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Sample records for intermediates decomposition studies

  1. Excess Sodium Tetraphenylborate and Intermediates Decomposition Studies

    SciTech Connect

    Barnes, M.J.

    1998-12-07

    The stability of excess amounts of sodium tetraphenylborate (NaTPB) in the In-Tank Precipitation (ITP) facility depends on a number of variables. Concentration of palladium, initial benzene, and sodium ion as well as temperature provide the best opportunities for controlling the decomposition rate. This study examined the influence of these four variable on the reactivity of palladium-catalyzed sodium tetraphenylborate decomposition. Also, single effects tests investigated the reactivity of simulants with continuous stirring and nitrogen ventilation, with very high benzene concentrations, under washed sodium concentrations, with very high palladium concentrations, and with minimal quantities of excess NaTPB.

  2. Excess Sodium Tetraphenylborate and Intermediates Decomposition Studies

    SciTech Connect

    Barnes, M.J.; Peterson , R.A.

    1998-04-01

    The stability of excess amounts of sodium tetraphenylborate (NaTPB) in the In-Tank Precipitation (ITP) facility depends on a number of variables. Concentration of palladium, initial benzene, and sodium ion as well as temperature provide the best opportunities for controlling the decomposition rate. This study examined the influence of these four variables on the reactivity of palladium-catalyzed sodium tetraphenylborate decomposition. Also, single effects tests investigated the reactivity of simulants with continuous stirring and nitrogen ventilation, with very high benzene concentrations, under washed sodium concentrations, with very high palladium concentrations, and with minimal quantities of excess NaTPB. These tests showed the following.The testing demonstrates that current facility configuration does not provide assured safety of operations relative to the hazards of benzene (in particular to maintain the tank headspace below 60 percent of the lower flammability limit (lfl) for benzene generation rates of greater than 7 mg/(L.h)) from possible accelerated reaction of excess NaTPB. Current maximal operating temperatures of 40 degrees C and the lack of protection against palladium entering Tank 48H provide insufficient protection against the onset of the reaction. Similarly, control of the amount of excess NaTPB, purification of the organic, or limiting the benzene content of the slurry (via stirring) and ionic strength of the waste mixture prove inadequate to assure safe operation.

  3. Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO3, U2O7, and UO4

    DOE PAGESBeta

    Guo, Xiaofeng; Wu, Di; Xu, Hongwu; Burns, Peter C.; Navrotsky, Alexandra

    2016-06-08

    The thermal decomposition of studtite (UO2)O2(H2O)2·2H2O results in a series of intermediate X-ray amorphous materials with general composition UO3+x (x = 0, 0.5, 1). As an extension of a structural study on U2O7, this work provides detailed calorimetric data on these amorphous oxygen-rich materials since their energetics and thermal stability are unknown. These were characterized in situ by thermogravimetry, and mass spectrometry. Ex situ X-ray diffraction and infrared spectroscopy characterized their chemical bonding and local structures. This detailed characterization formed the basis for obtaining formation enthalpies by high temperature oxide melt solution calorimetry. The thermodynamic data demonstrate the metastability ofmore » the amorphous UO3+x materials, and explain their irreversible and spontaneous reactions to generate oxygen and form metaschoepite. Thus, formation of studtite in the nuclear fuel cycle, followed by heat treatment, can produce metastable amorphous UO3+x materials that pose the risk of significant O2 gas. Quantitative knowledge of the energy landscape of amorphous UO3+x was provided for stability analysis and assessment of conditions for decomposition.« less

  4. Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO3, U2O7, and UO4

    NASA Astrophysics Data System (ADS)

    Guo, Xiaofeng; Wu, Di; Xu, Hongwu; Burns, Peter C.; Navrotsky, Alexandra

    2016-09-01

    The thermal decomposition of studtite (UO2)O2(H2O)2·2H2O results in a series of intermediate X-ray amorphous materials with general composition UO3+x (x = 0, 0.5, 1). As an extension of a structural study on U2O7, this work provides detailed calorimetric data on these amorphous oxygen-rich materials since their energetics and thermal stability are unknown. These were characterized in situ by thermogravimetry, and mass spectrometry. Ex situ X-ray diffraction and infrared spectroscopy characterized their chemical bonding and local structures. This detailed characterization formed the basis for obtaining formation enthalpies by high temperature oxide melt solution calorimetry. The thermodynamic data demonstrate the metastability of the amorphous UO3+x materials, and explain their irreversible and spontaneous reactions to generate oxygen and form metaschoepite. Thus, formation of studtite in the nuclear fuel cycle, followed by heat treatment, can produce metastable amorphous UO3+x materials that pose the risk of significant O2 gas. Quantitative knowledge of the energy landscape of amorphous UO3+x was provided for stability analysis and assessment of conditions for decomposition.

  5. Spin-trapping studies of peroxynitrite decomposition and of 3-morpholinosydnonimine N-ethylcarbamide autooxidation: direct evidence for metal-independent formation of free radical intermediates.

    PubMed

    Augusto, O; Gatti, R M; Radi, R

    1994-04-01

    Decomposition of peroxynitrite, the reaction product of superoxide and nitric oxide, was studied by electron paramagnetic resonance (EPR)-spin-trapping experiments with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). Proton-catalyzed decomposition of peroxynitrite at pH 7.5 resulted in the formation of the DMPO-hydroxyl radical adduct (DMPO-OH). Yields were low as DMPO-OH decomposes by direct reactions with peroxynitrite anion and nitrogen dioxide. The yield of DMPO-OH greatly increased in the presence of glutathione or cysteine. Both thiols inhibited the DMPO-OH signal decay by scavenging excess peroxynitrite anion and presumably nitrogen dioxide yielded during peroxynitrite decomposition. In turn, the reactions of peroxynitrite with either glutathione or cysteine resulted in the formation of thiyl radicals, detectable as the corresponding DMPO adduct. Systematic spin-trapping studies of peroxynitrite decomposition in the presence of glutathione established that DMPO-hydroxyl radical adduct formation was metal independent, occurring in a metal-free buffer and being unaffected by diethylene-triaminepentaacetic acid. Also, quantitative competition experiments with ethanol and formate demonstrated that the oxidant generated during peroxynitrite decomposition reacts with rate constants similar to those expected for free hydroxyl radical and forming the same free radical intermediates, alpha-ethyl-hydroxy and carbon dioxide radicals, respectively. Similar spin-trapping results were obtained in studies of the autooxidation of 3-morpholinosydnonimine, a sydnonimine which generates a flux of both superoxide and nitric oxide. The obtained results contribute for the understanding of the reactivity of peroxynitrite, a transient intermediate of emerging biological significance. PMID:8161194

  6. NTO decomposition studies

    SciTech Connect

    Oxley, J.C.; Smith, J.L.; Yeager, K.E.; Rogers, E.; Dong, X.X.

    1996-07-01

    To examine the thermal decomposition of 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO) in detail, isotopic labeling studies were undertaken. NTO samples labeled with {sup 15}N in three different locations [N(1) and N(2), N(4), and N(6)] were prepared. Upon thermolysis, the majority of the NTO condensed-phase product was a brown, insoluble residue, but small quantities of 2,4-dihydro-3H-1,2,4-triazol-3-one (TO) and triazole were detected. Gases comprised the remainder of the NTO decomposition products. The analysis of these gases is reported along with mechanistic implications of these observations.

  7. An isomer-specific study of solid nitromethane decomposition pathways - Detection of aci-nitromethane (H2CNO(OH)) and nitrosomethanol (HOCH2NO) intermediates

    NASA Astrophysics Data System (ADS)

    Maksyutenko, Pavlo; Förstel, Marko; Crandall, Parker; Sun, Bing-Jian; Wu, Mei-Hung; Chang, Agnes H. H.; Kaiser, Ralf I.

    2016-08-01

    An isomer specific study of energetic electron exposed nitromethane ices was performed via photoionization - reflectron time of flight mass spectrometry (PI-ReTOF-MS) of the subliming products employing tunable vacuum ultraviolet light for ionization. Supported by electronic structure calculations, nitromethane (CH3NO2) was found to isomerize to methyl nitrite (CH3ONO) and also via hydrogen migration to the hitherto elusive aci-nitromethane isomer (H2CNO(OH)). The latter isomerizes to nitrosomethanol (HOCH2NO) through hydroxyl group (OH) migration, and, probably, ring closure to the cyclic 2-hydroxy-oxaziridine isomer (c-H2CON(OH)) as well. The importance of hydrogen migrations was also verified via the nitrosomethane (CH3NO) - formaldehyde oxime isomer (CH2NOH) pair.

  8. Mechanistic insight into the hydrazine decomposition on Rh(111): effect of reaction intermediate on catalytic activity.

    PubMed

    Deng, Zhigang; Lu, Xiaoqing; Wen, Zengqiang; Wei, Shuxian; Liu, Yunjie; Fu, Dianling; Zhao, Lianming; Guo, Wenyue

    2013-10-14

    Periodic density functional theory (DFT) calculations have been performed to systematically investigate the effect of reaction intermediate on catalytic activity for hydrazine (N2H4) decomposition on Rh(111). Reaction mechanisms via intramolecular and NH2-assisted N2H4 decompositions are comparatively analyzed, including adsorption configuration, reaction energy and barrier of elementary step, and reaction network. Our results show that the most favorable N2H4 decomposition pathway starts with the initial N-N bond scission to the NH2 intermediate, followed by stepwise H stripping from adsorbed N2Hx (x = 1-4) species, and finally forms the N2 and NH3 products. Comparatively, the stepwise intramolecular dehydrogenation via N2H4→ N2H3→ N2H2→ N2H → N2, and N2H4→ NH2→ NH → N with or without NH2 promotion effect, are unfavorable due to higher energy barriers encountered. Energy barrier analysis, reaction rate constants, and electronic structures are used to identify the crucial competitive route. The promotion effect of the NH2 intermediate is structurally reflected in the weakening of the N-H bond and strengthening of the N-N bond in N2Hx in the coadsorption system; it results intrinsically from the less structural deformation of the adsorbate, and weakening of the interaction between dehydrogenated fragment and departing H in transition state. Our results highlight the crucial effect of reaction intermediate on catalytic activity and provide a theoretical approach to analyze the effect. PMID:23990024

  9. Thioozonide decomposition: sulfur and oxygen atom transfer. Evidence for the formation of a carbonyl O-sulfide intermediate

    SciTech Connect

    Matturro, M.G.; Reynolds, R.P.; Kastrup, R.V.; Pictroski, C.F.

    1986-05-14

    The chemistry of ozonides is of considerable interest from a practical and theoretical viewpoint. Thioozonide 1, formally the monosulfur-substituted ozonide of dimethylcyclobutadiene, has been proposed as an intermediate in the room temperature photooxidation of 2,5-dimethylthiophene. Subsequent low-temperature studies confirmed this structural assignment. When 1 is allowed to warm to room temperature, it rearranges to a mixture of sulfine 2 and cis- and trans-3-hexene-2,5-diones (3c and 3t). Recent examination of the thermal decomposition of 1 has led to a proposed mechanism involving a carbonyl sulfide 4 as an intermediate along the sulfur expulsion pathway to 3c; however, no experimental support for this hypothesis was given. Carbonyl O-sulfides have also been implicated as intermediates from the photolysis of oxathiiranes. The authors report evidence for the formation of 4 during the decomposition of 1 and that elemental sulfur (S/sub 8/) is formed during the reaction by concatenation of sulfur atoms or fragments (S/sub 2/, S/sub 3/, etc.).

  10. HCOOH decomposition on Pt(111): A DFT study

    NASA Astrophysics Data System (ADS)

    Scaranto, Jessica; Mavrikakis, Manos

    2016-06-01

    Formic acid (HCOOH) decomposition on transition metal surfaces is important for hydrogen production and for its electro-oxidation in direct HCOOH fuel cells. HCOOH can decompose through dehydrogenation leading to formation of CO2 and H2 or dehydration leading to CO and H2O; because CO can poison metal surfaces, dehydrogenation is typically the desirable decomposition path. Here we report a mechanistic analysis of HCOOH decomposition on Pt(111), obtained from a plane wave density functional theory (DFT-PW91) study. We analyzed the dehydrogenation mechanism by considering the two possible pathways involving the formate (HCOO) or the carboxyl (COOH) intermediate. We also considered several possible dehydration paths leading to CO formation. We studied HCOO and COOH decomposition both on the clean surface and in the presence of other relevant co-adsorbates. The results suggest that COOH formation is energetically more difficult than HCOO formation. In contrast, COOH dehydrogenation is easier than HCOO decomposition. We found that CO2 is the main product through both pathways and that CO is produced mainly through the dehydroxylation of the COOH intermediate.

  11. Decomposition

    USGS Publications Warehouse

    Middleton, Beth A.

    2014-01-01

    A cornerstone of ecosystem ecology, decomposition was recognized as a fundamental process driving the exchange of energy in ecosystems by early ecologists such as Lindeman 1942 and Odum 1960). In the history of ecology, studies of decomposition were incorporated into the International Biological Program in the 1960s to compare the nature of organic matter breakdown in various ecosystem types. Such studies still have an important role in ecological studies of today. More recent refinements have brought debates on the relative role microbes, invertebrates and environment in the breakdown and release of carbon into the atmosphere, as well as how nutrient cycling, production and other ecosystem processes regulated by decomposition may shift with climate change. Therefore, this bibliography examines the primary literature related to organic matter breakdown, but it also explores topics in which decomposition plays a key supporting role including vegetation composition, latitudinal gradients, altered ecosystems, anthropogenic impacts, carbon storage, and climate change models. Knowledge of these topics is relevant to both the study of ecosystem ecology as well projections of future conditions for human societies.

  12. Decomposition pathways of the excited Criegee intermediates in the ozonolysis of simple alkenes

    NASA Astrophysics Data System (ADS)

    Horie, O.; Moortgat, G. K.

    Ozonolysus of C 2H 4, C 3H 6, and trans-2-C 4H 8 was carried out at 758 ± 4 Torr and 297 ± 3 K in a 2 ℓ continuous-stirred tank-reactor coupled to a matrix-isolation FTIR spectrometer through molecular-beam sampling. The branching ratios of the decomposition channels of the activated Criegee intermediates CH 2OO ∗ and CH 3CHOO ∗ formed in the primary reactions were determined by means of a computer simulation based on the quantitative analysis of CH 3CHO, HCHO, CO 2, CO, CH 4, CH 3OH, HCOOH, and CH 3COOH. The fractions of the decomposition channels found are for CH2OO ∗: CO+H 2O 58%, CO 2+H 2 24%, CO 2+2H 18%, and for CH3CHOO∗: CH4+ CO2 30% , CH 3+CO 2+H 30%, CH 3+CO+OH 28%, CH 3OH+CO 12%. The results of the ozonolysis of C 3H 6 are described by combining the simulation models of the C 2H 4 and trans-2-C 4H 8 ozonolysis. The primary propene ozonide is found to split into CH3CHOO∗+ HCHO and CH2OO∗+ CH3CHO with the fraction of 62 and 38%, respectively.

  13. Two alternate kinetic routes for the decomposition of the phosphorylated intermediate of sarcoplasmic reticulum Ca2+-ATPase.

    PubMed

    Nakamura, Y

    1984-07-10

    The decomposition of the phosphorylated intermediate (EP) of sarcoplasmic reticulum ATPase, purified by the method of deoxycholic acid extraction, was studied by first phosphorylating with [gamma-32P]ATP, then diluting the reaction mixture with 20 volumes of medium containing nonradioactive ATP, and finally quenching serial samples with acid for determination of residual [32P]EP. The time course of [32P]EP decomposition consists of an initial fast phase followed by a slow phase. The two components of EP, EPfast (1.1 nmol/mg) and EPslow (2.8 nmol/mg), decomposed with the rate constants of 6 and 0.8 min-1, respectively, in the presence of 0.5 mM CaCl2, 5mM MgCl2, and 90 mM KCl at pH 7.0 and O degrees C. The sum of the hydrolytic activities corresponding to the two components accounts for the steady state velocity of the Pi production under the same conditions, indicating that the two components represent simultaneous pathways, rather than sequential steps of EP decomposition. As the time of phosphorylation with [gamma-32P]ATP is increased from 2 to 15 s, the fraction of EPfast decreases in favor of EPslow. This conversion decreases the rate of total Pi production by the enzyme following an initial Pi burst. Conversion of EPfast to EPslow is favored by millimolar concentrations of Ca2+. On the other hand, conversion of EPslow to EPfast is obtained by reducing Ca2+ or raising Mg2+ concentration, but is prevented by removal of ADP. The EPslow fraction decreases in favor of EPfast as the temperature is increased from 0 to 22 degrees C. PMID:6234309

  14. [Intermediate phenotype studies in psychiatric disorder].

    PubMed

    Hashimoto, Ryota

    2016-02-01

    The concept of intermediate phenotype was proposed by Dr. Weinberger of the National Institute of Mental Health (NIMH). The risk genes for mental disorders define intermediate phenotypes, neurobiological characteristics observed in psychiatric disorders, and intermediate phenotypes increase the risk of mental disorders. The author worked at Dr. Weinberger's laboratory, and after returning home, introduced the concept to Japan, creating a term "Chukanhyogengata" to translate "intermediate phenotype". Intermediate phenotype has been proposed as a tool for the identification of risk genes for mental disorders, spreading the concept as a biomarker for the bridging between genes and behaviors. Intermediate phenotype studies later became one of the main pillars of psychiatric research. As a large number of data and samples are needed for intermediate phenotype research, we built a research resource database that combines the brain phenotype and bioresources. We performed genome-wide association analysis of cognitive decline in schizophrenia and identified the DEGS2 gene using this sample. This research resource database was developed for a multicenter study by COCORO (Cognitive Genetics Collaborative Research Organization). COCORO carried out genome-wide association analysis of the gray matter volume of the superior temporal gyrus and identified genome-wide significant loci. In this paper, we introduce the concept and history of intermediate phenotype study of mental illness and the latest trends. We hope to contribute to the future development of mental illness research through translational research. PMID:27044135

  15. Numerical study of the accumulation dynamics of oil shale thermal decomposition products in the vicinity of a heating element

    NASA Astrophysics Data System (ADS)

    Knyazeva, A. G.; Maslov, A. L.

    2015-10-01

    This study proposes the model of thermal decomposition of oil shale heated by electrodes. Differences in thermal physical properties of phases (solid core and gas, reagents and decomposition products), flow of generated gases in pores, and thermal effects of decomposition reactions are taken into account. The consideration of concentration expansion phenomenon is one of the features of the described model. The solution was carried out numerically. The concentration change of intermediate and final reaction products were studied for various heating conditions.

  16. Density functional theory studies of HCOOH decomposition on Pd(111)

    NASA Astrophysics Data System (ADS)

    Scaranto, Jessica; Mavrikakis, Manos

    2016-08-01

    The investigation of formic acid (HCOOH) decomposition on transition metal surfaces is important to derive useful insights for vapor phase catalysis involving HCOOH and for the development of direct HCOOH fuel cells (DFAFC). Here we present the results obtained from periodic, self-consistent, density functional theory (DFT-GGA) calculations for the elementary steps involved in the gas-phase decomposition of HCOOH on Pd(111). Accordingly, we analyzed the minimum energy paths for HCOOH dehydrogenation to CO2 + H2 and dehydration to CO + H2O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easier than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in the presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.

  17. Spark decomposition studies of dielectric gas mixtures

    NASA Astrophysics Data System (ADS)

    Sauers, I.; Christophorou, L. G.

    The ultimate usefulness of a high voltage insulating gas depends not only on the ability of the gas to withstand high voltages, but also on the degradation of the gas resulting from spark discharges, corona or prolonged electrical stress and the effect(s) of the by-products on the equipment and, possibly, the environment. In view of these considerations, the study of long-range spark decomposition was undertaken in an effort to improve the decomposition characteristics of dielectric gases through proper tailoring of gas mixtures while maintaining high breakdown strengths. The data reported are on the analyses of gases sparked by capactive (0.1 micro F) discharge into a 0.5-mm gap, resulting in an energy input of approximately 5 J per spark. The nature of the decomposition products of SF6 formed by high voltage discharges observed is found to be critically dependent on impurities (particularly H2O), electrode material and insulating materials present in the system.

  18. Unimolecular Decomposition Rate of the Criegee Intermediate (CH3)2COO Measured Directly with UV Absorption Spectroscopy.

    PubMed

    Smith, Mica C; Chao, Wen; Takahashi, Kaito; Boering, Kristie A; Lin, Jim Jr-Min

    2016-07-14

    The unimolecular decomposition of (CH3)2COO and (CD3)2COO was measured by direct detection of the Criegee intermediate at temperatures from 283 to 323 K using time-resolved UV absorption spectroscopy. The unimolecular rate coefficient kd for (CH3)2COO shows a strong temperature dependence, increasing from 269 ± 82 s(-1) at 283 K to 916 ± 56 s(-1) at 323 K with an Arrhenius activation energy of ∼6 kcal mol(-1). The bimolecular rate coefficient for the reaction of (CH3)2COO with SO2, kSO2, was also determined in the temperature range 283 to 303 K. Our temperature-dependent values for kd and kSO2 are consistent with previously reported relative rate coefficients kd/kSO2 of (CH3)2COO formed from ozonolysis of tetramethyl ethylene. Quantum chemical calculations of kd for (CH3)2COO are consistent with the experiment, and the combination of experiment and theory for (CD3)2COO indicates that tunneling plays a significant role in (CH3)2COO unimolecular decomposition. The fast rates of unimolecular decomposition for (CH3)2COO measured here, in light of the relatively slow rate for the reaction of (CH3)2COO with water previously reported, suggest that thermal decomposition may compete with the reactions with water and with SO2 for atmospheric removal of the dimethyl-substituted Criegee intermediate. PMID:26985985

  19. Theoretical study of the decomposition pathways and products of C5- perfluorinated ketone (C5 PFK)

    NASA Astrophysics Data System (ADS)

    Fu, Yuwei; Wang, Xiaohua; Li, Xi; Yang, Aijun; Han, Guohui; Lu, Yanhui; Wu, Yi; Rong, Mingzhe

    2016-08-01

    Due to the high global warming potential (GWP) and increasing environmental concerns, efforts on searching the alternative gases to SF6, which is predominantly used as insulating and interrupting medium in high-voltage equipment, have become a hot topic in recent decades. Overcoming the drawbacks of the existing candidate gases, C5- perfluorinated ketone (C5 PFK) was reported as a promising gas with remarkable insulation capacity and the low GWP of approximately 1. Experimental measurements of the dielectric strength of this novel gas and its mixtures have been carried out, but the chemical decomposition pathways and products of C5 PFK during breakdown are still unknown, which are the essential factors in evaluating the electric strength of this gas in high-voltage equipment. Therefore, this paper is devoted to exploring all the possible decomposition pathways and species of C5 PFK by density functional theory (DFT). The structural optimizations, vibrational frequency calculations and energy calculations of the species involved in a considered pathway were carried out with DFT-(U)B3LYP/6-311G(d,p) method. Detailed potential energy surface was then investigated thoroughly by the same method. Lastly, six decomposition pathways of C5 PFK decomposition involving fission reactions and the reactions with a transition states were obtained. Important intermediate products were also determined. Among all the pathways studied, the favorable decomposition reactions of C5 PFK were found, involving C-C bond ruptures producing Ia and Ib in pathway I, followed by subsequent C-C bond ruptures and internal F atom transfers in the decomposition of Ia and Ib presented in pathways II + III and IV + V, respectively. Possible routes were pointed out in pathway III and lead to the decomposition of IIa, which is the main intermediate product found in pathway II of Ia decomposition. We also investigated the decomposition of Ib, which can undergo unimolecular reactions to give the formation

  20. Decomposition of diazomeldrum's acid: a threshold photoelectron spectroscopy study.

    PubMed

    Lang, Melanie; Holzmeier, Fabian; Fischer, Ingo; Hemberger, Patrick

    2014-11-26

    Derivatives of meldrum's acid are known precursors for a number of reactive intermediates. Therefore, we investigate diazomeldrum's acid (DMA) and its pyrolysis products by photoionization using vacuum ultraviolet (VUV) synchrotron radiation. The threshold photoelectron spectrum of DMA yields an ionization energy (IE) of 9.68 eV. Several channels for dissociative photoionization are observed. The first one is associated with loss of CH3, leading to a daughter ion with m/z = 155. Its appearance energy AE0K was determined to be 10.65 eV by fitting the experimental data using statistical theory. A second parallel channel leads to m/z = 69, corresponding to N2CHCO, with an AE0K of 10.72 eV. Several other channels open up at higher energy, among them the formation of acetone cation, a channel expected to be the result of a Wolff-rearrangement (WR) in the cation. When diazomeldrum's acid is heated in a pyrolysis reactor, three thermal decomposition pathways are observed. The major one is well-known and yields acetone, N2 and CO as consequence of the WR. However, two further channels were identified: The formation of 2-diazoethenone, NNCCO, together with acetone and CO2 as the second channel and E-formylketene (OCCHCHCO), propyne, N2 and O2 as a third one. 2-Diazoethenone and E-formylketene were identified based on their threshold photoelectron spectra and accurate ionization energies could be determined. Ionization energies for several isomers of both molecules were also computed. One of the key findings of this study is that acetone is observed upon decomposition of DMA in the neutral as well as in the ion and both point to a Wolff rearrangement to occur. However, the ion is subject to other decomposition channels favored at lower internal energies. PMID:25369422

  1. Study of condition-dependent decomposition reactions; Part I. The thermal behaviour and decomposition of 2-nitrobenzoyl chloride.

    PubMed

    Lever, Sarah D; Papadaki, Maria

    2004-11-11

    The risks associated with batch processing in the manufacture of chemicals and pharmaceuticals via highly exothermic reactions are of special interest due to the possibility of runaway reactions. o-Nitrated benzoyl chlorides are intermediates in the production of agrochemicals and are produced via the reaction of o-nitrated carboxylic acids with thionyl chloride in a solvent mixture. ortho-Nitrated acyl chlorides have exploded violently on attempted distillation on numerous occasions. An inadequate investigation of the process prior to large-scale operation is the most likely cause. Here we present preliminary results of studies on the decomposition of 2-nitrobenzoyl chloride. This study has revealed that the decomposition reaction is strongly condition dependent. The heating rate of the sample plays a preponderant role in the course of the decomposition reaction. That renders the interpretation of differential scanning calorimetry (DSC) or adiabatic calorimetry measurements, which are routinely used to assess the thermochemistry and safety of the large-scale reactions, problematic. Following this on-going study, we report here key features of the system that have been identified. PMID:15518968

  2. Decomposition studies of triisopropylantimony and triallylantimony

    NASA Astrophysics Data System (ADS)

    Li, S. H.; Larsen, C. A.; Stringfellow, G. B.; Gedridge, R. W.

    1991-06-01

    The pyrolysis of triisopropylantimony ((C3H7)3Sb) and triallylantimony ((C3H5)3Sb) has been investigated mass-spectrometrically in He and D2 using a SiO2 flow tube reactor at atmospheric pressure. Both temperature and time dependencies of percent decomposition were studied and the reaction products were analyzed. The overall decomposition processes for both compounds were found to be homogeneous and first order. (C3H7)3Sb pyrolyzes at 250-350° C with no effect of the ambient gas. However, C3H6, C3H8, and C6H14 (2,3-dimethylbutane) were produced in He whereas C3H3D appeared in D2. The pyrolysis is believed to begin via bond cleavage to generate the free C3H7 radicals that, in turn, recombine and disproportionate. Isopropyl radicals react slowly with D2, producing the C3H7D detected. For (C3H5)3Sb, the pyrolysis takes place at 100-160° C. The only major product is C6H10 (1,5-hexadiene). Both the pyrolysis rate and products were independent of the ambient. Two possible mechanisms, homolysis and reductive coupling, are discussed. Assuming that homolysis is the rate-limiting step for the pyrolysis of both (C3H7)3Sb and (C3H5)3Sb, bond strengths of 30.8 and 21.6 kcal/mole for C3H7—Sb and C3H6—Sb were determined from the experimental data. When either (C3H7)3Sb or (C3H5)3Sb was mixed with trimethylindium, a nonvolatile, liquid material, probably an adduct, was formed.

  3. Singular value decomposition with self-modeling applied to determine bacteriorhodopsin intermediate spectra: analysis of simulated data.

    PubMed

    Zimányi, L; Kulcsár, A; Lanyi, J K; Sears, D F; Saltiel, J

    1999-04-13

    An a priori model-independent method for the determination of accurate spectra of photocycle intermediates is developed. The method, singular value decomposition with self-modeling (SVD-SM), is tested on simulated difference spectra designed to mimic the photocycle of the Asp-96 --> Asn mutant of bacteriorhodopsin. Stoichiometric constraints, valid until the onset of the recovery of bleached bacteriorhodopsin at the end of the photocycle, guide the self-modeling procedure. The difference spectra of the intermediates are determined in eigenvector space by confining the search for their coordinates to a stoichiometric plane. In the absence of random noise, SVD-SM recovers the intermediate spectra and their time evolution nearly exactly. The recovery of input spectra and kinetics is excellent although somewhat less exact when realistic random noise is included in the input spectra. The difference between recovered and input kinetics is now visually discernible, but the same reaction scheme with nearly identical rate constants to those assumed in the simulation fits the output kinetics well. SVD-SM relegates the selection of a photocycle model to the late stage of the analysis. It thus avoids derivation of erroneous model-specific spectra that result from global model-fitting approaches that assume a model at the outset. PMID:10200275

  4. Density-based Energy Decomposition Analysis for Intermolecular Interactions with Variationally Determined Intermediate State Energies

    SciTech Connect

    Wu, Q.; Ayers, P.W.; Zhang, Y.

    2009-10-28

    The first purely density-based energy decomposition analysis (EDA) for intermolecular binding is developed within the density functional theory. The most important feature of this scheme is to variationally determine the frozen density energy, based on a constrained search formalism and implemented with the Wu-Yang algorithm [Q. Wu and W. Yang, J. Chem. Phys. 118, 2498 (2003) ]. This variational process dispenses with the Heitler-London antisymmetrization of wave functions used in most previous methods and calculates the electrostatic and Pauli repulsion energies together without any distortion of the frozen density, an important fact that enables a clean separation of these two terms from the relaxation (i.e., polarization and charge transfer) terms. The new EDA also employs the constrained density functional theory approach [Q. Wu and T. Van Voorhis, Phys. Rev. A 72, 24502 (2005)] to separate out charge transfer effects. Because the charge transfer energy is based on the density flow in real space, it has a small basis set dependence. Applications of this decomposition to hydrogen bonding in the water dimer and the formamide dimer show that the frozen density energy dominates the binding in these systems, consistent with the noncovalent nature of the interactions. A more detailed examination reveals how the interplay of electrostatics and the Pauli repulsion determines the distance and angular dependence of these hydrogen bonds.

  5. Studying Reaction Intermediates Formed at Graphenic Surfaces

    NASA Astrophysics Data System (ADS)

    Sarkar, Depanjan; Sen Gupta, Soujit; Narayanan, Rahul; Pradeep, Thalappil

    2014-03-01

    We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

  6. Mechanistic and kinetic studies of the thermal decomposition of TNAZ and NDNAZ

    SciTech Connect

    Anderson, K.; Homsy, J.; Behrens, R.; Bulusu, S.

    1998-12-31

    The authors have studied the mechanism and detailed reaction kinetics of the thermal decomposition of 1,3,3-trinitroazetidine (TNAZ), and separately, its key decomposition intermediate, 1-nitroso-3,3-dinitroacetidine (NDNAZ), using a simultaneous thermogravimetric modulated beam mass spectrometer (STMBMS). These decompositions were conducted in a sealed alumina cell with a 2.5 {micro}m orifice, at varying temperatures and at a range of isothermal temperatures (at 10 C intervals from 120--160 C for NDNAZ and 160--210 C for TNAZ). The gaseous products have been identified and their rates of formation have been measured as a function of time, temperature, and pressure. This system is complex, with TNAZ decomposing by four separate routes, one of which leads to NDNAZ, which itself decomposes by at least two distinct routes.

  7. Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory Study

    SciTech Connect

    Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter A.; Li, Sha; Mavrikakis, Manos

    2014-12-05

    We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxyl-mediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.

  8. Thermal decomposition studies of halogenated organic compounds

    SciTech Connect

    Michael, J.V.; Kumaran, S.S.

    1997-06-01

    Thermal decomposition results for CCl{sub 4}, CHCl{sub 3}, CH{sub 2}Cl{sub 2}, CH{sub 3}Cl, C{sub 3}H{sub 3}Cl, CFCl{sub 3}, CF{sub 2}Cl{sub 2}, CF{sub 3}Cl, CF{sub 2}HCl, CF{sub 3}I, CH{sub 3}I, C{sub 2}H{sub 5}I, C{sub 6}H{sub 5}I, and CCl{sub 2}O are presented. The results were obtained by shock tube techniques coupled with optical spectroscopic detection of transient species formed from dissociation. The method is illustrated with the CH{sub 3}I (+ Kr) {yields} CH{sub 3} + I (+ Kr) reaction where decomposition was monitored using I-atomic resonance absorption spectrometry (ARAS). Modern unimolecular rate theoretical analysis has been carried out on the present cases, and the conclusions from these calculations are discussed. Lastly, the possible destruction of halo-organics by incineration is considered and some implications are discussed.

  9. IN SITU INFRARED STUDY OF CATALYTIC DECOMPOSITION OF NO

    SciTech Connect

    KHALID ALMUSAITEER; RAM KRISHNAMURTHY; STEVEN S.C. CHUANG

    1998-08-18

    The growing concerns for the environment and increasingly stringent standards for NO emission have presented a major challenge to control NO emissions from electric utility plants and automobiles. Catalytic decomposition of NO is the most attractive approach for the control of NO emission for its simplicity. Successful development of an effective catalyst for NO decomposition will greatly decrease the equipment and operation cost of NO control. Due to lack of understanding of the mechanism of NO decomposition, efforts on the search of an effective catalyst have been unsuccessful. Scientific development of an effective catalyst requires fundamental understanding of the nature of active site, the rate-limiting step, and an approach to prolong the life of the catalyst. Research is proposed to study the reactivity of adsorbates for the direct NO decomposition and to investigate the feasibility of two novel approaches for improving catalyst activity and resistance to sintering. The first approach is the use of silanation to stabilize metal crystallites and supports for Cu-ZSM-5 and promoted Pt catalysts; the second is utilization of oxygen spillover and desorption to enhance NO decomposition activity. An innovative infrared reactor system will be used to observe and determine the dynamic behavior and the reactivity of adsorbates during NO decomposition, oxygen spillover, and silanation. A series of experiments including X-ray diffraction, temperature programmed desorption, temperature programmed reaction, X-ray photoelectron spectroscopy will be used to characterized the catalysts. The information obtained from this study will provide a scientific basis for developing an effective catalyst for the NO decomposition under practical flue gas conditions.

  10. In Situ Infrared Study of Catalytic Decomposition of NO

    SciTech Connect

    Cher-Dip Tan; Steven S.C. Chuang

    1997-07-17

    The growing concerns for the environment and increasingly stringent standards for NO emission have presented a major challenge to control NO emmissions from electric utility plants and automobiles. Catalytic decomposition of NO is the most attractive approach for the control of NO emission for its simplicity. Successful development of an effective catalyst for NO decomposition will greatly decrease the equipment and operation cost of NO control. Due to lack of understanding of the mechanism of NO decomposition, efforts on the search of an effective catalyst have been unsuccesful. Scientific development of an effective catalyst requires fundamental understanding of the nature of active site, the rate-limiting step, and an approach to prolong the life of the catalyst. Research is proposed to study the reactivity of adsorbates for the direct NO decomposition and to investigate the feasibility of two novel approaches for improving catalyst activity and resistance to sintering. The first approach is the use of silanation to stabilize metal crystallites and supports for Cu-ZSM-5 and promoted Pt catalysts; the second is utilization of oxygen spillover and desorption to enhance NO decomposition activity. An innovative infrared reactor system will be used to observe and determine the dynamic behavior and the reactivity of adsorbates during NO decomposition, oxygen spillover, and silanation. A series of experiments including X-ray diffraction, temperature programmed desorption, temperature programmed reaction, X-ray photoelectron spectroscopy will be used to characterized the catalysts. The information obtained from this study will provide a scientific basis for developing an effective catalyst for the NO decomposition under practical flue gas conditions.

  11. Comparative Density Functional Study of Methanol Decomposition on Cu4 and Co4 Clusters

    SciTech Connect

    Mehmood, Faisal; Greeley, Jeffrey P.; Zapol, Peter; Curtiss, Larry A.

    2010-11-18

    A density functional theory study of the decomposition of methanol on Cu4 and Co4 clusters is presented. The reaction intermediates and activation barriers have been determined for reaction steps to form H2 and CO. For both clusters, methanol decomposition initiated by C-H and O-H bond breaking was investigated. In the case of a Cu4 cluster, methanol dehydrogenation through hydroxymethyl (CH2OH), hydroxymethylene (CHOH), formyl (CHO), and carbon monoxide (CO) is found to be slightly more favorable. For a Co4 cluster, the dehydrogenation pathway through methoxy (CH3O) and formaldehyde (CH2O) is slightly more favorable. Each of these pathways results in formation of CO and H2. The Co cluster pathway is very favorable thermodynamically and kinetically for dehydrogenation. However, since CO binds strongly, it is likely to poison methanol decomposition to H2 and CO at low temperatures. In contrast, for the Cu cluster, CO poisoning is not likely to be a problem since it does not bind strongly, but the dehydrogenation steps are not energetically favorable. Pathways involving C-O bond cleavage are even less energetically favorable. The results are compared to our previous study of methanol decomposition on Pd4 and Pd8 clusters. Finally, all reaction energy changes and transition state energies, including those for the Pd clusters, are related in a linear, Broensted-Evans-Polanyi plot.

  12. Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO2, H2O and decomposition under boundary layer conditions.

    PubMed

    Newland, Mike J; Rickard, Andrew R; Alam, Mohammed S; Vereecken, Luc; Muñoz, Amalia; Ródenas, Milagros; Bloss, William J

    2015-02-14

    The removal of SO2 in the presence of alkene-ozone systems has been studied for ethene, cis-but-2-ene, trans-but-2-ene and 2,3-dimethyl-but-2-ene, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity for all four alkene-ozone systems confirming a significant reaction for stabilised Criegee intermediates (SCI) with H2O. The observed SO2 removal kinetics are consistent with relative rate constants, k(SCI + H2O)/k(SCI + SO2), of 3.3 (±1.1) × 10(-5) for CH2OO, 26 (±10) × 10(-5) for CH3CHOO derived from cis-but-2-ene, 33 (±10) × 10(-5) for CH3CHOO derived from trans-but-2-ene, and 8.7 (±2.5) × 10(-5) for (CH3)2COO derived from 2,3-dimethyl-but-2-ene. The relative rate constants for k(SCI decomposition)/k(SCI + SO2) are -2.3 (±3.5) × 10(11) cm(-3) for CH2OO, 13 (±43) × 10(11) cm(-3) for CH3CHOO derived from cis-but-2-ene, -14 (±31) × 10(11) cm(-3) for CH3CHOO derived from trans-but-2-ene and 63 (±14) × 10(11) cm(-3) for (CH3)2COO. Uncertainties are ±2σ and represent combined systematic and precision components. These values are derived following the approximation that a single SCI is present for each system; a more comprehensive interpretation, explicitly considering the differing reactivity for syn- and anti-SCI conformers, is also presented. This yields values of 3.5 (±3.1) × 10(-4) for k(SCI + H2O)/k(SCI + SO2) of anti-CH3CHOO and 1.2 (±1.1) × 10(13) for k(SCI decomposition)/k(SCI + SO2) of syn-CH3CHOO. The reaction of the water dimer with CH2OO is also considered, with a derived value for k(CH2OO + (H2O)2)/k(CH2OO + SO2) of 1.4 (±1.8) × 10(-2). The observed SO2 removal rate constants, which technically represent upper limits, are consistent with decomposition being a significant, structure dependent, sink in the atmosphere for syn-SCI. PMID:25562069

  13. Use of diethyldithiocarbamate as a probe to detect stable intermediates during the decomposition of several mutagenic and nonmutagenic N-nitroso compounds.

    PubMed

    Wiessler, M; Tacchi, A M; Pool, B L; Bertram, B

    1986-01-01

    By showing that methyldiethyldithiocarbamate is formed from the reaction of methylnitrosourea and disulfiram, we demonstrated in previous experiments that one of the anticarcinogenic/antimutagenic mechanisms of disulfiram is the scavenging of reactive species. We propose that this reaction may be employed additionally as a model for elucidating the following: (a) possible reactions between alkylating species and nucleophilic sites within the cell, and (b) the existence of stable intermediates during the metabolism of N-nitroso compounds. With structurally related pairs of nitrosoureas (n-propyl/isopropyl; cyclopropyl/allyl; 2-phenylethyl/l-phenylethyl), for which each alkylating group of the first compound can spontaneously rearrange to form the alkylating group of the second isomer, we investigated whether the alkylation proceeds via a monomolecular (sn1) or a bimolecular substitution (sn2). For this, we comparatively determined the relative mutagenic activities of each isomer in Salmonella typhimurium TA 1535, as well as their reactivities towards diethyldithiocarbamate (DDTC) by identifying the reaction products. These studies were aimed at revealing the possible formation of a free carbonium ion in the decomposition of several nitrosoureas in the rat liver supernatant fraction. Our system showed that DDTC reacts by two competing mechanisms: attack at the diazonium ion and at the free carbonium ion. Therefore the striking differences which were observed in the mutagenic potency of cyclopropylnitrosourea and N-nitrosoallylurea as well as of N-nitroso-2-phenylethylurea and N-nitroso-1-phenylethylurea cannot be explained only by the different electrophilic reactivities of the respective intermediates. PMID:3009486

  14. MHD oxidant intermediate temperature ceramic heater study

    NASA Technical Reports Server (NTRS)

    Carlson, A. W.; Chait, I. L.; Saari, D. P.; Marksberry, C. L.

    1981-01-01

    The use of three types of directly fired ceramic heaters for preheating oxygen enriched air to an intermediate temperature of 1144K was investigated. The three types of ceramic heaters are: (1) a fixed bed, periodic flow ceramic brick regenerative heater; (2) a ceramic pebble regenerative heater. The heater design, performance and operating characteristics under conditions in which the particulate matter is not solidified are evaluated. A comparison and overall evaluation of the three types of ceramic heaters and temperature range determination at which the particulate matter in the MHD exhaust gas is estimated to be a dry powder are presented.

  15. Organic residue decomposition: The minicontainer-system a multifunctional tool in decomposition studies.

    PubMed

    Eisenbeis, G; Lenz, R; Heiber, T

    1999-01-01

    The Minicontainer-test, first described by Eisenbeis (1993), was designed to study the kinetics of organic residue decomposition at a microsite level. It is derived from the litterbag technique and consists of polyethylene minicontainers (volume about 1.5 cm(3)) filled with a test substrate (litter, straw, cellulose, etc.). The minicontainers (MCs) are closed at either end with plastic gauze discs of variable mesh size (e.g. 20 microm, 250 microm, 500 microm or 2 mm). A definite number of such units are inserted into PVC-bars, which can be implanted into the soil horizontally or vertically, or be exposed on the soil surface horizontally. The bars are very stable and can be exposed in different environments for months to years. If required, the bars can be removed temporarily and stored, e.g. during soil cultivation. Should fresh litter be used, two phases of decomposition can be distinguished: a fast initial phase, which can be mainly related to the effect of leaching, and a second slow phase depending mainly on the activity of soil organisms and litter quality. Several questions can be addressed to investigations using MCs, e.g. 1) parts of the soil fauna which are involved in decomposition (nematodes, microarthropods, and smaller specimens of the macrofauna, e.g. enchytraeidae, diplopods and dipteran larvae) can be extracted from the litter substrate using a miniscale high gradient extractor, 2) the organic mass loss of litter can be determined, 3) microbial biomass (C(mic), N(mic)) can be assessed by fumigation extraction and 4) microbial activity (respiration) in the test substrate can also be assessed by use of standardised methods. Compared to litterbag studies, the larger number of small replicate units improves the statistical evaluation. Until today the Minicontainer-test has been applied in forestry and agriculture, e.g. studying the effects of liming, soil restoration and the application of insecticides, e.g. Diflubenzuron (Dimilin) and Btk (Bacillus

  16. Computational studies of polysiloxanes : oxidation potentials and decomposition reactions.

    SciTech Connect

    Assary, R. S.; Curtiss, L. A.; Redfern, P. C.; Zhang, Z.; Amine, K.

    2011-06-23

    Silicon-containing solvents have tremendous potential for application as electrolytes for electrical energy storage devices such as lithium-ion (air) batteries and supercapacitors. Quantum chemical methods were employed to investigate trends in oxidation potentials and decomposition reactions of a series of polysiloxanes. Various electron-donating and -withdrawing substituents can be used to tune the oxidation potential in shorter chain siloxanes but not in longer ones. Decomposition reactions of siloxanes in their oxidized states were investigated and compared against their carbon analogues. These studies suggest that the Si-O group provides added stability for siloxanes over their carbon analogues. Computational studies have also been performed for various disiloxanes and siloxanes with spacer groups to understand their thermochemical stability and oxidation potentials.

  17. Nuclear structure studies with intermediate energy probes

    SciTech Connect

    Lee, T.S.H.

    1993-10-01

    Nuclear structure studies with pions are reviewed. Results from a recent study of 1 p-shell nuclei using (e,e{prime}), ({pi}, {pi}{prime}), and ({gamma},{pi}) reactions are reported. Future nuclear structure studies with GeV electrons at CEBAF are also briefly discussed.

  18. Bringing Word Study to Intermediate Classrooms

    ERIC Educational Resources Information Center

    Bloodgood, Janet W.; Pacifici, Linda C.

    2004-01-01

    This article addresses word study for upper elementary and middle school classrooms. Word study is often neglected in classrooms due to misconceptions and fears of classroom teachers, especially teachers of older students. Conclusions from a research project conducted with teachers reveal both positive and negative understandings of implementing…

  19. Theoretical studies on the unimolecular decomposition of propanediols and glycerol.

    PubMed

    Ye, Lili; Zhang, Feng; Zhang, Lidong; Qi, Fei

    2012-05-10

    Polyols, a typical type of alcohol containing multiple hydroxyl groups, are being regarded as a new generation of a green energy platform. In this paper, the decomposition mechanisms for three polyol molecules, i.e., 1,2-propanediol, 1,3-propanediol, and glycerol, have been investigated by quantum chemistry calculations. The potential energy surfaces of propanediols and glycerol have been built by the QCISD(T) and CBS-QB3 methods, respectively. For the three molecules studied, the H(2)O-elimination and C-C bond dissociation reactions show great importance among all of the unimolecular decomposition channels. Rate constant calculations further demonstrate that the H(2)O-elimination reactions are predominant at low temperature and pressure, whereas the direct C-C bond dissociation reactions prevail at high temperature and pressure. The temperature and pressure dependence of calculated rate constants was demonstrated by the fitted Arrhenius equations. This work aims to better understand the thermal decomposition process of polyols and provide useful thermochemical and kinetic data for kinetic modeling of polyols-derived fuel combustion. PMID:22515339

  20. Nuclear structure studies at intermediate energies

    SciTech Connect

    Hintz, N.M.

    1990-07-01

    This report discusses the following topics: Search for dibaryon resonances; analysis of {sup 208}Pb({pi}{sup {plus minus}},{pi}{sup {plus minus}}) data; analysis of {sup 206,207,208}Pb(p,p{prime}) data; study of transition nuclei by (p,p{prime}); search for recoil free {delta}-production; search for low lying magnetic states; proton nucleus scattering and swelling of nucleons; measurement of spin observables in {sup 28}Si(p,p{prime}); strength of tensor force in nuclei; global analysis of (p,p{prime}) reactions to high spin states in {sup 28}Si and {sup 58}Ni and density dependent modifications; MRS Setup and development; and development of coincidence studies with the MRS.

  1. Computational Kinetic Study for the Unimolecular Decomposition Pathways of Cyclohexanone.

    PubMed

    Zaras, Aristotelis M; Dagaut, Philippe; Serinyel, Zeynep

    2015-07-16

    There has been evidence lately that several endophytic fungi can convert lignocellulosic biomass into ketones among other oxygenated compounds. Such compounds could prove useful as biofuels for internal combustion engines. Therefore, their combustion properties are of high interest. Cyclohexanone was identified as an interesting second-generation biofuel ( Boot , M. ; et al. Cyclic Oxygenates: A New Class of Second-Generation Biofuels for Diesel Engines? Energy Fuels 2009 , 23 , 1808 - 1817 ; Klein-Douwel , R. J. H. ; et al. Soot and Chemiluminescence in Diesel Combustion of Bio-Derived, Oxygenated and Reference Fuels . Proc. Combust. Inst. 2009 , 32 , 2817 - 2825 ). However, until recently ( Serinyel , Z. ; et al. Kinetics of Oxidation of Cyclohexanone in a Jet- Stirred Reactor: Experimental and Modeling . Proc. Combust. Inst. 2014 ; DOI: 10.1016/j.proci.2014.06.150 ), no previous studies on the kinetics of oxidation of that fuel could be found in the literature. In this work, we present the first theoretical kinetic study of the unimolecular decomposition pathways of cyclohexanone, a cyclic ketone that could demonstrate important fuel potential. Using the quantum composite G3B3 method, we identified six different decomposition pathways for cyclohexanone and computed the corresponding rate constants. The rate constants were calculated using the G3B3 method coupled with Rice-Ramsperger-Kassel-Marcus theory in the temperature range of 800-2000 K. Our calculations show that the kinetically more favorable channel for thermal decomposition is pathway 2 that produces 1,3-butadien-2-ol, which in turn can isomerize easily to methyl vinyl ketone through a small barrier. The results presented here can be used in a future kinetic combustion mechanism. PMID:25354027

  2. Bullying during the Intermediate School Phase: A South African Study

    ERIC Educational Resources Information Center

    Greeff, P.; Grobler, A. A.

    2008-01-01

    Bullying in the intermediate school phase was studied, using the Revised Olweus Bully/Victim Questionnaire (R-OBVQ). The total sample comprised 360 grade 4 to 6 pupils from English-medium, single-sex schools in Bloemfontein, South Africa. To ensure a more homogeneous sample, the grade (grades 4 to 6) and race (black and white) of the participants…

  3. Experimental study of hydrogen production by direct decomposition of water

    NASA Astrophysics Data System (ADS)

    Bilgen, E.; Galindo, J.; Baykara, S. Z.

    The hydrogen production by direct decomposition of water in a solar furnace is studied. The set-up is a horizontal axis system consisting of two 1.0 kW parabolic concentrators, both powered by a single heliostat. A temperature of 3000 K is possible. The water is fed to the reactor installed at the focal space of the concentrator, and the steam is decomposed at about 2500 K. The reactor consisted of a cylindrical cavity type refractory receiver covered with a silica cupola. The steam was introduced at a known rate into the cavity and the product gases were quenched. After the condensation of steam, hydrogen and oxygen were collected in a reservoir. Results indicate that with an optimized system, it is possible to produce hydrogen at about 70 percent rate of the theoretical value at the temperature level studied.

  4. Batch Studies of Sodium Tetraphenylborate Decomposition on Reduced Palladium Catalyst

    SciTech Connect

    Barnes, M.J.

    2001-02-13

    In these batch experiments we obtained preliminary information on palladium based catalytic decomposition of sodium tetraphenylborate (NaTPB). These preliminary data provide necessary data to design subsequent catalytic decomposition experiments for NaTPB using a continuous stirred tank reactor (CSTR).

  5. Copper Catalyzed Sodium Tetraphenylborate, Triphenylborane, Diphenylborinic Acid and Phenylboronic Acid Decomposition Kinetic Studies in Aqueous Alkaline Solutions

    SciTech Connect

    Crawford, C.L.

    1999-03-15

    This work studied the kinetics of copper-catalyzed decomposition of tetraphenylborate, triphenylborane, diphenylborinic acid and phenylboronic acid (NaTPB, 3PB, 2PB and 1PB, respectively) in aqueous alkaline solution over the temperature range of 25 to 70 degrees C. The statistically designed test matrices added copper sulfate to maximum concentrations of 10 mg/L. The relative rates of decomposition increase in the order of NaTPB < 1PB {tilde} 3PB < 2PB. Dependence of decomposition on the amount of added copper increases in the order of 3PB {tilde} 2PB < 1PB {tilde} NaTPB. Activation energies ranged from 82 to 143 kJ/mole over the temperature range studied. Final decomposition products predominately involved benzene and phenol. All 3PB, 2PB and 1PB intermediate phenylborate species proved relatively stable (< 8 percent decomposition over {tilde} 500 h) towards thermal hydrolysis in 1.5 M NaOH when contained in carbon-steel vessels sealed under air at ambient temperature (23 - 25 degrees C) with no added copper. Measurable (> 10-7 Mh-1) thermal hydrolysis of the phenylborate species occurs at 55 to 70 degrees C in alkaline (0.6-2.3 M OH-, 2-4.7 M Na+) solution with no added copper. The experiments suggest an important role for oxygen in copper-catalyzed phenylborate decomposition. NaTPB decomposes promptly under anoxic conditions while 3PB, 2PB and 1PB decompose faster in aerobic solutions. Benzene and phenol form as the predominant end-products from alkaline copper catalysis in static systems sealed under air. Both 2PB and 1PB decompose with near equal rates and quantitatively produce phenol under flowing air-purge conditions at 25 to 60 degrees C. Mechanisms for copper-catalyzed phenylborate decomposition likely involve a redox process giving loss of a phenyl group from the phenylborate with reduction of cupric ion, or dephenylation by reduced cuprous ion involving a phenylated copper intermediate.

  6. Novel Fragmentation Pathways of Anionic Adducts of Steroids Formed by Electrospray Anion Attachment Involving Regioselective Attachment, Regiospecific Decompositions, Charge-Induced Pathways, and Ion-Dipole Complex Intermediates

    NASA Astrophysics Data System (ADS)

    Rannulu, Nalaka S.; Cole, Richard B.

    2012-09-01

    The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion]- adducts of these steroids revealed that fluoride adduct [M + F]- precursors first lose HF to produce [M - H]- and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d4-pregnenolone, are also discussed.

  7. Fundamental mechanistic studies in formic acid decomposition on transition metal surfaces

    NASA Astrophysics Data System (ADS)

    Mavrikakis, Manos

    2014-03-01

    Formic acid (HCOOH) is a simple molecule that is an abundant product of biomass processing and can serve as an internal source of hydrogen for oxygen removal and upgrading of biomass to chemicals and fuels. In addition, HCOOH can be used as a fuel for low temperature direct fuel cells. We present a systematic study of the HCOOH decomposition reaction mechanism starting from first-principles and including reactivity experiments and microkinetic modeling. In particular, periodic self-consistent Density Functional Theory (DFT) calculations are performed to determine the stability of reactive intermediates and activation energy barriers of elementary steps. Pre-exponential factors are determined from vibrational frequency calculations. Mean-field microkinetic models are developed and calculated reaction rates and reaction orders are then compared with experimentally measured ones. These comparisons provide useful insights on the nature of the active site, most-abundant surface intermediates as a function of reaction conditions and feed composition. Trends across metals on the fundamental atomic-scale level up to selectivity trends will be discussed. Finally, we identify from first-principles alloy surfaces, which may possess better catalytic properties for selective dehydrogenation of HCOOH than monometallic surfaces, thereby guiding synthesis towards promising novel catalytic materials. Work supported as part of the Institute of Atom-efficient Chemical Transformation (IACT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  8. Radial velocity study of the intermediate polar EX Hydrae .

    NASA Astrophysics Data System (ADS)

    Ramirez-Torres, A.; Echevarria, J.; Michel, R.

    Intermediate Polars study from the canonical approach used for non magnetic systems is indeed controversial. Nevertheless, we present hereby high dispersion spectroscopic observations with simultaneous optical photometry of the intermediate polar EX Hya. A normalization method for doppler tomography throughout a complete observation run is introduced. We find rapid variations, orbital period averaged, in the Halpha emission line, with the capability to map the region where they come from in the velocity-space doppler tomogram. By applying the double-Gaussian method to the same line profile we determine a velocity semi-amplitude of the primary star K_1= 52 ± 5 \\: km s-1 which, even if suggests a lower value than recent results, is still within the error bars of the such estimations.

  9. Density functional theory studies on decomposition of ethyl-palladium complexes: an important role of cationic species

    NASA Astrophysics Data System (ADS)

    Raharintsalama, Rado; Munakata, Hiroaki; Koyama, Michihisa; Kubo, Momoji; Miyamoto, Akira

    2005-05-01

    Density functional theory calculations were applied to investigate the β-hydrogen-elimination of the ethyl-palladium complexes, cis-(Me 3P) 2(Et)PdHX, where X = Cl, Br or I, to form ethene and hydrido-palladium complexes. Effects of substitution of halogen ligands and coordination of solvent molecules on geometric parameters and energies were investigated. Studies on solvated reaction intermediates revealed the agostic ethyl-palladium complexes to be important in the decomposition processes of the ethyl-palladium complexes.

  10. Inter-year repeatability study of volatile organic compounds from surface decomposition of human analogues.

    PubMed

    Stadler, Sonja; Desaulniers, Jean-Paul; Forbes, Shari L

    2015-05-01

    Decomposition odour and volatile organic compounds (VOCs) have gained considerable attention recently due to their use by insects and scent detection canines to locate remains. However, a comprehensive and accurate profile of decomposition odour is yet to be confirmed. This is, in part, due to the geographical diversity in the studies conducted and the variation in the methodology and compounds being reported. To date, no repeatability studies of decomposition odour have been conducted in the same environment. In order to address this current gap in the scientific literature, this study conducted three replicate trials in order to evaluate the inter-year repeatability of the decomposition VOC profile in a southern Canadian environment. Surface decomposition trials were conducted during the spring and summer months and the VOCs were analysed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). This study was able to demonstrate that decomposition VOCs are produced consistently during their characteristic stages and that this relationship is maintained under varying environmental factors which influence the rate of decomposition. This consistent production of decomposition VOCs can lead to a better understanding of the mechanisms of soft tissue decomposition and their sources of variation, and it could potentially lead to improved applications of these compounds for the detection of decomposed remains. PMID:24867182

  11. Jellyfish (Cyanea nozakii) decomposition and its potential influence on marine environments studied via simulation experiments.

    PubMed

    Qu, Chang-Feng; Song, Jin-Ming; Li, Ning; Li, Xue-Gang; Yuan, Hua-Mao; Duan, Li-Qin; Ma, Qing-Xia

    2015-08-15

    A growing body of evidence suggests that the jellyfish population in Chinese seas is increasing, and decomposition of jellyfish strongly influences the marine ecosystem. This study investigated the change in water quality during Cyanea nozakii decomposition using simulation experiments. The results demonstrated that the amount of dissolved nutrients released by jellyfish was greater than the amount of particulate nutrients. NH4(+) was predominant in the dissolved matter, whereas the particulate matter was dominated by organic nitrogen and inorganic phosphorus. The high N/P ratios demonstrated that jellyfish decomposition may result in high nitrogen loads. The inorganic nutrients released by C. nozakii decomposition were important for primary production. Jellyfish decomposition caused decreases in the pH and oxygen consumption associated with acidification and hypoxia or anoxia; however, sediments partially mitigated the changes in the pH and oxygen. These results imply that jellyfish decomposition can result in potentially detrimental effects on marine environments. PMID:26088540

  12. Ozone decomposition

    PubMed Central

    Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho

    2014-01-01

    Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

  13. Ozone decomposition.

    PubMed

    Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho; Zaikov, Gennadi E

    2014-06-01

    Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

  14. An electrophysiological study of the intermediate syndrome of organophosphate poisoning.

    PubMed

    Lorenzoni, Paulo José; Gasparetto, Juliano; Kay, Cláudia Suemi Kamoi; Scola, Rosana Herminia; Werneck, Lineu César

    2010-09-01

    Acute organophosphate (OP) poisoning is commonly seen in emergency medicine. Neurologists must be alert to detect neuromuscular transmission failure and other neurological complications that follow OP poisoning. We report a 37-year-old male with acute OP poisoning to emphasize the electrophysiological abnormalities during the intermediate syndrome (IMS). Motor nerve conduction studies revealed that a single nerve stimulation evoked a repetitive compound muscle action potential, whereas repetitive nerve stimulation resulted in a combination of a decrement-increment pattern and a repetitive fade response. Thus, electrophysiological studies can be used to monitor patients with IMS, and these test results correlate well with clinical findings in acute OP poisoning. PMID:20483619

  15. An ab initio study of possible pathways in the thermal decomposition of NaAlH{sub 4}

    SciTech Connect

    Ojwang, J.G.O. Santen, Rutger van; Jan Kramer, Gert; Ke Xuezhi

    2008-11-15

    Density functional theory (DFT) has been used to study the structural stability of possible intermediate alanate structures, Na{sub 5}Al{sub 3}H{sub 14} and Na{sub 2}AlH{sub 5}, in the thermal decomposition of NaAlH{sub 4}. Na{sub 5}Al{sub 3}H{sub 14} crystallizes in the space group P4/mnc with lattice constants a=6.769A, c=10.289A and c/a=1.52. It is shown that both Na{sub 5}Al{sub 3}H{sub 14} and Na{sub 2}AlH{sub 5} have the right thermodynamics and can fit in as an intermediate state during the thermal decomposition process of NaAlH{sub 4}. The heat of formation of Na{sub 5}Al{sub 3}H{sub 14} is -60 kJ/mol H{sub 2}, which is intermediate between that of NaAlH{sub 4} (-51 kJ/mol H{sub 2}) and Na{sub 3}AlH{sub 6} (-69.7 kJ/mol H{sub 2}). An alternative decomposition pathway based on Na{sub 2}AlH{sub 5} has also been discussed. Frequency analysis showed that the least energetic Na{sub 2}AlH{sub 5} structure has imaginary frequencies, implying that it is unstable. The presence of soft phonon modes also shows that Na{sub 5}Al{sub 3}H{sub 14} is mechanically metastable. These results are consistent with the notion that they are the intermediate states that lead to the formation of AlH{sub 3}. This facilitates the mass transport of aluminum atoms in the decomposition pathway of NaAlH{sub 4}. - Projections of the Na{sub 5}Al{sub 3}H{sub 14} structure. Na atoms are represented by small spheres. The polyhedra represents the AlH{sub 6} moiety.

  16. Reprocessed polylactide: studies of thermo-oxidative decomposition.

    PubMed

    Badia, J D; Santonja-Blasco, L; Martínez-Felipe, A; Ribes-Greus, A

    2012-06-01

    The combustion process of virgin and reprocessed polylactide (PLA) was simulated by multi-rate linear non-isothermal thermogravimetric experiments under O(2). A complete methodology that accounted on the thermal stability and emission of gases was thoroughly developed. A new model, Thermal Decomposition Behavior, and novel parameters, the Zero-Decomposition Temperatures, were used to test the thermal stability of the materials under any linear heating rate. The release of gases was monitored by Evolved Gas Analysis with in-line FT-IR analysis. In addition, a kinetic analysis methodology that accounted for variable activation parameters showed that the decomposition process could be driven by the formation of bubbles in the melt. It was found that the combustion technologies for virgin PLA could be transferred for the energetic valorization of its recyclates. Combustion was pointed out as appropriate for the energetic valorization of PLA submitted to more than three successive reprocessing cycles. PMID:22481003

  17. Experimental and modeling study of the thermal decomposition of methyl decanoate

    PubMed Central

    Herbinet, Olivier; Glaude, Pierre-Alexandre; Warth, Valérie; Battin-Leclerc, Frédérique

    2013-01-01

    The experimental study of the thermal decomposition of methyl decanoate was performed in a jet-stirred reactor at temperatures ranging from 773 to 1123 K, at residence times between 1 and 4 s, at a pressure of 800 Torr (106.6 kPa) and at high dilution in helium (fuel inlet mole fraction of 0.0218). Species leaving the reactor were analyzed by gas chromatography. Main reaction products were hydrogen, carbon oxides, small hydrocarbons from C1 to C3, large 1-olefins from 1-butene to 1-nonene, and unsaturated esters with one double bond at the end of the alkyl chain from methyl-2-propenoate to methyl-8-nonenoate. At the highest temperatures, the formation of polyunsaturated species was observed: 1,3-butadiene, 1,3-cyclopentadiene, benzene, toluene, indene, and naphthalene. These results were compared with previous ones about the pyrolysis of n-dodecane, an n-alkane of similar size. The reactivity of both molecules was found to be very close. The alkane produces more olefins while the ester yields unsaturated oxygenated compounds. A detailed kinetic model for the thermal decomposition of methyl decanoate has been generated using the version of software EXGAS which was updated to take into account the specific chemistry involved in the oxidation of methyl esters. This model contains 324 species and 3231 reactions. It provided a very good prediction of the experimental data obtained in jet-stirred reactor. The formation of the major products was analyzed. The kinetic analysis showed that the retro-ene reactions of intermediate unsaturated methyl esters are of importance in low reactivity systems. PMID:23710078

  18. Studies of Corn Stover Decomposition Using the Litter Bag Technique

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Decomposition rates of residue from three genetically-modified corn hybrids expressing one or more Bt endotoxins were compared to that of residue from a near isogenic, unmodified hybrid. The corn hybrids were (i) DKC60-16 (Yieldguard Corn Borer), (ii) DKC60-12 (Yieldguard Corn Rootworm), (iii) DKC60...

  19. A Longitudinal Study on Human Outdoor Decomposition in Central Texas.

    PubMed

    Suckling, Joanna K; Spradley, M Katherine; Godde, Kanya

    2016-01-01

    The development of a methodology that estimates the postmortem interval (PMI) from stages of decomposition is a goal for which forensic practitioners strive. A proposed equation (Megyesi et al. 2005) that utilizes total body score (TBS) and accumulated degree days (ADD) was tested using longitudinal data collected from human remains donated to the Forensic Anthropology Research Facility (FARF) at Texas State University-San Marcos. Exact binomial tests examined the rate of the equation to successfully predict ADD. Statistically significant differences were found between ADD estimated by the equation and the observed value for decomposition stage. Differences remained significant after carnivore scavenged donations were removed from analysis. Low success rates for the equation to predict ADD from TBS and the wide standard errors demonstrate the need to re-evaluate the use of this equation and methodology for PMI estimation in different environments; rather, multivariate methods and equations should be derived that are environmentally specific. PMID:26258913

  20. A comparative density functional study of methanol decomposition on Cu{sub 4} and Co{sub 4} clusters.

    SciTech Connect

    Mehmood, F.; Greeley, J.; Zapol, P.; Curtiss, L. A.

    2010-08-12

    A density functional theory study of the decomposition of methanol on Cu{sub 4} and Co{sub 4} clusters is presented. The reaction intermediates and activation barriers have been determined for reaction steps to form H{sub 2} and CO. For both clusters, methanol decomposition initiated by C-H and O-H bond breaking was investigated. In the case of a Cu{sub 4} cluster, methanol dehydrogenation through hydroxymethyl (CH{sub 2}OH), hydroxymethylene (CHOH), formyl (CHO), and carbon monoxide (CO) is found to be slightly more favorable. For a Co{sub 4} cluster, the dehydrogenation pathway through methoxy (CH{sub 3}O) and formaldehyde (CH{sub 2}O) is slightly more favorable. Each of these pathways results in formation of CO and H{sub 2}. The Co cluster pathway is very favorable thermodynamically and kinetically for dehydrogenation. However, since CO binds strongly, it is likely to poison methanol decomposition to H{sub 2} and CO at low temperatures. In contrast, for the Cu cluster, CO poisoning is not likely to be a problem since it does not bind strongly, but the dehydrogenation steps are not energetically favorable. Pathways involving C-O bond cleavage are even less energetically favorable. The results are compared to our previous study of methanol decomposition on Pd{sub 4} and Pd{sub 8} clusters. Finally, all reaction energy changes and transition state energies, including those for the Pd clusters, are related in a linear, Broensted?Evans?Polanyi plot.

  1. Adiabatic calorimetric decomposition studies of 50 wt.% hydroxylamine/water.

    PubMed

    Cisneros, L O; Rogers, W J; Mannan, M S

    2001-03-19

    Calorimetric data can provide a basis for determining potential hazards in reactions, storage, and transportation of process chemicals. This work provides calorimetric data for the thermal decomposition behavior in air of 50wt.% hydroxylamine/water (HA), both with and without added stabilizers, which was measured in closed cells with an automatic pressure tracking adiabatic calorimeter (APTAC). Among the data provided are onset temperatures, reaction order, activation energies, pressures of noncondensable products, thermal stability at 100 degrees C, and the effect of HA storage time. Discussed also are the catalytic effects of carbon steel, stainless steel, stainless steel with silica coating, inconel, titanium, and titanium with silica coating on the reaction self-heat rates and onset temperatures. In borosilicate glass cells, HA was relatively stable at temperatures up to 133 degrees C, where the HA decomposition self-heat rate reached 0.05 degrees C/min. The added stabilizers appeared to reduce HA decomposition rates in glass cells and at ambient temperatures. The tested metals and metal surfaces coated with silica acted as catalysts to lower the onset temperatures and increase the self-heat rates. PMID:11165058

  2. Decomposition and plant-available nitrogen in biosolids: laboratory studies, field studies, and computer simulation.

    PubMed

    Gilmour, John T; Cogger, Craig G; Jacobs, Lee W; Evanylo, Gregory K; Sullivan, Dan M

    2003-01-01

    This research combines laboratory and field studies with computer simulation to characterize the amount of plant-available nitrogen (PAN) released when municipal biosolids are land-applied to agronomic crops. In the laboratory studies, biosolids were incubated in or on soil from the land application sites. Mean biosolids total C, organic N, and C to N ratio were 292 g kg(-1), 41.7 g kg(-1), and 7.5, respectively. Based on CO2 evolution at 25 degrees C and optimum soil moisture, 27 of the 37 biosolids-soil combinations had two decomposition phases. The mean rapid and slow fraction rate constants were 0.021 and 0.0015 d(-1), respectively, and the rapid fraction contained 23% of the total C assuming sequential decomposition. Where only one decomposition phase existed, the mean first order rate constant was 0.0046 d(-1). The mean rate constant for biosolids stored in lagoons for an extended time was 0.00097 d(-1). The only treatment process that was related to biosolids treatment was stabilization by storage in a lagoon. Biosolids addition rates (dry basis) ranged from 1.3 to 33.8 Mg ha(-1) with a mean value of 10.6 Mg ha(-1). A relationship between fertilizer N rate and crop response was used to estimate observed PAN at each site. Mean observed PAN during the growing season was 18.9 kg N Mg(-1) or 37% of the biosolids total N. Observed PAN was linearly related to biosolids total N. Predicted PAN using the computer model Decomposition, actual growing-season weather, actual analytical data, and laboratory decomposition kinetics compared well with observed PAN. The mean computer model prediction of growing-season PAN was 19.2 kg N Mg(-1) and the slope of the regression between predicted and observed PAN was not significantly different from unity. Predicted PAN obtained using mean decomposition kinetics was related to predicted PAN using actual decomposition kinetics suggesting that mean rate constants, actual weather, and actual analytical data could be used in

  3. Thermal decomposition studies of 1,3,3-trinitroazetidine (TNAZ) and 1-nitroso-3,3-dinitroazetidine (NDNAZ) by simultaneous thermogravimetric modulated beam mass spectroscopy

    SciTech Connect

    Behrens, R. Jr.; Bulusu, S.

    1995-12-01

    The initial results from a study of the thermal decomposition of TNAZ, TNAZ-1-{sup 15}NO{sub 2} and NDNAZ using the simultaneous thermogravimetric modulated beam mass spectrometer (STMBMS) are presented. The major products formed in the decomposition of TNAZ are NO{sub 2} and NO with slightly lesser amounts of H{sub 2}O, HCN, CO/N{sub 2}, CO{sub 2}/N{sub 2}O and NDNAZ. The major product formed in the decomposition of NDNAZ is NO with lesser amounts of H{sub 2}O, HCN, CO/N{sub 2}O. The lower molecular weight products are similar to those observed in RSFTIR and IRMPD studies conducted previously by others. However, this study has shown that the mononitroso analogue of TNAZ, NDNAZ, is an important intermediate formed during the decomposition of TNAZ. It plays an important role in determining the identity of the products formed in the decomposition of TNAZ. The temporal behaviors Of the ion signals associated with the various thermal decomposition products from TNAZ, TNAZ-1-{sup 15}NO{sub 2} and NDNAZ are also presented. The illustrate the evolution sequence of the various products that are associated with the different reaction pathways that control the decomposition of these materials. In particular, the study of the {sup 15}N-labeled sample revealed that NO{sub 2} originates from both the likely sites in the TNAZ molecule and that the cleavage of the nitramine-NO{sub 2} group precedes that of the C-NO{sub 2} cleavage, resulting in similar sequences in the formation of NO and NDNAZ also.

  4. Competing channels in the thermal decomposition of azidoacetone studied by pyrolysis in combination with molecular beam mass spectrometric techniques.

    PubMed

    O'Keeffe, Patrick; Scotti, Giorgio; Stranges, Domenico; Rodrigues, Paula; Barros, M Teresa; Costa, Maria L

    2008-04-10

    The thermal decomposition of azidoacetone (CH3COCH2N3) was studied using a combined experimental and computational approach. Flash pyrolysis at a range of temperatures (296-1250 K) was used to induce thermal decomposition, and the resulting products were expanded into a molecular beam and subsequently analyzed using electron bombardment ionization coupled to a quadrupole mass spectrometer. The advantages of this technique are that the parent molecules spend a very short time in the pyrolysis zone (20-30 mus) and that the subsequent expansion permits the stabilization of thermal products that are not observable using conventional pyrolysis methods. A detailed analysis of the mass spectra as a function of pyrolysis temperature revealed the participation of five thermal decomposition channels. Ab initio calculations on the stable structures and transition states of the azidoacetone system in combination with an analysis of the dissociative ionization pattern of each channel allowed the identity and mechanism of each channel to be elucidated. At low temperatures (296-800 K) the azide decomposes principally by the loss of N2 to yield the imine (CH3COCHNH), which can further decompose to CH3CO and CHNH. At low and intermediate temperatures a process involving the loss of N2 to yield CH3CHO and HCN is also open. Finally, at high temperatures (800-1250 K) a channel in which the azide decomposes to a stable cyclic amine (CO(CH2)2NH) (after loss of N2) is active. The last channel involves subsequent thermal decomposition of this cyclic amine to ketene (H2CCO) and methanimine (H2CNH). PMID:18341306

  5. Study of the kinetics of catalytic decomposition of hydrazine vapors on palladium

    NASA Technical Reports Server (NTRS)

    Khomenko, A. A.; Apelbaum, L. O.

    1987-01-01

    The decomposition rates of N2H4 on a palladium surface are studied. Experiments were conducted in a circulating unit at atmosphere pressure. The experimental method is described. The laws found for the reaction kinetics are explained by equations.

  6. Experimental studies of pion-nucleus interactions at intermediate energies

    SciTech Connect

    Not Available

    1991-12-31

    This report summarizes the work on experimental research in intermediate energy nuclear physics carried out at New Mexico State University in 1991 under a great from the US Department of Energy. Most of these studies have involved investigations of various pion-nucleus interactions. The work has been carried out both with the LAMPF accelerator at the Los Alamos National Laboratory and with the cyclotron at the Paul Scherrer Institute (PSI) near Zurich, Switzerland. Part of the experimental work involves measurements of new data on double-charge-exchange scattering, using facilities at LAMPF which we helped modify, and on pion absorption, using a new detector system at PSI that covers nearly the full solid-angle region which we helped construct. Other work involved preparation for future experiments using polarized nuclear targets and a new high-resolution spectrometer system for detecting {pi}{sup 0} mesons. We also presented several proposals for works to be done in future years, involving studies related to pi-mesonic atoms, fundamental pion-nucleon interactions, studies of the difference between charged and neutral pion interactions with the nucleon, studies of the isospin structure of pion-nucleus interactions, and pion scattering from polarized {sup 3}He targets. This work is aimed at improving our understanding of the pion-nucleon interaction, of the pion-nucleus interaction mechanism, and of nuclear structure.

  7. Urea and urea nitrate decomposition pathways: a quantum chemistry study.

    PubMed

    Tokmakov, Igor V; Alavi, Saman; Thompson, Donald L

    2006-03-01

    Electronic structure calculations have been performed to investigate the initial steps in the gas-phase decomposition of urea and urea nitrate. The most favorable decomposition pathway for an isolated urea molecule leads to HNCO and NH3. Gaseous urea nitrate formed by the association of urea and HNO3 has two isomeric forms, both of which are acid-base complexes stabilized by the hydrogen-bonding interactions involving the acidic proton of HNO3 and either the O or N atoms of urea, with binding energies (D0(o), calculated at the G2M level with BSSE correction) of 13.7 and 8.3 kcal/mol, respectively, and with estimated standard enthalpies of formation (delta(f)H298(o) of -102.3 and -97.1 kcal/mol, respectively. Both isomers can undergo relatively facile double proton transfer within cyclic hydrogen-bonded structures. In both cases, HNO3 plays a catalytic role for the (1,3) H-shifts in urea by acting as a donor of the first and an acceptor of the second protons transferred in a relay fashion. The double proton transfer in the carbonyl/hydrogen bond complex mediates the keto-enol tautomerization of urea, and in the other complex the result is the breakdown of the urea part to the HNCO and NH3 fragments. The enolic form of urea is not expected to accumulate in significant quantities due to its very fast conversion back to H2NC(O)NH2 which is barrierless in the presence of HNO3. The HNO3-catalyzed breakdown of urea to HNCO and NH3 is predicted to be the most favorable decomposition pathway for gaseous urea nitrate. Thus, HNCO + NH3 + HNO3 and their association products (e.g., ammonium nitrate and isocyanate) are expected to be the major initial products of the urea nitrate decomposition. This prediction is consistent with the experimental T-jump/FTIR data [Hiyoshi et al. 12th Int. Detonation Symp., Aug 11-16, San Diego, CA, 2002]. PMID:16494387

  8. Chunk decomposition contributes to forming new mental representations: An ERP study.

    PubMed

    Zhang, Zhonglu; Xing, Qiang; Li, Hong; Warren, Christopher Michael; Tang, Zhiwen; Che, Jingshang

    2015-06-26

    Whereas previous studies mainly focused on the role of chunk decomposition on how to break impasse in insight occurrence, our study aimed to investigate the role of chunk decomposition in forming new mental representations. For this purpose, the Chinese riddle comprehension task was employed in which the riddle involves either tight or loose chunk decomposition. The event-related potentials (ERPs) were measured after the onset of an answer hint, with which participants were instructed to comprehend the Chinese riddles. The behavioral results showed that participants performed worse on riddle comprehension in tight chunk condition than in loose chunk condition. In addition, we found larger N100 and P300 deflections in the former condition than in the latter condition. These findings suggest that early perceptual processing is crucially required by chunk decomposition, which contributes to forming new mental representations by integrating the perceptual and semantic information. PMID:25957557

  9. Revisiting formic acid decomposition on metallic powder catalysts: Exploding the HCOOH decomposition volcano curve

    NASA Astrophysics Data System (ADS)

    Tang, Yadan; Roberts, Charles A.; Perkins, Ryan T.; Wachs, Israel E.

    2016-08-01

    This study revisits the classic volcano curve for HCOOH decomposition by metal catalysts by taking a modern catalysis approach. The metal catalysts (Au, Ag, Cu, Pt, Pd, Ni, Rh, Co and Fe) were prepared by H2 reduction of the corresponding metal oxides. The number of surface active sites (Ns) was determined by formic acid chemisorption. In situ IR indicated that both monodentate and bidentate/bridged surface HCOO* were present on the metals. Heats of adsorption (ΔHads) for surface HCOO* values on metals were taken from recently reported DFT calculations. Kinetics for surface HCOO* decomposition (krds) were determined with TPD spectroscopy. Steady-state specific activity (TOF = activity/Ns) for HCOOH decomposition over the metals was calculated from steady-state activity (μmol/g-s) and Ns (μmol/g). Steady-state TOFs for HCOOH decomposition weakly correlated with surface HCOO* decomposition kinetics (krds) and ΔHads of surface HCOO* intermediates. The plot of TOF vs. ΔHads for HCOOH decomposition on metal catalysts does not reproduce the classic volcano curve, but shows that TOF depends on both ΔHads and decomposition kinetics (krds) of surface HCOO* intermediates. This is the first time that the classic catalysis study of HCOOH decomposition on metallic powder catalysts has been repeated since its original publication.

  10. Breast tissue decomposition with spectral distortion correction: A postmortem study

    PubMed Central

    Ding, Huanjun; Zhao, Bo; Baturin, Pavlo; Behroozi, Farnaz; Molloi, Sabee

    2014-01-01

    Purpose: To investigate the feasibility of an accurate measurement of water, lipid, and protein composition of breast tissue using a photon-counting spectral computed tomography (CT) with spectral distortion corrections. Methods: Thirty-eight postmortem breasts were imaged with a cadmium-zinc-telluride-based photon-counting spectral CT system at 100 kV. The energy-resolving capability of the photon-counting detector was used to separate photons into low and high energy bins with a splitting energy of 42 keV. The estimated mean glandular dose for each breast ranged from 1.8 to 2.2 mGy. Two spectral distortion correction techniques were implemented, respectively, on the raw images to correct the nonlinear detector response due to pulse pileup and charge-sharing artifacts. Dual energy decomposition was then used to characterize each breast in terms of water, lipid, and protein content. In the meantime, the breasts were chemically decomposed into their respective water, lipid, and protein components to provide a gold standard for comparison with dual energy decomposition results. Results: The accuracy of the tissue compositional measurement with spectral CT was determined by comparing to the reference standard from chemical analysis. The averaged root-mean-square error in percentage composition was reduced from 15.5% to 2.8% after spectral distortion corrections. Conclusions: The results indicate that spectral CT can be used to quantify the water, lipid, and protein content in breast tissue. The accuracy of the compositional analysis depends on the applied spectral distortion correction technique. PMID:25281953

  11. Breast tissue decomposition with spectral distortion correction: A postmortem study

    SciTech Connect

    Ding, Huanjun; Zhao, Bo; Baturin, Pavlo; Behroozi, Farnaz; Molloi, Sabee

    2014-10-15

    Purpose: To investigate the feasibility of an accurate measurement of water, lipid, and protein composition of breast tissue using a photon-counting spectral computed tomography (CT) with spectral distortion corrections. Methods: Thirty-eight postmortem breasts were imaged with a cadmium-zinc-telluride-based photon-counting spectral CT system at 100 kV. The energy-resolving capability of the photon-counting detector was used to separate photons into low and high energy bins with a splitting energy of 42 keV. The estimated mean glandular dose for each breast ranged from 1.8 to 2.2 mGy. Two spectral distortion correction techniques were implemented, respectively, on the raw images to correct the nonlinear detector response due to pulse pileup and charge-sharing artifacts. Dual energy decomposition was then used to characterize each breast in terms of water, lipid, and protein content. In the meantime, the breasts were chemically decomposed into their respective water, lipid, and protein components to provide a gold standard for comparison with dual energy decomposition results. Results: The accuracy of the tissue compositional measurement with spectral CT was determined by comparing to the reference standard from chemical analysis. The averaged root-mean-square error in percentage composition was reduced from 15.5% to 2.8% after spectral distortion corrections. Conclusions: The results indicate that spectral CT can be used to quantify the water, lipid, and protein content in breast tissue. The accuracy of the compositional analysis depends on the applied spectral distortion correction technique.

  12. Resonance Raman spectroscopic studies of enzymesubstrate intermediates at 5 K

    NASA Astrophysics Data System (ADS)

    Kim, Munsok; Carey, Paul R.

    1991-01-01

    A simple and versatile system for resonance Raman (RR) spectroscopic analysis of enzymesubstrate complexes at liquid helium temperatures is described. The system allows us to record high-quality RR spectra for dithioacyl papain intermediates (MeO-Phe-Gly- and MeO-Gly-Gly-Phe-Gly-C (dbnd S)S-papain) in ice matrices at 5 K. Based on established structure-spectra correlations, it is concluded that the active-site conformation of the intermediates about the φ', ψ' glycinic linkages and cysteine-25 side chain is B-G+-PH both in ice matrices at 5 K and in solution at room temperature.

  13. IN SITU INFRARED STUDY OF CATALYTIC DECOMPOSITION OF NITRIC OXIDE (NO)

    SciTech Connect

    Unknown

    1999-12-31

    The growing concerns for the environment and increasingly stringent standards for NO emission have presented a major challenge to control NO emissions from electric utility plants and automobiles. Catalytic decomposition of NO is the most attractive approach for the control of NO emission for its simplicity. Successful development of an effective catalyst for NO decomposition will greatly decrease the equipment and operation cost of NO control. Due to lack of understanding of the mechanism of NO decomposition, efforts on the search of an effective catalyst have been unsuccessful. Scientific development of an effective catalyst requires fundamental understanding of the nature of active site, the rate-limiting step, and an approach to prolong the life of the catalyst. The authors have investigated the feasibility of two novel approaches for improving catalyst activity and resistance to sintering. The first approach is the use of silanation to stabilize metal crystallites and supports for Cu-ZSM-5 and promoted Pt catalysts; the second is utilization of oxygen spillover and desorption to enhance NO decomposition activity. The silanation approach failed to stabilize Cu-ZSM-5 activity under hydrothermal condition. Silanation blocked the oxygen migration and inhibited oxygen desorption. Oxygen spillover was found to be an effective approach for promoting NO decomposition activity on Pt-based catalysts. Detailed mechanistic study revealed the oxygen inhibition in NO decomposition and reduction as the most critical issue in developing an effective catalytic approach for controlling NO emission.

  14. A Study of Japan for the Intermediate Grades.

    ERIC Educational Resources Information Center

    Sauer, Susan

    Arranged in outline form, this unit on Japan contains over 40 activities for intermediate grade students. Subjects covered are human and physical geography, social history, life style, communication and travel, occupations, recreation, art, education, government, and relations with the United States. Four to 10 activities are described under each…

  15. A radial velocity study of the intermediate polar EX Hydrae

    NASA Astrophysics Data System (ADS)

    Echevarría, J.; Ramírez-Torres, A.; Michel, R.; Hernández Santisteban, J. V.

    2016-09-01

    A study on the intermediate polar EX Hya is presented, based on simultaneous photometry and high-dispersion spectroscopic observations, during four consecutive nights. The strong photometric modulation related to the 67-min spin period of the primary star is clearly present, as well as the narrow eclipses associated with the orbital modulation. Since our eclipse timings have been obtained almost 91 000 cycles since the last reported observations, we present new linear ephemeris, although we cannot rule out a sinusoidal variation suggested by previous authors. The system shows double-peaked H α, H β and He I λ5876 Å emission lines, with almost no other lines present. As H α is the only line with enough S/N ratio in our observations, we have concentrated our efforts in its study, in order to obtain a reliable radial velocity semi-amplitude. From the profile of this line, we find two important components; one with a steep rise and velocities not larger than ˜1000 km s-1 and another broader component extending up to ˜2000 km s-1, which we interpret as coming mainly from the inner disc. A strong and variable hotspot is found and a stream-like structure is seen at times. We show that the best solution correspond to K1 = 58 ± 5 km s-1 from H α, from the two emission components, which are both in phase with the orbital modulation. We remark on a peculiar effect in the radial velocity curve around phase zero, which could be interpreted as a Rositter-MacLaughlin-like effect, which has been taken into account before deriving K1. This value is compatible with the values found in high resolution both in the ultraviolet and X-ray. Using the published inclination angle of i =78° ± 1° and semi-amplitude K2 = 432 ± 5 km s-1, we find: M1 = 0.78 ± 0.03 M⊙, M2 = 0.10 ± 0.02 M⊙ and a = 0.67 ± 0.01 R⊙. Doppler Tomography has been applied, to construct six Doppler tomograms for single orbital cycles spanning the four days of observations to support our conclusions

  16. Thermal decomposition pathway and desorption study of isopropanol and tert-butanol on Si(100)

    NASA Astrophysics Data System (ADS)

    Kim, Jaehyun; Kim, Kwansoo; Yong, Kijung

    2002-09-01

    Thermal decomposition pathway and desorption of isopropanol (IPA) and tert-butanol on Si(100) were studied using temperature programed desorption. Adsorbed alcohols studied were decomposed into atomic hydrogen and alkoxy on the surface. During heating the sample up to 1000 K, acetone, propylene, and hydrogen were desorbed as decomposition products of IPA on Si(100). Desorption pathways of IPA on Si(100) were largely consistent with those on metal surfaces: beta-hydride elimination reaction to acetone and C-O scission to propylene. For tert-butanol, which has no beta-hydrogen, isobutene and hydrogen were observed as main desorption products. copyright 2002 American Vacuum Society.

  17. Trend extraction using empirical mode decomposition and statistical empirical mode decomposition: Case study: Kuala Lumpur stock market

    NASA Astrophysics Data System (ADS)

    Jaber, Abobaker M.

    2014-12-01

    Two nonparametric methods for prediction and modeling of financial time series signals are proposed. The proposed techniques are designed to handle non-stationary and non-linearity behave and to extract meaningful signals for reliable prediction. Due to Fourier Transform (FT), the methods select significant decomposed signals that will be employed for signal prediction. The proposed techniques developed by coupling Holt-winter method with Empirical Mode Decomposition (EMD) and it is Extending the scope of empirical mode decomposition by smoothing (SEMD). To show performance of proposed techniques, we analyze daily closed price of Kuala Lumpur stock market index.

  18. The FB-Line and F-Canyon HAN/Nitric Acid Decomposition Study

    SciTech Connect

    Hang, T.

    1998-08-19

    Separations requested SRTC study the autocatalytic decomposition of the hydroxylamine nitrate which may occur in the presence of concentrated nitric acid with respect to making-up cold feed solutions. The data obtained from this study will provide Separations an envelope within which safe operations can be conducted.

  19. Improving interMediAte Risk management. MARK study

    PubMed Central

    2011-01-01

    Background Cardiovascular risk functions fail to identify more than 50% of patients who develop cardiovascular disease. This is especially evident in the intermediate-risk patients in which clinical management becomes difficult. Our purpose is to analyze if ankle-brachial index (ABI), measures of arterial stiffness, postprandial glucose, glycosylated hemoglobin, self-measured blood pressure and presence of comorbidity are independently associated to incidence of vascular events and whether they can improve the predictive capacity of current risk equations in the intermediate-risk population. Methods/Design This project involves 3 groups belonging to REDIAPP (RETICS RD06/0018) from 3 Spanish regions. We will recruit a multicenter cohort of 2688 patients at intermediate risk (coronary risk between 5 and 15% or vascular death risk between 3-5% over 10 years) and no history of atherosclerotic disease, selected at random. We will record socio-demographic data, information on diet, physical activity, comorbidity and intermittent claudication. We will measure ABI, pulse wave velocity and cardio ankle vascular index at rest and after a light intensity exercise. Blood pressure and anthropometric data will be also recorded. We will also quantify lipids, glucose and glycosylated hemoglobin in a fasting blood sample and postprandial capillary glucose. Eighteen months after the recruitment, patients will be followed up to determine the incidence of vascular events (later follow-ups are planned at 5 and 10 years). We will analyze whether the new proposed risk factors contribute to improve the risk functions based on classic risk factors. Discussion Primary prevention of cardiovascular diseases is a priority in public health policy of developed and developing countries. The fundamental strategy consists in identifying people in a high risk situation in which preventive measures are effective and efficient. Improvement of these predictions in our country will have an immediate

  20. Kinetic study of non-isothermal decomposition of a composite diasporic-boehmitic bauxite

    NASA Astrophysics Data System (ADS)

    Samouhos, M.; Angelopoulos, P.; Pilatos, G.; Taxiarchou, M.; Papageorgiou, S.

    2016-04-01

    In the current study, the kinetic of the thermal decomposition of a composite diasporic-boehmitic bauxite is investigated under non-isothermal heating conditions by means of thermogravimetric analysis. The calculation of activation energy (Ea) has been performed by various methods and the attained values range from 185000 to 190000 J.mol-1 for conversion rate of 0.5. The first-order kinetic model can adequately be used to describe thermal decomposition of bauxite composite, while the pre-exponential factor value was found to be 2.088*1011 min-1. The calculated activation energy value together with pre-exponential factor and the solid state kinetic model factors enable the simulation of the thermal decomposition under various heating conditions by the implementation of an ordinary differential equation. The calculated values are in satisfactory agreement with the experimental ones.

  1. Headspace analysis gas-phase infrared spectroscopy: a study of xanthate decomposition on mineral surfaces

    NASA Astrophysics Data System (ADS)

    Vreugdenhil, Andrew J.; Brienne, Stephane H. R.; Markwell, Ross D.; Butler, Ian S.; Finch, James A.

    1997-03-01

    The O-ethyldithiocarbonate (ethyl xanthate, CH 3CH 2OCS -2) anion is a widely used reagent in mineral processing for the separation of sulphide minerals by froth flotation. Ethyl xanthate interacts with mineral powders to produce a hydrophobic layer on the mineral surface. A novel infrared technique, headspace analysis gas-phase infrared spectroscopy (HAGIS) has been used to study the in situ thermal decomposition products of ethyl xanthate on mineral surfaces. These products include CS 2, COS, CO 2, CH 4, SO 2, and higher molecular weight alkyl-containing species. Decomposition pathways have been proposed with some information determined from 2H- and 13C-isotope labelling experiments.

  2. A statistical approach based on accumulated degree-days to predict decomposition-related processes in forensic studies.

    PubMed

    Michaud, Jean-Philippe; Moreau, Gaétan

    2011-01-01

    Using pig carcasses exposed over 3 years in rural fields during spring, summer, and fall, we studied the relationship between decomposition stages and degree-day accumulation (i) to verify the predictability of the decomposition stages used in forensic entomology to document carcass decomposition and (ii) to build a degree-day accumulation model applicable to various decomposition-related processes. Results indicate that the decomposition stages can be predicted with accuracy from temperature records and that a reliable degree-day index can be developed to study decomposition-related processes. The development of degree-day indices opens new doors for researchers and allows for the application of inferential tools unaffected by climatic variability, as well as for the inclusion of statistics in a science that is primarily descriptive and in need of validation methods in courtroom proceedings. PMID:21198596

  3. Study of entropy in intermediate-energy heavy ion collisions

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao-Ji; Guo, Wen-Jun; Li, Xian-Jie; Wang, Kuo

    2016-03-01

    Using the isospin-dependent quantum molecular dynamics model, the entropy of an intermediate-energy heavy ion collision system after the reaction and the number of deuteronlike and protonlike particles produced in the collision is calculated. In the collision, different parameters are used and the mass number used here is from 40 to 93 at incident energy from 150 MeV to 1050 MeV. We build a new model in which the density distribution of the reaction product is used to calculate the size of the entropy. The entropy calculated with this model is in good agreement with experimental values. Our data reveals that with the increase of the neutron-proton ratio and impact parameter, the entropy of the reaction system decreases, and it increases with the increase of system mass and reaction energy.

  4. Study of Humidity Effect on Benzene Decomposition by the Dielectric Barrier Discharge Nonthermal Plasma Reactor

    NASA Astrophysics Data System (ADS)

    Ma, Tianpeng; Zhao, Qiong; Liu, Jianqi; Zhong, Fangchuan

    2016-06-01

    The humidity effects on the benzene decomposition process were investigated by the dielectric barrier discharge (DBD) plasma reactor. The results showed that the water vapor played an important role in the benzene oxidation process. It was found that there was an optimum humidity value for the benzene removal efficiency, and at around 60% relative humidity (RH), the optimum benzene removal efficiency was achieved. At a SIE of 378 J/L, the removal efficiency was 66% at 0% RH, while the removal efficiency reached 75.3% at 60% RH and dropped to 69% at 80% RH. Furthermore, the addition of water inhibited the formation of ozone and NO2 remarkably. Both of the concentrations of ozone and NO2 decreased with increasing of the RH at the same specific input energy. At a SIE of 256 J/L, the concentrations of ozone and NO2 were 5.4 mg/L and 1791 ppm under dry conditions, whereas they were only 3.4 mg/L and 1119 ppm at 63.5% RH, respectively. Finally, the outlet gas after benzene degradation was qualitatively analyzed by FT-IR and GC-MS to determine possible intermediate byproducts. The results suggested that the byproducts in decomposition of benzene primarily consisted of phenol and substitutions of phenol. Based on these byproducts a benzene degradation mechanism was proposed. supported by National Natural Science Foundation of China (Nos. 11205007 and 11205029)

  5. Modeling study of carbonate decomposition in LLNL`s 4TU pilot oil shale retort

    SciTech Connect

    Thorsness, C.B.

    1994-10-14

    Lawrence Livermore National Laboratory`s (LLNL) 4 tonne-per-day oil shale Pilot Retort (4TU-Pilot) has been modeled to study the degree of carbonate decomposition occurring in the process. The modeling uses a simplified version of the processes occurring in the retort to allow parametric studies to be performed. The primary focus of the work is on the sensitivity of computed carbonate decomposition to the assumed manner in which solid material leaves the retort. It was found that for a variety of assumptions about solid passage and evolution within the process the computed carbonate decomposition varied by only a few percent. It was also determined that using available kinetic expressions based on literature data led to a consistent underestimate of the carbonate decomposition, from 12--17% low on an absolute basis and on a relative basis as much as a factor of seven times too low. A simplified kinetic expression based on limited data from laboratory experiments on the same shale as used in the 4TU-Pilot run was also employed and found to match the pilot results fairly well.

  6. Theoretical study of β-HMX decomposition mechanism of the solid phase under shock loadings

    NASA Astrophysics Data System (ADS)

    Ji, Guangfu; Ge, Nina; Chen, Xiangrong

    2015-06-01

    Study material properties under extreme conditions is a fundamental problem in the field of condensed matter physics. The decomposition mechanisms of energetic materials under the shock wave become a hot topic in recent years. In this paper, molecular dynamics simulations combined with multi-scale shock technology (MSST) are used to study the decomposition mechanism, shock sensitivity and electronic structure of β-HMX. First, the decomposition mechanism of β-HMX perfect crystal were studied at different shock speeds. We found that when the shock wave at a speed 8 km / s is loaded, the decomposition reaction start at N-NO2 bond breakage; when the shock wave at a speed of 10 km / s and 11 km / s is loaded, the the first decomposition reaction is CH bond breaking, and accompanied by the formation of five-membered ring and transfer of hydrogen ions. The simulation results also show that when the shock wave velocity is increased, the higher the pressure generated in the high-pressure N-NO2 bond cleavage was inhibited significantly. Secondly, the impact of its initial chemical reaction process along different crystal axis directions were studied, the results showed that along the a-axis and c-axis shock sensitivity is higher, and along the b-axis sensitivity is lower. We believe that the system of all sensitivity of direction is due to the rotation of the friction between the slip plane of crystals and molecules. Finally, we discussed the solid phase β-HMX electronic properties change under the shock wave loadings. We found that in the 11 km/s under the impact load, when the pressure reaches 130 GPa, zero bandgap is reached.

  7. Experimental study of two material decomposition methods using multi-bin photon counting detectors

    NASA Astrophysics Data System (ADS)

    Zimmerman, Kevin C.; Sidky, Emil Y.; Gilat Schmidt, Taly

    2014-03-01

    Photon-counting detectors with multi-bin pulse height analysis (PHA) are capable of extracting energy dependent information which can be exploited for material decomposition. Iterative decomposition algorithms have been previously implemented which require prior knowledge of the source spectrum, detector spectral response, and energy threshold settings. We experimentally investigated two material decomposition methods that do not require explicit knowledge of the source spectrum and spectral response. In the first method, the effective spectrum for each energy bin is estimated from calibration transmission measurements, followed by an iterative maximum likelihood decomposition algorithm. The second investigated method, first proposed and tested through simulations by Alvarez, uses a linearized maximum likelihood estimator which requires calibration transmission measurements. The Alvarez method has the advantage of being non-iterative. This study experimentally quantified and compared the material decomposition bias, as a percentage of material thickness, and standard deviation resulting from these two material decomposition estimators. Multi-energy x-ray transmission measurements were acquired through varying thicknesses of Teon, Delrin, and neoprene at two different flux settings and decomposed into PMMA and aluminum thicknesses using the investigated methods. In addition, a series of 200 equally spaced projections of a rod phantom were acquired over 360°. The multi-energy sinograms were decomposed using both empirical methods and then reconstructed using filtered backprojection producing two images representing each basis material. The Alvarez method decomposed Delrin into PMMA with a bias of 0.5-19% and decomposed neoprene into aluminum with a bias of less than 3%. The spectral estimation method decomposed Delrin into PMMA with a bias of 0.6-16% and decomposed neoprene into aluminum with a bias of 0.1-58%. In general, the spectral estimation method resulted in

  8. ELF communications system ecological monitoring program: Litter decomposition and microflora studies

    NASA Astrophysics Data System (ADS)

    Bruhn, Johann N.; Bagley, Susan T.; Pickens, James B.

    1994-10-01

    The U.S. Navy has completed a program monitoring flora, fauna, and ecological relationships for possible effects from electromagnetic fields produced by its Extremely Low Frequency (ELF) Communications System. This report documents studies of litter decomposition and soil microflora conducted near its transmitting antenna in Michigan. From 1982 through 1993 researchers from the Michigan Technological University (MTU) monitored overall litter decomposition, as well as microflora (bacteria and fungi) important both as processors of organic material and causative agents of tree disease. Studies were performed in areas near (treatment) and far (control) from the ELF antenna Study parameters included total number of streptomycete individuals and species; mass loss of maple, oak, and pine leaf litter; and frequency of red pine mortality from Armillaria root disease. The MTU research team used several statistical models; however, nested analysis of covariance was the most frequently used test. Based on the results of their study, MTU investigators conclude that the EM fields produced by the Naval Radio Transmitting Facility-Republic, Michigan did not affect soil bacteria populations or the spread of the root disease. Loss of foliar mass suggests a statistically significant, but modest, increase in the rate of litter decomposition, possibly associated with electromagnetic exposure.

  9. Kinetics of Methane Hydrate Decomposition Studied via in Situ Low Temperature X-ray Powder Diffraction

    SciTech Connect

    Everett, Susan M; Rawn, Claudia J; Keffer, David J.; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy Joe

    2013-01-01

    Gas hydrates are known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice termed self-preservation or anomalous preservation. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Two regions of slowed decomposition for methane hydrate, 180 200 K and 230 260 K, were observed, and the kinetics were studied by in situ low temperature x-ray powder diffraction. The kinetic constants for ice formation from methane hydrate were determined by the Avrami model within each region and activation energies, Ea, were determined by the Arrhenius plot. Ea determined from the data for 180 200 K was 42 kJ/mol and for 230 260 K was 22 kJ/mol. The higher Ea in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.

  10. ESR study of the heterogeneous radical decomposition of hydrogen peroxide vapor on glass and silica

    SciTech Connect

    Arutyunyan, A.Z.; Grigoryan, G.L.; Nalbandyan, A.B.

    1986-01-01

    This paper presents the results of a study carried out on the laws governing the accumulation of HO/sub 2/ radicals in the gas phase during the heterogeneous decomposition of hydrogen peroxide vapor on surfaces of Pyrex glass and silica tablets. It was found that for short contact times (10/sup -2/ sec) and low mixture pressures (of the order of several hundred Pa) the decomposition of H/sub 2/O/sub 2/ occurs mainly on the external surface of the tablets. Rates and activation energies were determined for the generation and heterogeneous decay of HO/sub 2/ radicals on these surfaces at 473-623 K. A low activation energy of 4.6 kJ/mole was obtained for the radical decay process.

  11. Studies of the kinetics of two parallel reactions: ammonia decomposition and nitriding of iron catalyst.

    PubMed

    Arabczyk, Walerian; Pelka, Rafat

    2009-01-15

    The reaction of ammonia decomposition and nitriding reaction as an example of the parallel reactions were studied. A surface reaction was assumed as the rate limiting step. The experiments were carried out in the range of temperatures from 623 to 723 K. Mixtures of different iron nitrides (gamma'-Fe(4)N, epsilon-Fe(3-2)N) were obtained. Differential tubular reactor with thermogravimetric (TG) measurement and analysis of the gas phase composition in the reaction volume was used. Reacting gases flowing through the reactor were mixed. Effective reactor volume was determined. The rate constants for ammonia decomposition and ammonia adsorption process at critical point between alpha-Fe and gamma'-Fe(4)N phases were estimated. The number of collisions and the sticking coefficient of ammonia over alpha-Fe phase were also assessed. PMID:19086865

  12. Theoretical study of the decomposition mechanisms and kinetics of the ingredients RDX in composition B.

    PubMed

    Zhang, Jian-Guo; Wang, Kun; Niu, Xiao-Qing; Zhang, Shao-Wen; Feng, Xiao-Jun; Zhang, Tong-Lai; Zhou, Zun-Ning

    2012-08-01

    RDX as a component in composition B (TNT + RDX) was first studied by us on its mechanism and kinetics of decomposition reactions in this paper. We have pointed out three possible pathways and found a new low-energy process of its decomposition. The N-N bond cleavage in composition B has higher dissociation energies than the monomer, but it is also the initial step. The optimized structures and the frequencies of all the stationary points were calculated at the B3LYP/6-31G(d) level. The minimum-energy paths were obtained by using the intrinsic reaction coordinate (IRC) theory, and the reaction potential energy curve was corrected with zero-point energy. Finally, the rate constants were calculated in a wide temperature region from 200 to 2500 K using TST, TST/Eckart theories. The obtained results also indicate that the tunneling effects are remarkable at low temperature (200 K

  13. Raman study of the temperature-induced decomposition of the fullerene dimers C120

    NASA Astrophysics Data System (ADS)

    Meletov, K. P.; Arvanitidis, J.; Christofilos, D.; Kourouklis, G. A.; Davydov, V. A.

    2016-06-01

    Raman spectra of the C120 crystalline fullerene dimers, synthesized by high-pressure/high-temperature (HPHT) treatment of the C60 fullerite, were measured at ambient and elevated temperatures (T > 130 °C) in order to study the kinetics of their thermal decomposition. Measurements exhibit an intensity decrease of the dimer-related pentagon pinch (PP) mode and an increase of the monomer's one. The relative intensity of the dimer's PP mode decreases exponentially with the thermal treatment time and becomes faster at elevated temperatures. The activation energy EA of the dimer decomposition, obtained from the Arrhenius dependence of the exponential decay time constant on temperature, is (1.71 ± 0.06) eV.

  14. Density functional theory study of ethanol decomposition on 3Ni/α-Al₂O₃(0001) surface.

    PubMed

    Chiang, Hsin-Ni; Wang, Chia-Ching; Cheng, Ya-Chin; Jiang, Jyh-Chiang; Hsieh, Horng-Ming

    2010-10-19

    We have investigated the decomposition of ethanol (EtOH) on a 3Ni/α-Al₂O₃(0001) surface using periodic density functional theory calculations. A triangular Ni trimer doped on a 2 × 2 α-Al₂O₃(0001) surface was used to represent the 3Ni/α-Al₂O₃(0001) surface. We considered several possible pathways for EtOH decomposition over the 3Ni/α-Al₂O₃(0001) surface, including dehydrogenation and C-C bond cleavage. Our calculated results indicated that (i) the 3Ni/α-Al₂O₃(0001) surface possesses high activity to inhibit coke formation and (ii) the CH₂CH₂O((a)) → CH₂CHO((a)) + H((a)) reaction is the rate-determining step for the overall reaction [CH₃CH₂OH((a)) → CH(2(a)) + CO((a)) + 4 H((a))] with an energy barrier of 1.20 eV. One feasible channel leading to C-C bond cleavage is weakening of the C-C bond in the stable CH₂CO intermediate via transformation of the adsorbed structure to a metastable structure, thereby increasing the coordination number of the two C atoms to the Ni trimer. In addition, we also investigated the nature of the metal-ethanol bonding through scrutiny of density of states (DOS) and electron density difference contour plots. The DOS analysis allowed us to characterize the state interactions between ethanol and the surfaces; the electron density difference plots provide evidence that is consistent with the prediction from DOS analysis. PMID:20839873

  15. DNA damage as an intermediate biomarker in intervention studies.

    PubMed

    Santella, R M

    1997-11-01

    The development of sensitive assays for measurement of DNA damage in humans has great potential for enhancing intervention studies. Methods for DNA adduct measurement include immunoassays, [32p] postlabeling, high-performance liquid chromatography with fluorescence or electrochemical detection, and gas chromatography/mass spectroscopy. It is now well established that DNA adducts are a marker of exposure to various environmental, lifestyle, or occupational chemical carcinogens. Our own studies concentrate on immunologic detection of adducts by enzyme-linked immunosorbent assay (ELISA) of isolated DNA or quantitative immunohistochemical analysis of intact cells. Polycyclic aromatic hydrocarbon (PAH)-DNA adducts are elevated in blood cells of foundry and coke oven workers, individuals with high levels of exposure to environmental air pollution, and smokers. The study in smokers also found an inverse relationship between serum antioxidants and PAH-DNA, and is the basis for an ongoing antioxidant intervention. DNA adducts of PAH and 4-aminobiphenyl and oxidative DNA damage (8-oxo-deoxyguanosine) are being measured in blood mononuclear cells and exfoliated oral and bladder cells from subjects on antioxidants or placebo. Data on published intervention studies investigating oxidative damage and general aromatic DNA adducts measured by postlabeling are also summarized. These studies have already demonstrated that DNA adducts can be modulated by interventions and suggest that they can provide important mechanistic information in support of larger scale studies. PMID:9349685

  16. Ester prodrugs of acyclic nucleoside thiophosphonates compared to phosphonates: synthesis, antiviral activity and decomposition study.

    PubMed

    Roux, Loïc; Priet, Stéphane; Payrot, Nadine; Weck, Clément; Fournier, Maëlenn; Zoulim, Fabien; Balzarini, Jan; Canard, Bruno; Alvarez, Karine

    2013-05-01

    9-[2-(Thiophosphonomethoxy)ethyl]adenine [S-PMEA, 8] and (R)-9-[2-(Thiophosphonomethoxy)propyl]adenine [S-PMPA, 9] are acyclic nucleoside thiophosphonates we described recently that display the same antiviral spectrum (DNA viruses) as approved and potent phosphonates PMEA and (R)-PMPA. Here, we describe the synthesis, antiviral activities in infected cell cultures and decomposition study of bis(pivaloyloxymethoxy)-S-PMEA [Bis-POM-S-PMEA, 13] and bis(isopropyloxymethylcarbonyl)-S-PMPA [Bis-POC-S-PMPA, 14] as orally bioavailable prodrugs of the S-PMEA 8 and S-PMPA 9, in comparison to the equivalent "non-thio" derivatives [Bis-POM-PMEA, 11] and [Bis-POC-PMPA, 12]. Compounds 11, 12, 13 and 14 were evaluated for their in vitro antiviral activity against HIV-1-, HIV-2-, HBV- and a broad panel of DNA viruses, and found to exhibit moderate to potent antiviral activity. In order to determine the decomposition pathway of the prodrugs 11, 12, 13 and 14 into parent compounds PMEA, PMPA, 8 and 9, kinetic data and decomposition pathways in several media are presented. As expected, bis-POM-S-PMEA 13 and bis-POC-S-PMPA 14 behaved as prodrugs of S-PMEA 8 and S-PMPA 9. However, thiophosphonates 8 and 9 were released very smoothly in cell extracts, in contrast to the release of PMEA and PMPA from "non-thio" prodrugs 11 and 12. PMID:23603046

  17. Study of thermal decomposition of methyl ethyl ketone peroxide using DSC and simulation.

    PubMed

    Tseng, Jo-Ming; Chang, Ying-Yu; Su, Teh-Sheng; Shu, Chi-Min

    2007-04-11

    Methyl ethyl ketone peroxide (MEKPO) is a typical organic peroxide with thermally unstable nature that has been broadly employed in the manufacturing process of acrylic resins, as a hardening agent for fiberglass-reinforced plastics, and as a curing agent for unsaturated polyester resins. The aim of this study was to identify the characteristics of MEKPO 31 wt.% while mixing with contaminants, such as H(2)SO(4), HCl, and NaCl under runaway conditions. To acquire the thermal runaway data, DSC and a simulation were used for thermal analysis. The results showed that the thermal decomposition of MEKPO and MEKPO+H(2)SO(4) follows two stages. The first one can be modeled by using an empirical nth order rate equation. The second stage can be modeled as autocatalytic. MEKPO+HCl and MEKPO+NaCl included two independent autocatalytic reactions. The decomposition of MEKPO in the presence of Cl- ions (added in MEKPO either in the form of HCl or NaCl) follows a significantly different path, an earlier decomposition "onset" temperature, higher amount of generated thermal power and smaller temperature of no return (T(NR)) and time to maximum rate (TMR) values. Simulations based on experimental data indicated that the effect of H(2)SO(4) was the most dangerous contaminant on MEKPO 31 wt.%. However, the impact of Cl ions was also important. It is therefore recommended that the means of fire fighting employed for this substance to be free of Cl-. PMID:16905247

  18. Kinetics of methane hydrate decomposition studied via in situ low temperature X-ray powder diffraction.

    PubMed

    Everett, S Michelle; Rawn, Claudia J; Keffer, David J; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy J

    2013-05-01

    Gas hydrate is known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Based on results from the decomposition of three nominally similar methane hydrate samples, the kinetics of two regions, 180-200 and 230-260 K, within the overall decomposition range 140-260 K, were studied by in situ low temperature X-ray powder diffraction. The kinetic rate constants, k(a), and the reaction mechanisms, n, for ice formation from methane hydrate were determined by the Avrami model within each region, and activation energies, E(a), were determined by the Arrhenius plot. E(a) determined from the data for 180-200 K was 42 kJ/mol and for 230-260 K was 22 kJ/mol. The higher E(a) in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions. PMID:23557375

  19. Study on the characteristic decomposition components of air-insulated switchgear cabinet under partial discharge

    NASA Astrophysics Data System (ADS)

    Gui, Yingang; Zhang, Xiaoxing; Zhang, Ying; Qiu, Yinjun; Chen, Lincong

    2016-07-01

    Air-insulated switchgear cabinet plays a critical role in entire power transmission and distribution system. Its stability directly affects the operational reliability of the power system. And the on-line gas detection method, which evaluates the insulation status of insulation equipment by detecting the decomposition components of filled air in cabinet, becomes an innovative way to ensure the running stability of air-insulated switchgear cabinet. In order to study the characteristic gas types and production regularity of decomposition components under partial discharge, three insulation defects: needle-plate, air-gap and impurity defect are proposed to simulate the insulation defects under partial discharge in air-insulated switchgear cabinet. Firstly, the generation pathways and mechanism of composition components are discussed. Then CO and NO2 are selected as the characteristic decomposition components to characterize the partial discharge due to their high concentration and chemical stability. Based on the different change regularity of CO and NO2 concentration under different insulation defect, it provides an effective way to evaluate and predict the insulation defect type and severity in the field.

  20. Macroalgal decomposition: Laboratory studies with particular regard to microorganisms and meiofauna

    NASA Astrophysics Data System (ADS)

    Rieper-Kirchner, M.

    1990-09-01

    The microbial degradation of North Sea macroalgae was studied in laboratory microcosms, containing autoclaved seawater and a mixture of equal parts of air-dried Delesseria sanguinea, Ulva lactuca, and Laminaria saccharina (red, green and brown algae, respectively). To determine the influence of different organisms on the decomposition rate (expressed in terms of algal dry weight loss relative to the material present at time zero) and their development during decomposition processes, yeast, flagellates, ciliates, nematodes and a harpacticoid copepod species were introduced to the microcosms. Results show that microbial degradation compared to the controls was enhanced in the presence of non-axenic nematodes ( Monhystera sp.) and protozoans, including bacterivorous ciliates ( Euplotes sp. and a Uronema-like sp.) and flagellates. No enhancement occurred with yeast ( Debaryomyces hansenii) or with the harpacticoid copepod Tisbe holothuriae. The most rapid algal dry weight loss (78.7% after 14 d at 18°C) occurred with the addition of raw seawater sampled near benthic algal vegetation and containing only the natural microorganisms present. These consisted mainly of bacteria with different morphological properties, whereby their numbers alone (viable counts) could not be correlated with algal dry weight loss. Although no single dominant species could be determined, lemon yellow pigmented colonies were frequently found. During decomposition in all microcosms the formation of algal particles 40 400 μm was observed, which were rapidly colonized by the other organisms present.

  1. Studies on the stability and decomposition of the Hagedorn-oxime HLö 7 in aqueous solution.

    PubMed

    Eyer, P; Ladstetter, B; Schäfer, W; Sonnenbichler, J

    1989-01-01

    HLö 7, (pyridinium, 1-[[[4-(aminoarbonyl)pyridinio]methoxy]methyl] -2,4-bis- [(hydroxyimino)methyl] diiodide) has been shown to be efficacious in soman poisoning of mice even in the absence of atropine. To assess possible risks involved in the administration of HLö 7 its degradation products were analyzed at pH 2.5 and pH 7.4, respectively. At pH 2.5, where HLö 7 in aqueous solution was assumed to possess maximal stability, the predicted shelf life (10% decomposition) was about 8 years for 10 mM solutions at 8 degrees C. The apparent energy of activation was 117 kJ/mol. At pH 2.5, attack on the aminal-acetal bond predominated with formation of pyridine-2,4-dialdoxime, 2-cyanopyridine-4-aldoxime, isonicotinamide, and formaldehyde. At pH 7.4, primary attack on the 2-aldoxime group resulted in formation of an intermediate 2-cyano-4-aldoxime derivative which mainly decomposed into cyanide and the corresponding 2-pyridinone, 1-[[[4-(aminocarbonyl)-pyridinio]methoxy]methyl]-4- [(hydroxyimino)methyl] diiodide. In addition, liberated cyanide reacted with the intermediate 2-cyano-4-aldoxime derivative with formation of 2-pyridinone, 1-[[[4-(aminocarbonyl)-pyridinio]-methoxy]methyl]-6-cyano-4- [(hydroxyimino)methyl] diiodide. This cyanide sequestering pathway became significant only at high concentrations (10 mM) of HLö 7, and was marginal at 1 mM HLö 7. PMID:2742503

  2. A Review of Study on Thermal Energy Transport System by Synthesis and Decomposition Reactions of Methanol

    NASA Astrophysics Data System (ADS)

    Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya

    The study on thermal energy transport system by synthesis and decomposition reactions of methanol was reviewed. To promote energy conservation and global environment protection, a two-step liquid-phase methanol synthesis process, which starts with carbonylation of methanol to methyl formate, then followed by the hydrogenolysis of the formate, was studied to recover wasted or unused discharged heat from industrial sources for the thermal energy demands of residential and commercial areas by chemical reactions. The research and development of the system were focused on the following three points. (1) Development of low-temperature decomposition and synthetic catalysts, (2) Development of liquid phase reactor (heat exchanger accompanying chemical reaction), (3) Simulation of the energy transport efficiency of entire system which contains heat recovery and supply sections. As the result of the development of catalyst, promising catalysts which agree with the development purposes for the methyl formate decomposition reaction and the synthetic reaction are being developed though some studies remain for the methanol decomposition and synthetic reactions. In the fundamental development of liquid phase reactor, the solubilities of CO and H2 gases in methanol and methyl formate were measured by the method of total pressure decrease due to absorption under pressures up to 1500kPa and temperatures up to 140°C. The diffusivity of CO gas in methanol was determined by measuring the diameter and solution time of single CO bubbles in methanol. The chemical reaction rate of methanol synthesis by hydrogenolysis of methyl formate was measured using a plate-type of Raney copper catalyst in a reactor with rectangular channel and in an autoclave reactor. The reaction characteristics were investigated by carrying out the experiments at various temperatures, flow rates and at various catalyst development conditions. We focused on the effect of Raney copper catalyst thickness on the liquid

  3. Thermal decomposition pathways for 1,1-diamino-2,2-dinitroethene (FOX-7)

    NASA Astrophysics Data System (ADS)

    Booth, Ryan S.; Butler, Laurie J.

    2014-10-01

    In this study, we computationally investigate the initial and subsequent steps in the chemical mechanism for the gas-phase thermal decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7). We determine the key exothermic step in the gas-phase thermal decomposition of FOX-7 and explore the similarities and differences between FOX-7 and other geminal dinitro energetic materials. The calculations reveal a mechanism for NO loss involving a 3-member cyclic intermediate, rather than a nitro-nitrite isomerization, that occurs in the radical intermediates formed throughout the decomposition mechanism.

  4. The application of the intermediate disturbance hypothesis to physical systems: a case study on floodplain soils

    NASA Astrophysics Data System (ADS)

    Rayburg, Scott; Neave, Melissa; Thompson-Laing, Justin

    2010-05-01

    Disturbances, defined as discrete events that disrupt physical and/or biological systems, are a component of every natural system. Disturbance ecology has been dominated, for the last 30 years or so, by the intermediate disturbance hypothesis that states that biological diversity will be maximised where disturbance occurs at an intermediate level. A wide range of disturbances and organisms have been examined with respect to the intermediate disturbance hypothesis and in many cases (especially with respect to sessile organisms) the theory has proven valid. In rivers, lakes, wetlands and floodplains, the predominant agent of disturbance is flooding. In flood disturbed environments, the intermediate disturbance hypothesis has been shown to apply to terrestrial and aquatic vegetation, but conflicting results have been observed when dealing with mobile organisms like macroinvertebrates, fish or amphibians. The argument for the validity of the intermediate disturbance hypothesis (irrespective of disturbance type) stems from the notion that an intermediate frequency of disturbance promotes diversity by: 1) preventing the competitive exclusion by the dominant species that can arise in infrequently disturbed sites; and 2) facilitating greater diversity than that observed in highly-disturbed sites where only species tolerant of the disturbance can thrive. A singular omission in this logic, and indeed in research into the intermediate disturbance hypothesis more generally, has been the lack of focus on its application or relation to physical systems. This study addresses this lack by investigating whether an intermediate level of flood disturbance leads to a greater diversity of soil character (assessed using a wide range of physical and geochemical soil properties). Four flood frequency (or disturbance frequency) categories are included in this study spanning the range from frequent through to infrequent flood disturbance. These are: a high-inundation-frequency flood zone

  5. The decomposition of methyltrichlorosilane: Studies in a high-temperature flow reactor

    SciTech Connect

    Allendorf, M.D.; Osterheld, T.H.; Melius, C.F.

    1994-01-01

    Experimental measurements of the decomposition of methyltrichlorosilane (MTS), a common silicon carbide precursor, in a high-temperature flow reactor are presented. The results indicate that methane and hydrogen chloride are major products of the decomposition. No chlorinated silane products were observed. Hydrogen carrier gas was found to increase the rate of MTS decomposition. The observations suggest a radical-chain mechanism for the decomposition. The implications for silicon carbide chemical vapor deposition are discussed.

  6. Radiolysis studies on reactive intermediates. Final report, February 1, 1970-August 31, 1980

    SciTech Connect

    Kevan, L.

    1980-08-01

    Research highlights are briefly reviewed concerning studies of excess and solvated electrons, development of new electron spin resonance methods for maximizing the geometrical information about the surroundings of paramagnetic species in disordered systems, atom and ion solvation, and studies on other reactive intermediates. Titles of 155 research publications and 182 scientific talks presented on these areas are given.

  7. Probing the Natural World, Level III, Teacher's Edition: Environmental Science. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the teacher's edition of one of the eight units of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). This unit and its activities focuses on environmental pollution and hazards. Optional excursions are suggested for students who wish to study an area in greater depth. An introduction describes the problem…

  8. Probing the Natural World, Level III, Teacher's Edition: Winds and Weather. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the teacher's edition of one of eight units of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). This unit focuses on weather, its measurement and prediction. Optional excursions are given for students who wish to study a topic in greater depth on an individualized basis. An introduction describes the…

  9. Decomposition of NO studied by infrared emission and CO laser absorption

    NASA Technical Reports Server (NTRS)

    Hanson, R. K.; Flower, W. L.; Monat, J. P.; Kruger, C. H.

    1974-01-01

    A diagnostic technique for monitoring the concentration of NO using absorption of CO laser radiation was developed and applied in a study of the decomposition kinetics of NO. Simultaneous measurements of infrared emission by NO at 5.3 microns were also made to validate the laser absorption technique. The data were obtained behind incident shocks in NO-N2O-Ar (or Kr) mixtures, with temperatures in the range 2400-4100 K. Rate constants for dominant reactions were inferred from comparisons with computer simulations of the reactive flow.

  10. Indium hydroxide to oxide decomposition observed in one nanocrystal during in situ transmission electron microscopy studies

    SciTech Connect

    Miehe, Gerhard; Lauterbach, Stefan; Kleebe, Hans-Joachim; Gurlo, Aleksander

    2013-02-15

    The high-resolution transmission electron microscopy (HR-TEM) is used to study, in situ, spatially resolved decomposition in individual nanocrystals of metal hydroxides and oxyhydroxides. This case study reports on the decomposition of indium hydroxide (c-In(OH){sub 3}) to bixbyite-type indium oxide (c-In{sub 2}O{sub 3}). The electron beam is focused onto a single cube-shaped In(OH){sub 3} crystal of {l_brace}100{r_brace} morphology with ca. 35 nm edge length and a sequence of HR-TEM images was recorded during electron beam irradiation. The frame-by-frame analysis of video sequences allows for the in situ, time-resolved observation of the shape and orientation of the transformed crystals, which in turn enables the evaluation of the kinetics of c-In{sub 2}O{sub 3} crystallization. Supplementary material (video of the transformation) related to this article can be found online at (10.1016/j.jssc.2012.09.022). After irradiation the shape of the parent cube-shaped crystal is preserved, however, its linear dimension (edge) is reduced by the factor 1.20. The corresponding spotted selected area electron diffraction (SAED) pattern representing zone [001] of c-In(OH){sub 3} is transformed to a diffuse strongly textured ring-like pattern of c-In{sub 2}O{sub 3} that indicates the transformed cube is no longer a single crystal but is disintegrated into individual c-In{sub 2}O{sub 3} domains with the size of about 5-10 nm. The induction time of approximately 15 s is estimated from the time-resolved Fourier transforms. The volume fraction of the transformed phase (c-In{sub 2}O{sub 3}), calculated from the shrinkage of the parent c-In(OH){sub 3} crystal in the recorded HR-TEM images, is used as a measure of the kinetics of c-In{sub 2}O{sub 3} crystallization within the framework of Avrami-Erofeev formalism. The Avrami exponent of {approx}3 is characteristic for a reaction mechanism with fast nucleation at the beginning of the reaction and subsequent three-dimensional growth of

  11. Study of intermediates from transition metal excited-state electron-transfer reactions

    SciTech Connect

    Hoffman, M.Z.

    1992-07-31

    Conventional and fast-kinetics techniques of photochemistry, photophysics, radiation chemistry, and electrochemistry were used to study the intermediates involved in transition metal excited-state electron-transfer reactions. These intermediates were excited state of Ru(II) and Cr(III) photosensitizers, their reduced forms, and species formed in reactions of redox quenchers and electron-transfer agents. Of particular concern was the back electron-transfer reaction between the geminate pair formed in the redox quenching of the photosensitizers, and the dependence of its rate on solution medium and temperature in competition with transformation and cage escape processes. (DLC)

  12. Pilot-scale UV/H2O2 study for emerging organic contaminants decomposition.

    PubMed

    Chu, Xiaona; Xiao, Yan; Hu, Jiangyong; Quek, Elaine; Xie, Rongjin; Pang, Thomas; Xing, Yongjie

    2016-03-01

    Human behaviors including consumption of drugs and use of personal care products, climate change, increased international travel, and the advent of water reclamation for direct potable use have led to the introduction of significant amounts of emerging organic contaminants into the aqueous environment. In addition, the lower detection limits associated with improved scientific methods of chemical analysis have resulted in a recent increase in documented incidences of these contaminants which previously were not routinely monitored in water. Such contaminants may cause known or suspected adverse ecological and/or human health effects at very low concentrations. Conventional drinking water treatment processes may not effectively remove these organic contaminants. Advanced oxidation process (AOP) is a promising treatment process for the removal of most of these emerging organic contaminants, and has been accepted worldwide as a suitable treatment process. In this study, different groups of emerging contaminants were studied for decomposition efficiency using pilot-scale UV/H2O2 oxidation setup, including EDCs, PPCPs, taste and odor (T&O), and perfluorinated compounds. Results found that MP UV/H2O2 AOP was efficient in removing all the selected contaminants except perfluorinated compounds. Study of the kinetics of the process showed that both light absorption and quantum yield of each compound affected the decomposition performance. Analysis of water quality parameters of the treated water indicated that the outcome of both UV photolysis and UV/H2O2 processes can be affected by changes in the feed water quality. PMID:26943602

  13. Canonical Decomposition of Ictal Scalp EEG and Accurate Source Localisation: Principles and Simulation Study

    PubMed Central

    De Vos, Maarten; De Lathauwer, Lieven; Vanrumste, Bart; Van Huffel, Sabine; Van Paesschen, W.

    2007-01-01

    Long-term electroencephalographic (EEG) recordings are important in the presurgical evaluation of refractory partial epilepsy for the delineation of the ictal onset zones. In this paper, we introduce a new concept for an automatic, fast, and objective localisation of the ictal onset zone in ictal EEG recordings. Canonical decomposition of ictal EEG decomposes the EEG in atoms. One or more atoms are related to the seizure activity. A single dipole was then fitted to model the potential distribution of each epileptic atom. In this study, we performed a simulation study in order to estimate the dipole localisation error. Ictal dipole localisation was very accurate, even at low signal-to-noise ratios, was not affected by seizure activity frequency or frequency changes, and was minimally affected by the waveform and depth of the ictal onset zone location. Ictal dipole localisation error using 21 electrodes was around 10.0 mm and improved more than tenfold in the range of 0.5–1.0 mm using 148 channels. In conclusion, our simulation study of canonical decomposition of ictal scalp EEG allowed a robust and accurate localisation of the ictal onset zone. PMID:18301715

  14. Reactions of C{sub 2}H{sub 5} radicals with O, O{sub 3}, and NO{sub 3}: Decomposition pathways of the intermediate C{sub 2}H{sub 5}O radical

    SciTech Connect

    Hoyermann, K.; Seeba, J.; Olzmann, M.; Viskolcz

    1999-07-22

    Alkoxy radicals are important species in the atmospheric degradation of hydrocarbons as well as in combustion processes. Additionally, they play a crucial role in the pyrolysis of oxygen-containing hydrocarbons. The reactions of C{sub 2}H{sub 5} with O, O{sub 3}, and NO{sub 3} have been investigated in a discharge flow reactor at room temperature and pressures between 1 and 3 mbar. The reaction products were detected by mass spectrometry with electron-impact ionization. The product pattern observed is explained in terms of the decomposition of an intermediately formed, chemically activated ethoxy radical. It is shown that, with this assumption, the experimentally determined branching ratios of the different product channels can be reproduced nearly quantitatively by RRKM calculations based on ab initio results for the stationary points of the potential energy surface of C{sub 2}H{sub 5}O. For C{sub 2}H{sub 5} + O and C{sub 2}H{sub 5} + O{sub 3}, the existence of an additional, parallel channel leading to OH has to be assumed.. High-pressure Arrhenius parameters for the unimolecular reactions of the ethoxy radical are given and discussed.

  15. A quantitative acoustic emission study on fracture processes in ceramics based on wavelet packet decomposition

    SciTech Connect

    Ning, J. G.; Chu, L.; Ren, H. L.

    2014-08-28

    We base a quantitative acoustic emission (AE) study on fracture processes in alumina ceramics on wavelet packet decomposition and AE source location. According to the frequency characteristics, as well as energy and ringdown counts of AE, the fracture process is divided into four stages: crack closure, nucleation, development, and critical failure. Each of the AE signals is decomposed by a 2-level wavelet package decomposition into four different (from-low-to-high) frequency bands (AA{sub 2}, AD{sub 2}, DA{sub 2}, and DD{sub 2}). The energy eigenvalues P{sub 0}, P{sub 1}, P{sub 2}, and P{sub 3} corresponding to these four frequency bands are calculated. By analyzing changes in P{sub 0} and P{sub 3} in the four stages, we determine the inverse relationship between AE frequency and the crack source size during ceramic fracture. AE signals with regard to crack nucleation can be expressed when P{sub 0} is less than 5 and P{sub 3} more than 60; whereas AE signals with regard to dangerous crack propagation can be expressed when more than 92% of P{sub 0} is greater than 4, and more than 95% of P{sub 3} is less than 45. Geiger location algorithm is used to locate AE sources and cracks in the sample. The results of this location algorithm are consistent with the positions of fractures in the sample when observed under a scanning electronic microscope; thus the locations of fractures located with Geiger's method can reflect the fracture process. The stage division by location results is in a good agreement with the division based on AE frequency characteristics. We find that both wavelet package decomposition and Geiger's AE source locations are suitable for the identification of the evolutionary process of cracks in alumina ceramics.

  16. An Observational Study of Intermediate Band Students' Self-Regulated Practice Behaviors

    ERIC Educational Resources Information Center

    Miksza, Peter; Prichard, Stephanie; Sorbo, Diana

    2012-01-01

    The purpose of this study was to investigate intermediate musicians' self-regulated practice behaviors. Thirty sixth- through eighth-grade students were observed practicing band repertoire individually for 20 min. Practice sessions were coded according to practice frame frequency and duration, length of musical passage selected, most prominent…

  17. Probing the Natural World, Level III, Record Book, Student Guide: In Orbit. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the student's edition of the Record Book which accompanies the unit "In Orbit" of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). Space is provided for answers to the questions from the student text as well as for the optional excursions and the self evaluation. An introductory note to the student…

  18. Probing the Natural World, Level III, Teacher's Edition: In Orbit. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the teacher's edition of one of the eight units of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). This unit focuses on the properties of sunlight, the use of spectrums and spectroscopes, the heat and energy of the sun, the measurement of astronomical distances, and the size of the sun. Optimal…

  19. Probing the Natural World, Level III, Record Book, Teacher's Edition: In Orbit. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the teacher's edition of the Record Book for the unit "In Orbit" of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). The correct answers to the questions from the text are recorded. An introductory note to the student explains how to use the book and is followed by the notes to the teacher. Answers are…

  20. Probing the Natural World, Level III, Student Guide: In Orbit. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the student's text of one unit of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). This unit focuses on the properties of sunlight, the use of spectrums and spectroscopes, the heat and energy of the sun, the measurement of astronomical distances, and the size of the sun. Activities are student-centered and…

  1. Probing the Natural World, Level III, Student Guide: Winds and Weather. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the student's text of one of the units of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). The chapters contain basic information about weather, its measurement and predictions, activities related to the subject, and optional excursions. A section of introductory notes to the student discusses how to use…

  2. Thermal decomposition studies of energetic materials using confined rapid thermolysis/FTIR spectroscopy

    SciTech Connect

    Kim, E.S.; Lee, H.S.; Mallery, C.F.; Thynell, S.T.

    1997-07-01

    An experimental setup for performing rapid thermolysis studies of small samples of energetic materials is described. In this setup, about 8 {micro}L of a liquid sample or about 2 mg of a solid sample is heated at rates exceeding 1,500 K/s to a set temperature where decomposition occurs. The rapid heating is achieved as a result of confining the sample between two closely spaced isothermal surfaces. The gaseous decomposition products depart from the confined space through a rectangular slit into the region of detection. The evolved gases are quantified using FTIR absorption spectroscopy by accounting for the instrument line shape. To illustrate the use of this setup, the thermolysis behaviors of three different energetic materials are examined. These materials include HMX, RDX, and HAN, all of which are considered as highly energetic propellant ingredients. The results obtained in this study of the temporal evolution of species concentrations from these ingredients are in reasonably close agreement with results available in the literature.

  3. Heterocycle chemistry on Pd(111): Thiophene and furan decomposition studied by LITD/FTMS

    SciTech Connect

    Caldwell, T.E.; Abdelrehim, I.M.; Land, D.P.

    1996-10-01

    The chemistry of sulfur- and oxygen-containing compounds on transition metal surfaces is of great interest due to the necessity of their removal from petroleum and biomass hydrocarbon resources. Compounds such as thiophene and furan have become models for understanding the interactions between these heterocompounds and catalyst surfaces. In particular, late transition metals have been shown to be useful promoters in hydrotreating catalysis, however very few UHV studies of heterocompounds on late transition metals have been performed. Recent results from this group using TDS and laser-induced thermal desorption with FT mass spectrometry indicate the low-temperature decomposition mechanism of these two compounds on clean Pd(111) differs significantly despite the similarity in their structures. Thiophene decomposition involves cleavage between the C-S bonds, resulting in the deposition of surface sulfur and the formation of a tightly bound C{sub 4} species on the surface which undergoes hydrogenation to form a significant amount of 1,3-butadiene. Furan, on the other hand, decomposes via elimination of {alpha}-H (desorbing as H{sub 2}) and CO{sub 3} leaving a C{sub 3}H{sub 3} species on the surface. Heating to 320K causes dimerization of some of the C{sub 3} species, forming a small amount of benzene. Deuterium labeling studies will be presented to further elucidate the mechanisms.

  4. Study of thermal decomposition mechanisms and low-level detection of explosives using pulsed photoacoustic technique

    NASA Astrophysics Data System (ADS)

    Yehya, F.; Chaudhary, A. K.; Srinivas, D.; Muralidharan, K.

    2015-11-01

    We report a novel time-resolved photoacoustic-based technique for studying the thermal decomposition mechanisms of some secondary explosives such as RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), picric acid, 4,6-dinitro-5-(4-nitro-1 H-imidazol-1-yl)-1 H-benzo[ d] [1-3] triazole, and 5-chloro-1-(4-nitrophenyl)-1 H-tetrazole. A comparison of the thermal decomposition mechanisms of these secondary explosives was made by detecting NO2 molecules released under controlled pyrolysis between 25 and 350 °C. The results show excellent agreement with the thermogravimetric and differential thermal analysis (TGA-DTA) results. A specially designed PA cell made of stainless steel was filled with explosive vapor and pumped using second harmonic, i.e., λ = 532 nm, pulses of duration 7 ns at a 10 Hz repetition rate, obtained using a Q-switched Nd:YAG laser. The use of a combination of PA and TGA-DTA techniques enables the study of NO2 generation, and this method can be used to scale the performance of these explosives as rocket fuels. The minimum detection limits of the four explosives were 38 ppmv to 69 ppbv, depending on their respective vapor pressures.

  5. Laser Spectroscopic Study on Oxygen Isotope Effects in Ozone Surface Decomposition

    NASA Astrophysics Data System (ADS)

    Minissale, Marco; Boursier, Corinne; Elandaloussi, Hadj; Te, Yao; Jeseck, Pascal; Rouille, Christian; Zanon-Willette, Thomas; Janssen, Christof

    2016-04-01

    The isotope kinetics of ozone formation in the Chapman reaction [1] O + O2 + M → O3 + M (1) provides the primary example for a chemically induced oxygen isotope anomaly and is associated with large [2] and mass independent [3] oxygen isotope enrichments in the product molecule, linked to a symmetry selection in the ozone formation kinetics [4-5]. The isotopic composition of ozone and its transfer to other molecules is a powerful tracer in the atmospheric and biogeochemical sciences [6] and serves as a primary model for a possible explanation of the oxygen isotopic heterogeneity in the Solar system [7-8]. Recently, the isotope fractionation in the photolytic decomposition process O3 + hν → O2 + O (2) using visible light has been studied in detail [9-10]. Much less is currently known about the isotope fractionation in the dry deposition or in the gas phase thermal decomposition of ozone O3 + M → O2 + O +M. (3) Here we report on first spectroscopic studies of non-photolytic ozone decomposition using a cw-quantum cascade laser at 9.5 μm. The concentration of individual ozone isotopomers (16O3,16O16O17O, and 16O17O16O) in a teflon coated reaction cell is followed in real time at temperatures between 25 and 150 °C. Observed ozone decay rates depend on homogeneous (reaction (3)) processes in the gas phase and on heterogeneous reactions on the wall. A preliminary analysis reveals agreement with currently recommended ozone decay rates in the gas phase and the absence of a large symmetry selection in the surface decomposition process, indicating the absence of a mass independent fractionation effect. This result is in agreement with previous mass spectrometer (MS) studies on heterogeneous ozone formation on pyrex [11], but contradicts an earlier MS study [12] on ozone surface decomposition on pyrex and quartz. Implications for atmospheric chemistry will be discussed. [1] Morton, J., Barnes, J., Schueler, B. and Mauersberger, K. J. Geophys. Res. 95, 901 - 907 (1990

  6. Density functional theory study of nitrous oxide decomposition over Fe- and Co-ZSM-5

    SciTech Connect

    Ryder, Jason A.; Chakraborty, Arup K.; Bell, Alexis T.

    2001-12-19

    Iron- and cobalt-exchanged ZSM-5 are active catalysts for the dissociation of nitrous oxide. In this study, density functional theory was used to assess a possible reaction pathway for the catalytic dissociation of N2O. The active center was taken to be mononuclear [FeO]+ or [CoO]+, and the surrounding portion of the zeolite was represented by a 24-atom cluster. The first step of N2O decomposition involves the formation of [FeO2]+ or [CoO2]+ and the release of N2. The metal-oxo species produced in this step then reacts with N2O again, to release N2 and O2. The apparent activation energies for N2O dissociation in Fe-ZSM-5 and Co-ZSM-5 are 39.4 and 34.6 kcal/mol, respectively. The preexponential factor for the apparent first-order rate coefficient is estimated to be of the order 107 s-1 Pa-1. While the calculated activation energy for Fe-ZSM-5 is in good agreement with that measured experimentally, the value of the preexponential factor is an order of magnitude smaller than that observed . The calculated activation energy for Co-ZSM-5 is higher than that reported experimentally. However, consistent with experiment, the rate of N2O decomposition on Co-ZSM-5 is predicted to be significantly higher than that on Fe-ZSM-5.

  7. Internal friction study of decomposition kinetics of SAF 2507 type duplex stainless steel

    SciTech Connect

    Smuk, O.; Smuk, S.; Hanninen, H.; Jagodzinski, Yu.; Tarasenko, O.

    1999-01-08

    During the last decade, super duplex stainless steels (DSSs) with increased nitrogen content have been an object of intensive studies. Present work is devoted to the study of the peculiarities of {delta}-ferrite decomposition in SAF 2507 type duplex steel, and redistribution of nitrogen between ferrite and austenite phases in a wide temperature range by means of internal fraction (IF). Unlike local methods of electron microscopy or engineering methods of hardness or impact toughness testing, which give basically information on the formation of brittle intermetallic phases, the internal friction technique allows to study the state of solid solution and kinetics of changes in the relative amounts of ferrite and austenite phases during thermal treatment.

  8. Intermediate and stable redox states of cytochrome c studied by low temperature resonance Raman spectroscopy.

    PubMed Central

    Cartling, B

    1983-01-01

    Stabilized intermediate redox states of cytochrome c are generated by radiolytic reduction of initially oxidized enzyme in glass matrices at liquid nitrogen temperature. In the intermediate states the heme group is reduced by hydrated electrons, whereas the protein conformation is restrained close to its oxidized form by the low-temperature glass matrix. The intermediate and stable redox states of cytochrome c at neutral and alkaline pH are studied by low-temperature resonance Raman spectroscopy using excitations in resonance with the B (Soret) and Q1 (beta) optical transitions. The assignments of the cytochrome c resonance Raman bands are discussed. The observed spectral characteristics of the intermediate states as well as of the alkaline transition in the oxidized state are interpreted in terms of oxidation-state marker modes, spin-state marker modes, heme iron--axial ligand stretching modes, totally symmetric in-plane porphyrin modes, nontotally symmetric in-plane modes, and out-of-plane modes. PMID:6311300

  9. Study of nonlinear interaction between bunched beam and intermediate cavities in a relativistic klystron amplifier

    SciTech Connect

    Wu, Y.; Xu, Z.; Li, Z. H.; Tang, C. X.

    2012-07-15

    In intermediate cavities of a relativistic klystron amplifier (RKA) driven by intense relativistic electron beam, the equivalent circuit model, which is widely adopted to investigate the interaction between bunched beam and the intermediate cavity in a conventional klystron design, is invalid due to the high gap voltage and the nonlinear beam loading in a RKA. According to Maxwell equations and Lorentz equation, the self-consistent equations for beam-wave interaction in the intermediate cavity are introduced to study the nonlinear interaction between bunched beam and the intermediate cavity in a RKA. Based on the equations, the effects of modulation depth and modulation frequency of the beam on the gap voltage amplitude and its phase are obtained. It is shown that the gap voltage is significantly lower than that estimated by the equivalent circuit model when the beam modulation is high. And the bandwidth becomes wider as the beam modulation depth increases. An S-band high gain relativistic klystron amplifier is designed based on the result. And the corresponding experiment is carried out on the linear transformer driver accelerator. The peak output power has achieved 1.2 GW with an efficiency of 28.6% and a gain of 46 dB in the corresponding experiment.

  10. Study of Oil spill in Norwegian area using Decomposition Techniques on RISAT-1 Hybrid Polarimetric Data.

    NASA Astrophysics Data System (ADS)

    Jayasri, P. V.; Usha Sundari, H. S. V.; Kumari, E. V. S. Sita; Prasad, A. V. V.

    2014-11-01

    Over past few years Synthetic Aperture Radar(SAR) has received a considerable attention for monitoring and detection of oil spill due to its unique capabilities to provide wide-area surveillance and day and night measurements, almost independently from atmospheric conditions. The critical part of the oil spill detection is to distinguish oil spills from other natural phenomena. Stokes vector analysis of the image data is studied to estimate the polarized circular and linear components of the backscatter signal which essentially utilize the degree of polarization(m) and relative phase (δ) of the target. In a controlled oil spill experiment conducted at Norwegian bay during 17th to 22nd June 2014, RISAT-1 hybrid polarimetry images were utilized to study the characteristics of oil spill in the sea. The preliminary results obtained by using polarimetric decomposition technique on hybrid polarimetric data to decipher the polarimetric characteristics of oil spills from natural waters are discussed in the paper.

  11. Candidate Gene Studies of a Promising Intermediate Phenotype: Failure to Replicate

    PubMed Central

    Hart, Amy B; de Wit, Harriet; Palmer, Abraham A

    2013-01-01

    Many candidate gene studies use ‘intermediate phenotypes' instead of disease diagnoses. It has been proposed that intermediate phenotypes have simpler genetic architectures such that individual alleles account for a larger percentage of trait variance. This implies that smaller samples can be used to identify genetic associations. Pharmacogenomic drug challenge studies may be an especially promising class of intermediate phenotype. We previously conducted a series of 12 candidate gene analyses of acute subjective and physiological responses to amphetamine in 99–162 healthy human volunteers (ADORA2A, SLC6A3, BDNF, SLC6A4, CSNK1E, SLC6A2, DRD2, FAAH, COMT, OPRM1). Here, we report our attempt to replicate these findings in over 200 additional participants ascertained using identical methodology. We were unable to replicate any of our previous findings. These results raise critical issues related to non-replication of candidate gene studies, such as power, sample size, multiple testing within and between studies, publication bias and the expectation that true allelic effect sizes are similar to those reported in genome-wide association studies. Many of these factors may have contributed to our failure to replicate our previous findings. Our results should instill caution in those considering similarly designed studies. PMID:23303064

  12. FTIR studies of H 2O and D 2O decomposition on porous silicon surfaces

    NASA Astrophysics Data System (ADS)

    Gupta, P.; Dillon, A. C.; Bracker, A. S.; George, S. M.

    1991-04-01

    The decomposition of H 2O and D 2O on silicon surfaces was studied using transmission Fourier-transform infrared (FTIR) spectroscopy. These FTIR studies were performed in situ in an ultrahigh vacuum chamber using high surface area porous silicon samples. The FTIR spectra revealed that H 2O (D 2O) initially dissociates upon adsorption at 300 K to form SiH (SiD) and SiOH (SiOD) surface species, i.e., H 2O → SiH + SiOH. The decomposition of these surface species was then monitored using the SiH (SiD) stretch at 2090 cm -1 (1513 cm -1), SiOH (SiOD) stretch at 3680 cm -1 (2707 cm -1) and the SiOSi stretch at 900-1100 cm -1. As the silicon surface was annealed to 650 K, the FTIR spectra revealed that the SiOH surface species progressively decomposed to SiOSi species and additional SiH species, i.e., SiOH → SiH + SiOSi. Above 650 K, the SiH surface species decreased concurrently with the desorption of H -1 from the porous silicon surface. New blue-shifted infrared features in the SiH stretching region were observed at 2119, 2176 and 2268 cm -1 after annealing above 600 K. Additional infrared studies of partially hydrogen-covered porous silicon surfaces exposed to O 2 suggested that these blue-shifted SiH stretching vibrations were associated with silicon surface atoms backbonded to one, two or three oxygen atoms, respectively.

  13. Aridity and decomposition processes in complex landscapes

    NASA Astrophysics Data System (ADS)

    Ossola, Alessandro; Nyman, Petter

    2015-04-01

    Decomposition of organic matter is a key biogeochemical process contributing to nutrient cycles, carbon fluxes and soil development. The activity of decomposers depends on microclimate, with temperature and rainfall being major drivers. In complex terrain the fine-scale variation in microclimate (and hence water availability) as a result of slope orientation is caused by differences in incoming radiation and surface temperature. Aridity, measured as the long-term balance between net radiation and rainfall, is a metric that can be used to represent variations in water availability within the landscape. Since aridity metrics can be obtained at fine spatial scales, they could theoretically be used to investigate how decomposition processes vary across complex landscapes. In this study, four research sites were selected in tall open sclerophyll forest along a aridity gradient (Budyko dryness index ranging from 1.56 -2.22) where microclimate, litter moisture and soil moisture were monitored continuously for one year. Litter bags were packed to estimate decomposition rates (k) using leaves of a tree species not present in the study area (Eucalyptus globulus) in order to avoid home-field advantage effects. Litter mass loss was measured to assess the activity of macro-decomposers (6mm litter bag mesh size), meso-decomposers (1 mm mesh), microbes above-ground (0.2 mm mesh) and microbes below-ground (2 cm depth, 0.2 mm mesh). Four replicates for each set of bags were installed at each site and bags were collected at 1, 2, 4, 7 and 12 months since installation. We first tested whether differences in microclimate due to slope orientation have significant effects on decomposition processes. Then the dryness index was related to decomposition rates to evaluate if small-scale variation in decomposition can be predicted using readily available information on rainfall and radiation. Decomposition rates (k), calculated fitting single pool negative exponential models, generally

  14. Decomposition of adsorbed VX on activated carbons studied by 31P MAS NMR.

    PubMed

    Columbus, Ishay; Waysbort, Daniel; Shmueli, Liora; Nir, Ido; Kaplan, Doron

    2006-06-15

    The fate of the persistent OP nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) on granular activated carbons that are used for gas filtration was studied by means of 31P magic angle spinning (MAS) NMR spectroscopy. VX as vapor or liquid was adsorbed on carbon granules, and MAS NMR spectra were recorded periodically. The results show that at least 90% of the adsorbed VX decomposes within 20 days or less to the nontoxic ethyl methylphosphonic acid (EMPA) and bis(S-2-diisopropylaminoethane) {(DES)2}. Decomposition occurred irrespective of the phase from which VX was loaded, the presence of metal impregnation on the carbon surface, and the water content of the carbon. Theoretical and practical aspects of the degradation are discussed. PMID:16830567

  15. Studies of Hydrogen Getter Material Self-decomposition and Reaction Capacity

    SciTech Connect

    Saab, A P; Dinh, L N

    2007-03-19

    Diacetylene based hydrogen getters are examined in order to gauge their self decomposition products, as well as to determine possible origins for observed losses in origins getter capacity. Simple long term (several months) thermal aging tests were conducted, with periodic solid solid-phase micro micro-extraction (SPME) sampling followed by GC/MS analysis. The results suggest that bis(diphenylethynyl) benzene tends to decompose to give phenyl contaminants more readily than diphenylbutadiyne. Transmission electron microscopy (TEM) and electron diffraction studies of the palladium catalyst following varying extents of reaction with hydrogen show that there is no change to the catalyst particles, indicating that any change in capacity originates from other causes. These causes are suggested by Sievert's-type experiments on the reaction of the getter with a low pressure (about 10 Torr) hydrogen atmosphere. The reaction data indicate that the getter capacity depends on the pressure of hydrogen to which the material is exposed, and also its thermal history.

  16. Decomposition of adsorbed VX on activated carbons studied by {sup 31}P MAS NMR

    SciTech Connect

    Ishay Columbus; Daniel Waysbort; Liora Shmueli; Ido Nir; Doron Kaplan

    2006-06-15

    The fate of the persistent OP nerve agent O-ethyl S-(2-(diisopropylamino)ethyl) methylphosphonothioate (VX) on granular activated carbons that are used for gas filtration was studied by means of 31P magic angle spinning (MAS) NMR spectroscopy. Four types of activated carbon were used, including coal-based BPL. VX as vapor or liquid was adsorbed on carbon granules, and MAS NMR spectra were recorded periodically. The results show that at least 90% of the adsorbed VX decomposes within 20 days or less to the nontoxic ethyl methylphosphonic acid (EMPA) and bis(S-2-diisopropylaminoethane) ((DES){sub 2}). Decomposition occurred irrespective of the phase from which VX was loaded, the presence of metal impregnation on the carbon surface, and the water content of the carbon. Theoretical and practical aspects of the degradation are discussed. 17 refs., 6 figs., 3 tabs.

  17. Laser Cavity Ringdown Studies of Peroxy Radical Intermediates in the Oxidation of Volatile Organic Compounds

    NASA Astrophysics Data System (ADS)

    Okumura, M.; Takematsu, K.; Eddingsaas, N. C.; Dodson, L. G.; Voss, M.; Nishimura, A.

    2012-12-01

    The detection of reactive intermediates in laboratory kinetics experiments provides a powerful method for determining reaction pathways in the oxidation of Volatile Organic Compounds (VOCs). Many Biogenic VOCs (BVOCs) such as isoprene are unsaturated, and their oxidation can proceed through initial addition of an OH, Cl or NO3 radicals, followed by addition of O2 to form peroxy radicals. We have used cavity ringdown spectroscopy to directly detect substituted peroxy radical intermediates formed in the initial oxidation of a number of unsaturated species, including ethene, propene, butene, butadiene, MBO-232, and MPAN. These experiments have allowed us to identify specific pathways in the oxidation of the parent unsaturated VOC species and to begin studying the rates of subsequent peroxy radical reactions. These studies shed light on the possible pathways for OVOC formation and likely impact on secondary aerosol formation.

  18. Comprehensive DFT study of nitrous oxide decomposition over Fe-ZSM-5.

    PubMed

    Heyden, Andreas; Peters, Baron; Bell, Alexis T; Keil, Frerich J

    2005-02-10

    The reaction mechanism for nitrous oxide decomposition has been studied on hydrated and dehydrated mononuclear iron sites in Fe-ZSM-5 using density functional theory. In total, 46 different surface species with different spin states (spin multiplicity M(S) = 4 or 6) and 63 elementary reactions were considered. Heats of adsorption, activation barriers, reaction rates, and minimum energy pathways were determined. The approximate minimum energy pathways and transition states were calculated using the "growing string method" and a modified "dimer method". Spin surface crossing (e.g., O(2) desorption) was considered. The minimum potential energy structure on the seam of two potential energy surfaces was determined with a multiplier penalty function algorithm by Powell and approximate rates of spin surface crossings were calculated. It was found that nitrous oxide decomposition is first order with respect to nitrous oxide concentration and zero order with respect to oxygen concentration. Water impurities in the gas stream have a strong inhibiting effect. In the concentration range of 1-100 ppb, the presence of water vapor influences the surface composition and the apparent rate coefficient. This is especially relevant in the temperature range of 600-700 K where most experimental kinetic studies are performed. Apparent activation barriers determined over this temperature range vary from 28.4 (1 ppb H(2)O) to 54.8 kcal/mol (100 ppb H(2)O). These results give an explanation why different research groups and different catalyst pretreatments often result in very different activation barriers and preexponential factors. Altogether perfect agreement with experimental results could be achieved. PMID:16851168

  19. [Studies in intermediate energy nuclear physics]. Technical progress report, [October 1, 1992--September 30, 1993

    SciTech Connect

    Peterson, R.J.

    1993-10-01

    This report summarizes work carried out between October 1, 1992 and September 30, 1993 at the Nuclear Physics Laboratory of the University of Colorado, Boulder. The experimental program in intermediate-energy nuclear physics is very broadly based; it includes pion-nucleon and pion-nucleus studies at LAMPF and TRIUMF, kaon-nucleus scattering at the AGS, and equipment development for experiments at the next generation of accelerator facilities.

  20. Size dependence of the thermal decomposition kinetics of nano- CaC2O4: A theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    Fu, Qingshan; Cui, Zixiang; Xue, Yongqiang

    2015-10-01

    In the processes of preparation and application of nanomaterials, the thermal decomposition of nanoparticles is often involved. An improved general theory of thermal decomposition kinetics of nanoparticles, developed over the past 10 years, was presented in this paper where the relations between reaction kinetic parameters and particle size were derived. Experimentally, the thermal decomposition kinetics of nano-sized calcium oxalate (nano- CaC2O4 with different sizes was studied by means of Thermogravimetry Analysis (TGA) at different heating rates. The values of the apparent activation energy and the logarithm of pre-exponential factor were calculated using the equation of Iterative Kissinger-Akahira-Sunose (IKAS) and its deformations. The influence regularities of particle size on the apparent activation energy and the pre-exponential factor were summarized, which are consistent with the thermal decomposition kinetics theory of nanoparticles. Based on the theory, the method of obtaining the surface thermodynamic properties by the determination of kinetic parameters was presented. Theoretical and experimental results show that the particle size, through the effect on the surface thermodynamic properties, has notable effect on the thermal decomposition kinetics. With the particle size decreasing, the partial molar surface enthalpy and the partial molar surface entropy increases, leading to the decrease of the apparent activation energy and the pre-exponential factor, respectively. Furthermore, the apparent activation energy, the pre-exponential factor, the partial molar surface enthalpy and the partial molar surface entropy are linearly related to the reciprocal of particle diameter, respectively.

  1. A comparative study of the decomposition of pig carcasses in a methyl methacrylate box and open air conditions.

    PubMed

    Li, Liangliang; Wang, Jiangfeng; Wang, Yu

    2016-08-01

    Analysis of the process of decomposition is essential in establishing the postmortem interval. However, despite the fact that insects are important players in body decomposition, their exact function within the decay process is still unclear. There is also limited knowledge as to how the decomposition process occurs in the absence of insects. In the present study, we compared the decomposition of a pig carcass in open air with that of one placed in a methyl methacrylate box to prevent insect contact. The pig carcass in the methyl methacrylate box was in the fresh stage for 1 day, the bloated stage from 2 d to 11 d, and underwent deflated decay from 12 d. In contrast, the pig carcass in open air went through the fresh, bloated, active decay and post-decay stages; and 22.3 h (0.93 d), 62.47 h (2.60 d), 123.63 h (5.15 d) and 246.5 h (10.27 d) following the start of the experiment respectively, prior to entering the skeletonization stage. A large amount of soft tissue were remained on the pig carcass in the methyl methacrylate box on 26 d, while only scattered bones remained on the pig carcass in open air. The results indicate that insects greatly accelerate the decomposition process. PMID:27314973

  2. Further studies into the photodissociation pathways of 2-bromo-2-nitropropane and the dissociation channels of the 2-nitro-2-propyl radical intermediate.

    PubMed

    Booth, Ryan S; Brynteson, Matthew D; Lee, Shih-Huang; Lin, J J; Butler, Laurie J

    2014-07-01

    These experiments investigate the decomposition mechanisms of geminal dinitro energetic materials by photolytically generating two key intermediates: 2-nitropropene and 2-nitro-2-propyl radicals. To characterize the unimolecular dissociation of each intermediate, we form them under collision-free conditions using the photodissociation of 2-bromo-2-nitropropane; the intermediates are formed at high internal energies and undergo a multitude of subsequent unimolecular dissociation events investigated herein. Complementing our prior work on this system, the new data obtained with a crossed-laser molecular beam scattering apparatus with VUV photoionization detection at Taiwan's National Synchrotron Radiation Research Center (NSRRC) and new velocity map imaging data better characterize two of the four primary 193 nm photodissociation channels. The C-Br photofission channel forming the 2-nitro-2-propyl radicals has a trimodal recoil kinetic energy distribution, P(ET), suggesting that the 2-nitro-2-propyl radicals are formed both in the ground electronic state and in two low-lying excited electronic states. The new data also revise the HBr photoelimination P(ET) forming the 2-nitropropene intermediate. We then resolved the multiple competing unimolecular dissociation channels of each photoproduct, confirming many of the channels detected in the prior study, but not all. The new data detected HONO product at m/e = 47 using 11.3 eV photoionization from both intermediates; analysis of the momentum-matched products allows us to establish that both 2-nitro-2-propyl → HONO + CH3CCH2 and 2-nitropropene → HONO + C3H4 occur. Photoionization at 9.5 eV allowed us to detect the mass 71 coproduct formed in OH loss from 2-nitro-2-propyl; a channel missed in our prior study. The dynamics of the highly exothermic 2-nitro-2-propyl → NO + acetone dissociation is also better characterized; it evidences a sideways scattered angular distribution. The detection of some stable 2

  3. Retrofit photovoltaic systems for intermediate sized applications-A design and market study

    SciTech Connect

    Noel, G.T.; Hagely, J.R.

    1982-09-01

    An assessment of the technical and economic feasibility of retrofitting a significant portion of the existing intermediate sector building/application inventory with photovoltaic systems is presented. The assessment includes the development of detailed engineering and architectural designs as well as cost estimates for 12 representative installations. Promising applications include retail stores, warehouses, office buildings, religious buildings, shopping centers, education buildings, hospitals, and industrial sites. A market study indicates that there is a national inventory of 1.5 to 2.0 million feasible intermediate sector applications, with the majority being in the 20 to 400 kW size range. The present cost of the major systems components and the cost of necessary building modifications are the primary current barriers to the realization of a large retrofit photovoltaic system market. The development of standardized modular system designs and installation techniques are feasible ways to minimize costs.

  4. Kinetic and microstructural studies of thermal decomposition in uranium mononitride compacts subjected to heating in high-purity helium

    NASA Astrophysics Data System (ADS)

    Lunev, A. V.; Mikhalchik, V. V.; Tenishev, A. V.; Baranov, V. G.

    2016-07-01

    Although uranium mononitride has a high melting point (≈3100 K), it often decomposes well below this temperature. The threshold and kinetics of thermal decomposition depend on samples' chemical content and on gas environment. However, most experiments with uranium nitride samples were done so far in vacuum conditions and did not allow thorough examination of reaction kinetics at high temperatures. This research focuses on studying the different stages of thermal decomposition in uranium nitride samples subjected to heating in helium. Mass loss and thermal effects are identified with simultaneous thermal analysis (STA), while scanning electron microscopy (SEM) and X-ray diffraction (XRD) are used to register phase and compositional changes. Thermal decomposition in uranium nitride samples is found to be a multi-stage process with the final stage characterized by uranium vaporization. The results are useful for estimating the high-temperature behaviour of uranium nitride fuel during its fabrication and performance in some of Gen IV reactors.

  5. A vibrational study of the adsorption and decomposition of formic acid and surface formate on Al(111)

    NASA Astrophysics Data System (ADS)

    Crowell, J. E.; Chen, J. G.; Yates, J. T., Jr.

    1986-09-01

    The adsorption and decomposition of formate and formic acid have been studied on the Al(111) surface using high resolution electron energy loss spectroscopy (EELS) and temperature programmed desorption (TPD). Formic acid reacts with clean Al(111) at 120 K to form a surface formate species. Molecular adsorption of formic acid occurs at 120 K only after saturation of the surface formate layer has been reached. Off-specular vibrational measurements have determined that the formate species is symmetrically bridge bonded through both oxygen atoms with C2v symmetry. A lower symmetry formate species of C1 symmetry is produced upon heating or electron bombardment of a condensed formic acid layer. Thermal or electron induced decomposition of a formate or a condensed formic acid layer is controlled by oxygen incorporation into the aluminum lattice, and results in complete decomposition and production of a carbon and oxygen covered surface. Only hydrogen is evolved from a formate-covered Al(111) surface.

  6. Causal Inference in Longitudinal Comparative Effectiveness Studies With Repeated Measures of A Continuous Intermediate Variable

    PubMed Central

    Wang, Chen-Pin; Jo, Booil; Brown, C. Hendricks

    2014-01-01

    We propose a principal stratification approach to assess causal effects in non-randomized longitudinal comparative effectiveness studies with a binary endpoint outcome and repeated measures of a continuous intermediate variable. Our method is an extension of the principal stratification approach by Lin et al. [10,11], originally proposed for a longitudinal randomized study to assess the treatment effect of a continuous outcome adjusting for the heterogeneity of a repeatedly measured binary intermediate variable. Our motivation for this work comes from a comparison of the effect of two glucose-lowering medications on a clinical cohort of patients with type 2 diabetes. Here we consider a causal inference problem assessing how well the two medications work relative to one another on two binary endpoint outcomes: cardiovascular disease related hospitalization and all-cause mortality. Clinically, these glucose-lowering medications can have differential effects on the intermediate outcome, glucose level over time. Ultimately we want to compare medication effects on the endpoint outcomes among individuals in the same glucose trajectory stratum while accounting for the heterogeneity in baseline covariates (i.e., to obtain “principal effects” on the endpoint outcomes). The proposed method involves a 3-step model estimation procedure. Step 1 identifies principal strata associated with the intermediate variable using hybrid growth mixture modeling analyses [13]. Step 2 obtains the stratum membership using the pseudoclass technique [17,18], and derives propensity scores for treatment assignment. Step 3 obtains the stratum-specific treatment effect on the endpoint outcome weighted by inverse propensity probabilities derived from Step 2. PMID:24577715

  7. Kinetic Study of the Acid Degradation of Lignin Model Compound Intermediates

    SciTech Connect

    Sturgeon, M.; Kim, S.; Chmely, S. C.; Foust, T. D.; Beckham, G. T.

    2012-01-01

    Lignin is a major constituent of biomass, which remains underutilized in selective biomass conversion strategies to renewable fuels and chemicals. Here we are interested in understanding the mechanisms related to the acid deconstruction of lignin with a combined theoretical and experimental approach. Two model dimers with a b-O-4 aryl ether linkage (2-phenoxy-1-phenethanol and 2-phenoxy-1-phenyl-1,3 propanediol) were synthesized and deconstructed in H2SO4. The major products of the acidolysis of the b-O-4 compounds consisted of phenol and two aldehydes, phenylacetaldehyde and benzaldehyde. Quantum mechanical calculations were employed to elucidate possible deconstruction mechanisms with transition state theory. To confirm the proposed mechanisms a kentic study of several possible intermediates was done under similar acidolysis conditions. Epoxystyrene and 1-phenyl-1,2-ethandiol were used as intermediates. 2-phenoxyvinylbenzene was synthesized and subsequently deconstructed in H2SO4. The kinetics and product distribution of these intermediates were then used in confirming our proposed mechanisms.

  8. Electron Paramagnetic Resonance and Electron-Nuclear Double Resonance Studies of the Reactions of Cryogenerated Hydroperoxoferric–Hemoprotein Intermediates

    PubMed Central

    2015-01-01

    The fleeting ferric peroxo and hydroperoxo intermediates of dioxygen activation by hemoproteins can be readily trapped and characterized during cryoradiolytic reduction of ferrous hemoprotein–O2 complexes at 77 K. Previous cryoannealing studies suggested that the relaxation of cryogenerated hydroperoxoferric intermediates of myoglobin (Mb), hemoglobin, and horseradish peroxidase (HRP), either trapped directly at 77 K or generated by cryoannealing of a trapped peroxo-ferric state, proceeds through dissociation of bound H2O2 and formation of the ferric heme without formation of the ferryl porphyrin π-cation radical intermediate, compound I (Cpd I). Herein we have reinvestigated the mechanism of decays of the cryogenerated hydroperoxyferric intermediates of α- and β-chains of human hemoglobin, HRP, and chloroperoxidase (CPO). The latter two proteins are well-known to form spectroscopically detectable quasistable Cpds I. Peroxoferric intermediates are trapped during 77 K cryoreduction of oxy Mb, α-chains, and β-chains of human hemoglobin and CPO. They convert into hydroperoxoferric intermediates during annealing at temperatures above 160 K. The hydroperoxoferric intermediate of HRP is trapped directly at 77 K. All studied hydroperoxoferric intermediates decay with measurable rates at temperatures above 170 K with appreciable solvent kinetic isotope effects. The hydroperoxoferric intermediate of β-chains converts to the S = 3/2 Cpd I, which in turn decays to an electron paramagnetic resonance (EPR)-silent product at temperature above 220 K. For all the other hemoproteins studied, cryoannealing of the hydroperoxo intermediate directly yields an EPR-silent majority product. In each case, a second follow-up 77 K γ-irradiation of the annealed samples yields low-spin EPR signals characteristic of cryoreduced ferrylheme (compound II, Cpd II). This indicates that in general the hydroperoxoferric intermediates relax to Cpd I during cryoanealing at low temperatures, but

  9. Role of Lactobacillus Species in the Intermediate Vaginal Flora in Early Pregnancy: A Retrospective Cohort Study

    PubMed Central

    Farr, Alex; Kiss, Herbert; Hagmann, Michael; Machal, Susanne; Holzer, Iris; Kueronya, Verena; Husslein, Peter Wolf; Petricevic, Ljubomir

    2015-01-01

    Background Poor obstetrical outcomes are associated with imbalances in the vaginal flora. The present study evaluated the role of vaginal Lactobacillus species in women with intermediate vaginal flora with regard to obstetrical outcomes. Methods We retrospectively analysed data from all women with singleton pregnancies who had undergone routine screening for asymptomatic vaginal infections at our tertiary referral centre between 2005 and 2014. Vaginal smears were Gram-stained and classified according to the Nugent scoring system as normal flora (score 0–3), intermediate vaginal flora (4–6), or bacterial vaginosis (7–10). Only women with intermediate vaginal flora were investigated. Women with a Nugent score of 4 were categorised into those with and without Lactobacilli. Follow-up smears were obtained 4–6 weeks after the initial smears. Descriptive data analysis, the Welch’s t-test, the Fisher’s exact test, and multiple regression analysis with adjustment for confounders were performed. Gestational age at delivery and birth weight were the outcome measures. Results At antenatal screening, 529/8421 women presented with intermediate vaginal flora. Amongst these, 349/529 (66%) had a Nugent score of 4, 94/529 (17.8%) a Nugent score of 5, and 86/529 (16.2%) a Nugent score of 6. Amongst those with a Nugent score of 4, 232/349 (66.5%) women were in the Lactobacilli group and 117/349 (33.5%) in the Non-Lactobacilli group. The preterm delivery rate was significantly lower in the Lactobacilli than in the Non-Lactobacilli group (OR 0.34, CI 0.21–0.55; p<0.001). Mean birth weight was 2979 ± 842 g and 2388 ± 1155 g in the study groups, respectively (MD 564.12, CI 346.23–781.92; p<0.001). On follow-up smears, bacterial vaginosis rates were 9% in the Lactobacilli and 7.8% in the Non-Lactobacilli group. Conclusions The absence of vaginal Lactobacillus species and any bacterial colonisation increases the risks of preterm delivery and low birth weight in women with

  10. Kinetic studies of the decomposition of CH 3COOH and CH 3COOD on SnO 2 single crystals

    NASA Astrophysics Data System (ADS)

    Thoren, W.; Kohl, D.; Heiland, G.

    1985-10-01

    The decomposition of CH 3COOH, CH 3COOD, and CH 4 on as grown SnO 2(101) faces, cleaned in UHV, was investigated by reactive scattering, thermal desorption spectroscopy (TDS), and four-probe surface conductivity measurements. After exposure to methane and acetic acid in TDS CO and CO 2 appear in a similar way. The spectra are different from the ones after exposures to CO. These findings are conceivable assuming a formate intermediate in equilibrium with CO and CO 2. This mechanism is known from the water gas shift reaction on ZnO. It implies a reaction of the methyl group of the acetic acid with lattice oxygen delivering surface hydrogen. On exposure to CH 3COOD also desorption of CH 3COOH, CH 4 and H 2O is observed. This exchange of H/D can only be caused by a decomposition of the methyl group. A complete reaction scheme is proposed explaining also a reversible and an irreversible increase of surface conductivity by hydrogen donors and oxygen vacancy donors, respectively.

  11. HPLC and HPLC/MS/MS Studies on Stress, Accelerated and Intermediate Degradation Tests of Antivirally Active Tricyclic Analog of Acyclovir.

    PubMed

    Lesniewska, Monika A; Dereziński, Paweł; Klupczyńska, Agnieszka; Kokot, Zenon J; Ostrowski, Tomasz; Zeidler, Joanna; Muszalska, Izabela

    2015-01-01

    The degradation behavior of a tricyclic analog of acyclovir [6-(4-MeOPh)-TACV] was determined in accordance with International Conference on Harmonization guidelines for good clinical practice under different stress conditions (neutral hydrolysis, strong acid/base degradation, oxidative decomposition, photodegradation, and thermal degradation). Accelerated [40±2°C/75%±5% relative humidity (RH)] and intermediate (30±2°C/65%±5% RH) stability tests were also performed. For observation of the degradation of the tested compound the RP-HPLC was used, whereas for the analysis of its degradation products HPLC/MS/MS was used. Degradation of the tested substance allowed its classification as unstable in neutral environment, acidic/alkaline medium, and in the presence of oxidizing agent. The tested compound was also light sensitive and was classified as photolabile both in solution and in the solid phase. However, the observed photodegradation in the solid phase was at a much lower level than in the case of photodegradation in solution. The study showed that both air temperature and RH had no significant effect on the stability of the tested substance during storage for 1 month at 100°C (dry heat) as well as during accelerated and intermediate tests. Based on the HPLC/MS/MS analysis, it can be concluded that acyclovir was formed as a degradation product of 6-(4-MeOPh)-TACV. PMID:26525242

  12. Case study for model validation : assessing a model for thermal decomposition of polyurethane foam.

    SciTech Connect

    Dowding, Kevin J.; Leslie, Ian H.; Hobbs, Michael L.; Rutherford, Brian Milne; Hills, Richard Guy; Pilch, Martin M.

    2004-10-01

    A case study is reported to document the details of a validation process to assess the accuracy of a mathematical model to represent experiments involving thermal decomposition of polyurethane foam. The focus of the report is to work through a validation process. The process addresses the following activities. The intended application of mathematical model is discussed to better understand the pertinent parameter space. The parameter space of the validation experiments is mapped to the application parameter space. The mathematical models, computer code to solve the models and its (code) verification are presented. Experimental data from two activities are used to validate mathematical models. The first experiment assesses the chemistry model alone and the second experiment assesses the model of coupled chemistry, conduction, and enclosure radiation. The model results of both experimental activities are summarized and uncertainty of the model to represent each experimental activity is estimated. The comparison between the experiment data and model results is quantified with various metrics. After addressing these activities, an assessment of the process for the case study is given. Weaknesses in the process are discussed and lessons learned are summarized.

  13. Soft X-ray-induced decomposition of amino acids: An XPS, massspectrometry, and NEXAFS study

    SciTech Connect

    Zubavichus, Y.; Fuchs, O.; Weinhardt, L.; Heske, C.; Umbach, E.; Denlinger, J.D.; Grunze, M.

    2003-02-26

    Decomposition of five amino acids, viz. alanine, serine,cysteine, aspartic acid, and asparagine under soft X-ray irradiation (MgKα X-ray source) in ultra-high vacuum has been studied by meansof XPS and mass-spectrometry. A comparative analysis of changes in XPSline shapes, stoichiometry, and residual gas composition indicates thatthe molecules decompose via severalpathways. Dehydration,decarboxylation, decarbonylation, deamination, and desulfurization ofpristine molecules accompanied by desorption of H2, H2O, CO2, CO, NH3,H2S are observed with rates depending on the specific amino acid. NEXAFSspectra of cysteine at the C, O, N K- and S L2,3-edges complement the XPSand mass-spectrometry data and show that exposure of the sample to anintense soft X-ray synchrotron beam results in a formation of C-C and C-Ndouble and triple bonds. Qualitatively, the studied amino acids can bearranged in the following ascending order for radiation stability: serine

  14. Decomposition of soil organic matter by ectomycorrhizal fungi studied by infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Nicolás, César; Tunlid, Anders; Persson, Per

    2015-04-01

    Boreal forests accumulate a fifth of the global soil organic matter (SOM) pool and play an important role in the carbon cycling. Most trees in these boreal forests live in symbiosis with ectomycorrhizal fungi (EMF) that sheath the plant root tips. In the symbiotic relationship, EMF provide nutrients from the soil to plants such as nitrogen and phosphorous, and trees give carbon in return to the fungi. When foraging for these nutrients, EMF use different strategies to explore the soil matrix. Long-distance exploration types grow far into the soil surroundings of the roots, while short-medium distance exploration ones grow close to the root tips. Despite these morphological differences among EMF, there is still little evidence of their functional role in the SOM decomposition. In this study, two ectomycorrhizal fungi Paxillus involutus and Laccaria bicolor, which belong to long and medium-distance smooth exploration types respectively, were grown in axenic cultures on SOM extracted from forest litter. To trigger the fungal decomposing activity, the extracts were supplemented with glucose. Chemical analysis and infrared spectroscopy were used to analyze the organic matter and chemometric tools such as principal component analysis (PCA), two-dimensional (2D) correlation analysis and multivariate curve resolution-alternating least squares (MCR-ALS) analysis were applied to further understand the chemical changes in the SOM. The first principal component of PCA explained 77% of the total variability and separated the treatments based on two infrared spectral regions: polysaccharides (970-1,150 cm-1) and carbonyl region (1,620-1,800 cm-1). Moreover, the 2D correlation analysis showed that the polysaccharides region in both treatments was negatively correlated with the carbonyl region, suggesting the production of oxidized compounds such as ketones during the uptake of glucose. The 2D correlation analysis also revealed that the diminution of intensity in the

  15. Thermal decomposition of t-butylamine borane studied by in situ solid state NMR

    SciTech Connect

    Feigerle, J.; Smyrl, N. R.; Morrell, J. S.; Stowe, A. C.

    2010-03-18

    of the amine borane fuel more feasible [22]. In the present study, tert-butylamine borane is investigated by heteronuclear in situ solid state NMR to understand hydrogen release from a hydrocarbon containing amine borane. tbutylamine borane has similar physical properties to amine borane with a melting point of 96 C. A single proton has been replaced with a t-butylamine group resulting in a weakening of the dihydrogen bonding framework. t-butylamine borane has a theoretical gravimetric hydrogen density of 15.1%; however, isobutane can also be evolved rather than hydrogen. If decomposition yields one mole isobutane and two moles hydrogen, 4.5 wt% H2 gas will be evolved. More importantly for the present work, the resulting spent fuel should be comprised of both (BNH)n and (CBNH)n polyimidoboranes.

  16. An experimental and modeling study of the thermal decomposition of siloxanes on alumina

    NASA Astrophysics Data System (ADS)

    Sonoc, Alexandru Catalin

    Siloxanes are contaminants in biogas produced at wastewater treatment plants and landfills. Siloxanes need to be removed to below 0.01 ppm (vol/vol) Si equivalent before biogas can be used as a fuel in solid oxide fuel cells without damaging them. In engines, the tolerance is no higher than 9.1 ppm (vol/vol) Si equivalent. Thermal decomposition in a packed bed of gamma alumina is a method that can remove siloxanes to the requisite tolerances. The kinetics of the decomposition reaction have not been previously studied and a kinetic model is necessary to design adsorption beds. Experiments with synthetic biogas and packed beds of activated gamma alumina were conducted to provide data to which kinetic models were fitted. The synthetic biogas used was a mixture of carbon dioxide and methane contaminated with octamethylcyclotetrasiloxane (D4) at concentrations between 32.3 and 72.7 ppm (vol/vol) Si equivalent. The alumina mass, contact times, and temperatures investigated were 0.0700 g, 5.0 to 8.0 ms, and 307 to 384 °C, respectively. The experiments consisted of exposing a heated bed of alumina, initially free of siloxanes, to a stream of synthetic biogas of constant D4 concentration and monitoring the bed exit D4 concentration. Eleven out of the twelve breakthrough curves obtained were adequately predicted by a model that assumed a first order surface reaction, shrinking core particle kinetics, and plug flow in the bed. There were no statistically significant correlations between quality of fit (sum of weighted squares residuals) and concentration, contact time, or temperature in these eleven experiments. The model was not adequate in predicting the breakthrough curve from the experiment at 307 °C and thus should only be used to predict breakthrough curves at temperatures between 333 and 384 °C. The estimated model parameters were 2.10 for intraparticle tortuosity, 406,000 m3˙m -2˙s-1 for Arrhenius pre-exponential factor, and 81.4 kJ˙mor-1 for activation energy.

  17. Inverse Kinematics Studies of Intermediate-Energy Reactions Relevant for SEE and Medical Problems

    SciTech Connect

    Aichelin, J.; Bargholtz, Ch.; Geren, L.; Tegner, P.-E.; Zartova, I.; Blomgren, J.; Olsson, N.; Budzanowski, A.; Czech, B.; Skwirczynska, I.; Chubarov, M.; Lozhkin, O.; Murin, Yu.; Pljuschev, V.; Zubkov, M.; Ekstroem, C.; Kolozhvari, A.; Persson, H.; Westerberg, L.; Jakobsson, B.

    2005-05-24

    The lack of systematic experimental checks on the intermediate-energy nuclear model simulations of heavily ionizing recoils from nucleon-nucleus collisions -- critical inputs for the Single Event Effect analysis of microelectronics and dosimetry calculations including high-LET components in the cancer tumor radiation therapy -- has been a primary motivation for a new experiment planned at the CELSIUS nuclear storage ring of The Svedberg Laboratory, Uppsala, Sweden. Details of the experiment and the first results from a feasibility study are presented here.

  18. Study of Tachyon Warm Intermediate and Logamediate Inflationary Universe from Loop Quantum Cosmological Perspective

    NASA Astrophysics Data System (ADS)

    Das Mandal, Jyotirmay; Debnath, Ujjal

    2016-08-01

    We have studied the tachyon intermediate and logamediate warm inflation in loop quantum cosmological background by taking the dissipative co-efficient Γ = Γ0 (where Γ0 is a constant) in “intermediate” inflation and Γ = V(ϕ), (where V(ϕ) is the potential of tachyonic field) in “logamediate” inflation. We have assumed slow-roll condition to construct scalar field ϕ, potential V, N-folds, etc. Various slow-roll parameters have also been obtained. We have analyzed the stability of this model through graphical representations.

  19. Decomposition techniques

    USGS Publications Warehouse

    Chao, T.T.; Sanzolone, R.F.

    1992-01-01

    Sample decomposition is a fundamental and integral step in the procedure of geochemical analysis. It is often the limiting factor to sample throughput, especially with the recent application of the fast and modern multi-element measurement instrumentation. The complexity of geological materials makes it necessary to choose the sample decomposition technique that is compatible with the specific objective of the analysis. When selecting a decomposition technique, consideration should be given to the chemical and mineralogical characteristics of the sample, elements to be determined, precision and accuracy requirements, sample throughput, technical capability of personnel, and time constraints. This paper addresses these concerns and discusses the attributes and limitations of many techniques of sample decomposition along with examples of their application to geochemical analysis. The chemical properties of reagents as to their function as decomposition agents are also reviewed. The section on acid dissolution techniques addresses the various inorganic acids that are used individually or in combination in both open and closed systems. Fluxes used in sample fusion are discussed. The promising microwave-oven technology and the emerging field of automation are also examined. A section on applications highlights the use of decomposition techniques for the determination of Au, platinum group elements (PGEs), Hg, U, hydride-forming elements, rare earth elements (REEs), and multi-elements in geological materials. Partial dissolution techniques used for geochemical exploration which have been treated in detail elsewhere are not discussed here; nor are fire-assaying for noble metals and decomposition techniques for X-ray fluorescence or nuclear methods be discussed. ?? 1992.

  20. Causal inference in longitudinal comparative effectiveness studies with repeated measures of a continuous intermediate variable.

    PubMed

    Wang, Chen-Pin; Jo, Booil; Brown, C Hendricks

    2014-09-10

    We propose a principal stratification approach to assess causal effects in nonrandomized longitudinal comparative effectiveness studies with a binary endpoint outcome and repeated measures of a continuous intermediate variable. Our method is an extension of the principal stratification approach originally proposed for the longitudinal randomized study "Prevention of Suicide in Primary Care Elderly: Collaborative Trial" to assess the treatment effect on the continuous Hamilton depression score adjusting for the heterogeneity of repeatedly measured binary compliance status. Our motivation for this work comes from a comparison of the effect of two glucose-lowering medications on a clinical cohort of patients with type 2 diabetes. Here, we consider a causal inference problem assessing how well the two medications work relative to one another on two binary endpoint outcomes: cardiovascular disease-related hospitalization and all-cause mortality. Clinically, these glucose-lowering medications can have differential effects on the intermediate outcome, glucose level over time. Ultimately, we want to compare medication effects on the endpoint outcomes among individuals in the same glucose trajectory stratum while accounting for the heterogeneity in baseline covariates (i.e., to obtain 'principal effects' on the endpoint outcomes). The proposed method involves a three-step model estimation procedure. Step 1 identifies principal strata associated with the intermediate variable using hybrid growth mixture modeling analyses. Step 2 obtains the stratum membership using the pseudoclass technique and derives propensity scores for treatment assignment. Step 3 obtains the stratum-specific treatment effect on the endpoint outcome weighted by inverse propensity probabilities derived from Step 2. PMID:24577715

  1. Material decomposition and virtual non-contrast imaging in photon counting computed tomography: an animal study

    NASA Astrophysics Data System (ADS)

    Gutjahr, R.; Polster, C.; Kappler, S.; Pietsch, H.; Jost, G.; Hahn, K.; Schöck, F.; Sedlmair, M.; Allmendinger, T.; Schmidt, B.; Krauss, B.; Flohr, T. G.

    2016-03-01

    The energy resolving capabilities of Photon Counting Detectors (PCD) in Computed Tomography (CT) facilitate energy-sensitive measurements. The provided image-information can be processed with Dual Energy and Multi Energy algorithms. A research PCD-CT firstly allows acquiring images with a close to clinical configuration of both the X-ray tube and the CT-detector. In this study, two algorithms (Material Decomposition and Virtual Non-Contrast-imaging (VNC)) are applied on a data set acquired from an anesthetized rabbit scanned using the PCD-CT system. Two contrast agents (CA) are applied: A gadolinium (Gd) based CA used to enhance contrasts for vascular imaging, and xenon (Xe) and air as a CA used to evaluate local ventilation of the animal's lung. Four different images are generated: a) A VNC image, suppressing any traces of the injected Gd imitating a native scan, b) a VNC image with a Gd-image as an overlay, where contrast enhancements in the vascular system are highlighted using colored labels, c) another VNC image with a Xe-image as an overlay, and d) a 3D rendered image of the animal's lung, filled with Xe, indicating local ventilation characteristics. All images are generated from two images based on energy bin information. It is shown that a modified version of a commercially available dual energy software framework is capable of providing images with diagnostic value obtained from the research PCD-CT system.

  2. Time Domain Strain/Stress Reconstruction Based on Empirical Mode Decomposition: Numerical Study and Experimental Validation.

    PubMed

    He, Jingjing; Zhou, Yibin; Guan, Xuefei; Zhang, Wei; Zhang, Weifang; Liu, Yongming

    2016-01-01

    Structural health monitoring has been studied by a number of researchers as well as various industries to keep up with the increasing demand for preventive maintenance routines. This work presents a novel method for reconstruct prompt, informed strain/stress responses at the hot spots of the structures based on strain measurements at remote locations. The structural responses measured from usage monitoring system at available locations are decomposed into modal responses using empirical mode decomposition. Transformation equations based on finite element modeling are derived to extrapolate the modal responses from the measured locations to critical locations where direct sensor measurements are not available. Then, two numerical examples (a two-span beam and a 19956-degree of freedom simplified airfoil) are used to demonstrate the overall reconstruction method. Finally, the present work investigates the effectiveness and accuracy of the method through a set of experiments conducted on an aluminium alloy cantilever beam commonly used in air vehicle and spacecraft. The experiments collect the vibration strain signals of the beam via optical fiber sensors. Reconstruction results are compared with theoretical solutions and a detailed error analysis is also provided. PMID:27537889

  3. Decomposition and entomological colonization of charred bodies – a pilot study

    PubMed Central

    Vanin, Stefano; Zanotti, Emma; Gibelli, Daniele; Taborelli, Anna; Andreola, Salvatore; Cattaneo, Cristina

    2013-01-01

    Aim To use forensic entomological approach to estimate the post mortem interval (PMI) in burnt remains. Methods Two experiments were performed in a field in the outskirts of Milan, in winter and summer 2007. Four 60-kg pigs were used: two for each experiment. One pig carcass was burnt until it reached the level 2-3 of the Glassman-Crow scale and the not-burnt carcass was used as a control. In order to describe the decomposition process and to collect the data useful for minimum PMI estimation, macroscopic, histological, and entomological analyses were performed. Results In the winter part of the experiment, the first insect activity on the burnt carcass began in the third week (Calliphora vomitoria) and at the beginning of the fourth week an increase in the number of species was observed. In the summer part, adult flies and first instar maggots (Phormia regina) appeared a few minutes/hours after the carcass exposure. Both in winter and summer, flies belonging to the first colonization wave (Calliphoridae) appeared on burnt and control pigs at the same time, whereas other species (Diptera and Coleoptera) appeared earlier on burnt pigs. Conclusion In forensic practice, burnt bodies are among the most neglected fields of entomological research, since they are supposed to be an inadequate substratum for insect colonization. Entomological approach for PMI estimation proved to be useful, although further studies on larger samples are needed. PMID:23986281

  4. Mechanistic Studies on the Radiolytic Decomposition of Perchlorates on the Martian Surface

    NASA Astrophysics Data System (ADS)

    Turner, Andrew M.; Abplanalp, Matthew J.; Kaiser, Ralf I.

    2016-04-01

    Perchlorates—inorganic compounds carrying the perchlorate ion ({{ClO}}4{}-)—were discovered at the north polar landing site of the Phoenix spacecraft and at the southern equatorial landing site of the Curiosity Rover within the Martian soil at levels of 0.4-0.6 wt%. This study explores in laboratory experiments the temperature-dependent decomposition mechanisms of hydrated perchlorates—namely magnesium perchlorate hexahydrate (Mg(ClO4)2·6H2O)—and provides yields of the oxygen-bearing species formed in these processes at Mars-relevant surface temperatures from 165 to 310 K in the presence of galactic cosmic-ray particles (GCRs). Our experiments reveal that the response of the perchlorates to the energetic electrons is dictated by the destruction of the perchlorate ion ({{ClO}}4{}-) and the inherent formation of chlorates ({{ClO}}3{}-) plus atomic oxygen (O). Isotopic substitution experiments reveal that the oxygen is released solely from the perchlorate ion and not from the water of hydration (H2O). As the mass spectrometer detects only molecular oxygen (O2) and no atomic oxygen (O), atomic oxygen recombines to molecular oxygen within the perchlorates, with the overall yield of molecular oxygen increasing as the temperature drops from 260 to 160 K. Absolute destruction rates and formation yields of oxygen are provided for the planetary modeling community.

  5. Shock-induced decomposition of high energy materials: A ReaxFF molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Tiwari, Subodh; Mishra, Ankit; Nomura, Ken-Ichi; Kalia, Rajiv; Nakano, Aiichiro; Vashishta, Priya

    Atomistic simulations of shock-induced detonation provide critical information about high-energy (HE) materials such as sensitivity, crystallographic anisotropy, detonation velocity, and reaction pathways. However, first principles methods are unable to handle systems large enough to describe shock appropriately. We report reactive-force-field ReaxFF simulations of shock-induced decomposition of 1, 3, 5-triamino-2, 3, 6-trinitrobenzene (TATB) and 1,1-diamino 2-2-dinitroethane (FOX-7) crystal. A flyer acts as mechanical stimuli to introduce a shock, which in turn initiated chemical reactions. Our simulation showed a shock speed of 9.8 km/s and 8.23 km/s for TATB and FOX-7, respectively. Reactivity analysis proves that FOX-7 is more reactive than TATB. Chemical reaction pathways analysis revealed similar pathways for the formation of N2 and H2O in both TATB and FOX-7. However, abundance of NH3 formation is specific to FOX-7. Large clusters formed during the reactions also shows different compositions between TATB and FOX-7. Carbon soot formation is much more pronounced in TATB. Overall, this study provides a detailed comparison between shock induced reaction pathway between FOX-7 and TATB. This work was supported by the Office of Naval Research Grant No. N000014-12-1-0555.

  6. Study of shock wave boundary layer interaction phenonemon using color schlieren and snapshot Proper Orthogonal Decomposition

    NASA Astrophysics Data System (ADS)

    Chaganti Subrahmanya Datta, Narendra

    The flow structure of shockwave boundary layer interaction (SWBLI) has been studied using Rainbow Schlieren Deflectometry (RSD), Ensemble Averaging, Fast Fourier Transform (FFT), and snapshot Proper Orthogonal Decomposition (POD) techniques. The Mach number of the approach free-stream was Mach = 3. Shockwave was generated with a 12° wedge. The color schlieren pictures are used to determine the transverse ray deflections at each pixel of the pictures taken using a high speed camera. The interaction region structure is described statistically with the ensemble average and, root mean square deflections. FFT technique is used to determine the dominant frequencies at different regions of the flow field. Results indicate that low frequency oscillations dominate the flow field. The POD technique results complement the findings of the ensemble averaging technique and show that distinct regions contain most of the energy in the flow field. These distinct regions are located around the reflected shock, around the shock wave reaching into the approach boundary layer and around the separation region over the edge of the separation bubble.

  7. In depth study of acrylamide formation in coffee during roasting: role of sucrose decomposition and lipid oxidation.

    PubMed

    Kocadağlı, Tolgahan; Göncüoğlu, Neslihan; Hamzalıoğlu, Aytül; Gökmen, Vural

    2012-09-01

    Coffee, as a source of acrylamide, needs to be investigated in depth to understand the contribution of different precursors. This study aimed to investigate the contributions of sucrose decomposition and lipid oxidation on acrylamide formation in coffee during roasting. Coffee beans and model systems were used to monitor the accumulation of neo-formed carbonyls during heating through sucrose decomposition and lipid oxidation. High resolution mass spectrometry analyses confirmed the formation of 5-hydroxymethylfurfural (HMF) and 3,4-dideoxyosone, which were identified as the major sugar decomposition products in both roasted coffee and model systems. Among others, 2-octenal, 2,4-decadienal, 2,4-heptadienal, 4-hydroxynonenal, and 4,5-epoxy-2-decenal were identified in relatively high quantities in roasted coffee. Formation and elimination of HMF in coffee during roasting had a kinetic pattern similar to those of acrylamide. Its concentration rapidly increased within 10 min followed by an exponential decrease afterward. The amount of lipid oxidation products tended to increase linearly during roasting. It was concluded from the results that roasting formed a pool of neo-formed carbonyls from sucrose decomposition and lipid oxidation, and they play certain role on acrylamide formation in coffee. PMID:22796869

  8. Decomposition Process of Alane and Gallane Compounds in Metal-Organic Chemical Vapor Deposition Studied by Surface Photo-Absorption

    NASA Astrophysics Data System (ADS)

    Yamauchi, Yoshiharu; Kobayashi, Naoki

    1992-09-01

    We used surface photo-absorption (SPA) to study trimethylamine alane (TMAA) and dimethylamine gallane (DMAG) decomposition processes on a substrate surface in metal-organic chemical vapor deposition. The decomposition onset temperatures of these group III hydride sources correspond to the substrate temperature at which the SPA reflectivity starts to increase during the supply of the group III source onto a group V stabilized surface. It was found that TMAA and DMAG start to decompose at about 150°C on an As-stabilized surface, which is much lower than the decomposition onsets of trialkyl Al and Ga compounds. Low temperature photoluminescence spectra exhibit dominant excitionic emissions for GaAs layers grown by DMAG at substrate temperatures above 400°C, indicating that carbon incorporation and the crystal quality deterioration due to incomplete decomposition on surface is much suppressed by using DMAG. A comparison of AlGaAs photoluminescence between layers by TMAA/triethylgallium and triethylaluminum/triethylgallium shows that the band-to-carbon acceptor transition is greatly reduced by using TMAA. TMAA and DMAG were verified to be promising group III sources for low-temperature and high-purity growth with low-carbon incorporation.

  9. Puget Sound Dissolved Oxygen Modeling Study: Development of an Intermediate-Scale Hydrodynamic Model

    SciTech Connect

    Yang, Zhaoqing; Khangaonkar, Tarang; Labiosa, Rochelle G.; Kim, Taeyun

    2010-11-30

    The Washington State Department of Ecology contracted with Pacific Northwest National Laboratory to develop an intermediate-scale hydrodynamic and water quality model to study dissolved oxygen and nutrient dynamics in Puget Sound and to help define potential Puget Sound-wide nutrient management strategies and decisions. Specifically, the project is expected to help determine 1) if current and potential future nitrogen loadings from point and non-point sources are significantly impairing water quality at a large scale and 2) what level of nutrient reductions are necessary to reduce or dominate human impacts to dissolved oxygen levels in the sensitive areas. In this study, an intermediate-scale hydrodynamic model of Puget Sound was developed to simulate the hydrodynamics of Puget Sound and the Northwest Straits for the year 2006. The model was constructed using the unstructured Finite Volume Coastal Ocean Model. The overall model grid resolution within Puget Sound in its present configuration is about 880 m. The model was driven by tides, river inflows, and meteorological forcing (wind and net heat flux) and simulated tidal circulations, temperature, and salinity distributions in Puget Sound. The model was validated against observed data of water surface elevation, velocity, temperature, and salinity at various stations within the study domain. Model validation indicated that the model simulates tidal elevations and currents in Puget Sound well and reproduces the general patterns of the temperature and salinity distributions.

  10. Study of phase decomposition and coarsening of γ′ precipitates in Ni-12 at.% Ti alloy

    SciTech Connect

    Garay-Reyes, C.G.; Hernández-Santiago, F.; Cayetano-Castro, N.; López-Hirata, V.M.; García-Rocha, J.; Hernández-Rivera, J.L.; Dorantes-Rosales, H.J.; Cruz-Rivera, J.J.

    2013-09-15

    The early stages of phase decomposition, morphological evolution of precipitates, coarsening kinetics of γ′ precipitates and micro-hardness in Ni-12 at.% Ti alloy are studied by transmission electron microscopy (TEM) and Vickers hardness tests (VHN). Disk-shaped specimens are solution treated at 1473 K (1200 °C) and aged at 823, 923 and 1023 K (550, 650 and 750 °C) during several periods of time. TEM results show that a conditional spinodal of order occurs at the beginning of the phase decomposition and exhibit the following decomposition sequence and morphological evolution of precipitates: α{sub sss} → γ″ irregular–cuboidal + γ{sub s} → γ′ cuboidal–parallelepiped + γ → η plates + γ. In general during the coarsening of γ′ precipitates, the experimental coarsening kinetics do not fit well to the LSW or TIDC (n = 2.281) theoretical models, however the activation energies determined using the TIDC and LSW theories (262.846 and 283.6075 kJ mol{sup −1}, respectively) are consistent with previously reported values. The highest hardness obtained at 823, 923 and 1023 K (550, 650 and 750 °C) is associated with the presence of γ′ precipitates. - Highlights: • It was studied the conditional spinodal during early stages of phase decomposition. • It was obtained decomposition sequence and morphological evolution of precipitates. • It was experimentally evaluated the coarsening kinetics of γ′ precipitates. • The maximum hardness is associated with the γ′ precipitates.

  11. Structure based aggregation studies reveal the presence of helix-rich intermediate during α-Synuclein aggregation

    PubMed Central

    Ghosh, Dhiman; Singh, Pradeep K.; Sahay, Shruti; Jha, Narendra Nath; Jacob, Reeba S.; Sen, Shamik; Kumar, Ashutosh; Riek, Roland; Maji, Samir K.

    2015-01-01

    Mechanistic understanding of nucleation dependent polymerization by α-synuclein (α-Syn) into toxic oligomers and amyloids is important for the drug development against Parkinson's disease. However the structural and morphological characterization during nucleation and subsequent fibrillation process of α-Syn is not clearly understood. Using a variety of complementary biophysical techniques monitoring entire pathway of nine different synucleins, we found that transition of unstructured conformation into β-sheet rich fibril formation involves helix-rich intermediates. These intermediates are common for all aggregating synucleins, contain high solvent-exposed hydrophobic surfaces, are cytotoxic to SHSY-5Y cells and accelerate α-Syn aggregation efficiently. A multidimensional NMR study characterizing the intermediate accompanied with site-specific fluorescence study suggests that the N-terminal and central portions mainly participate in the helix-rich intermediate formation while the C-terminus remained in an extended conformation. However, significant conformational transitions occur at the middle and at the C-terminus during helix to β-sheet transition as evident from Trp fluorescence study. Since partial helix-rich intermediates were also observed for other amyloidogenic proteins such as Aβ and IAPP, we hypothesize that this class of intermediates may be one of the important intermediates for amyloid formation pathway by many natively unstructured protein/peptides and represent a potential target for drug development against amyloid diseases. PMID:25784353

  12. Structure based aggregation studies reveal the presence of helix-rich intermediate during α-Synuclein aggregation.

    PubMed

    Ghosh, Dhiman; Singh, Pradeep K; Sahay, Shruti; Jha, Narendra Nath; Jacob, Reeba S; Sen, Shamik; Kumar, Ashutosh; Riek, Roland; Maji, Samir K

    2015-01-01

    Mechanistic understanding of nucleation dependent polymerization by α-synuclein (α-Syn) into toxic oligomers and amyloids is important for the drug development against Parkinson's disease. However the structural and morphological characterization during nucleation and subsequent fibrillation process of α-Syn is not clearly understood. Using a variety of complementary biophysical techniques monitoring entire pathway of nine different synucleins, we found that transition of unstructured conformation into β-sheet rich fibril formation involves helix-rich intermediates. These intermediates are common for all aggregating synucleins, contain high solvent-exposed hydrophobic surfaces, are cytotoxic to SHSY-5Y cells and accelerate α-Syn aggregation efficiently. A multidimensional NMR study characterizing the intermediate accompanied with site-specific fluorescence study suggests that the N-terminal and central portions mainly participate in the helix-rich intermediate formation while the C-terminus remained in an extended conformation. However, significant conformational transitions occur at the middle and at the C-terminus during helix to β-sheet transition as evident from Trp fluorescence study. Since partial helix-rich intermediates were also observed for other amyloidogenic proteins such as Aβ and IAPP, we hypothesize that this class of intermediates may be one of the important intermediates for amyloid formation pathway by many natively unstructured protein/peptides and represent a potential target for drug development against amyloid diseases. PMID:25784353

  13. Fundamental study of the austenite formation and decomposition in low-silicon, aluminum added TRIP steels

    NASA Astrophysics Data System (ADS)

    Garcia-Gonzalez, Jose Enrique

    2005-11-01

    TRIP (Transformation Induced Plasticity) steels are under development for automotive applications that require high strength and excellent formability. Conventional TRIP steels consist of a multiphase microstructure comprised of a ferrite matrix with a dispersion of bainite and metastable retained austenite. The high ductility exhibited by these steels results from the transformation of the metastable retained austenite to martensite during straining. In conventional TRIP steel processing, the multiphase microstructure is obtained by controlled cooling from the alpha + gamma region to an isothermal holding temperature. During this holding, bainite forms and carbon is rejected out into the austenite, which lowers the Ms temperature and stabilizes the austenite to room temperature. In this research project, a fundamental study of a low-Si, Mo-Nb added cold rolled TRIP steel with and without Al additions was conducted. In this study, the recrystallization of cold-rolled ferrite, the formation of austenite during intercritical annealing and the characteristics of the decomposition of the intercritically annealed austenite by controlled cooling rates were systematically assessed. Of special interest were: (i) the effect of the initial hot band microstructure, (ii) the formation of epitaxial ferrite during cooling from the intercritical annealing temperature to the isothermal holding temperature, (iii) the influence of the intercritically annealed austenite on the formation of bainite during the isothermal holding temperature, and (iv) the influence of the processing variables on the type, amount, composition and stability of the retained austenite. During this research study, techniques such as OM, SEM, EBSD, TEM, XRD and Magnetometry were used to fully characterize the microstructures. Furthermore, a Gleeble 3500 unit at US Steel Laboratories was used for dilatometry studies and to simulate different CGL processing routes, from which specimens were obtained to evaluate

  14. Denoising preterm EEG by signal decomposition and adaptive filtering: a comparative study.

    PubMed

    Navarro, X; Porée, F; Beuchée, A; Carrault, G

    2015-03-01

    Electroencephalography (EEG) from preterm infant monitoring systems is usually contaminated by several sources of noise that have to be removed in order to correctly interpret signals and perform automated analysis reliably. Band-pass and adaptive filters (AF) continue to be systematically applied, but their efficacy may be decreased facing preterm EEG patterns such as the tracé alternant and slow delta-waves. In this paper, we propose the combination of EEG decomposition with AF to improve the overall denoising process. Using artificially contaminated signals from real EEGs, we compared the quality of filtered signals applying different decomposition techniques: the discrete wavelet transform, the empirical mode decomposition (EMD) and a recent improved version, the complete ensemble EMD with adaptive noise. Simulations demonstrate that introducing EMD-based techniques prior to AF can reduce up to 30% the root mean squared errors in denoised EEGs. PMID:25659233

  15. Study on the validity of 3 × 3 Mueller matrix decomposition.

    PubMed

    Wang, Yunfei; Guo, Yihong; Zeng, Nan; Chen, Dongsheng; He, Honghui; Ma, Hui

    2015-06-01

    Using Monte Carlo simulations based on previously developed scattering models consisting of spherical and cylindrical scatterers imbedded in birefringent interstitial medium, we compare the polarization parameters extracted from the 3×3 and 4×4 Mueller matrix decomposition methods in forward and backward scattering directions. The results show that the parameters derived from the 3×3 Mueller matrix decomposition are usually not the same as those from the 4×4 Mueller matrix decomposition but display similar qualitative relations to changes in the microstructure of the sample, such as the density, size, and orientation distributions of the scatterers, and birefringence of the interstitial medium. The simulations are backed up by experiments when suitable samples are available. PMID:26039383

  16. Denaturation and intermediates study of two sturgeon hemoglobins by n-dodecyl trimethylammonium bromide

    PubMed Central

    Ariaeenejad, Shohreh; Habibi-Rezaei, Mehran; Kavousi, Kaveh; Jamili, Shahla; Fatemi, Mohammad Reza; Hong, Jun; Poursasan, Najmeh; Sheibani, Nader; Moosavi-Movahedi, Ali. A.

    2013-01-01

    Varieties of hemoglobin (Hb) forms exist in fish, which are usually well adapted to the different ecological conditions or various habitats. In the current study, Hbs from two Sturgeon species of the Southern Caspian Sea Basin were purified and studied upon interaction with n-dodecyl trimethylammonium bromide (DTAB; as a cationic surfactant) by various methods including UV-visible absorption, dynamic light scattering (DLS), and ANS fluorescence spectrophotometry. The chemometric analysis of Hbs was investigated upon interaction with DTAB under titration, using UV-visible absorption spectra. The chemometric resolution techniques were used to determine the number of the components and mole fraction of the oxidized Hbs. These results provided the evidence for the existence of three different molecular components including native (N), intermediate (I) and denatured (D) in sturgeon Hbs. According to the distribution of intermediates, which were broadened in a range of DTAB concentration, the aggregation states, DLS experiments, and thermal stability (Tm obtained by differential scanning calorimetry (DSC)), the Acipenser stellatus Hb was more stable compared to Acipenser persicus Hb. These results demonstrate a significant relationship between the stability of fish Hbs and the habitat depth requirements. PMID:23142155

  17. A study on intermediate buffer layer of coated Fiber Bragg Grating cryogenic temperature sensors

    NASA Astrophysics Data System (ADS)

    Freitas, R.; Araujo, F.; Araujo, J.; Neumann, H.; Ramalingam, R.

    2015-12-01

    The sensor characteristics of a coated Fiber Bragg grating (FBG) thermal sensor for cryogenic temperatures depends mainly on the coating materials. The sensitivity of the coated FBG can be improved by enhancing the effective thermal strain transfer between the different layers and the bare FBG. The dual coated FBG's has a primary layer and the secondary layer. The primary coating acts as an intermediate buffer between the secondary coating and the bare FBG. The outer secondary coating is normally made of metals with high thermal expansion coefficient. In this work, a detailed study is carried out on chromium and titanium intermediate buffer layers with various coating thicknesses and combinations. To improve the sensitivity, the secondary coating layer was tested with Indium, Lead and Tin. The sensors were then calibrated in a cryogenic temperature calibration facility at Institute of Technical Physics (ITEP), Karlsruhe Institute of Technology. The sensors were subjected to several thermal cycles between 4.2 and 80 K to study the sensor performance and its thermal characteristics. The sensor exhibits a Bragg wavelength shift of 13pm at 20K. The commercially available detection equipment with a resolution of 1pm can result in a temperature resolution of 0.076 K at 20K.

  18. Cryo-EM Studies of Microtubule Structural Intermediates and Kinetochore–Microtubule Interactions

    PubMed Central

    Nogales, Eva; Ramey, Vincent H.; Wang, Hong-Wei

    2014-01-01

    The existence of structural intermediates in the processes of microtubule assembly and disassembly, and their relationship with the nucleotide state of tubulin, have been the subject of significant study and recent controversy. The first part of this chapter describes experiments and methods designed to characterize, using cryo-electron microscopy (cryo-EM) and image analysis, the structure of stabilized tubulin assemblies that we propose mimic the growth and shortening states at microtubule ends. We further put forward the idea that these intermediates have important biological functions, especially during cellular processes where the dynamic character of microtubules is essential. One such process is the attachment of spindle microtubules to kinetochores in eukaryotic cell division. The second part of this chapter is consequently dedicated to studies of the yeast Dam1 kinetochore complex and its interaction with microtubules. This complex is essential for accurate chromosome segregation and is an important target of the Aurora B spindle check-point kinase. The Dam1 complex self-assembles in a microtubule-dependent manner into rings and spirals. The rings are able to track microtubule-depolymerizing ends against a load and in a highly processive manner, an essential property for their function in vivo. We describe the experimental in vitro protocols to produce biologically relevant self-assembled structures of Dam1 around microtubules and their structural characterization by cryo-EM. PMID:20466133

  19. Impact of the uncertainties of the ISM when studying the IMF at intermediate masses

    NASA Astrophysics Data System (ADS)

    Mor, R.; Robin, A. C.; Lemasle, B.; Figueras, F.

    We evaluate the impact of the uncertainties in the 3D structure of the Interstellar Medium (ISM) when studying the Initial Mass Function (IMF) at intermediate masses using classical Galactic Cepheids. For that we use the Besan\\c{c}on Galaxy Model (BGM, \\citealt{Robin2003} and \\citealt{Czekaj2014}) and assume different IMFs and different interstellar structure maps to simulate magnitude limited samples of young intermediate mass stars. As our strategy to derive the IMF is based on star counts (in proceedings \\cite{Mor2015} and Mor et al. 2016 in prep.), we quantify the differences in star counts by comparing the whole-sky simulations with Tycho-2 catalogue up to V_T=11 and using Healpix maps. Moreover we compare simulations with different extinction models up to Gaia magnitude G=20. As expected, larger discrepancies between simulations and observations are found in the Galactic Plane, showing that the interstellar extinction in the plane is one of the major source of uncertainty in our study. We show how even with the uncertainties due to the ISM we are able to distinguish between different IMFs.

  20. Ab inito molecular-dynamics study of EC decomposition process on Li2O2 surfaces

    NASA Astrophysics Data System (ADS)

    Ando, Yasunobu; Ikeshoji, Tamio; Otani, Minoru

    2015-03-01

    We have simulated electrochemical reactions of the EC molecule decomposition on Li2O2 substrate by ab initio molecular dynamics combined with the effective screening medium method. EC molecules adsorb onto the peroxide spontaneously. We find through the analysis of density of states that the adsorption state is stabilized by hybridization of the sp2 orbital and the surface states of the Li2O2. After adsorption, EC ring opens, which leads to the decomposition of the peroxide and the formation of a carboxy group. This kind of alkyl carbonates formed on the Li2O2 substrate was found in experiments actually Nanosystem Research Institute, AIST; ESICB, Kyoto University

  1. Study type and plant litter identity modulating the response of litter decomposition to warming, elevated CO2, and elevated O3: A meta-analysis

    NASA Astrophysics Data System (ADS)

    Yue, Kai; Peng, Changhui; Yang, Wanqin; Peng, Yan; Fang, Junmin; Wu, Fuzhong

    2015-03-01

    Plant litter decomposition is one of the most important ecosystem carbon flux processes in terrestrial ecosystems and is usually regarded as sensitive to climate change. The goal of the present study was to examine the effects of changing climate variables on litter decomposition. By synthesizing data from multiple terrestrial ecosystems, we quantified the response of the litter decomposition rate to the independent effects of warming, elevated carbon dioxide (CO2), elevated ozone (O3), and the combined effects of elevated CO2 + elevated O3. Across all case studies, warming increased the litter decomposition rate significantly by 4.4%, but this effect could be reduced as a result of the negatively significant effects of elevated CO2 and elevated CO2 + elevated O3. The combined effects of elevated CO2 + elevated O3 decreased the litter decomposition rate significantly, and the magnitude appeared to be higher than that of the elevated CO2 per se. Moreover, the study type (field versus laboratory), ecosystem type, and plant litter identity and functional traits (growth form and litter form) were all important moderators regulating the response of litter decomposition to climate warming and elevated CO2 and O3. Although litter decomposition rate may show a moderate change as a result of the effects of multiple changing climate variables, the process of litter decomposition would be strongly altered due to the differing mechanisms of the effects of each climate change variable, suggesting that the global carbon cycle and biogeochemistry could be substantially affected.

  2. Density Functional Theory Study of Selectivity Considerations for C–C Versus C–O Bond Scission in Glycerol Decomposition on Pt(111)

    SciTech Connect

    Liu, Bin; Greeley, Jeffrey

    2012-05-01

    Glycerol decomposition via a combination of dehydrogenation, C–C bond scission, and C–O bond scission reactions is examined on Pt(111) with periodic Density Functional Theory (DFT) calculations. Building upon a previous study focused on C–C bond scission in glycerol, the current work presents a first analysis of the competition between C–O and C–C bond cleavage in this reaction network. The thermochemistry of various species produced from C–O bond breaking in glycerol dehydrogenation intermediates is estimated using an extension of a previously introduced empirical correlation scheme, with parameters fit to DFT calculations. Brønsted–Evans–Polanyi (BEP) relationships are then used to estimate the kinetics of C–O bond breaking. When combined with the previous results, the thermochemical and kinetic analyses imply that, while C–O bond scission may be competitive with C–C bond scission during the early stages of glycerol dehydrogenation, the overall rates are likely to be very low. Later in the dehydrogenation process, where rates will be much higher, transition states for C–C bond scission involving decarbonylation are much lower in energy than are the corresponding transition states for C–O bond breaking, implying that the selectivity for C–C scission will be high for glycerol decomposition on smooth platinum surfaces. Finally, it is anticipated that the correlation schemes described in this work will provide an efficient strategy for estimating thermochemical and kinetic energetics for a variety of elementary bond breaking processes on Pt(111) and may ultimately facilitate computational catalyst design for these and related catalytic processes.

  3. The Products of the Thermal Decomposition of CH3CHO

    SciTech Connect

    Vasiliou, AnGayle; Piech, Krzysztof M.; Zhang, Xu; Nimlos, Mark R.; Ahmed, Musahid; Golan, Amir; Kostko, Oleg; Osborn, David L.; Daily, John W.; Stanton, John F.; Ellison, G. Barney

    2011-04-06

    We have used a heated 2 cm x 1 mm SiC microtubular (mu tubular) reactor to decompose acetaldehyde: CH3CHO + DELTA --> products. Thermal decomposition is followed at pressures of 75 - 150 Torr and at temperatures up to 1700 K, conditions that correspond to residence times of roughly 50 - 100 mu sec in the mu tubular reactor. The acetaldehyde decomposition products are identified by two independent techniques: VUV photoionization mass spectroscopy (PIMS) and infrared (IR) absorption spectroscopy after isolation in a cryogenic matrix. Besides CH3CHO, we have studied three isotopologues, CH3CDO, CD3CHO, and CD3CDO. We have identified the thermal decomposition products CH3(PIMS), CO (IR, PIMS), H (PIMS), H2 (PIMS), CH2CO (IR, PIMS), CH2=CHOH (IR, PIMS), H2O (IR, PIMS), and HC=CH (IR, PIMS). Plausible evidence has been found to support the idea that there are at least three different thermal decomposition pathways for CH3CHO: Radical decomposition: CH3CHO + DELTA --> CH3 + [HCO] --> CH3 + H + CO Elimination: CH3CHO + DELTA --> H2 + CH2=C=O. Isomerization/elimination: CH3CHO + DELTA --> [CH2=CH-OH] --> HC=CH + H2O. Both PIMS and IR spectroscopy show compelling evidence for the participation of vinylidene, CH2=C:, as an intermediate in the decomposition of vinyl alchohol: CH2=CH-OH + DELTA --> [CH2=C:] + H2O --> HC=CH + H2O.

  4. The Feasibility of Using Hydrogen Peroxide Decomposition Studies for High School Chemistry.

    ERIC Educational Resources Information Center

    Carter, Gillian E.

    1986-01-01

    Highlights difficulties that occur when teachers attempt to devise new experiments (use of hydrogen peroxide decomposition) and how seemingly useless results can be turned into productive student projects. Considers effects of ions present in tap water, pH, dust, and nature of vessel's surface. Reaction order and safety precautions are noted. (JN)

  5. Peat decomposition - shaping factors, significance in environmental studies and methods of determination; a literature review

    NASA Astrophysics Data System (ADS)

    Drzymulska, Danuta

    2016-03-01

    A review of literature data on the degree of peat decomposition - an important parameter that yields data on environmental conditions during the peat-forming process, i.e., humidity of the mire surface, is presented. A decrease in the rate of peat decomposition indicates a rise of the ground water table. In the case of bogs, which receive exclusively atmospheric (meteoric) water, data on changes in the wetness of past mire surfaces could even be treated as data on past climates. Different factors shaping the process of peat decomposition are also discussed, such as humidity of the substratum and climatic conditions, as well as the chemical composition of peat-forming plants. Methods for the determination of the degree of peat decomposition are also outlined, maintaining the division into field and laboratory analyses. Among the latter are methods based on physical and chemical features of peat and microscopic methods. Comparisons of results obtained by different methods can occasionally be difficult, which may be ascribed to different experience of researchers or the chemically undefined nature of many analyses of humification.

  6. ESTIMATION OF PHYTOPLANKTON DECOMPOSITION RATES USING TWO-STAGE CONTINUOUS FLOW STUDIES

    EPA Science Inventory

    A two-stage continuous flow (TSCF) system was used to quantify phytoplankton decomposition rates and to characterize the decay process as a function of phytoplankton species, phytoplankton physiological state, and the presence and character of a decomposer community. A TSCF syste...

  7. Thermal Decomposition of NCN: Shock-Tube Study, Quantum Chemical Calculations, and Master-Equation Modeling.

    PubMed

    Busch, Anna; González-García, Núria; Lendvay, György; Olzmann, Matthias

    2015-07-16

    The thermal decomposition of cyanonitrene, NCN, was studied behind reflected shock waves in the temperature range 1790-2960 K at pressures near 1 and 4 bar. Highly diluted mixtures of NCN3 in argon were shock-heated to produce NCN, and concentration-time profiles of C atoms as reaction product were monitored with atomic resonance absorption spectroscopy at 156.1 nm. Calibration was performed with methane pyrolysis experiments. Rate coefficients for the reaction (3)NCN + M → (3)C + N2 + M (R1) were determined from the initial slopes of the C atom concentration-time profiles. Reaction R1 was found to be in the low-pressure regime at the conditions of the experiments. The temperature dependence of the bimolecular rate coefficient can be expressed with the following Arrhenius equation: k1(bim) = (4.2 ± 2.1) × 10(14) exp[-242.3 kJ mol(-1)/(RT)] cm(3) mol(-1) s(-1). The rate coefficients were analyzed by using a master equation with specific rate coefficients from RRKM theory. The necessary molecular data and energies were calculated with quantum chemical methods up to the CCSD(T)/CBS//CCSD/cc-pVTZ level of theory. From the topography of the potential energy surface, it follows that reaction R1 proceeds via isomerization of NCN to CNN and subsequent C-N bond fission along a collinear reaction coordinate without a tight transition state. The calculations reproduce the magnitude and temperature dependence of the rate coefficient and confirm that reaction R1 is in the low-pressure regime under our experimental conditions. PMID:25853321

  8. Woodland Decomposition.

    ERIC Educational Resources Information Center

    Napier, J.

    1988-01-01

    Outlines the role of the main organisms involved in woodland decomposition and discusses some of the variables affecting the rate of nutrient cycling. Suggests practical work that may be of value to high school students either as standard practice or long-term projects. (CW)

  9. An ecological study of Bithynia snails, the first intermediate host of Opisthorchis viverrini in northeast Thailand.

    PubMed

    Wang, Yi-Chen; Ho, Richard Cheng Yong; Feng, Chen-Chieh; Namsanor, Jutamas; Sithithaworn, Paiboon

    2015-01-01

    Infection with the food-borne trematodiasis, liver fluke Opisthorchis viverrini, is a major public health concern in Southeast Asia. While epidemiology and parasitic incidence in humans are well studied, ecological information on the O. viverrini intermediate hosts remains limited. This study aimed to investigate the factors affecting the distribution and abundance of the first intermediate host, Bithynia siamensis goniomphalos snails. Water quality and snails were sampled in 31 sites in Muang District, Khon Kaen Province, Thailand from June 2012 to January 2013 to characterize the B.s. goniomphalos snail habitats. Species relative abundance and Shannon's diversity and evenness indices were employed to describe snail compositions and diversities across different habitat types. Statistical analyses were conducted to examine the extent to which the water quality variables and species interactions account for the relative abundance of B.s. goniomphalos snails. The results showed that the freshwater habitats of ponds, streams and rice paddies possessed significantly different abiotic water qualities, with water temperature and pH showing distinct statistical differences (P<0.05). Different habitats had different snail diversity and species evenness, with high B.s. goniomphalos snail abundance at rice paddy habitats. The differences in snail abundance might be due to the distinct sets of abiotic water qualities associated with each habitat types. The relative abundance of B.s. goniomphalos snails was found to be negatively correlated with that of Filopaludina martensi martensi snails (r=-0.46, P<0.05), underscoring the possible influence of species interaction on B.s. goniomphalos snail population. Field work observations revealed that rice planting seasons and irrigation could regulate snail population dynamics at rice paddy habitats. This study provides new ecological insights into the factors affecting Bithynia snail distribution and abundance. It bridges the

  10. Decomposition Pathways of Tetraalkylammonium Hydroxides: Experimental and DFT Studies and Their Implications for Alkaline Exchange Fuel Cell Membranes

    SciTech Connect

    Pivovar, B. S.; Edson, J. B.; Macomber, C. S.; Long, H.; Boncella, J. M.

    2012-01-01

    The mechanism of the thermal decomposition of a series of alkyl trimethyl ammonium hydroxides ([RMe{sub 3}N][OH], R = Et, n-Pr, i-Bu, PhCH{sub 2}, Me{sub 3}CCH{sub 2}) was studied using TGA, evolved gas analysis and NMR spectroscopy due to the importance of these and related ions in anion exchange fuel cell membranes. Isotopic labeling with deuterium showed that deprotonation of the methyl groups of the ammonium ions by deuteroxide establishes a rapid equilibrium between the tetraalkyl ammonium ions and the nitrogen ylide species and water that scrambles the deuterium with the proton on the methyl groups. The products of the thermal decomposition when R = Et, n-Pr, i-Bu are predominately olefins arising from Hoffmann elimination, while the neopentyl substituted ammonium ion gives only neopentyl trimethyl amine and methanol, the products of S{sub N}2 attack of hydroxide on the methyl groups. DFT studies of these reactions confirm the relative activation barriers that are observed in the experimental decomposition studies.

  11. Fission dynamics of intermediate-fissility systems: A study within a stochastic three-dimensional approach

    NASA Astrophysics Data System (ADS)

    Vardaci, E.; Nadtochy, P. N.; Di Nitto, A.; Brondi, A.; La Rana, G.; Moro, R.; Rath, P. K.; Ashaduzzaman, M.; Kozulin, E. M.; Knyazheva, G. N.; Itkis, I. M.; Cinausero, M.; Prete, G.; Fabris, D.; Montagnoli, G.; Gelli, N.

    2015-09-01

    The system of intermediate fissility 132Ce has been studied experimentally and theoretically to investigate the dissipation properties of nuclear matter. Cross sections of fusion-fission and evaporation-residue channels together with light charged particle multiplicities in both channels, their spectra, light charged particle-evaporation residue angular correlations, and mass-energy distribution of fission fragments have been measured. Theoretical analysis has been performed using a multidimensional stochastic approach coupled with a Hauser-Feshbach treatment of particle evaporation. The main conclusions are that the full one-body shape-dependent dissipation mechanism allows the reproduction of the full set of experimental data and that after a time τd=5 ×10-21 s from the equilibrium configuration of the compound nucleus, fission decay can occur in a time that can span several orders of magnitude.

  12. Design studies of the sulfur trioxide decomposition reactor for the sulfur-cycle hydrogen-production process

    SciTech Connect

    Lin, S.S.; Flaherty, R.

    1982-01-01

    The Sulfur Cycle is a two-step hybrid electrochemical/thermochemical process for decomposing water into hydrogen and oxygen. Integration of a complex chemical process with a solar heat source poses unique challenges with regard to process and equipment design. The conceptual design for a developmental test unit demonstrating the sulfur cycle was prepared in 1980. The test unit design is compatible with the power level of a large parabolic solar collector. One of the key components in the process is the sulfur trioxide decomposition reactor. The design studies of the sulfur trioxide decomposition reactor encompassing the thermodynamics, reaction kinetics, heat transfer, and mechanical considerations, are described along with a brief description of the test unit.

  13. Nanostructured copper, chromium, and tin oxide multicomponent materials as catalysts for methanol decomposition: 11C-radiolabeling study.

    PubMed

    Tsoncheva, Tanya; Sarkadi-Priboczki, Eva; Dimitrov, Momtchil; Genova, Izabela

    2013-01-01

    Copper and chromium modified tin oxide nanocomposites were obtained via incipient wetness impregnation of high surface area nanosized SnO(2) with the corresponding metal acetylacetonates and their further decomposition in air. Powder X-ray diffraction (XRD), Nitrogen physisorption, UV-Vis, and Temperature-programmed reduction (TPR) with hydrogen were applied for the samples characterization. The catalytic activity of the obtained materials was tested in methanol conversion. A new approach based on the selective coverage of the surface with (11)C-methanol was used for the characterization of the catalytic sites. It was demonstrated that the products distribution could be controlled by the surface coverage with methanol and the role of different active sites was discussed. The modification of SnO(2) with copper oxide increased the activity in methanol decomposition to CO(2)via dioxymethylene intermediates, but the catalyst suffered considerable loss of activity due to the reduction transformations by the reaction medium and formation of an inactive intermetallic alloy. The modification with chromium changed the acid-basic properties of SnO(2) by the formation of Cr(2)O(3) nanoparticles as well as anchored to the support chromate species. The former particles facilitated the formation of dimethyl ether (DME), while the latter species converted methanol predominantly to hydrocarbons. The fraction of chromate species increased in Cu-Cr-Sn oxide multicomponent nanocomposites and promoted the formation of hydrocarbons over DME at low temperatures, while at higher temperatures, the activity of the copper species leading to CO(2) formation was more pronounced. PMID:23031492

  14. Ammonia decomposition catalysis using lithium-calcium imide.

    PubMed

    Makepeace, Joshua W; Hunter, Hazel M A; Wood, Thomas J; Smith, Ronald I; Murray, Claire A; David, William I F

    2016-07-01

    Lithium-calcium imide is explored as a catalyst for the decomposition of ammonia. It shows the highest ammonia decomposition activity yet reported for a pure light metal amide or imide, comparable to lithium imide-amide at high temperature, with superior conversion observed at lower temperatures. Importantly, the post-reaction mass recovery of lithium-calcium imide is almost complete, indicating that it may be easier to contain than the other amide-imide catalysts reported to date. The basis of this improved recovery is that the catalyst is, at least partially, solid across the temperature range studied under ammonia flow. However, lithium-calcium imide itself is only stable at low and high temperatures under ammonia, with in situ powder diffraction showing the decomposition of the catalyst to lithium amide-imide and calcium imide at intermediate temperatures of 200-460 °C. PMID:27092374

  15. Formulation development of intermediate release Nimesulide tablets by CCRD for IVIVC studies.

    PubMed

    Hanif, Muhammad; Shoaib, Muhammad Harris; Yousuf, Rabia Ismail; Sattar, Shahnila; Nadeem, Muhammad; Hussain, Liaqat; MZia, Muhammad Usman; Muhammad, Iyad Naeem; Uzair, Muhammad; Qadir, Imran

    2014-07-01

    Simple and cost effective study consisting of three steps, comparison of micromeritic properties of different blends i.e. placebo without API and Nimesulide containing, Use of central composite design (CCRD) for intermediate release Nimesulide tablets and stability results of three selected Nimesulide tablet formulations which were calculated by using R Gui. Different concentrations of Avicel, hydroxypropyl methyl cellulose (HPMC) and magnesium stearate were used as variables in central composite design and two types blend i.e., with or without Nimesulide were selected for bulk density, tap density, percentage compressibility; angle of repose and Hausner's ratio. Blending rate constant was performed after applying the different mixing times like 3, 6, 9 and 12 minutes. Twenty intermediate release formulations were designed and three formulations were chosen for compression by direct compression method on the basis of compressibility index. Physicochemical properties and best release pattern in four hours in different dissolution medium were successfully measured. Relative densities, porosity of tablets were compared with tensile strength of tablet and weight variation, hardness, friability and dissolution was performed by simple experiments. Presence of Nimesulide in the bulk increased all micromeratic tests while 9 minutes was best mixing time. The hardness of NM containing tablets increased with the increase of relative density. The release pattern was further analyzed by model dependent i.e. zero order, first order and Higuchi, Korse-meyer and Pappas, Hixson Crowell and model independent kinetic model i.e., f2 value respectively. R Gui explained the F16 formulation shows the best result in stability studies with shelf life 72 months. PMID:25015441

  16. High altitude syndromes at intermediate altitudes: a pilot study in the Australian Alps.

    PubMed

    Slaney, Graham; Cook, Angus; Weinstein, Philip

    2013-10-01

    Our hypothesis is that symptoms of high altitude syndromes are detectable even at intermediate altitudes, as commonly encountered under Australian conditions (<2500 m above sea level). High altitude medicine has long recognised several syndromes associated with rapid ascent to altitudes above 2500 m, including high altitude pulmonary oedema (HAPE), high altitude cerebral oedema (HACE) and high altitude flatus expulsion (HAFE). Symptoms of high altitude syndromes are of growing concern because of the global trend toward increasing numbers of tourists and workers exposed to both rapid ascent and sustained physical activity at high altitude. However, in Australia, high altitude medicine has almost no profile because of our relatively low altitudes by international standards. Three factors lead us to believe that altitude sickness in Australia deserves more serious consideration: Australia is subject to rapid growth in alpine recreational industries; altitude sickness is highly variable between individuals, and some people do experience symptoms already at 1500 m; and there is potential for an occupational health and safety issue amongst workers. To test this hypothesis we examined the relationship between any high altitude symptoms and a rapid ascent to an intermediate altitude (1800 m) by undertaking an intervention study in a cohort of eight medical clinic staff, conducted during July of the 2012 (Southern Hemisphere) ski season, using self-reporting questionnaires, at Mansfield (316 m above sea level) and at the Ski Resort of Mt Buller (1800 m), Victoria, Australia. The intervention consisted of ascent by car from Mansfield to Mt Buller (approx. 40 min drive). Participants completed a self-reporting questionnaire including demographic data and information on frequency of normal homeostatic processes (fluid intake and output, food intake and output, symptoms including thirst and headaches, and frequency of passing wind or urine). Data were recorded in hourly periods

  17. A domain decomposition study of massively parallel computing in compressible gas dynamics

    NASA Astrophysics Data System (ADS)

    Wong, C. C.; Blottner, F. G.; Payne, J. L.; Soetrisno, M.

    1995-03-01

    The appropriate utilization of massively parallel computers for solving the Navier-Stokes equations is investigated and determined from an engineering perspective. The issues investigated are: (1) Should strip or patch domain decomposition of the spatial mesh be used to reduce computer time? (2) How many computer nodes should be used for a problem with a given sized mesh to reduce computer time? (3) Is the convergence of the Navier-Stokes solution procedure (LU-SGS) adversely influenced by the domain decomposition approach? The results of the paper show that the present Navier-Stokes solution technique has good performance on a massively parallel computer for transient flow problems. For steady-state problems with a large number of mesh cells, the solution procedure will require significant computer time due to an increased number of iterations to achieve a converged solution. There is an optimum number of computer nodes to use for a problem with a given global mesh size.

  18. Comparative study of ECG signal denoising by wavelet thresholding in empirical and variational mode decomposition domains.

    PubMed

    Lahmiri, Salim

    2014-09-01

    Hybrid denoising models based on combining empirical mode decomposition (EMD) and discrete wavelet transform (DWT) were found to be effective in removing additive Gaussian noise from electrocardiogram (ECG) signals. Recently, variational mode decomposition (VMD) has been proposed as a multiresolution technique that overcomes some of the limits of the EMD. Two ECG denoising approaches are compared. The first is based on denoising in the EMD domain by DWT thresholding, whereas the second is based on noise reduction in the VMD domain by DWT thresholding. Using signal-to-noise ratio and mean of squared errors as performance measures, simulation results show that the VMD-DWT approach outperforms the conventional EMD-DWT. In addition, a non-local means approach used as a reference technique provides better results than the VMD-DWT approach. PMID:26609387

  19. Theoretical Study of Decomposition Pathways for HArF and HKrF

    NASA Technical Reports Server (NTRS)

    Chaban, Galina M.; Lundell, Jan; Gerber, R. Benny; Kwak, Donchan (Technical Monitor)

    2002-01-01

    To provide theoretical insights into the stability and dynamics of the new rare gas compounds HArF and HKrF, reaction paths for decomposition processes HRgF to Rg + HF and HRgF to H + Rg + F (Rg = Ar, Kr) are calculated using ab initio electronic structure methods. The bending channels, HRgF to Rg + HF, are described by single-configurational MP2 and CCSD(T) electronic structure methods, while the linear decomposition paths, HRgF to H + Rg + F, require the use of multi-configurational wave functions that include dynamic correlation and are size extensive. HArF and HKrF molecules are found to be energetically stable with respect to atomic dissociation products (H + Rg + F) and separated by substantial energy barriers from Rg + HF products, which ensure their kinetic stability. The results are compatible with experimental data on these systems.

  20. Comparative study of ECG signal denoising by wavelet thresholding in empirical and variational mode decomposition domains

    PubMed Central

    2014-01-01

    Hybrid denoising models based on combining empirical mode decomposition (EMD) and discrete wavelet transform (DWT) were found to be effective in removing additive Gaussian noise from electrocardiogram (ECG) signals. Recently, variational mode decomposition (VMD) has been proposed as a multiresolution technique that overcomes some of the limits of the EMD. Two ECG denoising approaches are compared. The first is based on denoising in the EMD domain by DWT thresholding, whereas the second is based on noise reduction in the VMD domain by DWT thresholding. Using signal-to-noise ratio and mean of squared errors as performance measures, simulation results show that the VMD-DWT approach outperforms the conventional EMD–DWT. In addition, a non-local means approach used as a reference technique provides better results than the VMD-DWT approach. PMID:26609387

  1. 11C-radiolabeling study of methanol decomposition on copper oxide modified mesoporous SBA-15 silica

    NASA Astrophysics Data System (ADS)

    Tsoncheva, Tanya; Sarkadi-Priboczki, Eva

    2011-05-01

    11C-radiolabeling technique is applied to investigate methanol decomposition on copper oxide modified SBA-15. Nitrogen physisorption, XRD, FTIR, UV-vis and TPR techniques are used for catalyst characterization. Selective adsorption coverage of the catalytic active sites with 11C- and 12C-methanol molecules is carried out and the products of their conversion are followed. The mechanism of methyl formate, methylal and CO 2 formation from methanol is discussed.

  2. Clinical, neurophysiological and morphological study of dominant intermediate Charcot-Marie-Tooth type C neuropathy.

    PubMed

    Thomas, Florian P; Guergueltcheva, Velina; Gondim, Francisco A A; Tournev, Ivailo; Rao, Chitharanjan V; Ishpekova, Boryana; Kinsella, Laurence J; Pan, Yi; Geller, Thomas J; Litvinenko, Ivan; De Jonghe, Peter; Scherer, Steven S; Jordanova, Albena

    2016-03-01

    Dominant intermediate Charcot-Marie-Tooth neuropathy subtype C (DI-CMTC) was associated with mutations in the YARS gene, encoding tyrosyl-tRNA synthetase, in two large unrelated Bulgarian and US pedigrees and one sporadic case. Here for the first time we describe the clinical, neurophysiological and histopathological features, and phenotypic differences between these two DI-CMTC families. Twenty-one affected individuals from the US family and 27 from the Bulgarian family were evaluated. The mean age of onset in US subjects was 10.7 years in men and 7.3 years in women, while in the Bulgarian participants it was 18.2 years in men and 33.7 years in women. The course was slowly progressive. Extensor digitorum brevis atrophy was uniform. Atrophy and/or weakness of upper and lower limb muscles were found in over 50 % of the subjects. Nerve conduction studies (NCS) were abnormal in all US adults and five of six children and all Bulgarian patients except one asymptomatic 25-year-old man. Median motor NCS were in the range of 29.5-45.6 m/s in the US family and 24.7-57.8 m/s in the Bulgarian family. Sural sensory nerve action potentials were absent in 14/21 and 4/12 NCS from adult US and Bulgarian participants, respectively. Analysis of sural nerve biopsies from US patients revealed age-dependent morphological changes of axonal degeneration, absence of onion bulbs, and <10 % fibers with segmental remyelination. Our findings provide further insights into the diagnosis and pathology of intermediate CMT. They also extend the phenotypic spectrum of peripheral neuropathies associated with aminoacyl-tRNA synthetase mutations. PMID:26725087

  3. Intermediate-m ULF waves generated by substorm injection: a case study

    NASA Astrophysics Data System (ADS)

    Yeoman, T. K.; Klimushkin, D. Yu.; Mager, P. N.

    2010-08-01

    A case study of SuperDARN observations of Pc5 Alfvén ULF wave activity generated in the immediate aftermath of a modest-intensity substorm expansion phase onset is presented. Observations from the Hankasalmi radar reveal that the wave had a period of 580 s and was characterized by an intermediate azimuthal wave number (m=13), with an eastwards phase propagation. It had a significant poloidal component and a rapid equatorward phase propagation (~62° per degree of latitude). The total equatorward phase variation over the wave signatures visible in the radar field-of-view exceeded the 180° associated with field line resonances. The wave activity is interpreted as being stimulated by recently-injected energetic particles. Specifically the wave is thought to arise from an eastward drifting cloud of energetic electrons in a similar fashion to recent theoretical suggestions (Mager and Klimushkin, 2008; Zolotukhina et al., 2008; Mager et al., 2009). The azimuthal wave number m is determined by the wave eigenfrequency and the drift velocity of the source particle population. To create such an intermediate-m wave, the injected particles must have rather high energies for a given L-shell, in comparison to previous observations of wave events with equatorward polarization. The wave period is somewhat longer than previous observations of equatorward-propagating events. This may well be a consequence of the wave occurring very shortly after the substorm expansion, on stretched near-midnight field lines characterised by longer eigenfrequencies than those involved in previous observations.

  4. Methylamine adsorption and decomposition on B12N12 nanocage: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Esrafili, Mehdi D.; Nurazar, Roghaye

    2014-08-01

    Density functional theory calculations are performed to investigate the adsorption and decomposition of methylamine (CH3NH2) on the surface of a B12N12 fullerene-like nanocage. Two adsorption types and two reaction channels are identified. It is found that the electrical conductivity of the nanocage can be modified upon the adsorption of CH3NH2. The pathways of CH3NH2 decomposition via bond scission of the Csbnd N and Nsbnd H bonds are examined. The results indicate that Nsbnd H bond scission is the most favorable pathway on the B12N12 surface. The side reaction that generates CH3 and NH2 fragments is endothermic by 15.6 kcal/mol with an energy-barrier height of 81.5 kcal/mol. For the CH3NH2 decomposition on the B12N12 surface, the rate-determining step appears to be as the following reaction: CH3NH → CH3N + H.

  5. Symmetric tensor decomposition-configuration interaction study of BeH2

    NASA Astrophysics Data System (ADS)

    Kasamatsu, Shusuke; Uemura, Wataru; Sugino, Osamu

    2014-03-01

    The configuration interaction (CI) is a straightforward approach to describing interacting fermions. However, its application is hampered by the non-polynomially increasing computational time and memory requirements with the system size. To overcome this problem, we have been developing a variational method based on the canonical decomposition of the full-CI coefficients, which we call the symmetric tensor decomposition (STD)-CI. The applicability of STD-CI was tested for simple molecular systems, but here we test it using a stringent benchmark system, i.e., the insertion of Be into H2. The Be + H2 system is known for strong configurational degeneracy along the insertion pathway, and has been used for assessing a method's capability to treat correlated systems. We obtained errors compared to full CI results of ~10 mHartrees when using a rank 2 decomposition of the full CI coefficients. This is a huge improvement over Hartree-Fock results having errors of up to ~100 mHartrees in worst cases, although not as good as, e.g., CAS-CCSD with errors less than 1 mHartree.

  6. Thermodynamic and Kinetic Studies for Intensifying Selective Decomposition of Zinc Ferrite

    NASA Astrophysics Data System (ADS)

    Han, Junwei; Liu, Wei; Qin, Wenqing; Jiao, Fen; Wang, Dawei; Liang, Chao

    2016-01-01

    A novel method to intensify the selective decomposition of zinc ferrite by a roasting process including reduction and magnetization stages was proposed. The relevant thermodynamic analysis with HSC [enthalpy (H), entropy (S) and heat capacity (C)] Chemistry 5.0 and experimental research on a laboratory scale were investigated. The thermodynamic calculations show that increasing the temperature and the CO amount promote not only the decomposition of zinc ferrite but also the formation of wustite, which can be converted to magnetite using sufficient CO2 at 823 K. The experimental results indicate that the zinc ferrite was decomposed into zinc oxide and wustite by reduction roasting under a gas mixture of 20% CO, 20% CO2 and 60% N2 at 1023 K for 90 min, and the decomposition degree of zinc ferrite reached 94%. Then, the generated wustite was transformed into magnetite by magnetization roasting under CO2 atmosphere at 823 K for 75 min, after which the selective extraction of zinc from zinc ferrite could be well achieved by low acid leaching. Increasing temperature and time were conducive to the magnetization within low temperature range, but when the temperature was above 823 K the zinc ferrite could be regenerated.

  7. Theoretical study of the decomposition of formamide in the presence of water molecules.

    PubMed

    Nguyen, Vinh Son; Orlando, Thomas M; Leszczynski, Jerzy; Nguyen, Minh Tho

    2013-03-28

    Formamide (NH2CHO, FM) has been considered an active key precursor in prebiotic chemistry on early Earth. Under certain conditions such as dry lagoons, FM can decompose to produce reactants that lead to formation of more complex biomolecules. Specifically, FM decomposition follows many reactive channels producing small molecules such as H2, CO, H2O, HCN, HNC, NH3, and HNCO with comparable energy barriers in the range of 73-82 kcal/mol. Due to the likely presence of water on prebiotic Earth and the intrinsic presence of water following FM decomposition, we explore the effects of water oligomers, (H2O)n with n = 1-3, on its dehydration, dehydrogenation, and decarbonylation reactions using quantum chemical computations. Geometries are optimized using MP2/aug-cc-pVxZ calculations (x = D,T), and relative energies are evaluated using coupled-cluster theory CCSD(T) with the aug-cc-pVxZ basis sets (x = D, T, Q). Where possible the coupled-cluster energies are extrapolated to the complete basis set limit (CBS). Water classically acts as an efficient bifunctional catalyst for decomposition. With the presence of one water molecule, the dehydration pathway leading to HCN is favored. When two and three water molecules are involved, dehydration remains energetically favored over other channels and attains an energy barrier of ~30 kcal/mol. PMID:23461351

  8. Study of tribochemical decomposition of ionic liquids on a nascent steel surface

    NASA Astrophysics Data System (ADS)

    Lu, Renguo; Mori, Shigeyuki; Kobayashi, Kimihiro; Nanao, Hidetaka

    2009-08-01

    Tribological properties and the decomposition process of ionic liquids (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide) on a nascent surface of bearing steel 52100 were investigated by a ball-on-disk friction tester in a vacuum chamber equipped with a quadrupole mass spectrometer (Q-MS). Ionic liquids exhibited better tribological properties than synthetic hydrocarbon oil (multialkylated cyclopentane (MAC)) in high vacuum conditions. The induction period for decomposition of MAC was about 10 km, while no obvious gaseous products were observed for ionic liquids even after a sliding distance of 22 km under the same mechanical conditions. The mass spectra indicated that both the anionic and cationic moieties of ionic liquids decomposed on the nascent steel surface during friction processes. The cationic moiety with a longer alkyl chain was more difficult to decompose on the nascent steel surface than that with a shorter alkyl chain. XPS analysis revealed that the tribofilm formed by ionic liquid was mainly composed of FeF 2 and FeS, which deactivated the nascent surface. As a result, desorption rate of gaseous products decreased appreciably comparing with MAC. The critical load for the mechanical activation of the decomposition correspondingly increased from 1.1 N of MAC to 8 N of ionic liquids.

  9. Shock wave and modeling study of the thermal decomposition reactions of pentafluoroethane and 2-H-heptafluoropropane.

    PubMed

    Cobos, C J; Sölter, L; Tellbach, E; Troe, J

    2014-06-01

    The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) × 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism. PMID:24352693

  10. Infrared spectroscopic study on the thermal decomposition of external and internal gelation products of simulated mixed oxide nuclear fuel.

    PubMed

    Kumar, K Suresh; Bhat, N P

    2004-02-01

    The thermal decomposition of urania-ceria gel corresponding to the composition U(0.7)Ce(0.3)O(2+x) obtained through external and internal gelation routes were studied using infrared spectroscopy (IR). In the case of externally gelated compound, the gel decomposes with the release of H2O and NH3 below 500 degrees C. A part of the NH3 released is entrapped in the solid and above 500 degrees C self reduction occurs in which U(VI) in the gel is reduced to U3O8. The decomposition products were identified to be U3O8 and CeO2. In the case of internally gelated compound, decomposition similar to the one for externally gelated compound occurred below 500 degrees C. Above 500 degrees C the carbon present in the gel reduced U(VI) to UO2 which formed solid solution with CeO2 around 650 degrees C. PMID:14747073

  11. Probing the Cognitive Mechanism of Mental Representational Change During Chunk Decomposition: A Parametric fMRI Study.

    PubMed

    Tang, Xiaochen; Pang, Jiaoyan; Nie, Qi-Yang; Conci, Markus; Luo, Junlong; Luo, Jing

    2016-07-01

    Chunk decomposition plays an important role in cognitive flexibility in particular with regards to representational change, which is critical for insight problem solving and creative thinking. In this study, we investigated the cognitive mechanism of decomposing Chinese character chunks through a parametric fMRI design. Our results from this parametric manipulation revealed widely distributed activations in frontal, parietal, and occipital cortex and negative activations in parietal and visual areas in response to chunk tightness during decomposition. To mentally manipulate the element of a given old chunk, superior parietal lobe appears to support element restructuring in a goal-directed way, whereas the negatively activated inferior parietal lobe may support preventing irrelevant objects from being attended. Moreover, determining alternative ways of restructuring requires a constellation of frontal areas in the cognitive control network, such as the right lateral prefrontal cortex in inhibiting the predominant chunk representations, the presupplementary motor area in initiating a transition of mental task set, and the inferior frontal junction in establishing task sets. In conclusion, this suggests that chunk decomposition reflects mental transformation of problem representation from an inappropriate state to a new one alongside with an evaluation of novel and insightful solutions by the caudate in the dorsal striatum. PMID:26045566

  12. Observational Studies of the Clearing Phase in Proto-Planetary Disks Surrounding Intermediate Mass Stars

    NASA Technical Reports Server (NTRS)

    Grady, Carol A.

    1999-01-01

    A detailed study of circumstellar gas associated with young, intermediate-mass stars has demonstrated that, far from being unique or an infrequently occurring phenomenon, beta Pic-like infall activity is routinely observed in stars younger than 10-50 Myr when the observer's line of sight lies within 15 degrees of the disk mid-plane. Detailed studies of 2 Herbig Ae/Be stars, AB Aur and HD 163296 demonstrate that enhanced infall episodes last 20-60 hours, comparable to the duration of similar episodes in beta Pictoris. The infall activity is consistent with detection of the comae of swarms of star-grazing bodies of asteroidal to cometary composition. Episodic fluctuations in the infall activity are clearly present by approximately 6 Myr, and may indicate the presence of massive planets within the disk. This study has therefore, directly contributed to NASA's Origins of Planetary Systems theme by identifying under what conditions extra-solar planetesimals can be remotely sensed, indicating that such bodies appear to be routinely detectable among young stars in the 1-10 Myr range, and suggesting that temporal studies of spectroscopic variability may provide a means of identifying those systems harboring massive planets. This study has resulted in 2 refereed review papers, 13 other refereed papers, and 17 conference papers.

  13. Application of the model-free approach to the study of non-isothermal decomposition of un-irradiated and γ-irradiated hydrated gadolinium acetylacetonate

    NASA Astrophysics Data System (ADS)

    Mahfouz, R. M.; Ahmed, G. A.-W.; Alshammari, M. R.

    2014-06-01

    The non-isothermal decomposition of unirradiated and γ-irradiated hydrated gadolinium acetylacetone with 102 kGy γ-ray absorbed dose was carried out in air and in nitrogen atmospheres and in the temperature range of 25-1000°C. The results indicate that gadolinium acetylacetonate decomposes through four main decomposition steps leading to the formation of intermediate products whose chemical structure is independent of the gas atmosphere applied and on the investigated absorbed dose. The final product at 820°C was found to be Gd2O3 irrespective of the gas atmosphere and the irradiation conditions. The non-isothermal data were analyzed using linear Flynn-Wall-Ozawa and non-linear Vyazovkin (VYZ) iso-conversional methods. The results of the application of these free models on the present kinetic data showed that the activation energy, Ea is independent of α in a very wide conversion range (0.1-0.9) indicating that the decomposition process is controlled by a unique kinetic model. The results of the model-fitting analysis showed that the decomposition course of the four decomposition steps of hydrated gadolinium acetylacetone was controlled by the D3 Jander diffusion model. Pure phase of Gd2O3 nanoparticles was obtained by thermal oxidation of γ-irradiated GdAcAc.3 H2O at 800°C for 6 h. X-ray diffraction, transmission electron microscopy (TEM) and atomic force microscopy (AFM) techniques were employed for characterization of the as-synthesized nanoparticles. This is the first attempt to prepare Gd2O3 nanoparticles by solid-state thermal decomposition of γ-irradiated hydrated gadolinium acetylacetone.

  14. Experimental studies of pion-nucleus interactions at intermediate energies. Annual progress report

    SciTech Connect

    Not Available

    1991-12-31

    This report summarizes the work on experimental research in intermediate energy nuclear physics carried out at New Mexico State University in 1991 under a great from the US Department of Energy. Most of these studies have involved investigations of various pion-nucleus interactions. The work has been carried out both with the LAMPF accelerator at the Los Alamos National Laboratory and with the cyclotron at the Paul Scherrer Institute (PSI) near Zurich, Switzerland. Part of the experimental work involves measurements of new data on double-charge-exchange scattering, using facilities at LAMPF which we helped modify, and on pion absorption, using a new detector system at PSI that covers nearly the full solid-angle region which we helped construct. Other work involved preparation for future experiments using polarized nuclear targets and a new high-resolution spectrometer system for detecting {pi}{sup 0} mesons. We also presented several proposals for works to be done in future years, involving studies related to pi-mesonic atoms, fundamental pion-nucleon interactions, studies of the difference between charged and neutral pion interactions with the nucleon, studies of the isospin structure of pion-nucleus interactions, and pion scattering from polarized {sup 3}He targets. This work is aimed at improving our understanding of the pion-nucleon interaction, of the pion-nucleus interaction mechanism, and of nuclear structure.

  15. Influence of different forest system management practices on leaf litter decomposition rates, nutrient dynamics and the activity of ligninolytic enzymes: a case study from central European forests.

    PubMed

    Purahong, Witoon; Kapturska, Danuta; Pecyna, Marek J; Schulz, Elke; Schloter, Michael; Buscot, François; Hofrichter, Martin; Krüger, Dirk

    2014-01-01

    Leaf litter decomposition is the key ecological process that determines the sustainability of managed forest ecosystems, however very few studies hitherto have investigated this process with respect to silvicultural management practices. The aims of the present study were to investigate the effects of forest management practices on leaf litter decomposition rates, nutrient dynamics (C, N, Mg, K, Ca, P) and the activity of ligninolytic enzymes. We approached these questions using a 473 day long litterbag experiment. We found that age-class beech and spruce forests (high forest management intensity) had significantly higher decomposition rates and nutrient release (most nutrients) than unmanaged deciduous forest reserves (P<0.05). The site with near-to-nature forest management (low forest management intensity) exhibited no significant differences in litter decomposition rate, C release, lignin decomposition, and C/N, lignin/N and ligninolytic enzyme patterns compared to the unmanaged deciduous forest reserves, but most nutrient dynamics examined in this study were significantly faster under such near-to-nature forest management practices. Analyzing the activities of ligninolytic enzymes provided evidence that different forest system management practices affect litter decomposition by changing microbial enzyme activities, at least over the investigated time frame of 473 days (laccase, P<0.0001; manganese peroxidase (MnP), P = 0.0260). Our results also indicate that lignin decomposition is the rate limiting step in leaf litter decomposition and that MnP is one of the key oxidative enzymes of litter degradation. We demonstrate here that forest system management practices can significantly affect important ecological processes and services such as decomposition and nutrient cycling. PMID:24699676

  16. Synthesis Characterization and Decomposition Studies of tris[N-N-dibenzyidithocarbaso)Indium (III) Chemical Spray Deposition of Polycrystalline CuInS2 on Copper Films

    NASA Technical Reports Server (NTRS)

    Hehemann, David G.; Lau, J. Eva; Harris, Jerry D.; Hoops, Michael D.; Duffy, Norman V.

    2005-01-01

    This paper presents the results of the synthesis characterization and decomposition studies of tris[N-N-dibenzyidithocarbaso)Indium (III) with chemical spray deposition of polycrystalline CuInS2 on Copper Films.

  17. Studies of dielectric characteristics of BaBi 2Nb 2O 9 ferroelectrics prepared by chemical precursor decomposition method

    NASA Astrophysics Data System (ADS)

    Debasis, Dhak; Tanmay, Ghorai K.; Panchanan, Pramanik

    2007-01-01

    BaBiNb 2O 9 (BBN) powders in the nanometer range were prepared by chemical precursor decomposition method (CPD). TG-DTA showed that precursor sample got freed from organic contaminants at 575 °C. XRD showed that a single phase with the layered perovskite structure of BBN was formed after calcining at 600 °C. No intermediate phase was found during heat treatment at and above 600 °C. The crystallite size ( D) and the effective strain ( η) were found to be 26 nm and 0.000867, respectively, while the particle size obtained from TEM was 28 ± 2 nm. SEM revealed that the average grain size after sintering at 900 °C for 4 h was ˜1.67 μm. A relative density of ˜93% was obtained using a two-step sintering process at moderate pressure. Dielectric and ferroelectric properties were investigated in the temperature range 50-500 °C and frequencies from 1 kHz to 5 MHz. Strong dispersion of the complex relative dielectric constant was observed including typical relaxor features such as shift of permittivity maximum with frequency and broadening of the peak maximum. The high dielectric constant of 545 measured at 100 kHz and other properties of BBN ceramics were compared to that of BBN prepared by other conventional methods and found to be superior.

  18. Photonic crystal intermediate reflectors for micromorph solar cells: a comparative study.

    PubMed

    O'Brien, P G; Chutinan, A; Leong, K; Kherani, N P; Ozin, G A; Zukotynski, S

    2010-03-01

    Wave-optics analysis is performed to investigate the benefits of utilizing Bragg-reflectors and inverted ZnO opals as intermediate reflectors in micromorph cells. The Bragg-reflector and the inverted ZnO opal intermediate reflector increase the current generated in a 100 nm thick upper a-Si:H cell within a micromorph cell by as much as 20% and 13%, respectively. The current generated in the bottom muc-Si:H cell within the micromorph is also greater when the Bragg-reflector is used as the intermediate reflector. The Bragg-reflector outperforms the ZnO inverted opal because it has a larger stop-gap, is optically thin, and due to greater absorption losses that occur in the opaline intermediate reflectors. PMID:20389460

  19. Nonadiabatic decomposition of gas-phase RDX through conical intersections: an ONIOM-CASSCF study.

    PubMed

    Bhattacharya, A; Bernstein, E R

    2011-05-01

    Topographical exploration of nonadiabatically coupled ground- and excited-electronic-state potential energy surfaces (PESs) of the isolated RDX molecule was performed using the ONIOM methodology: Computational results were compared and contrasted with the previous experimental results for the decomposition of this nitramine energetic material following electronic excitation. One of the N-NO(2) moieties of the RDX molecule was considered to be an active site. Electronic excitation of RDX was assumed to be localized in the active site, which was treated with the CASSCF algorithm. The influence of the remainder of the molecule on the chosen active site was calculated by either a UFF MM or RHF QM method. Nitro-nitrite isomerization was predicted to be a major excited-electronic-state decomposition channel for the RDX molecule. This prediction directly corroborates previous experimental results obtained through photofragmentation-fragment detection techniques. Nitro-nitrite isomerization of RDX was found to occur through a series of conical intersections (CIs) and was finally predicted to produce rotationally cold but vibrationally hot distributions of NO products, also in good agreement with the experimental observation of rovibrational distributions of the NO product. The ONIOM (CASSCF:UFF) methodology predicts that the final step in the RDX dissociation occurs on its S(0) ground-electronic-state potential energy surface (PES). Thus, the present work clearly indicates that the ONIOM method, coupled with a suitable CASSCF method for the active site of the molecule, at which electronic excitation is assumed to be localized, can predict hitherto unexplored excited-electronic-state PESs of large energetic molecules such as RDX, HMX, and CL-20. A comparison of the decomposition mechanism for excited-electronic-state dimethylnitramine (DMNA), a simple analogue molecule of nitramine energetic materials, with that for RDX, an energetic material, was also performed. CASSCF

  20. The Csbnd O rotation in the gaseous glycine. An energy decomposition analysis study

    NASA Astrophysics Data System (ADS)

    Chang, Xin; Chen, ZuoChang; Su, Peifeng; Wu, Wei

    2015-11-01

    The physical origins of the Csbnd O rotations in glycine are explored theoretically. By the localized molecular orbital energy decomposition analysis (LMO-EDA) method, the rotation barriers are decomposed into the electrostatic, exchange-repulsion, polarization, correlation and geometrical relaxation terms. In general, the Csbnd O rotations are controlled by Pauli repulsion and polarization interactions. However, if the rotated conformer has obvious inter-group interaction between COOH and NH2, the physical origin of the Csbnd O rotation is changed, which is governed by polarization and correlation interactions.

  1. Experimental study of turbulence in isothermal jet impingement at intermediate plate spacings

    NASA Astrophysics Data System (ADS)

    Landfried, D. Tyler; Valentino, Alex; Mazumdar, Sagnik; Jana, Anirban; Kimber, Mark

    2013-11-01

    One fundamental problem in fluid dynamics is that of the axisymmetric round flow impinging on a plate placed some distance downstream of the jet. Impinging jets have a rich history of applications including small plate spacings, H/D ~ 1, such as encountered in electronics cooling, or large plate spacings, H/D ~ 102, such as vertical takeoff aircrafts and rocket engines. However, intermediate plate spacings, such as the lower plenum of the next generation nuclear reactors, are not typically studied. In this paper, an experimental study is conducted investigating the effect of the impingement plate on the flow behavior compared to the near free jet behavior when the plate is removed. Using air as the working fluid, a single jet is considered at jet Reynolds numbers of 10000, 20000, and 30000. A three-wire anemometer probe is used to quantify the mean components of velocities as well as the Reynolds stress and the third-order moments in the flow field at various distances between the jet outlet and the impingement plate. When present, the impingement plate is placed a distance of 8, 11, 14, and 17 diameters downstream of the jet. Additionally trends in the kinetic energy and dissipation are investigated for validation with numerical models.

  2. Reaction of stabilized Criegee intermediates from ozonolysis of limonene with sulfur dioxide: ab initio and DFT study.

    PubMed

    Jiang, Lei; Xu, Yi-sheng; Ding, Ai-zhong

    2010-12-01

    The mechanism of the reaction of the sulfur dioxide (SO(2)) with four stabilized Criegee intermediates (stabCI-CH(3)-OO, stabCI-OO, stabCIx-OO, and stabCH(2)OO) produced via the ozonolysis of limonene have been investigated using ab initio and DFT (density functional theory) methods. It has been shown that the intermediate adduct formed by the initiation of these reactions may be followed by two different reaction pathways such as H migration reaction to form carboxylic acids and rearrangement of oxygen to produce the sulfur trioxide (SO(3)) from the terminal oxygen of the COO group and SO(2). We found that the reaction of stabCI-OO and stabCH(2)OO with SO(2) can occur via both the aforementioned scenarios, whereas that of stabCI-CH(3)-OO and stabCIx-OO with SO(2) is limited to the second pathway only due to the absence of migrating H atoms. It has been shown that at the CCSD(T)/6-31G(d) + CF level of theory the activation energies of six reaction pathways are in the range of 14.18-22.59 kcal mol(-1), with the reaction between stabCIx-OO and SO(2) as the most favorable pathway of 14.18 kcal mol(-1) activation energy and that the reaction of stabCI-OO and stabCH(2)OO with SO(2) occurs mainly via the second reaction path. The thermochemical analysis of the reaction between SO(2) and stabilized Criegee intermediates indicates that the reaction of SO(2) and stabilized Criegee intermediates formed from the exocyclic primary ozonide decomposition is the main pathway of the SO(3) formation. This is likely to explain the large (~100%) difference in the production rate in the favor of the exocyclic compounds observed in recent experiments on the formation of H(2)SO(4) from exocyclic and endocyclic compounds. PMID:21053959

  3. Decomposition Pathways of Glycerol via C–H, O–H, and C–C Bond Scission on Pt(111): A Density Functional Theory Study

    SciTech Connect

    Liu, Bin; Greeley, Jeffrey P.

    2011-10-13

    Glycerol decomposition on Pt(111) via dehydrogenation or C–C bond scission is examined with periodic density functional theory (DFT) calculations. The thermochemistry of dehydrogenation intermediates is first estimated using an empirical correlation scheme with parameters fit to selected DFT calculations; the resulting estimates for the more stable intermediates are refined with full DFT calculations. Brønsted–Evans–Polanyi (BEP) relationships for dehydrogenation and C–C bond scission reactions are developed and used to estimate the kinetics of elementary dehydrogenation and C–C bond scission steps in the reaction network. The combined thermochemical and kinetic analysis implies that glycerol dehydrogenation products at intermediate levels of dehydrogenation are the most thermochemically stable. Additionally, although C–C bond scission transition state energies are high for glycerol and for intermediates at early stages of dehydrogenation, these energies decrease as the intermediates are successively dehydrogenated, reaching a minimum after the removal of several hydrogen atoms from glycerol. At these levels of dehydrogenation, the C–C scission transition state energies become comparable to those of O–H or C–H scission. These results suggest that C–C bonds are only broken after glycerol has been significantly dehydrogenated and demonstrate that DFT-based analyses, combined with simple correlation schemes, can be effective for elucidating general features of complex biomassic reaction networks.

  4. Decomposition Pathways of Glycerol via C–H, O–H, and C–C Bond Scission on Pt(111): A Density Functional Theory Study

    SciTech Connect

    Liu, Bin; Greeley, Jeffrey

    2011-09-01

    Glycerol decomposition on Pt(111) via dehydrogenation or C–C bond scission is examined with periodic density functional theory (DFT) calculations. The thermochemistry of dehydrogenation intermediates is first estimated using an empirical correlation scheme with parameters fit to selected DFT calculations; the resulting estimates for the more stable intermediates are refined with full DFT calculations. Brønsted–Evans–Polanyi (BEP) relationships for dehydrogenation and C–C bond scission reactions are developed and used to estimate the kinetics of elementary dehydrogenation and C–C bond scission steps in the reaction network. The combined thermochemical and kinetic analysis implies that glycerol dehydrogenation products at intermediate levels of dehydrogenation are the most thermochemically stable. Additionally, although C–C bond scission transition state energies are high for glycerol and for intermediates at early stages of dehydrogenation, these energies decrease as the intermediates are successively dehydrogenated, reaching a minimum after the removal of several hydrogen atoms from glycerol. At these levels of dehydrogenation, the C–C scission transition state energies become comparable to those of O–H or C–H scission. These results suggest that C–C bonds are only broken after glycerol has been significantly dehydrogenated and demonstrate that DFT-based analyses, combined with simple correlation schemes, can be effective for elucidating general features of complex biomassic reaction networks.

  5. Experimental studies of nucleon-nucleon and pion-nucleus interactions at intermediate energies

    SciTech Connect

    Not Available

    1990-10-01

    This report summarizes the work on experimental research in intermediate energy nuclear and particle physics carried out by New Mexico State University in 1988--91. Most of these studies have involved investigations of neutron-proton and pion-nucleus interactions. The neutron-proton research is part of a program of studies of interactions between polarized nucleons that we have been involved with for more than ten years. Its purpose has been to help complete the determination of the full set of ten complex nucleon-nucleon amplitudes at energies up to 800 MeV, as well as to continue investigating the possibility of the existence of dibaryon resonances. The give complex isospin-one amplitudes have been fairly well determined, partly as a result of this work. Our work in this period has involved measurements and analysis of data on elastic scattering and total cross sections for polarized neutrons on polarized protons. The pion-nucleus research continues our studies of this interaction in regions where it has not been well explored. One set of experiments includes studies of pion elastic and double-charge-exchange scattering at energies between 300 and 550 MeV, where our data is unique. Another involves elastic and single-charge-exchange scattering of pions from polarized nuclear targets, a new field of research which will give the first extensive set of information on spin-dependent pion-nucleus amplitudes. Still another involves the first set of detailed studies of the kinematic correlations among particles emitted following pion absorption in nuclei.

  6. Keratin intermediate filament structure. Crosslinking studies yield quantitative information on molecular dimensions and mechanism of assembly.

    PubMed

    Steinert, P M; Marekov, L N; Fraser, R D; Parry, D A

    1993-03-20

    One of the major obstacles to solving the full three-dimensional structure of keratin intermediate filaments (KIF) is the determination of the exact mode(s) of alignment of nearest-neighbor molecules; this in turn requires precise information of the lengths of the non-alpha-helical linker segments within the coiled-coil alpha-helical heterodimer molecule. In this study, we have induced lysine-lysine and cysteine-cysteine crosslinks between keratin intermediate filament molecules in small assembly-competent oligomers, isolated them and then characterized the natures and locations of the crosslinks. Of more than 100 found, 21 quantitatively major crosslinks were used to obtain the relative axial alignments of rod domain segments by least-squares fitting methods. Three dominant modes of alignment were found. In each case the molecules are antiparallel with the first involving molecules in approximate register (stagger = -0.2 nm), the second involving molecules staggered so as to bring the 1B segments into approximate alignment (stagger = -16.1 nm), and the third involving molecules staggered so as to bring the 2B segments into approximate alignment (stagger = 28.2 nm). In addition, the data enable quantitative estimates to be made for the first time of the lengths of the non-coiled-coil segments (L1 = 2.5 nm, L12 = 1.6 nm, L2 = 0.8 nm), and the total length of the rod domain (46.0 nm). Alignment of molecules according to these parameters permits construction of a two-dimensional surface lattice which displays a 1.6 nm (10 or 11 residue) overlap between similarly directed molecules. Together, the data predict six important overlapping sequence regions that recur about 16 times per 46 nm of filament length. Interestingly, synthetic peptides corresponding to these sequences, singly or in combination, significantly interfere with keratin filament structural integrity. These results thus represent the most significant set of structural constraints for KIF yet available and

  7. Theoretical Study of the Thermal Decomposition of Carboxylic Acids at Pyrolysis Temperature

    SciTech Connect

    Clark, J. M.; Robichaud, D. J.; Nimlos, M. R.

    2013-01-01

    Carboxylic acids are important in the processing of biomass into renewable fuels and chemicals. They are formed from the pretreatment and pyrolysis of hemicellulose biopolymers and are released from the decomposition of sugars. They result from the deconstruction of polyhydroxyalkanoates (bacterial carbon storage polymers) from fatty acids derived from algae, bacteria, and oil crops. The thermal deoxygenation of carboxylic acids is an important step in the conversion of biomass into aliphatic hydrocarbons suitable for use in renewable biofuels and as petrochemical replacements. Decarboxylation, a primary decomposition pathway under pyrolysis conditions, represents an ideal conversion process, because it eliminates two atoms of oxygen for every carbon atom removed. Problematically, additional deoxygenation processes exist (e.g. dehydration) that are in direct competition with decarboxylation and result in the formation of reactive and more fragmented end products. To better understand the competition between decarboxylation and other deoxygenation processes and to gain insight into possible catalysts that would favor decarboxylation, we have investigated the mechanisms and thermochemistry of the various unimolecular and bimolecular deoxygenation pathways for a family of C1-C4 organic acids using electronic structure calculations at the M06-2X/6-311++G(2df,p) level of theory.

  8. Skeletons in the Stream: A Temporal Study of In-Stream Leaf Decomposition

    NASA Astrophysics Data System (ADS)

    Delmonte, J. M.; Minshall, G. W.; Smith, R. J.

    2005-05-01

    Allochthonous leaf litter plays a pivotal role in streams. Laboratory exercises highlighting its ecological role can examine several components simultaneously. The rate of leaf decomposition is an ecosystem-level process that represents the composite effects of microbial, invertebrate, and physical activity. Leaves that fall into streams often cluster together in "packs" behind rocks and woody debris. In this exercise, students construct leaf packs by collecting leaves from surrounding vegetation or the ground. The leaves are placed into plastic mesh bags and secured in the stream. Subsets of the packs are collected at weekly intervals, colonizing invertebrates are removed and identified, and the remaining leaf material is dried and weighed. Students design and carry out their own experiments, the broad areas of which can include; (1) decomposition rates among streams or leaf type, (2) upstream-downstream effects, (3) distribution of shredding invertebrates, and (4) land-use correlations. We will present examples of results from both high school and college level experiments along with recommendations for successful implementation.

  9. A study of domain decomposition methods applied to the discretized Helmholtz equation

    NASA Astrophysics Data System (ADS)

    Tramel, Robert Wallace

    2001-09-01

    In this work a domain decomposition based preconditioner of the additive Schwarz type is developed and tested on the linear systems which arise out of the application of the Green's Function/Wave Expansion Discretization. (GFD/WED) method to Helmholtz's equation. In order to develop the additive Schwarz preconditioner, use is made of a class of one-sided Artificial Radiation Boundary Conditions (ARBC) developed during the course of this work. These ARBCs are computationally shown to be quite accurate for use on their own. The ARBC's are used to radiatively couple the various sub-domains which are naturally part of domain decomposition based methods in such a manner as to ensure that the system matrix, when restricted to the sub-domains, is non-singular. In addition, the inter-domain ARBC is constructed such that the solution to the global linear system is unaffected by the presence of the artificial boundaries. The efficacy and efficiency of the method is demonstrated on one, two, and three-dimensional test cases.

  10. Mössbauer and EPR Study of Reaction Intermediates of Cytochrome P450

    NASA Astrophysics Data System (ADS)

    Schünemann, V.; Trautwein, A. X.; Jung, C.; Terner, J.

    2002-06-01

    We present a complementary Mössbauer and EPR study on reaction intermediates of substrate-free and substrate-bound cytochrome P450cam from Pseudomonas putida prepared by the freeze-quench method from 57Fe-labeled P450cam using peroxy acetic acid as oxidizing agent. When reacting the substrate-free P450cam for 8 ms reaction time the reaction mixture consists of ˜85% of ferric low-spin iron (Fe(III)) with g-factors and hyperfine parameters of the starting material; the remaining ˜15% are identified as ferryl iron (Fe(IV); S Fe=1) by its Mössbauer signature. Parallel to the ferryl iron a tyrosine radical ( S rad=1/2) is formed. The two paramagnetic species are not exchange-coupled; however, they are close enough to significantly influence the (EPR) relaxation behavior of the radical spin. In the case of substrate-bound P450cam only trace amounts of the tyrosine radical are formed within 8 ms (<3%); within the accuracy of Mössbauer spectroscopy (5%) iron(IV) can not be detected. The results point to Tyr-96, which is hydrogen-bonded to the substrate camphor, as the candidate for the observed tyrosine radical.

  11. Study on an Efficient Dehumidifying Air-conditioning System utilizing Phase Change of Intermediate Pressure Refrigerant

    NASA Astrophysics Data System (ADS)

    Maeda, Kensaku; Inaba, Hideo

    The present study has proven a new dehumidifying system that aimed to reduce the sensible heat factor(SHF) of cooling process without using additional heat to relieve the internationally indicated conflict between energy saving and dehumidification necessary for keeping adequate indoor air quality (IAQ). In this system, we used intermediate pressure refrigerant in a vapor compression refrigerating cycle as heat transfer medium of a characteristic heat exchanger to precool the process air entering into an evaporator as well as to reheat the process air leaving from the evaporator. By this system, the present results achieved higher moisture removal and consequently higher efficiency of dehumidifying process. In addition to this fact, since this system has capability of integration into air-conditioning apparatus(HVAC system), it will be able to work for wide range of cooling load by variable SHF function. In the present paper, technical information, experimental results, and simulation results which assumed to apply this system into HVAC system are reported.

  12. Experimental and theoretical study on the structure and electronic spectra of imiquimod and its synthetic intermediates.

    PubMed

    Zhao, Bo; Rong, Yu-Zhi; Huang, Xiao-Hua; Shen, Jing-Shan

    2007-09-01

    Crystal structure of the imiquimod has been determined by single crystal X-ray analysis, imiquimod crystallizes in orthorhombic space group P2(1)2(1)2(1) and the molecules are linked along the c axis by the strong N-H ... N hydrogen bonds. A density functional theory (DFT) study on the electronic properties of imiquimod and its synthetic intermediates has been performed at B3LYP/6-31G* level, while taking solvent effects into account. Both the single configuration interaction (CIS) method and the time-dependent DFT (TDDFT) approaches have been used to calculate the electronic absorption spectra, and there is a good agreement between the calculated and experimental UV-visible absorption spectra. The fluorescence emission spectra of these three compounds in solution have also been measured, the relatively low fluorescence intensity is attributed to a chlorine-modulated heavy atom effect that enhances intersystem crossing between excited singlet and triplet states, and the relatively high fluorescence intensity of imiquimod results from an extended pi-conjugated system which enhances S(1)-->S(0) radiant transition. PMID:17601733

  13. Infrared matrix isolation and theoretical study of the initial intermediates in the reaction of ozone with cycloheptene

    NASA Astrophysics Data System (ADS)

    Pinelo, Laura; Ault, Bruce S.

    2012-10-01

    Matrix isolation combined with infrared spectroscopy resulted in the observation of early intermediates in the reaction of two conformers of cycloheptene and ozone, marking the first observation of these intermediates for a cyclic alkene with conformational isomerism. Spectral evidence supports the presence of the primary ozonide of the chair and boat conformers of cis-cycloheptene, which represents the first time two primary ozonide isomers have been observed for any alkene. In addition, at least one conformer of the Criegee intermediate formed through ring-opening of the cyclic primary ozonide, as well as stable end products. Both the Criegee intermediate and primary ozonide were observed in the spectra of the initial deposition in twin jet experiments. After the matrix was annealed to 36 K, peaks of the primary ozonide increased by ˜250% while the peak of the Criegee intermediate increased by ˜150%. Supporting data was obtained from 18O-labeled ozone experiments. In addition to experimental evidence, further justification was provided by theoretical calculations at the B3LYP/6-311++G(d,2p) level. The photochemical reactions of the trapped species were also studied. After irradiation of the secondary ozonide and stable products of the ozonolysis reaction, 1-hexanal and carbon dioxide were observed. Late, stable oxidation products of cycloheptene were observed in merged jet experiments.

  14. Conceptualizing and Estimating Process Speed in Studies Employing Ecological Momentary Assessment Designs: A Multilevel Variance Decomposition Approach

    PubMed Central

    Shiyko, Mariya P.; Ram, Nilam

    2012-01-01

    Researchers have been making use of ecological momentary assessment (EMA) and other study designs that sample feelings and behaviors in real time and in naturalistic settings to study temporal dynamics and contextual factors of a wide variety of psychological, physiological, and behavioral processes. As EMA designs become more widespread, questions are arising about the frequency of data sampling, with direct implications for participants’ burden and researchers’ ability to capture and study dynamic processes. Traditionally, spectral analytic techniques are used for time series data to identify process speed. However, the nature of EMA data, often collected with fewer than 100 measurements per person, sampled at randomly spaced intervals, and replete with planned and unplanned missingness, precludes application of traditional spectral analytic techniques. Building on principles of variance partitioning used in the generalizability theory of measurement and spectral analysis, we illustrate the utility of multilevel variance decompositions for isolating process speed in EMA-type data. Simulation and empirical data from a smoking-cessation study are used to demonstrate the method and to evaluate the process speed of smoking urges and quitting self-efficacy. Results of the multilevel variance decomposition approach can inform process-oriented theory and future EMA study designs. PMID:22707796

  15. Photocatalytic decomposition of cortisone acetate in aqueous solution.

    PubMed

    Romão, Joana Sobral; Hamdy, Mohamed S; Mul, Guido; Baltrusaitis, Jonas

    2015-01-23

    The photocatalytic decomposition of cortisone 21-acetate (CA), a model compound for the commonly used steroid, cortisone, was studied. CA was photocatalytically decomposed in a slurry reactor with the initial rates between 0.11 and 0.46 mg L(-1)min(-1) at 10 mg L(-1) concentration, using the following heterogeneous photocatalysts in decreasing order of their catalytic activity: ZnO>Evonik TiO2 P25>Hombikat TiO2>WO3. Due to the lack of ZnO stability in aqueous solutions, TiO2 P25 was chosen for further experiments. The decomposition reaction was found to be pseudo-first order and the rate constant decreased as a function of increasing initial CA concentration. Changing the initial pH of the CA solution did not affect the reaction rate significantly. The decomposition reaction in the presence of the oxidizing sacrificial agent sodium persulfate showed an observed decomposition rate constant of 0.004 min(-1), lower than that obtained for TiO2 P25 (0.040 min(-1)). The highest photocatalytic degradation rate constant was obtained combining both TiO2 P25 and S2O8(2-) (0.071 min(-1)) showing a synergistic effect. No reactive intermediates were detected using LC-MS showing fast photocatalytic decomposition kinetics of CA. PMID:24953705

  16. Reactivation of model cholinesterases by oximes and intermediate phosphyloximes: a computational study.

    PubMed

    Vyas, Shubham; Hadad, Christopher M

    2008-09-25

    Phosphyloximes (POX) are generated upon the reactivation of organophosphorus (OP)-inhibited cholinesterases (ChEs) by pyridinium oximes. These POXs are known to be potent inhibitors of the ChEs following reactivation. However, they can also decompose to give an OP derivative and a cyano derivative of the oxime when a base abstracts the benzylic proton. Using density functional theory, thermodynamic properties were calculated for the reactivation and decomposition pathways of three different oximes (2-PAM, 3-PAM and 4-PAM) with six different OPs (cyclosarin, paraoxon, sarin, tabun, VR and VX). For reactivation purposes, 2-PAM is predicted to be more efficient than 3- and 4-PAM. Based on atomic charges and relative energies, 2-POXs were found to be more inclined towards the decomposition process. PMID:18582852

  17. On the nature of the reaction intermediate in the HIV-1 protease: a quantum chemical study

    NASA Astrophysics Data System (ADS)

    Carnevale, V.; Raugei, S.; Piana, S.; Carloni, P.

    2008-07-01

    Several mechanistic aspects of Aspartic Proteases' enzymatic reaction are currently highly controversial. There is general consensus that the first step of the reaction involves a nucleophilic attack of a water molecule to the substrate carbonyl carbon with subsequent formation of a metastable intermediate (INT). However, the exact nature of this intermediate is subject of debate. While ab initio and QM/MM calculations predict that INT is a neutral gem-diol specie, empirical valence bond calculations suggest that the protein frame can stabilize a charged oxyanion intermediate. Here the relative stability of the gem diol and oxyanion intermediate is calculated by performing density functional and post-Hartree-Fock calculations. The robustness of the results is assessed by increasing the size of the system and of the basis set and by performing QM/MM calculations that explicitly include protein/solvent electrostatic effects. Our results suggest that the neutral gem-diol intermediate is 20-30 kcal/mol more stable than the charged oxyanion. It is therefore concluded that only the neutral specie is populated during the enzymatic reaction.

  18. Layerwise decomposition of water dynamics in reverse micelles: A simulation study of two-dimensional infrared spectrum

    NASA Astrophysics Data System (ADS)

    Biswas, Rajib; Furtado, Jonathan; Bagchi, Biman

    2013-10-01

    We present computer simulation study of two-dimensional infrared spectroscopy (2D-IR) of water confined in reverse micelles (RMs) of various sizes. The present study is motivated by the need to understand the altered dynamics of confined water by performing layerwise decomposition of water, with an aim to quantify the relative contributions of different layers water molecules to the calculated 2D-IR spectrum. The 0-1 transition spectra clearly show substantial elongation, due to inhomogeneous broadening and incomplete spectral diffusion, along the diagonal in the surface water layer of different sized RMs. Fitting of the frequency fluctuation correlation functions reveal that the motion of the surface water molecules is sub-diffusive and indicate the constrained nature of their dynamics. This is further supported by two peak nature of the angular analogue of van Hove correlation function. With increasing system size, the water molecules become more diffusive in nature and spectral diffusion almost completes in the central layer of the larger size RMs. Comparisons between experiments and simulations establish the correspondence between the spectral decomposition available in experiments with the spatial decomposition available in simulations. Simulations also allow a quantitative exploration of the relative role of water, sodium ions, and sulfonate head groups in vibrational dephasing. Interestingly, the negative cross correlation between force on oxygen and hydrogen of O-H bond in bulk water significantly decreases in the surface layer of each RM. This negative cross correlation gradually increases in the central water pool with increasing RMs size and this is found to be partly responsible for the faster relaxation rate of water in the central pool.

  19. Nitrous oxide decomposition over Fe-ZSM-5 in the presence of nitric oxide: a comprehensive DFT study.

    PubMed

    Heyden, Andreas; Hansen, Niels; Bell, Alexis T; Keil, Frerich J

    2006-08-31

    A number of experimental studies have shown recently that ppm-level additions of nitric oxide (NO) enhance the rate of nitrous oxide (N(2)O) decomposition catalyzed by Fe-ZSM-5 at low temperatures. In the present work, the NO-assisted N(2)O decomposition over mononuclear iron sites in Fe-ZSM-5 was studied on a molecular level using density functional theory (DFT) and transition-state theory. A reaction network consisting of over 100 elementary reactions was considered. The structure and energies of potential-energy minima were determined for all stable species, as were the structures and energies of all transition states. Reactions involving changes in spin potential-energy surfaces were also taken into account. In the absence of NO and at temperatures below 690 K, most active single iron sites (Z(-)[FeO](+)) are poisoned by small concentrations of water in the gas phase; however, in the presence of NO, these poisoned sites are converted into a novel active iron center (Z(-)[FeOH](+)). These latter sites are capable of promoting the dissociation of N(2)O into a surface oxygen atom and gas-phase N(2). The surface oxygen atom is removed by reaction with NO or nitrogen dioxide (NO(2)). N(2)O dissociation is the rate-limiting step in the reaction mechanism. At higher temperatures, water desorbs from inactive iron sites and the reaction mechanism for N(2)O decomposition becomes independent of NO, reverting to the reaction mechanism previously reported by Heyden et al. [J. Phys. Chem. B 2005, 109, 1857]. PMID:16928005

  20. Spectral computed tomography for quantitative decomposition of vulnerable plaques using a dual-energy technique: a Monte Carlo simulation study

    NASA Astrophysics Data System (ADS)

    Jo, B. D.; Park, S.-J.; Kim, H. M.; Kim, D. H.; Kim, H.-J.

    2016-02-01

    A spectral computed tomography (CT) system based on an energy-resolved photon-counting Cadmium Zinc Telluride (CZT) detector with a dual energy technique can provide spectral information and can possibly distinguish between two or more materials with a single X-ray exposure using energy thresholds. This work provides the potential for three-material decomposition of vulnerable plaques using two inverse fitting functions. Additionally, there exists the possibility of using gold nanoparticles as a contrast agent for the spectral CT system in conjunction with a CZT photon-counting detector. In this simulation study, we used fan beam CT geometry that consisted of a 90 kVp X-ray spectrum and performed calculations by using the SpekCal program (REAL Software, Inc.) with Monte Carlo simulations. A basic test phantom was imaged with the spectral CT system for the calibration and decomposition process. This phantom contained three different materials, including lipid, iodine and gold nanoparticles, with six holes 3 mm in diameter. In addition to reducing pile-up and charge sharing effect, the photon counting detector was considered an ideal detector. Then, the accuracy of material decomposition techniques with two inverse fitting functions were evaluated between decomposed images and reference images in terms of root mean square error (RMSE). The results showed that decomposed images had a good volumetric fraction for each material, and the RMSE between the measured and true volumes of lipid, iodine and gold nanoparticle fractions varied from 12.51% to 1.29% for inverse fitting functions. The study indicated that spectral CT in conjunction with a CZT photon-counting detector in conjunction with a dual energy technique can be used to identifying materials and may be a promising modality for quantifying material properties of vulnerable plaques.

  1. Evaluation of a Thermodynamically Based Soil Microbial Decomposition Model Based on a 13c Tracer Study in Arctic Tundra Soils

    NASA Astrophysics Data System (ADS)

    Zhu, X.; Tang, J.; Riley, W. J.; Wallenstein, M. D.; Cotrufo, M. F.; Machmuller, M. B.; Lynch, L.

    2014-12-01

    The incorporation of explicit representation of biological complexity in soil carbon decomposition models may improve our ability to accurately predict terrestrial carbon-climate feedbacks. A new generation of microbe-explicit soil decomposition models (MEMs) are being developed that represent soil biological complexity, but only a few take into account detailed biotic and abiotic components and competitive interactions in the complex soil system. In view of this, we have developed a thermodynamically based MEM with a detailed component network (polymeric organic carbon, dissolved organic carbon, microbes, extracellular enzymes, and mineral surfaces), in which competitive interactions and microbial metabolism are modeled using Equilibrium Chemistry Approximation kinetics and Dynamic Energy Budget theory, respectively. The model behavior has been tested and is qualitatively consistent with many empirical studies, but further evaluation of the model with field or lab experimental data in specific ecosystems is needed. Stable carbon isotope (13C) tracer experiments provide a means to directly evaluate soil carbon dynamics simulated by MEMs. In this study, we further develop the model to explicitly account for different carbon isotopes, including 13C and 14C. Isotopic fractionations in soil decomposition processes, including soil organic matter transformations and microbial metabolism, are considered. The 13C signals of different soil components derived from a 13C tracer experiment in Arctic tundra soils are used to test the model behavior and identify needed parametric and structural improvements. Our modeling and data comparison identify several key mechanisms that need to be included in MEMs. Finally, we present an analysis of the relative benefits and costs of additional complexity in MEMs compared to traditional pool-based modeling structures.

  2. A Study of The Binary and Anomalous Stellar Populations in Two Intermediate-Aged Open Clusters

    NASA Astrophysics Data System (ADS)

    Mathieu, Robert D.; Milliman, Katelyn; Geller, Aaron M.; Gosnell, Natalie

    2010-08-01

    ``Anomalous'' stars, such as blue stragglers and more recently sub- subgiants, have been an enduring challenge for stellar evolution theory. It is now clear that in star clusters these systems are closely linked to the binary star populations. Furthermore, sophisticated N-body models show that stellar dynamical processes play a central role in the formation of such anomalous stars. These stars trace the interface between the classical fields of stellar evolution and stellar dynamics. We propose to expand our highly successful radial-velocity survey to include two new rich open clusters NGC 7789 (1.8 Gyr, -0.1 dex) and NGC 2506 (2.1 Gyr, -0.4 dex) as part of the WIYN Open Cluster Study (WOCS). Though these two clusters are both of intermediate age and of similar richness, they have quite different blue straggler populations. NGC 2506 has only 10 known blue stragglers, while NGC 7789 has at least 27, among the largest known populations of blue stragglers in an open cluster. Defining the hard-binary populations in these two clusters is critical for understanding the factors that determine blue straggler production rates. Our proposed observations will establish the hard- binary fraction and frequency distributions of orbital parameters (periods, eccentricities, mass-ratios, etc.) for orbital periods approaching the hard-soft boundary, and will provide a comprehensive survey of the blue stragglers and other anomalous stars, including secure cluster memberships and binary properties. These data will then form direct constraints for detailed N-body open cluster simulations from which we will study the impact of the hard-binary population on the production rates and mechanisms of blue stragglers.

  3. Multiple 'Stable' States of Antarctic Intermediate Water: A Study from the Subantarctic South-West Atlantic.

    NASA Astrophysics Data System (ADS)

    Roberts, J.; Hodell, D. A.; Peck, V. L.; Kender, S.

    2014-12-01

    Modelling studies suggest that density changes in Antarctic Intermediate Water (AAIW) played a significant role in the reorganisation of Atlantic Meridional Overturning Circulation over the last glacial period. From its principal site of formation in the SE Pacific, a significant proportion of AAIW is entrained in the Antarctic circumpolar current and enters the Atlantic through Drake Passage. Air-sea interaction within the subAntarctic SW Atlantic modifies this AAIW further, producing a cooler and fresher Atlantic end member of AAIW. Our core site is located where this branch of AAIW subducts and travels northwards along the western margin of the Atlantic basin. We present the first high-resolution, multi-proxy study of AAIW in the sub-Antarctic SW Atlantic over the last 140 kyrs. Here, we focus on the temperature and salinity records over the last two glacial terminations and at the onset of the last glaciation. We use a combination of benthic stable isotopes and elemental ratios (Mg/Ca) on the shallow infaunal species Uvigerina peregrina to reconstruct AAIW temperature and salinity. Our records suggest that AAIW temperature both increased and decreased in a step-wise manner over the last 120 kyrs hinting at 3 'stable' states for AAIW through the last glacial cycle (see shaded areas within figure). Another common feature is a transient interval of apparently warm, saline AAIW observed at the onset of both glacial terminations - could this be evidence of the 'deep, salty blob' or of increased outflow of Pacific surface waters? We identify some fundamental differences between termination I and termination II; AAIW appears to have been markedly warmer during MIS6 than at the LGM. Furthermore, the glacial-interglacial potential density difference is much greater over termination I than termination II.

  4. Study of the Thermal Decomposition of Some Components of Biomass by Desorption Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Palianytsia, Borys; Kulik, Tetiana; Dudik, Olesia; Cherniavska, Tetiana; Tonkha, Oksana

    The investigation of thermal transformations of lignin samples have been carried out using temperature programmed desorption mass spectrometry method (TPD-MS). Main stages and products of lignin pyrolysis have been identified. The first stages (Tmax = 230 °C and Tmax = 300 °C) are attributed to thermal transformations of lignin peripheral polysaccharide fragments such as hemicellulose and cellulose respectively. The second stage (Tmax = 335 °C) is associated with desorption of lignin structural elements in the molecular forms as a result of depolymerization processes of polymeric blocks of lignin. The third stage (Tmax = 370 °C) correspond to a deeper decomposition of lignin and characterized by desorption of smaller structural fragments in molecular forms (m/z = 110, pyrocatechol). Pressure-temperature curves of pyrolysis of lignin samples have been analyzed.

  5. ERP and Adaptive Autoregressive identification with spectral power decomposition to study rapid auditory processing in infants.

    PubMed

    Piazza, C; Cantiani, C; Tacchino, G; Molteni, M; Reni, G; Bianchi, A M

    2014-01-01

    The ability to process rapidly-occurring auditory stimuli plays an important role in the mechanisms of language acquisition. For this reason, the research community has begun to investigate infant auditory processing, particularly using the Event Related Potentials (ERP) technique. In this paper we approach this issue by means of time domain and time-frequency domain analysis. For the latter, we propose the use of Adaptive Autoregressive (AAR) identification with spectral power decomposition. Results show EEG delta-theta oscillation enhancement related to the processing of acoustic frequency and duration changes, suggesting that, as expected, power modulation encodes rapid auditory processing (RAP) in infants and that the time-frequency analysis method proposed is able to identify this modulation. PMID:25571014

  6. Intermediate Heat Transfer Loop Study for High Temperature Gas-Cooled Reactor

    SciTech Connect

    C. H. Oh; C. Davis; S. Sherman

    2008-08-01

    A number of possible configurations for a system that transfers heat between the nuclear reactor and the hydrogen and/or electrical generation plants were identified. These configurations included both direct and indirect cycles for the production of electricity. Both helium and liquid salts were considered as the working fluid in the intermediate heat transport loop. Methods were developed to perform thermal-hydraulic and cycleefficiency evaluations of the different configurations and coolants. The thermal-hydraulic evaluations estimated the sizes of various components in the intermediate heat transport loop for the different configurations. This paper also includes a portion of stress analyses performed on pipe configurations.

  7. Study of photovoltaic cost elements. Volume 5: Installation cost model for intermediate PV systems: Users manual

    NASA Astrophysics Data System (ADS)

    Ayers, J. B.

    1981-07-01

    A cost modeling methodology is presented for estimating installation costs associated with intermediate photovoltaic (PV) systems. With only a parametric description of an intermediate power system, the model can be used to develop an installation cost estimate for that system. The model is based on conventional cost-estimating procedures widely used by the construction industry and was validated by comparing estimates for the same 10 systems made independently by a cost engineering firm. A description of the model is included as well as an example of its use with a 200 KW solar breeder plant design to be located in Rockville, Maryland.

  8. Probing the Natural World, Level III, Teacher's Edition: Why You're You. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the teacher's edition of one of the eight units of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). The chapters include basic information about heredity, activities, and optional "excursions." The answers to all activities are included. An introduction describes the work of Gregor Mendel and his…

  9. Probing the Natural World, Level III, Record Book, Student Guide: Why You're You. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the student's edition of the Record Book of one of the eight units of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). Space is provided for answers to the questions from the text as well as for the "excursions" and the self evaluation. An introductory note to the student explains how to use the book. (SA)

  10. Probing the Natural World, Level III, Student Guide: Why You're You. Intermediate Science Curriculum Study.

    ERIC Educational Resources Information Center

    Bonar, John R., Ed.; Hathway, James A., Ed.

    This is the student's text of one of the eight units of the Intermediate Science Curriculum Study (ISCS) for level III students (grade 9). The chapters include basic information about heredity, activities, and optional "excursions." A section on introductory notes to the student explains how to use the book. Data tables and empty spaces within the…