOx formation from the combustion of monodisperse n-heptane sprays doped with fuel-nitrogen additives

    NASA Technical Reports Server (NTRS)

    Sarv, Hamid; Cernansky, Nicholas P.

    1989-01-01

    A series of experiments with simulated synthetic fuels were conducted in order to investigate the effect of droplet size on the conversion of fuel-nitrogen to NOx. Pyridine and pyrrole were added to n-heptane as nitrogen-containing additives and burned as monodisperse fuel droplets under various operating conditions in a spray combustion facility. The experimental results indicate that under stoichiometric and fuel-rich conditions, reducing the droplet size increases the efficiency of fuel-N conversion to NOx. This observation is associated with improved oxidation of the pyrolysis fragments of the additive by better oxygen penetration through the droplet flame zone. The dominant reactions by which fuel-N is transformed to NOx were also considered analytically by a premixed laminar flame code. The calculations are compared to the small droplet size results.

  5. Hydrocracking of n-heptane with a NiO-MoO/sub 3//HY ultrastable zeolite as catalyst

    SciTech Connect

    Vazquez, M.I.; Escardino, A.; Aucejo, A.

    1988-11-01

    The hydrocracking of n-heptane has been studied in a continuous, tubular, plug flow reactor using a 4 wt NiO-8 wt% MoO/sub 3//HYUS zeolite as catalyst, to try to obtain a network of reactions to account for the formation of the various products observed. In view of the products obtained and depending on whether they are primary or secondary, a series of simultaneous parallel reaction schemes have been proposed to explain the network of the reaction. The kinetic parameters of these reactions have been obtained from the initial selectives of the products. The values of the apparent activation energies obtained for the isomerization, hydrogenolysis, cracking, and disproportionation reactions were 99.1, 169.6, 221.4, and 195.9 kJ/mol, respectively.

  6. A comprehensive skeletal mechanism for the oxidation of n-heptane generated by chemistry-guided reduction

    SciTech Connect

    Zeuch, Thomas; Moreac, Gladys; Ahmed, Syed Sayeed; Mauss, Fabian

    2008-12-15

    Applied to the primary reference fuel n-heptane, we present the chemistry-guided reduction (CGR) formalism for generating kinetic hydrocarbon oxidation models. The approach is based on chemical lumping and species removal with the necessity analysis method, a combined reaction flow and sensitivity analysis. Independent of the fuel size, the CGR formalism generates very compact submodels for the alkane low-temperature oxidation and provides a general concept for the development of compact oxidation models for large model fuel components such as n-decane and n-tetradecane. A defined sequence of simplification steps, consisting of the compilation of a compact detailed chemical model, the application of linear chemical lumping, and finally species removal based on species necessity values, allows a significantly increased degree of reduction compared to the simple application of the necessity analysis, previously published species, or reaction removal methods. The skeletal model derived by this procedure consists of 110 species and 1170 forward and backward reactions and is validated against the full range of combustion conditions including low and high temperatures, fuel-lean and fuel-rich mixtures, pressures between 1 and 40 bar, and local (species concentration profiles in flames, plug flow and jet-stirred reactors, and reaction sensitivity coefficients) and global parameters (ignition delay times in shock tube experiments, ignition timing in a HCCI engine, and flame speeds). The species removal is based on calculations using a minimum number of parameter configurations, but complemented by a very broad parameter variation in the process of compiling the kinetic input data. We further demonstrate that the inclusion of sensitivity coefficients in the validation process allows efficient control of the reduction process. Additionally, a compact high-temperature n-heptane oxidation model of 47 species and 468 reactions was generated by the application of necessity analysis to the skeletal mechanism. (author)

  7. Steady-state and time-resolved spectroscopic investigations on the existence of stable methanol/AOT/n-heptane reverse micelles.

    PubMed

    Wang, Jia-Pei; Chen, Jun-Sheng; Zhao, Guang-Jiu

    2014-06-01

    In this work, we have reported our study on the controversial issue whether methanol molecules can be effectively encapsulated by surfactant AOT to form true reverse micelles. We compared the different photophysical properties of coumarin 153 (C153) in methanol/AOT/n-heptane reverse micelles and methanol/n-heptane binary mixture by means of steady-state absorption, fluorescence and time-resolved fluorescence spectroscopies. In the reverse micelles, the fluorescence emission spectra of C153 were dependent on the excitation wavelength, while in binary mixtures, the excitation wavelength dependence was not observed. The biexponential decay curves of C153 in reverse micelles give a further confirmation for the two different environments where C153 molecules reside in. In other words, C153 molecules can exist both inside the core of the reverse micelles and outside of it. These results proved that the methanol can be effectively encapsulated by AOT in n-heptane solvents to form stable methanol/AOT/n-heptane reverse micelles. PMID:24703660

  8. The relevance of 4,5-dihydroxy-2-hexanone in the excretion kinetics of n-hexane metabolites in rat and man.

    PubMed

    Fedtke, N; Bolt, H M

    1987-12-01

    Male Wistar rats were exposed to n-hexane concentrations between 50 and 3000 ppm for 8 h, and urinary excretion kinetics of the n-hexane metabolites 1-hexanol, 2-hexanol, 3-hexanol, 2-hexanone, 2,5-hexanedione, and 4,5-dihydroxy-2-hexanone were assessed. The amounts of metabolites excreted were linearly dependent on the n-hexane exposure concentration, up to an exposure of about 300 ppm. Above 300 ppm exposure the metabolite excretion indicated saturation kinetics in the metabolism of n-hexane. In its quantity, the newly described 4,5-dihydroxy-2-hexanone was the second metabolite, its amount in the urine being about ten times higher than that of excreted 2,5-hexanedione. Using gas chromatography-mass spectrometry the occurrence of 4,5-dihydroxy-2-hexanone as an n-hexane metabolite in urine of man was confirmed after exposure of a male volunteer to a mean of 217 ppm n-hexane for 4 h (laboratory exposure). Twenty-six hours after starting this exposure the excretion of 4,5-dihydroxy-2-hexanone (as a result of the n-hexane exposure) reached a level which was four times higher than the excretion of 2,5-hexanedione. The results in both rat and man indicate the relevance of 4,5-dihydroxy-2-hexanone as a metabolite of n-hexane metabolism. Formation of this metabolite may be viewed as a route of detoxification. PMID:3439885

  9. Platinum-tin catalysts supported on silica highly selective for n-hexane dehydrogenation

    SciTech Connect

    Llorca, J.; Homs, N.; Sales, J.; Piscina, P.R. de la

    1997-02-01

    Silica-supported Pt-Sn catalysts were prepared by two-step impregnation from [PtCl{sub 2}(PPh{sub 3}){sub 2}] and SnCl{sub 2} solutions of appropriate concentrations to yield Pt/Sn atomic ratios ranging from 0.2 to 5.0. In these systems, the presence of true Pt-Sn alloys was confirmed by X-ray diffraction, transmission electron microscopy, energy dispersive X-ray analysis and electron nanodiffraction. Pt and PtSn alloy phases were found on catalysts with Pt/Sn > 1, PtSn alloy alone on the catalyst with Pt/Sn = 1 and PtSn and PtSn{sub 2} alloys, together with Sn in the catalysts with Pt/Sn < 1. All these catalysts were tested in the skeletal reactions of n-hexane at 753 K and atmospheric pressure. The selectivity of Pt changed significantly when alloyed with tin. For Sn-rich compositions a segregation of tin toward the catalyst surface was shown by photoelectron spectroscopy, and high hydrogenolysis selectivity and fast deactivation were observed. In contrast, Pt-rich catalysts, in which a well defined PtSn alloy was observed, were much more stable and exhibited high selectivity to dehydrogenation reaction while maintaining low conversions to benzene and hydrogenolysis products. This selectivity pattern can be interpreted in terms of a change in adsorption properties due to differences in the number of adjacent Pt atoms required for the various reaction pathways. 24 refs., 11 figs., 3 tabs.

  10. Calculating the Krichevsky function and parameter for an n-hexane + water system from direct densitometric measurements

    NASA Astrophysics Data System (ADS)

    Rasulov, S. M.; Orakova, S. M.; Abdulagatov, I. M.

    2015-01-01

    Based on experimental pVTx data, a theoretical study of the thermodynamic properties of a binary n-hexane + water system is performed for ten water concentrations (0.166, 0.201, 0.234, 0.237, 0.347, 0.615, 0.827, 0.918, 0.935, and 0.964 mole fractions of H2O) along different isochors. Constant volume piezometer measurements are made in the temperature, density, and pressure intervals of 303.65-690.55 K, 66.87-801.20 kg/m3, and 65.7 MPa. Based on the pVTx data and using different methods, the Krichevsky parameter is determined near the critical properties of the pure solvent ( n-hexane or water).

  11. A model of reduced kinetics for alkane oxidation using constituents and species: Proof of concept for n-heptane

    SciTech Connect

    Harstad, Kenneth; Bellan, Josette

    2010-08-15

    A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement in the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately scaled global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The concept is tested by using tabular information from the LLNL skeletal mechanism in conjunction with CHEMKIN II. The test reveals that the similarity concept is indeed justified and that the combustion temperature is well predicted, but that the ignition time is overpredicted. To palliate this deficiency, functional modeling is incorporated into our conceptual reduction. Due to the reduction process, models are also included for the global constituent molar density, the kinetics-induced enthalpy evolution of the heavy species, the contribution to the reaction rate of the unsteady lights from the heavies, the molar density evolution of oxygen and water, the mole fractions of the quasi-steady light species and the mean molar heat capacity of the heavy species. The model is compact in that there are only nine species-related progress variables. Results are presented comparing the performance of the model for predicting the temperature and species evolution with that of the skeletal mechanism. The model reproduces the ignition time over a wide range of equivalence ratios, initial pressure and initial temperature. (author)

  12. In Vitro Anti-Listerial Activities of Crude n-Hexane and Aqueous Extracts of Garcinia kola (heckel) Seeds

    PubMed Central

    Penduka, Dambudzo; Okoh, Anthony I.

    2011-01-01

    We assessed the anti-Listerial activities of crude n-hexane and aqueous extracts of Garcinia kola seeds against a panel of 42 Listeria isolates previously isolated from wastewater effluents in the Eastern Cape Province of South Africa and belonging to Listeria monocytogenes, Listeria grayi and Listeria ivanovii species. The n-hexane fraction was active against 45% of the test bacteria with zones of inhibition ranging between 817 mm, while the aqueous fraction was active against 29% with zones of inhibition ranging between 811 mm. The minimum inhibitory concentrations (MIC) were within the ranges of 0.0790.625 mg/mL for the n-hexane extract and 10 to >10 mg/mL for the aqueous extract. The rate of kill experiment carried out for the n-hexane extract only, revealed complete elimination of the initial bacterial population for L. grayi (LAL 15) at 3 and 4 MIC after 90 and 60 min; L. monocytogenes (LAL 8) at 3 and 4 MIC after 60 and 15 min; L. ivanovii (LEL 18) at 3 and 4 MIC after 120 and 15 min; L. ivanovii (LEL 30) at 2, 3 and 4 MIC values after 105, 90 and 15 min exposure time respectively. The rate of kill activities were time- and concentration-dependant and the extract proved to be bactericidal as it achieved a more than 3log10 decrease in viable cell counts after 2 h exposure time for all of the four test organisms at 3 and 4 MIC values. The results therefore show the potential presence of anti-Listerial compounds in Garcinia kola seeds that can be exploited in effective anti-Listerial chemotherapy. PMID:22072929

  13. Inhalation reproductive toxicology studies: Male dominant lethal study of n-hexane in Swiss (CD-1) mice: Final report

    SciTech Connect

    Mast, T.J.; Rommereim, R.L.; Evanoff, J.J.; Sasser, L.B.; Decker, J.R.; Stoney, K.H.; Weigel, R.J.; Westerberg, R.B.

    1988-08-01

    The straight-chain hydrocarbon, n-hexane, is a volatile, ubiquitous solvent routinely used in industrial environments; consequently, the opportunity for industrial, environmental or accidental exposure to hexane vapors is significant. Although myelinated nerve tissue is the primary target organ of hexane, the testes have also been identified as being sensitive to hexacarbon exposure. The objective of this study was to evaluate male dominant lethal effects in Swiss (CD-1) mice after exposure to 0, 200, 1000, or 5000 ppM n-hexane, 20 h/day for 5 consecutive days. Each exposure concentration consisted of 30 randomly selected, proven male breeders; 4 groups. The mice were weighed just prior to the first day of exposure and at weekly intervals until sacrifice. Ten males in each dose group were sacrificed one day after the cessation of exposure, and their testes and epididymides were removed for evaluation of the germinal epithelium. The remaining male mice, 20 per group, were individually housed in hanging wire-mesh breeding cages where they were mated with unexposed, virgin females for eight weekly intervals; new females were provided each week. The mated females were sacrificed 12 days after the last day of cohabitation and their reproductive status and the number and viability of the implants were recorded. The appearance and behavior of the male mice were unremarkable throughout the study period and no evidence of n-hexane toxicity was observed. 18 refs., 3 figs., 11 tabs.

  14. Evolution of the isotropic to nematic phase transition in binary mixtures of octylcyanobiphenyl and n-hexane

    NASA Astrophysics Data System (ADS)

    Sigdel, K. P.; Iannacchione, G. S.

    2010-07-01

    High-resolution calorimetry has been performed to study the effect of dilution by a nonmesogenic, low-molecular weight solvent (linear n-hexane) on the isotropic-nematic (I-N) phase transition in the liquid crystal (LC) octylcyanobiphenyl (8CB) as a function of n-hexane concentration. Numerous temperature scans were performed without continuous mixing for pure 8CB and all mixture samples of n-hexane mole fraction ranging from xhex=0.02 to 0.12. The I-N specific heat peak remains first-order for all samples and shifts toward lower temperature nonlinearly while the two-phase I +N coexistence width broadens linearly with increasing xhex. Multiple heating and cooling scans are reproducible and indicate phase separation, if it occurs, must be on very short length scales and is reversible. These results may be a consequence of a competition between random dilution effects and the tendency to phase separate. It is shown that solvent dilution of a LC, if miscible and depending on solvent structure, can lead to a controlled altering of the intermolecular potentials and softening of the LC viscoelastic properties.

  15. The effect of Sn on the reactions of n-hexane and cyclohexane over polycrystalline Pt foils

    SciTech Connect

    Fujikawa, T.; Ribeiro, F.H.; Somorjai, G.A.

    1998-08-15

    The modification of the catalytic properties of a polycrystalline platinum foil by the addition of tin was studied by the reactions of n-hexane and cyclohexane in excess H{sub 2}. The reactions were studied at 13.3 kPa of n-hexane, 450 kPa of H{sub 2} and 740 K, and 6.7 kPa of cyclohexane, 450 kPa of H{sub 2} and 573 K. The Pt-Sn catalyst was characterized by Auger electron spectroscopy and by temperature-programmed desorption of CO before and after the reactions. The sites that bind CO most strongly on the Pt foil also have the highest initial turnover rate and are the first ones to be poisoned by carbon deposits from hydrocarbon reactions or by sulfur when a sulfur-containing compound (thiophene) is present in the feed. The addition of tin can block these sites preferentially, thus decreasing the undesirable high initial hydrogenolysis rate of platinum catalysts in reforming reactions and eliminating the need for presulfiding the catalyst. Also, tin suppressed the hydrogenolysis reaction preferentially to the isomerization and cyclization reactions thus increasing the selectivities to isomerization and cyclization. The amount of carbon deposited was smaller on tin containing platinum catalysts during the dehydrogenation of cyclohexane and n-hexane.

  16. Analysis of petroleum contaminated soils by spectral modeling and pure response profile recovery of n-hexane.

    PubMed

    Chakraborty, Somsubhra; Weindorf, David C; Li, Bin; Ali, Md Nasim; Majumdar, K; Ray, D P

    2014-07-01

    This pilot study compared penalized spline regression (PSR) and random forest (RF) regression using visible and near-infrared diffuse reflectance spectroscopy (VisNIR DRS) derived spectra of 164 petroleum contaminated soils after two different spectral pretreatments [first derivative (FD) and standard normal variate (SNV) followed by detrending] for rapid quantification of soil petroleum contamination. Additionally, a new analytical approach was proposed for the recovery of the pure spectral and concentration profiles of n-hexane present in the unresolved mixture of petroleum contaminated soils using multivariate curve resolution alternating least squares (MCR-ALS). The PSR model using FD spectra (r(2)=0.87, RMSE=0.580 log10mgkg(-1), and residual prediction deviation=2.78) outperformed all other models tested. Quantitative results obtained by MCR-ALS for n-hexane in presence of interferences (r(2)=0.65 and RMSE 0.261 log10mgkg(-1)) were comparable to those obtained using FD (PSR) model. Furthermore, MCR ALS was able to recover pure spectra of n-hexane. PMID:24686115

  17. OH time-histories during oxidation of n-heptane and methylcyclohexane at high pressures and temperatures

    SciTech Connect

    Vasu, Subith S.; Davidson, David F.; Hanson, Ronald K.

    2009-04-15

    OH concentration time-histories during n-heptane and methylcyclohexane (MCH) oxidation were measured behind reflected shock waves in a heated, high-pressure shock tube. Experimental conditions covered temperatures of 1121 to 1332 K, pressures near 15 atm, and initial fuel concentrations of 750 and 1000 ppm (by volume), and an equivalence ratio of 0.5 with O{sub 2} as the oxidizer and argon as the bath gas. OH concentrations were measured using narrow-linewidth ring-dye laser absorption near the R-branchhead of the OH A-X(0,0) system at 306.47 nm. These current measurements together with our recent results for n-dodecane oxidation [S.S. Vasu, D.F. Davidson, Z. Hong, V. Vasudevan, R.K. Hanson, Proc. Combust. Inst. 32 (2009), doi:10.1016/j.proci.2008.05.006] provide critically needed validation targets for jet fuel surrogate kinetic mechanisms and further improve understanding of high-pressure, high-temperature oxidation chemistry. Detailed comparisons of these OH time-histories with the predictions of various kinetic mechanisms were made. Sensitivity and pathway analyses for these reference fuel components were performed, leading to reaction rate recommendations with improved model performance. Current results are the first quantitative measurements of OH time-histories during high-pressure oxidation of these fuels, and hence are a critical step toward development of accurate reaction models for jet fuel surrogates. (author)

  18. Measurements and simulations of mixing and autoignition of an n-heptane plume in a turbulent flow of heated air

    SciTech Connect

    Markides, C.N.; De Paola, G.; Mastorakos, E.

    2007-04-15

    The autoignition of a gaseous n-heptane plume in heated turbulent air has been investigated experimentally and numerically with the conditional moment closure and a CFD code. It has been demonstrated that, consistent with previous experimental results for hydrogen and acetylene, the increased scalar dissipation rate created by faster co-flowing air delays autoignition, as revealed by a disproportionate increase of ignition length with air velocity. The predicted mean and variance of the mixture fraction, the mixture fraction PDF and the conditional scalar dissipation rate are in good agreement with experimental results obtained with acetone-tracer PLIF. The first-order, spatially averaged CMC model reproduces the experimental trends quite well, despite the neglect of conditional fluctuations and spatial dependence of the conditional averages. This is attributed to the fact that for a significant period of time before autoignition the conditional scalar dissipation rate at the most reactive mixture fraction is much smaller than the critical value above which autoignition is precluded. (author)

  19. Linear time reduction of large kinetic mechanisms with directed relation graph: n-Heptane and iso-octane

    SciTech Connect

    Lu, Tianfeng; Law, Chung K.

    2006-01-01

    The algorithm of directed relation graph recently developed for skeletal mechanism reduction was extended to overall linear time operation, thereby greatly facilitating the computational effort in mechanism reduction, particularly for those involving large mechanisms. Together with a two-stage reduction strategy and using the kinetic responses of autoignition and perfectly stirred reactor (PSR) with extensive parametric variations as the criteria in eliminating unimportant species, a detailed 561-species n-heptane mechanism and a detailed 857-species iso-octane mechanism were successfully reduced to skeletal mechanisms consisting of 188 and 233 species, respectively. These skeletal mechanisms were demonstrated to mimic well the performance of the detailed mechanisms, not only for the autoignition and PSR systems based on which the reduced mechanisms were developed but also for the independent system of jet-stirred reactor. It was further observed that the accuracy of calculated species concentrations was equivalently bounded by the user-specified error threshold value and that the reduction time for a single reaction state is only about 50 ms for the large iso-octane mechanism.

  20. Environmentally friendly efficient coupling of n-heptane by sulfated tri-component metal oxides in slurry bubble column reactor.

    PubMed

    Ma, Hongzhu; Xiao, Jing; Wang, Bo

    2009-07-30

    SO(4)(2-)/M(x)O(y) is of the greatest interest in solid catalysts and green catalysts. Slurry bubble column reactors are of considerable interest in industrial processes and various biochemical processes. The cetane number (CN) has widely used diesel fuel quality parameter related to the ignition delay time (and combustion quality) of a fuel. CN improvement of diesel fuels is a difficult task that refiners will face in the near future. For that purpose, the tests were designed in which n-heptane is used as the reactant in the air or ozone atmosphere at room temperature (RT) and local atmospheric pressure (LAP) using different catalysts of sulfated tri-component metal oxides SO(4)(2-)/Fe(2)O(3)-TiO2-SnO(2) (SFTSn) and SO(4)(2-)/MnO(2)-TiO2-SnO(2) (SMTSn) in slurry bubble column reactor. The products distribution was analyzed by gas chromatography-mass spectrometry (GC-MS) method and the results show that the relative selectivity of long linear alkane (C(12)-C(28)) reaches the maximum (87.330%) when SMTSn is used as catalyst in flow air at 60 min. Diesel fuel components with higher cetane numbers can be easily obtained from this study. PMID:19124196

  1. Structure sensitivity of n-heptane dehydrocyclization and hydrogenolysis catalyzed by platinum single crystals at atmospheric pressure

    SciTech Connect

    Gillespie, W.D.; Herz, R.K.; Petersen, E.E.; Somorjai, G.A.

    1981-07-01

    The dehydrocyclization and hydrogenolysis of n-heptane catalyzed by platinum single-crystal surfaces have been investigated at temperatures from 533 to 603 K in the range of 1 atm total pressure. The flat (111), stepped (557), and kinked (10, 8, 7) and (25, 10, 7) surfaces used in this study were characterized under ultrahigh vacuum by low-energy electron diffraction and Auger electron spectroscopy before and after reaction experiments. The initial rate of dehydrocyclization to toluene on the four surfaces increased in the selectivity of toluene production versus hydrogenolysis increased by an order of magnitude in the order (111) approx. = (25, 10, 7) < (557) approx. = (10, 8, 7). Hydrogenolysis, however, increased in the order (557) < (10, 8, 7) < (25,10,7). As a result, the selectivity of toluene production versus hydrogenslysis increased by an order of magnitude in the orders (25, 10, 7) < (111) < (10, 8, 7) < (557). The sum of the rates of hydrogenolysis and toluene production remains relatively constant. The effect of preoxidation of the single-crystal catalysts was to increase the rate of hydrogenolysis and decrease the rate of dehydrocyclization. In general, the reaction rates decreased with increasing reaction time. This decrease was shown to be the result of the deposition of irreversibly adsorbed carbonaceous species.

  2. THE STRUCTURE SENSITIVITY OF n-HEPTANE DEHYDROCYCLIZATION AND HYDROGENOLYSIS CATALYZED BY PLATINUM SINGLE CRYSTALS AT ATMOSPHERIC PRESSURE

    SciTech Connect

    Gillespie, W. D.; Herz, R. K.; Petersen, E. E.; Somorjai, G. A.

    1980-09-01

    The dehydrocyclization and hydrogenolysis of n~heptane catalyzed by platinum single crystal surfaces have been investigated at temperatures from 533 to 603 K in the range of one atmosphere total pressure, The flat (111), stepped (557), and kinked (10,8,7) and (25,10,7) surfaces used tn this study were characterized in ultrahigh vacuum by low energy electron diffraction and Auger electron spectroscopy before and after reaction experiments. The rate of dehydrocyclization to toluene on the four surfaces increased in the order (111) (25,10,7) (557) (10,8,7), Hydrogenolysis, however, increased in the order (557) (10,8,7) (111) (25,10,7), As a result, the selectivity of toluene production versus hydrogenolysis increased by an order of magnitude in the order (25,10,7) (111) (10,8,7) (557). The sum of the rates of hydrogenolysis and toluene production remains relatively constant. The effect of preoxidation of the single crystal catalysts was to increase the rate of hydrogenolysis and decrease the rate of dehydrocyclization, Iri general, the reaction rates decreased with increasing reaction time. This decrease was shown to be the result of the depositon of irreversibly adsorbed carbonaceous species.

  3. Application of headspace solid phase dynamic extraction gas chromatography/mass spectrometry (HS-SPDE-GC/MS) for biomonitoring of n-heptane and its metabolites in blood.

    PubMed

    Rossbach, Bernd; Kegel, Peter; Letzel, Stephan

    2012-04-25

    Solid phase dynamic extraction (SPDE) is an innovative sample preparation and enrichment technique in connection with gas chromatography (GC). Using SPDE, we developed a method for simultaneous determination of n-heptane and its mono-oxygenated metabolites heptane-4-one, 3-one, 2-one, 4-ol, 3-ol, 2-ol, and 1-ol in blood. After adjustment of various extraction and desorption parameters, method validation resulted in limits of detection (LOD) between 0.006 (heptane-4-one) and 0.021mg/L (heptane-1-ol). Intra-assay coefficients of variation ranged between 4.8% and 20.8% while relative recovery ranged between 100% and 117% (spiked concentration 0.128mg/L, n=8). The method was applied to blood samples, which have been collected from 20 volunteers after controlled inhalative exposure to 167, 333, and 500ppm n-heptane. After 3h of exposure, n-heptane and heptane-2-one were detectable in all samples in concentrations ranging up to 2.903 and 0.495mg/L, while the concentrations of the remaining analytes were closer to the respective LOD or even below. A significant linear relationship with ambient exposure (R(2)=0.701, p<0.001, n=55) was found for n-heptane in blood, which could be helpful for evaluation of biological exposure limits in future. Due to its high abundance in blood, 2-heptanone could be an interesting candidate as a biomarker also in alternative matrices such as urine or saliva. PMID:21903155

  4. Theoretical Basis for Estimated Test Times and Conditions for Drop Tower and Space-Based Droplet Burning Experiments With Methanol and N-Heptane

    NASA Technical Reports Server (NTRS)

    Marchese, Anthony J.; Dryer, Fredrick L.; Choi, Mun Y.

    1994-01-01

    In order to develop an extensive envelope of test conditions for NASA's space-based Droplet Combustion Experiment (DCE) as well those droplet experiments which can be performed using a drop tower, the transient vaporization and combustion of methanol and n-heptane droplets were simulated using a recently developed fully time-dependent, spherically symmetric droplet combustion model. The transient vaporization of methanol and n-heptane was modeled to characterize the instantaneous gas phase composition surrounding the droplet prior to the introduction of an ignition source. The results for methanol/air showed that the entire gas phase surrounding a 2 mm methanol droplet deployed in zero-g .quickly falls outside the lean flammability limit. The gas phase surrounding an identically-sized n-heptane droplet, on the other hand, remains flammable. The combustion of methanol was then modeled considering a detailed gas phase chemical kinetic mechanism (168 steps, 26 species) and the effect of the dissolution of flame-generated water into the liquid droplet. These results were used to determine the critical ignition diameter required to achieve quasi-steady droplet combustion in a given oxidizing environment. For droplet diameters greater than the critical ignition diameter, the model predicted a finite diameter at which the flame would extinguish. These extinction diameters were found to vary significantly with initial droplet diameter. This phenomenon appears to be unique to the transient heat transfer, mass transfer and chemical kinetics of the system and thus has not been reported elsewhere to date. The extinction diameter was also shown to vary significantly with the liquid phase Lewis number since the amount of water present in the droplet at extinction is largely governed by the rate at which water is transported into the droplet via mass diffusion. Finally, the numerical results for n-heptane combustion were obtained using both 2 step and 96 step semi-emperical chemical kinetic mechanisms. Neither mechanism exhibited the variation of extinction diameter with initial diameter.

  5. Experimental Study of the Density and Viscosity of n-Heptane at Temperatures from 298 K to 470 K and Pressure upto 245 MPa

    NASA Astrophysics Data System (ADS)

    Sagdeev, D. I.; Fomina, M. G.; Mukhamedzyanov, G. Kh.; Abdulagatov, I. M.

    2013-01-01

    The density and viscosity of n-heptane have been simultaneously measured over the temperature range from 298 K to 470 K and at pressures up to 245 MPa using the hydrostatic weighing and falling-body techniques, respectively. The expanded uncertainty of the density, pressure, temperature, and viscosity measurements at the 95 % confidence level with a coverage factor of k= 2 is estimated to be 0.15 % to 0.30 %, 0.05 %, 0.02 K, and 1.5 % to 2.0 % (depending on temperature and pressure ranges), respectively. The measured densities were used to develop a Tait-type equation of state for liquid n-heptane. Theoretically based Arrhenius-Andrade and Vogel-Tamman-Fulcher type equations with pressure-dependent coefficients were used to describe the temperature and pressure dependences of the measured viscosities for liquid n-heptane. The measured values of the density and viscosity were compared in detail with reported data and with the values calculated from a reference EOS and correlation models for the viscosity.

  6. Droplet-droplet interactions investigated using a combination of electrochemical and dynamic light scattering techniques. The case of water/BHDC/benzene:n-heptane system.

    PubMed

    Florez Tabares, Jun Sebastin; Correa, N Mariano; Silber, Juana J; Sereno, Leonides E; Molina, Patricia G

    2015-04-21

    In this contribution the electrochemistry of [Fe(CN)6](4-/3-) as the probe molecule was investigated in benzyl-n-hexadecyldimethylammonium chloride (BHDC) reverse micelles (RMs) varying the composition of the external solvent (benzene:n-heptane mixtures) and the surfactant concentration, at a fixed water content and probe concentration. The electrochemical and dynamic light scattering results show that in water/BHDC/benzene:n-heptane systems the aggregate sizes increase on increasing BHDC concentration. This behavior was unexpected since it is known that for water/BHDC/benzene RM systems keeping the water content constant and the surfactant concentration below 0.2 M, the droplet sizes are independent of the concentration of the surfactant. We explain the results considering that on changing the external solvent to benzene:n-heptane mixtures, RMs tend to associate in clusters and equilibrium between free RMs and droplet clusters is established. A model is presented which, using electrochemical and dynamic light scattering data, allows calculating the aggregation number of the RMs, the number of RMs that form the droplet clusters and the standard electron transfer heterogeneous rate constant. PMID:25727358

  7. Combustion Characteristics in a Non-Premixed Cool-Flame Regime of n-Heptane in Microgravity

    NASA Technical Reports Server (NTRS)

    Takahashi, Fumiaki; Katta, Viswanath R.; Hicks, Michael C.

    2015-01-01

    A series of distinct phenomena have recently been observed in single-fuel-droplet combustion tests performed on the International Space Station (ISS). This study attempts to simulate the observed flame behavior numerically using a gaseous n-heptane fuel source in zero gravity and a time-dependent axisymmetric (2D) code, which includes a detailed reaction mechanism (127 species and 1130 reactions), diffusive transport, and a radiation model (for CH4, CO, CO2, H2O, and soot). The calculated combustion characteristics depend strongly on the air velocity around the fuel source. In a near-quiescent air environment (< or = 2 mm/s), with a sufficiently large fuel injection velocity (1 cm/s), a growing spherical diffusion flame extinguishes at ˜1200 K due to radiative heat losses. This is typically followed by a transition to the low-temperature (cool-flame) regime with a reaction zone (at ˜700 K) in close proximity to the fuel source. The 'cool flame' regime is formed due to the negative temperature coefficient in the low-temperature chemistry. After a relatively long period (˜18 s) of the cool flame regime, a flash re-ignition occurs, associated with flame-edge propagation and subsequent extinction of the re-ignited flame. In a low-speed (˜3 mm/s) airstream (which simulates the slight droplet movement), the diffusion flame is enhanced upstream and experiences a local extinction downstream at ˜1200 K, followed by steady flame pulsations (˜0.4 Hz). At higher air velocities (4-10 mm/s), the locally extinguished flame becomes steady state. The present axisymmetric computational approach helps in revealing the non-premixed 'cool flame' structure and 2D flame-flow interactions observed in recent microgravity droplet combustion experiments.

  8. [An experimental study on the neurotoxicity of 2-octanone and 2-hexanol, a metabolite of n-hexane].

    PubMed

    Misumi, J; Nagano, M; Nomura, S

    1982-09-01

    An electrophysiological study of the neurotoxicity of 2-octanone (an analogue of methyl n-butyl ketone) and 2-hexanol (a metabolite of n-hexane) was conducted on rats as a part of the study to determine the specific molecular arrangement required for the development of peripheral neuropathy. The compound 2-octanone or 2-hexanol was administered subcutaneously in the daily dose of 400 mg/kg of each compound into the back of seven rats, weighing 290 g, 5 days per week for a period of 21 weeks. Animals treated with 2-octanone for 21 weeks failed to exhibit apparent clinical and neurophysiological evidence except a slight inhibition of weight gain and narcotic effects after treatment with the compound. The same doses of 2-hexanol for 21 weeks caused hypersalivation, gait disturbances, crossing phenomena of hind limbs and a failure of normal growth. Retardation of the conduction velocity in the motor and sensory nerve fibers and the prolonged motor latencies of the tail nerves (distal part) began to appear at the 14th week of the experiment when 9.6 g in the total dose had been given to each animal. These changes were intensified in the subsequent course of the experiment. Our previous experiments and the present results showed that n-hexane barely produced peripheral neuropathy in doses over 10.5 g, and that 2-hexanone (MBK), 2,5-hexanediol or 2,5-hexanedione never failed to produce a neuropathy even in doses less than 9.6 g of each compound. The above results suggest that the neurotoxic potency of 2-hexanol is greater than that of n-hexane but less than that of MBK, 2,5-hexanediol or 2,5-hexanedione. PMID:6296504

  9. Hydrocarbon fuel effects in solid-oxide fuel cell operation: an experimental and modeling study of n-hexane pyrolysis.

    PubMed

    Randolph, Katie L; Dean, Anthony M

    2007-08-21

    Pyrolysis experiments of n-hexane were performed and the product distribution and fuel consumption were measured as a function of temperature. The experimental temperatures ranged from 550-675 degrees C, with a pressure of approximately 1 atm, and residence times of approximately 5 s. N-Hexane was used as a model compound to represent the linear alkanes that might be found in practical hydrocarbon fuels. Under these conditions, high fuel conversion was observed at the higher temperatures and a wide range of products were formed. The experimental observations were compared to predictions from a plug-flow model using a reaction mechanism consisting of 205 species and 1403 reactions. The hydrogen abstraction and isomerization rate coefficients in this model were based on CBS-QB3 calculations. The only model modification was adjustment of the A-factor of the initiation rates to match conversion at one temperature. This model was able to successfully predict the observed trends in both product selectivities as well as fuel conversion over the temperature range. The mechanism was also used to capture the trends previously observed in n-butane pyrolysis under similar experimental conditions. Significant differences in the sensitivity coefficients for the hexane and butane systems are discussed in terms of the competition between beta-scission and isomerization of the initial radicals formed. The kinetic model predicts that n-hexane will be completely converted within 0.1 s in the higher temperature environment ( approximately 800 degrees C) of the anode channel of a solid-oxide fuel cell (SOFC). This result clearly illustrates the need to explicitly account for gas-phase reactions in SOFC models for those cases where hydrocarbons, especially those larger than methane, are fed directly to an SOFC. PMID:17687473

  10. Determination of urinary 2,5-hexanedione concentration by an improved analytical method as an index of exposure to n-hexane.

    PubMed Central

    Saito, I; Shibata, E; Huang, J; Hisanaga, N; Ono, Y; Takeuchi, Y

    1991-01-01

    2,5-Hexanedione is a main metabolite of n-hexane and is considered as the cause of n-hexane polyneuropathy. Therefore, it is useful to measure 2,5-hexanedione for biological monitoring of exposure to n-hexane. The analytical methods existing for n-hexane metabolites, however, were controversial and not established enough. Hence, a simple and precise method for determination of urinary 2,5-hexanedione has been developed. Five ml of urine was acidified to pH 0.5 with concentrated hydrochloric acid and heated for 30 minutes at 90-100 degrees C. After cooling in water, sodium chloride and dichloromethane containing internal standard were added. The sample was shaken and centrifuged. 2,5-Hexanedione concentration in an aliquot of dichloromethane extract was quantified by gas chromatography using a widebore column (DB-1701). Urinary concentration of 2,5-hexanedione showed a good correlation with exposure to n-hexane (n = 50, r = 0.973, p less than 0.001). This method is simple and precise for analysis of urinary 2,5-hexanedione as an index of exposure to n-hexane. PMID:1878315

  11. Determination of urinary 2,5-hexanedione concentration by an improved analytical method as an index of exposure to n-hexane.

    PubMed

    Saito, I; Shibata, E; Huang, J; Hisanaga, N; Ono, Y; Takeuchi, Y

    1991-08-01

    2,5-Hexanedione is a main metabolite of n-hexane and is considered as the cause of n-hexane polyneuropathy. Therefore, it is useful to measure 2,5-hexanedione for biological monitoring of exposure to n-hexane. The analytical methods existing for n-hexane metabolites, however, were controversial and not established enough. Hence, a simple and precise method for determination of urinary 2,5-hexanedione has been developed. Five ml of urine was acidified to pH 0.5 with concentrated hydrochloric acid and heated for 30 minutes at 90-100 degrees C. After cooling in water, sodium chloride and dichloromethane containing internal standard were added. The sample was shaken and centrifuged. 2,5-Hexanedione concentration in an aliquot of dichloromethane extract was quantified by gas chromatography using a widebore column (DB-1701). Urinary concentration of 2,5-hexanedione showed a good correlation with exposure to n-hexane (n = 50, r = 0.973, p less than 0.001). This method is simple and precise for analysis of urinary 2,5-hexanedione as an index of exposure to n-hexane. PMID:1878315

  12. Catalytic performance of V2O5-MoO3/γ-Al2O3 catalysts for partial oxidation of n-hexane1

    NASA Astrophysics Data System (ADS)

    Mahmoudian, R.; Khodadadi, Z.; Mahdavi, Vahid; Salehi, Mohammed

    2016-01-01

    In the current study, a series of V2O5-MoO3 catalyst supported on γ-Al2O3 with various V2O5 and MoO3 loadings was prepared by wet impregnation technique. The characterization of prepared catalysts includes BET surface area, powder X-ray diffraction (XRD), and oxygen chemisorptions. The partial oxidation of n-hexane by air over V2O5-MoO3/γ-Al2O3 catalysts was carried out under flow condition in a fixed bed glass reactor. The effect of V2O5 loading, temperature, MoO3 loading, and n-hexane LHSV on the n-hexane conversion and the product selectivity were investigated. The partial oxygenated products of n-hexane oxidation were ethanol, acetic anhydride, acetic acid, and acetaldehyde. The 10% V2O5-1%MoO3/γ-Al2O3 was found in most active and selective catalyst during partial oxidation of n-hexane. The results indicated that by increasing the temperature, the n-hexane conversion increases as well, although the selectivity of the products passes through a maximum by increasing the temperature.

  13. Rat lung and liver microsomal cytochrome P-450 isozymes involved in the hydroxylation of n-hexane.

    PubMed

    Toftgrd, R; Haaparanta, T; Eng, L; Halpert, J

    1986-11-01

    The primary metabolism of n-hexane in rat lung and liver microsomes was investigated. In liver microsomes from untreated animals the formation of each of the metabolites, 1-, 2- and 3-hexanol, was best described kinetically by a two-enzyme system, whereas for lung microsomes a one-enzyme system was indicated for each metabolite. Cytochrome P-450-PB-B, the major cytochrome P-450 isozyme induced in rat liver by phenobarbital, appeared to be responsible for the formation of 2- and 3-hexanol in lung microsomes from untreated rats as judged by antibody inhibition studies. The presence of this isozyme was confirmed by immunoblotting. In contrast, formation of 1-hexanol in rat lung was catalyzed by a cytochrome P-450 isozyme different from the major isozymes induced by either phenobarbital or beta-naphthoflavone. Similarly, formation of 2,5-hexanediol from 2-hexanol was catalyzed by a P-450 isozyme different from cytochrome P-450-PB-B and present in liver but not in lung microsomes. Furthermore, alcohol dehydrogenase activity with hexanols or hexanediol as the substrate was found exclusively in liver cytosol. These results suggest that inhaled n-hexane must be transported to the liver either intact or in the form of 2-hexanol before the neurotoxic metabolite 2,5-hexanedione can be formed. PMID:3778502

  14. Preferred orientation of n -hexane crystallized in silicon nanochannels: A combined x-ray diffraction and sorption isotherm study.

    PubMed

    Henschel, Anke; Kumar, Pushpendra; Hofmann, Tommy; Knorr, Klaus; Huber, Patrick

    2009-03-01

    We present an x-ray diffraction study on n -hexane in tubular silicon channels of approximately 10 nm diameter both as a function of the filling fraction f of the channels and as a function of temperature. Upon cooling, confined n -hexane crystallizes in a triclinic phase typical of the bulk crystalline state. However, the anisotropic spatial confinement leads to a preferred orientation of the confined crystallites, where the 001 crystallographic direction coincides with the long axis of the channels. The magnitude of this preferred orientation increases with the filling fraction, which corroborates the assumption of a Bridgman-type crystallization process being responsible for the peculiar crystalline texture. This growth process predicts for a channel-like confinement an alignment of the fastest crystallization direction parallel to the long channel axis. It is expected to be increasingly effective with the length of solidifying liquid parcels and thus with increasing f . In fact, the fastest solidification front is expected to sweep over the full silicon nanochannel for f=1 , in agreement with our observation of a practically perfect texture for entirely filled nanochannels. PMID:19391998

  15. Crystallization of thin water films on graphite: Effects of n-hexane, formaldehyde, acetone, and methanol additives

    NASA Astrophysics Data System (ADS)

    Souda, Ryutaro

    2015-12-01

    Interactions of molecular additives with amorphous solid water have been investigated using time-of-flight secondary ion mass spectrometry and temperature programmed desorption. The crystallization temperature of water on a clean graphite substrate decreases from the bulk value of 160 K to 150 K when water deposition temperature increases from 20 K to 100 K. This phenomenon is induced by the formation of a specifically oriented water layer at the interface, as evidenced by that a submonolayer of n-hexane adspecies on graphite quenches this behavior. Thermal desorption spectra of additives reflect their hydration forms. The n-hexane molecules are trapped in the interior of a porous water film via hydrophobic hydration and released explosively during crystallization. The thermal desorption spectra of methanol resemble those of water from multilayer films because methanol can enter the hydrogen-bond network of water via hydrophilic hydration. The hydration of formaldehyde is hydrophobic in nature despite the presence of the polar carbonyl group. Features of both hydrophilic and hydrophobic hydrations are identifiable in acetone-water interactions; the branching ratio depends on the water preparation method and substrate.

  16. Influence of metal-support interactions on the reaction of n-hexane over supported Pt catalysts

    SciTech Connect

    Anderson, J.B.F.; Burch, R.; Cairns, J.A.

    1987-10-01

    The hydrogenolysis and skeletal rearrangement reactions of n-hexane have been investigated on Pt catalysts supported on silica and titania. The results show that the product distribution is dependent on the choice of support but that Pt/titania catalysts in the normal state are similar to Pt/titania catalysts in the strong metal-support interaction (SMSI) state. It is observed that in the SMSI state, when more than 99% of the Pt is inaccessible to hydrogen, the activity is only slightly reduced. Surprisingly, the selectivity for hydrogenolysis versus skeletal isomerization is almost the same in normal and in SMSI catalysts. The results provide evidence that the same active center is involved in both the hydrogenolysis and the skeletal rearrangement reactions, and do not support the contention that hydrogenolysis requires a larger ensemble of Pt atoms than skeletal rearrangement. The results are interpreted in terms of an active center consisting of a single Pt atom located in the planes of the small Pt crystallites. The precise selectivity observed may depend on the local environment of the Pt atom during the sojourn of the n-hexane molecule on the active center.

  17. Reflectometric measurement of n-hexane adsorption on ZnO2 nanohybrid film modified by hydrophobic gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Seb?k, Dniel; Csap, Edit; brahm, Nra; Dkny, Imre

    2015-04-01

    Zinc-peroxide/poly(styrenesulfonate) nanohybrid thin films (containing 20 bilayers: [ZnO2/PSS]20, d ? 500 nm) were prepared using layer-by-layer (LbL) method. The thin film surface was functionalized by different surface modifying agents (silanes, alkylthiols and hydrophobized nanoparticles). Based on the experimental results of quartz crystal microbalance (QCM) and contact angle measurements (as prequalifications) the octanethiol covered gold nanoparticles (OT-AuNPs) were selected for further vapour adsorption studies. Reflectometric interference spectroscopy (RIfS) was used to measure n-hexane vapour adsorption on the original and modified nanohybrid films in a gas flow platform. The thin film provides only the principle of the measurement (by interference phenomenon), the selectivity and hydrophobicity is controlled and enhanced by surface functionalization (by dispersion interaction between the alkyl chains). The interference pattern shift (??) caused by the increase of the optical thickness of the thin film due to vapour adsorption was investigated. It was found that due to the surface functionalization by hydrophobic nanoparticles the effect of water vapour adsorption decreased significantly, while for n-hexane opposite tendency was observed (the effective refractive index and thus the interference pattern shift increased drastically). The correlation between QCM technique and optical method (RIfS) was specified: linear specific adsorbed amount vs. wavelength shift calibration curves were determined in the pr = 0-0.4 relative vapour pressure range. The thin film is suitable for sensorial application (e.g. volatile organic compound/VOC sensor).

  18. How TOPO affects the interface of the novel mixed water/AOT:TOPO/n-heptane reverse micelles: dynamic light scattering and Fourier transform infrared spectroscopy studies.

    PubMed

    Odella, Emmanuel; Falcone, R Daro; Silber, Juana J; Correa, N Mariano

    2014-08-01

    In this work we report for the first time the formation of two reverse micelle (RM) media produced by the nonionic surfactant tri-n-octyl phosphine oxide (TOPO) in n-heptane and the one produced by mixing the anionic sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT) with different TOPO contents dissolved in n-heptane. Dynamic light scattering (DLS) experiments reveal the formation of water/TOPO/n-heptane RMs (TOPO RMs) and water/AOT:TOPO/n-heptane RMs (mixed RMs) since the droplet sizes increase as the water content increases. The addition of TOPO to the system at constant W0 (W0 = [water]/([AOT] + [TOPO])) causes the droplet sizes of mixed RMs to decrease compared with the AOT RMs. In addition, the decrease is larger when the water content is low (W0 = 0.5) but the effect is negligible at the maximum W0 value analyzed (W0 = 2). These results are not expected for mixtures of different nonionic surfactants with AOT and were explained considering the unique TOPO structure. Thus, at W0 = 0.5, we suggest that the percentage of TOPO molecules at the mixed RM interface is higher than those corresponding to the bulk solution. On the other hand, at W0 = 2 the RM interface is comprised mainly of AOT molecules. The FT-IR experiments performed by monitoring monodeuterated water frequency (?(OD)) in TOPO RMs show bound and "bulk-like" water structure even at very low water content. On the other hand, for mixed RMs the water structure depends on the water content. At low W0 value, there are two kinds of water molecules, and at W0 value around 2 only bound water exists. The Fourier transform infrared (FT-IR) experiments performed on the symmetric (?(s)SO3) and asymmetric (?(a)SO3) sulfonate stretching bands of AOT reveal the existence of a strong Na(+)?TOPO complex in the mixed RMs. The results show that adding TOPO to form mixed surfactant RMs with AOT reduces their size, changes the nature of water to have a "bulk-like" character and diminishes the ion pairing of the sulfonate group with Na(+). PMID:24947471

  19. Chemical surface modification of polycrystalline platinum thin-films to promote preferential chemisorption of n-hexane, piperidine, and cyclohexane

    SciTech Connect

    Thomas, V.; Schwank, J.; Gland, J.

    1994-12-31

    In this study, hard/soft Lewis acid-base (HSAB) principles are used to modify a thin-polycrystalline platinum film to promote preferential chemisorption of molecules such as piperidine, n-hexane, and cyclohexane. Specifically, the particle size and electron density distribution of the platinum surface is modified using thermal treatment and co-adsorption of electro-positive and negative species. These studies are conducted in an ultra-high vacuum chamber. The platinum surface is characterized, before and after modification protocols, using a variety of in-situ and ex-situ techniques. These include temperature programmed desorption (TPD), both resistance change and work function measurements, and both X-ray photoelectron spectroscopy and diffraction.

  20. Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

    PubMed

    Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

    2015-08-19

    Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brnsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed. PMID:26168190

  1. Enhancement of (S)-2,3-dichloro-1-propanol production by recombinant whole-cell biocatalyst in n-heptane-aqueous biphasic system.

    PubMed

    Zou, Shu-Ping; Zheng, Yu-Guo; Du, Er-Hong; Hu, Zhong-Ce

    2014-10-20

    The enantioselective resolution of (R,S)-2,3-dichloro-1-propanol ((R,S)-DCP) to (S)-DCP by whole cells of a recombinant Escherichia coli expressing halohydrin dehalogenase (HHDH) activity was limited by product inhibition. To solve this problem to improve the productivity of (S)-DCP, an n-heptane-aqueous biphasic system was adopted in this work. The influential operational parameters including phase volumetric ratio, buffer pH and reaction temperature were optimized. Under the optimal reaction conditions, significant improvements of substrate concentration and biocatalyst productivity (375 mM and 7.64 mmol (S)-DCP g(-1) cell) were achieved in this n-heptane-aqueous biphasic system compared with aqueous single-phase system (150 mM and 2.97 mmol g(-1)cell). The scale-up biosynthesis of (S)-DCP was successfully performed in a 2-L stirred reactor, resulting in a 128.8 mM (S)-DCP with enantiomeric excess of 99.1% and average productivity of 2.07 g (S)-DCPL(-1) h(-1), respectively. PMID:25152426

  2. Comparison of the effects of nitrogen poisoning on molybdenum oxycarbide and Pt/{beta}-zeolite catalysts in the isomerization of n-heptane

    SciTech Connect

    Del Gallo, P.; Pham-Huu, C.; York, A.P.E.; Ledoux, M.J.

    1996-10-01

    The effect of nitrogen-containing compounds was studied over MoO{sub 3}-carbon-modified and Pt-(1.5 wt %)/{beta}-zeolite catalysts using n-heptane isomerization as the test reaction and piperidine and pyridine as the poisoning molecules. n-Heptane isomerization performed over both catalysts under pure feed showed no deactivation as a function of time on stream. At a pressure of 6 bar the MoO{sub 3}-carbon-modified catalyst exhibited a high resistance to deactivation up to 10 ppm of nitrogen, while the Pt-based catalyst was strongly deactivated down to 30% of its initial activity after 20 h. At higher concentrations of nitrogen ({ge}40 wt ppm) deactivation occurred over both catalysts as a function of time. Results obtained after different regeneration regimes on the MoO{sub 3}-carbon-modified deactivated catalyst led to the conclusion that the deactivation observed was essentially due to coke formation. Finally, increasing the total pressure allowed a better resistance to deactivation by hydrogenating the coke residues over the MoO{sub 3}-carbon-modified catalyst.

  3. Metabolic interaction of n-hexane and methyl ethyl ketone in vitro in a head space rat liver S9 vial equilibration system.

    PubMed

    Mortensen, B; Zahlsen, K; Nilsen, O G

    1998-02-01

    Methyl ethyl ketone pretreatment induced rat liver cytochrome P450 and increased significantly the in vitro metabolism of n-hexane and the formation of 2,5-hexanedione in rat liver S9. No significant changes were, however, found in the levels of the intermediate metabolites 2-hexanol, 2,5-hexanediol or methyl n-butyl ketone. Methyl ethyl ketone added in vitro to untreated (non-induced) liver S9 inhibited in a non-competitive pattern the metabolism of n-hexane and decreased significantly and in a dose-dependent way the levels of methyl n-butyl ketone and 2,5-hexanedione. When methyl ethyl ketone and n-hexane were added in vitro to in vivo methyl ethyl ketone pretreated (induced liver S9, the significant increase in the formation of 2,5-hexanedione was maintained, an increase which was only to a minor extent influenced by the in vitro addition of methyl ethyl ketone. These findings are in agreement with an in vivo induction by methyl ethyl ketone of key enzyme(s) in a generally minor metabolic pathway for the conversion of n-hexane to 2,5-hexanedione in rat liver, a pathway which is not influenced by the presence of methyl ethyl ketone itself. The results obtained in this study indicate that the head space equilibration technique is well suited for screening studies of metabolic interactions between organic solvents. PMID:9498234

  4. Correlation between Levels of 2, 5-Hexanedione and Pyrrole Adducts in Tissues of Rats Exposure to n-Hexane for 5-Days

    PubMed Central

    Yin, Hongyin; Guo, Ying; Zeng, Tao; Zhao, Xiulan; Xie, Keqin

    2013-01-01

    Background The formation of pyrrole adducts might be responsible for peripheral nerve injury caused by n-hexane. The internal dose of pyrrole adducts would supply more information for the neurotoxicity of n-hexane. The current study was designed to investigate the tissue distributions of 2, 5-hexanedione (2,5-HD) and pyrrole adducts in rats exposed to n-hexane, and analyze the correlation between pyrrole adducts and 2,5-HD in tissues. Methods Male Wistar rats were given daily dose of 500,1000, 2000, 4000 mg/kg bw n-hexane by gavage for 5 days. The rats were sacrificed 24 hours after the last administration. The levels of 2, 5-hexanedione and pyrrole adducts in tissues were measured by gas chromatography and Ehrlichs reagent, respectively. The correlations between 2, 5-hexanedione and pyrrole adducts were analyzed by linear regression Results Dose-dependent effects were observed between the dosage of n-hexane and 2, 5-hexanedione, and pyrrole adducts in tissues. The highest level of 2, 5-hexanedione was found in urine and the lowest in sciatic nerve, while the highest level of pyrrole adducts was seen in liver and the lowest in serum. There were significant correlations among the free 2, 5-hexanedione, total 2, 5-hexanedione and pyrrole adducts within the same tissues. Pyrrole adducts in serum showed the most significant correlation with free 2, 5-hexanedione or pyrrole adducts in tissues. Conclusion The findings suggested that pyrrole adducts in serum might be a better indicator for the internal dose of free 2, 5-hexanedione and pyrrole adducts in tissues. PMID:24098756

  5. Inhalation of isopropanol: induction of activating and deactivating enzymes in rat kidney and liver. Increased microsomal metabolism of n-hexane.

    PubMed

    Zahlsen, K; Aarstad, K; Nilsen, O G

    1985-01-01

    Rats were exposed to isopropanol by inhalation of 200,2000 and 8000 ppm for 2 weeks with a daily exposure of 6 h. A pilot group exposed to 8000 ppm was given a recovery period of 4 weeks. Kidney and liver microsomal metabolism of n-hexane was investigated in vitro concomitant with activities of cytochrome P-450 and GSH enzymes and blood concentration of isopropanol and its metabolite acetone. A dose dependent increase was observed in the formation of all metabolites of n-hexane in both organs. Of special interest was the 9%, 80% and 198% increase of the preneurotoxic metabolite 2-hexanol in kidney microsomes. Cytochrome P-450 was increased 14%, 40% and 43% in kidney after 200, 2000 and 8000 ppm, respectively, and 10% and 19% in liver at 2000 and 8000 ppm. The activity of glutathione S-transferase was unaffected in kidney but elevated in liver, while GSH levels were elevated in both organs. The elevated level of kidney cytochrome P-450 did not return to normal during the 4-week-recovery period in contrast to liver cytochrome P-450. It is thus indicated that cytochrome P-450 and associated microsomal enzymes are more easily inducible and the changes more persistent in kidney than in liver. Our observations suggest that cytochrome P-450-mediated metabolic activation of n-hexane in the kidneys may have toxicological relevance in addition to liver metabolism, and that coexposure to isopropanol and n-hexane may represent an enhancement of the health hazard from n-hexane, possibly due to the isopropanol metabolite acetone. PMID:3969680

  6. Reference Correlation of the Thermal Conductivity of n-Heptane from the Triple Point to 600 K and up to 250 MPa

    NASA Astrophysics Data System (ADS)

    Assael, M. J.; Bogdanou, I.; Mylona, S. K.; Huber, M. L.; Perkins, R. A.; Vesovic, V.

    2013-06-01

    This paper contains new, representative reference equations for the thermal conductivity of n-heptane. The equations are based in part upon a body of experimental data that have been critically assessed for internal consistency and for agreement with theory whenever possible. In the case of the dilute-gas thermal conductivity, a theoretically based correlation was adopted in order to extend the temperature range of the experimental data. Moreover, in the critical region, the experimentally observed enhancement of the thermal conductivity is well represented by theoretically based equations containing just one adjustable parameter. The correlations are applicable for the temperature range from the triple point to 600 K and pressures up to 250 MPa. The overall uncertainty (considered to be estimates of a combined expanded uncertainty with a coverage factor of 2) of the proposed correlation is estimated, for pressures less than 250 MPa and temperatures less than 600 K, to be less than 4%.

  7. A molecular dynamics study of the coupling of torsional motions to self-diffusion in liquid n-hexane

    NASA Astrophysics Data System (ADS)

    Travis, Karl P.; Brown, David; Clarke, Julian H. R.

    1995-02-01

    Dynamic coupling of molecular flexibility with self-diffusion has been studied for a model of liquid n-hexane using the technique of frozen distribution sampling (FDS) [Travis et al., J. Chem. Phys. 98, 1524 (1993)]. FDS facilitates comparison of transport properties between a liquid of flexible molecules and a liquid in which the molecular shape fluctuations are frozen in an equilibrium distribution; thus the two liquids have identical equilibrium configurational properties. The diffusion coefficient of model hexane was found to increase by a factor of 20 on raising the temperature from 200 and 1000 K; coupling with torsional motions enhances the diffusion coefficient by about 20% over the whole of this range. At each temperature a quantitative measure of the coupling was obtained by making comparisons with self-diffusion in a liquid for which the potential restricting torsional motion is removedcalled flexane [D. Brown and J. H. R. Clarke, J. Chem. Phys. 86, 1542 (1987)]. Using FDS it was confirmed that the enhancement of the diffusion coefficient in flexane as compared to hexane arises from differences in the short time dynamics and not from differences in the static structure of the two liquids. For hexane a coupling parameter is defined which shows that the extent of dynamic coupling increases from 10% at 200 K and appears to have reached a maximum by 1000 K. The coupling mechanism is discussed using power spectra obtained from the relative velocities of the methylene (and methyl) groups relative to the molecular centers of mass. It is concluded that torsional oscillations mainly involving the outer dihedral angles provide the probable mechanism for the coupling.

  8. Determination of n-hexane metabolites by liquid chromatography/mass spectrometry. 2. Glucuronide-conjugated metabolites in untreated urine samples by electrospray ionization.

    PubMed

    Manini, P; Andreoli, R; Mutti, A; Bergamaschi, E; Niessen, W M

    1998-01-01

    A liquid chromatography atmospheric pressure electrospray mass spectrometry (ESI-LC/MS) system was evaluated for the identification and characterization of n-hexane conjugated metabolites (glucuronides) in untreated urine samples. Chromatography of glucuronides was obtained under ion-suppressed reversed-phase conditions, by using high-speed (3 cm, 3 microns) columns and formic acid (2 mM) as modifier in the mobile phase. The mass spectrometer was operated in negative ion (NI) mode. For the first time, four glucuronides were identified by ESI-LC/MS in untreated urine samples of rats exposed to n-hexane: 2-hexanol-glucuronide, 5-hydroxy-2-hexanone-glucuronide, 2,5-hexanediol-glucuronide and 4,5-dihydroxy-2-hexanone-glucuronide. Confirmation of the conjugated metabolites was obtained by LC/MS/MS experiments. Gas chromatography/mass spectrometry (GC/MS) and atmospheric pressure chemical ionization (APCI) LC/MS analyses were performed on the same samples. An integrated approach GC/MS-LC/MS for the semi-quantitative analysis of n-hexane glucuronides, whose standards are not commercially available, is discussed and proposed here. In order to understand the fate of the metabolites during sample pre-treatment, a study about the effects of enzymatic and acid hydrolysis on urine samples was conducted on glucuronides isolated by solid-phase extraction. Combined analyses by GC/MS and LC/MS enabled us to distinguish 'true' n-hexane metabolites from compounds resulting from sample treatment and handling (i.e. enzymatic and acid hydrolysis, extraction and GC injection). PMID:9807835

  9. Inhalation reproductive toxicology studies: Sperm morphology study of n-hexane in B6C3F1 mice: Final report

    SciTech Connect

    Mast, T.J.; Hackett, P.L.; Decker, J.R.; Westerberg, R.B.; Sasser, L.B.; McClanahan, B.J.; Rommereim, R.L.; Evanoff, J.J.

    1988-08-01

    The straight-chain hydrocarbon, n-hexane, is a volatile, ubiquitous solvent routinely used in industrial environments. Although myelinated nerve tissue is the primary target organ of hexane, the testes have also been identified as being sensitive to hexacarbon exposure. The objective of this study was to evaluate the epididymal sperm morphology of male B6D3F1 mice 5 weeks after exposure to 0, 200, 1000, or 5000 ppM n-hexane, 20 h/day for 5 consecutive days. Two concurrent positive control groups of animals were injected intraperitoneally with either 200 or 250 mg/kg ethyl methanesulfonate, a known mutagen, once each day for 5 consecutive days. The mice were weighed just prior to the first day of exposure and at weekly intervals until sacrifice. During the fifth post-exposure week the animals were killed and examined for gross lesions of the reproductive tract and suspensions of the epididymal sperm were prepared for morphological evaluations. The appearance and behavior of the mice were unremarkable throughout the experiment and there were no deaths. No evidence of lesions in any organ was noted at sacrifice. Mean body weights of male mice exposed to n-hexane were not significantly different from those for the 0-ppM animals at any time during the study. Analyses of the sperm morphology data obtained 5 weeks post-exposure (the only time point examined) indicated that exposure of male mice to relatively high concentrations of n-hexane vapor for 5 days produced no significant effects on the morphology of sperm relative to that of the 0-ppM control group. 24 refs., 2 figs., 7 tabs.

  10. Characterization of digestive enzymes from de-oiled mackerel (Scomber japonicus) muscle obtained by supercritical carbon dioxide and n-hexane extraction as a comparative study.

    PubMed

    Asaduzzaman, A K M; Chun, Byung-Soo

    2015-06-01

    The oil in mackerel muscle was extracted using an environmental friendly solvent, supercritical carbon dioxide (SC-CO2) at a semi-batch flow extraction process and an n-hexane. The SC-CO2 was carried out at temperature 45 °C and pressures ranging from 15 to 25 MPa. The flow rate of CO2 (27 g/min) was constant at the entire extraction period of 2 h. The highest oil extracted residues after SC-CO2 extraction was used for activity measurement of digestive enzymes. Four digestive enzymes were found in water soluble extracts after n-hexane and SC-CO2 treated samples. Amylase, lipase and trypsin activities were higher in water soluble extracts after SC-CO2 treated samples except protease. Among the four digestive enzymes, the activity of amylase was highest and the value was 44.57 uM/min/mg of protein. The water soluble extracts of SC-CO2 and n-hexane treated mackerel samples showed same alkaline optimum pH and pH stability for each of the digestive enzymes. Optimum temperature of amylase, lipase, protease and trypsin was 40, 50, 60 and 30 °C, respectively of both extracts. More than 80 % temperature stability of amylase, lipase, protease and trypsin were retained at mentioned optimum temperature in water soluble extracts of both treated samples. Based on protein patterns, prominent protein band showed in water soluble extracts after SC-CO2 treated samples indicates no denaturation of protein than untreated and n-hexane. PMID:26028731

  11. Rate constant for OH with selected large alkanes : shock-tube measurements and an improved group scheme.

    SciTech Connect

    Sivaramakrishnan, R.; Michael, J. V.; Chemical Sciences and Engineering Division

    2009-04-06

    High-temperature rate constant experiments on OH with the five large (C{sub 5}-C{sub 8}) saturated hydrocarbons n-heptane, 2,2,3,3-tetramethylbutane (2,2,3,3-TMB), n-pentane, n-hexane, and 2,3-dimethylbutane (2,3-DMB) were performed with the reflected-shock-tube technique using multipass absorption spectrometric detection of OH radicals at 308 nm. Single-point determinations at {approx}1200 K on n-heptane, 2,2,3,3-TMB, n-hexane, and 2,3-DMB were previously reported by Cohen and co-workers; however, the present work substantially extends the database to both lower and higher temperature. The present experiments span a wide temperature range, 789-1308 K, and represent the first direct measurements of rate constants at T > 800 K for n-pentane. The present work utilized 48 optical passes corresponding to a total path length of {approx}4.2 m. As a result of this increased path length, the high OH concentration detection sensitivity permitted pseudo-first-order analyses for unambiguously measuring rate constants.

  12. Selective inhibition by chloramphenicol of cytochrome P-450 isozymes in rat lung and liver involved in the hydroxylation of n-hexane.

    PubMed

    Nslund, B M; Halpert, J

    1984-10-01

    Treatment of rats with chloramphenicol causes a dose-dependent and regioselective inhibition of the metabolism of the organic solvent n-hexane in both liver and lung microsomes. A dose of chloramphenicol of 100 mg kg-1 administered i.v. or i.p. results in more than 50% inhibition of 2-hexanol formation catalyzed by microsomes from both organs, but causes no inhibition of 1-hexanol formation. The effects of chloramphenicol on 3-hexanol formation are somewhat organ-specific. In the liver 3-hexanol formation is inhibited to almost the same extent as 2-hexanol formation, whereas in the lung the inhibition of the formation of 3-hexanol is markedly less. Phenobarbital induces n-hexane metabolism in the liver but not the lung, but decreases the inhibitory potency of chloramphenicol toward both organs. In vitro chloramphenicol causes both reversible and irreversible inhibition of 2-hexanol formation in control lung microsomes. The irreversible inhibition is accompanied by the covalent binding of metabolites of chloramphenicol to the lung microsomes. The covalent binding is completely inhibited by antibodies to the major phenobarbital-induced isozyme of rat liver cytochrome P-450. These antibodies also cause more than 90% inhibition of 2-hexanol formation by lung microsomes. The results suggest that chloramphenicol acts as a selective suicide substrate of a constitutive isozyme of rat lung cytochrome P-450 involved in the 2-hydroxylation of n-hexane. PMID:6491971

  13. In vitro effect of n-hexane and its metabolites on selected enzymes in glycolysis, pentose phosphate pathway and citric acid cycle.

    PubMed

    Sabri, M I

    1984-04-01

    The effect of n-hexane, 2-hexanol, 5-hydroxy-2-hexanone, 2,5-hexanediol, methyl n-butyl ketone ( MnBK ) and 2,5-hexanedione (2,5-HD) has been studied in vitro on crystalline glyceraldehyde-3-phosphate dehydrogenase (GAPDH), DL-glyceraldehyde-3-phosphate: NAD oxidoreductase (phosphorylating) EC. 1.2.1.12 and phosphofructokinase (PFK) ATP: D-fructose-6-phosphate-1-phosphotransferase; EC. 2.7.1.11 and lactic dehydrogenase (LDH) L-lactate: NAD+ oxidoreductase, EC. 1.1.1.27. MnBK and 2,5-HD both inhibited GAPDH and PFK activities selectively. n-Hexane and 2-hexanol had no effect on GAPDH and PFK activities; 5-hydroxy-2-hexanone and 2,5-hexanediol exhibited a slight inhibitory effect on these enzymes. Neither metabolites of n-hexane have any effect on LDH activity. 2,5-Hexanedione did not inhibit transketolase (D-sedoheptulose-7-phosphate: D-glyceraldehyde-3-phosphate glycolaldehyde transferase, EC. 2.2.1.1) and succinate dehydrogenase (succinate: 2,6-dichlorophenol-indophenol oxidoreductase, EC. 1.3.99.1) activities. The levels of ATP were reduced in 2,5-HD-treated cat sciatic nerves and returned to normal levels by exposing the nerve to sodium pyruvate. PMID:6232975

  14. Gestational N-hexane inhalation alters the expression of genes related to ovarian hormone production and DNA methylation states in adult female F1 rat offspring.

    PubMed

    Li, Hong; Zhang, Chenyun; Ni, Feng; Guo, Suhua; Wang, Wenxiang; Liu, Jing; Lu, Xiaoli; Huang, Huiling; Zhang, Wenchang

    2015-12-15

    Research has revealed that n-hexane can disrupt adult female endocrine functions; however, few reports have focused on endocrine changes in adult F1 females after maternal exposure during gestation. In this study, female Wistar rats inhaled 100, 500, 2500, or 12,500 ppm n-hexane for 4 h daily during their initial 20 gestational days. The F1 female offspring exhibited abnormal oestrus cycles. Compared with the controls, the in vitro-cultured ovarian granulosa cells of the 12,500 ppm group showed significantly reduced in vitro progesterone and oestradiol secretion. Elevated progesterone secretion was observed in the 500 ppm group, and decreased and significantly upregulated mRNA expression of the Star, Cyp11a1, Cyp17a1, and Hsd3b genes was observed in the 12,500 ppm and 500 ppm groups, respectively. The protein expression levels were consistent with the mRNA expression levels. Methylation screening of the promoter regions of these genes was performed using MeDIP-chip and confirmed by methylation-sensitive high-resolution melting (MS-HRM), and the observed methylation state changes of the promoter regions were correlated with the gene expression levels. The results suggest that the hormone levels in the female offspring after gestational n-hexane inhalation correspond to the expression levels and DNA methylation states of the hormone production genes. PMID:26410608

  15. An experimental and numerical investigation of n-heptane/air counterflow partially premixed flames and emission of NO{sub x} and PAH species

    SciTech Connect

    Berta, Paolo; Aggarwal, Suresh K.; Puri, Ishwar K.

    2006-06-15

    An experimental and numerical investigation of counterflow prevaporized partially premixed n-heptane flames is reported. The major objective is to provide well-resolved experimental data regarding the detailed structure and emission characteristics of these flames, including profiles of C{sub 1}-C{sub 6}, and aromatic species (benzene and toluene) that play an important role in soot formation. n-Heptane is considered a surrogate for liquid hydrocarbon fuels used in many propulsion and power generation systems. A counterflow geometry is employed, since it provides a nearly one-dimensional flat flame that facilitates both detailed measurements and simulations using comprehensive chemistry and transport models. The measurements are compared with predictions using a detailed n-heptane oxidation mechanism that includes the chemistry of NO{sub x} and PAH formation. The reaction mechanism was synergistically improved using pathway analysis and measured benzene profiles and then used to characterize the effects of partial premixing and strain rate on the flame structure and the production of NO{sub x} and soot precursors. Measurements and predictions exhibit excellent agreement for temperature and major species profiles (N{sub 2}, O{sub 2}, n-C{sub 7}H{sub 16}, CO{sub 2}, CO, H{sub 2}), and reasonably good agreement for intermediate (CH{sub 4}, C{sub 2}H{sub 4}, C{sub 2}H{sub 2}, C{sub 3}H{sub x}) and higher hydrocarbon species (C{sub 4}H{sub 8}, C{sub 4}H{sub 6}, C{sub 4}H{sub 4}, C{sub 4}H{sub 2}, C{sub 5}H{sub 10}, C{sub 6}H{sub 12}) and aromatic species (toluene and benzene). Both the measurements and predictions also indicate the existence of two partially premixed regimes; a double flame regime for f<5.0, characterized by spatially separated rich premixed and nonpremixed reaction zones, and a merged flame regime for f>5.0. The NO{sub x} and soot precursor emissions exhibit strong dependence on partial premixing and strain rate in the first regime and relatively weak dependence in the second regime. At higher levels of partial premixing, NO{sub x} emission is increased due to increased residence time and higher peak temperature. In contrast, the emissions of acetylene and PAH species are reduced by partial premixing because their peak locations move away from the stagnation plane, resulting in lower residence time, and the increased amount of oxygen in the system drives the reactions to the oxidation pathways. The effects of partial premixing and strain rate on the production of PAH species become progressively stronger as the number of aromatic rings increases. (author)

  16. Auto-ignition of toluene-doped n-heptane and iso-octane/air mixtures: High-pressure shock-tube experiments and kinetics modeling

    SciTech Connect

    Hartmann, M.; Fikri, M.; Schulz, C.; Gushterova, I.; Schiessl, R.; Maas, U.

    2011-01-15

    Toluene is often used as a fluorescent tracer for fuel concentration measurements, but without considering whether it affects the auto-ignition properties of the base fuel. We investigate the auto-ignition of pure toluene and its influence on the auto-ignition of n-heptane and iso-octane/air mixtures under engine-relevant conditions at typical tracer concentrations. Ignition delay times {tau}{sub ign} were measured behind reflected shock waves in mixtures with air at {phi}=1.0 and 0.5 at p=40 bar, over a temperature range of T=700-1200 K and compared to numerical results using two different mechanisms. Based on the models, information is derived about the relative influence of toluene on {tau}{sub ign} on the base fuels as function of temperature. For typical toluene tracer concentrations {<=}10%, the ignition delay time {tau}{sub ign} changes by less than 10% in the relevant pressure and temperature range. (author)

  17. Multi-timescale modeling of ignition and flame regimes of n-heptane-air mixtures near spark assisted homogeneous charge compression ignition conditions

    SciTech Connect

    Ju, Yiguang; Sun, Wenting; Burke, M. P.; Gou, Xiaolong; Chen, Zheng

    2011-01-01

    The flame regimes of ignition and flame propagation as well as transitions between different flame regimes of n-heptane-air mixtures in a one-dimensional, cylindrical, spark assisted homogeneously charged compression ignition (HCCI) reactor are numerically modeled using a multi-timescale method with reduced kinetic mechanism. It is found that the initial mixture temperature and pressure have a dramatic impact on flame dynamics. Depending on the initial temperature gradient, there exist at least six different combustion regimes, an initial single flame front propagation regime, a coupled low temperature and high temperature double-flame regime, a decoupled low temperature and high temperature double-flame regime, a low temperature ignition regime, a single high temperature flame regime, and a hot ignition regime. The results show that the low temperature and high temperature flames have distinct kinetic and transport properties as well as flame speeds, and are strongly influenced by the low temperature chemistry. The pressure and heat release rates are affected by the appearance of different flame regimes and the transitions between them. Furthermore, it is found that the critical temperature gradient for ignition and acoustic wave coupling becomes singular at the negative temperature coefficient (NTC) region. The results show that both the NTC effect and the acoustic wave propagation in a closed reactor have a dramatic impact on the ignition front and acoustic interaction.

  18. Electric percolation of water-in-oil microemulsions: The application of effective medium theory to system sodium dodecylbenzenesulfonate (DDBS)/n-pentanol/n-heptane/water

    SciTech Connect

    Gu, G.; Wang, W.; Yan, H.

    1996-03-01

    The electric conductive behavior of the system water/sodium dodecylbenzenesulfonate (DDBS)/n-pentanol/n-heptane has been studied. The results showed that the system has an intrinsic electric percolation phenomenon. The water induced percolation threshold, {phi}{sub d}{sup p}, varies over a wide range and is higher than the theoretically predicted value of below 1/3. To use the changed form of the effective medium theory, a second-order polynomial relationship between {sigma}{phi}{sub d} and the conductivity {sigma} of system, is much better than to use the plot of {sigma} versus {phi}{sub d} in fitting the conductivity data of W/O microemulsion, where {phi}{sub d} is the volume fraction of the disperse phase. A linear equation exists when the volume fraction {phi}{sub d} of the disperse phase does not exceed percolation threshold {phi}{sub d}{sup p} much more. The content P of n-pentanol and DDBS affects the properties of the system significantly, but the influences on the limit conductivity of the disperse phase and that of the continuous phase are in the same tendency; also the distribution of alcohol among inner water core, surfactant shell, and continuous phase are changed.

  19. A detailed chemical kinetic reaction mechanism for the oxidation of iso-octane and n-heptane over an extended temperature range and its application to analysis of engine knock

    SciTech Connect

    Westbrook, C.K.; Warnatz, J.; Pitz, W.J.

    1988-01-11

    A detailed chemical kinetic reaction is developed to describe the oxidation of n-heptane, iso-octane, and their mixtures over a wide range of operating conditions. In addition to a high temperature submechanism, reaction paths are included to describe the lower temperature regimes in which the rate and intermediate products of oxidation are controlled by addition of molecular oxygen to alkyl and isomerized alkylperoxy radicals, internal H atom abstractions, and reactions involving O-heterocyclic species. The mechanism is then used to study the influence of fuel composition on knocking in internal combustion engines. Autoignition of mixtures of iso-octane and n-heptane is examined. The computations reproduce the variations of autoignition delay time with octane number and these variations are interpreted in terms of detailed differences in the structure of the two primary reference fuels. Sensitivity analyses of the computations are also presented. 30 refs., 2 figs.

  20. Analysis of n-hexane, 2-hexanone, 2,5-hexanedione, and related chemicals by capillary gas chromatography and high-performance liquid chromatography.

    PubMed

    Nomeir, A A; Abou-Donia, M B

    1985-12-01

    Analytical methods, using capillary gas chromatography and normal-phase high-performance liquid chromatography, were developed for the analysis of the neurotoxic chemicals n-hexane, 2-hexanone, and 2,5-hexanedione and their suspected metabolites. Two gas chromatographic methods, using a 50-m glass capillary OV 101 column and cyclohexane as an internal standard, were employed. In both methods, the injector and detector temperatures were 220 and 280 degrees C, respectively. In method I the following temperature program was used: isothermic at 50 degrees C for 30 min, followed by a temperature increase of 10 degrees C/min to a final temperature of 180 degrees C, which was then maintained for 7 min. This method was used to analyze the following compounds: n-hexane, 2,5-dimethylfuran, 2-hexanone, 3-hexanone, hexanal, 1-hexanol, 2-hexanol, 3-hexanol, 5-hydroxy-2-hexanone, gamma-valerolactone, 2,5-hexanedione, and 2,5-hexanediol. Method II, which was developed for n-hexane and eight of its more common metabolites, used the following temperature program: isothermic at 70 degrees C for 15 min, followed by a temperature increase of 40 degrees C/min to a final temperature of 220 degrees C, which was maintained for 5 min. A linear relationship between peak area and amount injected was observed over a 100-fold range. The minimum detectable amounts ranged from 0.05 to 1 microgram, depending on the compound. Normal-phase HPLC, using a 5-micron silica cartridge fitted into an RCM-100 radial-compression separation system, was utilized to analyze 2-hexanone and its metabolites 2,5-dimethylfuran, gamma-valerolactone, 5-hydroxy-2-hexanone, and 2,5-hexanedione.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:4096376

  1. Effect of total hydroalcholic extract of Nigella sativa and its n-hexane and ethyl acetate fractions on ACHN and GP-293 cell lines.

    PubMed

    Shahraki, Samira; Khajavirad, Abolfazl; Shafei, Mohammad Naser; Mahmoudi, Mahmoud; Tabasi, Nafisa Sadat

    2016-01-01

    Medicinal plants are noted for their many advantages including the ability to treat diseases such as cancer. In this study, we examined the antitumor effect of the medicinal plant Nigella sativa on the morphology, survival, and apoptosis of ACHN (human renal adenocarcinoma) and GP-293 (normal renal epithelial) cell lines. From a hydroalcoholic extract of N. sativa, n-hexane and ethyl acetate fractions were extracted. Cells were treated with various concentrations of total hydroalcholic extract and n-hexane and ethyl acetate fractions; cell viability, morphological changes, and apoptosis were then determined. Results were presented as mean ± standard error of the mean (SEM). One-way analysis of variance (ANOVA) was applied for the statistical analysis of the data. The total extract and the fractions in a dose- and time-dependent manner reduced the cell viability in ACHN with no effect on the GP-293 cell line. In addition, the total extract resulted in more morphological changes in the ACHN cells compared to the GP-293 cells. The effect of the total extract in inducing apoptosis after 48 hours in the ACHN cell line was greater than in GP-293. In addition, the effect of the two fractions was lower than the total extract at all used concentrations. Therefore, the effect of total extract and n-hexane and ethyl acetate fractions of N. sativa on cell viability and apoptosis in the ACHN cell line is greater than in the GP-293 cell line. However, the effect of the total extract is higher than either of the two fractions on their own. PMID:26870685

  2. Effect of total hydroalcholic extract of Nigella sativa and its n-hexane and ethyl acetate fractions on ACHN and GP-293 cell lines

    PubMed Central

    Shahraki, Samira; Khajavirad, Abolfazl; Shafei, Mohammad Naser; Mahmoudi, Mahmoud; Tabasi, Nafisa Sadat

    2015-01-01

    Medicinal plants are noted for their many advantages including the ability to treat diseases such as cancer. In this study, we examined the antitumor effect of the medicinal plant Nigella sativa on the morphology, survival, and apoptosis of ACHN (human renal adenocarcinoma) and GP-293 (normal renal epithelial) cell lines. From a hydroalcoholic extract of N.sativa, n-hexane and ethyl acetate fractions were extracted. Cells were treated with various concentrations of total hydroalcholic extract and n-hexane and ethyl acetate fractions; cell viability, morphological changes, and apoptosis were then determined. Results were presented as meanstandard error of the mean (SEM). One-way analysis of variance (ANOVA) was applied for the statistical analysis of the data. The total extract and the fractions in a dose- and time-dependent manner reduced the cell viability in ACHN with no effect on the GP-293 cell line. In addition, the total extract resulted in more morphological changes in the ACHN cells compared to the GP-293 cells. The effect of the total extract in inducing apoptosis after 48 hours in the ACHN cell line was greater than in GP-293. In addition, the effect of the two fractions was lower than the total extract at all used concentrations. Therefore, the effect of total extract and n-hexane and ethyl acetate fractions of N.sativa on cell viability and apoptosis in the ACHN cell line is greater than in the GP-293 cell line. However, the effect of the total extract is higher than either of the two fractions on their own. PMID:26870685

  3. Steam reforming of n-hexane on pellet and monolithic catalyst beds. A comparative study on improvements due to heat transfer

    NASA Technical Reports Server (NTRS)

    1981-01-01

    Monolithic catalysts with higher available active surface areas and better thermal conductivity than conventional pellets beds, making possible the steam reforming of fuels heavier than naphtha, were examined. Performance comparisons were made between conventional pellet beds and honeycomb monolith catalysts using n-hexane as the fuel. Metal-supported monoliths were examined. These offer higher structural stability and higher thermal conductivity than ceramic supports. Data from two metal monoliths of different nickel catalyst loadings were compared to pellets under the same operating conditions. Improved heat transfer and better conversion efficiencies were obtained with the monolith having higher catalyst loading. Surface-gas interaction was observed throughout the length of the monoliths.

  4. Regio-selectivity of purified forms of rabbit liver microsomal cytochrome P-450 in the metabolism of benzo(a)pyrene, n-hexane and 7-ethoxyresorufin.

    PubMed

    Nilsen, O G; Toftgrd, R; Eng, L; Gustafsson, J A

    1981-05-01

    The specificity of electrophoretically homogeneous preparations of rabbit liver microsomal cytochrome P-450LM2-4 towards oxygenation of n-hexane, 7-ethoxyresorufin and benzo(a)pyrene was examined using a reconstituted system consisting of cytochrome P-450, NADPH-cytochrome P-450 reductase and dilauroylphosphatidylcholine. Epoxide hydrase was included when benzo(a)pyrene was used as substrate. Cytochrome P-450LM2 was most active in n-hexane and benzo(a)pyrene oxygenation especially with regard to the formation of 2-hexanol, B(a)P-4,5-dihydrodiol and B(a)P-phenol metabolites. 7-Ethoxyresorufin was, however, a very poor substrate for cytochrome P-450LM2. Cytochrome P-450LM3 had less activity towards the investigated substrates while cytochrome P-450LM4 preferentially formed 2- and 3-hexanol, resorufin and B(a)P-9,10-dihydrodiol. Cytochrome P-450LM4 isolated after pretreatment with 3-methylcholanthrene or phenobarbital showed roughly the same characteristics except in the formation of 1-hexanol where cytochrome P-450LM4 isolated after phenobarbital treatment was the most effective. The formation of B(a)P-4,5- and -9,10-dihydrodiols was greatly increased by incorporation of epoxide hydrase. Our results indicate a certain specificity of the different forms of cytochrome P-450 in the liver microsomes although some overlap in activities was observed. PMID:7336952

  5. Solid-liquid work of adhesion of coarse-grained models of n-hexane on graphene layers derived from the conditional reversible work method.

    PubMed

    Ardham, Vikram Reddy; Deichmann, Gregor; van der Vegt, Nico F A; Leroy, Frdric

    2015-12-28

    We address the question of how reducing the number of degrees of freedom modifies the interfacial thermodynamic properties of heterogeneous solid-liquid systems. We consider the example of n-hexane interacting with multi-layer graphene which we model both with fully atomistic and coarse-grained (CG) models. The CG models are obtained by means of the conditional reversible work (CRW) method. The interfacial thermodynamics of these models is characterized by the solid-liquid work of adhesion WSL calculated by means of the dry-surface methodology through molecular dynamics simulations. We find that the CRW potentials lead to values of WSL that are larger than the atomistic ones. Clear understanding of the relationship between the structure of n-hexane in the vicinity of the surface and WSL is elucidated through a detailed study of the energy and entropy components of WSL. We highlight the crucial role played by the solid-liquid energy fluctuations. Our approach suggests that CG potentials should be designed in such a way that they preserve the range of solid-liquid interaction energies, but also their fluctuations in order to preserve the reference atomistic value of WSL. Our study thus opens perspectives into deriving CG interaction potentials that preserve the thermodynamics of solid-liquid contacts and will find application in studies that intend to address materials driven by interfaces. PMID:26723620

  6. Solid-liquid work of adhesion of coarse-grained models of n-hexane on graphene layers derived from the conditional reversible work method

    NASA Astrophysics Data System (ADS)

    Ardham, Vikram Reddy; Deichmann, Gregor; van der Vegt, Nico F. A.; Leroy, Frdric

    2015-12-01

    We address the question of how reducing the number of degrees of freedom modifies the interfacial thermodynamic properties of heterogeneous solid-liquid systems. We consider the example of n-hexane interacting with multi-layer graphene which we model both with fully atomistic and coarse-grained (CG) models. The CG models are obtained by means of the conditional reversible work (CRW) method. The interfacial thermodynamics of these models is characterized by the solid-liquid work of adhesion WSL calculated by means of the dry-surface methodology through molecular dynamics simulations. We find that the CRW potentials lead to values of WSL that are larger than the atomistic ones. Clear understanding of the relationship between the structure of n-hexane in the vicinity of the surface and WSL is elucidated through a detailed study of the energy and entropy components of WSL. We highlight the crucial role played by the solid-liquid energy fluctuations. Our approach suggests that CG potentials should be designed in such a way that they preserve the range of solid-liquid interaction energies, but also their fluctuations in order to preserve the reference atomistic value of WSL. Our study thus opens perspectives into deriving CG interaction potentials that preserve the thermodynamics of solid-liquid contacts and will find application in studies that intend to address materials driven by interfaces.

  7. Heterogeneous nitration reactions of polycyclic aromatic hydrocarbons and n-hexane soot by exposure to NO 3/NO 2/N 2O 5

    NASA Astrophysics Data System (ADS)

    Kwamena, N.-O. A.; Abbatt, J. P. D.

    Although heterogeneous reactions of polycyclic aromatic hydrocarbons (PAHs) with atmospheric oxidants may be important loss processes for PAHs, our understanding of their kinetics and products is incomplete. A product study of the reaction of two PAHs (i.e., anthracene and pyrene) and n-hexane soot with NO 3 and N 2O 5 using a variety of analytical techniques (XPS, DRIFTS, GC-MS, optical absorption) was undertaken. The goal was to characterize the products of these heterogeneous nitration reactions to aid in reaction mechanism development. NitroPAHs were found to be the products of the nitration of anthracene and pyrene whereas evidence of both nitro and carbonyl functional groups were observed on the surface of n-hexane soot samples following exposure to a mixed flow of NO 3 and N 2O 5. Absorption experiments indicate that the nitration of PAHs alter the optical properties of the particles to which they are adsorbed, giving rise to absorption intensity in the near UV and visible portions of the spectrum.

  8. Separation of n-hexane/acetone mixtures by pervaporation using high density polyethylene/ethylene propylene diene terpolymer rubber blend membranes.

    PubMed

    Kumar, P V Anil; Anilkumar, S; Varughese, K T; Thomas, Sabu

    2012-01-15

    Polymer membranes were prepared by blending high density polyethylene (HDPE) with ethylene propylene diene terpolymer rubber (EPDM). These blend membranes were evaluated for the selective separation of n-hexane from acetone. The flux and selectivity of the membranes were determined both as a function of the blend composition and feed mixture composition. Results showed that polymer blending method could be very useful to develop new membranes with improved selectivity. Pervaporation properties could be optimized by adjusting the blend composition. The effects of blend ratio, feed composition, and penetrant size on the pervaporation process were analyzed. The permeation properties have been explained on the basis of interaction between the membrane and solvents and blend morphology. Flux increases with increasing alkane content in the feed composition. PMID:22118848

  9. Probing mechanisms of axonopathy. Part II: Protein targets of 2,5-hexanedione, the neurotoxic metabolite of the aliphatic solvent n-hexane.

    PubMed

    Tshala-Katumbay, Desire; Monterroso, Victor; Kayton, Robert; Lasarev, Michael; Sabri, Mohammad; Spencer, Peter

    2009-02-01

    Neuroprotein changes in the spinal cord of rodents with aliphatic gamma-diketone axonopathy induced by 2,5-hexanedione (2,5-HD) are compared with those reported previously in aromatic gamma-diketone-like axonopathy induced by 1,2-diacetylbenzene (1,2-DAB). Sprague-Dawley rats were treated intraperitoneally with 500 mg/kg/day 2,5-HD, equimolar doses of 2,3-hexanedione (negative control), or an equivalent amount of saline containing 50% dimethyl sulfoxide (vehicle), 5 days a week, for 3 weeks. Analysis of the lumbosacral proteome by 2-dimensional differential in-gel electrophoresis and matrix-assisted laser desorption ionization time-of-flight/tandem mass spectrometry revealed 34 proteins markedly modified by 2,5-HD of which neurofilament triplet L, gelsolin, protein disulfide isomerase, glutathione S-transferase, nicotinamide adenine dinucleotide (reduced) dehydrogenase 1 alpha, pyruvate kinase, and fatty acid synthase were also modified by 1,2-DAB. The expression of proteins involved in maintaining the physical integrity of the cytoskeleton or controlling the redox and protein-folding mechanisms was reduced, whereas that of proteins supporting energy metabolism was mainly increased. The similarity of the neuroproteomic patterns of 2,5-HD and 1,2-DAB axonopathy suggests common biomarkers and/or mechanisms of neurotoxicity associated with exposure to their parent chemicals, namely the industrial solvents n-hexane and 1,2-diethylbenzene, respectively. PMID:19033394

  10. Probing Mechanisms of Axonopathy. Part II: Protein Targets of 2,5-Hexanedione, the Neurotoxic Metabolite of the Aliphatic Solvent n-Hexane

    PubMed Central

    Tshala-Katumbay, Desire; Monterroso, Victor; Kayton, Robert; Lasarev, Michael; Sabri, Mohammad; Spencer, Peter

    2009-01-01

    Neuroprotein changes in the spinal cord of rodents with aliphatic ?-diketone axonopathy induced by 2,5-hexanedione (2,5-HD) are compared with those reported previously in aromatic ?-diketonelike axonopathy induced by 1,2-diacetylbenzene (1,2-DAB). Sprague-Dawley rats were treated intraperitoneally with 500 mg/kg/day 2,5-HD, equimolar doses of 2,3-hexanedione (negative control), or an equivalent amount of saline containing 50% dimethyl sulfoxide (vehicle), 5 days a week, for 3 weeks. Analysis of the lumbosacral proteome by 2-dimensional differential in-gel electrophoresis and matrix-assisted laser desorption ionization time-of-flight/tandem mass spectrometry revealed 34 proteins markedly modified by 2,5-HD of which neurofilament triplet L, gelsolin, protein disulfide isomerase, glutathione S-transferase, nicotinamide adenine dinucleotide (reduced) dehydrogenase 1?, pyruvate kinase, and fatty acid synthase were also modified by 1,2-DAB. The expression of proteins involved in maintaining the physical integrity of the cytoskeleton or controlling the redox and protein-folding mechanisms was reduced, whereas that of proteins supporting energy metabolism was mainly increased. The similarity of the neuroproteomic patterns of 2,5-HD and 1,2-DAB axonopathy suggests common biomarkers and/or mechanisms of neurotoxicity associated with exposure to their parent chemicals, namely the industrial solvents n-hexane and 1,2-diethylbenzene, respectively. PMID:19033394

  11. Mechanism of resolution enhancement for the electron spin echo detected electron spin resonance spectrum of alkyl radical in. gamma. -irradiated n-hexane single crystals

    SciTech Connect

    Ichikawa, T.; Yoshida, H.

    1988-10-06

    The electron spin echo detected ESR spectrum of 1-ethylbutyl radicals in a ..gamma..-irradiated n-hexane single crystal was measured at 77 K as a function of the time of the longitudinal relaxation, t/sub 1/. The longitudinal relaxation was caused by the spectral diffusion induced by the modulation of isotropic hyperfine coupling constants, so that the relaxation rate did not depend on the direction of the crystal with respect to the static magnetic field. Analysis of the thermal motion of the radical in the crystal revealed that the slow twisting motion of the C-C bond induces the modulation of mainly isotropic ..beta..-proton hyperfine coupling constants. The resolution of the ESE-detected ESR spectrum increased with increasing t/sub 1/. The observed spectra compared well with the t/sub 1/-dependent ESR spectra calculated by utilizing a spectral diffusion model in which the spectral shape of each hyperfine line at t/sub 1/ = 0 is equivalent to the distribution of the diffusion time in the spectral space.

  12. Impact of choice of alkane deposition solvent on 4-fluorobenzoic acid layers adsorbed on silver nanostructures

    NASA Astrophysics Data System (ADS)

    Cordova, Scott; Schiefer, Elizabeth; Bonde, Ashley; Razer, Taylor; Chen, TsungYen; Perry, Donald

    2010-09-01

    Surface-enhanced infrared absorption (SEIRA) experiments revealed that the chain length and evaporation rate of alkane deposition solvents altered 4-fluorobenzoic acid (4FBA) adsorption. 4FBA did not dissociate in the multilayer with the fast-evaporating n-pentane deposition solvent. However, with n-hexane and heavier solvents, the evaporation rate was slow enough to allow significant formation of 4-fluorobenzoate ions (4FBI) in the multilayer. Strong intermolecular attractions were present with heavier deposition solvents as evidenced by the incorporation of n-heptane into the 4FBI multilayer. This work will apply to many synthetic, biological, and environmental areas involving the interaction of metal nanostructures with oxygenated or halogenated hydrocarbons.

  13. Excess enthalpies for 1,1,1-trichloroethane with alkanes, ketones, and esters

    SciTech Connect

    Gmehling, J. . Technische Chemie)

    1993-01-01

    Excess enthalpies provide quantitative information about the temperature dependence of the excess Gibbs energy G[sup E]. This information should therefore be used together with other results (vapor-liquid equilibria, liquid-liquid equilibria, limiting activity coefficients, and azeotropic data) for fitting simultaneously temperature-dependent G[sup E] model parameters or interaction parameters of group contribution methods. Although a large number of H[sup E] measurements have been published, results at temperatures other than 298.15 K are scarce. In this paper a flow calorimeter is described, and excess enthalpy data are given for the test systems n-hexane + cyclohexane, benzene + cyclohexane, and methanol + water at 298.15 K as well as for 1,1,1-trichloroethane + n-pentane, + n-heptane, + acetone, + 2-butanone, + methyl acetate, and + ethyl acetate at 363.15 K. These results were used for the systematic development of the group contribution method (modified UNIFAC) developed at Dortmund.

  14. Kinetics of cracking of n-decane and n-hexane on zeolites H-ZSM-5 and HY in the temperature range 500 to 780 K

    SciTech Connect

    Riekert, L.; Zhou, J.-Q. )

    1992-10-01

    The kinetics of cracking of n-decane and n-hexane were investigated by observing the composition of the gas phase in contact with zeolite catalysts H-ZSM-5 and HY in a well-mixed closed system (gradientless batch-reactor). Catalyst temperature was varied from 473 K to 773 K, partial pressures of reactant paraffin between 0.5 and 20 mbar. For ZSM-5 the influence of crystal size and of Si/Al-ratio on the kinetics was investigated. At temperatures above 673 K, the rates of cracking on H-ZSM-5 are first order in the partial pressures of paraffin; an estimate of diffusivity under reaction conditions is obtained from the influence of crystal size on observed rates at T > 700 K. Between 473 K and 673 K, the rate of reaction of pure n-decane on H-ZSM-5 exhibits a maximum near 300 C and decreases with temperature to a minimum near 630 K. An induction period followed by autocatalysis was observed with n-decane as reactant in this temperature-range, depending on Si/Al ratio and degree of deactivation of the zeolite. It can be suppressed by addition of olefin to reactant paraffin. These phenomena are also observed in a less pronounced way with dealuminated HY, which deactivates more rapidly. A mathematical model based on a dual pathway of carbenium ion and protolytic cracking as postulated by Haag and Dessau represents the observations qualitatively and in an approximate way also quantitatively.

  15. N,N'-(Hexane-1,6-diyl)bis(4-methyl-N-(oxiran-2-ylmethyl)benzenesulfonamide): Synthesis via cyclodextrin mediated N-alkylation in aqueous solution and further Prilezhaev epoxidation

    PubMed Central

    Fischer, Julian; Millan, Simon

    2013-01-01

    Summary N-alkylation of N,N'-(hexane-1,6-diyl)bis(4-methylbenzenesulfonamide) with allyl bromide and subsequent Prilezhaev reaction with m-chloroperbenzoic acid to give N,N'-(hexane-1,6-diyl)bis(4-methyl-N-(oxiran-2-ylmethyl)benzenesulfonamide) is described. This twofold alkylation was performed in aqueous solution, whereby α-, and randomly methylated β-cyclodextrin were used as adequate phase transfer catalysts and the cyclodextrin–guest complexes were characterized by 1H NMR and 2D NMR ROESY spectroscopy. Finally, the curing properties of the diepoxide with lysine-based α-amino-ε-caprolactam were analyzed by rheological measurements. PMID:24367447

  16. High-temperature catalytic reforming of n-hexane over supported and core-shell Pt nanoparticle catalysts: role of oxide-metal interface and thermal stability.

    PubMed

    An, Kwangjin; Zhang, Qiao; Alayoglu, Selim; Musselwhite, Nathan; Shin, Jae-Youn; Somorjai, Gabor A

    2014-08-13

    Designing catalysts with high thermal stability and resistance to deactivation while simultaneously maintaining their catalytic activity and selectivity is of key importance in high-temperature reforming reactions. We prepared Pt nanoparticle catalysts supported on either mesoporous SiO2 or TiO2. Sandwich-type Pt core@shell catalysts (SiO2@Pt@SiO2 and SiO2@Pt@TiO2) were also synthesized from Pt nanoparticles deposited on SiO2 spheres, which were encapsulated by either mesoporous SiO2 or TiO2 shells. n-Hexane reforming was carried out over these four catalysts at 240-500 C with a hexane/H2 ratio of 1:5 to investigate thermal stability and the role of the support. For the production of high-octane gasoline, branched C6 isomers are more highly desired than other cyclic, aromatic, and cracking products. Over Pt/TiO2 catalyst, production of 2-methylpentane and 3-methylpentane via isomerization was increased selectively up to 420 C by charge transfer at Pt-TiO2 interfaces, as compared to Pt/SiO2. When thermal stability was compared between supported catalysts and sandwich-type core@shell catalysts, the Pt/SiO2 catalyst suffered sintering above 400 C, whereas the SiO2@Pt@SiO2 catalyst preserved the Pt nanoparticle size and shape up to 500 C. The SiO2@Pt@TiO2 catalyst led to Pt nanoparticle sintering due to incomplete protection of the TiO2 shells during the reaction at 500 C. Interestingly, over the Pt/TiO2 catalyst, the average size of Pt nanoparticles was maintained even after 500 C without sintering. In situ ambient pressure X-ray photoelectron spectroscopy demonstrated that the Pt/TiO2 catalyst did not exhibit TiO2 overgrowth on the Pt surface or deactivation by Pt sintering up to 600 C. The extraordinarily high stability of the Pt/TiO2 catalyst promoted high reaction rates (2.0 ?mol g(-1) s(-1)), which was 8 times greater than other catalysts and high isomer selectivity (53.0% of C6 isomers at 440 C). By the strong metal-support interaction, the Pt/TiO2 was turned out as the best catalyst with great thermal stability as well as high reaction rate and product selectivity in high-temperature reforming reaction. PMID:25078630

  17. Enzymatic hydrolysis of N-benzoyl-L-tyrosine p-nitroanilide by ?-chymotrypsin in DMSO-water/AOT/n-heptane reverse micelles. A unique interfacial effect on the enzymatic activity.

    PubMed

    Moyano, Fernando; Setien, Evangelina; Silber, Juana J; Correa, N Mariano

    2013-07-01

    The reverse micelle (RM) media are very good as nanoreactors because they can create a unique microenvironment for carrying out a variety of chemical and biochemical reactions. The aim of the present work is to determine the influence of different water-dimethyl sulfoxide (DMSO) mixtures encapsulated in 1,4-bis-2-ethylhexylsulfosuccinate (AOT)/n-heptane RMs on the enzymatic hydrolysis of N-benzoyl-L-tyrosine p-nitroanilide (Bz-Try-pNA) by ?-chymotrypsin (?-CT). The reaction was first studied in homogeneous media at different DMSO-water mixture compositions and in DMSO-water/AOT/n-heptane RMs. The hydrolysis rates of Bz-Try-pNA catalyzed by ?-CT were determined by UV-vis spectroscopy. The reaction follows the Michaelis-Menten mechanism and the kinetic parameters: kcat, KM, and kcat/KM were evaluated under different conditions. In this homogeneous media, DMSO plays an important role in the solubilization process of the peptide which is almost insoluble in water, but it has a tremendous impact on the inactivation of ?-CT. It is shown that the enzyme dissolved in a 20% molar ratio of the DMSO-water mixture does not present enzymatic activity. Dynamic light scattering has been used to assess the formation of DMSO-water/AOT/heptane RMs at different DMSO compositions. The results also show that there is preferential solvation of the AOT RM interface by water molecules. To test the use of these RMs as nanoreactors, the kinetic parameters for the enzymatic reaction in these systems have been evaluated. The parameters were determined at fixed W(S) {W(S) = ([water] + [DMSO])/[AOT] = 20} at different DMSO-water compositions. The results show that the Michaelis-Menten mechanism is valid for ?-CT in all the RM systems studied and that the reaction takes place at the RM interface. Surprisingly, it was observed that the enzyme encapsulated by the RMs show catalytic effects with similar kcat/KM values at any DMSO composition investigated, which evidence that DMSO molecules are localized far from the RM interface. PMID:23734596

  18. Calorimetric investigation of the solubilization of water-in-sodium dodecylbenzenesulfonate reversed micelles and water-in-oil microemulsions in mixed solvent of n-heptane and n-pentanol

    SciTech Connect

    Gu, G.; Wang, W. . Technical Physics Dept.); Yan, H. . Inst. of Chemistry)

    1994-10-01

    Thermal behavior of sodium dodecylbenzenesulfonate (DDBS) reversed micelles with n-pentanol and n-heptane as mixed apolar solvents was studied by titrating water into anhydrous reversed micelles with a Tronac model 450 calorimeter. The solubilization of water can be described in terms of deformation of molecular structure of water, adsorption of water, ionization of surfactant, dilution of counterions, and swelling of droplets. A specific radius of anhydrous reversed micelles, R[sub s] = (1 + [radical]6/2)r[sub 0], relating to a transition from exothermic type to endothermic type is proposed, where r[sub 0] is the molecular radius of water. The partial molar enthalpy of water against R, the molar ratio of water to surfactant, shows an exothermic type with one peak at low P and two peaks at high P, where P is the mass percentages of DDBS and n-pentanol in the mixture. Structural parameters of the droplet, such as radii of the disperse phase (R[sub d]) and the water core (R[sub w]), as well as the average aggregation number (N) and the compact effective head group area (a[sub s] + Ia[sub a], where a[sub s] and a[sub a] are head group areas of surfactant and alcohol per molecule and I is the molar ratio of alcohol to surfactant in interfacial layer), have been derived without any approximation in the densities of the disperse phase.

  19. Experimental neurotoxicity and urinary metabolites of the C5-C7 aliphatic hydrocarbons used as glue solvents in shoe manufacture.

    PubMed

    Frontali, N; Amantini, M C; Spagnolo, A; Guarcini, A M; Saltari, M C; Brugnone, F; Perbellini, L

    1981-12-01

    Rats were intermittently exposed (9 to 10 h/d, 5 to 6 d/week) to controlled concentrations of single analytical grad solvents in ambient air. After periods ranging from 7 to 30 weeks the animals were perfused with glutaraldehyde and samples of nerves were processed for light microscopy of sections and of teased fibers. Animals treated with n-hexane at 5000 ppm (14 weeks) or 2500 ppm (30 weeks) developed the typical giant axonal degeneration already described in rats treated continuously with 400 to 600 ppm of the same solvent for 7 weeks or more. No such alterations were found in rats subjected to the following intermittent respiratory treatments: n-hexane 500 ppm (30 weeks) or 1500 ppm (14 weeks), cyclohexane 1500 or 2500 (30 weeks), n-pentane 3000 ppm (30 weeks), n-heptane 1500 ppm (30 weeks), 2-methylpentane 1500 ppm (14 weeks), and 3-methylpentane 1500 ppm (14 weeks). The following metabolites were found in the urine of rats according to treatment (in parenthesis): 2-methyl-2-pentanol (2-methylpentane); 3-methyl-2-pentanol and 3-methyl-3-pentanol (3-methylpentane), 2-hexanol, 3-hexanol, gamma-valerolactone, 2,5-dimethylfuran, and 2,5-hexanedione (n-hexane). 2-Hexanol was found to be the main urinary metabolite of n-hexane, while 2,5-hexanedione was present only in a lesser proportion. This feature of rat metabolism suggests that in this species 2,5-hexanedione reaches an effective level at its site of action during intermittent respiratory treatment with n-hexane with difficulty and explains the high concentrations necessary to cause polyneuropathy in rats subjected to this treatment. PMID:6277548

  20. Influence of analyte overloading on retention in gas-liquid chromatography: a molecular simulation view.

    PubMed

    Wick, Collin D; Siepmann, J Ilja; Schures, Mark R

    2002-01-01

    In an attempt to elucidate the molecular basis for concentration (isotherm) effects on retention in gas-liquid chromatography, configurational-bias Monte Carlo simulations in the Gibbs ensemble were carried out to investigate changes in analyte partitioning caused by overloading a model chromatographic system with either an alkane or an alcohol. Squalane was used as the stationary-phase material, and the analytes included n-pentane, n-hexane, n-heptane, 1 -butanol, and 1-pentanol. Three systems were studied that differed in the mobile-phase composition: (i) a helium vapor, (ii) a n-hexane vapor, and (iii) a 1-pentanol-saturated helium vapor. While the amount of helium that partitions into the stationary phase is very small, both n-hexane and 1-pentanol partition strongly into and thereby swell the stationary phase. Although the swelling of the stationary phase leads to a reduction in the partition coefficients for the alkane solutes for both the n-hexane- and 1-pentanol-swollen stationary phases, the effects on the alcohol solutes differ markedly. Whereas saturation by n-hexane causes a decrease of the alcohol partition contants (to an extent similar to that for the alkane solutes), the saturation by 1-pentanol causes a dramatic increase of the alcohol partition coefficients; e.g., the Kovats index of 1-butanol increases by more than 150 Kovats units. The formation of hydrogen-bonded alcohol aggregates in the liquid phase is the microscopic origin for the dramatic effect of 1-pentanol saturation on the retention of alcohols. PMID:11795813

  1. Crystal structure of bis­(benzyl­amine-κN)[5,10,15,20-tetra­kis­(4-chloro­phen­yl)porphyrinato-κ4 N]iron(II) n-hexane monosolvate

    PubMed Central

    Dhifaoui, Selma; Harhouri, Wafa; Bujacz, Anna; Nasri, Habib

    2016-01-01

    In the title compound, [FeII(C44H24Cl4N4)(C6H5CH2NH2)2]·C6H14 or [FeII(TPP-Cl)(BzNH2)2]·n-hexane [where TPP-Cl and BzNH2 are 5,10,15,20-tetra­kis­(4-chloro­phen­yl)porphyrinate and benzyl­amine ligands, respectively], the FeII cation lies on an inversion centre and is octa­hedrally coordinated by the four pyrrole N atoms of the porphyrin ligand in the equatorial plane and by two amine N atoms of the benzyl­amine ligand in the axial sites. The crystal structure also contains one inversion-symmetric n-hexane solvent mol­ecule per complex mol­ecule. The average Fe—Npyrrole bond length [1.994 (3) Å] indicates a low-spin complex. The crystal packing is sustained by N—H⋯Cl and C—H⋯Cl hydrogen-bonding inter­actions and by C—H⋯π inter­molecular inter­actions, leading to a three-dimensional network structure. PMID:26870596

  2. Transport properties of nonelectrolyte liquid mixturesII. Viscosity coefficients for the n-hexane + n-hexadecane system at temperatures from 25 to 100C at pressures up to the freezing pressure or 500 MPa

    NASA Astrophysics Data System (ADS)

    Dymond, J. H.; Young, K. J.; Isdale, J. D.

    1980-12-01

    Viscosity coefficients measured with an estimated accuracy of 2% using a self-centering falling body viscometer are reported for n-hexane, n-hexadecane, and four binary mixtures at 25, 50, 75, and 100C at pressures up to the freezing pressure or 500 MPa. The data for a given composition at different temperatures and pressures are very satisfactorily correlated by a plot of ?, defined as 104 ?V 2/3/( MT)1/2 in the cgs system of units, or generally, 9.118107 ? V 2/3/( MRT)1/2, versus log V', as suggested by the hard-sphere theories, where V' = V V 0( T R)/ V 0( T) and V 0 represents the close-packed volume at temperature T and reference temperature T R . The experimental results for all compositions are fitted, generally well within the estimated uncertainty, by the equation 1 10765_2004_Article_BF00516563_TeX2GIFE1.gif ln ? ' = {text{ - 1}}{text{.0 + }}{BV_0 }/{V - V_0 } where B and V 0 are temperature and composition dependent. Values of B and V 0 for the mixtures are simply related to values for the pure liquids, and viscosity coefficients calculated on the basis of this equation have an estimated accuracy of 3%. The effectiveness of the recently recommended empirical Grunberg and Nissan equation is investigated. It is found that the parameter G is pressure dependent, as well as composition dependent, but is practically temperature independent.

  3. Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

    NASA Technical Reports Server (NTRS)

    DeMore, W.; Bayes, K.

    1998-01-01

    Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.

  4. Comparative effect of organosulfur compounds on catalysts for the n-heptane isomerization reaction at medium pressure: Mo{sub 2}C-oxygen-modified, MoO{sub 3}-carbon-modified, Pt/{gamma}-Al{sub 2}O{sub 3}, and Pt/{beta}-zeolite catalysts

    SciTech Connect

    York, A.P.E.; Pham-Huu, C.; Del Gallo, P.; Ledoux, M.J.; Blekkan, E.A.

    1996-03-01

    Molybdenum oxycarbide formed from oxidized Mo{sub 2}C or reduced MoO{sub 3} is an active and very selective catalyst for the isomerization of n-heptane compared to supported Pt. Deactivation experiments performed on the catalysts with different concentrations of organosulfur compounds show that molybdenum oxycarbide exhibits a very high resistance to deactivation, whereas with platinum-based catalysts deactivation occurs even at low sulfur concentration in the feed. Deactivation can be slowed by increasing the hydrogen partial pressure from 6 to 20 bar. In these conditions, the molybdenum oxycarbide shows no deactivation with sulfur concentrations up to 120 ppm of S. In addition, the deactivated molybdenum catalysts can be easily regenerated by mild oxidative treatment under flowing air at atmospheric pressure and 723 K for 2 h followed by a reactivation period under the hydrogen and hydrocarbon mixture.

  5. Benchmark thermochemistry of the C(n)H(2n+2) alkane isomers (n = 2-8) and performance of DFT and composite ab initio methods for dispersion-driven isomeric equilibria.

    PubMed

    Karton, Amir; Gruzman, David; Martin, Jan M L

    2009-07-23

    The thermochemistry of linear and branched alkanes with up to eight carbons has been reexamined by means of W4, W3.2lite and W1h theories. "Quasi-W4" atomization energies have been obtained via isodesmic and hypohomodesmotic reactions. Our best atomization energies at 0 K (in kcal/mol) are 1220.04 for n-butane, 1497.01 for n-pentane, 1774.15 for n-hexane, 2051.17 for n-heptane, 2328.30 for n-octane, 1221.73 for isobutane, 1498.27 for isopentane, 1501.01 for neopentane, 1775.22 for isohexane, 1774.61 for 3-methylpentane, 1775.67 for diisopropyl, 1777.27 for neohexane, 2052.43 for isoheptane, 2054.41 for neoheptane, 2330.67 for isooctane, and 2330.81 for hexamethylethane. Our best estimates for DeltaH(f,298K)(o) are -30.00 for n-butane, -34.84 for n-pentane, -39.84 for n-hexane, -44.74 for n-heptane, -49.71 for n-octane, -32.01 for isobutane, -36.49 for isopentane, -39.69 for neopentane, -41.42 for isohexane, -40.72 for 3-methylpentane, -42.08 for diisopropyl, -43.77 for neohexane, -46.43 for isoheptane, -48.84 for neoheptane, -53.29 for isooctane, and -53.68 for hexamethylethane. These are in excellent agreement (typically better than 1 kJ/mol) with the experimental heats of formation at 298 K obtained from the CCCBDB and/or NIST Chemistry WebBook databases. However, at 0 K, a large discrepancy between theory and experiment (1.1 kcal/mol) is observed for only neopentane. This deviation is mainly due to the erroneous heat content function for neopentane used in calculating the 0 K CCCBDB value. The thermochemistry of these systems, especially that of the larger alkanes, is an extremely difficult test for density functional methods. A posteriori corrections for dispersion are essential. Particularly for the atomization energies, the B2GP-PLYP and B2K-PLYP double hybrids and the PW6B95 hybrid meta-GGA clearly outperform other DFT functionals. PMID:19569667

  6. Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: Nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors

    SciTech Connect

    Abdelsayed, Victor; Samy El-Shall, M.

    2014-08-07

    This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicates that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor. Strong correlation is found between the seed nanoparticle's size and the degree of the supersaturation of the condensing vapor. This result and the agreement among the calculated Kelvin diameters and the size of the nucleating Al nanoparticles determined by transmission electron microscopy provide strong proof for the development of a new approach for the separation and characterization of heterogeneous nuclei formed in organic vapors. These processes can take place in the atmosphere by a combination of several organic species including polar compounds which could be very efficient in activating charged nanoparticles and cluster ions of atmospheric relevance.

  7. Fully atomistic molecular-mechanical model of liquid alkane oils: Computational validation.

    PubMed

    Zahariev, Tsvetan K; Slavchov, Radomir I; Tadjer, Alia V; Ivanova, Anela N

    2014-04-15

    Fully atomistic molecular dynamics simulations were performed on liquid n-pentane, n-hexane, and n-heptane to derive an atomistic model for middle-chain-length alkanes. All simulations were based on existing molecular-mechanical parameters for alkanes. The computational protocol was optimized, for example, in terms of thermo- and barostat, to reproduce properly the properties of the liquids. The model was validated by comparison of thermal, structural, and dynamic properties of the normal alkane liquids to experimental data. Two different combinations of temperature and pressure coupling algorithms were tested. A simple differential approach was applied to evaluate fluctuation-related properties with sufficient accuracy. Analysis of the data reveals a satisfactory representation of the hydrophobic systems behavior. Thermodynamic parameters are close to the experimental values and exhibit correct temperature dependence. The observed intramolecular geometry corresponds to extended conformations domination, whereas the intermolecular structure demonstrates all characteristics of liquid systems. Cavity size distribution function was calculated from coordinates analysis and was applied to study the solubility of gases in hexane and heptane oils. This study provides a platform for further in-depth research on hydrophobic solutions and multicomponent systems. PMID:24554590

  8. Rate constants for OH with selected large alkanes : shock-tube measurements and an improved group scheme.

    SciTech Connect

    Sivaramakrishnan, R.; Michael, J. V.; Chemical Sciences and Engineering Division

    2009-04-30

    High-temperature rate constant experiments on OH with the five large (C{sub 5}-C{sub 8}) saturated hydrocarbons n-heptane, 2,2,3,3-tetramethylbutane (2,2,3,3-TMB), n-pentane, n-hexane, and 2,3-dimethylbutane (2,3-DMB) were performed with the reflected-shock-tube technique using multipass absorption spectrometric detection of OH radicals at 308 nm. Single-point determinations at {approx}1200 K on n-heptane, 2,2,3,3-TMB, n-hexane, and 2,3-DMB were previously reported by Cohen and co-workers; however, the present work substantially extends the database to both lower and higher temperature. The present experiments span a wide temperature range, 789-1308 K, and represent the first direct measurements of rate constants at T > 800 K for n-pentane. The present work utilized 48 optical passes corresponding to a total path length of {approx}4.2 m. As a result of this increased path length, the high OH concentration detection sensitivity permitted pseudo-first-order analyses for unambiguously measuring rate constants. The experimental results can be expressed in Arrhenius form in units of cm{sup 3} molecule{sup -1} s{sup -1} as follows: K{sub OH+n-heptane} = (2.48 {+-} 0.17) x 10{sup -10} exp[(-1927 {+-} 69 K)/T] (838-1287 K); k{sub OH+2,2,3,3-TMB} = (8.26 {+-} 0.89) x 10{sup -11} exp[(-1337 {+-} 94 K)/T] (789-1061 K); K{sub OH+n-pentane} = (1.60 {+-} 0.25) x 10{sup -10} exp[(-1903 {+-} 146 K)/T] (823-1308 K); K{sub OH+n-hexane} = (2.79 {+-} 0.39) x 10{sup -10} exp[(-2301 {+-} 134 K)/T] (798-1299 K); and k{sub OH+2,3-DMB} = (1.27 {+-} 0.16) x 10{sup -10} exp[(-1617 {+-} 118 K)/T] (843-1292 K). The available experimental data, along with lower-T determinations, were used to obtain evaluations of the experimental rate constants over the temperature range from {approx}230 to 1300 K for most of the title reactions. These extended-temperature-range evaluations, given as three-parameter fits, are as follows: k{sub OH+n-heptane} = 2.059 x 10{sup -5}T{sup 1.401} exp(33 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (241-1287 K); k{sub OH+2,2,3,3-TMB} = 6.835 x 10{sup -17}T{sup 1.886} exp(-365 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (290-1180 K); k{sub OH+n-pentane} = 2.495 x 10{sup -16}T{sup 1.649} exp(80 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (224-1308 K); k{sub OH+n-hexane} = 3.959 x 10{sup -18}T{sup 2.218} exp(443 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (292-1299 K); and k{sub OH+2,3-DMB} = 2.287 x 10{sup -17}T{sup 1.958} exp(365 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (220-1292 K). The experimental data and the evaluations obtained for these five larger alkanes in the present work were used along with prior data/evaluations obtained in this laboratory for H abstractions by OH from a series of smaller alkanes (C{sub 3}?C{sub 5}) to devise rate rules for abstractions from various types of primary, secondary, and tertiary H atoms. Specifically, the current scheme was applied with good success to H abstractions by OH from a series of n-alkanes (n-octane through n-hexadecane). The total rate constants using this group scheme for reactions of OH with selected large alkanes are given as three-parameter fits in this article. The rate constants for the various abstraction channels in any large n-alkane can also be obtained using the groups listed in this article. The present group scheme serves to reduce the uncertainties in rate constants for OH + alkane reactions.

  9. Determination of thermodynamic properties of poly (cyclohexyl methacrylate) by inverse gas chromatography.

    PubMed

    Kaya, Ismet; Pala, Cigdem Yigit

    2014-07-01

    In this work, some thermodynamic properties of poly (cyclohexyl methacrylate) were studied by inverse gas chromatography (IGC). For this purpose, the polymeric substance was coated on Chromosorb W and which was filled into a glass column. The retention times (t(r)) of the probes were determined from the interactions of poly (cyclohexyl methacrylate) with n-pentane, n-hexane, n-heptane, n-octane, n-decane, methanol, ethanol, 2-propanol, butanol, acetone, ethyl methyl ketone, benzene, toluene and o-xylene by IGC technique. Then, the specific volume (Vg(0)) was determined for each probe molecule. By using (1/T; lnVg(0)) graphics, the glass transition temperature of poly (cyclohexyl methacrylate) was found to be 373 K. The adsorption heat under the glass transition temperature (deltaH(a)), and partial molar heat of sorption above the glass transition (deltaH1(S)), partial molar free energy of sorption (deltaG1(S)) and partial molar entropy of sorption (deltaS1(S)) belonging to sorption for every probe were calculated. The partial molar heat of mixing at infinite dilution (deltaH1(infinity)), partial molar free energy of mixing at infinite dilution (deltaG1(infinity)), Flory-Huggins interaction parameter (chi12(infinity)) and weight fraction activity coefficient (a1/w1)(infinity) values of polymer-solute systems were calculated at different column temperatures. The solubility parameters (delta2) of the polymer were obtained by IGC technique. PMID:25255568

  10. Transport properties of nonelectrolyte liquid mixturesIII. Viscosity coefficients for n-octane, n-dodecane, and equimolar mixtures of n-octane + n-dodecane and n-hexane + n-dodecane from 25 to 100C at pressures up to the freezing pressure or 500 MPa

    NASA Astrophysics Data System (ADS)

    Dymond, J. H.; Robertson, J.; Isdale, J. D.

    1981-06-01

    Viscosity coefficients measured with an estimated accuracy of 2% using a new design of self-centering falling body viscometer are reported for n-octane, n-dodecane, and equimolar mixtures of n-octane + n-dodecane and n-hexane + n-dodecane at 25, 50, 75, and 100C at pressures up to the freezing pressure or 500 MPa. The data for a given composition at different temperatures and pressures are very satisfactorily correlated by a plot of ?, defined as 104?V2/3/( MT)1/2 in the cgs system of units or, generally, 9.118107?V2/3/( MRT)1/2, versus log V', where V' = V V 0( T R)/ V 0( T) and V 0 represents the close-packed volume at temperature T and reference temperature T R. The experimental results are fitted, generally well within the estimated uncertainty, by the equation 10765_2004_Article_BF00503937_TeX2GIFE1.gif ln ? ' = - 1.0 + {BV_0 }/{V - V_0 } , where B and V 0 are temperature and composition dependent. Values of B and V 0 for the mixtures are simply related to values for the pure liquids. The binary mixing rule of Grunberg and Nissan is investigated. Values of the mixing parameter G are positive, tend to increase with increases in pressure, and also increase with increases in difference in carbon number of the two pure components.

  11. Reversible cerebral and brain stem dysfunction in n: Hexane neuropathy

    PubMed Central

    Puri, Vinod; Gupta, Abhijit Das; Chaudhry, Neera; Saran, Ravindra Kumar

    2015-01-01

    A 18-year-old male, screen printer by profession developed sensory motor polyneuropathy, change in his behavior, bilateral 6th and 7th cranial nerve palsies, down beat nystagmus and cerebellar dysarthria. He had bilaterally prolonged P100 latency; left: 137 ms; right: 144 ms. P 37 was not recordable on either side while N 20 was normal. The inter latency difference between Ipsilateral R2 and Contralateral R2 was 6.15 ms, on the left side and normal on the right side. In the follow-up, there was normalization of the blink reflex study, improvement in P100 latency [left: 114 ms; right: 120 ms.] but worsening of peripheral nerve conductions. The sequential clinical recovery was of the behavioral dysfunction, down beat nystagmus, 6th nerve, 7th nerve involvement and ataxia, in that order. Sural nerve biopsy showed loss of large diameter myelinated fibers. PMID:26713026

  12. Reversible cerebral and brain stem dysfunction in n: Hexane neuropathy.

    PubMed

    Puri, Vinod; Gupta, Abhijit Das; Chaudhry, Neera; Saran, Ravindra Kumar

    2015-01-01

    A 18-year-old male, screen printer by profession developed sensory motor polyneuropathy, change in his behavior, bilateral 6(th) and 7(th) cranial nerve palsies, down beat nystagmus and cerebellar dysarthria. He had bilaterally prolonged P100 latency; left: 137 ms; right: 144 ms. P 37 was not recordable on either side while N 20 was normal. The inter latency difference between Ipsilateral R2 and Contralateral R2 was 6.15 ms, on the left side and normal on the right side. In the follow-up, there was normalization of the blink reflex study, improvement in P100 latency [left: 114 ms; right: 120 ms.] but worsening of peripheral nerve conductions. The sequential clinical recovery was of the behavioral dysfunction, down beat nystagmus, 6(th) nerve, 7(th) nerve involvement and ataxia, in that order. Sural nerve biopsy showed loss of large diameter myelinated fibers. PMID:26713026

  13. [Surface characterization of urushiol-titanium chelate polymers by inverse gas chromatography].

    PubMed

    Xu, Yanlian; Lin, Jinhuo; Xia, Jianrong; Hu, Binghuan

    2011-03-01

    Urushiol-titanium chelate polymer (UTP), the reaction product of urushiol with titanium compound, is a special eco-friendly polymer with excellent performances, such as strong acids-resistance, strong alkalis-resistance, salt solution-resistance and several organic solvent-resistance. Inverse gas chromatography (IGC) was used to measure the dispersive component of surface free energy (gamma(s)d) and the Lewis acid-base parameters of UTP in this work. The gamma(s)d and the acid/base characters of UTP' surfaces were estimated by the retention time with different non-polar and polar probes at infinite dilution region. n-Pentane (C5), n-hexane (C6), n-heptane (C7), n-octane (C8) and n-nonane (C9) were chosen as the non-polar probes to characterize the gamma(s)d. Trichloromethane (CHCl3), tetrahydrofuran (THF) and acetone were chosen as polar probes to detect the Lewis acid-base parameters. The specific free energy (deltaG(a)AB) and the enthalpy (deltaH(a)AB) of adsorption corresponding to acid-base surface interactions were determined. By correlating deltaH(a)AB with the donor and acceptor numbers of the probes, the acidic (K(a)) and the basic (K(b)) parameters of the samples were calculated. The results showed that the dispersive components of the free energy of UTP were 37.68, 33.53, 35.92, 24.01 and 31.32 mJ/m2 at 70, 80, 90, 100 and 110 degrees C, respectively. The Lewis acidic number K(a) of UTP was 0.185 3, and the Lewis basic number K(b) was 0.966 2. The results were of great importance to the study of the surface properties and the applications for urushiol-metal chelate polymers. PMID:21657056

  14. Molecular simulation of concurrent gas-liquid interfacial adsorption and partitioning in gas-liquid chromatography.

    PubMed

    Wick, Collin D; Siepmann, J Ilja; Schure, Mark R

    2002-07-15

    The importance of adsorption at the gas-liquid interface on retention in gas-liquid chromatography has been controversial since the pioneering work of Martin in the 1960s. In particular, experimental studies using chromatographic and static techniques to quantify partitioning and adsorption of polar analytes on nonpolar liquid phases yielded conflicting results. In this work, Monte Carlo simulations were carried out for a free-standing liquid slab of squalane surrounded by a helium vapor to investigate interfacial adsorption effects for n-pentane, n-hexane, n-heptane, 1-butanol, and benzene solutes at infinite dilution. The simulations indicate preferential adsorption for the flexible alkane and alcohol solutes in a narrow region just inside the Gibbs dividing surface, but no such effect was observed for the rigid benzene solute. Nevertheless, the extent of the interfacial enrichment is small, as measured by the partition coefficient between the bulk liquid and the interfacial region (K(bulk-interface) approximately 1.5). In addition, a region that is slightly depleted for all solute molecules is found to separate the interfacial and bulk regions of the squalane slab. Thus, adsorption at the gas-liquid interface should not contribute significantly to the retentive behavior observed in gas-liquid chromatography on nonpolar capillary columns but might play a role in packed-bed columns with low bonded-phase loadings. The origin for the small enrichments and more favorable free energies for solutes at the interface is that the enthalpies of solvation decrease to a smaller relative extent than the entropies of solvation compared to the bulk liquid. PMID:12139063

  15. Characteristics of atmospheric non-methane hydrocarbons in Foshan City, China.

    PubMed

    Tan, Jihua; Guo, Songjun; Ma, Yongliang; He, Kebin; Yang, Fumo; Yu, Yongchang; Wang, Jiewen

    2011-12-01

    Foshan is the most air-polluted city in Pearl River Delta. Non-methane hydrocarbons (NMHCs) were investigated for the first time in Foshan in winter 2008. Ethene, ethane, ethyne, propane, i-pentane, and toluene were the most abundant hydrocarbons and observed to be higher in Foshan than those in many other cities in China. Different from other cities, ethene and ethane were observed to be the two highest compounds in Foshan. Generally, the most abundant hydrocarbons showed high mixing ratios in the morning (0930-1030 hours), decreased to the lowest level in the afternoon (1430-1530 hours), and increased to higher value in the evening (1930-2030 hours). But i-pentane exhibited a different diurnal pattern with the highest level (13.4 5.8 ppbv) in the afternoon, implying the acceleration of solvent evaporation resulting from higher temperature. Correlation coefficients (R(2)?= 66% for n = 6 at 95% confidence level) of the individual hydrocarbons with ethyne and i-pentane indicated vehicular emissions were the main sources of ethene, propene, i-butene, isoprene, benzene and toluene, while gasoline evaporation was responsible for n-pentane, n-hexane, and n-heptane. The good correlation of most of the hydrocarbons with ethyne, indicating vehicular emissions, were the main sources of NMHCs. B/T ratio was 0.36 0.06, implying vehicular emissions acted as the major contributors as well as additional emissions of toluene emitted from solvent usage. According to investigation, it also suggested that LPG leakage was the main source of propane, while NG leakage was responsible for ethane in Foshan City. PMID:21380924

  16. Viscometric determination of the onset of asphaltene flocculation: A novel method

    SciTech Connect

    Escobedo, J.; Mansoori, G.A.

    1995-05-01

    A new technique for the determination of the onset of asphaltene flocculation has been developed through accurate viscosity measurements of a crude oil being diluted with a precipitating agent (n-pentane, n-heptane, n-nonane). This detection method is based on experimental observations of an increase in the viscosity of a crude oil-asphaltene-precipitating agent suspension in which asphaltene particle aggregation occurs. The key point in this development is the phenomenon of asphaltene flocculation induced by the addition of a n-paraffin hydrocarbon (i.e. n-heptane, n-pentane, n-nonane) to crude oil. The onset of asphaltene flocculation is detected graphically, and its location is enhanced by comparison of the analyte curve with a reference system. The reference system was developed using polar and non-precipitating solvents (i.e. toluene, benzene, THF).

  17. pVT data of poly(isobutylene) in n-heptane

    NASA Astrophysics Data System (ADS)

    Wohlfarth, Ch.

    This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Brnstein - Group VIII `Advanced Materials and Technologies'.

  18. pVT data of polypropylene, atactic in n-heptane

    NASA Astrophysics Data System (ADS)

    Wohlfarth, Ch.

    This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Brnstein - Group VIII `Advanced Materials and Technologies'.

  19. Enthalpy of dilution of poly(isobutylene) in n-heptane

    NASA Astrophysics Data System (ADS)

    Wohlfarth, Ch.

    This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Brnstein - Group VIII `Advanced Materials and Technologies'.

  20. Analysis of the n-heptane soluble fraction of coal hydrogenolysis products by HPLC

    SciTech Connect

    Bodily, D.M.; Miller, J.W.; England, M.J.

    1983-01-01

    Samples of heavy oils produced by the hydrogenolysis of coal were extracted with heptane, and the heptane fraction was separated by high performance liquid chromatography (HPLC) and characterized by various analytical methods. Results of analyses for various properties of liquids derived from various coals are presented. The HPLC offers the potential for separating and characterizing coal-derived liquids; however, the samples analyzed did not show major differences even though they were produced from different coals with different degrees of conversion. (BLM)

  1. [Study on adsorption properties of organic vapor on activated carbons].

    PubMed

    Cai, Dao-Fei; Huang, Wei-Qiu; Wang, Dan-Li; Zhang, Lin; Yang, Guang

    2013-12-01

    Adsorption technology is widely used in oil vapor recovery, and adsorbents have decisive effect on separation. Three kinds of activated carbon (AC) were chosen to study their adsorption properties and adsorption energy, where n-hexane and n-heptane acted as adsorbate and adsorption experiments were conducted at 293.15 K. At the same time, regression formula of Logistic model was used to fit the throughout curves of active carbons. The results showed that: surface area and pore volume of activated carbon were the main factors affecting its adsorption properties; the adsorption behavior of n-hexane and n-heptane were corresponding to Langmuir adsorption isotherm model; adsorption energy of these three kinds of activated carbon became greater with increasing specific surface area. Fitting curve of Logistic model had high similarity with the experimental results, which could be used in the prediction of breakthrough curves of activated carbons. PMID:24640910

  2. In vitro quantitative structure-activity relationship assessment of pyrrole adducts production by gamma-diketone-forming neurotoxic solvents.

    PubMed

    Sanz, P; Flores, I C; Soriano, T; Repetto, G; Repetto, M

    1995-10-01

    Organic solvents that are metabolically transformable into gamma-diketones produce central- peripheral distal axonopathy. One of the mechanisms proposed to explain the development of this neuropathy has been the formation of pyrrole adducts between gamma-diketone metabolites and -amine groups of lysine residues on the neuronal cytoskeletal proteins. In vivo studies on the neurotoxic capability of different solvents, derivatives of n-hexane and n-heptane, have previously established the quantitative structure-activity sequence. An in vitro assay for the quantification of pyrrole adduct formation is reported here that allows prediction of neurotoxic potency, using an index of neurotoxic potential. The kinetics of pyrrole adduct formation was established by incubation of each solvent with a purified microsomal fraction of liver from rats preinduced with phenobarbital. The solvents assayed in the in vitro system were 2-hexanone, 3,4-dimethylhexane, 2,5-hexanedione, 3,4-dimethyl-2,5-hexanedione, 2-hexanol and 2,5-hex- anediol as derivatives of n-hexane; and 4-heptanone, 5-methyl-3-heptanone, 6-methyl-2,4-heptanedione and 4-heptanol as derivatives of n-heptane. The results indicate good correlation between neurotoxic potency in vivo and quantitative production of adducts in vitro with both n-hexane and n-heptane derivatives. PMID:20650157

  3. Removal of n-hexane by Fusarium solani with a gas-phase biofilter.

    PubMed

    Arriaga, Sonia; Revah, Sergio

    2005-12-01

    A gas-phase biofilter inoculated with the fungus Fusarium solani, isolated from a consortium grown on hexane vapors, was used to degrade this compound. The biofilter, packed with perlite and operated with an empty bed residence time of 60 s, was supplied with hexane concentrations between 0.5 gm(-3) and 11 gm(-3). Biofilter performance was evaluated over 100 days of operation. Several strategies for supplying the nutritive mineral medium were assayed to maintain favorable conditions for the fungal growth and activity. The Fusarium system was able to sustain an average elimination capacity of 90 gm(-3)(reactor) h(-1) with a maximum of 130 gm(-3)(reactor) h(-1) . The mass transfer limitations due to high biomass development in the biofilter were confirmed in batch experiments. Bacterial contamination was observed, but experiments in the biofilter and in batch reactors using selective inhibitors and controlled pH confirmed the predominant role of the fungus. Results indicate that fungal biofilters can be an effective alternative to conventional abatement technologies for treating hydrophobic compounds. PMID:15933872

  4. Aerobic/anaerobic/aerobic sequenced biodegradation of a mixture of chlorinated ethenes, ethanes and methanes in batch bioreactors.

    PubMed

    Frascari, Dario; Fraraccio, Serena; Nocentini, Massimo; Pinelli, Davide

    2013-01-01

    A novel aerobic/anaerobic/aerobic treatment was implemented in batch reactors containing aquifer materials from a site contaminated by tetrachloroethylene (PCE), trichloroethylene (TCE), vinyl chloride (VC), 1,1,2-trichloroethane (1,1,2-TCA) and chloroform (CF). Consortia grown aerobically on methane, propane, n-pentane and n-hexane completely biodegraded the chlorinated solvent mixture, via aerobic cometabolism of VC, CF, TCE and 1,1,2-TCA, followed by PCE reductive dechlorination (RD) to 1,2-cis-dichlorothylene (cis-DCE) or TCE, and cis-DCE/TCE cometabolism in a further aerobic phase. n-Hexane was the best substrate. No electron donor was supplied for RD, which likely utilized cellular material produced during the aerobic phase. Chloride release was stoichiometric with chlorinated solvent biodegradation. According to the Lepidium sativum ecotoxicity test, a decreased toxicity was observed with propane, n-pentane and n-hexane, but not methane. A kinetic study of PCE RD allowed to estimate the PCE maximum specific rate (0.57 0.07 mg mg(protein)(-1) day(-1)) and half-saturation constant (6.7 1.5 mg L(-1)). PMID:23201903

  5. Impact of n-heptane as surfactant in the formation of CdO nanowires through microwave combustion

    NASA Astrophysics Data System (ADS)

    Sathya Raj, D.; Jayaprakash, R.; Prakash, T.; kumar, Sanjay; Neri, G.; Krishnakumar, T.

    2013-02-01

    A microwave-assisted combustion route for the preparation of cadmium oxide (CdO) nanowire is carried and its characterization results are discussed. This method resembles a supportive way in the formation of CdO nanowire which is confirmed with the structure and morphological analysis carried for the prepared sample. Microwave combustion method is a cost effective and less time consumption to achieve CdO nanowires. The controlled shapes and size are attained due to microwave irradiation. Yielded sample is investigated with Fourier transformation infra-red (FTIR) spectra, X-ray diffraction (XRD) pattern, energy dispersive X-ray (EDX) spectra and transmission electron microscopy (TEM) with SAED pattern. The formation of CdO phase with a face centered cubic structure is confirmed from XRD spectra and the presence of Cdsbnd O metallic bond is also confirmed with FTIR spectra. The formation of CdO nanowires is visualized through the TEM images and presence of elements is also recorded from EDX spectra.

  6. Photocurrent enhancement in nonpolar liquids by the addition of electron scavengers

    SciTech Connect

    Howell, G.A.; Lee, K.; Tweeten, D.W.; Lipsky, S.

    1988-07-14

    The photocurrent from anthracene, triphenylamine, and N,N,N',N'-tetramethyl-p-phenylenediamine excited above their ionization thresholds in liquid n-pentane or n-hexane is found to be enhanced by the addition of low concentrations (/approx lt/0.02 M) of the electron scavengers perfluoromethylcyclohexane or perfluorodecalin. The enhancement is not observed in solvents of higher electron mobility (e.g.,. cyclohexane, isooctane, etc.) or for scavengers of lower electron affinity (e.g., n-perfluorohexane). For the solute naphthalene, no enhancement is observed under any conditions. The effects of excitation energy and applied electric field strength are reported.

  7. Retama monosperma n-hexane extract induces cell cycle arrest and extrinsic pathway-dependent apoptosis in Jurkat cells

    PubMed Central

    2014-01-01

    Background Retama monosperma L. (Boiss.) or Genista monosperma L. (Lam.), locally named as “R’tam”, is an annual and spontaneous plant belonging to the Fabaceae family. In Morocco, Retama genus is located in desert regions and across the Middle Atlas and it has been widely used in traditional medicine in many countries. In this study, we show that Retama monosperma hexane extract presents significant anti-leukemic effects against human Jurkat cells. Methods Human Jurkat cells, together with other cell lines were screened with different concentrations of Retama monosperma hexane extract at different time intervals. Growth inhibition was determined using luminescent-based viability assays. Cell cycle arrest and apoptosis were measured by flow cytometry analysis. Combined caspase 3 and 7 activities were measured using luminometric caspase assays and immunoblots were performed to analyze expression of relevant pro- and anti-apoptotic proteins. GC-MS were used to determine the chemical constituents of the active extract. Results Retama monosperma hexane extract (Rm-HE) showed significant cytotoxicity against Jurkat cells, whereas it proved to be essentially ineffective against both normal mouse fibroblasts (NIH3T3) and normal lymphocytes (TK-6). Cytometric analysis indicated that Rm-HE promoted cell cycle arrest and apoptosis induction accompanied by DNA damage induction indicated by an increase in p-H2A.X levels. Rm-HE induced apoptosis was partially JNK-dependent and characterized by an increase in Fas-L levels together with activation of caspases 8, 3, 7 and 9, whereas neither the pro-apoptotic nor anti-apoptotic mitochondrial membrane proteins analyzed were significantly altered. Chemical identification analysis indicated that α-linolenic acid, campesterol, stigmasterol and sitosterol were the major bioactive components within the extract. Conclusions Our data suggest that bioactive compounds present in Rm-HE show significant anti leukemic activity inducing cell cycle arrest and cell death that operates, at least partially, through the extrinsic apoptosis pathway. PMID:24460687

  8. Trapping of Methanol, Hydrogen Cyanide, and n-Hexane in Water Ice, above Its Transformation Temperature to the Crystalline Form

    NASA Astrophysics Data System (ADS)

    Notesco, G.; Bar-Nun, A.

    1997-04-01

    HCN and n-C 6H 14were found experimentally to be trapped in water ice, when codeposited with water vapor on a cold plate, at 140 K and CH 3OH even at 160 K. At these temperatures at least part of the water ice is cystalline. These three gases have relatively high sublimation temperatures, whereas the gases studied earlier, Ar, Kr, Xe, CO, CH 4, and N 2, which have lower sublimination temperatures, are trapped only in amorphous water ice, up to ˜100 K. It seems that the major factor determining the efficiency of gas trapping by water ice, during codeposition of a gas-water vapor mixture on a cold plate, is the sublimation temperatures of the gases to be trapped. Those with a high sublimation temperature remain, during codeposition, longer in the pores of the water ice which are open to the surface, until they are covered by additional ice layers. Only methanol seems to form a clathrate hydrate, in agreement with the experimental results of D. Blake et al.(1991), Science254, 548-551), which points to the importance of the interaction of the gas molecules with the water molecules in the ice. Consequently, comets and icy satellites that were formed in the Jupiter-Saturn region and their subnebulae could trap CH 3OH, HCN, and heavy hydrocarbons, whereas comets and icy satellites that were formed in the Uranus-Neptune region, at the outskirts of the Saturnian subnebulae (Titan), and beyond the planets in the Kuiper belt could trap also gases having lower sublimation temperatures.

  9. Catalytic reactions of n-alkanes on. beta. -W sub 2 C and WC: The effect of surface oxygen on reaction pathways

    SciTech Connect

    Ribeiro, F.H.; Boudart, M.; Dalla Betta, R.A. ); Iglesia, E. )

    1991-08-01

    Tungsten carbide powders with WC and {beta}-W{sub 2}C structures catalyze alkane hydrogenolysis reactions. Alkanes adsorb on fresh carbide surfaces strongly leading to rapid deactivation by carbon fragments and to high selectivity to hydrogenolysis products. n-Hexane isomerization or dehydrocyclization products were not observed on fresh carbides. Chemisorbed oxygen lowers the binding energy of adsorbed intermediates and decreases both hydrogenolysis and deactivation rates. Oxygen-exposed carbides catalyze n-hexane and n-heptane isomerization with high selectivity (74-99%). Isomerization involves methyl-shift pathways that require alkene intermediates. These results and the well-known acid properties of WO{sub x} surface species suggest that oxygen-exposed tungsten carbides catalyze bifunctional (dehydrogenation/carbenium-ion) alkane isomerization pathways.

  10. Polydiacetylene-embedded microbeads for colorimetric and volumetric sensing of hydrocarbons.

    PubMed

    Hong, Jaesung; Park, Dong-Hoon; Baek, Sunghoon; Song, Simon; Lee, Chan Woo; Kim, Jong-Man

    2015-04-22

    Rational design of a hydrocarbon sensor that enables visual differentiation of saturated aliphatic hydrocarbons (SAHCs) is very difficult owing to the lack of useful functional groups that can interact with the sensor system. Here, we report a microbead embedded with polydiacetylene that undergoes faster swelling and faster blue-to-red color change in response to the hydrocarbons of shorter alkyl chains. Accordingly, visual differentiation among n-pentane, n-heptane, n-nonane, and n-undecane was readily achieved. By taking advantage of the collective effect, construction of a sensor system with amplified response was possible. Combination of microfluidic technology (for bead preparation), PDMS (swellable polymeric matrix), and polydiacetylene (colorimetric material) was key to enabling this unique hydrocarbon sensor. PMID:25821999

  11. Combustion of liquid fuels in a flowing combustion gas environment at high pressures

    NASA Technical Reports Server (NTRS)

    Canada, G. S.; Faeth, G. M.

    1975-01-01

    The combustion of fuel droplets in gases which simulate combustion chamber conditions was considered both experimentally and theoretically. The fuel droplets were simulated by porous spheres and allowed to gasify in combustion gases produced by a burner. Tests were conducted for pressures of 1-40 atm, temperatures of 600-1500 K, oxygen concentrations of 0-13% (molar) and approach Reynolds numbers of 40-680. The fuels considered in the tests included methanol, ethanol, propanol-1, n-pentane, n-heptane and n-decane. Measurements were made of both the rate of gasification of the droplet and the liquid surface temperature. Measurements were compared with theory, involving various models of gas phase transport properties with a multiplicative correction for the effect of forced convection.

  12. Dynamics of pyrenesemicarbazide and pyrenethiosemicarbazide in reverse micelle of AOT in n-heptane: Probing critical penetration of water molecules toward the palisade

    NASA Astrophysics Data System (ADS)

    Maity, Arnab; Das, Shrabanti; Ghosh, Prasun; Das, Tarasankar; Seth, Sourav Kanti; Mondal, Somen; Gupta, Parna; Purkayastha, Pradipta

    2013-11-01

    In the present work, we have introduced two similar probe molecules with pyrene tags that can reside in different positions in the reverse micelles and show opposite dynamism on excitation. Herein, we have changed the concentration of water in the reverse micellar core gradually and monitored the spectrochemical changes in the dynamism of the two designed probe molecules. The results indicate that water molecules penetrate through the interface of the reverse micelles up a certain critical amount.

  13. Kinetic inhibitor effects on methane/propane clathrate hydrate-crystal growth at the gas/water and water/ n-heptane interfaces

    NASA Astrophysics Data System (ADS)

    Kumar, Rajnish; Lee, Ju Dong; Song, Myungho; Englezos, Peter

    2008-03-01

    The influence of the kinetic inhibitor poly( N-vinylpyrrolidone) or PVP on hydrate methane/propane hydrate formation was studied in pre-saturated liquid water with and without the presence of heptane under different undercooling conditions. It was found that when the inhibitor concentration was 0.1 wt%, hydrate formation started as a film at the gas/water interface similar to the crystal behavior without inhibitor. When the inhibitor concentration was 0.5 wt% hydrate formation started at the wall above the gas/water interface and the hydrate film at the gas/water interface was observed as well. However, for inhibitor concentration 1.0 wt%, the hydrate started forming from water droplets attached to the wall above the gas/liquid interface and grew catastrophically. When the inhibitor concentration was 0.1 wt% and undercooling was 13.7 or 8.1 K whiskery or fiber-type hydrate crystals, respectively, were seen within the liquid pool. This morphology was not observed in the absence of PVP. When inhibitor concentration was 0.5 or 1.0 wt% or undercooling was 3.2 K, there was no crystal growth within the liquid pool. Floating crystals were also observed, but were needle-type and thus different from the equiaxed floating crystals found in the system without the inhibitor.

  14. Extraction of gold(III) from hydrochloric acid solutions by CTAB/n-heptane/iso-amyl alcohol/Na2SO3 microemulsion.

    PubMed

    Lu, Wenjuan; Lu, Yanmin; Liu, Fei; Shang, Kai; Wang, Wei; Yang, Yanzhao

    2011-02-28

    The extraction of Au(III) from hydrochloric acid solutions by microemulsion was studied. The extraction experiments were carried out using cetyltrimethylammonium bromide (CTAB) as surfactant and iso-amyl alcohol as co-surfactant. Au(III) was found to be extracted into the microemulsion phase due to ion pair formation such as AuCl(4)(-)CTAB(+). The influence of temperature on the extraction of Au(III) has been investigated at temperatures ranging from 288 to 313 K. Temperature was found to decrease the distribution of Au(III). Thermodynamic parameters like enthalpy and entropy of the extraction, calculated by applying Van't Hoff equation, were -36.76 kJ mol(-1) and -84.87 J mol(-1) K(-1), respectively. Furthermore, the influence of the concentrations of hydrogen ion and chloride anion on the extraction efficiency (E%) were verified. Au(III) was extracted quantitatively (E%>99%) and selectively at the whole range of HCl concentrations (0.2-5 M). Recovery of gold from electrical waste and treatment of CTAB wastewater generated from the extraction were also discussed. Thus, the extraction of Au(III) from hydrochloric acid solutions by microemulsion is an effective approach. PMID:21236565

  15. LIQUID-LIQUID EQUILIBRIA FOR THREE- AND FOUR-COMPONENT SYSTEMS COMPRISED OF WATER + ETHANOL + TOLUENE + N-HEPTANE AT 293 K (R821114)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  16. A kinetic study of n-heptane catalytic cracking over a commercial Y-type zeolite under supercritical and subcritical conditions

    SciTech Connect

    Dardas, Z.; Sueer, M.G.; Ma, Y.H.; Moser, W.R.

    1996-09-01

    Heptane catalytic cracking over a commercial Y-type zeolite (Promoted Octacat) was studied at 475{degrees}C under subcritical and supercritical hydrocarbon conditions. Kinetic measurements showed that the activity of the catalyst was substantially higher during supercritical cracking, suggesting stabilization of the catalyst toward rapid deactivation. A mechanism based on kinetic and in situ cylindrical internal reflectance FTIR (CIR-FTIR) results was developed to explain the performance of the catalyst under supercritical conditions. The dense supercritical reaction medium, well known for its enhanced solubilization capabilities, continuously removes the newly formed coke through solubilization from the zeolite supercages, pore mouths, and the external surface. This results in a higher number of available active sites to perform catalytic cracking and in lower pore diffusion limitations due to the avoidance of pore blockage. The significantly higher yields of the olefinic and paraffinic reaction products and the higher paraffin/olefin ratios under supercritical cracking conditions are in agreement with the above mechanism. Finally, it was shown that a partial regeneration of a moderately deactivated cracking catalyst is possible by the supercritical reaction medium. Reactivation of a severely deactivated catalyst could not be achieved. 36 refs., 16 figs., 4 tabs.

  17. Adsorption calorimetry and enhanced oil recovery: Three component systems, topical report. [Decyltrimethylammonium bromide/water/sodium bromide methanol/toluene/n-heptane

    SciTech Connect

    Noll, L.A.

    1988-03-01

    One objective of this project is to determine the adsorptive losses of EOR chemicals on minerals in a systematic manner and expand adsorption models for incorporation as an adsorption module into chemical flooding simulators. The Woodbury-Noll adsorption model was developed which fits both amount and heat of adsorption simultaneously. Two ternary systems were selected with a view to extending the Woodbury-Noll adsorption model to these systems. In the first of these systems, DTAB/NaBr/H20/silica, competitive effects are not present. In the second system, methanol/toluene/heptane/silica, competitive adsoprtion is present. Flow adsorption calorimetry was carried out on these ternary systems and on their respective binaries. Adsorption calorimetry of DTAB from solutions with added electrolyte showed that the heat and the amount of adsorption increased when the salt content was raised to 3 percent, being approximately constant thereafter. However, the increase in salinity above this amount moved the plateau region to lower surfactant concentrations. Adsorption of DTAB at 45)degree)C resulted in lower adsorption than at 25)degree)C, but the heat release was only slightly lower. The heat and amount of adsorption of methanol from heptane onto silica are both markedly reduced by the presence of toluene in the solution. Densities of the surfactant solutions and of the binaries of methanol/toluene/heptane system are reported. 6 refs., 20 figs., 13 tabs.

  18. High pressure combustion of liquid fuels. [alcohol and n-paraffin fuels

    NASA Technical Reports Server (NTRS)

    Canada, G. S.

    1974-01-01

    Measurements were made of the burning rates and liquid surface temperatures for a number of alcohol and n-paraffin fuels under natural and forced convection conditions. Porous spheres ranging in size from 0.64-1.9 cm O.D. were emloyed to simulate the fuel droplets. The natural convection cold gas tests considered the combustion in air of methanol, ethanol, propanol-1, n-pentane, n-heptane, and n-decane droplets at pressures up to 78 atmospheres. The pressure levels of the natural convection tests were high enough so that near critical combustion was observed for methanol and ethanol vaporization rates and liquid surface temperature measurements were made of droplets burning in a simulated combustion chamber environment. Ambient oxygen molar concentrations included 13%, 9.5% and pure evaporation. Fuels used in the forced convection atmospheric tests included those listed above for the natural convection tests. The ambient gas temperature ranged from 600 to 1500 K and the Reynolds number varied from 30 to 300. The high pressure forced convection tests employed ethanol and n-heptane as fuels over a pressure range of one to 40 atmospheres. The ambient gas temperature was 1145 K for the two combustion cases and 1255 K for the evaporation case.

  19. An analytical system for the measurement of stable hydrogen isotopes in ambient volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Meisehen, T.; Bühler, F.; Koppmann, R.; Krebsbach, M.

    2015-07-01

    Stable isotope measurements in atmospheric volatile organic compounds (VOC) are an excellent tool to analyse chemical and dynamical processes in the atmosphere. While up to now isotope studies of VOC in ambient air mainly focus on carbon isotopes, we herein present a new measurement system to investigate hydrogen isotope ratios in atmospheric VOC. This system consisting of a GC-P-IRMS (Gas Chromatography Pyrolysis Isotope Ratio Mass Spectrometer) and a preconcentration system was thoroughly characterised using a working standard. A precision of better than 9 ‰ (in δD) is achieved for n-pentane, 2-methyl-1,3-butadiene (isoprene), n-heptane, 4-methyl-pentane-2-one (4-methyl-2-pentanone), methylbenzene (toluene), n-octane, ethylbenzene, m/p-xylene, and 1,2,4-trimethylbenzene. A comparison with independent measurements via elemental analysis shows an accuracy of better than 9 ‰ for n-pentane, n-heptane, 4-methyl-2-pentanone, toluene, and n-octane. Above a compound specific minimum peak area the obtained δD values are constant within the standard deviations. In addition, a remarkable influence of the pyrolysis process on the isotope ratios is found and discussed. Reliable measurements are only possible if the ceramic tube used for the pyrolysis is sufficiently conditioned, i.e. the inner surface is covered with a carbon layer. It is essential to verify this conditioning regularly and to renew it if required. Furthermore, influences of a necessary H3+ correction and the pyrolysis temperature on the isotope ratios are discussed. Finally, the applicability to measure hydrogen isotope ratios in VOC at ambient levels is demonstrated with measurements of outside air on five different days in February and March 2015. The measured hydrogen isotope ratios range from -136 to -105 ‰ for n-pentane, from -86 to -63 ‰ for toluene, from -39 to -15 ‰ for ethylbenzene, from -99 to -68 ‰ for m/p-xylene, and from -45 to -34 ‰ for o-xylene.

  20. Dynamics of CN+alkane reactions by crossed-beam dc slice imaging

    SciTech Connect

    Huang Cunshun; Li Wen; Estillore, Armando D.; Suits, Arthur G.

    2008-08-21

    The hydrogen atom abstraction reactions of CN (X {sup 2}{sigma}{sup +}) with alkanes have been studied using the crossed molecular beam technique with dc slice ion imaging at collision energies of 7.5 and 10.8 kcal/mol. The product alkyl radical images were obtained via single photon ionization at 157 nm for the reactions of CN (X {sup 2}{sigma}{sup +}) with n-butane, n-pentane, n-hexane, and cyclohexane. From analysis of the images, we obtained the center-of-mass frame product angular distributions and translational energy distributions directly. The results indicate that the products are largely backscattered and that most of the available energy ({approx}80%-85%) goes to the internal energy of the products. The reaction dynamics is discussed in light of recent kinetics data, theoretical calculations, and results for related halogen and oxygen atom reactions.

  1. Contribution of electronically excited states to the radiation chemistry of organic systems. Progress report, July 1, 1985-February 28, 1986

    SciTech Connect

    Lipsky, S.

    1986-01-01

    The attachment of thermal electrons by cyclic perfluorocarbons has been shown to enhance the photocurrent from TMPD in solvents in which the electron thermalization range is low. The effect has been studied with perfluorodecalin and perfluoromethylcyclohexane in n-pentane and n-hexane as a function of scavenger concentration, excitation energy and applied electric field strength. The mechanism of the effect suggests a technique for separating epithermal from thermal electron scavenging processes. Contact charge transfer absorption maxima have been located in six hydrocarbon-cyclic perfluorocarbon systems, and correlate well with the known gas-phase ionization potentials of the hydrocarbon. Concentration studies indicate one to one complexes when the hydrocarbon is dissolved in a perfluorocarbon solvent. Fluorescence quantum yields and fluorescence spectra have been obtained for cyclopentane, cycloheptane, cyclooctane, cyclodecane and a number of their alkyl derivatives.

  2. Effects of light and copper ions on volatile aldehydes of milk and milk fractions

    SciTech Connect

    Jeno, W.; Bassette, R.; Crang, R.E.

    1988-09-01

    Raw, laboratory-pasteurized and plant-pasteurized homogenized milks were exposed to copper ions (5 ppm), to sunlight or fluorescent light and the effects determined on the composition of volatile aldehydes. The greatest change due to copper treatment was an increase in n-hexanal; acetaldehyde showed the least response in each of the sources of milk. The responses were similar from all three sources of milk with laboratory-pasteurized milk samples showing the greatest responses for each aldehyde analyzed. Similar milk samples exposed to sunlight also showed an increase in volatile aldehydes from all milk sources but with the greatest response being acetaldehyde and n-pentanal components. The milk fraction most susceptible to changes in the presence of light was neutralized whey, whereas resuspended cream was most susceptible to copper exposure. Overall, dialyzed whey appeared to be influenced more than other milk fractions by both light and copper ions.

  3. Photoconductivity induced by single-proton excitation of aromatic molecules in liquid hydrocarbons

    SciTech Connect

    Holroyd, R.A.; Preses, J.M.; Boettcher, E.H.; Schmidt, W.F.

    1984-02-16

    The spectral dependence of the photoconductivity of several aromatic solutes (anthracene, 1,2-benzanthracene, perylene, pyrene, azulene, ..cap alpha..-methylnaphthalene, and triphenylamine) in liquid hydrocarbon solvents (neopentane, 2,2,4-trimethylpentane(2,2,4-TMP), 2,2,4,4-tetramethylpentane (2,2,4,4-TMP), and n-pentane) are reported. In liquids which exhibit high thermal electron mobilities, relative maxima or shoulders are detected in the photoconductivity spectra. The corresponding transitions are thought to involve the formation of Rydberg states as precursors of separated charges. For anthracene and azulene, the transitions occur at approximately the same energy where Rydberg lines are observed in the gas phase. Quenching of the photoconductivity by perfluoromethylcyclohexane and by perfluoro-n-hexane supports this hypothesis.

  4. Enhancing the rate of the Diels-Alder reaction using CO2 + ethanol and CO2 + n-hexane mixed solvents of different phase regions.

    PubMed

    Wang, Bo; Han, Buxing; Jiang, Tao; Zhang, Zhaofu; Xie, Ye; Li, Wenjing; Wu, Weize

    2005-12-22

    The reaction rate of the Diels-Alder reaction between N-ethylmaleimide and 9-hydroxymethylanthrance in CO2 + ethanol and CO2 + hexane mixed solvents of different compositions were determined by in situ UV/vis spectroscopy at 318.15 K and different pressures. The density of the mixed solvents at different pressures was also determined and the isothermal compressibility was calculated using the density data. The activation volume of the reaction was calculated based on the dependence of rate constant (kc) on pressure. It was demonstrated that the kc was very sensitive to the pressure in the mixed solvents near the critical region and the kc increased dramatically as pressure approached dew points, critical point, and bubble points of the mixed solvents. However, the kc in the mixed solvents outside the critical region or in pure CO2 was not sensitive to pressure. At suitable conditions, kc could be 40 times larger than that in acetonitrile. The activation volume of the reaction was nearly independent of pressure as the pressure was much higher than the phase separation pressure of the mixed solvents, while it increased considerably as pressure approached the bubble points, critical point, and dew points from high pressure. The clustering of the solvent molecules with the reactants and the activated complex in the reaction systems near the phase boundary in the critical region may be the main reason for the interesting phenomena observed. This work also shows that, using pure CO2 as the solvent, the reaction cannot be carried out in the critical region of the solvent due to the limitations of the reactants, while it can be conducted in the critical region of mixed solvents of suitable compositions, where the solvents are highly compressible and the reaction rate can be tuned effectively by pressure. PMID:16375413

  5. Thermodiffusion in ternary hydrocarbon mixtures. Part 1: n-dodecane/isobutylbenzene/tetralin

    NASA Astrophysics Data System (ADS)

    Srinivasan, Seshasai; Saghir, M. Ziad

    2011-09-01

    Experiments are to be performed on board the ISS to understand the thermodiffusion behavior in ternary hydrocarbon mixtures of n-dodecane/isobutylbenzene/tetralin. This will be followed by additional experiments with these components as well as mixtures of n-hexane/n-heptane/n-dodecane and n-decane/isobutylbenzene/tetralin. For these additional experiments, the temperature of the mixture is yet to be determined. In a three part series, by applying the theory in the literature, thermodiffusion coefficients of all these mixtures have been determined. The predictions have been made using the thermodiffusion model of Firoozabadi as well as two correlations from the literature. In this first part, thermodiffusion coefficients of twelve mixtures of n-dodecane/isobutylbenzene/tetralin have been estimated. From the results it is proposed that the future experiments be performed at 318 K and 1 atm. Certain mixtures have also been identified as important experiments due to conflicting predictions by the theoretical methods.

  6. Ethylene and phenylene bridged polysilsesquioxanes functionalized by amine and thiol groups as adsorbents of volatile organic compounds

    NASA Astrophysics Data System (ADS)

    D?browski, A.; Barczak, M.; Robens, E.; Stolyarchuk, N. V.; Yurchenko, G. R.; Matkovskii, O. K.; Zub, Yu. L.

    2007-04-01

    Ethylene and phenylene bridged polysilsesquioxane xerogels having amine and thiol groups attached to the surface have been obtained by the sol-gel method from 1,2-bis(triethoxysilyl)ethane or 1,4-bis(triethoxysilyl)benzene and functionalized silanes in the presence of an ammonium fluoride catalyst in an ethanol solution. The synthesized samples have a porous structure (700-850 m 2/g) and a high content of functional groups (1.4-1.9 mmol/g). The obtained porous bridged polysilsesquioxanes exhibit a considerable affinity for adsorbing several organic compounds ( n-hexane, n-heptane, benzene, cyclohexane, acetonitrile and triethylamine) from the gas phase. The sample with an ethylene bridge and amino groups in the surface layer has the highest uptake of all compounds. Data from adsorption measurements show that functionalized organosilicon materials can be used as effective adsorbents of organic contaminants from the gas phase.

  7. Hindered diffusion of petroleum-derived asphaltenes

    SciTech Connect

    Baltus, R.E.

    1982-01-01

    Diffusion coefficients of petroleum asphalatenes of molecular weight 2000 to 64,000 in small pores were measured using a model porous system. Mica membranes were prepared by a track-etch process to yield parallel pores of identical geometry. Initial experiments were conducted to measure diffusion rates of linear hydrocarbons of known diffusivity in n-heptane, methanol, isopropanol and tetrahydrofuran (THF) solvents and yielded some unexpected results. Diffusion rates in n-heptane solvent were lower than expected, based on a known pore area. Similar results were observed in n-hexane solvent by Baker (1978). However, when experiments were conducted in methanol, isopropanol and THF solvents, diffusion rates consistent with a known pore area were observed. Discrepancy in diffusion rates in the hydrocarbon solvents might be due to the presence of small amounts of water within the pores. Experiments were then conducted to measure diffusion rates of asphaltenes in THF solvent. Samples were collected and fractionated and analyzed using Gel Permeation Chromatography. Diffusion coefficients of five fractions were determined in pores of order 70 to 2000 A radius. The results from these experiments were compared to the theoretical prediction for the hindered diffusion of rigid spherical solutes and found to be in general agreement with theory when the equivalent size of the asphaltenes was described in terms of their radius from the Stokes-Einstein equation.

  8. Alternatives for Benzene in the Extraction of Bitumen Fume from Exposure Sample Media.

    PubMed

    Sutter, Benjamin; Ravera, Christel; Hussard, Caroline; Langlois, Eddy

    2016-01-01

    Benzene is frequently used to extract collected bitumen fumes from personal sampler substrates. However, this solvent is particularly dangerous because of its carcinogenicity (group 1 of the International Agency for Research on Cancer classification). Therefore, to prevent the exposure of laboratory technicians to benzene during the fume extraction step from samplers, a compromise had to be found to identify a less toxic solvent with the same extraction capacity. To compare the extraction capacities of selected solvents, bitumen fumes were generated in the laboratory from three different batches of road surfacing bitumen collected on dedicated bitumen fume samplers. The samplers were then extracted by benzene and the solvents tested. Of 11 selected solvents less toxic than benzene and used in studies on bitumen and bitumen fume analyses, n-hexane and n-heptane were identified as alternatives to benzene. In particular, the results demonstrated that n-heptane was the best candidate solvent for benzene replacement, due to its extraction efficiency comparable to benzene for the three bitumen fumes tested and its low toxicity, which is highly compatible with benzene replacement. PMID:26400870

  9. An analytical system for the measurement of stable hydrogen isotopes in ambient volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Meisehen, T.; Bühler, F.; Koppmann, R.; Krebsbach, M.

    2015-10-01

    Stable isotope measurements in atmospheric volatile organic compounds (VOCs) are an excellent tool to analyse chemical and dynamical processes in the atmosphere. While up to now isotope studies of VOCs in ambient air have mainly focussed on carbon isotopes, we herein present a new measurement system to investigate hydrogen isotope ratios in atmospheric VOCs. This system, consisting of a gas chromatography pyrolysis isotope ratio mass spectrometer (GC-P-IRMS) and a pre-concentration system, was thoroughly characterised using a VOC test mixture. A precision of better than 9 ‰ (in δ 2H) is achieved for n-pentane, 2-methyl-1,3-butadiene (isoprene), n-heptane, 4-methyl-pentane-2-one (4-methyl-2-pentanone), methylbenzene (toluene), n-octane, ethylbenzene, m/p-xylene and 1,2,4-trimethylbenzene. A comparison with independent measurements via elemental analysis shows an accuracy of better than 9 ‰ for n-pentane, n-heptane, 4-methyl-2-pentanone, toluene and n-octane. Above a minimum required pre-concentrated compound mass the obtained δ 2H values are constant within the standard deviations. In addition, a remarkable influence of the pyrolysis process on the isotope ratios is found and discussed. Reliable measurements are only possible if the ceramic tube used for the pyrolysis is sufficiently conditioned, i.e. the inner surface is covered with a carbon layer. It is essential to verify this conditioning regularly and to renew it if required. Furthermore, influences of a necessary H3+ correction and the pyrolysis temperature on the isotope ratios are discussed. Finally, the applicability to measure hydrogen isotope ratios in VOCs at ambient levels is demonstrated with measurements of outside air on 5 different days in February and March 2015. The measured hydrogen isotope ratios range from -136 to -105 ‰ forn-pentane, from -86 to -63 ‰ for toluene, from -39 to -15 ‰ for ethylbenzene, from -99 to -68 ‰ for m/p-xylene and from -45 to -34 ‰ for o-xylene.

  10. Analysis of polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans in particulate and oily films on impervious surfaces.

    PubMed

    Klees, Marcel; Hiester, Ernst; Schmidt, Torsten C

    2015-12-15

    During this study wipe sampling was applied to various impervious surfaces for the determination of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs) area concentrations. To that end, a wipe sampling method based on solvent wetted cotton wipes was evaluated and transfer efficiencies of PCBs and PCDD/PCDFs in particulate films (PFs) and oily liquid films (OFs) during sampling were investigated. For PFs sufficient transfer efficiencies of low concentrated PCB and PCDD/PCDF congeners in 1g/m(2) spiking surrogate were achieved after the first wipe using n-hexane as wetting solvent. Transfer efficiencies for OFs were the highest in the first wipe if n-hexane or n-heptane were used rather than toluene. The spiking experiments of OFs showed a log-linear correlation between the number of wiping procedures and transfer efficiency which indicates that transfer efficiencies were constant in subsequent wipes. Furthermore, it was successfully demonstrated that pressurized liquid extraction is a suitable tool for the extraction of wipe samples. Finally, the feasibility of this wipe sampling method was demonstrated on various impervious surfaces of different origin, and concentration levels of PCBs and PCDD/PCDFs in wipe samples are discussed. Hereby, remarkably high ∑CB6 concentrations of up to 1400μg/m(2) (taken at a transformer recycling site) were detected. PMID:26318221

  11. [Exposure to glues containing technical heptane: a clinical and electrophysiological study].

    PubMed

    Valentini, F; Agnesi, R; Dal Vecchio, L; Fabbro, A; Gasparini, N; Gori, G; Sturaro, A; Todros, A; Sparta, S; Bartolucci, G B

    1994-01-01

    Polyneuropathy caused by n-hexane contained in glues was, until recently, the typical occupational disease of shoemakers. Glues no longer contain large concentrations of this solvent, and in some cases, it as been completely replaced by other hydrocarbons. The authors investigated the health status in a group of shoemakers using glues containing 35% technical heptane. The same glue, not containing n-hexane, was used by a shoemaker who worked at home; she developed an otherwise unexplainable peripheral polyneuropathy. For each of the 16 subjects, the following procedures were carried out: environmental sampling, biological monitoring for Mek and heptane metabolites, a neurological and electromyographic examination. No neurological abnormalities were found in the workers that could be attributable to occupational exposure, probably due to the low level environmental contamination (< 100 mg/m3 n-heptane) found in the 7 factories and workshops studied where acceptable hygiene conditions existed. The time course and ratio of urinary metabolites of heptane were also studied, the latter showing a predominance of 2- and 3- heptanol in the initial phase and 2-5 heptandione at the end of the work week; probably, the presence of other solvents, such as Mek, can modify the ratio of metabolites and consequently the formation of neurotoxic compounds could result. PMID:7731410

  12. Re-Os dating of maltenes and asphaltenes within single samples of crude oil

    NASA Astrophysics Data System (ADS)

    Georgiev, Svetoslav V.; Stein, Holly J.; Hannah, Judith L.; Galimberti, Roberto; Nali, Micaela; Yang, Gang; Zimmerman, Aaron

    2016-04-01

    Re-Os geochronology of oil may constrain the timing of oil formation and improve oil-source and oil-oil correlations. Typically, asphaltene (ASPH), the heaviest and most Re-Os rich oil fraction, from multiple oils within an oil field or a larger petroleum system are analyzed to obtain sufficient spread in Re-Os isotopic ratios, a mathematical necessity for precise Re-Os isochrons. Here we offer a new approach for Re-Os geochronology of oil based on isotopic analyses of different fractions within a single sample of crude oil. We studied three oils from the Gela oil field, southern Sicily, Italy, recovered from Triassic-Jurassic stratigraphic intervals (Streppenosa, Noto, and Sciacca Formations) within the Gela-1 well. ASPH (insoluble in n-alkane) and maltene (MALT, soluble in n-alkane) fractions of oil were separated using n-pentane, n-hexane, n-heptane and n-decane solvents. The ASPH contents of the Sciacca and Noto oils (26-33 wt%) are notably higher compared to the Streppenosa oil (7-12 wt% ASPH). We present an optimized Re-Os procedure with sample digestion in a high-pressure asher, followed by isotopic measurements using negative thermal ionization mass spectrometry. Very high metal contents of Gela oils allowed acquisition of precise Re-Os data. Systematic variations between the type of solvent used for ASPH precipitation and the ASPH content of the oil (also known from the literature) and the Re-Os contents of the ASPH and MALT fractions (first observed in this study) provide important practical applications for Re-Os analyses of oil. Most Re and Os (∼96-98%) in the Noto oil are hosted in the ASPH fraction. In contrast, a significant portion of Re and Os (∼33-34%) is stored in the MALT fraction of the lighter, but heavily biodegraded Streppenosa oil. Collectively, our new data on alkane distribution, hopane and sterane biomarkers, major and trace element contents, and Re-Os concentrations and isotopic ratios of the oils and their fractions support the presence of two oil families. Streppenosa oil, a heavily biodegraded oil generated at an early stage of thermal maturation from a shaly source rock, is clearly distinct from the Noto and Sciacca oils, both generated at peak maturation from a carbonate source rock with no subsequent biodegradation. Two Re-Os ages were obtained. Crude oil and ASPH from Noto and Sciacca oil yield a Model 1 isochron age of 27.5 ± 4.6 Ma with an initial 187Os/188Os of 3.89 ± 0.43 (MSWD = 1.6, n = 19). We interpret this Oligocene age as the time of initial oil generation, that was probably related to the onset of regional collisional tectonics in southern Sicily. ASPH and crude oil from the Streppenosa oil yield scattered data, perhaps related to effects of biodegradation. Streppenosa MALT yield a Model 1 age of 200.0 ± 5.2 Ma and initial 187Os/188Os of 1.39 ± 0.11 (MSWD = 0.52; n = 4). This age and initial Os-isotopic composition are consistent with rapid oil generation shortly after Late Triassic source-rock formation, perhaps driven by magmatic-related heating. Here we document a potentially powerful geochronological tool that can be applied to single samples of crude oil. Within each oil, the 187Os/188Os and most of the 187Re/188Os ratios in the MALT fractions are lower than in the corresponding ASPH fractions. Crude oils, being physical mixtures of ASPH and MALT, have intermediate Re-Os isotopic ratios. Hence, the needed spread in data points for a Re-Os isochron is obtained by analyzing components of a single crude oil. This approach eliminates pitfalls in interpretation of Re-Os data from multiple oils with possibly different generation, migration, or reservoir modification history.

  13. Hydrochloroethers in the troposphere: Kinetics with Cl atoms, lifetimes and atmospheric acceptability indices

    NASA Astrophysics Data System (ADS)

    Dalmasso, Pablo R.; Taccone, Ral A.; Nieto, Jorge D.; Cometto, Pablo M.; Lane, Silvia I.

    2012-02-01

    Rate constants for the gas-phase reactions of chlorine atoms with 2-chloroethyl ethyl ether ( k1) and bis(2-chloroethyl) ether ( k2) were determined for the first time using a conventional relative rate technique. Experiments were carried out at (298 2) K and atmospheric pressure using synthetic air as bath gas. The decay rates of the hydrochloroethers were measured relative to those of n-pentane and n-heptane. The following rate constants were derived in units of cm 3 molecule -1 s -1: k1 = (1.7 0.5) 10 -10 and k2 = (1.0 0.3) 10 -10. The rate constants obtained are compared with previous literature data to indicate reactivity trends and are used to estimate the global atmospheric lifetimes ( ?global) of the studied hydrochloroethers. Radiative forcing efficiencies (RE) of the ethers were determined from their integrated IR absorption cross-sections. Using ?global and RE, estimations were made of atmospheric hazard indices of the two chlorinated ethers such as the ozone depletion potential (ODP) and the global warming potential (GWP).

  14. Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

    NASA Astrophysics Data System (ADS)

    Dalmasso, Pablo R.; Taccone, Ral A.; Nieto, Jorge D.; Cometto, Pablo M.; Lane, Silvia I.

    2010-05-01

    Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether ( k1), 2-chloroethyl ethyl ether ( k2) and bis(2-chloroethyl) ether ( k3) have been measured. Experiments were carried out at (298 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k1 = (5.2 1.2) 10 -12, k2 = (8.3 1.9) 10 -12 and k3 = (7.6 1.9) 10 -12, in units of cm 3 molecule -1 s -1. This is the first experimental determination of k2 and k3 under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.

  15. Gas-Phase Reaction of Hydroxyl Radical with p-Cymene over an Extended Temperature Range.

    PubMed

    Bedjanian, Yuri; Morin, Julien; Romanias, Manolis N

    2015-11-12

    The kinetics of the reaction of OH radicals with p-cymene has been studied in the temperature range of 243-898 K using a flow reactor combined with a quadrupole mass spectrometer: OH + p-cymene ? products. The reaction rate constant was determined as a result of absolute measurements, from OH decay kinetics in excess of p-cymene and employing the relative rate method with OH reactions with n-pentane, n-heptane,1,3-dioxane, HBr, and Br2 as the reference ones. For the rate coefficient of the H atom abstraction channel, the expression k1b = (3.70 0.42) 10(-11) exp[-(772 72)/T] was obtained over the temperature range of 381-898 K. The total rate constant (addition + abstraction) determined at T = 243-320 K was k1 = (1.82 0.48) 10(-12) exp[(607 70)/T] or, in a biexponential form, k1 = k1a + k1b = 3.7 10(-11) exp(-772/T) + 6.3 10(-13) exp(856/T), independent of the pressure between 1 and 5 Torr of helium. In addition, our results indicate that the reaction pathway involving alkyl radical elimination upon initial addition of OH to p-cymene is most probably unimportant. PMID:26473634

  16. Fuel droplet burning rates at high pressures.

    NASA Technical Reports Server (NTRS)

    Canada, G. S.; Faeth, G. M.

    1973-01-01

    Combustion of methanol, ethanol, propanol-1, n-pentane, n-heptane, and n-decane was observed in air under natural convection conditions, at pressures up to 100 atm. The droplets were simulated by porous spheres, with diameters in the range from 0.63 to 1.90 cm. The pressure levels of the tests were high enough so that near-critical combustion was observed for methanol and ethanol. Due to the high pressures, the phase-equilibrium models of the analysis included both the conventional low-pressure approach as well as high-pressure versions, allowing for real gas effects and the solubility of combustion-product gases in the liquid phase. The burning-rate predictions of the various theories were similar, and in fair agreement with the data. The high-pressure theory gave the best prediction for the liquid-surface temperatures of ethanol and propanol-1 at high pressure. The experiments indicated the approach of critical burning conditions for methanol and ethanol at pressures on the order of 80 to 100 atm, which was in good agreement with the predictions of both the low- and high-pressure analysis.

  17. The actions of some general anaesthetics on the potassium current of the squid giant axon.

    PubMed Central

    Haydon, D A; Urban, B W

    1986-01-01

    A number of small organic molecules with general anaesthetic action have been examined for their effects on the voltage-dependent potassium current of the squid giant axon. They include representatives of the three classes of anaesthetics examined in previous studies on the sodium current (Haydon & Urban, 1983a, b, c), i.e. the non-polar molecules n-pentane, cyclopentane and CCl4, several n-alkanols and the inhalation anaesthetics chloroform, halothane, diethyl ether and methoxyflurane. Potassium currents under voltage clamp were recorded in intact and in intracellularly perfused axons before, during and after exposure to the test substances, and the records were fitted with equations similar to those proposed by Hodgkin & Huxley (1952). Shifts in the curves of the steady-state activation against membrane potential and reductions in the potassium conductance at 60 or 70 mV membrane potential have been tabulated. On the same intact axons, all the anaesthetics with the exception of methoxyflurane reduced potassium currents less than sodium currents by about a factor of two or more. For the n-alkanols, butanol to decanol, the concentrations required to reduce the potassium current at 60 mV membrane potential by 50% were determined. For n-butanol to n-heptanol, the standard free energy per CH2 for adsorption to the site of action was estimated to be -2.91 kJ mol-1 as compared with -3.04 kJ mol-1 for reduction of the sodium current. The magnitude of the free energy decreased for alkanols with longer chain lengths. At anaesthetic concentrations that reduce the sodium current by 50%, the hydrophobic substances n-pentane and cyclopentane reduced the maximal sodium conductance, gNa, and the potassium conductance at 70 mV, gK70, equally by about a third, while the n-alkanols reduced both parameters by less than 10%. By contrast, diethyl ether and methoxyflurane were more effective in reducing the maximal potassium conductance. All of the test substances examined, except n-pentane and n-hexane, shifted the voltage dependence of the potassium steady-state activation in the depolarizing direction. A broad qualitative correlation was found between the shifts in the activation curves for sodium and potassium currents but, quantitatively, the agreement between the two shifts was poor. In n-decanol and methoxyflurane solutions, the voltage-clamped potassium currents exhibited pronounced inactivation-like behaviour. These currents can be fitted by the Hodgkin-Huxley formalism if an inactivation term analogous to the sodium current inactivation is added.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:3746676

  18. A new model for pressure-induced shifts of electronic absorption bands as applied to neat CS sub 2 and CS sub 2 in n-hexane and dichloromethane solutions

    SciTech Connect

    Agnew, S.F.; Swanson, B.I. )

    1990-01-25

    The authors propose a model for the pressure dependence of electronic absorption spectra and apply it to the authors data on CS{sub 2} both in neat phase and in hexane and dichloromethane solid solutions. They believe that their data represent a rather severe test of this model and argue that any model for the pressure dependence of electronic absorption spectra must include certain minimal effects - dispersive or dielectric and repulsive or volume effects - in order to adequately represent the data. They discuss previous models at some length in order to delineate the limits of their applicability. They further acknowledge and define the limits of the applicability of their model to solvent-induced shifts in general.

  19. Stable Carbon Isotope Ratios and Mixing Ratios of Several VOC Including n-Hexane, Benzene, Toluene, p-Xylene, n-Octane, and n-Decane Measured During the Border Air Quality Study Campaign (June-July, 2007)

    NASA Astrophysics Data System (ADS)

    Kornilova, A.; Moukhtar, S.; Huang, L.; Rudolph, J.

    2008-12-01

    Many important secondary pollutants are formed during the oxidation of Volatile Organic Compounds (VOC) in the atmosphere. These organic compounds can contribute significant mass to atmospheric particulate matter (PM) and therefore impact physical properties and composition of aerosols. Despite numerous studies, the formation processes for atmospheric PM are still not well understood. While there have been very extensive laboratory investigations of PM formation, nearly all of these studies have been conducted at VOC concentrations which exceed ambient atmospheric levels by several orders of magnitude. Consequently there is substantial uncertainty in the extrapolation of laboratory results to the atmosphere. Recently it has been demonstrated that stable carbon isotopic composition measurements can be very valuable in providing increased insight into the chemical and transport processes of VOC in the troposphere. Studies showed that isotope ratio measurements could aid in the determination of photochemical processing of individual VOC. It is expected that applying isotope measurements to studies of VOC oxidation products in the atmosphere will allow to establish quantitative relationship between the amount of precursor oxidized and the concentration of secondary pollutants formed during this process. Thus, the yield of secondary organic aerosols (SOA) from this reaction can be calculated. A cartridge technique was developed for field sampling of VOC and subsequent laboratory analysis by gas chromatography coupled with isotope ratio mass spectrometry. It was first implemented during the BAQS field study (June-July, 2007) parallel to PM sampling. Stable carbon isotopic composition and concentrations of several VOC were determined and compared to those of PM. The results of these measurements will be presented and discussed.

  20. A predictive method for crude oil volatile organic compounds emission from soil: evaporation and diffusion behavior investigation of binary gas mixtures.

    PubMed

    Wang, Haijing; Fischer, Thomas; Wieprecht, Wolfgang; Mller, Detlev

    2015-05-01

    Due to their mobility and toxicity, crude oil volatile organic compounds (VOCs) are representative components for oil pipeline contaminated sites detection. Therefore, contaminated location risk assessment, with airborne light detection and ranging (LIDAR) survey, in particular, requires ground-based determinative methods for oil VOCs, the interaction between oil VOCs and soil, and information on how they diffuse from underground into atmosphere. First, we developed a method for determination of crude oil VOC binary mixtures (take n-pentane and n-hexane as examples), taking synergistic effects of VOC mixtures on polydimethylsiloxane (PDMS) solid-phase microextraction (SPME) fibers into consideration. Using this method, we further aim to extract VOCs from small volumes, for example, from soil pores, using a custom-made sampling device for nondestructive SPME fiber intrusion, and to study VOC transport through heterogeneous porous media. Second, specific surface Brunauer-Emmett-Teller(BET) analysis was conducted and used for estimation of VOC isotherm parameters in soil. Finally, two models were fitted for VOC emission prediction, and the results were compared to the experimental emission results. It was found that free diffusion mode worked well, and an empirical correction factor seems to be needed for the other model to adapt to our condition for single and binary systems. PMID:25572270

  1. Biodegradation of petroleum hydrocarbon vapors: laboratory studies on rates and kinetics in unsaturated alluvial sand

    NASA Astrophysics Data System (ADS)

    Hhener, Patrick; Duwig, Cline; Pasteris, Gabriele; Kaufmann, Karin; Dakhel, Nathalie; Harms, Hauke

    2003-10-01

    Predictions of natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone rely critically on information about microbial biodegradation kinetics. This study aims at determining kinetic rate laws for the aerobic biodegradation of a mixture of 12 volatile petroleum hydrocarbons and methyl tert-butyl ether (MTBE) in unsaturated alluvial sand. Laboratory column and batch experiments were performed at room temperature under aerobic conditions, and a reactive transport model for VOC vapors in soil gas coupled to Monod-type degradation kinetics was used for data interpretation. In the column experiment, an acclimatization of 23 days took place before steady-state diffusive vapor transport through the horizontal column was achieved. Monod kinetic parameters Ks and vmax could be derived from the concentration profiles of toluene, m-xylene, n-octane, and n-hexane, because substrate saturation was approached with these compounds under the experimental conditions. The removal of cyclic alkanes, isooctane, and 1,2,4-trimethylbenzene followed first-order kinetics over the whole concentration range applied. MTBE, n-pentane, and chlorofluorocarbons (CFCs) were not visibly degraded. Batch experiments suggested first-order disappearance rate laws for all VOCs except n-octane, which decreased following zero-order kinetics in live batch experiments. For many compounds including MTBE, disappearance rates in abiotic batch experiments were as high as in live batches indicating sorption. It was concluded that the column approach is preferable for determining biodegradation rate parameters to be used in risk assessment models.

  2. First steps in photophysics. I. Fluorescence yield and radiative rate coefficient of 9,10-bis(phenylethynyl)anthracene in paraffins.

    PubMed

    Demeter, Attila

    2014-10-30

    The fluorescence quantum yield of 9,10-bis(phenylethynyl)anthracene (BPEA) is almost unity in every examined solvent. Using different hydrocarbons, one can make a convenient and sufficiently accurate experimental test for determination of the extent of the refractive index correction needed in fluorescence quantum yield determination on a given fluorometer. By comparison of the measurements in n-pentane-cis-decaline or n-hexane-toluene solvent pairs, the requirement of the n(2) correction is confirmed for most of the fluorometers; however, for one of the examined pieces of equipment the necessary correction proved to be slightly lower. By excited state's lifetime measurements, the refractive index dependence of the fluorescence rate coefficient was reexamined. At 25 C for BPEA the relationship is in agreement with Bakhshiev's prediction: the experimentally determined exponent of n in the rate coefficient deriving equation is around 1.32 using different paraffins as solvents. The negative temperature coefficient of the radiative rate in part originates from the temperature dependence of the refractive index, while also a small intrinsic contribution has been found. PMID:25296291

  3. Modeling VOC Sorption and Transport in Glassy Polymeric Membranes

    NASA Astrophysics Data System (ADS)

    De Angelis, Maria Grazia; Olivieri, Luca; Sarti, G. C.

    2010-06-01

    In this work we evaluated the sorption, diffusion and permeation of a series of volatile organic compounds (VOCs) (acetone, n-butane, n-pentane, n-hexane, ethanol, methanol, chloroform and toluene) into glassy polymers of increasing fractional free volume (FFV): Polycarbonate (PC), Amorphous Teflon AF1600 and AF2400, poly-trimethylsilyl norbornene (PTMSN) and poly[1-(trimethylsilyl)-1-propyne] (PTMSP). Based on some experimental data of sorption and diffusion, and on theoretical and empirical models for the solubility and diffusion coefficients, the permeability for vapor/N2 mixtures was evaluated. These parameters are useful for the membrane separation processes and for other applications such as chemical sensors. The ideal separation factors of glassy polymeric membranes versus mixtures of VOCs and N2 were estimated at various pressures and compositions and at 25 C. The selectivity vs. permeability maps for the mixtures considered were plotted, showing that some of these materials show potentially the same selective ability of rubbery polymeric films. In particular it is shown that, the higher the FFV, the better the vapor/gas selectivity.

  4. Structural properties and catalytic activity in selective oxidation of In-containing ZSM-5 catalysts

    NASA Astrophysics Data System (ADS)

    Halsz, Jnos; Nyri, Wanda; Meretei, Edit; Hannus, Istvn; Nagy, Jnos B.; Kiricsi, Imre

    2003-06-01

    The characteristics of In-containing ZSM-5 zeolites prepared by different method have been investigated in the correlation of catalytic activity in the oxidative reaction of pentane and hexane. The zeolite catalysts have been prepared using four different methods: (i) ion-exchange in In(NO 3) 3 solution; (ii) solid state ion-exchange in oxidative atmosphere; (iii) solid state ion-exchange in reductive atmosphere; (iv) isomorphous substitution of aluminum for indium in the synthesis. The catalysts have been characterized by thermal analytical, XRD, nitrogen adsorption, IR, UV-VIS, 29Si MAS NMR, 27Al MAS NMR spectroscopic methods. Conversion of n-pentane and n-hexane has been studied in a fixed bed flow reactor in the presence or in the absence of dioxygen. High cracking activity is characteristic of the catalysts with high surface Brnsted acidity due to the oxidative treatment, while the catalyst pre-treated in reductive atmosphere having Lewis acidity are effective in the dehydrogenation and aromatization reactions of pentane and hexane. However, the significant increase of aromatic selectivity in the case of the catalyst prepared by solid state ion-exchange could be accounted to rapid dehydrogenation caused by isolated In 2O particles formed in reductive atmosphere. Synergism, namely intimate contact between these particles and the framework silicate structure can be assumed as active sites for the dehydrogenation and aromatization of alkenes.

  5. Long-Term Incubation Reveals Methanogenic Biodegradation of C5 and C6 iso-Alkanes in Oil Sands Tailings.

    PubMed

    Siddique, Tariq; Mohamad Shahimin, Mohd Faidz; Zamir, Saima; Semple, Kathleen; Li, Carmen; Foght, Julia M

    2015-12-15

    iso-Alkanes are major components of petroleum and have been considered recalcitrant to biodegradation under methanogenic conditions. However, indigenous microbes in oil sands tailings ponds exposed to solvents rich in 2-methylbutane, 2-methylpentane, 3-methylpentane, n-pentane, and n-hexane produce methane in situ. We incubated defined mixtures of iso- or n-alkanes with mature fine tailings from two tailings ponds of different ages historically exposed to different solvents: one, ?10 years old, receiving C5-C6 paraffins and the other, ?35 years old, receiving naphtha. A lengthy incubation (>6 years) revealed iso-alkane biodegradation after lag phases of 900-1800 and ?280 days, respectively, before the onset of methanogenesis, although lag phases were shorter with n-alkanes (?650-1675 and ?170 days, respectively). 2-Methylpentane and both n-alkanes were completely depleted during ?2400 days of incubation, whereas 2-methylbutane and 3-methylpentane were partially depleted only during active degradation of 2-methylpentane, suggesting co-metabolism. In both cases, pyrotag sequencing of 16S rRNA genes showed codominance of Peptococcaceae with acetoclastic (Methanosaeta) and hydrogenotrophic (Methanoregula and Methanolinea) methanogens. These observations are important for predicting long-term greenhouse-gas emissions from oil sands tailings ponds and extend the known range of hydrocarbons susceptible to methanogenic biodegradation in petroleum-impacted anaerobic environments. PMID:26571341

  6. Hot Surface Ignition and Flame Propagation of Hydrocarbon Air Mixtures

    NASA Astrophysics Data System (ADS)

    Boettcher, Philipp; Ventura, Brian; Blanquart, Guillaume; Shepherd, Joseph

    2010-11-01

    To mitigate the risk of accidental explosions in industrial facilities and in the aviation industry, the mechanisms and parameters leading to ignition must be investigated. Of particular are isolated hot surfaces in contact with gaseous hydrocarbon fuels, and thus ignition of premixed n-hexane air and n-heptane air mixtures is examined using a high temperature glow plug. Measurements include schlieren visualization, particle streaks, pressure, and temperature measurements in the plume created by the hot surface. These measurements are performed for experiments in both air and combustion mixtures ranging in equivalence ratio from 0.5 (near the lower flammability limit) to 3.0. This allows for comparison of ignition temperature, flame speed, pressure rise, and temperature distribution with a computational flame model. For equivalence ratios above 0.7 the ignition temperature was observed to be insensitive to increasing fuel concentration and showed good agreement with the model. Three distinct combustion modes are observed that scale with the Richardson number: single flame, multiple flames, and puffing. These behaviors show the transition from flame propagation dominated to buoyancy dominated behavior, with puffing cycles of the order 10 Hz.

  7. Comparative study of free and immobilized lipase from Bacillus aerius and its application in synthesis of ethyl ferulate.

    PubMed

    Saun, Nitin Kumar; Narwal, Sunil Kumar; Dogra, Priyanka; Chauhan, Ghanshyam Singh; Gupta, Reena

    2014-01-01

    In the present study, a purified lipase from Bacillus aerius immobilized on celite matrix was used for synthesis of ethyl ferulate. The celite-bound lipase exposed to glutaraldehyde showed 90.02% binding efficiency. It took two hours to bind maximally onto the support. The pH and temperature optima of the immobilized lipase were same as those of free enzyme i.e 9.5 and 55C. Among different substrates both free and immobilized lipase showed maximum affinity towards p-nitrophenyl palmitate (p-NPP). The lipase activity was found to be stimulated in the presence of Mg(2+) in case of free enzyme while Zn(2+) and Fe(3+) showed stimulatory effect on immobilized lipase whereas salt ions as well as chelating agents inhibited activity of both free and immobilized lipase. Maximum enzyme activity was observed in n-hexane as organic solvent followed by n-heptane for both free and immobilized lipase, however CCl4, acetone and benzene inhibited the enzyme activity. Moreover, all the selected detergents (SDS, Triton X-100, Tween 80 and Tween 20) had an inhibitory effect on both free and immobilized enzyme activity. The celite bound lipase (1.5%) efficiently performed maximum esterification (2.51 moles/l) of ethanol and ferulic acid (100 mM each, at a molar ratio of 1:3) when incubated at 55C for 48 h resulting in the formation of ester ethyl ferulate. PMID:25099909

  8. Monitoring of Selected Skin-Borne Volatile Markers of Entrapped Humans by Selective Reagent Ionization Time of Flight Mass Spectrometry in NO+ Mode

    PubMed Central

    2014-01-01

    Selective reagent ionization time-of-flight mass spectrometry with NO+ as the reagent ion (SRI-TOF-MS (NO+)) was applied for near real-time monitoring of selected skin-borne constituents which are potential markers of human presence. The experimental protocol involved a group of 10 healthy volunteers enclosed in a body plethysmography chamber mimicking the entrapment environment. A total of 12 preselected omnipresent in human scent volatiles were quantitatively monitored. Among them there were six aldehydes (n-propanal, n-hexanal, n-heptanal, n-octanal, n-nonanal, and 2 methyl 2-propenal), four ketones (acetone, 2-butanone, 3-buten-2-one, and 6-methyl-5-hepten-2-one), one hydrocarbon (2-methyl 2-pentene), and one terpene (DL-limonene). The observed median emission rates ranged from 0.28 to 44.8 nmol × person–1 × min–1 (16–1530 fmol × cm–2 × min–1). Within the compounds under study, ketones in general and acetone in particular exhibited the highest abundances. The findings of this study provide invaluable information about formation and evolution of a human-specific chemical fingerprint, which could be used for the early location of entrapped victims during urban search and rescue operations (USaR). PMID:24611620

  9. Infrared band intensities of saturated hydrocarbons

    NASA Technical Reports Server (NTRS)

    Pinkley, L. W.; Sethna, P. P.; Williams, D.

    1978-01-01

    Kramers-Kronig analysis is applied to measured values of spectral reflectance at near-normal incidence to determine the real and the imaginary parts of the complex index of refraction for methane, ethane, propane, n-butane, n-hexane, n-heptane, and n-decane in the liquid state. The results indicate that the strengths of the characteristic bands as measured by the integral of the imaginary part are roughly constant for all the liquid alkanes except for methane. The intensity of the CH valence vibration bands in the spectra of the alkanes except methane is directly proportional to the number of CH groups per unit volume. The relations for the intensity of the bands due to CH2 and CH3 deformations are examined. Characteristic band intensities of the type established for NH4(+) and SO4(2-) groups in solutions and crystals cannot be extended to the more closely coupled CH2 and CH3 groups in alkane molecules.

  10. Viscosities of nonelectrolyte liquid mixtures. III. Selected binary and quaternary mixtures

    NASA Astrophysics Data System (ADS)

    Wakefield, D. L.

    1988-05-01

    This paper is the final in a series of three viscosity and density studies of pure n-alkanes and selected binary and quaternary mixtures. A standard U-tube viscometer was used for viscosity measurements, and a Pyrex flask-type pycnometer was used for density determinations. Results are given here for pure alkane and selected binary mixtures of n-tetradecane + n-octane, for selected quaternary mixtures of n-hexadecane + n-dodecane + n-decane + n-hexane, and for pure and selected quaternary mixtures of n-hexadecane + n-dodecane + n-nonane + n-heptane at 303.16 and 308.16 K. The principle of congruence was tested, as was the Grunberg and Nissan equation, as they have been shown to be useful as prediction techniques for other n-alkane binary mixtures. Comparisons were made between the two groups of quaternary alkane mixtures and the binary n-tetradecane + n-octane mixtures of the same pseudo composition to understand better the dependence of mixture viscosities on the composition parameter.

  11. High-performance liquid chromatographic enantioseparation of naphthol-substituted tetrahydroisoquinolines on polysaccharide-based chiral stationary phases.

    PubMed

    Ilisz, István; Gecse, Zsanett; Szatmári, István; Fülöp, Ferenc; Péter, Antal

    2014-01-01

    The stereoisomers of 15 naphthol-substituted tetrahydroisoquinoline analogs were separated on chiral stationary phases containing the chiral selectors cellulose tris-(3,5-dimethylphenyl carbamate) (Cellulose 1), cellulose tris-(3-chloro-4-methylphenyl carbamate) (Cellulose 2), cellulose tris-(4-methylbenzoate) (Cellulose 3) and cellulose tris-(4-chloro-3-methylphenyl carbamate) (Cellulose 4). Experiments were performed in normal-phase mode with n-heptane(n-hexane)-alcohol-diethylamine mobile phases in the temperature range 5-40 °C. Thermodynamic parameters were calculated from plots of lnk or lnα vs 1/T. On the Cellulose 1 column, Δ(ΔH°) ranged from -6.8 to 5.9 kJ/mol, Δ(ΔS°) from -16.7 to 21.0 J/mol/K and the Gibbs energy, -Δ(ΔG°) from 0.2 to 1.5 kJ/mol; on the Cellulose 2 column, Δ(ΔH°) ranged from -7.8 to 2.5 kJ/mol, Δ(ΔS°) from -16.1 to 13.2 J/mol/K and - Δ(ΔG°) from 0.7 to 3.0 kJ/mol. Both enthalpy- and entropy-controlled enantioseparations were observed. The latter was advantageous with regard to the shorter retention and greater selectivity at high temperature. PMID:23897777

  12. Testing of the abiotic degradation of chemicals in the atmosphere: the smog chamber approach

    SciTech Connect

    Kloepffer, W.H.; Haag, F.; Kohl, E.G.; Frank, R.

    1988-06-01

    Methods for measuring the hydroxyl-, ozone-, and direct photochemical reactivity of a substance in one specially designed medium size smog chamber are described. Rate coefficients for the reaction of OH with n-hexane, n-heptane, ethene, ethyne, chloroform, trichloroethene, methanol, 2-propanol, benzene, o-xylene, 1,4-dichlorobenzene, 1,2,4-trichlorobenzene, p-chloroaniline, naphthalene, acenaphthene, 1,4-dichloronaphthalene, biphenyl, and fluorenone are given and discussed. An upper limit of 5 X 10(-13) cm3/sec is given for the sum penta- and hexa-chlorobiphenyls (PCB). Rate coefficients for the ozone reaction are given for beta-pinene, limonene, delta 3-carene, cineol, vinyl chloride and 1,3-butadiene. In cases where the literature data are available for comparison, the rate coefficients (kappa OH and kappa O3) reported here compare favorably with the best data reported. The direct photochemical reactivity has been shown to be measurable if the chamber is cleaned carefully. Preliminary results on benzophenone are reported. The methods described here, except that of direct photochemical reactivity, are in agreement with those proposed to OECD. Moreover, part of the Draft OECD Test Guideline (Berlin, 1987) on Photochemical-Oxidative Degradation in the Atmosphere is based on work described here and on closely related work in other laboratories.

  13. Volatile organic compounds in the air of Izmir, Turkey

    NASA Astrophysics Data System (ADS)

    Muezzinoglu, Aysen; Odabasi, Mustafa; Onat, Levent

    A sampling program was conducted to determine the ambient VOC levels in the city of Izmir, Turkey during daytime and overnight periods between mid-August and mid-September 1998. Sampling sites were selected at high-density traffic roads and junctions far from stationary VOC sources. Samples were analyzed for benzene, toluene, m, p-xylene and o-xylene (BTX), alkylbenzenes (ethylbenzene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene), n-hexane and, n-heptane. Results were compared with similar data from other cities around the world and for probable health dangers and sources of the compounds. Results of this study indicated that Izmir has rather high ambient BTX concentrations compared to many polluted cities in the world. Toluene was the most abundant VOC in Izmir air and was followed by xylenes, benzene and alkylbenzenes, respectively. All were strongly dependent on the expected daily variations of traffic flow in the city. The concentrations of other VOCs correlated well with benzene concentration at most sampling sites, excluding Gumuldur station indicating that ambient VOC levels were mainly affected by motor vehicle emissions. The toluene-to-benzene ratios for urban and non-urban sites were in good agreement with previously reported values, indicating a good relationship between the motor vehicle emissions and ambient VOC levels.

  14. CRADA Final Report: Optimized Catalysts for the Cracking of Heavier Petroleum Feedstocks

    SciTech Connect

    Somorjai, Gabor A.

    2003-01-02

    Catalysts lower the activation energy required for chemical reactions to proceed and are widely used in petroleum refining and chemical manufacturing. The useful lifetime and, thus, the value of an industrial catalyst are limited by a process known as deactivation in which the efficiency of the catalyst declines over time. Understanding this deactivation process is essential for developing new catalysts with longer useful lifetimes. In this project a new surface science tool, ultraviolet (UV) Raman spectroscopy, was used to identify chemical species on the surfaces of catalysts in-situ under actual reaction conditions. In collaboration with Catalytica this tool was applied to study deactivation in a series of important industrial catalysts. In the specific case of "reforming" catalysts are used to dehydrogenate and cyclize n-hexane and n-heptane to form benzene and toluene for the production of high octane gasoline, the buildup and polymerization of carbonaceous reaction byproducts on the surface of the catalyst was studied in-situ by this new method. The information on catalyst reaction and deactivation mechanisms has been found to be useful to the industrial partner in improving their catalysts. These improvements could have a major impact on the efficiency of petroleum refining and gasoline production. In addition, the new surface science tools developed by this project will have general applicability to the study of catalysis and to the field of surface science in general.

  15. Acid-catalyzed cracking of paraffinic hydrocarbons. 3. Evidence for the protonated cyclopropane mechanism from hydrocracking/hydroisomerization experiments

    SciTech Connect

    Tiong Sie, S. )

    1993-03-01

    The mechanism for acid-catalyzed cracking proposed in the first paper of this series, which assumes a protonated dialkylcyclopropane carbonium ion as intermediate instead of a classical carbenium ion, has been applied to rationalize experimental results obtained in the hydrocracking/hydroisomerization of normal paraffins. The new mechanism is shown to be capable of explaining many characteristics of the hydrocracking process which cannot be understood via the classical theory, such as the virtual absence of methane and ethane as cracked products, the relatively low production of propane as compared to the higher hydrocarbons, and characteristic patterns in the branching of the cracked fragments. The new mechanism also makes it clear why crackability increases so rapidly with increasing number of carbon atoms above n-heptane and why n-hexane and lower hydrocarbons are so difficult to crack. An explanation is also offered for the ease with which high selectivities can be achieved in the isomerization of C[sub 5]/C[sub 6], as contrasted with the difficulty of isomerizing C[sub 7+] without significant cracking.

  16. Observed trends in ambient concentrations of C 2-C 8 hydrocarbons in the United Kingdom over the period from 1993 to 2004

    NASA Astrophysics Data System (ADS)

    Dollard, G. J.; Dumitrean, P.; Telling, S.; Dixon, J.; Derwent, R. G.

    Hourly measurements of up to 26 C 2-C 8 hydrocarbons have been made at eight urban background sites, three urban-industrial sites, a kerbside and a rural site in the UK from 1993 onwards up until the end of December 2004. Average annual mean benzene and 1,3-butadiene concentrations at urban background locations have declined at about -20% per year and the observed declines have exactly mimicked the inferred declines in benzene and 1,3-butadiene emissions over the same period. Ninety-day rolling mean concentrations of ethylene, propylene, n- and i-butane, n- and i-pentane, isoprene and propane at urban and rural sites have also declined steadily by between -10% and -30% per year. Rolling mean concentrations of acetylene, 2- and 3-methylpentane, n-hexane, n-heptane, cis- and trans-but-2-ene, cis- and trans-pent-2-ene, toluene, ethylbenzene and o-, m- and p-xylene at a roadside location in London have all declined at between -14% and -21% per year. These declines demonstrate that motor vehicle exhaust catalysts and evaporative canisters have effectively and efficiently controlled vehicular emissions of hydrocarbons in the UK. Urban ethane concentrations arising largely from natural gas leakage have remained largely unchanged over this same period.

  17. Enhancement of the spectral selectivity of complex samples by measuring them in a frozen state at low temperatures in order to improve accuracy for quantitative analysis. Part I. Raman spectroscopic compositional analysis of synthetic hydrocarbon mixtures.

    PubMed

    Hwang, Jinyoung; Chung, Hoeil

    2013-03-01

    A simple strategy for enhancing the Raman spectral selectivity of complex mixture samples by measuring them in a frozen state at low temperatures has been demonstrated and proven to improve the accuracy for compositional analysis. For evaluation, the Raman spectra of synthetic hydrocarbon mixtures that were composed of eleven hydrocarbons (n-hexane, n-heptane, n-octane, n-nonane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and indan) were continuously collected during the elevation of their temperature from cryogenic to near room temperature. The accuracy of determination of n-paraffin concentrations improved significantly when the samples were measured at the temperature range between approximately -175 and -155 C in comparison to the measurements at room temperature. However, the improvement of accuracy was relatively marginal for the concentration determination of naphthenic and aromatic components. Since n-paraffins are easily compressible and deformable in frozen conditions, the subsequent spectral variations could be diverse depending on their molecular structures. Due to this fact, the spectral discrimination among the paraffin components, as well as in comparison to other components, was enhanced and the improved spectral selectivity eventually led to more accurate determination of concentrations. Overall, the proposed strategy is simple and effective, so it is applicable for analysis of real complex mixture samples. PMID:23340768

  18. Separation and aquatic toxicity of enantiomers of the organophosphorus insecticide trichloronate.

    PubMed

    Liu, Weiping; Lin, Kunde; Gan, Jianying

    2006-09-01

    Many of the organophosphorus pesticides (OPs) currently used are chiral and therefore consist of mixture of enantiomers. Despite the fact that the biological processes of chiral pesticides are enantioselective, the acute aquatic toxicity of chiral OPs with respect to enantioselectivity has so far received limited research. In this study, the enantiomeric separation and acute aquatic toxicity of trichloronate were investigated. Baseline enantioseparation of trichloronate was successfully achieved using high-performance liquid chromatography on a Chiralcel OJ column, with a mobile phase of n-hexane/n-heptane/ethanol (90/5/5, v/v/v) at the flow rate of 1.0 ml min(-1) and room temperature. The resolved enantiomers were characterized for their optical rotation and by gas chromatography coupled with mass spectrometry. Significant differences were found between the enantiomers in acute aquatic toxicity to Ceriodaphnia dubia and Daphnia magna. The (-)-trichloronate was 8-11 times more toxic to the test organisms than its (+)-form, while the racemate showed intermediate toxicity. These results suggest that assessment of the environmental safety of chiral OPs should take stereospecificity into consideration. PMID:16845672

  19. Investigation of thermodynamic properties of poly(methyl methacrylate-co-n-butylacrylate-co-cyclopentyl styryl-polyhedral oligomeric silsesquioxane) by inverse gas chromatography.

    PubMed

    Zou, Qi-Chao; Zhang, Shi-Ling; Wang, Shi-Min; Wu, Li-Min

    2006-10-01

    The thermodynamic properties of poly(methyl methacrylate-co-butyl acrylate-co-cyclo -pentylstyryl polyhedral oligomeric silsesquioxane) (poly(MMA-co-BA-co-styryl-POSS)) were investigated by means of inverse gas chromatography (IGC) using 20 different kinds of solvents as the probes. Some thermodynamic parameters, such as molar heats of sorption, weight fraction activity coefficient, Flory-Huggins interaction parameter, partial molar heats of mixing and solubility parameter were obtained to judge the interactions between POSS-contained polymers and solvents and the solubility of the polymers in these solvents. It was found that acetates, aromatic hydrocarbons and hydrocarbon halides were good solvents, n-hexane, ethanol, n-propanol, n-butanol and n-pentanol were moderate solvents, while n-heptane, n-octane, n-nonane, n-decane and methanol were poor solvents for all POSS-contained polymers within the experimental temperature range. Incorporation of POSS in polymer increased the solubility of polymers in solvents, and the more the POSS in polymer was, the better the solubility was and stronger the hydrogen bonding interaction was, but the POSS content in polymers seemed to have no obvious influence on the solubility parameter of polymers. PMID:16846607

  20. A rapid and efficient method for directed screening of lipase-producing Burkholderia cepacia complex strains with organic solvent tolerance from rhizosphere.

    PubMed

    Shu, Zhengyu; Lin, Ruifeng; Jiang, Huan; Zhang, Yanfeng; Wang, Mingzi; Huang, Jianzhong

    2009-06-01

    Lipase from Burkholderia cepacia strain is one of the most versatile biocatalysts and is used widely in many biotechnological application fields including detergent additives, the resolution of racemic compounds, etc. Based on the known whole genomic information of B. cepacia strain, both ampicillin and kanamycin were added to the TB-T medium to screen B. cepacia complex stains from rhizosphere soil samples. The selected colonies from the modified TB-T medium were then qualitatively determined the ability to produce extracellular lipase on the rhodamine B-olive oil agar plates. A total of 35 lipolytic pseudo-B. cepacia complex strains were isolated and the positive rate of lipolytic bacteria was 65%. Among them, 15 pseudo-B. cepacia complex strains showed tolerance to benzene, n-hexane and n-heptane at concentration of 10% (V/V) and were identified by the recA gene sequence. All of the 14 lipolytic bacteria were identified as B. cepacia complex strains except that the recA gene sequence of one lipolytic bacterium, strain ZMB009, was not obtained. PMID:19447345

  1. [Cloning and expression of organic solvent tolerant lipase gene from Staphylococcus saprophyticus M36].

    PubMed

    Tang, Yanchong; Lu, Yaping; L, Fengxia; Bie, Xiaomei; Guo, Yao; Lu, Zhaoxin

    2009-12-01

    Lipases are important biocatalysts that are widely used in food processing and bio-diesel production. However, organic solvents could inactivate some lipases during applications. Therefore, the efficient cloning and expression of the organic solvent-tolerant lipase is important to its application. In this work, we first found out an organic solvent-tolerant lipase from Staphylococcus saprophyticus M36 and amplified the 741 bp Lipase gene lip3 (GenBank Accession No. FJ979867), by PCR, which encoded a 31.6 kD polypeptide of 247 amino acid residues. But the lipase shared 83% identity with tentative lip3 gene of Staphylococcus saprophyticus (GenBank Accession No. AP008934). We connected the gene with expression vector pET-DsbA, transformed it into Escherichia coli BL21 (DE3), and obtained the recombinant pET-DsbA-lip3. With the induction by 0.4 mmol/L of isopropyl beta-D-thiogalactopyranoside at pH 8.0, OD600 1.0, 25 degrees C for 12 h, the lipase activity reached up to 25.8 U/mL. The lipase expressed was stable in the presence of methanol, n-hexane, and isooctane, n-heptane. PMID:20352979

  2. n-Aldehydes (C6-C10) in snow samples collected at the high alpine research station Jungfraujoch during CLACE 5

    NASA Astrophysics Data System (ADS)

    Sieg, K.; Starokozhev, E.; Fries, E.; Sala, S.; Pttmann, W.

    2009-03-01

    Samples of freshly fallen snow were collected at the high alpine research station Jungfraujoch, Switzerland, during the Cloud and Aerosol Characterization Experiments (CLACE) 5 in February and March 2006. Sampling was carried out on the Sphinx platform. Headspace-solid-phase-dynamic extraction (HS-SPDE) combined with gas chromatography/mass spectrometry (GC/MS) was used to quantify C6-C10 n-aldehydes in the snow samples. The most abundant n-aldehyde was n-hexanal (median concentration 1.324 ?g L-1) followed by n-nonanal, n-decanal, n-octanal and n-heptanal (median concentrations 1.239, 0.863, 0.460, and 0.304 ?g L-1, respectively). A wide range of concentrations was found among individual snow samples, even for samples taken at the same time. Higher median concentrations of all n-aldehydes were observed when air masses reached Jungfraujoch from the north-northwest in comparison to air masses arriving from the southeast-southwest. Results suggest that the n-aldehydes detected most likely are of direct and indirect biogenic origin, and that they entered the snow through the particle phase.

  3. Biodiesel production using waste frying oil

    SciTech Connect

    Charpe, Trupti W.; Rathod, Virendra K.

    2011-01-15

    Research highlights: {yields} Waste sunflower frying oil is successfully converted to biodiesel using lipase as catalyst. {yields} Various process parameters that affects the conversion of transesterification reaction such as temperature, enzyme concentration, methanol: oil ratio and solvent are optimized. {yields} Inhibitory effect of methanol on lipase is reduced by adding methanol in three stages. {yields} Polar solvents like n-hexane and n-heptane increases the conversion of tranesterification reaction. - Abstract: Waste sunflower frying oil is used in biodiesel production by transesterification using an enzyme as a catalyst in a batch reactor. Various microbial lipases have been used in transesterification reaction to select an optimum lipase. The effects of various parameters such as temperature, methanol:oil ratio, enzyme concentration and solvent on the conversion of methyl ester have been studied. The Pseudomonas fluorescens enzyme yielded the highest conversion. Using the P. fluorescens enzyme, the optimum conditions included a temperature of 45 deg. C, an enzyme concentration of 5% and a methanol:oil molar ratio 3:1. To avoid an inhibitory effect, the addition of methanol was performed in three stages. The conversion obtained after 24 h of reaction increased from 55.8% to 63.84% because of the stage-wise addition of methanol. The addition of a non-polar solvent result in a higher conversion compared to polar solvents. Transesterification of waste sunflower frying oil under the optimum conditions and single-stage methanol addition was compared to the refined sunflower oil.

  4. Interpolation between State Points in the Simulated Perturbation Contributions of Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Vahid, Amir; Gray, Neil H.; Elliott, J. Richard

    2009-03-01

    Polymeric mixtures of hydrocarbons, alcohols have been simulated with discontinuous potential models to characterize the Helmholtz energy of the repulsive reference fluids (A0) along with the first and second order perturbation contributions (A1, A2) as functions of density and composition. Taken together, these terms generate a complete equation of state for the mixture, including temperature effects as well as density and composition. The specific hydrocarbons studied were methane, ethane, propane, n-butane, n-hexane, n-heptane, n-decane, and benzene. The specific alcohols were water, methanol, ethanol, n-propanol, and n-octanol. Unfortunately, a slight inconsistency was encountered when the trend observed for these small molecules was extrapolated to the long chain limit. Therefore, we extend the analysis to mixtures of n-alkanes, branched hydrocarbons, and aromatics with polymeric molecules of: n-alkanes, ethyl-styrenes, ethyl-propylenes, and isoprenes. The perturbation contributions can be accurately characterized by van der Waals mixing rules and compared with the MCSL SAFT and Guggenheim-Staverman theories.

  5. High pressure droplet burning experiments in reduced gravity

    NASA Technical Reports Server (NTRS)

    Chauveau, Christian; Goekalp, Iskender

    1995-01-01

    A parametric investigation of single droplet gasification regimes is helpful in providing the necessary physical ideas for sub-grid models used in spray combustion numerical prediction codes. A research program has been initiated at the LCSR to explore the vaporization regimes of single and interacting hydrocarbon and liquid oxygen droplets under high pressure conditions. This paper summarizes the status of the LCSR program on the high pressure burning of single fuel droplets; recent results obtained under normal and reduced gravity conditions with suspended droplets are presented. In the work described here, parabolic flights of the CNES Caravelle is used to create a reduced gravity environment of the order of 10(exp -2) g(sub O). For all the droplet burning experiments reported here, the suspended droplet initial diameters are scattered around 1.5 mm; and the ambient air temperature is 300 K. The ambient pressure is varied between 0.1 MPa and 12 MPa. Four fuels are investigated: methanol (Pc = 7.9 MPa), n-heptane (Pc = 2.74 MPa), n-hexane (Pc = 3.01 MPa) and n-octane (Pc = 2.48 MPa).

  6. Thermochemistry of C7H16 to C10H22 alkane isomers: primary, secondary, and tertiary C-H bond dissociation energies and effects of branching.

    PubMed

    Hudzik, Jason M; Bozzelli, Joseph W; Simmie, John M

    2014-10-01

    Standard enthalpies of formation (?Hf298) of methyl, ethyl, primary and secondary propyl, and n-butyl radicals are evaluated and used in work reactions to determine internal consistency. They are then used to calculate the enthalpy of formation for the tert-butyl radical. Other thermochemical properties including standard entropies (S(T)), heat capacities (Cp(T)), and carbon-hydrogen bond dissociation energies (C-H BDEs) are reported for n-pentane, n-heptane, 2-methylhexane, 2,3-dimethylpentane, and several branched higher carbon number alkanes and their radicals. ?Hf298 and C-H BDEs are calculated using isodesmic work reactions at the B3LYP (6-31G(d,p) and 6-311G(2d,2p) basis sets), CBS-QB3, CBS-APNO, and G3MP2B3 levels of theory. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level for contributions to entropy and heat capacities. Enthalpy calculations for these hydrocarbon radical species are shown to have consistency with the CBS-QB3 and CBS-APNO methods using all work reactions. Our recommended ideal gas phase ?Hf298 values are from the average of all CBS-QB3, CBS-APNO, and for G3MP2B3, only where the reference and target radical are identical types, and are compared with literature values. Calculated values show agreement between the composite calculation methods and the different work reactions. Secondary and tertiary C-H bonds in the more highly branched alkanes are shown to have bond energies that are several kcal mol(-1) lower than the BDEs in corresponding smaller molecules often used as reference species. Entropies and heat capacities are calculated and compared to literature values (when available) when all internal rotors are considered. PMID:25180943

  7. Transferable Potentials for Phase Equilibria. 4. United-Atom Description of Linear and Branched Alkenes and Alkylbenzenes

    SciTech Connect

    WICK,COLLIN D.; MARTIN,MARCUS G.; SIEPMANN,J. ILJA

    2000-07-12

    The Transferable Potentials for Phase Equilibria-United Atom (TraPPE-UA) force field for hydrocarbons is extended to alkenes and alkylbenzenes by introducing the following pseudo-atoms: CH{sub 2}(sp{sup 2}), CH(sp{sup 2}), CH(aro), R-C(aro) for the link to aliphatic side chains, and C(aro) for the link of two benzene rings. In this united-atom force field, the nonbonded interactions of the hydrocarbon pseudo-atoms are solely governed by Lennard-Jones 12-6 potentials, and the Lennard-Jones well depth and size parameters for the new pseudo-atoms were determined by fitting to the single-component vapor-liquid phase equilibria of a few selected model compounds. Configurational-bias Monte Carlo simulations in the NVT version of the Gibbs ensemble were carried out to calculate the single-component vapor-liquid coexistence curves for ethene, propene, 1-butene, trans- and cis-2-butene. 2-methylpropene, 1,5-hexadiene, 1-octene, benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene, o-, m-, and p-xylene, and naphthalene. The phase diagrams for the binary mixtures of (supercritical) ethene/n-heptane and benzene/n-pentane were determined from simulations in the NpT Gibbs ensemble. Although the TraPPE-UA force field is rather simple and makes use of relatively few different pseudo-atoms, its performance, as judged by comparisons to other popular force fields and available experimental data, is very satisfactory.

  8. D/H Isotope Ratio Measurements of Atmospheric Volatile Organic Compounds

    NASA Astrophysics Data System (ADS)

    Meisehen, Thomas; Bühler, Fred; Koppmann, Ralf; Krebsbach, Marc

    2015-04-01

    Analysis of isotope ratios in atmospheric volatile organic compounds (VOC) is a reliable method to allocate their sources, to estimate atmospheric residence times and investigate physical and chemical processes on various temporal and spatial scales. Most investigations yet focus on carbon isotope ratios. Certainly more detailed information can be gained by the ratio of deuterium (D) to hydrogen (H) in VOC, especially due to the high mass ratio. Combining measurements of carbon and hydrogen isotopes could lead to considerable improvement in our understanding of atmospheric processes. For this purpose we set up and thoroughly characterised a gas chromatograph pyrolysis isotope ratio mass spectrometer to measure the D/H ratio in atmospheric VOC. From a custom-made gas standard mixture VOC were adsorbed on Tenax®TA which has the advantage that CO2 is not preconcentrated when measuring ambient air samples. Our results show that the pyrolysis method has significant impact on the D/H ratios. A pyrolysis temperature of at least 1723 K and conditioning of the ceramic tube on a regular basis is essential to obtain reproducible D/H isotope ratios. For an independent comparison D/H ratios of the pure VOC used in the gas standard were determined using elemental analysis by Agroisolab (Jülich, Germany). Comparisons of 10 VOC show perfect agreement within the standard deviations of our measurements and the errors given by Agroisolab, e.g. for n-pentane, toluene, 4-methyl-2-pentanone and n-octane. A slight mean difference of 5.1 o was obtained for n-heptane while significant mean differences of 15.5 o and 20.3 o arose for 1,2,4-trimethylbenzene and isoprene, respectively. We further demonstrate the stability of our system and show that the sample preparation does not affect the isotope ratios. Moreover the applicability of our system to ambient air samples is demonstrated.

  9. n-Aldehydes (C6-C10) in snow samples collected at the high alpine research station Jungfraujoch during CLACE 5

    NASA Astrophysics Data System (ADS)

    Sieg, K.; Starokozhev, E.; Fries, E.; Sala, S.; Pttmann, W.

    2009-04-01

    C6-C10 n-aldehydes were analyzed in samples of freshly fallen snow collected at the high alpine research station Jungfraujoch, Switzerland, during the Cloud and Aerosol Characterization Experiments (CLACE) 5 in February and March 2006. Sampling was carried out on the Sphinx platform. Headspace - solid phase dynamic extraction (HS-SPDE) combined with gas chromatography/mass spectrometry (GC/MS) was used to quantify n-aldehydes in melted snow samples. n-Hexanal was identified as the most abundant n-aldehyde (median concentration 1.324 g L-1) followed by n-nonanal, n-decanal, n-octanal and n-heptanal (median concentrations 1.239, 0.863, 0.460 and 0.304 g L-1, respectively). A wide range of concentrations of n-aldehydes was found in snow samples from Jungfraujoch, even for samples collected at the same time during the same snowfall event. According to their physical and chemical characteristics, n-aldehydes are expected to be primarily linked to aerosol particles in the atmosphere suggesting the uptake of n-aldehydes into snow via the particle phase. Particle scavenging can occur during snow formation in clouds. The high concentration variations of the n-aldehydes among the snow samples can be explained assuming that aerosol particles, which are loaded with n-aldehydes, are heterogeneously distributed throughout the snow samples. Higher median concentrations of all n-aldehydes were observed when air masses reached Jungfraujoch from the north-northwest in comparison to air masses arriving from the southeast-southwest. The sources of atmospheric n-aldehydes present at Jungfraujoch are most likely to be related to direct and indirect biogenic emissions. The presence of n-aldehydes as semivolatile constituents of direct biogenic emissions from vegetation has been reported previously in studies of Ciccioli et al. [1], Yokouchi et al. [2] and Kesselmeier and Staudt [3]. The distribution pattern of the n-aldehydes in emissions from vegetation largely matches with the n-aldehyde pattern found in snow collected at Jungfraujoch. One exception is the significantly higher proportion of n-hexanal in the Jungfraujoch samples compared to vegetation emission. Additionally, indirect biogenic emissions can contribute to the atmospheric concentrations of n-aldehydes through oxidation of precursor compounds of biogenic origin. In this context, Moise and Rudich [4] and Thornberry and Abbatt [5] proposed the preferential formation of n-nonanal and n-hexanal from the cleavage by ozonolysis of double bonds in unsaturated fatty acids (namely oleic acid and linoleic acids). The predominance of n-hexanal and n-nonanal among the C6-C10 n-aldehydes in the snow samples collected at Jungfraujoch during CLACE 5 is therefore an argument for the formation of the aldehydes through oxidation of unsaturated fatty acids in the atmosphere. Anthropogenic emissions of n-aldehydes i.e. from fossil fuel burning are thought to be negligible in the air masses reaching Jungfraujoch. References: [1] P. Ciccioli, E. Brancaleoni, M. Frattoni, A. Cecinato, A. Brachetti, Atmos. Environ., Part A 27 (1993) 1891. [2] Y. Yokouchi, H. Mukai, K. Nakajima, Y. Ambe, Atmos. Environ., Part A 24 (1990) 439. [3] J. Kesselmeier, M. Staudt, J. Atmos. Chem. 33 (1999) 23. [4] T. Moise, Y. Rudich, J. Phys. Chem. 106 (2002) 6469. [5] T. Thornberry, J.P.D. Abbatt, Phys. Chem. Chem. Phys. 6 (2004) 84.

  10. METHYL KETONE METABOLISM IN HYDROCARBON-UTILIZING MYCOBACTERIA

    PubMed Central

    Lukins, H. B.; Foster, J. W.

    1963-01-01

    Lukins, H. B. (University of Texas, Austin) and J. W. Foster. Methyl ketone metabolism in hydrocarbon-utilizing mycobacteria. J. Bacteriol. 85: 10741087. 1963.Species of Mycobacterium especially M. smegmatis 422, produced the homologous methyl ketones during the oxidation of propane, n-butane, n-pentane, or n-hexane. A carrier-trapping experiment demonstrated the formation of 2-undecanone, as well as 1,11-undecanedioic acid, during the oxidation of undecane-1-C14. Aliphatic alkane-utilizing mycobacteria were able to grow at the expense of several aliphatic methyl ketones as sole sources of carbon. Other ketones which did not support growth were oxidized by resting bacterial suspensions. M. smegmatis 422 cells grown on propane or acetone were simultaneously adapted to oxidize both substrates, as well as n-propanol. n-Propanol cells were unadapted to propane or acetone. Acetone produced from propane in a medium enriched in D2O contained a negligible quantity of D, presumably eliminating propylene as an intermediate in the oxidation. Cells grown at the expense of alkanes or methyl ketones in the presence of O218 had a higher content of O18 than did cells grown on terminally oxidized compounds, e.g., primary alcohols or fatty acids. An oxygenase reaction is postulated for the attack on methyl ketones. Acetol was isolated and characterized as an oxidation product of acetone by M. smegmatis 422. Acetol-grown cells had a higher O18 content than did n-propanol cells, and its utilization appears to involve at least one oxygenase reaction. Acetol produced from acetone in the presence of O218 was not enriched in the isotope, indicating the occurrence of exchange reactions or of oxygenation reactions at a later stage in the assimilation of acetone and acetol. PMID:14043998

  11. Investigation of the impact of organic solvent type and solution pH on the extraction efficiency of naphthenic acids from oil sands process-affected water.

    PubMed

    Huang, Rongfu; McPhedran, Kerry N; Sun, Nian; Chelme-Ayala, Pamela; Gamal El-Din, Mohamed

    2016-03-01

    Naphthenic acids (NAs) from oil sand process-affected water (OSPW) were liquid-liquid extracted using six organic solvents (n-pentane, n-hexane, cyclohexane, dichloromethane, ethyl ether, and ethyl acetate) at three pHs (2.0, 8.5, and 12.0). The NAs exist in ionic (ions) and non-ionic (molecules) forms in the water phase depending on their dissociation constants and the solution pH. Results showed the extractability of NA molecules depends on the solvent polarity and the extractability of NA ions on the water solubility in solvent. The organic solvent type and solution pH were found to not only impact the extracted amounts of each NA species, but also the NAs distribution in terms of molecule carbon number and hydrogen deficiency. Overall, it is concluded that ethyl ether can be used as an alternative to dichloromethane (DCM) given their similar extraction efficiencies and extracted NA profiles. This is important since DCM is known to have metabolic toxicity and transitioning to the safer ethyl ether would eliminate laboratory DCM exposures and risk to human health. Despite the higher extraction efficiency of NAs at pH 2.0, extraction at pH 12.0 could be useful for targeted extraction of low-concentration nonpolar organic compounds in OSPW. This knowledge may assist in the determination of the specific NAs species that are known to have chronic, sub-chronic and acute toxicity to various organisms, and the potential targeting of treatment to these NAs species. PMID:26741553

  12. Anthropogenic emissions of nonmethane hydrocarbons in the northeastern United States: Measured seasonal variations from 1992-1996 and 1999-2001

    NASA Astrophysics Data System (ADS)

    Lee, Ben H.; Munger, J. William; Wofsy, Steven C.; Goldstein, Allen H.

    2006-10-01

    Harvard Forest, a rural site located in central Massachusetts downwind of major urban-industrial centers, provides an excellent location to observe a typical regional mixture of anthropogenic trace gases. Air that arrives at Harvard Forest from the southwest is affected by emissions from the U.S. east coast urban corridor and may have residual influence from emissions in the upper Ohio Valley and Great Lakes region farther to the west. Because of its relatively long distance from large individual emission sources, pollution plumes reaching the site are a homogenized mixture of regional anthropogenic emissions. Concentrations of C2-C6 hydrocarbons along with CO and NOy were measured nearly continuously from August 1992 through July 1996 and from June 1999 through November 2001. By correlating observed concentrations to acetylene, which is almost solely produced during combustion, we are able to detect seasonal trends in relative emissions for this series of trace gases. Seasonal changes in n-butane and i-butane emissions may largely be influenced by different gasoline formulations in late spring and summer. Shifts in evaporation rates due to the annual temperature cycle could induce a seasonal pattern for n-pentane, i-pentane and n-hexane emissions. Emissions of ethane and propane lack clear seasonality relative to acetylene emissions and also correlate less with acetylene than other gases, indicating that emissions of these two gases are strongly influenced by sources not associated with fuel combustion. Changes in the observed correlations of CO2 and CO relative to acetylene are consistent with published changes in the estimated emissions of CO2 and CO over the past decade, though variability in the observations makes it difficult to precisely quantify these changes.

  13. Molecular dynamics averaging of Xe chemical shifts in liquids

    NASA Astrophysics Data System (ADS)

    Jameson, Cynthia J.; Sears, Devin N.; Murad, Sohail

    2004-11-01

    The Xe nuclear magnetic resonance chemical shift differences that afford the discrimination between various biological environments are of current interest for biosensor applications and medical diagnostic purposes. In many such environments the Xe signal appears close to that in water. We calculate average Xe chemical shifts (relative to the free Xe atom) in solution in eleven liquids: water, isobutane, perfluoro-isobutane, n-butane, n-pentane, neopentane, perfluoroneopentane, n-hexane, n-octane, n-perfluorooctane, and perfluorooctyl bromide. The latter is a liquid used for intravenous Xe delivery. We calculate quantum mechanically the Xe shielding response in Xe-molecule van der Waals complexes, from which calculations we develop Xe (atomic site) interpolating functions that reproduce the ab initio Xe shielding response in the complex. By assuming additivity, these Xe-site shielding functions can be used to calculate the shielding for any configuration of such molecules around Xe. The averaging over configurations is done via molecular dynamics (MD). The simulations were carried out using a MD technique that one of us had developed previously for the simulation of Henry's constants of gases dissolved in liquids. It is based on separating a gaseous compartment in the MD system from the solvent using a semipermeable membrane that is permeable only to the gas molecules. We reproduce the experimental trends in the Xe chemical shifts in n-alkanes with increasing number of carbons and the large chemical shift difference between Xe in water and in perfluorooctyl bromide. We also reproduce the trend for a given solvent of decreasing Xe chemical shift with increasing temperature. We predict chemical shift differences between Xe in alkanes vs their perfluoro counterparts.

  14. Characteristics of volatile organic compounds (VOCs) emitted from a petroleum refinery in Beijing, China

    NASA Astrophysics Data System (ADS)

    Wei, Wei; Cheng, Shuiyuan; Li, Guohao; Wang, Gang; Wang, Haiyan

    2014-06-01

    This study made a field VOCs (volatile organic compounds) measurement for a petroleum refinery in Beijing by determining 56 PAMS VOCs, which are demanded for photochemical assessment in US, and obtained the characteristics of VOCs emitted from the whole refinery and from its inner main devices. During the monitoring period, this refinery brought about an average increase of 61 ppbv in the ambient TVOCs (sum of the PAMS VOCs) at the refinery surrounding area, while the background of TVOCs there was only 10-30 ppbv. In chemical profile, the VOCs emitted from the whole refinery was characteristic by isobutane (8.7%), n-butane (7.9%), isopentane (6.3%), n-pentane (4.9%%), n-hexane (7.6%), C6 branched alkanes (6.0%), propene (12.7%), 1-butene (4.1%), benzene (7.8%), and toluene (5.9%). On the other hand, the measurement for the inner 5 devices, catalytic cracking units (CCU2 and CCU3), catalytic reforming unit (CRU), tank farm (TF), and wastewater treatment(WT), revealed the higher level of VOCs pollutions (about several hundred ppbv of TVOCs), and the individual differences in VOCs chemical profiles. Based on the measured speciated VOCs data at the surrounding downwind area, PMF receptor model was applied to identify the VOCs sources in the refinery. Then, coupling with the VOCs chemical profiles measured at the device areas, we concluded that CCU1/3 contributes to 25.9% of the TVOCs at the surrounding downwind area by volume, followed by CCU2 (24.7%), CRU (18.9%), TF (18.3%) and WT (12.0%), which was accordant with the research of US EPA (2008). Finally, ozone formation potentials of the 5 devices were also calculated by MIR technique, which showed that catalytic cracking units, accounting for about 55.6% to photochemical ozone formation, should be given the consideration of VOCs control firstly.

  15. Investigating the validity of the Knudsen prescription for diffusivities in a mesoporous covalent organic framework

    SciTech Connect

    Krishna, Rajamani; van Baten, Jasper M.

    2011-04-27

    Molecular dynamics (MD) simulations were performed to determine the self-diffusivity (Di,self) and the Maxwell–Stefan diffusivity (ÐI) of hydrogen, argon, carbon dioxide, methane, ethane, propane, n-butane, n-pentane, and n-hexane in BTP-COF, which is a covalent organic framework (COF) that has one-dimensional 3.4-nm-sized channels. The MD simulations show that the zero-loading diffusivity (ÐI(0)) is consistently lower, by up to a factor of 10, than the Knudsen diffusivity (Di,Kn) values. The ratio ÐI(0)/Di,Kn is found to correlate with the isosteric heat of adsorption, which, in turn, is a reflection of the binding energy for adsorption on the pore walls: the stronger the binding energy, the lower the ratio ÐI(0)/Di,Kn. The diffusion selectivity, which is defined by the ratio D1,self/D2,self for binary mixtures, was determined to be significantly different from the Knudsen selectivity (M2/M1)1/2, where MI is the molar mass of species i. For mixtures in which component 2 is more strongly adsorbed than component 1, the expression (D1,self/D2,self)/(M2/M1)1/2 has values in the range of 1–10; the departures from the Knudsen selectivity increased with increasing differences in adsorption strengths of the constituent species. The results of this study have implications in the modeling of diffusion within mesoporous structures, such as MCM-41 and SBA-15.

  16. Selective hydroxylation of alkanes by an extracellular fungal peroxygenase

    PubMed Central

    Peter, Sebastian; Kinne, Matthias; Wang, Xiaoshi; Ullrich, Ren; Kayser, Gernot; Groves, John T.; Hofrichter, Martin

    2013-01-01

    Fungal peroxygenases are novel extracellular heme-thiolate biocatalysts that are capable of catalyzing the selective monooxygenation of diverse organic compounds, using only H2O2 as a cosubstrate. Little is known about the physiological role or the catalytic mechanism of these enzymes. We have found that the peroxygenase secreted by Agrocybe aegerita catalyzes the H2O2-dependent hydroxylation of linear alkanes at the 2-position and 3-position with high efficiency, as well as the regioselective monooxygenation of branched and cyclic alkanes. Experiments with n-heptane and n-octane showed that the hydroxylation proceeded with complete stereoselectivity for the (R)-enantiomer of the corresponding 3-alcohol. Investigations with a number of model substrates provided information about the route of alkane hydroxylation: (a) the hydroxylation of cyclohexane mediated by H218O2 resulted in complete incorporation of 18O into the hydroxyl group of the product cyclohexanol; (b) the hydroxylation of n-hexane-1,1,1,2,2,3,3-D7 showed a large intramolecular deuterium isotope effect [(kH/kD)obs] of 16.0 1.0 for 2-hexanol and 8.9 0.9 for 3-hexanol; and (c) the hydroxylation of the radical clock norcarane led to an estimated radical lifetime of 9.4 ps and an oxygen rebound rate of 1.06 1011 s?1. These results point to a hydrogen abstraction and oxygen rebound mechanism for alkane hydroxylation. The peroxygenase appeared to lack activity on long-chain alkanes (> C16) and highly branched alkanes (e.g. tetramethylpentane), but otherwise exhibited a broad substrate range. It may accordingly have a role in the bioconversion of natural and anthropogenic alkane-containing structures (including alkyl chains of complex biomaterials) in soils, plant litter, and wood. PMID:21812933

  17. Growth of Rhodococcus sp. strain BCP1 on gaseous n-alkanes: new metabolic insights and transcriptional analysis of two soluble di-iron monooxygenase genes.

    PubMed

    Cappelletti, Martina; Presentato, Alessandro; Milazzo, Giorgio; Turner, Raymond J; Fedi, Stefano; Frascari, Dario; Zannoni, Davide

    2015-01-01

    Rhodococcus sp. strain BCP1 was initially isolated for its ability to grow on gaseous n-alkanes, which act as inducers for the co-metabolic degradation of low-chlorinated compounds. Here, both molecular and metabolic features of BCP1 cells grown on gaseous and short-chain n-alkanes (up to n-heptane) were examined in detail. We show that propane metabolism generated terminal and sub-terminal oxidation products such as 1- and 2-propanol, whereas 1-butanol was the only terminal oxidation product detected from n-butane metabolism. Two gene clusters, prmABCD and smoABCD-coding for Soluble Di-Iron Monooxgenases (SDIMOs) involved in gaseous n-alkanes oxidation-were detected in the BCP1 genome. By means of Reverse Transcriptase-quantitative PCR (RT-qPCR) analysis, a set of substrates inducing the expression of the sdimo genes in BCP1 were assessed as well as their transcriptional repression in the presence of sugars, organic acids, or during the cell growth on rich medium (Luria-Bertani broth). The transcriptional start sites of both the sdimo gene clusters were identified by means of primer extension experiments. Finally, proteomic studies revealed changes in the protein pattern induced by growth on gaseous- (n-butane) and/or liquid (n-hexane) short-chain n-alkanes as compared to growth on succinate. Among the differently expressed protein spots, two chaperonins and an isocytrate lyase were identified along with oxidoreductases involved in oxidation reactions downstream of the initial monooxygenase reaction step. PMID:26029173

  18. Growth of Rhodococcus sp. strain BCP1 on gaseous n-alkanes: new metabolic insights and transcriptional analysis of two soluble di-iron monooxygenase genes

    PubMed Central

    Cappelletti, Martina; Presentato, Alessandro; Milazzo, Giorgio; Turner, Raymond J.; Fedi, Stefano; Frascari, Dario; Zannoni, Davide

    2015-01-01

    Rhodococcus sp. strain BCP1 was initially isolated for its ability to grow on gaseous n-alkanes, which act as inducers for the co-metabolic degradation of low-chlorinated compounds. Here, both molecular and metabolic features of BCP1 cells grown on gaseous and short-chain n-alkanes (up to n-heptane) were examined in detail. We show that propane metabolism generated terminal and sub-terminal oxidation products such as 1- and 2-propanol, whereas 1-butanol was the only terminal oxidation product detected from n-butane metabolism. Two gene clusters, prmABCD and smoABCDcoding for Soluble Di-Iron Monooxgenases (SDIMOs) involved in gaseous n-alkanes oxidationwere detected in the BCP1 genome. By means of Reverse Transcriptase-quantitative PCR (RT-qPCR) analysis, a set of substrates inducing the expression of the sdimo genes in BCP1 were assessed as well as their transcriptional repression in the presence of sugars, organic acids, or during the cell growth on rich medium (LuriaBertani broth). The transcriptional start sites of both the sdimo gene clusters were identified by means of primer extension experiments. Finally, proteomic studies revealed changes in the protein pattern induced by growth on gaseous- (n-butane) and/or liquid (n-hexane) short-chain n-alkanes as compared to growth on succinate. Among the differently expressed protein spots, two chaperonins and an isocytrate lyase were identified along with oxidoreductases involved in oxidation reactions downstream of the initial monooxygenase reaction step. PMID:26029173

  19. Isolation and identification of some unknown substances in disposable nitrile-butadiene rubber gloves used for food handling.

    PubMed

    Mutsuga, M; Wakui, C; Kawamura, Y; Maitani, T

    2002-11-01

    In Japan, disposable gloves made from nitrile-butadiene rubber (NBR) are frequently used in contact with foods. In a previous paper, we investigated substances migrating from various gloves made of polyvinyl chloride, polyethylene, natural rubber and NBR. Zinc di-n-butyldithiocarbamate (ZDBC), diethyldithiocarbamate (ZDEC) used as vulcanization accelerators, di(2-ethylhexyl)phthalate (DEHP) used as a plasticizer and many unknown compounds that migrated from NBR gloves into n-heptane were detected by GC/MS. In this paper, six unknown compounds were obtained from one kind of NBR glove by n-hexane extraction and each was isolated by silica gel chromatography. From the results of NMR and mass spectral analysis of the six unknown compounds, their structures are proposed as 1,4-dione-2,5-bis(1,1-dimethylpropyl)cyclohexadiene (1), 2-(1,1-dimethylethyl)-4-(1,1,3,3-tetra methylbutyl)phenol (2), 2,6-bis(1,1-dimethylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (3), 2,4-bis(1,1,3,3-tetramethylbutyl)phenol (4), 2-(1,1-dimethylethyl)4,6-bis(1,1,3,3-tetramethylbutyl)phenol (5) and 2,4,6-tris(1,1,3,3-tetramethylbutyl)phenol (6). Compound 1 was observed in five of the seven kinds of NBR gloves, and compounds 2-4 and 6, which are not listed in Chemical Abstract (CA), were present in four kinds of gloves. PMID:12456282

  20. Simultaneous indoor and outdoor on-line hourly monitoring of atmospheric volatile organic compounds in an urban building. The role of inside and outside sources.

    PubMed

    de Blas, Maite; Navazo, Marino; Alonso, Lucio; Durana, Nieves; Gomez, Maria Carmen; Iza, Jon

    2012-06-01

    Indoor air quality (IAQ) has become a very important issue in recent years. As in developed countries people spend more than 90% of their time indoors, besides outdoor pollution assessment, the indoor one is also required. IAQ is not only affected by indoor sources linked to indoor activities, outdoor sources such as road or street traffic and industrial and commercial activities have their role too. Volatile organic compounds (VOCs) frequently show higher indoor mixing ratios with respect to the outdoor ones, and monitoring is required to report their indoor mixing ratios. Many studies have reported average indoor VOCs' mixing ratios in different environments, but their temporal variability has not been well documented. The main objective of this work was to simultaneously measure VOCs' indoor and outdoor mixing ratios with high time-resolution in order to assess the effect of sources inside and outside the building upon indoor mixing ratios of individual VOCs. Simultaneous hourly, continuous, and on-line measurements of C(2)-C(11) VOCs were performed inside and outside the School of Engineering of Bilbao (ETSI) building, located in the city center of Bilbao, an urban area in Northern Spain. The analysis of simultaneous data allowed the classification of VOCs based on their main sources. Some VOCs were mainly emitted by indoor sources (1-pentene, 2-methylpentane, n-hexane, methylcyclopentane, benzene, 1-heptene+2,2,4-trimethylbenzene, and tetrachloroethylene) or by outdoor sources (n-heptane, C(8) alkanes except trimethylpentanes and C(9) aromatics). Other VOCs, such as toluene, were emitted by both indoor and outdoor sources. The isoprene indoor pattern indicated that its main indoor source could be the air exhaled by people occupying the building. Some halocarbons, such as trichloroethylene, tetrachloroethylene, and carbon tetrachloride may be generated from the use inside the building of chlorine bleach containing products. PMID:22542255

  1. Ultrafast molecular dynamics of biofuel extraction for microalgae and bacteria milking: blocking membrane folding pathways to damaged lipid-bilayer conformations with nanomicelles.

    PubMed

    Gillet, Jean-Numa

    2015-01-01

    Cell milking is a 100% renewable green energy for CO2 by extraction of biofuels inside the cytosol of photosynthetic micro-organisms as microalgae and bacteria. The cells are exposed to a hydrophobic solvent forming holes and cracks through their membranes from which the biofuels can leak out. In protein folding, the goal would be to find pathways to the unique functional protein conformer. However, in the lipid-bilayer interaction with the solvent for milking, the objective is to block the pathways for damaged membrane conformations of low free energy with undesired nanostructures, using the solvent properties, as shown with an ab initio structural bioinformatic model. Statistical thermodynamics is used to compute the free energy (including entropy) from the molecular dynamics trajectory of the biomolecular system with many conformational changes. This model can be extended to the general problem of biomolecules folding as for proteins and nucleic acids. Using an adaptation of the Einstein diffusion law, the conformational change dynamics of the lipid bilayer depends on the two diffusion coefficients of the solvent: D1 before the irreversible folding transition time and the much smaller D2 thereafter. In contrast to the n-hexane and n-heptane hydrocarbons of smaller size, the residual D2=4.7 10(-7)cm(2)/s of the n-decane solvent, with the highest partition coefficient among the three extractors, is the only to present a D2 value that is significantly below the critical threshold of 10(-6)cm(2)/s. Therefore, the membrane would resist to long hydrocarbons and the exposed cells would remain viable for milking. PMID:24735062

  2. Switching from photochemical to photothermal mechanism in laser ablation of benzene solutions

    NASA Astrophysics Data System (ADS)

    Hatanaka, Koji; Kawao, Mitsushi; Tsuboi, Yasuyuki; Fukumura, Hiroshi; Masuhara, Hiroshi

    1997-12-01

    Nanosecond KrF excimer laser ablation of benzyl chloride, benzyl alcohol, toluene, ethylbenzene, and n-propylbenzene diluted in n-hexane, n-heptane, dichloromethane, and 1,2-dichloroethane was investigated by time-resolved photographic, photoacoustic, and absorbance measurements. Ablation threshold values, Fth, for high concentration solutions (?=250 cm-1, 0.6-1 M) were confirmed to be correlated to photochemical reactivity (?-bond cleavage) of the solute molecules, whereas no distinct relation between Fth and boiling point of solvents was observed. Time-resolved absorbance at the laser wavelength was almost constant during the excitation pulse, which means that the main light-absorbing molecules were fixed to the ground-state solutes. It is considered that this type of ablation is initiated by the photochemical fragmentation. On the contrary, Fth observed in relatively low concentration solutions (?=25 cm-1, 0.06-0.1 M) were about twice higher than those for the high concentration solutions, and had no direct correlation with the photochemical reactivity of the solute molecules. The time-resolved absorbance increased during the excitation pulse, and was ascribed to the fact that benzyl radicals produced by the photodissociation of solute molecules absorbed the excitation photons and converted them into heat through "a cyclic multiphotonic absorption process." Furthermore, morphological aspects observed in nanosecond photography exhibited appreciable differences by varying the solute concentrations. These results clearly mean a concentration-dependent ablation mechanism; the ablation mechanism of the benzene derivative solutions switches from photochemical to photothermal as the solute concentration decreases.

  3. Recovery of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) from Ralstonia eutropha cultures with non-halogenated solvents.

    PubMed

    Riedel, Sebastian L; Brigham, Christopher J; Budde, Charles F; Bader, Johannes; Rha, Chokyun; Stahl, Ulf; Sinskey, Anthony J

    2013-02-01

    Reduced downstream costs, together with high purity recovery of polyhydroxyalkanoate (PHA), will accelerate the commercialization of high quality PHA-based products. In this work, a process was designed for effective recovery of the copolymer poly(hydroxybutyrate-co-hydroxyhexanoate) (P(HB-co-HHx)) containing high levels of HHx (>15?mol%) from Ralstonia eutropha biomass using non-halogenated solvents. Several non-halogenated solvents (methyl isobutyl ketone, methyl ethyl ketone, and butyl acetate and ethyl acetate) were found to effectively dissolve the polymer. Isoamyl alcohol was found to be not suitable for extraction of polymer. All PHA extractions were performed from both dry and wet cells at volumes ranging from 2?mL to 3?L using a PHA to solvent ratio of 2% (w/v). Ethyl acetate showed both high recovery levels and high product purities (up to 99%) when using dry cells as starting material. Recovery from wet cells, however, eliminates a biomass drying step during the downstream process, potentially saving time and cost. When wet cells were used, methyl isobutyl ketone (MIBK) was shown to be the most favorable solvent for PHA recovery. Purities of up to 99% and total recovery yields of up to 84% from wet cells were reached. During polymer recovery with either MIBK or butyl acetate, fractionation of the extracted PHA occurred, based on the HHx content of the polymer. PHA with higher HHx content (17-30?mol%) remained completely in solution, while polymer with a lower HHx content (11-16?mol%) formed a gel-like phase. All PHA in solution could be precipitated by addition of threefold volumes of n-hexane or n-heptane to unfiltered PHA solutions. Effective recycling of the solvents in this system is predicted due to the large differences in the boiling points between solvent and precipitant. Our findings show that two non-halogenated solvents are good candidates to replace halogenated solvents like chloroform for recovery of high quality PHA. PMID:22903730

  4. Selective hydroxylation of alkanes by an extracellular fungal peroxygenase.

    PubMed

    Peter, Sebastian; Kinne, Matthias; Wang, Xiaoshi; Ullrich, Ren; Kayser, Gernot; Groves, John T; Hofrichter, Martin

    2011-10-01

    Fungal peroxygenases are novel extracellular heme-thiolate biocatalysts that are capable of catalyzing the selective monooxygenation of diverse organic compounds, using only H(2)O(2) as a cosubstrate. Little is known about the physiological role or the catalytic mechanism of these enzymes. We have found that the peroxygenase secreted by Agrocybe aegerita catalyzes the H(2)O(2)-dependent hydroxylation of linear alkanes at the 2-position and 3-position with high efficiency, as well as the regioselective monooxygenation of branched and cyclic alkanes. Experiments with n-heptane and n-octane showed that the hydroxylation proceeded with complete stereoselectivity for the (R)-enantiomer of the corresponding 3-alcohol. Investigations with a number of model substrates provided information about the route of alkane hydroxylation: (a) the hydroxylation of cyclohexane mediated by H(2)(18)(2) resulted in complete incorporation of (18)O into the hydroxyl group of the product cyclohexanol; (b) the hydroxylation of n-hexane-1,1,1,2,2,3,3-D(7) showed a large intramolecular deuterium isotope effect [(k(H)/k(D))(obs)] of 16.0 1.0 for 2-hexanol and 8.9 0.9 for 3-hexanol; and (c) the hydroxylation of the radical clock norcarane led to an estimated radical lifetime of 9.4 ps and an oxygen rebound rate of 1.06 10(11) s(-1). These results point to a hydrogen abstraction and oxygen rebound mechanism for alkane hydroxylation. The peroxygenase appeared to lack activity on long-chain alkanes (> C(16)) and highly branched alkanes (e.g. tetramethylpentane), but otherwise exhibited a broad substrate range. It may accordingly have a role in the bioconversion of natural and anthropogenic alkane-containing structures (including alkyl chains of complex biomaterials) in soils, plant litter, and wood. PMID:21812933

  5. Application of high-performance liquid chromatography with ultraviolet diode array detection and refractive index detection to the determination of class composition and to the analysis of gasoline.

    PubMed

    Kamiński, Marian; Kartanowicz, Rafał; Przyjazny, Andrzej

    2004-03-12

    A method of effective application of normal-phase high-performance liquid chromatography (NP-HPLC) with ultraviolet diode array detection (DAD) and refractive index detection (RID) for the determination of class composition of gasoline and its components, i.e. for the determination of content of alkenes, aromatic and saturated hydrocarbons in gasoline meeting modern quality standards, has been developed. An aminopropyl-bonded silica stationary phase was used along with n-hexane or n-heptane as the mobile phase. A DAD signal integrated over the 207-240 nm range was used to determine alkenes. This eliminates the necessity of separating alkenes from saturates, because the latter do not absorb UV radiation above 200 nm. The content of aromatic hydrocarbons is determined by means of a refractive index detector. Calibration was based on hydrocarbon type composition determined by the fluorescent indicator adsorption method, ASTM D1319. The results obtained by the developed method were found to be consistent with those obtained by fluorescent indicator adsorption or by a multidimensional GC method (PIONA) (ASTM D5443). The method can be applied to gasoline meeting recent quality standards, irrespective of refining technology used in the production of gasoline components, including gasoline with various contents of oxygenates. The developed method cannot be used to determine the hydrocarbon type composition of gasoline that contains as a component the so-called pyrocondensate, i.e. the fraction with a boiling point up to 220 degrees C, obtained through thermal pyrolysis of distillation residues of crude oil or coal and, consequently, does not meet the quality standards. The paper includes the procedure for identification of this type of gasoline. PMID:15032352

  6. Determination of thermodynamic properties of isotactic poly(1-butene) at infinite dilution using density and inverse gas chromatography.

    PubMed

    Koz?owska, Marta Karolina; Doma?ska, Urszula; Lempert, Ma?gorzata; Rogalski, Marek

    2005-03-18

    The partial molar volumes, V1(M), and the molar volume of isotactic crystalline low-molecular-weight poly(1-butene), iPBu-1, V1, have been calculated from the measured density of {iPBu-1 + solvent (n-hexane, n-heptane, n-nonane, n-decane, p-xylene, cyclohexane and chloroform)} systems. Some of the thermodynamic quantities were also obtained for the iPBu-1 with eight hydrocarbons (n-octane, n-decane, n-undecane, n-dodecane, n-tridecane, o-xylene, m-xylene, p-xylene) by the method of inverse gas chromatography at various temperatures. The weight fraction activity coefficients of the solvent at infinite dilution, omega2(infinity) and the Flory-Huggins thermodynamic interaction parameters, chi21(infinity), between polymer and solvents were determined. The partial molar free energy, deltaG2(infinity), the partial molar heat of mixing, deltaH2(infinity), at infinite dilution and the polymer solubility parameter, delta1, were calculated. Additionally, the (solid + liquid) binary mixtures equilibria, SLE, of iPBu-1 with three hydrocarbons (n-octane, n-decane and m-xylene) were studied by a dynamic method. By performing these experiments over a large concentration range, the T-x phase diagrams of the polymer-solvent systems were constructed. The excess Gibbs energy models were used to describe the nonideal behaviour of the liquid phase. The omega2(infinity) were determined from the solubility measurements and were predicted by using the UNIFAC FV model. PMID:15830936

  7. 21 CFR 175.350 - Vinyl acetate/crotonic acid copolymer.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... polyolefin films intended for packaging food, subject to the provisions of this section. (a) The copolymer... chloroform-soluble portion of the water extractives of the coated film obtained with distilled water at 120...-soluble portion of the n-heptane extractives of the coated film obtained with n-heptane at 70 F for...

  8. 21 CFR 177.1950 - Vinyl chloride-ethylene copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... (deionized), freshly distilled water. (ii) n-Heptane. Reagent grade, freshly distilled n-heptane shall be...) of this section. (a) A slurry of Amberlite IRA-400, or equivalent, is made with distilled water in a... 200 milliliters of water. The column is washed with distilled water until the effluent is neutral...

  9. 21 CFR 177.1980 - Vinyl chloride-propylene copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... (deionized), freshly distilled water. (ii) n-Heptane. Reagent grade, freshly distilled n-heptane shall be... in water, rinsed with distilled water, and placed in a 400-milliliter beaker. The bomb cover is... distilled water and a watch glass and heated until the melt has dissolved. The bomb is removed,...

  10. 21 CFR 177.1980 - Vinyl chloride-propylene copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... distilled water. (ii) n-Heptane. Reagent grade, freshly distilled n-heptane shall be used. (2) Determination... minute after the water at the top has evaporated. The bomb is quenched in water, rinsed with distilled... in the same 400-milliliter beaker. The bomb is covered with distilled water and a watch glass...

  11. 21 CFR 177.1980 - Vinyl chloride-propylene copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... (deionized), freshly distilled water. (ii) n-Heptane. Reagent grade, freshly distilled n-heptane shall be... in water, rinsed with distilled water, and placed in a 400-milliliter beaker. The bomb cover is... distilled water and a watch glass and heated until the melt has dissolved. The bomb is removed,...

  12. Effects of biomass burning on summertime nonmethane hydrocarbon concentrations in the Canadian wetlands

    NASA Technical Reports Server (NTRS)

    Blake, D. R.; Smith, T. W., Jr.; Chen, T.-Y.; Whipple, W. J.; Rowland, F. S.

    1994-01-01

    Approximately 900 whole air samples were collected and assayed for selected C2-C10 hydrocarbons and seven halocarbons during the 5-week Arctic Boundary Layer Expedition (ABLE) 3B conducted in eastern Canadian wetland areas. In more than half of the 46 vertical profiles flown, enhanced nonmethane hydrocarbon (NMHC) concentrations attributable to plumes from Canadian forest fires were observed. Urban plumes, also enhanced in many NMHCs, were separately identified by their high correlation with elevated levels of perchloroethene. Emission factors relative to ethane were determined for 21 hydrocarbons released from Canadian biomass burning. Using these data for ethane, ethyne, propane, n-butane, and carbon monoxide enhancements from the literature, global emissions of these four NMHCs were estimated. Because of its very short atmospheric lifetime and its below detection limit background mixing ratio, 1,3-butadiene is an excellent indicator of recent combustion. No statistically significant emissions of nitrous oxide, isoprene, or CFC 12 were observed in the biomass-burning plumes encountered during ABLE 3B. The presence of the short-lived biogenically emitted isoprene at altitudes as high as 3000 m implies that mixing within the planetary boundary layer (PBL) was rapid. Although background levels of the longer-lived NMHCs in this Canadian region increase during the fire season, isoprene still dominated local hydroxyl radical photochemistry within the PBL except in the immediate vicinity of active fires. The average biomass-burning emission ratios for hydrocarbons from an active fire sampled within minutes of combustion were, relative to ethane, ethene, 2.45; ethyne 0.57; propane, 0.25; propene, 0.73; propyne, 0.06; n-butane, 0.09; i-butane, 0.01; 1-butene, 0.14; cis-2-butene, 0.02; trans-2-butene, 0.03; i-butylene, 0.07; 1,3-butadiene, 0.12; n-pentane, 0.05; i-pentane, 0.03; 1-pentene, 0.06; n-hexane, 0.05; 1-hexene, 0.07; benzene, 0.37; toluene, 0.16.

  13. Enhancing chemical identification efficiency by SAW sensor transients through a data enrichment and information fusion strategya simulation study

    NASA Astrophysics Data System (ADS)

    Singh, Prashant; Yadava, R. D. S.

    2013-05-01

    The paper proposes a new approach for improving the odor recognition efficiency of a surface acoustic wave (SAW) transient sensor system based on a single polymer coating. The vapor identity information is hidden in transient response shapes through dependences on specific vapor solvation and diffusion parameters in the polymer coating. The variations in the vapor exposure and purge durations and the sensor operating frequency have been used to create diversity in transient shapes via termination of the vapor-polymer equilibration process up to different stages. The transient signals were analyzed by the discrete wavelet transform using Daubechies-4 mother wavelet basis. The wavelet approximation coefficients were then processed by principal component analysis for creating feature space. The set of principal components define the vapor identity information. In an attempt to enhance vapor class separability we analyze two types of information fusion methods. In one, the sensor operation frequency is fixed and the sensing and purge durations are varied, and in the second, the sensing and purge durations are fixed and the sensor operating frequency is varied. The fusion is achieved by concatenation of discrete wavelet coefficients corresponding to various transients prior to the principal component analysis. The simulation experiments with polyisobutylene SAW sensor coating for operation frequencies over [55-160] MHz and sensing durations over [5-60] s were analyzed. The target vapors are seven volatile organics: chloroform, chlorobenzene, o-dichlorobenzene, n-heptane, toluene, n-hexane and n-octane whose concentrations were varied over [10-100] ppm. The simulation data were generated using a SAW sensor transient response model that incorporates the viscoelastic effects due to polymer coating and an additive noise source in the output. The analysis reveals that: (i) in single transient analysis the class separability increases with sensing duration for a given frequency of operation, and also with frequency for a given sensing duration, and (ii) the information fusion based on both the multiple sensing cycles and the multiple sensing frequencies enhances the class separability by nearly an order of magnitude.

  14. Comprehensive 2-D chromatography of random and block methacrylate copolymers.

    PubMed

    van Hulst, Monique; van der Horst, Aschwin; Kok, Wim Th; Schoenmakers, Peter J

    2010-06-01

    A comprehensive 2-D separation method was developed for the characterization of methacrylate copolymers. In both dimensions conditions were employed that give a critical separation for the homopolymer of one of the monomers in the copolymer, and exclusion behaviour for the other. The 2-D separation was realized by using a normal-phase column in one dimension and a reversed phase column in the other, and by precisely tuning the compositions of the two mobile phases employed. In the normal-phase dimension mixtures of THF and n-hexane or n-heptane were used as mobile phase, and in the reversed-phase dimension mixtures of ACN and THF. Moreover, stationary phase particles had to be selected for both columns that gave an exclusion window appropriate for the molecular size of the sample polymers to be characterized. The 2-D critical chromatography principle was tested with a polystyrene (PS)-polymethylmethacrylate (PMMA) block copolymer and with block and random polybutylmethacrylate (PBMA)-PMMA copolymers. Ideally, the retention time for a copolymer in both dimensions of this system would depend on the size of only one of the blocks, or on the contribution of only one of the monomers to the size of a random copolymer. However, it was found that the elution of the PS-PMMA block copolymer depended on the size of both blocks, even when the corresponding homopolymer of one of the monomers showed critical elution behaviour. Therefore, the method could not be calibrated for block sizes by using homopolymer standards alone. Still, it was shown that the method can be used to determine differences between samples (PS-PMMA and PBMA-PMMA) with respect to total molecular size or block sizes separately, or to average size and chemical composition for random copolymers. Block and random PBMA-PMMA copolymers showed a distinctly different pattern in the 2-D plots obtained with 2-D critical chromatography. This difference was shown to be related to the different procedures followed in the polymerization process, and the different molecular distributions resulting from these. PMID:20309901

  15. Immiscible Systems

    ERIC Educational Resources Information Center

    Eckelmann, Jens; Luning, Ulrich

    2013-01-01

    layers of liquids. The setup of both demonstrations is such that one homogeneous layer in a multiphasic mixture separates into two new layers upon shaking. The solvents used are methanol, toluene, petroleum ether or "n"-pentane, silicone oil, perfluoroheptanes,

  16. C-H\\ctdot O hydrogen bonding in a 4-fluorobenzoate multilayer induced by silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Perry, Donald A.; Schiefer, Elizabeth M.; Cordova, James S.; Bonde, Ashley M.; Razer, Taylor M.; Primm, Katherine M.; Chen, Tsung Yen; Biris, Alexandru S.

    2011-08-01

    SERS, SEIRA, and DFT calculations showed silver nanoparticles can stimulate C-H⋯O hydrogen bonding in 4-fluorobenzoate ion/ n-heptane multilayers. SERS/DFT demonstrated that 4-fluorobenzoic acid (4FBA) adsorbed as a 4-fluorobenzoate (4FBT) monolayer on nanosilver. Ionization of 4FBA to 4FBT occurred in the multilayer when 4FBA was deposited in n-heptane onto nanosilver. Frequency shifts in SEIRA bands of 4FBT COO stretch and n-heptane CH bend modes illustrated a change in the degree of C-H⋯O hydrogen bonding as more 4FBT/ n-heptane was adsorbed to the multilayer. This work will influence many research areas such as sensors formed from thin organic layers on metal nanoparticles.

  17. 21 CFR 177.1655 - Polysulfone resins.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... extracted at reflux temperatures for 6 hours with the solvents—distilled water, 50 percent (by volume) ethyl alcohol in distilled water, 3 percent acetic acid in distilled water, and n-heptane, yield...

  18. 21 CFR 177.2415 - Poly(aryletherketone) resins.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... milligrams per square inch of food contact surface: Distilled water, 50 percent (by volume) ethanol in distilled water, 3 percent acetic acid in distilled water, and n-heptane. In testing the final food...

  19. 21 CFR 177.1655 - Polysulfone resins.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... with the solvents—distilled water, 50 percent (by volume) ethyl alcohol in distilled water, 3 percent acetic acid in distilled water, and n-heptane, yield total extractives in each extracting solvent not...

  20. 21 CFR 177.2440 - Polyethersulfone resins.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... food-contact surface: distilled water, 50 percent (by volume) ethyl alcohol in distilled water, 3 percent acetic acid in distilled water, and n-heptane. (Note: In testing the finished food-contact...

  1. 21 CFR 177.1556 - Polyaryletherketone resins.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... temperature for 2 hours with the following solvents: Distilled water, 50 percent (by volume) ethyl alcohol in distilled water, 3 percent acetic acid (by weight) in distilled water, and n-heptane. (d) In testing...

  2. 21 CFR 177.2415 - Poly(aryletherketone) resins.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... milligrams per square inch of food contact surface: Distilled water, 50 percent (by volume) ethanol in distilled water, 3 percent acetic acid in distilled water, and n-heptane. In testing the final food...

  3. 21 CFR 177.1030 - Acrylonitrile/butadiene/styrene/methyl methacrylate copolymer.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... article when exposed to distilled water, 3 percent acetic acid, 50 percent ethanol, and n-heptane for 10... square inch of acrylonitrile monomer when exposed to distilled water, 3 percent acetic acid and...

  4. 21 CFR 177.1550 - Perfluorocarbon resins.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... shall be extracted at reflux temperatures for 2 hours separately with distilled water, 50 percent... reflux temperatures for 2 hours separately with distilled water, 8 percent ethanol, and n-heptane:...

  5. 21 CFR 177.1655 - Polysulfone resins.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... extracted at reflux temperatures for 6 hours with the solvents—distilled water, 50 percent (by volume) ethyl alcohol in distilled water, 3 percent acetic acid in distilled water, and n-heptane, yield...

  6. 40 CFR Appendix: Table 1 to... - List of Hazardous Air Pollutants (HAP) for Subpart HHH

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Acetaldehyde 71432 Benzene (includes benzene in gasoline) 75150 Carbon disulfide 463581 Carbonyl sulfide 100414 Ethyl benzene 107211 Ethylene glycol 75050 Acetaldehyde 50000 Formaldehyde 110543 n-Hexane...

  7. Research on Volatile Organic Compounds in the Mexico City Metropolitan Area (MCMA) in two campaigns collected in the Winter-2011 and Spring-2012

    NASA Astrophysics Data System (ADS)

    Magaa, M.; Gonzlez-Vargas, S.; Blanco, S.; Watanabe, T.; Maeda, T.; Cardenas, B.

    2013-05-01

    Because of the importance of information on the concentration and speciation of Volatile Organic Compounds (VOC) in the atmosphere for the development of regulatory programs or emission control, is necessary to determine the type and the concentrations of reactive and toxic VOC in atmospheric air. The aim of this study is to determine the speciation and quantification of VOC in the atmospheric air of the Mexico City Metropolitan Area (MCMA), from samples obtained in November-December 2011 (cold-dry) and March-April (warm-dry). This study presents the results of characterization of VOC in ambient air in the MCMA conducted during 2011-2012. Sampling of VOC was done in two sampling campaigns: from November 17th to December 11th, 2011, and March 1st to April 6th, 2012 through collection of ambient air each six days in six liters stainless steel SUMMA canisters of 24 hours integrated samples, in three sites (Merced: commercial area with vehicular sources, Pedregal: residential area with vehicular sources and San Agustin: industrial sources with heavy traffic), in the MCMA. The analysis of samples was carried out with two chromatographic systems: 1) method equivalent to the EPA's Method TO-14, and 2) GC/MSD coupled to a preconcentrator ENTECH, for the analysis of the compounds listed in EPA method TO15. It was investigated the concentration of 111 volatile organic compounds, (ozone precursors and toxic compounds). It was found that concentrations of 23 species, constitute 80% of the total VOC concentration tested: ethane, propane, isobutane, n-butane, n-pentane, n-hexane, isopentane, methylcyclopentane, ethylene, propylene, acetylene, benzene, toluene, ethylbenzene, m/p-xylene, o-xylene, 1,2,4-trimethylbenzene, ethyl and isopropyl alcohols, acetone, 2-butanone, MTBE and ethyl acetate. Both in 2011 and 2012, the highest concentrations measured in the three sites were for compounds associated with the combustion of LPG gas: propane, n-butane. The highest concentrations of 25.214.5 ppbV and 16.69 ppbV for butane and propane respectively, was achieved in Merced in 2011 and 14.73.5 ppbV and 28.46.7 ppbV for the same compounds, in San Agustin in 2012). In the case of vehicular emissions, in both campaigns, 2011 and 2012, Merced showed the highest levels: 12.34.8 ppbV, 2.71.1 ppbV and 4.33.3 ppbV for toluene, benzene and MTBE respectively in 2011 and 9.486.5 ppbV, 1.50.9 ppbV and 2.41.0 ppbV for the same compounds in 2012. The compounds which comes from industrial emissions, have the lowest average concentrations in all stations. The VOCs measurement in atmospheric air, allowed determinate that the main source of VOC in the three studied sites of the MCMA are emissions of LPG gas and vehicular emissions. The highest concentrations were found during the cold-dry period in 2011. These data are consistent with continuous measurements determined in the southeastern MCMA during 2000-2007.

  8. Effect of film thickness and viscoelasticity on separability of vapour classes by wavelet and principal component analyses of polymer-coated surface acoustic wave sensor transients

    NASA Astrophysics Data System (ADS)

    Singh, Prashant; Yadava, R. D. S.

    2011-02-01

    The transient response of a polymer-coated surface acoustic wave (SAW) vapour sensor depends on partitioning and diffusion of vapour species into the polymer in conjunction with its thickness and viscoelastic properties. The shapes of transient signals carry information about vapour identities due to specificity of the partition coefficient and the diffusion coefficient. The analysis of transient signals therefore offers a simpler approach for vapour identification in comparison to conventional electronic nose systems that employ a broadly selective sensor array. The transient response-based methods are however not developed to a similar level of maturity as their sensor array counterparts. The main reason for this is associated with complex signal generation kinetics and polymer viscoelasticity. The latter is independent of vapour identities (assuming low concentrations) but influences sensor response through nonlinear dependences on polymer thickness and viscoelastic coefficients. In this paper, we endeavour to find out whether viscoelasticity and its manifestation through thickness dependences could be turned into an advantage for transient-based vapour identification. Using an established SAW sensor model with additive noise we analyse sensor transients by wavelet decomposition and principal component analysis (PCA) for various combinations of polymer thickness, viscoelastic storage and loss moduli and noise level. We calculate vapour class separability measures defined on the basis of scatter matrices of principal components of wavelet coefficients to determine the discrimination ability of sensor transients for various combinations of film thickness and viscoelastic parameters. The simulation experiments are performed by considering a polyisobutylene-coated SAW oscillator sensor under exposure to seven volatile organic compounds (chloroform, chlorobenzene, o-dichlorobenzene, n-heptane, toluene, n-hexane and n-octane). The film thicknesses are varied from thin film (where mass loading dominates) to thick film through fundamental film resonance (where viscoelastic effects dominate) to very thick film regions spanning over a few higher order resonances. The storage and loss shear moduli are varied to simulate conditions of glassy, glassy-rubbery and rubbery phases of polymer. The transient response generation incorporates an additive noise source with uniform distribution over a specified range. Effect of noise variation on class separability is also studied. A comparison of the wavelet transform method is made with the phase space-based partial-least-squares regression method for feature extraction. In conclusion, it is found that (i) vapour class separability increases with polymer thickness for all viscoelastic conditions from glassy to rubbery, except near film resonances, (ii) near resonance class separability dramatically declines for films with no or low loss, (iii) by imparting finite viscoelastic losses to polymer coatings, not only are the detrimental effects of film resonance eliminated but also the sensor performance improves, and (iv) viscoelastic effects produce better noise immunity in thick film sensors. This analysis provides a new perspective for designing high-performance transient sensors through optimization of film thickness for specific polymer selections.

  9. Solvent effect in ?-phosphorylated nitroxides. Part 4: detection of traces of water by electron paramagnetic resonance.

    PubMed

    Audran, Grard; Bosco, Lionel; Brmond, Paul; Butscher, Teddy; Marque, Sylvain R A

    2016-01-28

    For decades, the nitrogene hyperfine coupling constant aN of nitroxides has been applied to probe their environment using EPR. However, the small changes observed (?2 G from n-pentane to water) with the solvent polarity allow only a qualitative discussion. A stable ?-phosphorylated nitroxide exhibiting a small change in aN (?3 G from n-pentane to water) and a striking change (?25 G from n-pentane to water) in phosphorus hyperfine coupling constant aP with the polarity of solvent was prepared and used to develop the first procedure for the titration of water in THF by EPR, down to 0.1% v/v. PMID:26647997

  10. Electron transport in Paracoccus halodenitrificans and the role of Ubiquinone

    NASA Technical Reports Server (NTRS)

    Hochstein, L. I.; Cronin, S. E.

    1984-01-01

    The membrane-bound NADH oxidase of Paracoccus halodenitrificans was inhibited by dicoumarol, 2-n-heptyl-4-hydroxyquinoline-N-oxide (HQNO), and exposure to ultraviolet light (at 366 nm). When the membranes were extracted with n-pentane, NADH oxidase activity was lost. Partial restoration was achieved by adding the ubiquinone fraction extracted from the membranes. Succinate oxidation was not inhibited by dicoumarol or HQNO but was affected by ultraviolet irradiation or n-pentane extraction. However, the addition of the ubiquinone fraction to the n-pentane-extracted membranes did not restore enzyme activity. These observations suggested the reducing equivalents from succinate entered the respiratory chain on the oxygen side of the HQNO-sensitive site and probably did not proceed through a quinone.

  11. Electron Transport in Paracoccus Halodenitrificans and the Role of Ubiquinone

    NASA Technical Reports Server (NTRS)

    Hochstein, L. I.; Cronin, S. E.

    1983-01-01

    The membrane-bound NADH oxidase of Paracoccus halodenitrificans was inhibited by dicoumarol, 2-n-heptyl-4-hydroxyquinoline-N-oxide (HQNO), and exposure to ultraviolet light (at 366 nm). When the membranes were extracted with n-pentane, NADH oxidase activity was lost. Partial restoration was achieved by adding the ubiquinone fraction extracted from the membranes. Succinate oxidation was not inhibited by dicoumarol or HQNO but was affected by ultraviolet irradiation or n-pentane extraction. However, the addition of the ubiquinone fraction to the n-pentane-extracted membranes did not restore enzyme activity. These observations suggested the reducing equivalents from succinate entered the respiratory chain on the oxygen side of the HQNO-sensitive site and probably did not proceed through a quinone.

  12. Low severity upgrading of F-T waxes with solid superacids. Quarterly report, March 1, 1993--May 31, 1993

    SciTech Connect

    Tierney, J.W.; Wender, I.

    1993-09-01

    The upgrading of Fischer-Tropsch waxes with solid superacids continued this quarter, the isomerization and hydrocracking of n-pentane were examined by in situ FT-IR. It was found that the intensity of protonic acid sites was weakened as n-pentane was introduced into the IR cell, indicating that protonic acid sites tend to donate a proton to n-paraffins. There was no evidence of olefinic intermediates. It is likely that, as we previously proposed, isomerization and hydrocracking over Pt/ZrO{sub 2}/SO{sub 4} catalyst proceed through initial protonation of n-alkanes to form carbonium ions which are then isomerized and hydrocracked.

  13. Understanding nanofluid stability through molecular simulation

    SciTech Connect

    Dang, Liem X.; Annapureddy, Harsha V.; Sun, Xiuquan; Thallapally, Praveen K.; McGrail, B. Peter

    2012-11-01

    We performed molecular dynamics simulations to study solvation of a nanoparticle and nanoparticle-nanoparticle interactions in an n-hexane solution. Structural signatures are barely observed between the nanoparticle and n-hexane molecules because of weak binding and steric effects. The dynamic properties of the n-hexane molecule, on the other hand, are significantly influenced by the solvated nanoparticle. The diffusion of n-hexane molecules inside the nanoparticle is significantly decreased mainly because of the loss of dimensions of translation. Because one translational degree of freedom is lost by colliding with the wall of nanoparticle, the n-hexane molecules outside the nanoparticle diffuse 30% slower than the molecules in pure solution. The computed free energy profiles illustrate that the arrangement of the nanoparticles in bulk n-hexane solution are dependent on the orientation and functional group. We found that the n-hexane solvent exerts some effects on the interactions between the solvated nanoparticles. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences and by the Office of Energy Efficiency and Renewable Energy, Geothermal Technologies Program. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  14. Thermal Ignition

    NASA Astrophysics Data System (ADS)

    Boettcher, Philipp Andreas

    Accidental ignition of flammable gases is a critical safety concern in many industrial applications. Particularly in the aviation industry, the main areas of concern on an aircraft are the fuel tank and adjoining regions, where spilled fuel has a high likelihood of creating a flammable mixture. To this end, a fundamental understanding of the ignition phenomenon is necessary in order to develop more accurate test methods and standards as a means of designing safer air vehicles. The focus of this work is thermal ignition, particularly auto-ignition with emphasis on the effect of heating rate, hot surface ignition and flame propagation, and puffing flames. Combustion of hydrocarbon fuels is traditionally separated into slow reaction, cool flame, and ignition regimes based on pressure and temperature. Standard tests, such as the ASTM E659, are used to determine the lowest temperature required to ignite a specific fuel mixed with air at atmospheric pressure. It is expected that the initial pressure and the rate at which the mixture is heated also influences the limiting temperature and the type of combustion. This study investigates the effect of heating rate, between 4 and 15 K/min, and initial pressure, in the range of 25 to 100 kPa, on ignition of n-hexane air mixtures. Mixtures with equivalence ratio ranging from 0.6 to 1.2 were investigated. The problem is also modeled computationally using an extension of Semenov's classical auto-ignition theory with a detailed chemical mechanism. Experiments and simulations both show that in the same reactor either a slow reaction or an ignition event can take place depending on the heating rate. Analysis of the detailed chemistry demonstrates that a mixture which approaches the ignition region slowly undergoes a significant modification of its composition. This change in composition induces a progressive shift of the explosion limit until the mixture is no longer flammable. A mixture that approaches the ignition region sufficiently rapidly undergoes only a moderate amount of thermal decomposition and explodes quite violently. This behavior can also be captured and analyzed using a one-step reaction model, where the heat release is in competition with the depletion of reactants. Hot surface ignition is examined using a glow plug or heated nickel element in a series of premixed n-hexane air mixtures. High-speed schlieren photography, a thermocouple, and a fast response pressure transducer are used to record flame characteristics such as ignition temperature, flame speed, pressure rises, and combustion mode. The ignition event is captured by considering the dominant balance of diffusion and chemical reaction that occurs near a hot surface. Experiments and models show a dependence of ignition temperature on mixture composition, initial pressure, and hot surface size. The mixtures exhibit the known lower flammability limit where the maximum temperature of the hot surface was insufficient at igniting the mixture. Away from the lower flammability limit, the ignition temperature drops to an almost constant value over a wide range of equivalence ratios (0.7 to 2.8) with large variations as the upper flammability limit is approached. Variations in the initial pressure and equivalence ratio also give rise to different modes of combustion: single flame, re-ignition, and puffing flames. These results are successfully compared to computational results obtained using a flamelet model and a detailed chemical mechanism for n-heptane. These different regimes can be delineated by considering the competition between inertia, i.e., flame propagation, and buoyancy, which can be expressed in the Richardson number. In experiments of hot surface ignition and subsequent flame propagation a 10 Hz puffing flame instability is visible in mixtures that are stagnant and premixed prior to the ignition sequence. By varying the size of the hot surface, power input, and combustion vessel volume, we determined that the instability is a function of the interaction of the flame with the fluid flow induced by the combustio

  15. Modeling the Auto-Ignition of Biodiesel Blends with a Multi-Step Model

    SciTech Connect

    Toulson, Dr. Elisa; Allen, Casey M; Miller, Dennis J; McFarlane, Joanna; Schock, Harold; Lee, Tonghun

    2011-01-01

    There is growing interest in using biodiesel in place of or in blends with petrodiesel in diesel engines; however, biodiesel oxidation chemistry is complicated to directly model and existing surrogate kinetic models are very large, making them computationally expensive. The present study describes a method for predicting the ignition behavior of blends of n-heptane and methyl butanoate, fuels whose blends have been used in the past as a surrogate for biodiesel. The autoignition is predicted using a multistep (8-step) model in order to reduce computational time and make this a viable tool for implementation into engine simulation codes. A detailed reaction mechanism for n-heptane-methyl butanoate blends was used as a basis for validating the multistep model results. The ignition delay trends predicted by the multistep model for the n-heptane-methyl butanoate blends matched well with that of the detailed CHEMKIN model for the majority of conditions tested.

  16. Droplet flame extinction in reactive environments

    SciTech Connect

    Gore, J.P.; Meng, W.H.; Jang, J.H.

    1989-01-01

    The structure and extinction of envelope flames around a porous sphere burning either methanol or n-heptane in a forced flow of air containing premixed methane, acetylene, or hydrogen is studied. Measurements of extinction velocities and flame temperatures are reported. The results indicate that the stability of the envelope flames is enhanced by fuel gases in the ambient. The largest increase in stretch rates at extinction is observed for acetylene/air mixtures, followed by hydrogen/air and methane/air mixtures. Effects of ambient fuel gases on flames with methanol are somewhat stronger than those with n-heptane. 27 references.

  17. Immiscible Systems

    ERIC Educational Resources Information Center

    Eckelmann, Jens; Luning, Ulrich

    2013-01-01

    layers of liquids. The setup of both demonstrations is such that one homogeneous layer in a multiphasic mixture separates into two new layers upon shaking. The solvents used are methanol, toluene, petroleum ether or "n"-pentane, silicone oil, perfluoroheptanes,…

  18. Conservative and dissipative force field for simulation of coarse-grained alkane molecules: A bottom-up approach

    SciTech Connect

    Trément, Sébastien; Rousseau, Bernard; Schnell, Benoît; Petitjean, Laurent; Couty, Marc

    2014-04-07

    We apply operational procedures available in the literature to the construction of coarse-grained conservative and friction forces for use in dissipative particle dynamics (DPD) simulations. The full procedure rely on a bottom-up approach: large molecular dynamics trajectories of n-pentane and n-decane modeled with an anisotropic united atom model serve as input for the force field generation. As a consequence, the coarse-grained model is expected to reproduce at least semi-quantitatively structural and dynamical properties of the underlying atomistic model. Two different coarse-graining levels are studied, corresponding to five and ten carbon atoms per DPD bead. The influence of the coarse-graining level on the generated force fields contributions, namely, the conservative and the friction part, is discussed. It is shown that the coarse-grained model of n-pentane correctly reproduces self-diffusion and viscosity coefficients of real n-pentane, while the fully coarse-grained model for n-decane at ambient temperature over-predicts diffusion by a factor of 2. However, when the n-pentane coarse-grained model is used as a building block for larger molecule (e.g., n-decane as a two blobs model), a much better agreement with experimental data is obtained, suggesting that the force field constructed is transferable to large macro-molecular systems.

  19. Conservative and dissipative force field for simulation of coarse-grained alkane molecules: A bottom-up approach

    NASA Astrophysics Data System (ADS)

    Trément, Sébastien; Schnell, Benoît.; Petitjean, Laurent; Couty, Marc; Rousseau, Bernard

    2014-04-01

    We apply operational procedures available in the literature to the construction of coarse-grained conservative and friction forces for use in dissipative particle dynamics (DPD) simulations. The full procedure rely on a bottom-up approach: large molecular dynamics trajectories of n-pentane and n-decane modeled with an anisotropic united atom model serve as input for the force field generation. As a consequence, the coarse-grained model is expected to reproduce at least semi-quantitatively structural and dynamical properties of the underlying atomistic model. Two different coarse-graining levels are studied, corresponding to five and ten carbon atoms per DPD bead. The influence of the coarse-graining level on the generated force fields contributions, namely, the conservative and the friction part, is discussed. It is shown that the coarse-grained model of n-pentane correctly reproduces self-diffusion and viscosity coefficients of real n-pentane, while the fully coarse-grained model for n-decane at ambient temperature over-predicts diffusion by a factor of 2. However, when the n-pentane coarse-grained model is used as a building block for larger molecule (e.g., n-decane as a two blobs model), a much better agreement with experimental data is obtained, suggesting that the force field constructed is transferable to large macro-molecular systems.

  20. A predictive method for volatile organic compounds emission from soil: Evaporation and diffusion behavior investigation of a representative component of crude oil.

    PubMed

    Wang, Haijing; Fischer, Thomas; Wieprecht, Wolfgang; Möller, Detlev

    2015-10-15

    Pipelines are convenient, economical and widely used mode of transportation of crude oil. However, the inevitable or otherwise accidents during such transport of crude oil lead to large scale oil spills, which consequently result in both soil and air pollution. When such pollution occurs, crude oil VOC concentrations in air, soil pollution evaluation and VOC propagation in soil provide important evidence for airborne detection of oils spills. Therefore, several issues, including determination method for VOC, isotherm parameters of VOC sorption on soil surfaces, and VOC diffusion flux simulation, are significant. In our previous study, n-butane and n-pentane were proved to be the maximum VOCs in studied crude oils. Therefore, a predictive method using n-pentane as a representative component is proposed in this paper. Firstly, a headspace solid phase microextraction (SPME) method was developed for determination of n-pentane in non-equilibrium mass transfer conditions. Secondly, Brunauer-Emmett-Teller (BET) analysis with liquid nitrogen was carried out to predict isotherm parameters for n-pentane. Finally, two models were used to predict the emission process. Probably influenced by gas vapor density below and above the soil layer, the experimental data amounted to 74% of the deduced value from the simplified analytical model. However, the free diffusion model fitted well with the experimental results. PMID:26026407

  1. Method for removing sulfur compounds from C/sub 6/ and lower alkanes

    SciTech Connect

    Keyworth, D.A.

    1989-03-28

    A process is described for recovering a low sulfur content hydrocarbon fraction having a boiling point of n-hexane or less from a hydrocarbon stream containing hydrocarbons boiling at or below the boiling point of hexane and organic sulfur compounds comprising monosulfides boiling at or below the boiling point of n-hexane. It consists of contacting the hydrocarbon stream with a dilute aqueous solution of sodium hypochlorite for a time sufficient to convert a selected amount of monosulfide compounds present to compounds having boiling points above the boiling point of n-hexane, separating an aqueous phase and a hydrocarbon phase and fractionally distilling the hydrocarbon phase to recover a hydrocarbon fraction having a boiling point of n-hexane or less, and having a reduced amount of the organic sulfur compounds.

  2. 40 CFR 420.131 - Specialized definitions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... AND STANDARDS IRON AND STEEL MANUFACTURING POINT SOURCE CATEGORY Other Operations Subcategory § 420... or cold process that agglomerates (presses together) iron-bearing materials into small lumps without... total recoverable oil & grease measured as n-hexane extractable materials....

  3. 40 CFR 420.131 - Specialized definitions.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... AND STANDARDS IRON AND STEEL MANUFACTURING POINT SOURCE CATEGORY Other Operations Subcategory § 420... or cold process that agglomerates (presses together) iron-bearing materials into small lumps without... total recoverable oil & grease measured as n-hexane extractable materials....

  4. Antioxidant activity of Vitex agnus-castus L. extracts.

    PubMed

    Sa?lam, Hsniye; Pabucuo?lu, Aysun; Kivak, Bijen

    2007-11-01

    The ethanol, n-hexane and water extracts of Vitex agnus-castus L. leaves and fruits were screened for antioxidant activity. The antioxidant activity of plant extracts was determined by an improved assay based on the decolorization of the radical monocation of 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS.+). The water and ethanol extracts showed stronger antioxidant activity than the n-hexane extracts. PMID:17600861

  5. Rate constants for the reaction of muonium with aromatic compounds

    NASA Astrophysics Data System (ADS)

    Louwrier, P. W. F.; Brinkman, G. A.; Roduner, E.

    1986-12-01

    Rate constants for the reaction of muonium with benzene in water, methanol and n-hexane and for the reaction of muonium with p-difluorobenzene, anilin, hexafluorobenzene and styrene are reported. All rate constants are below the calculated diffusion controlled limit. The activation energy for the reaction of muonium with benzene in n-hexane is very small, indicating the possibility of tunnelling by muonium.

  6. Toxic polyneuropathy due to glue sniffing

    PubMed Central

    Goto, Ikuo; Matsumura, Mutsuro; Inoue, Naohide; Murai, Yoshiyuki; Shida, Kenshiro; Santa, Tetsuji; Kuroiwa, Yoshigoro

    1974-01-01

    Four cases of toxic polyneuropathy due to glue-sniffing were reported. Neurological examination revealed motor predominant mixed type polyneuropathy. The cause of polyneuropathies in these cases was considered to be due to the inhalation of the vaporized elements of the adhesive agent, which contain mainly n-hexane and toluene. N-hexane is considered to be chiefly responsible for the polyneuropathy, though toluene also could have some influence on the illness. Images PMID:4369386

  7. Developing hexanal as an odor reference standard for sensory analysis of drinking water.

    PubMed

    Omr-Ozbek, Pinar; Dietrich, Andrea M

    2008-05-01

    There are many analytical and sensory methods to analyze drinking water for flavor and off-flavors before it reaches consumers. Flavor profile analysis (FPA) is one of the most comprehensive methods. A well-trained panel is essential for FPA and although taste standards are well established, FPA training lacks an odor reference standard. In search of an odor reference standard, four different panel groups were trained and tested for n-hexanal at various concentrations (1-1000 microg/L) over 14 months. The Weber-Fechner plots for n-hexanal showed a linear and overlapping relationship for all panels. Analytical measurements demonstrated that the headspace concentration of n-hexanal was constant after 5 sniffs at 45 degrees C and it remained constant during FPA sessions for up to 4 h. The panelists liked the grassy odor of n-hexanal, which did not result in fatigue, and testing demonstrated that approximately 95% of the population can detect n-hexanal's odor. n-Hexanal is proposed as an odor reference standard for FPA training to define odor intensities because it is chemically stable, follows Weber-Fechner law, mimics grassy odors found in drinking water, and was acceptable to the human panelists. PMID:18280533

  8. Continuous and Batch Distillation in an Oldershaw Tray Column

    ERIC Educational Resources Information Center

    Silva, Carlos M.; Vaz, Raquel V.; Santiago, Ana S.; Lito, Patricia F.

    2011-01-01

    The importance of distillation in the separation field prompts the inclusion of distillation experiments in the chemical engineering curricula. This work describes the performance of an Oldershaw column in the rectification of a cyclohexane/n-heptane mixture. Total reflux distillation, continuous rectification under partial reflux, and batch…

  9. Using Nuclear Magnetic Resonance Spectroscopy for Measuring Ternary Phase Diagrams

    ERIC Educational Resources Information Center

    Woodworth, Jennifer K.; Terrance, Jacob C.; Hoffmann, Markus M.

    2006-01-01

    A laboratory experiment is presented for the upper-level undergraduate physical chemistry curriculum in which the ternary phase diagram of water, 1-propanol and n-heptane is measured using proton nuclear magnetic resonance (NMR) spectroscopy. The experiment builds upon basic concepts of NMR spectral analysis, typically taught in the undergraduate

  10. Continuous and Batch Distillation in an Oldershaw Tray Column

    ERIC Educational Resources Information Center

    Silva, Carlos M.; Vaz, Raquel V.; Santiago, Ana S.; Lito, Patricia F.

    2011-01-01

    The importance of distillation in the separation field prompts the inclusion of distillation experiments in the chemical engineering curricula. This work describes the performance of an Oldershaw column in the rectification of a cyclohexane/n-heptane mixture. Total reflux distillation, continuous rectification under partial reflux, and batch

  11. LOW OZONE-DEPLETING HALOCARBONS AS TOTAL-FLOOD AGENTS: VOLUME 2. LABORATORY-SCALE FIRE SUPPRESSION AND EXPLOSION PREVENTION TESTING

    EPA Science Inventory

    The report gives results from (1) flame suppression testing of potential Halon-1301 (CF3Br) replacement chemicals in a laboratory cup burner using n-heptane fuel and (2) explosion prevention (inertion) testing in a small-scale explosion sphere using propane and methane as fuels. ...

  12. Using Nuclear Magnetic Resonance Spectroscopy for Measuring Ternary Phase Diagrams

    ERIC Educational Resources Information Center

    Woodworth, Jennifer K.; Terrance, Jacob C.; Hoffmann, Markus M.

    2006-01-01

    A laboratory experiment is presented for the upper-level undergraduate physical chemistry curriculum in which the ternary phase diagram of water, 1-propanol and n-heptane is measured using proton nuclear magnetic resonance (NMR) spectroscopy. The experiment builds upon basic concepts of NMR spectral analysis, typically taught in the undergraduate…

  13. 21 CFR 177.1556 - Polyaryletherketone resins.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...-contact surface, when extracted at reflux temperature for 2 hours with the following solvents: Distilled water, 50 percent (by volume) ethyl alcohol in distilled water, 3 percent acetic acid (by weight) in distilled water, and n-heptane. (d) In testing the finished food-contact article made of...

  14. 21 CFR 177.1030 - Acrylonitrile/butadiene/styrene/methyl methacrylate copolymer.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... per square inch surface area of the food-contact article when exposed to distilled water, 3 percent... to distilled water, 3 percent acetic acid and n-heptane at 190 °F for 2 hours, cooled to 120 °F...

  15. 21 CFR 177.1556 - Polyaryletherketone resins.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...-contact surface, when extracted at reflux temperature for 2 hours with the following solvents: Distilled water, 50 percent (by volume) ethyl alcohol in distilled water, 3 percent acetic acid (by weight) in distilled water, and n-heptane. (d) In testing the finished food-contact article made of...

  16. 21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... contact article is exposed to distilled water, 3 percent acetic acid, or n-heptane for 8 days at 120 °F... acrylonitrile monomer when exposed to distilled water and 3 percent acetic acid at 150 °F for 15 days...

  17. 21 CFR 177.1560 - Polyarylsulfone resins.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...: distilled water at 121 °C (250 °F), 50 percent (by volume) ethyl alcohol in distilled water at 71.1 °C (160 °F), 3 percent acetic acid in distilled water at 100 °C (212 °F), and n-heptane at 65.6 °C (150...

  18. 21 CFR 177.1030 - Acrylonitrile/butadiene/styrene/methyl methacrylate copolymer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... per square inch surface area of the food-contact article when exposed to distilled water, 3 percent... to distilled water, 3 percent acetic acid and n-heptane at 190 °F for 2 hours, cooled to 120 °F...

  19. 21 CFR 177.1970 - Vinyl chloride-lauryl vinyl ether copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... than 10 percent will pass through a U.S. Standard Sieve No. 200. (1) Reagents—(i) Water. All water used in these procedures shall be demineralized (deionized), freshly distilled water. (ii) n-Heptane...-percent when extracted with water at 150 °F for 2 hours. (ii) Total extractives do not exceed 0.60...

  20. HCCI experiments with toluene reference fuels modeled by a semidetailed chemical kinetic model

    SciTech Connect

    Andrae, J.C.G.; Brinck, T.; Kalghatgi, G.T.

    2008-12-15

    A semidetailed mechanism (137 species and 633 reactions) and new experiments in a homogeneous charge compression ignition (HCCI) engine on the autoignition of toluene reference fuels are presented. Skeletal mechanisms for isooctane and n-heptane were added to a detailed toluene submechanism. The model shows generally good agreement with ignition delay times measured in a shock tube and a rapid compression machine and is sensitive to changes in temperature, pressure, and mixture strength. The addition of reactions involving the formation and destruction of benzylperoxide radical was crucial to modeling toluene shock tube data. Laminar burning velocities for benzene and toluene were well predicted by the model after some revision of the high-temperature chemistry. Moreover, laminar burning velocities of a real gasoline at 353 and 500 K could be predicted by the model using a toluene reference fuel as a surrogate. The model also captures the experimentally observed differences in combustion phasing of toluene/n-heptane mixtures, compared to a primary reference fuel of the same research octane number, in HCCI engines as the intake pressure and temperature are changed. For high intake pressures and low intake temperatures, a sensitivity analysis at the moment of maximum heat release rate shows that the consumption of phenoxy radicals is rate-limiting when a toluene/n-heptane fuel is used, which makes this fuel more resistant to autoignition than the primary reference fuel. Typical CPU times encountered in zero-dimensional calculations were on the order of seconds and minutes in laminar flame speed calculations. Cross reactions between benzylperoxy radicals and n-heptane improved the model predictions of shock tube experiments for {phi}=1.0 and temperatures lower than 800 K for an n-heptane/toluene fuel mixture, but cross reactions had no influence on HCCI simulations. (author)

  1. Numerical investigation of spontaneous flame propagation under RCCI conditions

    SciTech Connect

    Bhagatwala, Ankit V; Sankaran, Ramanan; Kokjohn, Sage; Chen, Jacqueline H

    2015-06-30

    This paper presents results from one and two-dimensional direct numerical simulations under Reactivity Controlled Compression Ignition (RCCI) conditions of a primary reference fuel (PRF) mixture consisting of n-heptane and iso-octane. RCCI uses in-cylinder blending of two fuels with different autoignition characteristics to control combustion phasing and the rate of heat release. These simulations employ an improved model of compression heating through mass source/sink terms developed in a previous work by Bhagatwala et al. (2014), which incorporates feedback from the flow to follow a predetermined experimental pressure trace. Two-dimensional simulations explored parametric variations with respect to temperature stratification, pressure profiles and n-heptane concentration. Furthermore, statistics derived from analysis of diffusion/reaction balances locally normal to the flame surface were used to elucidate combustion characteristics for the different cases. Both deflagration and spontaneous ignition fronts were observed to co-exist, however it was found that higher n-heptane concentration provided a greater degree of flame propagation, whereas lower n-heptane concentration (higher fraction of iso-octane) resulted in more spontaneous ignition fronts. A significant finding was that simulations initialized with a uniform initial temperature and a stratified n-heptane concentration field, resulted in a large fraction of combustion occurring through flame propagation. The proportion of spontaneous ignition fronts increased at higher pressures due to shorter ignition delay when other factors were held constant. For the same pressure and fuel concentration, the contribution of flame propagation to the overall combustion was found to depend on the level of thermal stratification, with higher initial temperature gradients resulting in more deflagration and lower gradients generating more ignition fronts. Statistics of ignition delay are computed to assess the Zel’dovich (1980) theory for the mode of combustion propagation based on ignition delay gradients.

  2. Numerical investigation of spontaneous flame propagation under RCCI conditions

    DOE PAGESBeta

    Bhagatwala, Ankit V; Sankaran, Ramanan; Kokjohn, Sage; Chen, Jacqueline H

    2015-06-30

    This paper presents results from one and two-dimensional direct numerical simulations under Reactivity Controlled Compression Ignition (RCCI) conditions of a primary reference fuel (PRF) mixture consisting of n-heptane and iso-octane. RCCI uses in-cylinder blending of two fuels with different autoignition characteristics to control combustion phasing and the rate of heat release. These simulations employ an improved model of compression heating through mass source/sink terms developed in a previous work by Bhagatwala et al. (2014), which incorporates feedback from the flow to follow a predetermined experimental pressure trace. Two-dimensional simulations explored parametric variations with respect to temperature stratification, pressure profiles andmore » n-heptane concentration. Furthermore, statistics derived from analysis of diffusion/reaction balances locally normal to the flame surface were used to elucidate combustion characteristics for the different cases. Both deflagration and spontaneous ignition fronts were observed to co-exist, however it was found that higher n-heptane concentration provided a greater degree of flame propagation, whereas lower n-heptane concentration (higher fraction of iso-octane) resulted in more spontaneous ignition fronts. A significant finding was that simulations initialized with a uniform initial temperature and a stratified n-heptane concentration field, resulted in a large fraction of combustion occurring through flame propagation. The proportion of spontaneous ignition fronts increased at higher pressures due to shorter ignition delay when other factors were held constant. For the same pressure and fuel concentration, the contribution of flame propagation to the overall combustion was found to depend on the level of thermal stratification, with higher initial temperature gradients resulting in more deflagration and lower gradients generating more ignition fronts. Statistics of ignition delay are computed to assess the Zel’dovich (1980) theory for the mode of combustion propagation based on ignition delay gradients.« less

  3. Investigation of coal structure. Quarterly report, October 1, 1992--December 31, 1992

    SciTech Connect

    Not Available

    1993-01-01

    The method was applied to standard polymers under the same condition above. The particle size distribution with volume diameters of polyvinylpyrrolidone (average molecular mass; 10,000) was measured at sample/solvent = 0.50 g/100 ml. This polymer readily dissolve in methanol and water, while the polymer does not dissolve in n-hexane and toluene, and toluene is a slightly better solvent than n-hexane. Figure 3 shows the particle size distributions in n-hexane (a) and toluene (b-1 and -2). The distribution in toluene changed time to time, and two representative distributions are shown. The mean volume diameters-were 14 {mu}m in n-hexane and 18 and 31 {mu}m in toluene. The particle size distribution of cross-linked polyvinylpyrrolidone was further examined in methanol and n-hexane. Figure 4 compares these distributions with scanned counts at sample/solvent = 0.50 g/100 ml. As a significant portion of particles was over 250 {mu}m with volume diameters, the distributions are presented with scanned counts. Figure 4 compared the specific swelling ratio (Q`) versus sample/solvent (w/w %) in the same solvents for this sample. It is seen that methanol is a good solvent than n-hexane and swells the sample. It is also seen that the swelling is dependent on the sample concentration. Therefore, the particle size in good solvent methanol is expected to be larger due to swelling. However, the particle size was smaller in methanol than in n-hexane (Figure 4). The dependence of sample concentration on solvent swelling in methanol (Figure 5) is interpreted as follows: Polymer particles disaggregated at low sample concentration and the interparticle voidage of the swollen polymer after centrifugation changed depending upon disaggregation.

  4. Investigation of coal structure

    SciTech Connect

    Not Available

    1993-01-01

    The method was applied to standard polymers under the same condition above. The particle size distribution with volume diameters of polyvinylpyrrolidone (average molecular mass; 10,000) was measured at sample/solvent = 0.50 g/100 ml. This polymer readily dissolve in methanol and water, while the polymer does not dissolve in n-hexane and toluene, and toluene is a slightly better solvent than n-hexane. Figure 3 shows the particle size distributions in n-hexane (a) and toluene (b-1 and -2). The distribution in toluene changed time to time, and two representative distributions are shown. The mean volume diameters-were 14 [mu]m in n-hexane and 18 and 31 [mu]m in toluene. The particle size distribution of cross-linked polyvinylpyrrolidone was further examined in methanol and n-hexane. Figure 4 compares these distributions with scanned counts at sample/solvent = 0.50 g/100 ml. As a significant portion of particles was over 250 [mu]m with volume diameters, the distributions are presented with scanned counts. Figure 4 compared the specific swelling ratio (Q') versus sample/solvent (w/w %) in the same solvents for this sample. It is seen that methanol is a good solvent than n-hexane and swells the sample. It is also seen that the swelling is dependent on the sample concentration. Therefore, the particle size in good solvent methanol is expected to be larger due to swelling. However, the particle size was smaller in methanol than in n-hexane (Figure 4). The dependence of sample concentration on solvent swelling in methanol (Figure 5) is interpreted as follows: Polymer particles disaggregated at low sample concentration and the interparticle voidage of the swollen polymer after centrifugation changed depending upon disaggregation.

  5. Elimination of hydrophobic volatile organic compounds in fungal biofilters: reducing start-up time using different carbon sources.

    PubMed

    Vergara-Fernndez, Alberto; Hernndez, Sergio; Revah, Sergio

    2011-04-01

    Fungal biofilters have been recently studied as an alternative to the bacterial systems for the elimination of hydrophobic volatile organic compounds (VOC). Fungi foster reduced transport limitation of hydrophobic VOCs due to their hydrophobic surface and extended gas exchange area associated to the hyphal growth. Nevertheless, one of their principal drawbacks is their slow growth, which is critical in the start-up of fungal biofilters. This work compares the use of different carbon sources (glycerol, 1-hexanol, wheat bran, and n-hexane) to reduce the start-up period and sustain high n-hexane elimination capacities (EC) in biofilters inoculated with Fusarium solani. Four parallel experiments were performed with the different media and the EC, the n-hexane partition coefficient, the biomass production and the specific consumption rate were evaluated. Biofilters were operated with a residence time of 1.3?min and an inlet n-hexane load of 325?g?m(-3) (reactor) h(-1). The time to attain maximum EC once gaseous n-hexane was fed was reduced in the three experiments with alternate substrates, as compared to the 36 days needed with the control where only n-hexane was added. The shortest adaptation period was 7 days when wheat bran was initially used obtaining a maximum EC of 160?g?m(-3) (reactor) h(-1) and a critical load of 55?g?m(-3) (reactor) h(-1). The results were also consistent with the pressure drop, the amount of biomass produced and its affinity for the gaseous n-hexane, as represented by its partition coefficient. PMID:21404250

  6. The effect of Artemisia annua on broiler performance, on intestinal microbiota and on the course of a Clostridium perfringens infection applying a necrotic enteritis disease model.

    PubMed

    Engberg, Ricarda Margarete; Grevsen, Kai; Ivarsen, Elise; Fretté, Xavier; Christensen, Lars Porskjær; Højberg, Ole; Jensen, Bent Borg; Canibe, Nuria

    2012-01-01

    The aerial parts of the plant Artemisia annua contain essential oils having antimicrobial properties against Clostridium perfringens Type A, the causal agent for necrotic enteritis in broilers. In two experiments, the influence of increasing dietary concentrations of dried A. annua leaves (0, 5, 10 and 20 g/kg) and n-hexane extract from fresh A. annua leaves (0, 125, 250 and 500 mg/kg) on broiler performance was investigated. Dried plant material decreased feed intake and body weight in a dose-dependent manner, and 10 and 20 g/kg diet tended to improve the feed conversion ratio. The n-hexane extract also reduced feed intake, but broiler weight tended to decrease only at the highest dietary concentration. The feed conversion ratio tended to improve when birds received 250 and 500 mg/kg n-hexane extract. In a third experiment, a necrotic enteritis disease model was applied to investigate the effect of the dietary addition of dried A. annua leaves (10 g/kg on top) or n-hexane extract of A. annua (250 mg/kg) on the severity of the disease in broilers. The addition of n-hexane extract reduced the intestinal C. perfringens numbers and the severity of the disease-related small intestinal lesions. Over the infection period from day 17 to day 27, birds supplemented with the n-hexane extract gained more weight than both the challenged control birds and birds receiving dried plant material. The results indicate that n-hexane extracts derived from A. annua can modulate the course of necrotic enteritis and compensate to a certain extent for the disease-associated weight losses. PMID:22834551

  7. Multicomponent vapor-liquid equilibria measurements for the development of an extractive distillation process for the processing of gas issuing from a CO/sub 2/ enhanced oil recovery project

    SciTech Connect

    Hong, J.H.; Kobayashi, R.

    1987-02-01

    This paper provides vapor-liquid equilibria data for the design of the upper section of the all-important column treating the stabilized feed gas from CO/sub 2/ enhanced oil recovery (EOR) projects. Again, the extractive agent is represented by n-pentane. The simulated feed gas containing the methane, liquified petroleum gas (LPG) components, and H/sub 2/S is added to n-pentane to form quasi-binary mixtures. A comparison of the K values obtained by the addition of methane to an otherwise similar methane-free gas shows that the effect of methane on the K values of the other constituents becomes increasingly pronounced as the pressure increases.

  8. Enthalpies, excess volumes, and specific heats of critical and supercritical binary mixtures

    NASA Astrophysics Data System (ADS)

    Kiselev, S. B.; Rainwater, J. C.

    1998-07-01

    A scaling-law crossover thermodynamic model is applied to caloric properties of five binary mixtures, carbon dioxide + ethane, ethane + propane, n-pentane + benzene, n-pentane + acetone, and ammonia + water. Enthalpy increments, excess enthalpies, excess volumes, and specific heats are calculated on the phase boundaries and in the near-critical and supercritical one-phase regions, and calculated values agree well with experimental data. The method requires as input the mixture excess critical compressibility factor, as obtained from critical loci, which in this approach are determined from modified Leung-Griffiths correlations. The only additional variables needed are the acentric factors of the pure components and a few fitting parameters which describe the unknown thermodynamic energies along the critical locus and which are not needed for the phase boundary and supercritical properties in pressure-temperature-density space.

  9. An investigation into the role of rat skeletal muscle as a site for xenobiotic metabolism using microsomes and isolated cells.

    PubMed

    Crosbie, S J; Blain, P G; Williams, F M

    1997-03-01

    1. The role of skeletal muscle microsomes as a site of extrahepatic xenobiotic metabolism using n-hexane as a model substrate was investigated. The observed cytochrome P450-dependent metabolism was compared with that found with liver, and brain microsomal fractions. 2. Rat skeletal muscle microsomes metabolised n-hexane to 1-, 2- and 3-hexanol at rates 40-300 times lower than observed with rat liver microsomes. 3. Fast-twitch extensor digitorum longus muscle (EDL) microsomes had twice as much n-hexane hydroxylase activity as the slow-twitch soleus and furthermore the EDL microsomes produced 2-hexanol, a bioactivation product of n-hexane, as a major metabolite. 4. Metabolism of hexane to 1-, 2- and 3-hexanol and 2-hexanon was demonstrated in cultured rat myoblasts. 5. Ethoxyresorufin and pentoxyresorufin O-dealkylation were not detected in either muscle microsomes or myoblasts although immunocytochemical localisation studies were suggestive of the presence of cytochrome P-450. 6. In conclusion, rat skeletal muscle has a low level of xenobiotic metabolism activity. The relevance to neuromuscular toxicity of n-hexane is discussed. PMID:9088966

  10. Effects of direct exposure of green odour components on dopamine release from rat brain striatal slices and PC12 cells.

    PubMed

    Kako, Hironari; Fukumoto, Syuichi; Kobayashi, Yoko; Yokogoshi, Hidehiko

    2008-03-28

    The effects of odour components on dopamine release from rat brain striatal slices and rat pheochromocytoma (PC12) cells were examined. The striatal slices were directly stimulated with 0.5% odour-including Krebs buffer using a superfusion method. In this experiment, (Z)-3-hexenol, (E)-2-hexenal, n-hexanal, 1,8-cineole or Eucalyptus globulus essential oil was used as an odour component. The concentrations of monoamines released in perfusate were measured by HPLC-ECD. Dopamine release from brain slices was significantly enhanced by perfusion of each odour-including solution. In particular, administration of n-hexanal caused a 9-fold increase in dopamine release. The dopamine release by n-hexanal increased linearly with the concentration of n-hexanal up to 0.5% and was maximal at 0.5%. Since PC12 cells have the ability to release dopamine, the effects of four green odour compounds, (Z)-3-hexenol, (E)-2-hexenal, n-hexanal and n-hexanol, on dopamine release were examined. These odour compounds dose dependently increased dopamine release from PC12 cells, and different patterns of dopamine release were observed with aldehyde or alcohol. Odour compounds thus appear to increase dopamine release from dopamine-releasing cells, with differences between aldehydes and alcohols in pattern of release. Dopamine regulates brain functions such as reward, mood, and attention. Green odours may in turn regulate such brain functions through the stimulation of dopamine release. PMID:18355650

  11. High-pressure soot formation and diffusion flame extinction characteristics of gaseous and liquid fuels

    NASA Astrophysics Data System (ADS)

    Karatas, Ahmet Emre

    High-pressure soot formation and flame stability characteristics were studied experimentally in laminar diffusion flames. For the former, radially resolved soot volume fraction and temperature profiles were measured in axisymmetric co-flow laminar diffusion flames of pre-vaporized n-heptane-air, undiluted ethylene-air, and nitrogen and carbon dioxide diluted ethylene-air at elevated pressures. Abel inversion was used to re-construct radially resolved data from the line-of-sight spectral soot emission measurements. For the latter, flame extinction strain rate was measured in counterflow laminar diffusion flames of C1-4 alcohols and hydrocarbon fuels of n-heptane, n-octane, iso-octane, toluene, Jet-A, and biodiesel. The luminous flame height, as marked by visible soot radiation, of the nitrogen- and helium-diluted n-heptane and nitrogen- and carbon dioxide-diluted ethylene flames stayed constant at all pressures. In pure ethylene flames, flame heights initially increased with pressure, but changed little above 5 atm. The maximum soot yield as a function of pressure in nitrogen-diluted n-heptane diffusion flames indicate that n-heptane flames are slightly more sensitive to pressure than gaseous alkane hydrocarbon flames at least up to 7 atm. Ethylene's maximum soot volume fractions were much higher than those of ethane and n-heptane diluted with nitrogen (fuel to nitrogen mass flow ratio is about 0.5). Pressure dependence of the peak carbon conversion to soot, defined as the percentage of fuel's carbon content converted to soot, was assessed and compared to previous measurements with other gaseous fuels. Maximum soot volume fractions were consistently lower in carbon dioxide-diluted flames between 5 and 15 atm but approached similar values to those in nitrogen-diluted flames at 20 atm. This observation implies that the chemical soot suppression effect of carbon dioxide, previously demonstrated at atmospheric pressure, is also present at elevated pressures up to 15 atm, but fades off beyond 15 atm. In flame stability experiments, the extinction strain rates increased with decreasing dilution. In general, the fuels with higher carbon number and fuels with more compact structures were found to be more prone to extinction. Counterflow laminar diffusion flames established at the impingement of reactants with a top-hat (axially uniform) velocity profile were found to be more resistant to extinction than those with a parabolic exit velocity profile. Multiple solutions to the flame stability were observed for certain hydrocarbons.

  12. Cometabolism of Methyl tertiary Butyl Ether and Gaseous n-Alkanes by Pseudomonas mendocina KR-1 Grown on C5 to C8 n-Alkanes

    PubMed Central

    Smith, Christy A.; O'Reilly, Kirk T.; Hyman, Michael R.

    2003-01-01

    Pseudomonas mendocina KR-1 grew well on toluene, n-alkanes (C5 to C8), and 1 alcohols (C2 to C8) but not on other aromatics, gaseous n-alkanes (C1 to C4), isoalkanes (C4 to C6), 2 alcohols (C3 to C8), methyl tertiary butyl ether (MTBE), or tertiary butyl alcohol (TBA). Cells grown under carbon-limited conditions on n-alkanes in the presence of MTBE (42 ?mol) oxidized up to 94% of the added MTBE to TBA. Less than 3% of the added MTBE was oxidized to TBA when cells were grown on either 1 alcohols, toluene, or dextrose in the presence of MTBE. Concentrated n-pentane-grown cells oxidized MTBE to TBA without a lag phase and without generating tertiary butyl formate (TBF) as an intermediate. Neither TBF nor TBA was consumed by n-pentane-grown cells, while formaldehyde, the expected C1 product of MTBE dealkylation, was rapidly consumed. Similar Ks values for MTBE were observed for cells grown on C5 to C8 n-alkanes (12.95 2.04 mM), suggesting that the same enzyme oxidizes MTBE in cells grown on each n-alkane. All growth-supporting n-alkanes (C5 to C8) inhibited MTBE oxidation by resting n-pentane-grown cells. Propane (Ki = 53 ?M) and n-butane (Ki = 16 ?M) also inhibited MTBE oxidation, and both gases were also consumed by cells during growth on n-pentane. Cultures grown on C5 to C8 n-alkanes also exhibited up to twofold-higher levels of growth in the presence of propane or n-butane, whereas no growth stimulation was observed with methane, ethane, MTBE, TBA, or formaldehyde. The results are discussed in terms of their impacts on our understanding of MTBE biodegradation and cometabolism. PMID:14660389

  13. Numerical study of multicomponent droplet vaporization at near critical conditions

    NASA Technical Reports Server (NTRS)

    Hsieh, Kwang-Chung; Shuen, Jian-Shun; Yang, Vigor

    1988-01-01

    A comprehensive numerical analysis of multicomponent droplet vaporization at near critical conditions has been carried out. The model is based on the full time-dependent conservation equations and accommodates various important high-pressure phenomena. As an example, the case involving a two-component (n-pentane and n-octane) fuel droplet in nitrogen gas is studied. The influences of transient effects, surface regression, ambient gas solubility, and phase-equilibrium relations on vaporization mechanisms are examined in detail.

  14. A coupled implicit method for chemical non-equilibrium flows at all speeds

    NASA Technical Reports Server (NTRS)

    Shuen, Jian-Shun; Chen, Kuo-Huey; Choi, Yunho

    1993-01-01

    The present time-accurate coupled-solution procedure addresses the chemical nonequilibrium Navier-Stokes equations over a wide Mach-number range uses, in conjunction with the strong conservation form of the governing equations, five unknown primitive variables. The numerical tests undertaken address steady convergent-divergent nozzle flows with air dissociation/recombination, dump combustor flows with n-pentane/air chemistry, and unsteady nonreacting cavity flows.

  15. Electron drift velocities and electron mobilities in fast room-temperature dielectric liquids and their corresponding vapors

    NASA Astrophysics Data System (ADS)

    Faidas, H.; Christophorou, L. G.; McCorkle, D. L.; Carter, J. G.

    1990-09-01

    The drift velocity, w, of excess electrons as a function of the applied uniform electric field, E, in liquid tetramethylsilane (TMS), 2,2,4,4-tetramethylpentane (TMP), tetramethyltin (TMT), and in mixtures of TMS with TMP (molar ratio, M = 1.31/1) and n-pentane ( M = 102/1; 17/1; 5.6/1) has been measured up to E-values of 10 5 V cm -1 or density ( N)-reduced ele ctric held E/ N-values of 3 10 -17 V cm 2. The maximum w attained for these liquids, and the corresponding values of E are: 7.2 10 6 cm s -1 at 125 kV cm -1 for TMS, 6.0 10 6 cm s -1 at 75 kV cm -1 for TMS, 2.6 10 6 cm s -1 at 115 kV cm -1 for TMP, 3.2 10 6 cm s -1 at 105 kV cm -1 for TMS/TMP ( M = 1.31/1), 6.8 10 6 cm s -1 at 105 kV cm -1 for TMS/n-pentane ( M = 102/1), 6.8 10 6 cm s -1 at 145 kV cm -1 for TMS/n-pentane ( M = 17/1), and 4.9 10 6 cm s -1 at 145 kV cm -1 for TMS/n-pentane ( M = 5.6/1). The thermal-electron mobilities in the above liquid media are respectively 119.3, 85.7, 31.8, 39.1, 118, 85, and 47.6 cm 2 s -1 V -1. Also, w was measured as a function of E/ N for TMS, TMP, and neopentane vapors at room temperature and is compared with that in the corresponding liquids. Properties of these media which make them desirable for radiation detectors are discussed.

  16. Instrumental studies on silicone oil adsorption to the surface of intraocular lenses

    NASA Astrophysics Data System (ADS)

    Kim, Chun Ho; Joo, Choun-Ki; Chun, Heung Jae; Yoo, Bok Ryul; Noh, Dong Il; Shim, Young Bock

    2012-12-01

    The purpose of this study was to examine the degree of adherence of silicone oil to various intraocular lenses (IOLs) through comparison of the physico-chemical properties of the oil and IOLs. Four kinds of IOLs comprising various biomaterials were examined: PMMA (720A), PHEMA (IOGEL 1103), Acrysof (MA60BM), and silicone (SI30NB). Each lens was immersed in silicone oil or carboxylated silicone (CS-PDMS) oil for 72 h. For determination of the changes in chemical and elemental compositions on the surfaces of IOLs caused by the contact with silicone oil, IOLs were washed and rinsed with n-pentane to remove as much of the adsorbed silicone oil as possible, then subjected to Fourier transform infrared spectroscopic (FTIR) and X-ray photoelectron spectroscopic (XPS) analyses. The results of FTIR studies strongly indicate that washing with n-pentane completely removed the adhered silicone oil on the surfaces of PHEMA and Acrysof IOLs, whereas the residual silicone oil was detected on the surfaces of PMMA and silicone IOLs. XPS studies showed that silicone oil coverage of PMMA lenses was 12%, even after washing with n-pentane. In the case of silicone IOLs, the relative O1s peak area of carboxyl group in the residual CS-PDMS oil was found to be 2.7%. Considering that 2.8% carboxyl group-substituted silicone oil was used in the present study, CS-PDMS oil covered the entire surface of the silicone IOLs.

  17. Solidification and loss of hydrostaticity in liquid media used for pressure measurements

    NASA Astrophysics Data System (ADS)

    Torikachvili, M. S.; Kim, S. K.; Colombier, E.; Bud'ko, S. L.; Canfield, P. C.

    2015-12-01

    We carried out a study of the pressure dependence of the solidification temperature in nine pressure transmitting media that are liquid at ambient temperature, under pressures up to 2.3 GPa. These fluids are 1:1 isopentane/n-pentane, 4:6 light mineral oil/n-pentane, 1:1 isoamyl alcohol/n-pentane, 4:1 methanol/ethanol, 1:1 FC72/FC84 (Fluorinert), Daphne 7373, isopentane, and Dow Corning PMX silicone oils 200 and 60 000 cS. We relied on the high sensitivity of the electrical resistivity of Ba(Fe1-xRux)2As2 single crystals to the freezing of the pressure media and cross-checked with corresponding anomalies observed in the resistance of the manganin coil that served as the ambient temperature resistive manometer. In addition to establishing the temperature-pressure line separating the liquid (hydrostatic) and frozen (non-hydrostatic) phases, these data permit rough estimates of the freezing pressure of these media at ambient temperature. This pressure establishes the extreme limit for the medium to be considered hydrostatic. For higher applied pressures, the medium has to be treated as non-hydrostatic.

  18. Liquid CO2 extraction of Jasminum grandiflorum and comparison with conventional processes.

    PubMed

    Prakash, Om; Sahoo, Deeptanjali; Rout, Prasant Kumar

    2012-01-01

    The concrete (0.35%) of Jasminum grandiflorum L. flowers was prepared by extraction in n-pentane, and the absolute (0.27%) by fractionation of the n-pentane extract (concrete) with cold methanol. Direct extraction of flowers with liquid CO2 gave a relatively fat-free product in 0.26% yield. The liquid CO2 extract was enriched with terpenoids and benzenoids, thus providing the organoleptically accepted product. The major compounds, such as benzyl acetate, (E,E)-alpha-farnesene and (Z)-3-hexenyl benzoate, along with compounds like indole, methyl anthranilate, (Z)-jasmone, (Z)-methyl jasmonoate and (Z)-methyl epi-jasmonoate, are responsible for the high diffusivity of the jasmine fragrance. These compounds have been obtained with improved recoveries in the liquid CO2 extract. On the other hand, the yield of the essential oil was poor (0.05%), and some polar compounds (oxygenated terpenoids) were recovered in less amounts in comparison with either the n-pentane or liquid CO2 extract. PMID:22428256

  19. Solidification and loss of hydrostaticity in liquid media used for pressure measurements.

    PubMed

    Torikachvili, M S; Kim, S K; Colombier, E; Bud'ko, S L; Canfield, P C

    2015-12-01

    We carried out a study of the pressure dependence of the solidification temperature in nine pressure transmitting media that are liquid at ambient temperature, under pressures up to 2.3 GPa. These fluids are 1:1 isopentane/n-pentane, 4:6 light mineral oil/n-pentane, 1:1 isoamyl alcohol/n-pentane, 4:1 methanol/ethanol, 1:1 FC72/FC84 (Fluorinert), Daphne 7373, isopentane, and Dow Corning PMX silicone oils 200 and 60?000 cS. We relied on the high sensitivity of the electrical resistivity of Ba(Fe1-xRux)2As2 single crystals to the freezing of the pressure media and cross-checked with corresponding anomalies observed in the resistance of the manganin coil that served as the ambient temperature resistive manometer. In addition to establishing the temperature-pressure line separating the liquid (hydrostatic) and frozen (non-hydrostatic) phases, these data permit rough estimates of the freezing pressure of these media at ambient temperature. This pressure establishes the extreme limit for the medium to be considered hydrostatic. For higher applied pressures, the medium has to be treated as non-hydrostatic. PMID:26724044

  20. Transport properties of nonelectrolyte liquid mixturesI. Viscosity coefficients for n-alkane mixtures at saturation pressure from 283 to 378 K

    NASA Astrophysics Data System (ADS)

    Dymond, J. H.; Young, K. J.

    1980-12-01

    Viscosity coefficient measurements at saturation pressure are reported for n-hexane + n-hexadecane, n-hexane + n-octane + n-hexadecane, and n-hexane + n-octane + n-dodecane + n-hexadecane at temperatures from 283 to 378 K. The results show that the Congruence Principle applies to the molar excess Gibbs free energy of activation for flow, ?* G E, at temperatures other than 298 K. However, curves of ?* G E versus index number of the mixture are temperature dependent, and this must be taken into account for accurate prediction of mixture viscosity coefficients by this approach. The purely empirical equation of Grunberg and Nissan; 1 10765_2004_Article_BF00516562_TeX2GIFE1.gif ln ? = x_1 ln ? _1 + x_2 ln ? _2 + x_1 x_2 G which has the advantage of not involving molar volumes, satisfactorily reproduces the experimental results for the binary mixture, but G is definitely composition dependent.

  1. Hydrophobic response of the fungus Rhinocladiella similis in the biofiltration with volatile organic compounds with different polarity.

    PubMed

    Vigueras, Gabriel; Arriaga, Sonia; Shirai, Keiko; Morales, Marcia; Revah, Sergio

    2009-08-01

    Rhinocladiella similis biodegraded volatile organic compounds (VOCs) of different polarity in gas-phase biofilters. Elimination capacities, (EC) of 74 g(hexane) m(-3) h(-1), 230 g(ethanol) m(-3) h(-1), 85 g(toluene) m(-3) h(-1) and 30 g(phenol) m(-3) h(-1) were obtained. EC values correlated with the solubility of the VOCs. R. similis grown with n-hexane or ethanol in biofilters packed with Perlite showed that the surface hydrophobicity was higher with n-hexane than ethanol. The hydrophobin-like proteins extracted from the mycelium produced with n-hexane (15 kDa) were different from those in the ethanol biofilter (8.5 kDa and 7 kDa). PMID:19343504

  2. Contrasting nonaqueous against aqueous solvation on the basis of scaled-particle theory.

    PubMed

    Ashbaugh, Henry S; Pratt, Lawrence R

    2007-08-01

    Normal hexane is adopted as a typical organic solvent for comparison with liquid water in modern theories of hydrophobic hydration, and detailed results are worked-out here for the C-atom density in contact with a hard-sphere solute, rhoCG(R), for the full range of solute radii. The intramolecular structure of an n-hexane molecule introduces qualitative changes in G(R) compared to scaled-particle models for liquid water. Also worked-out is a revised scaled-particle model implemented with molecular simulation results for liquid n-hexane. The classic scaled-particle model, acknowledging the intramolecular structure of an n-hexane molecule, is in qualitative agreement with the revised scaled-particle model results, and is consistent in sizing the methyl/methylene sites which compose n-hexane in the simulation model. The classic and revised scaled-particle models disagree for length scales greater than the radius of a methyl group, however. The liquid-vapor surface tension of n-hexane predicted by the classic scaled-particle model is too large, though the temperature variation is reasonable; this contrasts with the classic scaled-particle theory for water which predicts a reasonable magnitude of the water liquid-vapor surface tension, but an incorrect sign for the temperature derivative at moderate temperatures. Judging on the basis of the arbitrary condition that drying is indicated when G(R)<1, hard spheres dry at smaller sizes in n-hexane than in liquid water. PMID:17636979

  3. Laboratory Evaluations of the Fractions Efficacy of Annona senegalensis (Annonaceae) Leaf Extract on Immature Stage Development of Malarial and Filarial Mosquito Vectors

    PubMed Central

    Lame, Younoussa; Nukenine, Elias Nchiwan; Pierre, Danga Yinyang Simon; Elijah, Ajaegbu Eze; Esimone, Charles Okechukwu

    2015-01-01

    Background: Within the framework to control mosquitoes, ovicidal, larvicidal and pupicidal activity of Annona senegalensis leaf extract and its 4 fractions against Anopheles gambiae and Culex quinquefasciatus were evaluated in the laboratory conditions. Methods: Ovicidal test was performed by submitting at least 100 eggs of mosquitoes to 125, 250, 500, 1000 and 2000 ppm concentrations, while larvicidal and pupicidal effects were assessed by submitting 25 larvae or pupae to the concentrations of 2500, 1250, 625 and 312.5 ppm of plant extract or fractions of A. senegalensis. Results: The eggs of An. gambiae were most affected by N-hexane (0.00% hatchability) and chloroform (03.67% hatchability) fractions compared to Cx. quinquefasciatus where at least 25 % hatchability were recorded at 2000 ppm. For larvicidal test, N-hexane (LC50= 298.8 ppm) and chloroform (LC50= 418.3 ppm) fractions were more effective than other fractions on An. gambiae larvae while, a moderate effectiveness was also observed with N-hexane (LC50= 2087.6 ppm), chloroform (LC50= 9010.1 ppm) fractions on Cx. quinquefasciatus larvae. The highest mortality percent of the pupae were also recorded with N-hexane and chloroform fractions on An. gambiae at 2500 ppm. As for Cx. quinquefasciatus only 50 % and 36 % mortality were recorded with N-hexane and chloroform fractions respectively. Conclusion: The extract of A. senegalensis was toxic on immature stage of mosquito species tested. By splitting methanolic crude extract, only N-hexane and chloroform fractions were revealed to possess a mosquitocidal effects and could be considered and utilized for future immature mosquito vectors control. PMID:26623434

  4. Laser extinction technique for measurements of carbon particles concentration during combustion

    NASA Astrophysics Data System (ADS)

    Di Sante, R.

    2013-06-01

    Particulate matter (PM) from diesel engines originate from soot particles which form during combustion and is notoriously a major source of concern as an airborne contaminant in the environment. The mechanisms by which soot is generated in diesel engines are still not completely understood and the use of optical techniques in a controllable environment is crucial for this purpose. This work focuses on the development and application of the laser extinction technique to the study of soot formation evolution in a rapid compression machine (RCM). A suitable optical arrangement to determine soot kinetics with high temporal resolution is presented together with the results obtained in the case of rich n-heptane, toluene and toluene/n-heptane mixtures under different conditions of pressure and temperature. The experimental investigation is focused on the fuel-rich premixed turbulent flame.

  5. Upgrading light hydrocarbons via tandem catalysis: a dual homogeneous Ta/Ir system for alkane/alkene coupling.

    PubMed

    Leitch, David C; Lam, Yan Choi; Labinger, Jay A; Bercaw, John E

    2013-07-17

    Light alkanes and alkenes are abundant but are underutilized as energy carriers because of their high volatility and low energy density. A tandem catalytic approach for the coupling of alkanes and alkenes has been developed in order to upgrade these light hydrocarbons into heavier fuel molecules. This process involves alkane dehydrogenation by a pincer-ligated iridium complex and alkene dimerization by a Cp*TaCl2(alkene) catalyst. These two homogeneous catalysts operate with up to 60/30 cooperative turnovers (Ir/Ta) in the dimerization of 1-hexene/n-heptane, giving C13/C14 products in 40% yield. This dual system can also effect the catalytic dimerization of n-heptane (neohexene as the H2 acceptor) with cooperative turnover numbers of 22/3 (Ir/Ta). PMID:23799786

  6. Autoignition of gasoline surrogates mixtures at intermediate temperatures and high pressures

    SciTech Connect

    Fikri, M.; Herzler, J.; Starke, R.; Schulz, C.; Roth, P.; Kalghatgi, G.T.

    2008-01-15

    Ignition times were determined in high-pressure shock-tube experiments for various stoichiometric mixtures of two multicomponent model fuels in air for the validation of ignition delay simulations based on chemical kinetic models. The fuel blends were n-heptane (18%)/isooctane (62%)/ethanol (20%) by liquid volume (14.5%/44.5%/41% by mole fraction) and n-heptane (20%)/toluene (45%)/isooctane (25%)/diisobutylene (10%) by liquid volume (17.5%/55%/19.5%/8.0% by mole fraction). These fuels have octane numbers comparable to a standard European gasoline of 95 RON and 85 MON. The experimental conditions cover temperatures from 690 to 1200 K and pressures at 10, 30, and 50 bar. The obtained ignition time data are scaled with respect to pressure and compared to previous results reported in the literature. (author)

  7. Possible room temperature superconductivity in conductors obtained by bringing alkanes into contact with a graphite surface.

    PubMed

    Kawashima, Yasushi

    2013-05-01

    Electrical resistances of conductors obtained by bringing alkanes into contact with a graphite surface have been investigated at room temperatures. Ring current in a ring-shaped container into which n-octane-soaked thin graphite flakes were compressed did not decay for 50 days at room temperature. After two HOPG plates were immersed into n-heptane and n-octane at room temperature, changes in resistances of the two samples were measured by four terminal technique. The measurement showed that the resistances of these samples decrease to less than the smallest resistance that can be measured with a high resolution digital voltmeter (0.1?V). The observation of persistent currents in the ring-shaped container suggests that the HOPG plates immersed in n-heptane and n-octane really entered zero-resistance state at room temperature. These results suggest that room temperature superconductor may be obtained by bringing alkanes into contact with a graphite surface. PMID:23826513

  8. Reduction of Large Detailed Chemical Kinetic Mechanisms for Autoignition Using Joint Analyses of Reaction Rates and Sensitivities

    SciTech Connect

    Saylam, A; Ribaucour, M; Pitz, W J; Minetti, R

    2006-11-29

    A new technique of reduction of detailed mechanisms for autoignition, which is based on two analysis methods is described. An analysis of reaction rates is coupled to an analysis of reaction sensitivity for the detection of redundant reactions. Thresholds associated with the two analyses have a great influence on the size and efficiency of the reduced mechanism. Rules of selection of the thresholds are defined. The reduction technique has been successfully applied to detailed autoignition mechanisms of two reference hydrocarbons: n-heptane and iso-octane. The efficiency of the technique and the ability of the reduced mechanisms to reproduce well the results generated by the full mechanism are discussed. A speedup of calculations by a factor of 5.9 for n-heptane mechanism and by a factor of 16.7 for iso-octane mechanism is obtained without losing accuracy of the prediction of autoignition delay times and concentrations of intermediate species.

  9. Possible room temperature superconductivity in conductors obtained by bringing alkanes into contact with a graphite surface

    NASA Astrophysics Data System (ADS)

    Kawashima, Yasushi

    2013-05-01

    Electrical resistances of conductors obtained by bringing alkanes into contact with a graphite surface have been investigated at room temperatures. Ring current in a ring-shaped container into which n-octane-soaked thin graphite flakes were compressed did not decay for 50 days at room temperature. After two HOPG plates were immersed into n-heptane and n-octane at room temperature, changes in resistances of the two samples were measured by four terminal technique. The measurement showed that the resistances of these samples decrease to less than the smallest resistance that can be measured with a high resolution digital voltmeter (0.1?V). The observation of persistent currents in the ring-shaped container suggests that the HOPG plates immersed in n-heptane and n-octane really entered zero-resistance state at room temperature. These results suggest that room temperature superconductor may be obtained by bringing alkanes into contact with a graphite surface.

  10. Combined small-angle x-ray scattering/extended x-ray absorption fine structure study of coated Co nanoclusters in bis(2-ethylhexyl)sulfosuccinate

    NASA Astrophysics Data System (ADS)

    Longo, A.; Giordano, F.; Giannici, F.; Martorana, A.; Portale, G.; Ruggirello, A.; Turco Liveri, V.

    2009-06-01

    Chemically stable cobalt nanostructures have been prepared with Co(II) reduction in the confined space of cobalt bis(2-ethylhexyl)sulfosuccinate, Co(AOT)2, reverse micelles dispersed in n-heptane. The reaction was carried out by adding a solution of sodium borohydride in ethanol (1% weight) to a 0.2M micellar solution of Co(AOT)2 in n-heptane at a reductant to Co(II) molar ratio of 4. This procedure involves the rapid formation of surfactant-coated Co nanoparticles followed by their slow separation as nanostructures embedded in a sodium bis(2-ethylhexyl)sulfosuccinate matrix. The resulting composites, characterized by extended x-ray absorption fine structure and small-angle x-ray scattering, showed the presence of subnanometer sized cobalt nanoparticles aggregated together to form elongated structures coated by the surfactant molecules.

  11. Molecular structure and component blending effects on knock related chemistry

    SciTech Connect

    Brezinsky, K.; Dryer, F.L.

    1987-01-01

    Atmospheric pressure flow reactor experiments were conducted on the oxidation and pyrolysis of n-octane and iso-octane and the oxidation of blends of iso-octane and n-heptane have led to the conclusions that a) the difference in knocking tendency of fuels may result primarily from the comparative oxidation rates of the intermediates rather than the rate of attack on the initial fuel molecule, b) certain small unsaturated hydrocarbons interfere with the oxidation of other intermediates and serve as model compounds for the development of octane number enhancers, c) high temperature homogeneous oxidation chemistry of n-heptane/iso-octane mixtures and single component paraffin fuels can be correlated with the global phenomena of octane number measurement in a test engine, d) the contribution of thermal and oxidative processes to the rapid decay of the initial fuel can be evaluated from rate parameters from pyrolysis studies of pure hydrocarbon fuels.

  12. Possible room temperature superconductivity in conductors obtained by bringing alkanes into contact with a graphite surface

    PubMed Central

    Kawashima, Yasushi

    2013-01-01

    Electrical resistances of conductors obtained by bringing alkanes into contact with a graphite surface have been investigated at room temperatures. Ring current in a ring-shaped container into which n-octane-soaked thin graphite flakes were compressed did not decay for 50 days at room temperature. After two HOPG plates were immersed into n-heptane and n-octane at room temperature, changes in resistances of the two samples were measured by four terminal technique. The measurement showed that the resistances of these samples decrease to less than the smallest resistance that can be measured with a high resolution digital voltmeter (0.1?V). The observation of persistent currents in the ring-shaped container suggests that the HOPG plates immersed in n-heptane and n-octane really entered zero-resistance state at room temperature. These results suggest that room temperature superconductor may be obtained by bringing alkanes into contact with a graphite surface. PMID:23826513

  13. Rotational Isomers, Intramolecular Hydrogen Bond, and IR Spectra of o-Vinylphenol

    NASA Astrophysics Data System (ADS)

    Glazunov, V. P.; Berdyshev, D. V.; Balaneva, N. N.; Radchenko, O. S.; Novikov, V. L.

    2014-03-01

    Absorption bands of OH stretching vibrations in IR spectra of o-vinylphenol ( o-VP) in the weakly polar solvents CCl4 and n-hexane were studied. Several rotamers of the free OH group were observed for o-VP in n-hexane. The fraction of o-VP rotamers with an O-H…π intramolecular hydrogen bond (IHB) was less than 20% according to experimental estimates for CCl4 solutions and calculations in the gas phase and cyclohexane. The theoretical effective enthalpy of the o-VP IHB was estimated for rotamer A (-ΔH = 0.20 kcal/mol).

  14. Hydration of ammonia, methylamine, and methanol in amorphous solid water

    NASA Astrophysics Data System (ADS)

    Souda, Ryutaro

    2016-02-01

    Interactions of polar protic molecules with amorphous solid water (ASW) have been investigated using temperature-programmed desorption and time-of-flight secondary ion mass spectrometry. The ammonia and methylamine are incorporated into the interior of porous ASW films. They are caged by water molecules and are released during water crystallization. In contrast, the methanol-water interaction is not influenced by pores of ASW. The methanol additives tend to survive water crystallization and are released during ASW film evaporation. The hydration of n-hexane in ASW is influenced significantly by methanol additives because n-hexane is accommodated in a methanol-induced hydration shell.

  15. HPLC determination of flumethrin, deltamethrin, cypermethrin, and cyhalothrin residues in the milk and blood of lactating dairy cows.

    PubMed

    Bissacot, D Z; Vassilieff, I

    1997-09-01

    A procedure to determine residue concentrations of synthetic pyrethroid insecticides (flumethrin, deltamethrin, cypermethrin and cyhalothrin) in the milk and blood of lactating dairy cows was developed. Extraction was performed with acetoritrile, n-hexane partitioning, and silica gel column cleanup with n-hexane and diethyl ether. Analysis was carried out by high-performance liquid chromatography and ultraviolet detection. Recovery of the four pyrethroids averaged 78 to 91% with a minimum detectable concentration of 0.001 mg/kg. The method was reproducible and sensitive. PMID:9288595

  16. Isolation and identification of fatty acid amides from Shengli coal

    SciTech Connect

    Ming-Jie Ding; Zhi-Min Zong; Ying Zong; Xiao-Dong Ou-Yang; Yao-Guo Huang; Lei Zhou; Feng Wang; Jiang-Pei Cao; Xian-Yong Wei

    2008-07-15

    Shengli coal, a Chinese brown coal, was extracted with carbon disulfide and the extract was gradiently eluted with n-hexane and ethyl acetate (EA)/n-hexane mixed solvents with different concentrations of EA in a silica gel-filled column. A series of fatty acid amides, including fourteen alkanamides (C{sub 15}-C{sub 28}) and three alkenamides (C{sub 18} and C{sub 22}), were isolated from the coal by this method and analyzed with a gas chromatography/mass spectrometry. 26 refs., 2 figs., 2 tabs.

  17. Experiments And Model Development For The Investigation Of Sooting And Radiation Effects In Microgravity Droplet Combustion

    NASA Technical Reports Server (NTRS)

    Yozgatligil, Ahmet; Choi, Mun Young; Dryer, Frederick L.; Kazakov, Andrei; Dobashi, Ritsu

    2003-01-01

    This study involves flight experiments (for droplets between 1.5 to 5 mm) and supportive ground-based experiments, with concurrent numerical model development and validation. The experiments involve two fuels: n-heptane, and ethanol. The diagnostic measurements include light extinction for soot volume fraction, two-wavelength pyrometry and thin-filament pyrometry for temperature, spectral detection for OH chemiluminescence, broadband radiometry for flame emission, and thermophoretic sampling with subsequent transmission electron microscopy for soot aerosol property calculations.

  18. Combustion characteristics in the transition region of liquid fuel sprays

    NASA Technical Reports Server (NTRS)

    Cernansky, N. P.; Namer, I.; Tidona, R. J.; Sarv, H.

    1984-01-01

    A monodisperse aerosol generator was modified to study ignition requirements, flammability limits, and flame speeds in the transition region. An ignition system was developed and tested. The fabrication of an optical drop sizing system is nearly complete. Preliminary measurements of droplet size effects on the minimum ignition energy for n-heptane sprays performed. Parameteric studies of droplet size effects on minimum ignition energies of various fuels including alcohols are in progress.

  19. Experiments on the effect of initial diameter in spherically symmetric droplet combustion of sooting fuels

    NASA Technical Reports Server (NTRS)

    Jackson, G. S.; Avedisian, C. T.

    1993-01-01

    The effect of initial droplet diameter on the burning rate of sooting fuels (n-heptane and 1-chloro-octane) is studied experimentally at low gravity. A 1.2 s drop tower provided a low gravity environment to minimize buoyancy and achieve spherically symmetric flames for stationary droplets. Free-floating and fiber supported droplets were burned, and both methods gave matching results for droplets of similar initial diameter.

  20. Efficient High-Pressure State Equations

    NASA Technical Reports Server (NTRS)

    Harstad, Kenneth G.; Miller, Richard S.; Bellan, Josette

    1997-01-01

    A method is presented for a relatively accurate, noniterative, computationally efficient calculation of high-pressure fluid-mixture equations of state, especially targeted to gas turbines and rocket engines. Pressures above I bar and temperatures above 100 K are addressed The method is based on curve fitting an effective reference state relative to departure functions formed using the Peng-Robinson cubic state equation Fit parameters for H2, O2, N2, propane, methane, n-heptane, and methanol are given.

  1. Transition from cool flame to thermal flame in compression ignition process

    SciTech Connect

    Yamada, Hiroyuki; Suzaki, Kotaro; Goto, Yuichi; Tezaki, Atsumu

    2008-07-15

    The mechanism that initiates thermal flames in compression ignition has been studied. Experimentally, a homogeneous charge compression ignition (HCCI) engine was used with DME, n-heptane, and n-decane. Arrhenius plots of the heat release rate in the HCCI experiments showed that rates of heat release with DME, n-heptane, and n-decane exhibited a certain activation energy that is identical to that of the H{sub 2}O{sub 2} decomposition reaction. The same feature was observed in diesel engine operation using ordinary diesel fuel with advanced ignition timing to make ignition occur after the end of fuel injection. These experimental results were reproduced in nondimensional simulations using kinetic mechanisms for DME, n-heptane, and n-decane, the last being developed by extending the n-heptane mechanism. Methanol addition, which suppresses low-temperature oxidation (LTO) and delays the ignition timing, had no effect on the activation energy obtained from the Arrhenius plot of heat release rate. Nevertheless, methanol addition lowered the heat release rates during the prethermal flame process. This is because H{sub 2}O{sub 2} formation during cool flame was reduced by adding methanol. The mechanism during the transition process from cool flame to thermal flame can be explained quantitatively using thermal explosion theory, in which the rate-determining reaction is H{sub 2}O{sub 2} decomposition, assuming that heat release in this period is caused by partial oxidation of DME and HCHO initiated with the reaction with OH produced though H{sub 2}O{sub 2} decomposition. (author)

  2. Adsorption from the liquid phase on silica gels of various structural heterogeneity

    SciTech Connect

    Goworek, J.; Derylo-Marczewska, A.; Borowka, A.

    1999-08-31

    Competition of liquid components for silica gel surface was tested for binary liquid mixtures: methanol + benzene and 2-propanol + n-heptane. The adsorption isotherms were measured using silica gels for column chromatography Si-40 and Si-100 from Merck. On the basis of specific surface excess isotherms the surface layer capacities were calculated. Taking into account the properties of the bulk solutions, the influence of geometrical structure of silicas on the composition of the surface phase is discussed.

  3. Fire Smoke Particle Size Measurement Based on the Multiwavelength and Multiangle Light Scattering Method

    NASA Astrophysics Data System (ADS)

    Shu, Xue-Ming; Fang, Jun; Shao, Quan; Yuan, Hong-Yong; Fan, Wei-Cheng

    2006-02-01

    A multiwavelength and multiangle mathematical model (MWMA) is developed, and the corresponding influence factors of the model are analysed by the numerical calculation. Combined with measurement data of radiation flux and the curve in theoretical calculation, particle sizes of different materials can be obtained. It is found that smoke particle size gradually decreases from land plaster, cotton wick, beech wood, polyurethane, sandalwood, decahydronaphthalene, to N-heptane.

  4. Study of Fischer-Tropsch model compounds reacting over ZSM-5. [MS Thesis

    SciTech Connect

    Riley, M.G.

    1984-08-01

    The decomposition of three Fischer-Tropsch model compounds (1-decanol, decanal, and n-heptane) over ZSM-5 catalysts ion exchanged with nickel, zinc, and hydrogen was studied. The mechanisms of decomposition and the reaction kinetics of the model compounds were investigated as well as how exchanging the ZSM-5 with different cations affected the mechanisms, kinetics, and product distribution. The mechanism for 1-decanol decomposition was found to be formation of di-n-decyl ether, which then dehydrated to form 1-decene. Decanal was seen to decompose by three different mecanisms: Aldol condensation, cleavage of CO to form n-nonane, and reduction to 1-decanol. Heptane was seen to follow classical carbonium ion chemistry. First order rate constants and activation energies were calculated for n-heptane/Ni-ZSM-5, 1-decanol/Ni-ZSM-5, 1-decanol/H-ZSM-5, decanal/Ni-ZSM-5, and decanal/H-ZSM-5. The activation energies for decomposition were found to be 21 +- 4 Kcal/gmole for 1-decanol to 1-decene; 32 +- 3 Kcal/gmole for n-heptane; and 15 +- 3 Kcal/gmole on Ni-ZSM-5 and 21 +- 1 Kcal/gmole on H-ZSM-5 for decanal decomposing to n-nonane and CO. H-ZSM-5 was determined to be the most active catalyst of the three tested for decomposition of oxygenates. N-ZSM-5 was the most effective catalyst in the cracking of n-heptane. Due to its superior ability to decompose oxygenates, H-ZSM-5 appears to be the best choice for a Fischer-Tropsch liquid up-grading catalyst. For Fischer-Tropsch liquids with high linear alkane contents a small amount of nickel or other dehydrogenation catalyst added to the H-ZSM-5 would probably prove beneficial. 26 references, 12 figures, 8 tables.

  5. Study of absorption spectra of gasolines and other hydrocarbon mixtures in the second overtone region of the CH3, CH2, CH groups

    NASA Astrophysics Data System (ADS)

    Muradov, V. G.; Sannikov, D. G.

    2007-03-01

    We have obtained experimental and model absorption spectra for individual hydrocarbons (toluene, benzene, n-heptane, and iso-octane) and their mixtures in the near IR range (? = 1080 1220 nm). We model the spectra of nonsynthetic gasolines obtained under the same conditions by combining the spectra of three pure hydrocarbons. We show that the octane number of the studied gasoline is linearly related to the toluene (or benzene) concentrations in the model mixture.

  6. Ignition Delays of Alkyl Thiophosphites with White and Red Fuming Nitric Acids Within Temperature Range 80 to -105 F

    NASA Technical Reports Server (NTRS)

    Miller, Riley O; Ladanyi, Dezso J

    1953-01-01

    Ignition delays of alkyl thiophosphites were obtained in a modified open-cup apparatus and a small-scale rocket engine apparatus. At -40 F, mixed alkyl thiophosphites gave short delays with white fuming nitric acid containing 2 percent water and red fuming nitric acids of widely varying compositions. At -40 F and higher, triethyl trithiophosphite blended with as much as 40 percent n-heptane gave satisfactory self-igniting properties at temperatures as low as -76 F.

  7. A convenient method for preparation of pure standards of peroxyacetyl nitrate for atmospheric analyses

    NASA Astrophysics Data System (ADS)

    Nielsen, Torben; Hansen, Anne Maria; Thomsen, Erling Lund

    Peroxyacetyl nitrate (PAN) is synthesized by nitration of peracetic acid (1.2 M), extracted by n- heptane, and purified with normal-phase high-performance liquid chromatography. The purified PAN solution is free of acetyl nitrate. The content of PAN is determined by means of hydrolysis of PAN into nitrite, and determination by ion chromatography of nitrite and nitrate (formed by oxidation of nitrite). The purified PAN solution is used for the calibration of the gas Chromatograph with electron capture detection.

  8. Interrelation between the structural and transport properties of pervaporation membranes with diffusion layers based on poly-?-benzyl-L-glutamate

    NASA Astrophysics Data System (ADS)

    Kononova, S. V.; Kremnev, R. V.; Baklagina, Yu. G.; Volchek, B. Z.; Vlasova, E. N.; Shabsels, B. M.; Romashkova, K. A.; Romanov, D. P.; Arkhipov, S. N.; Bogomazov, A. V.; Uchytil, P.

    2011-05-01

    The interrelation between the transport properties of pervaporation membranes (used to separate toluene-n-heptane mixtures) and the structure of poly-?-benzyl- L-glutamate diffusion layers has been studied. The decrease in the membrane selectivity while increasing the flux at the transition from 3 to 50 wt % toluene in the mixture under separation is accompanied by a change in the ordered structure of poly-?-benzyl- L-glutamate structure without variation in the ?-helical conformation of the polypeptide chain.

  9. 21 CFR 177.1630 - Polyethylene phthalate polymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... temperatures and times indicated: (a) Distilled water at 49 °C (120 °F) for 24 hours; (b) n-Heptane at 49 °C...) Specifications. (i) The food contact surface, when exposed to distilled water at 250 °F for 2 hours, yields...) Specifications. (i) The food contact surface, when exposed to distilled water at 250 °F for 2 hours...

  10. A tabulated chemistry approach for numerical modeling of diesel spray evaporation in a 'stabilized cool flame' environment

    SciTech Connect

    Kolaitis, D.I.; Founti, M.A.

    2006-04-15

    Droplet evaporation in a 'stabilized cool flame' environment leads to a homogeneous, heated air-fuel vapor mixture that can be subsequently either burnt or utilized in fuel-reforming applications for fuel cell systems. The paper investigates the locally occurring physico-chemical phenomena in an atmospheric pressure, diesel spray, stabilized cool flame reactor, utilizing a tabulated chemistry approach in conjunction with a two-phase, Eulerian-Lagrangian computational fluid dynamics code. Actual diesel oil physical properties are used to model spray evaporation in the two-phase simulations, whereas the corresponding chemistry is represented by n-heptane. A lookup table is constructed by performing a plethora of perfectly stirred reactor simulations, utilizing a semidetailed n-heptane oxidation chemical kinetics mechanism. The overall exothermicity of the preignition n-heptane oxidation chemistry and the fuel consumption rates are examined as a function of selected independent parameters, namely temperature, fuel concentration, and residence time; their influence on cool flame reactivity is thoroughly studied. It is shown that the tabulated chemistry approach allows accurate investigation of the chemical phenomena with low computational cost. The two-phase flow inside the stabilized cool flame reactor is simulated, utilizing the developed lookup table. Predictions are presented for a variety of test cases and are compared to available experimental data, with satisfactory agreement. Model validation tests indicate that prediction quality improves with increasing values of air temperature at the reactor's inlet. (author)

  11. Novel pyrromethene dyes with N-ethyl carbazole at the meso position: a comprehensive photophysical, lasing, photostability and TD-DFT study.

    PubMed

    Thorat, Kishor G; Kamble, Priyadarshani; Ray, Alok K; Sekar, Nagaiyan

    2015-07-14

    Two novel BODIPY (pyrromethene, PM) dyes containing N-ethyl carbazole at the meso position are synthesized and their photophysical properties in different solvents and the photochemical stabilities and laser performances in n-heptane are investigated. The n-heptane solution of the dyes was used as a gain medium in a constructed narrow band dye laser, pumped by a Q-switched (10 Hz) frequency-doubled (532 nm) Nd:YAG laser and the results gave enhanced photo stabilities and similar peak efficiencies of the synthesized dyes as compared to parent dye PM567. When substituted at the meso position with N-alkyl carbazole, photostability is found to be increased in comparison to PM567, and also when substituted at 2- and 6-positions with a benzyl group instead of an ethyl group along with N-ethyl carbazole at the meso position, the photo stability is further increased in n-heptane. A comprehensive study on structural, photophysical and electronic properties of dyes by means of DFT and TD-DFT in the solvents of various polarities has revealed remarkable characteristics of the BODIPY chromophore. PMID:26074136

  12. Structural and phase transformations during ball milling of titanium in medium of liquid hydrocarbons

    NASA Astrophysics Data System (ADS)

    Dorofeev, G. A.; Lubnin, A. N.; Lad'yanov, V. I.; Mukhgalin, V. V.; Puskkarev, B. E.

    2014-02-01

    It has been shown using X-ray diffraction, scanning electron microscopy, and chemical analysis that, upon ball milling of ?-titanium in liquid organic media (toluene and n-heptane), a nanocrystalline fcc phase is formed that is a metastable carbohydride Ti(C,H) deficient in hydrogen and carbon compared to stable carbohydrides. The dimensions of powder particles after milling in toluene and n-heptane differ substantially (are 5-10 and 20-30 ?m, respectively. It has been shown that the kinetics of the formation of Ti(C,H) is independent of the milling medium. The atomic ratios H/C in the products of mechanosynthesis agree well with those corresponding to the employed organic media, i.e., H/C = 1.1 for toluene and 2.3 for n-heptane. A solid-liquid mechanism of mechanosynthesis is suggested, which includes repeated processes of particle fracturing with the formation of fresh surfaces, adsorption of liquid hydrocarbons on these surfaces, and subsequent cold welding of the newly formed particles. It is assumed that the formation of the fcc phase in the process of milling is connected with the generation of stacking faults in ?-Ti. Upon annealing at 550C, the fcc phase decomposes with the formation of stable titanium carbide TiC (annealing in a vacuum) or stable titanium carbohydride and a ?-Ti(H) solid solution (annealing in argon) with a partial reverse transformation Ti(C,H) ? ?-Ti in both cases.

  13. Observations of soot during droplet combustion at low gravity - Heptane and heptane/monochloroalkane mixtures

    NASA Technical Reports Server (NTRS)

    Jackson, G. S.; Avedisian, C. T.; Yang, J. C.

    1992-01-01

    Experimental observations of the combustion of sooting fuel droplets, performed in a drop tower to create a low gravity environment, are reported. Free n-heptane droplets and suspended droplets of heptane, monochloroalkanes, and mixtures of monochloro-octane and heptane were studied. Initial droplet diameters ranged from 0.4 to 1.1. mm. The results suggest that soot may influence droplet vaporization rates. Spherical symmetry of the flame allowed for extended observation of soot agglomerates inside the droplet flame. Effects of slight convective flows were also observed, both through variations of natural convection around the suspended droplets and through variations in the drift velocities of the unsupported droplets. Slight convective flows around the suspended droplets reduced flame luminosity as well as soot accumulation inside the flame and increased droplet vaporization rates. Mixing monochloro-octane with n-heptane demonstrated the effectiveness of n-heptane in reducing soot emissions from the flames of the chlorinated fuels. Finally, trends of initial droplet diameter with burning rate were observed and may be linked to the effect of droplet size upon soot formation inside the flame.

  14. A reduced chemical kinetic model for IC engine combustion simulations with primary reference fuels

    SciTech Connect

    Ra, Youngchul; Reitz, Rolf D.

    2008-12-15

    A reduced chemical kinetic mechanism for the oxidation of primary reference fuel (PRF) has been developed and applied to model internal combustion engines. Starting from an existing reduced reaction mechanism for n-heptane oxidation, a new reduced n-heptane mechanism was generated by including an additional five species and their relevant reactions, by updating the reaction rate constants of several reactions pertaining to oxidation of carbon monoxide and hydrogen, and by optimizing reaction rate constants of selected reactions. Using a similar approach, a reduced mechanism for iso-octane oxidation was built and combined with the n-heptane mechanism to form a PRF mechanism. The final version of the PRF mechanism consists of 41 species and 130 reactions. Validation of the present PRF mechanism was performed with measurements from shock tube tests, and HCCI and direct injection engine experiments available in the literature. The results show that the present PRF mechanism gives reliable performance for combustion predictions, as well as computational efficiency improvements for multidimensional CFD simulations. (author)

  15. Reverse shape selectivity in the liquid-phase adsorption of xylene isomers in zirconium terephthalate MOF UiO-66.

    PubMed

    Moreira, Mariana A; Santos, Joo C; Ferreira, Alexandre F P; Loureiro, Jos M; Ragon, Florence; Horcajada, Patricia; Shim, Kyu-E; Hwang, Young-K; Lee, U-Hwang; Chang, Jong-S; Serre, Christian; Rodrigues, Alrio E

    2012-04-01

    Powder, agglomerates, and tablets of the microporous zirconium(IV) terephthalate metal-organic framework UiO-66 were evaluated for the selective adsorption and separation of xylene isomers in the liquid phase using n-heptane as the eluent. Pulse experiments, performed at 313 K in the presence of n-heptane, revealed the o-xylene preference of this material, which was further confirmed by binary and multicomponent breakthrough experiments in the presence of m- and p-xylene, resulting in selectivities at 313 K of 1.8 and 2.4 with regards to m-xylene and p-xylene, respectively. Additionally, because p-xylene is the less retained isomer, UiO-66 presents a selectivity pattern that is reverse of that of the xylenes' molecular dimension with respect to shape selectivity. The shaping of the material as tablets did not significantly change its selectivity toward the o-xylene isomer or toward p-xylene, which was the less retained isomer, despite a loss in capacity. Finally, the selectivity behavior of UiO-66 in the liquid n-heptane phase makes it a suitable material for o-xylene separation in the extract (heavy product) or p-xylene separation in the raffinate (light product) by simulated moving bed technology. PMID:22404208

  16. Stability and aerosolization of pressurized metered dose inhalers containing thymopentin nanoparticles produced using a bottom-up process.

    PubMed

    Tan, Yinhe; Yang, Zhiwen; Pan, Xin; Chen, Meiwan; Feng, Min; Wang, Lili; Liu, Hu; Shan, Ziyun; Wu, Chuanbin

    2012-05-10

    The objective of this study was to investigate the stability and aerosolization of pressurized metered dose inhalers (pMDIs) containing thymopentin nanoparticles. Thymopentin nanoparticles, fabricated by a bottom-up process, were suspended in hydrofluoroalkane (HFA) 134a together with cineole and/or n-heptane to produce pMDI formulations. The stability study of the pMDIs obtained was carried out at ambient temperature for 6 months. The amount of thymopentin and the aerosolization properties of pMDIs were determined using high-performance liquid chromatography (HPLC) and a twin-stage impinger (TSI), respectively. Based on the results, thymopentin nanoparticles were readily suspended in HFA 134a with the aid of cineole and/or n-heptane to form physically stable pMDI formulations, and more than 98% of the labeled amount of thymopentin and over 50% of the fine particle fraction (FPF) of the pMDIs were achieved. During storage, it was found that for all pMDIs more than 97% of the labeled amount of thymopentin and FPF greater than 47% were achieved. Moreover, the size of thymopentin nanoparticles in propellant containing cineole and n-heptane showed little change. It is, therefore, concluded that the pMDIs comprising thymopentin nanoparticles developed in this study were stable and suitable for inhalation therapy for systemic action. PMID:22343132

  17. Fuel-Specific Effect of Exhaust Gas Residuals on HCCI Combustion: A Modeling Study

    SciTech Connect

    Szybist, James P

    2008-01-01

    A modeling study was performed to investigate fuel-specific effects of exhaust gas recirculation (EGR) components on homogeneous charge compression ignition (HCCI) combustion at conditions relevant to the negative valve overlap (NVO) strategy using CHEMKIN-PRO. Four single-component fuels with well-established kinetic models were chosen: n-heptane, iso-octane, ethanol, and toluene. These fuels were chosen because they span a wide range of fuel chemistries, and produce a wide compositions range of complete stoichiometric products (CSP). The simulated engine conditions combined a typical spark ignition engine compression ratio (11.34) and high intake charge temperatures (500-550 K) that are relevant to NVO HCCI. It was found that over the conditions investigated, all the fuels had overlapping start of combustion (SOC) phasing, despite the wide range in octane number (RON = 0 to 120). The effect of the EGR components CO2 and H2O was to suppress the compression temperature because of their higher heat capacities, which retarded SOC. For a concentration of O2 higher than the stoichiometric amount, or excess O2, there was an effect of advancing SOC for n-heptane, iso-octane, and toluene, but SOC for ethanol was not advanced. Low temperature heat release (LTHR) for n-heptane was also found to be highly dependent on excess O2, and mild endothermic reaction was observed for cases when excess O2 was not present.

  18. Transition metal catalysis in the generation of petroleum: A genetic anomaly in Ordovician oils

    SciTech Connect

    Mango, F.D. )

    1992-10-01

    The transition metals, captured from sedimentary waters by chlorophyll, have been proposed as the catalytic agents that convert n-alkane biolipids into the rearranged light hydrocarbons in petroleum. Certain ancient oils (Ordovician) display a depletion in chlorophyll, suggesting that they may have been derived from sedimentary rocks also depleted in transition metals. These oils show anomalously high concentrations of n-heptane relative to their respective rearranged isoalkane and cycloalkane products. This extraordinary enrichment in light n-alkanes appears unique to the chlorophyll-deficient Ordovician oils. The high concentrations of n-heptane may have resulted from the thermal cracking of higher n-alkanes, which are known to be dominant components of the kerogenous precursors to the Ordovician oils. However, the methylhexanes, which have no thermolytic precursors enriched in the kerogenous source, show a proportionate increase in concentration. The contention, therefore, that thermal cracking might explain the n-heptane anomaly is untenable since a kerogenous starting material enriched in n-alkanes and depleted in isoalkanes cannot reasonably crack to a light hydrocarbon product enriched in both n-alkanes and isoalkanes. According to a postulated catalytic cycle, n-alkane and isoalkane concentrations are controlled by the relative rates of two divergent pathways. If the various transition metals that may catalyze these reactions differ in activity, then a unique distribution of metals created by a chlorophyll deficiency could explain the Ordovician anomaly.

  19. [Simulation of migration from internal can coatings].

    PubMed

    Uematsu, Yoko; Hirata, Keiko; Suzuki, Kumi; Iida, Kenji; Kaneko, Reiko; Kamata, Kunihiro; Miyamura, Akane

    2003-02-01

    Migration from can-coatings into retorted canned food simulants (canned oil and water, 121 degrees C, 30 min) was investigated through HPLC with a fluorescence detector and evaporative light scattering detector, and by measurements of residue on evaporation and consumption of potassium permanganate. HPLC analysis revealed that migration into the canned oil was hundreds of times more than that into n-heptane (25 degrees C, 60 min, the official test conditions according to the Japanese Food Sanitation Law), whereas it was similar to the migration into isooctane-butyl acetate mixtures (60 degrees C, 60 min), and that migration into the canned water was several times more than that into water (95 degrees C, 30 min, the official test conditions). Residue on evaporation for the n-heptane extract was several-fold lower than 30 ppm (the official limit), whereas that for the isooctane-butyl acetate mixtures exceeded 30 ppm. Consumption of potassium permanganate for the canned water was 30 times higher than that for the water extract (95 degrees C, 30 min). The official test conditions for can-coatings, in particular the use of n-heptane as an oil simulant, were suggested to lead to substantial underestimation of migration into canned food. PMID:12749194

  20. Purification of antibiotics from the biocontrol agent Streptomyces anulatus S37 by centrifugal partition chromatography.

    PubMed

    Couillerot, Olivier; Loqman, Souad; Toribio, Alix; Hubert, Jane; Gandner, La; Nuzillard, Jean-Marc; Ouhdouch, Yedir; Clment, Christophe; Barka, Essaid Ait; Renault, Jean-Hugues

    2014-01-01

    A novel actinomycete strain, Streptomyces anulatus S37, has been isolated from the rhizosphere of healthy Moroccan Vitis vinifera on the basis on its ability to promote grapevine growth and to induce natural defences against various phytopathogens. In the present work, the main bioactive metabolites produced by S. anulatus S37 were isolated. A crude n-BuOH extract of the S37 fermentation broth was firstly partitioned in a biphasic solvent system composed of n-heptane, methanol, and water (5:1.5:3.5, v/v). The most active organic fraction (1.1g) as revealed by TLC-bioautography was subsequently separated by a two-step centrifugal partition chromatography procedure. The first separation was performed in the ascending mode at 6mL/min with the biphasic solvent system n-heptane, ethyl acetate, methanol and water (2:1:2:1, v/v), to finally recover 40mg of a pure compound identified as streptochlorin by NMR spectroscopy. In a second separation, the solvent system n-heptane, acetonitrile, and water (5:5:4, v/v) was used in the ascending mode at 3mL/min to purify 135mg of nigericin and 53mg of piericidin A1. Assays performed with the three compounds have confirmed their inhibitory impact on the growth of Botryris cinerea in dual confrontation and also on V. vinifera L. plantlets. PMID:24291716

  1. The oxidation of a gasoline surrogate in the negative temperature coefficient region

    SciTech Connect

    Lenhert, David B.; Miller, David L.; Cernansky, Nicholas P.; Owens, Kevin G.

    2009-03-15

    This experimental study investigated the preignition reactivity behavior of a gasoline surrogate in a pressurized flow reactor over the low and intermediate temperature regime (600-800 K) at elevated pressure (8 atm). The surrogate mixture, a volumetric blend of 4.6% 1-pentene, 31.8% toluene, 14.0% n-heptane, and 49.6% 2,2,4-trimethyl-pentane (iso-octane), was shown to reproduce the low and intermediate temperature reactivity of full boiling range fuels in a previous study. Each of the surrogate components were examined individually to identify the major intermediate species in order to improve existing kinetic models, where appropriate, and to provide a basis for examining constituent interactions in the surrogate mixture. n-Heptane and 1-pentene started reacting at 630 K and 640 K, respectively, and both fuels exhibited a strong negative temperature coefficient (NTC) behavior starting at 700 and 710 K, respectively. Iso-octane showed a small level of reactivity at 630 K and a weak NTC behavior starting at 665 K. Neat toluene was unreactive at these temperatures. The surrogate started reacting at 630 K and exhibited a strong NTC behavior starting at 693 K. The extent of fuel consumption varied for each of the surrogate constituents and was related to their general autoignition behavior. Most of the intermediates identified during the surrogate oxidation were species observed during the oxidation of the neat constituents; however, the surrogate mixture did exhibit a significant increase in intermediates associated with iso-octane oxidation, but not from n-heptane. While neat toluene was unreactive at these temperatures, in the mixture it reacted with the radical pool generated by the other surrogate components, forming benzaldehyde, benzene, phenol, and ethyl-benzene. The observed n-heptane, iso-octane, and surrogate oxidation behavior was compared to predictions using existing kinetic models. The n-heptane model reasonably predicted the disappearance of the fuel, but overpredicted the formation of several of the smaller intermediates. The iso-octane model significantly overpredicted the reaction of the fuel and formation of the intermediates. The 1-pentene model reasonably predicted the fuel consumption, but underestimated the importance of radical addition to the double bond. The results of this study provide a critical experimental foundation for the investigation of surrogate mixtures and for validation of kinetic models. (author)

  2. New aromatic esters from Galinsoga parviflora.

    PubMed

    Afza, Nighat; Yasmeen, Shazia; Ferheen, Sadia; Malik, Abdul; Ali, Muhammad Irfan; Kalhoro, Mahboob Ali; Ifzal, Rehana

    2012-01-01

    Galinosoates A-C (1-3), new aromatic esters, have been isolated from the n-hexane soluble fraction of Galinsoga parviflora. Their structures were assigned from the spectral data including IR, HR-EI-MS, 1D and 2D NMR. PMID:22348678

  3. Molecular mechanism of hydrocarbons binding to the metalorganic framework

    SciTech Connect

    Sun, Xiuquan; Wick, Collin D.; Thallapally, Praveen K.; McGrail, B. Peter; Dang, Liem X.

    2011-01-07

    The adsorption and diffusivity of methane, ethane, n-butane, n-hexane and cyclohexane in a metal organic framework (MOF) with the organic linker tetrakis[4-(carboxyphenyl)oxamethyl]methane, the metal salt, Zn2+, and organic pillar, 4,4-bipyridin was studied using molecular dynamics simulations. For the n-alkanes, the longer the chain, the lower the free energy of adsorption, which was attributed to a greater number of contacts between the alkane and MOF. Cyclohexane had a slightly higher adsorption free energy than n-hexane. Furthermore, for cyclo- and n-hexane, there were no significant differences in adsorption free energies between systems with low to moderate loadings. The diffusivity of the n-alkanes was found to strongly depend on chain length with slower diffusion for longer chains. Cyclohexane had no effective diffusion, suggesting that the selectivity the MOF has towards n-hexane over cyclohexane is the result of kinetics instead of energetics. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  4. RATE CONSTANTS FOR THE REACTION OF OH RADICALS WITH A SERIES OF ALKENES AND DIALKENES AT 295 + OR - 1 K

    EPA Science Inventory

    Using a relative rate technique, rate constants for the gas phase reactions of the OH radical with n-butane, n-hexane and a series of alkenes and dialkenes, relative to that for propene, have been determined in one atmosphere of air at 295 + or - 1K. The resulting rate constant d...

  5. Adsorption capacity study of carbon nanopowder produced by laser pyrolisis

    NASA Astrophysics Data System (ADS)

    Sonu, Marcel; Savu, Ion; Pastean, Laurentiu; Voicu, Ion N.; Soare, Iuliana; Morjan, Ion G.; Grigoriu, Constantin

    2004-10-01

    The paper presents the experimental results on adsorption properties of carbon nanopowders which have been obtained by laser pyrolysis of hydrocarbon-based mixtures. We have investigated the adsorption of benzene, n-hexane and ciclohexane. The influence of the nanocarbon morphology (which depends on gaseous precursors and synthesis conditions) on adsorption characteristics is reported.

  6. Protective effect of Emilia sonchifolia (L.) against high protein diet induced oxidative stress in pancreas of Wistar rats

    PubMed Central

    Sophia, Dominic; Ragavendran, Paramasivam; Raj, Chinthamony Arul; Gopalakrishnan, Velliyur Kanniappan

    2012-01-01

    Objectives: The present study was undertaken to investigate the oxidative damage, the biochemical and histopathological changes in the pancreas of the Wistar rats which was fed high protein diet and the recovery after the oral administration of the n-hexane extract of the herb, Emilia sonchifolia. Materials and Methods: The rats fed with high protein diet for a period of 30 days and treated with n-hexane extract of Emilia sonchifolia (250 mg/kg body weight). Body weight, pancreatic weight, serum amylase, lipase, aspartate transaminase, alanine transaminase, urea, uric acid, creatinine, DNA and RNA content of the pancreas, pancreatic enzymatic and non-enzymatic antioxidants such as superoxide dismutase, catalase, glutathione peroxidase, reduced glutathione, and vitamin C were evaluated. Results and Discussion: At the end of the study the rats gained less body weight and showed a significant (P < 0.05) increase in serum levels of amylase, lipase, aspartate transaminase, alanine transaminase, urea, uric acid, creatinine, tissue DNA, and RNA content and showed a significant (P < 0.05) decrease in the pancreatic antioxidants. Treatment with the n-hexane extract ameliorated the damage caused by high protein diet. This was also evidenced by histopathological studies. Conclusion: From the results, it was suggested that the n-hexane extract of Emilia sonchifolia has an effective medicinal property and can act as a pancreato-protective herb. PMID:22368400

  7. In vitro antioxidant activity and inhibitory effect, on oleic acid-induced hepatic steatosis, of fractions and subfractions from oat (Avena sativa L.) ethanol extract

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Oats (Avena sativa L.) were extracted with 80% aqueous ethanol and the extract was successively isolated by liquid-liquid partition to yield n-hexane, ethyl acetate, n-butanol and water layers. Among these extractions the ethyl acetate (EA) layer exhibited the highest total phenolic content (TPC), t...

  8. 40 CFR 795.232 - Inhalation and dermal pharmacokinetics of commercial hexane.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... the Office of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. This material... reporting requirements as specified in 40 CFR part 792, the following information shall be reported. (i... and n-hexane. (C) Results of chromatography. (iii) A full description of the sensitivity,...

  9. 40 CFR 795.232 - Inhalation and dermal pharmacokinetics of commercial hexane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Director of the Office of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. This... reporting requirements as specified in 40 CFR part 792, the following information shall be reported. (i... and n-hexane. (C) Results of chromatography. (iii) A full description of the sensitivity,...

  10. Cytotoxicity and modulation of cancer-related signaling by (Z)- and (E)- 3,4,3´,5´ tetramethoxystilbene isolated from Eugenia rigida

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The leaves of E. rigida DC (Myrtaceae) were collected from Puerto Rico in March, 2006. The sample was identified by Mr. F. Axelrod and a voucher specimen (3008783) was deposited at the Herbarium of Missouri Botanical Garden, St. Louis, MO. Air-dried powdered leaves (107 g) were soaked in n-hexane an...

  11. Ethyl acetate-n-butanol gradient solvent system for high-speed countercurrent chromatography to screen bioactive substances in okra.

    PubMed

    Ying, Hao; Jiang, Heyuan; Liu, Huan; Chen, Fangjuan; Du, Qizhen

    2014-09-12

    High-speed countercurrent chromatographic separation (HSCCC) possesses the property of zero-loss of sample, which is very useful for the screening of bioactive components. In the present study, the ethyl acetate-n-butanol gradient HSCCC solvent system composed of n-hexane-ethyl acetate-n-butanol-water was investigated for the screening of bioactive substances. To screen the antiproliferative compounds in okra extract, we used the stationary phase ethyl acetate-n-butanol-water (1:1:10) as the stationary phase, and eluted the antiproliferative components by 6-steps of gradient using mobile phases n-hexane-ethyl acetate (1:2), n-hexane-ethyl acetate (1:4), n-hexane-ethyl acetate (0:4), n-butanol-ethyl acetate (1:4) n-butanol-ethyl acetate (1:2), n-butanol-ethyl acetate (2:2), and n-butanol-ethyl acetate (2:1). The fractions collected from HSCCC separation with the gradient solvent system were assayed for antiproliferative activity against cancer cells. Bioactive components were identified: a major anti-cancer compound, 4'-hydroxy phenethyl trans-ferulate, with middle activity, and a minor anti-cancer compound, carolignan, with strong activity. The result shows that the gradient solvent system is potential for the screening of bioactive compounds from natural products. PMID:25069743

  12. SPECTROFLUOROMETRIC AND HIGH-PERFORMANCE LIQUID CHROMATOGRAPHIC DETERMINATION OF a-TOCOPHEROL ACETATE IN OLIVE OIL

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A high performance liquid chromatographic (HPLC) method was developed for the quantitative determination of '-acetate tocopherol in olive oil. After extracts in n-hexane, acetate '- tocopherol were quantitatively analyzed by HPLC with fluorimetric detector. The presence of acetate '- tocopherol in...

  13. South American plants III: Isolation of fulvoplumierin from Himatanthus sucuuba (M. Arg.) Woodson (Apocynaceae).

    PubMed

    Perdue, G P; Blomster, R N

    1978-09-01

    The bark of Himatanthus sucuuba was screened for pharmacological and anticancer activities. The lactone, fulvoplumierin (C14H12O4), was isolated from the n-hexane fraction. The identity was proven by elemental analysis and IR, mass spectral, and melting-point determinations. Reference samples were used for comparison. PMID:690844

  14. Control of charcoal rot fungus Macrophomina phaseolina by extracts of Datura metel.

    PubMed

    Javaid, Arshad; Saddique, Amna

    2012-01-01

    Methanolic leaf and fruit extracts of Datura metel were found highly effective in suppressing against Macrophomina phaseolina, the cause of charcoal rot disease. These extracts were further subjected to successive fractionation with n-hexane, chloroform, ethyl acetate and n-butanol. All the concentrations (3.125-200?mg?mL?) of chloroform, ethyl acetate and n-butanol fractions of leaf extract, and n-hexane fraction of fruit extract completely inhibited the target fungal growth. Two compounds A and B from the n-hexane fraction of fruit extract and compound C from n-butanol fraction of leaf extract were obtained by TLC. Compound B exhibited the best antifungal activity with an MIC value of 7.81?g?mL? that was at par with that of commercial fungicide mancozeb (80% w/w). This study concludes that M. phaseolina can be effectively controlled by natural antifungal compounds in n-hexane fraction of methanolic fruit extract of D. metel. PMID:22004473

  15. Fischer-Tropsch synthesis in supercritical reaction media. Progress report, October 1, 1992--December 31, 1992

    SciTech Connect

    Subramaniam, B.; Bochniak, D.; Snavely, K.

    1993-01-01

    Our goals for this quarter were to complete construction of the reactor and analytical units for carrying out Fischer-Tropsch (F-T) synthesis in liquid (n-hexadecane) and in supercritical n-hexane phases. Progress during this quarter was slower than expected.

  16. Fischer-Tropsch synthesis in supercritical reaction media

    SciTech Connect

    Subramaniam, B.; Bochniak, D.; Snavely, K.

    1993-01-01

    Our goals for this quarter were to complete construction of the reactor and analytical units for carrying out Fischer-Tropsch (F-T) synthesis in liquid (n-hexadecane) and in supercritical n-hexane phases. Progress during this quarter was slower than expected.

  17. [Chromatographic separation of aminoglutethimide enantiomers on cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phase].

    PubMed

    Lin, Xiaoiian; Gong, Rujin; Li, Ping; Yu, Jianguo

    2014-08-01

    Aminoglutethimide (AG) has been used clinically as a drug in the treatment of hormone-dependent metastatic breast cancer. It was reported that S-(-)-AG enantiomer had small activity and sometimes might cause side effects. Therefore, it was of great significance to obtain the high-purity R-(+)-AG by enantioseparation. In this work, aminoglutethimide enantiomers were separated by high performance liquid chromatography (HPLC) using an analytical column which was packed with cellulose tris(3,5-dimethylphenylcarbamate) stationary phase (Chiralcel OD-H). The solubilities of racemic AG in two different solvent compositions, n-hexane/ethanol and n-hexane/isopropanol, were measured, separately. The effects of alcohol content and monoethanolamine additive on the separation performance of racemic AG by HPLC were investigated. According to the experiments, n-hexane-ethanol (30:70, v/v) with 0.1% monoethanolamine additive was selected as the mobile phase. The separation factor, resolution, asymmetry factor, number of theoretical plates and maximum column capacity were measured and analyzed for the chromatographic separation of racemic AG at a flow-rate of 0. 6 mL/min and column temperature of 25-40 °C, with Chiralcel OD-H as stationary phase and n-hexane-ethanol (30:70, v/v) with 0. 1% monoethanolamine as mobile phase. This work provides the basic information of chromatographic separation for the batch and continuous production of aminoglutethimide enantiomers. PMID:25434126

  18. Neuropathy in a petrol sniffer.

    PubMed Central

    Hall, D M; Ramsey, J; Schwartz, M S; Dookun, D

    1986-01-01

    A 4 year old boy developed a profound motor neuropathy after repeated deliberate inhalation of petroleum vapour. The condition was characterised by extreme slowing of the nerve conduction velocity. He made a gradual recovery over six months. The neuropathy was attributed to the N-hexane component of petroleum. PMID:3021070

  19. VANADIUM PHOSPHORUS OXIDE AS AN EFFICIENT CATALYST FOR HYDROCARBON OXIDATIONS USING HYDROGEN PEROXIDE

    EPA Science Inventory

    Calcined vanadium phosphorus oxide (VPO) prepared by an organic route is found to be an efficient catalyst for the oxidation of various alkanes such as cyclopentane, cyclohexane, n-hexane, cycloheptane, cyclooctane, cyclodecane and adamantane in acetonitrile solvent using the env...

  20. KINETICS AND SELECTIVITY OF DEEP CATALYTIC OXIDATION OF VOLATILE ORGANIC COMPOUND MIXTURES

    EPA Science Inventory

    The paper gives results of a fundamental study of low-temperature deep (complete) oxidation of n-hexane, benzene, and ethyl-acetate over a 0.1% Pt, 3% Ni/gamma-AL203 catalyst. (NOTE: Deep catalytic combustion of volatile organic compounds--VOCs--is emerging as an important emissi...

  1. Effect of Polarity of Activated Carbon Surface, Solvent and Adsorbate on Adsorption of Aromatic Compounds from Liquid Phase.

    PubMed

    Goto, Tatsuru; Amano, Yoshimasa; Machida, Motoi; Imazeki, Fumio

    2015-01-01

    In this study, introduction of acidic functional groups onto a carbon surface and their removal were carried out through two oxidation methods and outgassing to investigate the adsorption mechanism of aromatic compounds which have different polarity (benzene and nitrobenzene). Adsorption experiments for these aromatics in aqueous solution and n-hexane solution were conducted in order to obtain the adsorption isotherms for commercial activated carbon (BAC) as a starting material, its two types of oxidized BAC samples (OXs), and their outgassed samples at 900 °C (OGs). Adsorption and desorption kinetics of nitrobenzene for the BAC, OXs and OGs in aqueous solution were also examined. The results showed that the adsorption of benzene molecules was significantly hindered by abundant acidic functional groups in aqueous solution, whereas the adsorbed amount of nitrobenzene on OXs gradually increased as the solution concentration increased, indicating that nitrobenzene can adsorb favourably on a hydrophilic surface due to its high dipole moment, in contrast to benzene. In n-hexane solution, it was difficult for benzene to adsorb on any sample owing to the high affinity between benzene and n-hexane solvent. On the other hand, adsorbed amounts of nitrobenzene on OXs were larger than those of OGs in n-hexane solution, implying that nitrobenzene can adsorb two adsorption sites, graphene layers and surface acidic functional groups. The observed adsorption and desorption rate constants of nitrobenzene on the OXs were lower than those on the BAC due to disturbance of diffusion by the acidic functional groups. PMID:26329866

  2. Novel modified zeolites for energy-efficient hydrocarbon separations.

    SciTech Connect

    Arruebo, Manuel; Dong, Junhang; Anderson, Thomas (Burns and McDonnell, Kansas City, MO); Gu, Xuehong; Gray, Gary (Goodyear Chemical Company, Akron, OH); Bennett, Ron (Goodyear Chemical Company, Akron, OH); Nenoff, Tina Maria; Kartin, Mutlu; Johnson, Kaylynn (Goodyear Chemical Company, Akron, OH); Falconer, John; Noble, Richard

    2006-11-01

    We present synthesis, characterization and testing results of our applied research project, which focuses on the effects of surface and skeletal modification of zeolites for significant enhancements in current hydrocarbon (HC) separations. Zeolites are commonly used by the chemical and petroleum industries as catalysts and ion-exchangers. They have high potential for separations owing to their unique pore structures and adsorption properties and their thermal, mechanical and chemical properties. Because of zeolites separation properties, low cost, and robustness in industrial process, they are natural choice for use as industrial adsorbents. This is a multidisciplinary effort to research, design, develop, engineer, and test new and improved materials for the separation of branched vs. linear organic molecules found in commercially important HC streams via adsorption based separations. The focus of this project was the surface and framework modification of the commercially available zeolites, while tuning the adsorption properties and the selectivities of the bulk and membrane separations. In particular, we are interested with our partners at Goodyear Chemical, on how to apply the modified zeolites to feedstock isoprene purification. For the characterization and the property measurements of the new and improved materials powder X-ray diffraction (PXRD), Residual Gas Analyzer-Mass Spectroscopy (RGA-MS), Electron Microscopy (SEM/EDAX), temperature programmed desorption (TPD) and surface area techniques were utilized. In-situ carbonization of MFI zeolite membranes allowed for the maximum separation of isoprene from n-pentane, with a 4.1% enrichment of the binary stream with n-pentane. In four component streams, a modified MFI membrane had high selectivities for n-pentane and 1-3-pentadiene over isoprene but virtually no separation for the 2-methyl-2-butene/isoprene pair.

  3. Hydrostatic limits of 11 pressure transmitting media

    NASA Astrophysics Data System (ADS)

    Klotz, S.; Chervin, J.-C.; Munsch, P.; LeMarchand, G.

    2009-04-01

    We present a systematic and comparative study of the pressure-induced solidification of 11 frequently used pressure transmitting fluids using the ruby fluorescence technique in a diamond anvil cell. These fluids are 1 : 1 and 5 : 1 iso-n pentane, 4 : 1 deuterated methanol-ethanol, 16 : 3 : 1 deuterated methanol-ethanol-water, 1 : 1 FC84-FC87 Fluorinert, Daphne 7474, silicone oil, as well as nitrogen, neon, argon and helium. The data provide practical guidelines for the use of these fluids in high pressure experiments up to 50 GPa.

  4. Investigation of Molecular Exchange Using DEXSY with Ultra-High Pulsed Field Gradients

    NASA Astrophysics Data System (ADS)

    Gratz, Marcel; Galvosas, Petrik

    2008-12-01

    Diffusion exchange spectroscopy has been employed for the investigation of water exchange between different regions of a cosmetic lotion as well as for the exchange of n-pentane between the inter- and intra-crystalline space in zeolite NaX. We successfully combined this two-dimensional (2D) NMR experiment with methods for the application of ultra-high pulsed field gradients of up to 35 T/m, resulting in observation times and mixing times as short as 2 ms and 2.8 ms, respectively.

  5. Investigation of Molecular Exchange Using DEXSY with Ultra-High Pulsed Field Gradients

    SciTech Connect

    Gratz, Marcel; Galvosas, Petrik

    2008-12-05

    Diffusion exchange spectroscopy has been employed for the investigation of water exchange between different regions of a cosmetic lotion as well as for the exchange of n-pentane between the inter- and intra-crystalline space in zeolite NaX. We successfully combined this two-dimensional (2D) NMR experiment with methods for the application of ultra-high pulsed field gradients of up to 35 T/m, resulting in observation times and mixing times as short as 2 ms and 2.8 ms, respectively.

  6. Efficient analysis of highly complex nuclear magnetic resonance spectra of flexible solutes in ordered liquids by using molecular dynamics

    NASA Astrophysics Data System (ADS)

    Weber, Adrian C. J.; Pizzirusso, Antonio; Muccioli, Luca; Zannoni, Claudio; Meerts, W. Leo; de Lange, Cornelis A.; Burnell, E. Elliott

    2012-05-01

    The NMR spectra of n-pentane as solute in the liquid crystal 5CB are measured at several temperatures in the nematic phase. Atomistic molecular dynamics simulations of this system are carried out to predict the dipolar couplings of the orientationally ordered pentane, and the spectra predicted from these simulations are compared with the NMR experimental ones. The simulation predictions provide an excellent starting point for analysis of the experimental NMR spectra using the covariance matrix adaptation evolutionary strategy. This shows both the power of atomistic simulations for aiding spectral analysis and the success of atomistic molecular dynamics in modeling these anisotropic systems.

  7. Anti-inflammatory, Anti-estrogenic, and Anti-implantation Activity of Bergia suffruticosa (Delile) Fenzl

    PubMed Central

    Bind, Sandeep Kumar; Jivrajani, Mehul; Anandjiwala, Sheetal; Nivsarkar, Manish

    2015-01-01

    Background: Bergia suffruticosa (Delile) Fenzl (Syn. Bergia odorata Edgew) (Elatinaceae family) is used traditionally to repair bones and is applied as a poultice on sores. It is also used for stomach troubles and as an antidote to scorpion stings. So far, very little scientific work has been reported to validate its ethnomedical uses in the alleviation of pain, bone repair, etc., Objective: This study was designed to explore the anti-inflammatory and anti-implantation potential of n-hexane extract of B. suffruticosa whole plant in mice along with identification of its chemical constituents. Materials and Methods: n-Hexane extract of B. suffruticosa whole plant was screened for acute and chronic anti-inflammatory activity followed by an anti-estrogenic activity. Eventually, n-hexane extract was tested for anti-implantation activity by exploiting markers of uterine receptivity, lipid peroxidation, and superoxide enzyme activity. The extract was administered orally at a dose of 100 mg/kg body weight in each study. Results: Thin layer chromatography fingerprint profile of n-hexane extract revealed the presence of lupeol and β-sitosterol. The n-hexane extract reduced the edema by 80% in acute inflammation, whereas it reduced edema to 75% on the 5th day in chronic inflammation. The n-hexane extract reduced elevated malonaldehyde level from 6 to 2.5 nmol/g × 10−5 and increased superoxide dismutase enzyme activity from 0 to 350 units/g in treated animals on the 5th day of pregnancy. Moreover, extract decreased uterine weight from 0.33 to 0.2 g in estradiol treated animals. Conclusion: These results indicate that n-hexane extract of B. suffruticosa is having potent anti-inflammatory, anti-estrogenic, and anti-implantation activity. This is the first report of all the pharmacological activities of B. suffruticosa mentioned above. SUMMARY TLC fingerprint profile of n-hexane extract of Bergia suffruticosa whole plant revealed the presence of lupeol and β-sitosteroln-Hexane extract showed in vivo anti-inflammatory activity in both acute and chronic model of inflammation in ratsn-Hexane extract possess significant anti-estrogenic activityn-Hexane extract altered the levels superoxide anion radical and superoxide dismutase enzyme activity during the blastocyst implantationAnti-implantation activity of n-hexane extract is attributed to its anti-inflammatory and anti-estrogenic potential. Abbreviations used: TLC: Thin layer chromatography; LPO: Lipid peroxidation; SOD: Superoxide dismutase; B. suffruticosa: Bergia suffruticosa; TNF-α: Tumor necrosis factor-α; NO: Nitric oxide; IL-1: Interleukin-1; LIF: Leukemia inhibitory factor; CSF-1: Colony-stimulating factor; COX: Cyclooxygenase; SDS: Sodium dodecyl sulfate; IAEC: Animal House Ethics Committee; CPCSEA: Committee for the Purpose of Control and Supervision of Experiments on Animals; HBSS: Hank's balanced salt solution; MDA: Malonaldehyde; and TBA: Thiobarbituric acid. PMID:26929574

  8. Simple solvothermal synthesis of hydrophobic magnetic monodispersed Fe{sub 3}O{sub 4} nanoparticles

    SciTech Connect

    Liu, Jing; Wang, Lu; Wang, Jing; Zhang, Lantong

    2013-02-15

    Graphical abstract: A facile method to produce monodispersed magnetite nanoparticles is based on the solvothermal reaction of iron acetylacetonate (Fe(acac)3) decomposition. The sizes ranged from 7 to 12 nm, which could be controlled by adjusting the volume ratio of oleylamine to n-hexane. Display Omitted Highlights: ► The solvethermal reaction of Fe(acac){sub 3} decomposition was carried out at mild temperature in the presence of oleylamine and n-hexane. ► The size of nanocrystals is controlled by adjusting the volume ratio of oleylamine to n-hexane. ► The low-boiling-point solvent n-hexane offered autogenous pressure parameter after gasified in the reaction temperature. ► The as prepared hydrophobic monodisperse Fe{sub 3}O{sub 4} NPs can be used to prepare the magnetic micelles for future biomedical applications. -- Abstract: A new solvothermal method is proposed for the preparation of Fe{sub 3}O{sub 4} nanoparticles (NPs) from iron acetylacetonate in the presence of oleylamine and n-hexane. The products are characterized by X-ray powder diffraction, infrared (IR) spectroscopy, transmission electron microscopy, thermogravimetry/differential thermogravimetry (TG/DTG) analysis, and vibrating sample magnetometery. The new procedure yields superparamagnetic monodispersed Fe{sub 3}O{sub 4} particles with sizes ranging from 7 nm to 12 nm. The nanocrystal sizes are controlled by adjusting the volume ratio of oleylamine to n-hexane. IR and TG/DTG analyses indicate that the oleylamine molecules, as stabilizers, are adsorbed on the surface of Fe{sub 3}O{sub 4} NPs as bilayer adsorption models. The surface adsorption quantities of oleylamine on 7.5 and 10.4 nm-diameter Fe{sub 3}O{sub 4} NPs are 18% and 11%, respectively. The hydrophobic surface of the obtained nanocrystals is passivated by adsorbed organic solvent molecules. These molecules provide stability against agglomeration, enable solubility in nonpolar solvents, and allow the formation of magnetic polymer micelles.

  9. Molecular dynamics simulation study of solvent effects on conformation and dynamics of polyethylene oxide and polypropylene oxide chains in water and in common organic solvents

    NASA Astrophysics Data System (ADS)

    Hezaveh, Samira; Samanta, Susruta; Milano, Giuseppe; Roccatano, Danilo

    2012-03-01

    In this paper, the conformation and dynamics properties of polyethylene oxide (PEO) and polypropylene oxide (PPO) polymer chains at 298 K have been studied in the melt and at infinite dilution condition in water, methanol, chloroform, carbon tetrachloride, and n-heptane using molecular dynamics simulations. The calculated density of PEO melt with chain lengths of n = 2, 3, 4, 5 and, for PPO, n = 7 are in good agreement with the available experimental data. The conformational properties of PEO and PPO show an increasing gauche preference for the O-C-C-O dihedral in the following order water>methanol>chloroform>carbon tetrachloride = n-heptane. On the contrary, the preference for trans conformation has a maximum in carbon tetrachloride and n-heptane followed in the order by chloroform, methanol, and water. The PEO conformational preferences are in qualitative agreement with results of NMR studies. PEO chains formed different types of hydrogen bonds with polar solvent molecules. In particular, the occurrence of bifurcated hydrogen bonding in chloroform was also observed. Radii of gyration of PEO chains of length larger than n = 9 monomers showed a good agreement with light scattering data in water and in methanol. For the shorter chains the observed deviations are probably due to the enhanced hydrophobic effects caused by the terminal methyl groups. For PEO the fitting of end-to-end distance distributions with the semi-flexible chain model at 298 K provided persistence lengths of 0.375 and 0.387 nm in water and methanol, respectively. Finally, the radius of gyration of Pluronic P85 turned out to be 2.25 0.4 nm at 293 K in water in agreement with experimental data.

  10. The Effects of Fuel Composition and Compression Ratio on Thermal Efficiency in an HCCI Engine

    SciTech Connect

    Szybist, James P; Bunting, Bruce G

    2007-01-01

    The effects of variable compression ratio (CR) and fuel composition on thermal efficiency were investigated in a homogeneous charge compression ignition (HCCI) engine using blends of n-heptane and toluene with research octane numbers (RON) of 0 to 88. Experiments were conducted by performing CR sweeps at multiple intake temperatures using both unthrottled operation, and constant equivalence ratio conditions by throttling to compensate for varying air density. It was found that CR is effective at changing and controlling HCCI combustion phasing midpoint, denoted here as CA 50. Thermal efficiency was a strong function of CA 50, with overly advanced CA 50 leading to efficiency decreases. Increases in CR at a constant CA 50 for a given fuel composition did, in most cases, increase efficiency, but the relationship was weaker than the dependence of efficiency on CA 50. The increase in efficiency with higher CR was fuel-dependent, so that the fuels requiring a higher CR to achieve ignition did not gain a proportionate efficiency increase. For example, n-heptane achieved an indicated thermal efficiency (ITE) of 38% at a CR of 9:1, whereas a 50 wt% blend of toluene with n-heptane required a CR of 12:1 to achieve the same ITE. A simple heat balance around the engine showed that higher toluene content fuels had higher cooling losses. The high toluene fuels exhibited higher rates of maximum pressure rise than the lower octane fuels. The increased cooling losses can be attributed to the higher pressure rise rates, which are a driving force for heat transfer.

  11. Structure and dynamics of 1,2-dimethoxyethane and 1,2-dimethoxypropane in aqueous and non-aqueous solutions: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Hezaveh, Samira; Samanta, Susruta; Milano, Giuseppe; Roccatano, Danilo

    2011-10-01

    Herein, we report a comparative modelling study of 1,2-dimethoxyethane (DME) and 1,2-dimethoxypropane (DMP) at 298 K and 318 K in the liquid state, water mixtures, and at infinite dilution condition in water, methanol, carbon tetrachloride, and n-heptane. Both DME and DMP are united-atom models compatible with GROMOS/OPLS force fields. Calculated thermodynamic and structural properties of the pure DME and DMP liquids resulted in excellent agreement with the experimental data. In aqueous solutions, densities, diffusion coefficients, and concentration dependent conformers of DME, were in agreement with experimental data. The calculated free energy of solvation (?Ghyd) at 298 K is equal to -22.1 0.8 kJ mol-1 in good agreement with the experimental value of 20.2 kJ mol-1. In addition, the free energy of solvation of DME in non-aqueous solvents follows the trend methanol ? water < carbon tetrachloride < n-heptane, consistently with the dielectric constant of the solvents. On contrary, the presence of an extra methyl group on chiral carbon makes DMP less soluble than DME in water (?Ghyd = -16.0 1.1 kJ mol-1) but more soluble in non-polar solvents as n-heptane. Finally, for the DMP the chiral discrimination of the two enantiomers was calculated as solvation free energy difference of one DMP isomer in the solution of the other. The obtained value of ??GRS = -3.7 1.4 kJ mol-1 indicates a net chiral discrimination of the two enantiomers.

  12. Autoignition of toluene reference fuels at high pressures modeled with detailed chemical kinetics

    SciTech Connect

    Andrae, J.C.G.; Bjoernbom, P.; Cracknell, R.F.; Kalghatgi, G.T.

    2007-04-15

    A detailed chemical kinetic model for the autoignition of toluene reference fuels (TRF) is presented. The toluene submechanism added to the Lawrence Livermore Primary Reference Fuel (PRF) mechanism was developed using recent shock tube autoignition delay time data under conditions relevant to HCCI combustion. For two-component fuels the model was validated against recent high-pressure shock tube autoignition delay time data for a mixture consisting of 35% n-heptane and 65% toluene by liquid volume. Important features of the autoignition of the mixture proved to be cross-acceleration effects, where hydroperoxy radicals produced during n-heptane oxidation dramatically increased the oxidation rate of toluene compared to the case when toluene alone was oxidized. Rate constants for the reaction of benzyl and hydroperoxyl radicals previously used in the modeling of the oxidation of toluene alone were untenably high for modeling of the mixture. To model both systems it was found necessary to use a lower rate and introduce an additional branching route in the reaction between benzyl radicals and O{sub 2}. Good agreement between experiments and predictions was found when the model was validated against shock tube autoignition delay data for gasoline surrogate fuels consisting of mixtures of 63-69% isooctane, 14-20% toluene, and 17% n-heptane by liquid volume. Cross reactions such as hydrogen abstractions between toluene and alkyl and alkylperoxy radicals and between the PRF were introduced for completion of chemical description. They were only of small importance for modeling autoignition delays from shock tube experiments, even at low temperatures. A single-zone engine model was used to evaluate how well the validated mechanism could capture autoignition behavior of toluene reference fuels in a homogeneous charge compression ignition (HCCI) engine. The model could qualitatively predict the experiments, except in the case with boosted intake pressure, where the initial temperature had to be increased significantly in order to predict the point of autoignition. (author)

  13. A comprehensive detailed chemical kinetic reaction mechanism for combustion of n-alkane hydrocarbons from n-octane to n-hexadecane

    SciTech Connect

    Westbrook, Charles K.; Pitz, William J.; Herbinet, Olivier; Silke, Emma J.; Curran, Henry J.

    2009-01-15

    Detailed chemical kinetic reaction mechanisms have been developed to describe the pyrolysis and oxidation of nine n-alkanes larger than n-heptane, including n-octane (n-C{sub 8}H{sub 18}), n-nonane (n-C{sub 9}H{sub 20}), n-decane (n-C{sub 10}H{sub 22}), n-undecane (n-C{sub 11}H{sub 24}), n-dodecane (n-C{sub 12}H{sub 26}), n-tridecane (n-C{sub 13}H{sub 28}), n-tetradecane (n-C{sub 14}H{sub 30}), n-pentadecane (n-C{sub 15}H{sub 32}), and n-hexadecane (n-C{sub 16}H{sub 34}). These mechanisms include both high temperature and low temperature reaction pathways. The mechanisms are based on previous mechanisms for the primary reference fuels n-heptane and iso-octane, using the reaction classes first developed for n-heptane. Individual reaction class rules are as simple as possible in order to focus on the parallelism between all of the n-alkane fuels included in the mechanisms. These mechanisms are validated through extensive comparisons between computed and experimental data from a wide variety of different sources. In addition, numerical experiments are carried out to examine features of n-alkane combustion in which the detailed mechanisms can be used to compare reactivities of different n-alkane fuels. The mechanisms for these n-alkanes are presented as a single detailed mechanism, which can be edited to produce efficient mechanisms for any of the n-alkanes included, and the entire mechanism, with supporting thermochemical and transport data, together with an explanatory glossary explaining notations and structural details, is available for download from our web page. (author)

  14. Theoretical study of binding and permeation of ether-based polymers through interfaces.

    PubMed

    Samanta, Susruta; Hezaveh, Samira; Roccatano, Danilo

    2013-11-27

    We present a molecular dynamics simulation study on the interactions of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and their ABA-type block copolymer, poloxamers, at water/n-heptane and 1,2-dimyristoyl-sn-glycero-3-phospatidycholine (DMPC) lipid bilayer/water interfaces. The partition coefficients in water/1-octanol of the linear polyethers up to three monomers were calculated. The partition coefficients evidenced a higher hydrophobicity of the PPO in comparison to PEO. At the water/n-heptane interface, the polymers tend to adopt elongated conformations in agreement with similar experimental ellipsometry studies of different poloxamers. In the case of the poloxamers at the n-heptane/water interface, the stronger preference of the PPO block for the hydrophobic phase resulted in bottle-brush-type polymer conformations. At lipid bilayer/water interface, the PEO polymers, as expected from their hydrophilic nature, are weakly adsorbed on the surface of the lipid bilayer and locate in the water phase close to the headgroups. The free energy barriers of permeation calculated for short polymer chains suggest a thermodynamics propensity for the water phase that increase with the chain length. The lower affinity of PEO for the hydrophobic interior of the lipid bilayer resulted in the spontaneous expulsion within the simulation time. On the contrary, PPO chains and poloxamers have a longer residence time inside the bilayer, and they tend to concentrate in the tail region of the bilayer near the polar headgroups. In addition, polymers with PPO unit length comparable to the thickness of the hydrophobic region of the bilayer tend to span across the bilayer. PMID:24219592

  15. Recent Advances In Science Support For Isolated Droplet Combustion Experiments

    NASA Technical Reports Server (NTRS)

    Dryer, F. L.; Kazakov, A.; Urban, B. D.; Kroenlein, K.

    2003-01-01

    In a joint program involving Prof. F.A. Williams of the University of California, San Diego and Dr. V. Nayagam of the National Center for Microgravity Research, the combustion characteristics of isolated liquid fuel droplets of n-heptane, n-decane, methanol, methanol-water, ethanol and ethanol-water having initial diameters between about 1 mm and 6 mm continues to be investigated. The objectives of the work are to improve fundamental knowledge of droplet combustion dynamics for pure fuels and fuel-water mixtures through microgravity experiments and theoretical analyses. The Princeton contributions support the engineering design, data analysis, and data interpretation requirements for the study of initially single component, spherically symmetric, isolated droplet combustion studies through experiments and numerical modeling. UCSD contributions are described in a companion communication in this conference. The Princeton effort also addresses the analyses of Fiber Supported Droplet Combustion (FSDC) experiments conducted with the above fuels and collaborative work with others who are investigating droplet combustion in the presence of steady convection. A thorough interpretation of droplet burning behavior for n-heptane and n-decane over a relatively wide range of conditions also involves the influences of sooting on the combustion behavior, and this particular aspect on isolated burning of droplets is under consideration in a collaborative program underway with Drexel University. This collaboration is addressed in another communication at this conference. The one-dimensional, time-dependent, numerical modeling approach that we have continued to evolve for analyzing isolated, quiescent droplet combustion data has been further applied to investigate several facets of isolated droplet burning of simple alcohols, n-heptane, and n-decane. Some of the new results are described below.

  16. Self-ignition of S.I. engine model fuels: A shock tube investigation at high pressure

    SciTech Connect

    Fieweger, K.; Blumenthal, R.; Adomeit, G.

    1997-06-01

    The self-ignition of several spark-ignition (SI) engine fuels (iso-octane, methanol, methyl tert-butyl ether and three different mixtures of iso-octane and n-heptane), mixed with air, was investigated experimentally under relevant engine conditions by the shock tube technique. Typical modes of the self-ignition process were registered cinematographically. For temperatures relevant to piston engine combustion, the self-ignition process always starts as an inhomogeneous, deflagrative mild ignition. This instant is defined by the ignition delay time, {tau}{sub defl}. The deflagration process in most cases is followed by a secondary explosion (DDT). This transition defines a second ignition delay time, {tau}{sub DDT}, which is a suitable approximation for the chemical ignition delay time, if the change of the thermodynamic conditions of the unburned test gas due to deflagration is taken into account. For iso-octane at p = 40 bar, a NTC (negative temperature coefficient), behavior connected with a two step (cool flame) self-ignition at low temperatures was observed. This process was very pronounced for rich and less pronounced for stoichiometric mixtures. The results of the {tau}{sub DDT} delays of the stoichiometric mixtures were shortened by the primary deflagration process in the temperature range between 800 and 1,000 K. Various mixtures of iso-octane and n-heptane were investigated. The results show a strong influence of the n-heptane fraction in the mixture, both on the ignition delay time and on the mode of self-ignition. The self-ignition of methanol and MTBE (methyl tert-butyl ether) is characterized by a very pronounced initial deflagration. For temperatures below 900 K (methanol: 800 K), no secondary explosion occurs. Taking into account the pressure increase due to deflagration, the measured delays {tau}{sub DDT} of the secondary explosion are shortened by up to one order of magnitude.

  17. Photoisomerization and reorientational mobility of symmetric carbocyanines in AOT/alkane/polar solvent microemulsions

    NASA Astrophysics Data System (ADS)

    Dandapat, Manika; Basu, Saswati; Ghosh, Deborin; Mandal, Debabrata

    2014-07-01

    Molecular motion of carbocyanine fluorophores DOCI, DODCI and DTDCI were studied in AOT/n-heptane microemulsions containing added polar solvents: water, methanol or acetonitrile. The response varied remarkably depending on the nature of the fluorophore and polar solvent. When the amount of added polar solvent was low, molecular mobility was invariably retarded, due to a combination of electrostatic and hydrophobic forces that induce the guest fluorophore to cling to the AOT molecules of the host reverse micelle. However, at high amounts of added methanol or water, these interactions diminished considerably, causing increase in the mobility of the guest fluorophores up to different extents.

  18. Imaging the Dynamics of Cl(^2P3/2) Reactions with Selected Hydrocarbons

    NASA Astrophysics Data System (ADS)

    Visger, Laura; Estillore, Armando; Suits, Arthur

    2010-03-01

    The crossed molecular beam method coupled with dc slice ion imaging technique provides promising results in understanding the dynamics of complex reaction processes. Advances in beam intensities and probe sensivity, in conjunction with the sliced imaging approach, yield the means to study this reactivity rapidly and in a systematic way. Using these strategies, we studied the reaction of Cl(^2P3/2) atoms with selected hydrocarbons: n-butane; cis-2-butene; hexane; 1-hexene; 2-hexene; 1,5-hexadiene; n-heptane; and 2-methylhexane. The product alkyl radical images were detected via single photon ionization at 157 nm, directly yielding the product flux-velocity contour maps.

  19. 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.

  20. Analysis of aromatic constituents in multicomponent hydrocarbon mixtures by infrared spectroscopy using multiple linear regression

    NASA Astrophysics Data System (ADS)

    Vesnin, V. L.; Muradov, V. G.

    2012-09-01

    Absorption spectra of multicomponent hydrocarbon mixtures based on n-heptane and isooctane with addition of benzene (up to 1%) and toluene and o-xylene (up to 20%) were investigated experimentally in the region of the first overtones of the hydrocarbon groups (? = 1620-1780 nm). It was shown that their concentrations could be determined separately by using a multiple linear regression method. The optimum result was obtained by including four wavelengths at 1671, 1680, 1685, and 1695 nm, which took into account absorption of CH groups in benzene, toluene, and o-xylene and CH3 groups, respectively.

  1. Efficient High Pressure MixtureState Equations

    NASA Technical Reports Server (NTRS)

    Harstad, K. G.; Miller, R. S.; Bellan, J.

    1996-01-01

    A method is presented for an accurate noniterative, computationally efficient calculation of high pressure fluid mixture equations of state, especially targeted to gas turbines and rocket engines. Pressures above 1 bar and temperatures above 100 K are addressed. The method is based on curve fitting an effective reference state relative to departure funcitons formed using the Peng-Robinson cubic state equation. Fit parameters for H(sub 2), O(sub 2), N(sub 2), propane, n-heptane and methanol are given.

  2. Hydrogen bond fluctuations and dispersive interactions of alcohol/alkane mixtures. An ultrasonic relaxation study

    NASA Astrophysics Data System (ADS)

    Kaatze, Udo; Behrends, Ralph

    2011-06-01

    The relaxation behaviour of 1-hexanol/n-heptane and 1-dodecanol/n-tetradecane mixtures has been studied at some compositions using ultrasonic attenuation spectrometry in the frequency range 0.4-3000 MHz. All mixtures reveal a relaxation term due to hydrogen network fluctuations. It is discussed in conjunction with the principle dielectric relaxation of alcohol/alkane mixtures, indicating a dynamically micro-heterogeneous liquid structure. The spectra of the long-chain alcohol system display an additional relaxation due to the structural isomerisation of the hydrocarbon chains. In terms of a torsional oscillator model this relaxation reveals the effect of molecular ordering on the enthalpy of activation.

  3. Superbenzene-porphyrin conjugates.

    PubMed

    Lungerich, Dominik; Hitzenberger, Jakob F; Marcia, Mario; Hampel, Frank; Drewello, Thomas; Jux, Norbert

    2014-11-01

    A free-base porphyrin carrying two hexabenzocoronene (HBC) substituents in a trans arrangement and its zinc complex have been prepared. The compounds were characterized extensively and found to form tricationic dimers in the gas phase. X-ray crystallography confirms for the zinc complex a profound ?-stacking of the HBC moieties. In contrast, the free-base porphyrin incarcerates n-heptane which essentially prevents ?-stacking. Upon excitation of the HBC substituents, efficient energy transfer to the central porphyrin is observed. PMID:25244699

  4. Selective nonspecific solvation under dielectric saturation and fluorescence spectra of dye solutions in binary solvents.

    PubMed

    Bakhshiev, N G; Kiselev, M B

    1991-09-01

    The influence of selective nonspecific solvation on the fluorescence spectra of three substitutedN-methylphthalimides in a binary solvent system consisting of a nonpolar (n-heptane) and a polar (pyridine) component has been studied under conditions close to dielectric saturation. The substantially nonlinearity of the effect is confirmation that the spectral shifts of fluorescence bands depend on the number of polar solvent molecules involved in solvating the dye molecule. The measured fluorescence spectral shifts determined by substituting one nonpolar solvent molecula with a polar one in the proximity of the dye molecule agree quantitatively with the forecasts of the previously proposed semiempirical theory which describes this nonlinear solvation phenomenon. PMID:24242995

  5. Low and intermediate temperature oxidation of ethanol and ethanol-PRF blends: An experimental and modeling study

    SciTech Connect

    Haas, Francis M.; Chaos, Marcos; Dryer, Frederick L.

    2009-12-15

    In this brief communication, we present new experimental species profile measurements for the low and intermediate temperature oxidation of ethanol under knock-prone conditions. These experiments show that ethanol exhibits no global low temperature reactivity at these conditions, although we note the heterogeneous decomposition of ethanol to ethylene and water. Similar behavior is reported for an E85 blend in n-heptane. Kinetic modeling results are presented to complement these experiments and elucidate the interaction of ethanol and primary reference fuels undergoing cooxidation. (author)

  6. Standard test method for existent gum in fuels by jet evaporation

    SciTech Connect

    Not Available

    1980-01-01

    This method covers determination of the existent gum in motor gasoline and aircraft fuels at the time of test. Provisions are made for the determination of the unwashed gum content of motor gasoline. Summary of method: a measured quantity of fuel is evaporated under controlled conditions of temperature and flow of air or steam. For aviation gasoline and aircraft turbine fuel, the resulting residue is weighed and reported as milligrams per 100 mL. For motor gasoline, the residue is weighed before and after extracting with n-heptane and the results reported as milligrams per 100 mL.

  7. Photoinduced underwater superoleophobicity of TiO2 thin films.

    PubMed

    Sawai, Yusuke; Nishimoto, Shunsuke; Kameshima, Yoshikazu; Fujii, Eiji; Miyake, Michihiro

    2013-06-11

    The photoinduced wettabilities of water, n-hexadecane, dodecane, and n-heptane on a flat TiO2 surface prepared by a sol-gel method-based coating were investigated. An amphiphilic surface produced by UV irradiation exhibited underwater superoleophobicity with an extremely high static oil contact angle (CA) of over 160. The TiO2 surface almost completely repelled the oil droplet in water. A robust TiO2 surface with no fragile nanomicrostructure was fabricated on a Ti mesh with a pore size of approximately 150 ?m. The fabricated mesh was found to be applicable as an oil/water separation filter. PMID:23701360

  8. A Ternary Phase Diagram for a Less Hazardous System

    NASA Astrophysics Data System (ADS)

    Udale, Barbara A.; Wells, John D.

    1995-12-01

    The ternary phase diagram for the partially miscible liquid system n-propanol-n-heptane-water can be determined readily in an undergraduate laboratory experiment. The coexistence curve is obtained from titration results. Tie lines are then estimated from the compositions of pairs of phases in equilibrium, the propanol concentrations being determined by gas chromatography. The reagents are less hazardous than those of the classic acetic acid-chloroform-water system, and the gas chromatographic analysis has more interest for students than the acid-base titrations of the older experiment.

  9. Premixed ignition behavior of alternative diesel fuel-relevant compounds in a motored engine experiment

    SciTech Connect

    Szybist, James P.; Boehman, Andre L.; Haworth, Daniel C.; Koga, Hibiki

    2007-04-15

    A motored engine study using premixed charges of fuel and air at a wide range of diesel-relevant equivalence ratios was performed to investigate autoignition differences among surrogates for conventional diesel fuel, gas-to-liquid (GTL) diesel fuel, and biodiesel, as well as n-heptane. Experiments were performed by delivering a premixed charge of vaporized fuel and air and increasing the compression ratio in a stepwise manner to increase the extent of reaction while monitoring the exhaust composition via Fourier transform infrared (FTIR) spectrometry and collecting condensable exhaust gas for subsequent gas chromatography/mass spectrometry (GC/MS) analysis. Each fuel demonstrated a two-stage ignition process, with a low-temperature heat release (LTHR) event followed by the main combustion, or high-temperature heat release (HTHR). Among the three diesel-relevant fuels, the magnitude of LTHR was highest for GTL diesel, followed by methyl decanoate, and conventional diesel fuel last. FTIR analysis of the exhaust for n-heptane, the conventional diesel surrogate, and the GTL diesel surrogate revealed that LTHR produces high concentrations of aldehydes and CO while producing only negligible amounts of CO{sub 2}. Methyl decanoate differed from the other two-stage ignition fuels only in that there were significant amounts of CO{sub 2} produced during LTHR; this was the result of decarboxylation of the ester group, not the result of oxidation. GC/MS analysis of LTHR exhaust condensate for n-heptane revealed high concentrations of 2,5-heptanedione, a di-ketone that can be closely tied to species in existing autoignition models for n-heptane. GC/MS analysis of the LTHR condensate for conventional diesel fuel and GTL diesel fuel revealed a series of high molecular weight aldehydes and ketones, which were expected, as well as a series of organic acids, which are not commonly reported as products of combustion. The GC/MS analysis of the methyl decanoate exhaust condensate revealed that the aliphatic chain acts similarly to n-paraffins during LTHR, while the ester group remains intact. Thus, although the FTIR data revealed that decarboxylation occurs at significant levels for methyl decanoate, it was concluded that this occurs after the aliphatic chain has been largely consumed by other LTHR reactions. (author)

  10. Velocity profiles in laminar diffusion flames

    NASA Technical Reports Server (NTRS)

    Lyons, Valerie J.; Margle, Janice M.

    1986-01-01

    Velocity profiles in vertical laminar diffusion flames were measured by using laser Doppler velocimetry (LDV). Four fuels were used: n-heptane, iso-octane, cyclohexane, and ethyl alcohol. The velocity profiles were similar for all the fuels, although there were some differences in the peak velocities. The data compared favorably with the theoretical velocity predictions. The differences could be attributed to errors in experimental positioning and in the prediction of temperature profiles. Error in the predicted temperature profiles are probably due to the difficulty in predicting the radiative heat losses from the flame.

  11. The effect of initial diameter in sperically symmetric droplet combustion of sooting fuels

    NASA Technical Reports Server (NTRS)

    Jackson, G. S.; Avedisian, C. T.

    1994-01-01

    The effect of initial droplet diameter on the burning rate of sooting fuels - n-heptane and 1-chloro-octane - was examined experimentally at low gravity. A 1.2s drop tower provided a low gravity environment to minimize buoyancy and achieve spherically symmetric flames for stationary droplets. Free-floating and fiber-supported droplets were burned, and both techniques gave matching results for droplets of similar initial diameter. Burning rate constants for both fuels were measured for a large number of droplets ranging from 0.4 to 1.1mm in initial diameter.

  12. The role of water in the formation of reversed micelles: An antimicellization agent

    USGS Publications Warehouse

    Yu, Z.-J.; Zhou, N.-F.; Neuman, R.D.

    1992-01-01

    Micellization of sodium bis(2-ethylhexyl) phosphate in n-heptane has been studied under controlled environmental conditions by dynamic and static light scattering. The results clearly show that a trace amount of water has a very dramatic effect on reversed micellization. In contrast with results in the literature, water can function as an antimicellization agent. The generality of and the evidence for supporting the current view that water is a prerequisite for the formation of reversed micelles are discussed and criticized. ?? 1992 American Chemical Society.

  13. Frequency response of a vaporization process to distorted acoustic disturbances

    NASA Technical Reports Server (NTRS)

    Heidmann, M. F.

    1972-01-01

    The open-loop response properties expressed as the mass vaporized in phase and out of phase with the pressure oscillations were numerically evaluated for a vaporizing n-heptane droplet. The evaluation includes the frequency dependence introduced by periodic oscillation in droplet mass and temperature. A given response was achieved over a much broader range of frequency with harmonically distorted disturbances than with sinusoidal disturbances. The results infer that distortion increases the probability of incurring spontaneous and triggered instability in any rocket engine combustor by broadening the frequency range over which the vaporization process can support an instability.

  14. Testing of high-octane fuels in the single-cylinder airplane engine

    NASA Technical Reports Server (NTRS)

    Seeber, Fritz

    1940-01-01

    One of the most important properties of aviation fuels for spark-ignition engines is their knock rating. The CFR engine tests of fuels of 87 octane and above does not always correspond entirely to the actual behavior of these fuels in the airplane engine. A method is therefore developed which, in contrast to the octane number determination, permits a testing of the fuel under various temperatures and fuel mixture conditions. The following reference fuels were employed: 1) Primary fuels; isooctane and n-heptane; 2) Secondary fuels; pure benzene and synthetic benzine.

  15. Fatty and resinic acids extractions from crude tall oil

    SciTech Connect

    Nogueira, J.M.F.

    1996-11-01

    The separation of fatty and resinic acidic fractions from crude tall-oil soap solutions with n-heptane by the technique of dissociation extraction is discussed. The theory of the overall process is supported by a systematic study developed to cover the high selectivity demonstrated in the differential solubility and the aptness between fatty and diterpenic acids to both liquids phases. To study the main factors affecting those liquid-liquid extraction systems and the amphiphilic behavior of such molecules involved, sodium salts aqueous solutions of crude tall oil and synthetic mixtures as molecular acidic models were used.

  16. CONTROL OF LASER RADIATION PARAMETERS: Efficient 510 ? 578-nm conversion of emission of copper vapour lasers

    NASA Astrophysics Data System (ADS)

    D'yachkov, Aleksei B.; Labozin, Valerii P.

    2002-09-01

    The results of experiments on the 510 ? 578-nm conversion of high-power radiation from a copper vapour laser (CVL) in a dye cell are presented. The use of the efficient laser dye Pyrromethane 597 (PM-597) made it possible to convert the 120-W CVL radiation (72 W at 510 nm + 48 W at 578 nm) into 102-W radiation at 578 nm, which is equivalent to a conversion efficiency of 85%. Photostability of the dye in various solvents is studied. The photostability (more than 45 GJ mole-1) of PM-597 in n-heptane is found to be higher than that of Rh 6G in ethanol.

  17. Long Duration Exposure Facility (LDEF) low-temperature Heat Pipe Experiment Package (HEPP)

    NASA Technical Reports Server (NTRS)

    Mcintosh, Roy; Brennan, Patrick J.

    1991-01-01

    The flight test results are discussed obtained with the Heat Pipe Experiment Package (HEPP). The HEPP was designed to demonstrate the performance of an ethane constant conductance heat pipe (CCHP) and an ethane heat pipe diode in microgravity. These heat pipes have a nominal operating temperature range of 140 to 250 K. Also, included in the HEPP is a Phase Change Material (PCM) canister which provides temperature stability through melting and freezing of the n-heptane PCM. A comparison of pre-flight, flight, and post-flight thermal performance is also presented.

  18. Microwave assisted methodology for the determination of organic pollutants in organic municipal wastes and soils: extraction of polychlorinated biphenyls using heat transformer disks.

    PubMed

    Dring, R A; Gth, S

    2000-12-01

    Known benefits of microwave assisted extraction (MAE) of polychlorinated biphenyls (PCB) from solid matrices could be proven by the described approach using n-heptane as solely applied extraction solvent. Heat transfer within the extraction vessels was achieved by heat transformer disks which absorb microwave energy and transform it into heat rapidly and independently of the temperature present in the sample-solvent system. Disadvantageous co-extraction of polar substances could be ruled out and thus clean-up of the samples was simplified and sufficient for subsequent GC-MS analysis. Comparison with other extraction techniques confirmed the efficiency of this method also for aged samples. PMID:11227548

  19. Explosion characteristics of flammable organic vapors in nitrous oxide atmosphere.

    PubMed

    Koshiba, Yusuke; Takigawa, Tomihisa; Matsuoka, Yusaku; Ohtani, Hideo

    2010-11-15

    Despite unexpected explosion accidents caused by nitrous oxide have occurred, few systematic studies have been reported on explosion characteristics of flammable gases in nitrous oxide atmosphere compared to those in air or oxygen. The objective of this paper is to characterize explosion properties of mixtures of n-pentane, diethyl ether, diethylamine, or n-butyraldehyde with nitrous oxide and nitrogen using three parameters: explosion limit, peak explosion pressure, and time to the peak explosion pressure. Then, similar mixtures of n-pentane, diethyl ether, diethylamine, or n-butyraldehyde with oxygen and nitrogen were prepared to compare their explosion characteristics with the mixtures containing nitrous oxide. The explosion experiments were performed in a cylindrical vessel at atmospheric pressure and room temperature. The measurements showed that explosion ranges of the mixtures containing nitrous oxide were narrow compared to those of the mixtures containing oxygen. On the other hand, the maximum explosion pressures of the mixtures containing nitrous oxide were higher than those of the mixtures containing oxygen. Moreover, our experiments revealed that these mixtures differed in equivalence ratios at which the maximum explosion pressures were observed: the pressures of the mixtures containing nitrous oxide were observed at stoichiometry; in contrast, those of the mixtures containing oxygen were found at fuel-rich area. Chemical equilibrium calculations confirmed these behaviors. PMID:20719432

  20. Neurotoxic metabolites of "commercial hexane" in the urine of shoe factory workers.

    PubMed

    Perbellini, L; Brugnone, F; Gaffuri, E

    1981-12-01

    Urinary metabolites were tested in 41 shoe-factory workers exposed to a mixture of 10 solvents among which "commercial hexane" was the prevailing component. Cyclohexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, and trichloroethanol were determined in connection with exposure to cyclohexane, 2-methylpentane, 3-methylpentane, and trichloroethylene, respectively. 2-Hexanol, 2,5-hexanedione, 2,5-dimethylfuran, and gamma-valerolactone were all determined in connection with n-hexane exposure only. 2,5-Hexanedione was the principal n-hexane metabolite found in the workers' urine. This finding of the experimentally proven neurotoxin 2,5-hexanedione in the urine of shoe-factory workers exposed to "commercial hexane" is consistent with the idea that this compound is responsible for the development of neuropathy in this group of individuals. PMID:6277549