WorldWideScience

Sample records for group decomposition kinetics

  1. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  2. Non-isothermal decomposition kinetics of magnesite

    OpenAIRE

    Maitra, S; Mukherjee, S.; Saha, N; Pramanik, J

    2007-01-01

    Kinetics of thermal decomposition of Indian magnesite was studied by thermo-gravimetric analysis under non-isothermal condition. Coats and Redfern Integral approximation method was used to determine the kinetic parameters. Using the kinetic parameters different kinetic functions were analyzed with the experimental data to ascertain the decomposition mechanism of magnesium carbonate and it was observed that the decomposition reaction followed a contracting sphere kinetic mechanism.

  3. Thermal Decomposition Kinetics of HMX

    Energy Technology Data Exchange (ETDEWEB)

    Burnham, A K; Weese, R K

    2004-11-18

    Nucleation-growth kinetic expressions are derived for thermal decomposition of HMX from a variety of thermal analysis data types, including mass loss for isothermal and constant rate heating in an open pan and heat flow for isothermal and constant rate heating in open and closed pans. Conditions are identified in which thermal runaway is small to nonexistent, which typically means temperatures less than 255 C and heating rates less than 1 C/min. Activation energies are typically in the 140 to 165 kJ/mol range for open pan experiments and about 150 to 165 kJ/mol for sealed pan experiments. Our activation energies tend to be slightly lower than those derived from data supplied by the University of Utah, which we consider the best previous thermal analysis work. The reaction clearly displays more than one process, and most likely three processes, which are most clearly evident in open pan experiments. The reaction is accelerated in closed pan experiments, and one global reaction appears to fit the data well. Comparison of our rate measurements with additional literature sources for open and closed low temperature pyrolysis from Sandia gives a likely activation energy of 165 kJ/mol at 10% conversion.

  4. Thermal Decomposition Kinetics of HMX

    Energy Technology Data Exchange (ETDEWEB)

    Burnham, A K; Weese, R K

    2004-05-05

    Nucleation-growth kinetic expressions are derived for thermal decomposition of HMX from a variety of types of data, including mass loss for isothermal and constant rate heating in an open pan, and heat flow for isothermal and constant rate heating in open and closed pans. Conditions are identified in which thermal runaway is small to nonexistent, which typically means temperatures less than 255 C and heating rates less than 1 C/min. Activation energies are typically in the 140 to 150 kJ/mol regime for open pan experiments and about 160 kJ/mol for sealed pan experiments. Our activation energies are about 10% lower than those derived from data supplied by the University of Utah, which we consider the best previous work. The reaction clearly displays more than one process, and most likely three processes, which are most clearly evident in open pan experiments. The reaction is accelerated for closed pan experiments, and one global reaction appears to fit the data well.

  5. Thermal Decomposition Kinetics of HMX

    Energy Technology Data Exchange (ETDEWEB)

    Burnham, A K; Weese, R K

    2005-03-17

    Nucleation-growth kinetic expressions are derived for thermal decomposition of HMX from a variety of types of data, including mass loss for isothermal and constant rate heating in an open pan, and heat flow for isothermal and constant rate heating in open and closed pans. Conditions are identified in which thermal runaway is small to nonexistent, which typically means temperatures less than 255 C and heating rates less than 1 C/min. Activation energies are typically in the 140 to 165 kJ/mol regime for open pan experiments and about 150-165 kJ/mol for sealed-pan experiments. The reaction clearly displays more than one process, and most likely three processes, which are most clearly evident in open pan experiments. The reaction is accelerated for closed pan experiments, and one global reaction fits the data fairly well. Our A-E values lie in the middle of the values given in a compensation-law plot by Brill et al. (1994). Comparison with additional open and closed low temperature pyrolysis experiments support an activation energy of 165 kJ/mol at 10% conversion.

  6. Effect of the substitutional groups on the electrochemistry, kinetic of thermal decomposition and kinetic of substitution of some uranyl Schiff base complexes

    Energy Technology Data Exchange (ETDEWEB)

    Asadi, Zahra; Nasrollahi, Rahele; Ranjkeshshorkaei, Mohammad; Firuzabadi, Fahimeh Dehghani [Shiraz Univ. (Iran, Islamic Republic of). Chemistry Dept.; Dusek, Michal; Fejfarova, Karla [ASCR, Prague (Czech Republic). Inst. of Physics

    2016-05-15

    Uranyl(VI) complexes, [UO{sub 2}(X-saloph)(solvent)], where saloph denotes N,N{sup '}-bis(salicylidene)-1,2-phenylenediamine and X = NO{sub 2}, Cl, Me, H; were synthesized and characterized by 61H NMR, IR, UV-Vis spectroscopy, thermal gravimetry (TG), cyclic voltammetry, elemental analysis (C.H.N) and X-ray crystallography. X-ray crystallography of [UO{sub 2}(4-nitro-saloph)(DMF)] revealed coordination of the uranyl by the tetradentate Schiff base ligand and one solvent molecule, resulting in seven-coordinated uranium. The complex of [UO{sub 2}(4-nitro-saloph)(DMF)] was also synthesized in nano form. Transmission electron microscopy image showed nano-particles with sizes between 30 and 35 nm. The TG method and analysis of Coats-Redfern plots revealed that the kinetics of thermal decomposition of the complexes is of the first-order in all stages. The kinetics and mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was investigated by spectrophotometric method. The second-order rate constants at four temperatures and the activation parameters showed an associative mechanism for all corresponding complexes with the following trend: 4-Nitro > 4-Cl > H > 4-Me. It was concluded that the steric and electronic properties of the complexes were important for the reaction rate. For analysis of anticancer properties of uranyl Schiff base complexes, cell culture and MTT assay was carried out. These results showed a reduction of jurkat cell line concentration across the complexes.

  7. Thermal Decomposition Kinetics of Triethylene Glycol Dinitrate

    Institute of Scientific and Technical Information of China (English)

    CHEN,Pei(陈沛); ZHAO,Feng-Qi(赵凤起); LUO,Yang(罗阳); HU,Rong-Zu(胡荣祖); LI,Shang-Wen(李上文); GAO,Yin(高茵)

    2004-01-01

    The thermal behavior and kinetic parameters of the decomposition reaction of triethylene glycol dinitrate (TEGDN) in a temperature-programmed mode at different pressures (0.1, 2, 4 and 6 MPa) have been investigated by means of DSC and TG-DTG. The results show that the properties of the thermal decomposition of TEGDN are affected by the change of pressure, and the kinetic model function, the apparent activation energy Ea and TEGDN obtained by the values Teo and Tpo of the onset temperature Te and the peak temperature TP when the heating rate tends to zero are 191.05,209.86 ℃ at 0.1 MPa, 207.59 and 221.65 ℃ at 2 MPa, respectively.

  8. Gauss decomposition for quantum groups and duality

    CERN Document Server

    Damaskinsky, E V; Lyakhovsky, V D; Sokolov, M A

    1995-01-01

    The Gauss decomposition of quantum groups and supergroups are considered. The main attention is paid to the R-matrix formulation of the Gauss decomposition and its properties as well as its relation to the contraction procedure. Duality aspects of the Gauss decomposition are also touched. For clarity of exposition a few simple examples are considered in some details.

  9. Kinetic energy decomposition scheme based on information theory.

    Science.gov (United States)

    Imamura, Yutaka; Suzuki, Jun; Nakai, Hiromi

    2013-12-15

    We proposed a novel kinetic energy decomposition analysis based on information theory. Since the Hirshfeld partitioning for electron densities can be formulated in terms of Kullback-Leibler information deficiency in information theory, a similar partitioning for kinetic energy densities was newly proposed. The numerical assessments confirm that the current kinetic energy decomposition scheme provides reasonable chemical pictures for ionic and covalent molecules, and can also estimate atomic energies using a correction with viral ratios.

  10. Groups possessing extensive hierarchical decompositions

    CERN Document Server

    Januszkiewicz, T; Leary, I J

    2009-01-01

    Kropholler's class of groups is the smallest class of groups which contains all finite groups and is closed under the following operator: whenever $G$ admits a finite-dimensional contractible $G$-CW-complex in which all stabilizer groups are in the class, then $G$ is itself in the class. Kropholler's class admits a hierarchical structure, i.e., a natural filtration indexed by the ordinals. For example, stage 0 of the hierarchy is the class of all finite groups, and stage 1 contains all groups of finite virtual cohomological dimension. We show that for each countable ordinal $\\alpha$, there is a countable group that is in Kropholler's class which does not appear until the $\\alpha+1$st stage of the hierarchy. Previously this was known only for $\\alpha= 0$, 1 and 2. The groups that we construct contain torsion. We also review the construction of a torsion-free group that lies in the third stage of the hierarchy.

  11. STUDY ON THERMAL DECOMPOSITION KINETICS OF URUSHIOL METAL CHELATE POLYMERS

    Institute of Scientific and Technical Information of China (English)

    HU Binghuan; CHEN Riyao; LIN Jinhuo; CHEN Wending

    1994-01-01

    The thermal decomposition kinetics of urushiol-Cu, urushiol-Nd and urushiol-Ti chelate polymers has been studied by non-isothermal thermogravimetry. The results suggest that the thermal decomposition kinetics of three chelate polymers are all of first order. Their average activation energy values of the thermal decomposition calculated by Ozawa-(Ⅰ) method are 110.79,136.98 and 163.64 kJ mol-1respectively,which increase linearly with the metal valence of the metal chelate polymers

  12. The Thermal Decomposition Kinetics of Polysiloxane/Polymethylacrylate IPNs Materials

    Institute of Scientific and Technical Information of China (English)

    HUANG Zhixiong; XIE Wenfeng; CHENG Dongcai

    2006-01-01

    Polydimethylsiloxane/polymethylacrylate(PDMS/PMA) interpenetratrating polymer networks(IPNs) was fabricated by simultaneous synthesis and characterized by thermogravimetry (TG). The kinetics of the thermal decomposition of polysiloxane/polymethylacrylate IPNs in N2 and air was studied at different heating rates. It was observed that there were two decomposition peaks both in N2 and air, which showed that thermal decomposition process obeyed two-step pyrolysis mechanism and accorded with the two compositions of IPN. Kinetic parameters were determined during simultaneous integration of the Doyle equation and the IPN/s kinetics equation was one-order equation in N2 and Air. The decomposition activation energy in N2 and air were 147.405 kJ·monl-1 and 192.656 kJ·monl-1 respectively.

  13. Kinetics of the Exothermic Decomposition Reaction of s-Tripicryaminotrinitrobenzene

    Institute of Scientific and Technical Information of China (English)

    ZHAO Feng-qi; HU Rong-zu; GAO Hong-xu; LUO Yang; GAO Sheng-li; SONG Ji-rong; SHI Qi-zhen

    2007-01-01

    The kinetic parameters of the exothermic decomposition reaction of s-Tripicryaminotrinitrobenzene under linear temperature rise condition are studied by means of DSC. The results show that the empirical kinetic model function in difs-1, respectively. The critical temperature of thermal explosion of the compound is 267.36 ℃.

  14. Thermal Decomposition Kinetics of Ni(Ⅱ) Complex with Norfloxacin

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    The thermal decomposition of the [Ni(NFA)2(NO3)2]*2H2O (NFA=C16H18FN3O3, norfloxacin) and its kinetics were studied under the non-isothermal condition in nitrogen by TG-DTG and DTA methods. The intermediate and residue for each decomposition were identified from TG curve. The Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method were used to analyze the non-isothermal kinetic data. The possible reaction mechanisms were investigated by comparing the kinetic parameters. The kinetic equation for the third stage and the mathematical expressions for the kinetic compensation effects of the third stage were obtained.

  15. Solid-state decomposition kinetics of pentaerythritol tetranitrate

    Energy Technology Data Exchange (ETDEWEB)

    Pickard, J.M.

    1990-01-01

    Decomposition of pentaerythritol tetranitrate (PETN) was monitored at constant volume under variable pressures of NO{sub 2} using differential scanning calorimetry(DSC). Decomposition involved a slow initial reaction followed by an autocatalytic transition at longer times. The apparent induction time(time-to-maximum rate) for autocatalysis was found to be dependent upon sample mass and the initial pressure of NO{sub 2}. A global kinetic model consistent with observed product distributions and the free radical chain decomposition mechanisms proposed for simpler alkyl nitrates was found to yield calculated induction times in accord with experiment. 13 refs., 3 figs.

  16. Thermal stability and kinetic of decomposition of nitrated HTPB.

    Science.gov (United States)

    Wang, Qingfa; Wang, Li; Zhang, Xiangwen; Mi, Zhentao

    2009-12-30

    Nitrated HTPB (NHTPB) is a potential energetic binder to replace the conventional inert binder, HTPB, for the composite solid propellants and plastic bonded explosives (PBXs). The thermal stability of the NHTPB sample with 10% double bonds converted to dinitrate ester group (10% NHTPB) was evaluated by high-pressure differential scanning calorimeter (PDSC) measurement. The influences of pressure (0.1, 2.5 and 5.0 MPa) and the heating rate (4, 6, 8 and 10 degrees C min(-1)) on the DSC behavior of the 10% NHTPB sample were investigated. The decomposition temperature of this compound decreased with the increase of pressure, meanwhile, increased as the heating rate increasing. The thermal decomposition at 150-250 degrees C followed a first-order law. The kinetic parameters and thermodynamic parameters for the 10% NHTPB sample at 150-250 degrees C under ambient pressure were obtained from the DSC data by non-isothermal methods proposed by ASTM E698 and Flynn-Wall-Ozawa. The critical temperature for this compound was estimated at about 154 degrees C.

  17. Belousov-Zhabotinsky oscillatory reaction. Kinetics of malonic acid decomposition

    Directory of Open Access Journals (Sweden)

    LJILJANA KOLAR-ANIC

    2000-10-01

    Full Text Available The kinetics of the Belousov-Zhabotinsky (BZ oscillatory reaction was analyzed. With this aim, the time evolution of a reaction mixture composed of malonic acid, bromate, sulfuric acid and cerium(III was studied at 298 K. Pseudo-first order kinetics with respect to malonic acid as the species undergoing decomposition with a corresponding rate constant, k = 7.5×10-3 min-1, was found.

  18. First-principle based modeling of urea decomposition kinetics in aqueous solutions

    Science.gov (United States)

    Nicolle, André; Cagnina, Stefania; de Bruin, Theodorus

    2016-11-01

    This study aims at validating a multi-scale modeling methodology based on an implicit solvent model for urea thermal decomposition pathways in aqueous solutions. The influence of the number of cooperative water molecules on kinetics was highlighted. The obtained kinetic model is able to accurately reproduce urea decomposition in aqueous phase under a variety of experimental conditions from different research groups. The model also highlights the competition between HNCO desorption to gas phase and hydrolysis in aqueous phase, which may influence SCR depollution process operation.

  19. Kinetics of the decomposition reaction of phosphorite concentrate

    Directory of Open Access Journals (Sweden)

    Huang Run

    2014-01-01

    Full Text Available Apatite is the raw material, which is mainly used in phosphate fertilizer, and part are used in yellow phosphorus, red phosphorus, and phosphoric acid in the industry. With the decrease of the high grade phosphorite lump, the agglomeration process is necessary for the phosphorite concentrate after beneficiation process. The decomposition behavior and the phase transformation are of vital importance for the agglomeration process of phosphorite. In this study, the thermal kinetic analysis method was used to study the kinetics of the decomposition of phosphorite concentrate. The phosphorite concentrate was heated under various heating rate, and the phases in the sample heated were examined by the X-ray diffraction method. It was found that the main phases in the phosphorite are fluorapatiteCa5(PO43F, quartz SiO2,and dolomite CaMg(CO32.The endothermic DSC peak corresponding to the mass loss caused by the decomposition of dolomite covers from 600°C to 850°C. The activation energy of the decomposition of dolomite, which increases with the increase in the extent of conversion, is about 71.6~123.6kJ/mol. The mechanism equation for the decomposition of dolomite agrees with the Valensi equation and G-B equation.

  20. Decomposition kinetics of expanded austenite with high nitrogen contents

    DEFF Research Database (Denmark)

    Christiansen, Thomas; Somers, Marcel A. J.

    2006-01-01

    This paper addresses the decomposition kinetics of synthesized homogeneous expanded austenite formed by gaseous nitriding of stainless steel AISI 304L and AISI 316L with nitrogen contents up to 38 at.% nitrogen. Isochronal annealing experiments were carried out in both inert (N2) and reducing (H2......) atmospheres. Differential thermal analysis (DTA) and thermogravimetry were applied for identification of the decomposition reactions and X-ray diffraction analysis was applied for phase analysis. CrN precipitated upon annealing; the activation energies are 187 kJ/mol and 128 kJ/mol for AISI 316L and AISI 304L...

  1. Thermal Decomposition Kinetics of Abietic Acid in Static Air

    Institute of Scientific and Technical Information of China (English)

    NONG Weijian; CHEN Xiaopeng; WANG Linlin; LIANG Jiezhen; ZHONG Lingping; TONG Zhangfa

    2013-01-01

    The thermal decomposition of abietic acid in air was investigated under non-isothermal condition using thermograv,imetric analysis-differential thermal analysis (TGA-DTA) technique with heating rates of 5,10,15 and 25 K·min 1.The non-isothermal kinetic parameters were obtained via the analysis of the therrnogravimetric and differential thermogravimetric (TG-DTG) curves by using Flynn-Wall-Ozawa method and Kissinger method.The thermal decomposition mechanism of abietic acid was studied with four integral methods (Satava-Sesták,MacCallum-Tanner,ordinary integral and Agrawal).The results show that the thermal decomposition mechanism is nucleation and growth,and the mechanism function is Avrami-Erofeev equation with n equates 1/2.The activation energy and the pre-exponential factor are 64.04 kJ·mol-and 5.89×10 s-1,respectively.

  2. New mass loss kinetic model for thermal decomposition of biomass

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Based on non-isothermal experimental results for eight Chinese biomass species, a new kinetic model,named as the "pseudo bi-component separate-stage model (PBSM)", is developed in this note to describe the mass loss behavior of biomass thermal decomposition. This model gains an advantage over the commonly used "pseudo single-component overall model (PSOM)" and "pseudo multi-component overall model (PMOM)". By means of integral analysis it is indicated that the new model is suitable to describe the mass loss kinetics of wood and leaf samples under relatively low heating rates (e.g. 10°C/rin, used in this work).``

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

    Science.gov (United States)

    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.

  4. Sonolysis induced decomposition of metal carbonyls: kinetics and product characterization.

    Science.gov (United States)

    Mahajan, Devinder; Papish, Elizabeth T; Pandya, Kaumudi

    2004-09-01

    The decomposition kinetics of Fe(CO)5 and Mo(CO)6 induced by sonolysis in hexadecane solvent was studied as a function of temperature (303-343 K) under an inert atmosphere. The decomposition data, obtained over at least two half lives in most of the runs, yielded first-order rate constant (k) values with correlation co-efficient (R2) > 0.95. The products were characterized by various spectroscopic techniques. The transmission electron microscopy (TEM) yielded images from which the mean particle diameter (MPD) of approximately 10 nm for Fe and Mo2C). The one-step production of high-yield pyrophoric products demonstrated the applicability of sonolysis to effectively produce gram-quantity of zero-valent metals.

  5. Kinetics of the thermal decomposition of pine needles

    Directory of Open Access Journals (Sweden)

    Dhaundiyal Alok

    2015-12-01

    Full Text Available A kinetic study of the pyrolysis process of pine needles was examined using a thermogravimetric analyser. The weight loss was measured in nitrogen atmosphere at a purge flow rate of 100 ml/min. The samples were heated over a range of temperature of 19°C–600°C with a heating rate of 10°C/min. The results obtained from the thermal decomposition process indicate that there are three main stages: dehydration, active and passive pyrolysis. The kinetic parameters for the different samples, such as activation energy and pre-exponential factor, are obtained by the shrinking core model (reaction-controlled regime, the model-free, and the first-order model. Experimental results showed that the shrinking model is in good agreement and can be successfully used to understand degradation mechanism of loose biomass. The result obtained from the reaction-controlled regime represented actual values of kinetic parameters which are the same for the whole pyrolysis process; whereas the model-free method presented apparent values of kinetic parameters, as they are dependent on the unknown function ϕ(C, on the sum of the parameters of the physical processes, and on the chemical reactions that happen simultaneously during pyrolysis. Experimental results showed that values of kinetic constant from the first-order model and the SCM are in good agreement and can be successfully used to understand the behaviour of loose biomass (pine needles in the presence of inert atmosphere. Using TGA results, the simulating pyrolysis can be done, with the help of computer software, to achieve a comprehensive detail of the devolatilization process of different types of biomasses.

  6. A boundary matching micro/macro decomposition for kinetic equations

    CERN Document Server

    Lemou, Mohammed

    2010-01-01

    We introduce a new micro/macro decomposition of collisional kinetic equations which naturally incorporates the exact space boundary conditions. The idea is to write the distribution fonction $f$ in all its domain as the sum of a Maxwellian adapted to the boundary (which is not the usual Maxwellian associated with $f$) and a reminder kinetic part. This Maxwellian is defined such that its 'incoming' velocity moments coincide with the 'incoming' velocity moments of the distribution function. Important consequences of this strategy are the following. i) No artificial boundary condition is needed in the micro/macro models and the exact boundary condition on $f$ is naturally transposed to the macro part of the model. ii) It provides a new class of the so-called 'Asymptotic preserving' (AP) numerical schemes: such schemes are consistent with the original kinetic equation for all fixed positive value of the Knudsen number $\\eps$, and if $\\eps \\to 0 $ with fixed numerical parameters then these schemes degenerate into ...

  7. Decomposition Kinetics for Mass Loss and Heat Released for HMX

    Energy Technology Data Exchange (ETDEWEB)

    Weese, R K; Burnham, A K

    2004-07-27

    Nucleation-growth kinetic expressions are derived for thermal decomposition of HMX from a variety of types of data, including mass loss for isothermal and constant rate heating in an open pan, and heat flow for isothermal and constant rate heating in open and closed pans. Conditions are identified in which thermal runaway is small to nonexistent, which typically means temperatures less than 255 C and heating rates less than 1 C/min. Activation energies are typically in the 140 to 150 kJ/mol regime for open pan experiments and about 160 kJ/mol for sealed pan experiments. The reaction clearly displays more than one process, and most likely three processes, which are most clearly evident in open pan experiments. The reaction is accelerated for closed pan experiments, and one global reaction appears to fit the data well.

  8. Thermal Decomposition of 3-Bromopropene. A Theoretical Kinetic Investigation.

    Science.gov (United States)

    Tucceri, María E; Badenes, María P; Bracco, Larisa L B; Cobos, Carlos J

    2016-04-21

    A detailed kinetic study of the gas-phase thermal decomposition of 3-bromopropene over wide temperature and pressure ranges was performed. Quantum chemical calculations employing the density functional theory methods B3LYP, BMK, and M06-2X and the CBS-QB3 and G4 ab initio composite models provide the relevant part of the potential energy surfaces and the molecular properties of the species involved in the CH2═CH-CH2Br → CH2═C═CH2 + HBr (1) and CH2═CH-CH2Br → CH2═CH-CH2 + Br (2) reaction channels. Transition-state theory and unimolecular reaction rate theory calculations show that the simple bond fission reaction ( 2 ) is the predominant decomposition channel and that all reported experimental studies are very close to the high-pressure limit of this process. Over the 500-1400 K range a rate constant for the primary dissociation of k2,∞ = 4.8 × 10(14) exp(-55.0 kcal mol(-1)/RT) s(-1) is predicted at the G4 level. The calculated k1,∞ values lie between 50 to 260 times smaller. A value of 10.6 ± 1.5 kcal mol(-1) for the standard enthalpy of formation of 3-bromopropene at 298 K was estimated from G4 thermochemical calculations.

  9. Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate Monohydrate

    Institute of Scientific and Technical Information of China (English)

    WU,Jian; YUAN,Ai-Qun; HUANG,Zai-Yin; TONG,Zhang-Fa; CHEN,Jie; LIANG,Rong-Lan

    2007-01-01

    Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is (28.795±0.182) kJ/mol (298.15 K), and the standard molar enthalpy of formation of the title complex is (-2185.43±13.80)kJ/mol (298.15 K). Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction: an nth-order reaction (Fn) with n=4.28, E1=147.35 kJ/mol, A1=3.63×1013 s-1 is followed by a second-order reaction (F2) with E2=212.71 kJ/mol, A2= 1.82×1018 s-1.

  10. Apparent kinetics of high temperature oxidative decomposition of microalgal biomass.

    Science.gov (United States)

    Ali, Saad Aldin M; Razzak, Shaikh A; Hossain, Mohammad M

    2015-01-01

    The oxidative thermal characteristics of two microalgae species biomass Nannochloropsis oculta and Chlorella vulgaris have been investigated. The apparent kinetic parameters for the microalgal biomass oxidation process are estimated by fitting the experimental data to the nth order rate model. Also, the iso-conversional methods Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) were used to evaluate the apparent activation energy. The results indicate that biomass of different microalgae strains exhibit different thermal behavior and characteristics. In addition, growth parameters and medium composition can affect the biomass productivity and composition. This would have significant impact on the thermal decomposition trend of the biomass. The kinetic modeling of the oxidation reaction with direct model fitting method shows good prediction to the experimental data. The apparent activation energies estimated by KAS and FWO methods for N. oculta were 149.2 and 151.8kJ/mol, respectively, while for C. vulgaris were 214.4 and 213.4kJ/mol, respectively.

  11. Mechanism and Kinetic Parameters of Thermal Decomposition of Cobalt Dichloride Hexahydrate

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The thermal decomposition of the cobalt dichloride hexahydrate and its kinetics were studied by TG and DTG technique under the non-isothermal condition with nitrogen atnosphere.The non-isothermal kinetic data and kinetic parameters were evaluated by means of integral and differential methods.The most probable mechanism functions of the thermal decomposition reaction for the first stage are:f(α)=(1-α)2 and g(α)=(1-α)-1-1.

  12. Empirical and physics based mathematical models of uranium hydride decomposition kinetics with quantified uncertainties.

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher N.; Gharagozloo, Patricia E.

    2013-10-01

    Metal particle beds have recently become a major technique for hydrogen storage. In order to extract hydrogen from such beds, it is crucial to understand the decomposition kinetics of the metal hydride. We are interested in obtaining a a better understanding of the uranium hydride (UH3) decomposition kinetics. We first developed an empirical model by fitting data compiled from different experimental studies in the literature and quantified the uncertainty resulting from the scattered data. We found that the decomposition time range predicted by the obtained kinetics was in a good agreement with published experimental results. Secondly, we developed a physics based mathematical model to simulate the rate of hydrogen diffusion in a hydride particle during the decomposition. We used this model to simulate the decomposition of the particles for temperatures ranging from 300K to 1000K while propagating parametric uncertainty and evaluated the kinetics from the results. We compared the kinetics parameters derived from the empirical and physics based models and found that the uncertainty in the kinetics predicted by the physics based model covers the scattered experimental data. Finally, we used the physics-based kinetics parameters to simulate the effects of boundary resistances and powder morphological changes during decomposition in a continuum level model. We found that the species change within the bed occurring during the decomposition accelerates the hydrogen flow by increasing the bed permeability, while the pressure buildup and the thermal barrier forming at the wall significantly impede the hydrogen extraction.

  13. Conservation Rules of Direct Sum Decomposition of Groups

    Directory of Open Access Journals (Sweden)

    Nakasho Kazuhisa

    2016-03-01

    Full Text Available In this article, conservation rules of the direct sum decomposition of groups are mainly discussed. In the first section, we prepare miscellaneous definitions and theorems for further formalization in Mizar [5]. In the next three sections, we formalized the fact that the property of direct sum decomposition is preserved against the substitutions of the subscript set, flattening of direct sum, and layering of direct sum, respectively. We referred to [14], [13] [6] and [11] in the formalization.

  14. Kinetics of decomposition of undercooled austenite formed in the critical range of temperatures

    Science.gov (United States)

    Shveikin, V. P.; Khotinov, V. A.; Farber, V. M.

    2007-11-01

    Using dilatometric and microstructural methods, the thermokinetic diagrams of decomposition of undercooled austenite formed upon heating in the intercritical temperature range have been constructed for a group of steels with 0.05 0.10% C, 0.15 1.63% Mn, 0.17 1.18% Si, and 0.003% B. The effect of the compositions of the steels, temperature of heating in the two-phase region, and rate of subsequent cooling on the kinetics of the formation of austenite and products of its decomposition has been considered. The carbon content in austenite at different temperatures of its formation has been estimated from the position of the temperature of the onset of the martensitic transformation.

  15. Kinetic analysis of overlapping multistep thermal decomposition comprising exothermic and endothermic processes: thermolysis of ammonium dinitramide.

    Science.gov (United States)

    Muravyev, Nikita V; Koga, Nobuyoshi; Meerov, Dmitry B; Pivkina, Alla N

    2017-01-25

    This study focused on kinetic modeling of a specific type of multistep heterogeneous reaction comprising exothermic and endothermic reaction steps, as exemplified by the practical kinetic analysis of the experimental kinetic curves for the thermal decomposition of molten ammonium dinitramide (ADN). It is known that the thermal decomposition of ADN occurs as a consecutive two step mass-loss process comprising the decomposition of ADN and subsequent evaporation/decomposition of in situ generated ammonium nitrate. These reaction steps provide exothermic and endothermic contributions, respectively, to the overall thermal effect. The overall reaction process was deconvoluted into two reaction steps using simultaneously recorded thermogravimetry and differential scanning calorimetry (TG-DSC) curves by considering the different physical meanings of the kinetic data derived from TG and DSC by P value analysis. The kinetic data thus separated into exothermic and endothermic reaction steps were kinetically characterized using kinetic computation methods including isoconversional method, combined kinetic analysis, and master plot method. The overall kinetic behavior was reproduced as the sum of the kinetic equations for each reaction step considering the contributions to the rate data derived from TG and DSC. During reproduction of the kinetic behavior, the kinetic parameters and contributions of each reaction step were optimized using kinetic deconvolution analysis. As a result, the thermal decomposition of ADN was successfully modeled as partially overlapping exothermic and endothermic reaction steps. The logic of the kinetic modeling was critically examined, and the practical usefulness of phenomenological modeling for the thermal decomposition of ADN was illustrated to demonstrate the validity of the methodology and its applicability to similar complex reaction processes.

  16. Kinetics of Platinum-Catalyzed Decomposition of Hydrogen Peroxide

    Science.gov (United States)

    Vetter, Tiffany A.; Colombo, D. Philip, Jr.

    2003-07-01

    CIBA Vision Corporation markets a contact lens cleaning system that consists of an AOSEPT disinfectant solution and an AOSEPT lens cup. The disinfectant is a buffered 3.0% m/v hydrogen peroxide solution and the cup includes a platinum-coated AOSEPT disc. The hydrogen peroxide disinfects by killing bacteria, fungi, and viruses found on the contact lenses. Because the concentration of hydrogen peroxide needed to disinfect is irritating to eyes, the hydrogen peroxide needs to be neutralized, or decomposed, before the contact lenses can be used again. A general chemistry experiment is described where the kinetics of the catalyzed decomposition of the hydrogen peroxide are studied by measuring the amount of oxygen generated as a function of time. The order of the reaction with respect to the hydrogen peroxide, the rate constant, and the energy of activation are determined. The integrated rate law is used to determine the time required to decompose the hydrogen peroxide to a concentration that is safe for eyes.

  17. Thermal decomposition kinetics of sorghum straw via thermogravimetric analysis.

    Science.gov (United States)

    Dhyani, Vaibhav; Kumar, Jitendra; Bhaskar, Thallada

    2017-09-01

    The thermal decomposition of sorghum straw was investigated by non-isothermal thermogravimetric analysis, where the determination of kinetic triplet (activation energy, pre-exponential factor, and reaction model), was the key objective. The activation energy was determined using different isoconversional methods: Friedman, Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Starink, Iterative method of Chai & Chen, Vyazovkin AIC method, and Li & Tang equation. The pre-exponential factor was calculated using Kissinger's equation; while the reaction model was predicted by comparison of z-master plot obtained from experimental values with the theoretical plots. The values of activation energy obtained from isoconversional methods were further used for evaluation of thermodynamic parameters, enthalpy, entropy and Gibbs free energy. Results showed three zones of pyrolysis having average activation energy values of 151.21kJ/mol, 116.15kJ/mol, and 136.65kJ/mol respectively. The data was well fitting with two-dimension 'Valensi' model for conversion values from 0 to 0.4 with a coefficient of determination (R(2)) value of 0.988, and with third order reaction model for values from 0.4 to 0.9 with an R(2) value of 0.843. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Thermal Decomposition Kinetics of Lead 2,4,6-Trinitroresorcinate Monohydrate

    Institute of Scientific and Technical Information of China (English)

    HU Rong-zu; YAO Pu; LI Jing; CHEN San-ping; GAO Sheng-li; ZHAO Feng-qi; SONG Ji-rong; SHI Qi-zhen; CHEN Pei; LUO Yang; ZHAO Hong-an

    2004-01-01

    The non-isothermal decomposition of lead 2,4,6-trinitroresorcinate monohydrate, Pb (TNR) · H2O. was investigated by means of TG-DTA, DSC and IR. The thermal decomposition mechanism and the dissociated kinetics were also investigated. The kinetic parameters were obtained from the analysis of the DSC curves by integral and differential methods. The most probable kinetic model function of the dehydration reaction of Pb(TNR) · H2O was suggested by the comparison of the kinetic parameters.

  19. NMR analysis, protonation equilibria and decomposition kinetics of tolperisone.

    Science.gov (United States)

    Orgován, Gábor; Tihanyi, Károly; Noszál, Béla

    2009-12-05

    The rate constants of spontaneous and hydroxide-catalyzed decomposition and the tautomer-specific protonation constants of tolperisone, a classical muscle relaxant were determined. A solution NMR method without any separation techniques was elaborated to quantitate the progress of decomposition. All the rate and equilibrium constants were determined at four different temperatures and the activation parameters were calculated. The molecular mechanism of decomposition is proposed.

  20. Equivalent Expressions of Direct Sum Decomposition of Groups1

    Directory of Open Access Journals (Sweden)

    Nakasho Kazuhisa

    2015-03-01

    Full Text Available In this article, the equivalent expressions of the direct sum decomposition of groups are mainly discussed. In the first section, we formalize the fact that the internal direct sum decomposition can be defined as normal subgroups and some of their properties. In the second section, we formalize an equivalent form of internal direct sum of commutative groups. In the last section, we formalize that the external direct sum leads an internal direct sum. We referred to [19], [18] [8] and [14] in the formalization.

  1. Kinetic study of rigid polyurethane foams thermal decomposition by artificial neural network

    OpenAIRE

    Ferreira, Bárbara D. L.; Silva, Virgínia R.; Yoshida, Maria Irene; Sebastião,Rita C. O.

    2016-01-01

    Kinetic models of solid thermal decomposition are traditionally used for individual fit of isothermal decomposition experimental data. However, this methodology can provide unacceptable errors in some cases. To solve this problem, a neural network (MLP) was developed and adopted in this work. The implemented algorithm uses the rate constants as predetermined weights between the input and intermediate layer and kinetic models as activation functions of neurons in the hidden layer. The contribu...

  2. Decomposition studies of group 6 hexacarbonyl complexes. Pt. 2. Modelling of the decomposition process

    Energy Technology Data Exchange (ETDEWEB)

    Usoltsev, Ilya; Eichler, Robert; Tuerler, Andreas [Paul Scherrer Institut (PSI), Villigen (Switzerland); Bern Univ. (Switzerland)

    2016-11-01

    The decomposition behavior of group 6 metal hexacarbonyl complexes (M(CO){sub 6}) in a tubular flow reactor is simulated. A microscopic Monte-Carlo based model is presented for assessing the first bond dissociation enthalpy of M(CO){sub 6} complexes. The suggested approach superimposes a microscopic model of gas adsorption chromatography with a first-order heterogeneous decomposition model. The experimental data on the decomposition of Mo(CO){sub 6} and W(CO){sub 6} are successfully simulated by introducing available thermodynamic data. Thermodynamic data predicted by relativistic density functional theory is used in our model to deduce the most probable experimental behavior of the corresponding Sg carbonyl complex. Thus, the design of a chemical experiment with Sg(CO){sub 6} is suggested, which is sensitive to benchmark our theoretical understanding of the bond stability in carbonyl compounds of the heaviest elements.

  3. A High Temperature Kinetic Study for the Thermal Unimolecular Decomposition of Diethyl Carbonate

    KAUST Repository

    AlAbbad, Mohammad

    2017-07-08

    Thermal unimolecular decomposition of diethyl carbonate (DEC) was investigated in a shock tube by measuring ethylene concentration with a CO2 gas laser over 900 - 1200 K and 1.2 – 2.8 bar. Rate coefficients were extracted using a simple kinetic scheme comprising of thermal decomposition of DEC as initial step followed by rapid thermal decomposition of the intermediate ethyl-hydrogen-carbonate. Our results were further analysed using ab initio and master equation calculations to obtain pressure- and temperature- dependence of rate coefficients. Similar to alkyl esters, unimolecular decomposition of DEC is found to undergo six-center retro-ene elimination of ethylene in a concerted manner.

  4. A high temperature kinetic study for the thermal unimolecular decomposition of diethyl carbonate

    Science.gov (United States)

    AlAbbad, Mohammed; Giri, Binod Raj; Szőri, Milan; Viskolcz, Béla; Farooq, Aamir

    2017-09-01

    Thermal unimolecular decomposition of diethyl carbonate (DEC) was investigated in a shock tube by measuring ethylene concentration with a CO2 gas laser over 900-1200 K and 1.2-2.8 bar. Rate coefficients were extracted using a simple kinetic scheme comprising of thermal decomposition of DEC as initial step followed by rapid thermal decomposition of the intermediate ethyl hydrogen carbonate. Our results were further analysed using ab initio and master equation calculations to obtain pressure- and temperature-dependence of rate coefficients. Similar to alkyl esters, unimolecular decomposition of DEC is found to undergo six-center retro-ene elimination of ethylene in a concerted manner.

  5. Pressure Dependent Decomposition Kinetics of the Energetic Material HMX up to 3.6 GPa

    Energy Technology Data Exchange (ETDEWEB)

    Glascoe, E A; Zaug, J M; Burnham, A K

    2009-05-29

    The effect of pressure on the thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low to moderate pressures (i.e. between ambient pressure and 1 GPa) and decelerates the decomposition at higher pressures. The decomposition acceleration is attributed to pressure enhanced autocatalysis whereas the deceleration at high pressures is attributed pressure inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both {beta} and {delta} phase HMX are sensitive to pressure in the thermally induced decomposition kinetics.

  6. Kinetics of the Thermal Decomposition of Magnesium Salicylate Powder in Air

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Simultaneous thermogravimetry-differential thermal analysis (TG-DTA) was used to study the kinetics and the degradation of magnesium salicylate(C14H10MgO6) in air. The results show that the decomposition proceeds through two steps. The kinetics of the first decomposition step was studied. The activation energies were calculated by using the Friedman and Flynn Wall Ozawa (FWO) methods, and the most probable kinetic model function was estimated using the multiple linear regression method. The values of the correlated kinetic parameters for the first decomposition step are E= 152.97 kJ/mol, lg(A/S-1) = 10. 78, f(α) = (1 -α)n(1 + Kcatα) , n =0.691, and Kcat =1.3048.

  7. Kinetic study of rigid polyurethane foams thermal decomposition by artificial neural network

    CERN Document Server

    Ferreira, Bárbara D L; Yoshida, Maria Irene; Sebastião, Rita C O

    2016-01-01

    Kinetic models of solid thermal decomposition are traditionally used for individual fit of isothermal decomposition experimental data. However, this methodology can provide unacceptable errors in some cases. To solve this problem, a neural network (MLP) was developed and adopted in this work. The implemented algorithm uses the rate constants as predetermined weights between the input and intermediate layer and kinetic models as activation functions of neurons in the hidden layer. The contribution of each model in the overall fit of the experimental data is calculated as the weights between the intermediate and output layer. In this way, the phenomenon is better described as a sum of kinetic processes. Two rigid polyurethane foam samples: loaded with Al2O3 and no inorganic filler were used in this work. The R3 model described the thermal decomposition kinetic process for all temperatures for both foams with smaller residual error. However, the network residual errors are on average 102 times lower compared to ...

  8. Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Hongyan, E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L., E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil [Propellants Branch, Rocket Propulsion Division, Aerospace Systems Directorate, Air Force Research Laboratory, AFRL/RQRP, 10 E. Saturn Blvd., Edwards AFB, California 93524 (United States)

    2015-05-28

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH{sub 2} group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C{sub 2v} symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which

  9. An algebraic Birkhoff decomposition for the continuous renormalization group

    CERN Document Server

    Girelli, F; Martinetti, P

    2004-01-01

    This paper aims at presenting the first steps towards a formulation of the Exact Renormalization Group Equation in the Hopf algebra setting of Connes and Kreimer. It mostly deals with some algebraic preliminaries allowing to formulate perturbative renormalization within the theory of differential equations. The relation between renormalization, formulated as a change of boundary condition for a differential equation, and an algebraic Birkhoff decomposition for rooted trees is explicited.

  10. Definition and Properties of Direct Sum Decomposition of Groups1

    Directory of Open Access Journals (Sweden)

    Nakasho Kazuhisa

    2015-03-01

    Full Text Available In this article, direct sum decomposition of group is mainly discussed. In the second section, support of element of direct product group is defined and its properties are formalized. It is formalized here that an element of direct product group belongs to its direct sum if and only if support of the element is finite. In the third section, product map and sum map are prepared. In the fourth section, internal and external direct sum are defined. In the last section, an equivalent form of internal direct sum is proved. We referred to [23], [22], [8] and [18] in the formalization.

  11. The kinetics and mechanism of induced thermal decomposition of peroxomonosulphate by phase transfer catalysts

    Indian Academy of Sciences (India)

    T Balakrishnan; S Damodar Kumar

    2000-08-01

    The kinetics of induced decomposition of potassium peroxomonosulphate (PMS) by the phase transfer catalysts (PTC), viz. tetrabutylammonium chloride [TBAC] and tetrabutylphosphonium chloride [TBPC] have been investigated. The effect of [PMS], [PTC], ionic strength of the medium and temperature on the rate of decomposition of PMS was studied. The rate of decomposition of PMS was monitored under pseudo-first-order condition at a constant temperature (50 ± 0 1°C). The rate of decomposition was first order with respect to PMS for TBAC and half order for TBPC. The order with respect of PTC was found to be unity for TBAC and half order for TBPC. A suitable kinetic scheme has been proposed to account for the experimental data and its significance is discussed.

  12. A kinetic study of non-isothermal decomposition process of anhydrous nickel nitrate under air atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Jankovic, B., E-mail: bojanjan@ffh.bg.ac.r [Faculty of Physical Chemistry, University of Belgrade, Studentski Trg 12-16, P. O. Box 137, 11001 Belgrade (Serbia); Mentus, S. [Faculty of Physical Chemistry, University of Belgrade, Studentski Trg 12-16, P. O. Box 137, 11001 Belgrade (Serbia); Jelic, D. [Faculty of Medicine, University of Banja Luka, 78000 Banja Luka (Bosnia and Herzegowina)

    2009-08-01

    The non-isothermal decomposition process of anhydrous nickel nitrate under air atmosphere was investigated. The kinetic analysis of decomposition process was performed using Friedman (FR), Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) isoconversional methods. The kinetic model was determined by the Malek's method. The composite differential method I was used for checking the established reaction model. It was found that the value of E{sub a} calculated by composite differential method (E{sub a}=147.1 kJ mol{sup -1}) represents the medium value between the values of the apparent activation energy calculated by FR (E{sub a,FR}=152.8 kJ mol{sup -1}) and FWO (E{sub a,FWO}=143.1 kJ mol{sup -1}) methods. Using two special functions (y(alpha) and z(alpha)), it was found that the two-parameter autocatalytic model (Sestak-Berggren (SB) kinetic model) with kinetic exponents M=0.23 and N=1.14 is the most adequate one to describe the decomposition kinetics of the studied system at various heating rates. The obtained non-isothermal differential conversion curves from the experimental data show the results being accordant with those theoretically calculated. It was concluded that the SB kinetic model can be used for a quantitative description of non-isothermal decomposition process of anhydrous nickel nitrate which involves the partially overlapping nucleation and growth phases.

  13. Methods for calculating the kinetic parameters of carbonate decomposition from thermal analysis data

    Science.gov (United States)

    Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.; Godunov, E. B.; Kramer, S. M.; Terekhova, M. V.

    2016-07-01

    A procedure is proposed for an analysis of the data on the decomposition of inorganic carbonates (MgCO3, CaCO3, SrCO3, MnCO3, CoCO3) on the basis of results of thermogravimetric studies. The activation energy and the rate constant for carbonate decomposition are calculated taking into account the main points of the heterogeneous reaction kinetics. A comparative analysis of the obtained results is performed.

  14. Kinetic Study and Thermal Decomposition Behavior of Lignite Coal

    Directory of Open Access Journals (Sweden)

    Mehran Heydari

    2015-01-01

    Full Text Available A thermogravimetric analyzer was employed to investigate the thermal behavior and extract the kinetic parameters of Canadian lignite coal. The pyrolysis experiments were conducted in temperatures ranging from 298 K to 1173 K under inert atmosphere utilizing six different heating rates of 1, 6, 9, 12, 15, and 18 K min−1, respectively. There are different techniques for analyzing the kinetics of solid-state reactions that can generally be classified into two categories: model-fitting and model-free methods. Historically, model-fitting methods are broadly used in solid-state kinetics and show an excellent fit to the experimental data but produce uncertain kinetic parameters especially for nonisothermal conditions. In this work, different model-free techniques such as the Kissinger method and the isoconversional methods of Ozawa, Kissinger-Akahira-Sunose, and Friedman are employed and compared in order to analyze nonisothermal kinetic data and investigate thermal behavior of a lignite coal. Experimental results showed that the activation energy values obtained by the isoconversional methods were in good agreement, but Friedman method was considered to be the best among the model-free methods to evaluate kinetic parameters for solid-state reactions. These results can provide useful information to predict kinetic model of coal pyrolysis and optimization of the process conditions.

  15. The influence of temperature on the decomposition kinetics of peracetic acid in solutions

    Directory of Open Access Journals (Sweden)

    L. Kunigk

    2001-06-01

    Full Text Available Peracetic acid is a powerful sanitizer that has only recently been introduced in the Brazilian food industry. The main disadvantage of this sanitizer is its decomposition rate. The main purpose of this paper is to present results obtained in experiments carried out to study the decomposition kinetics of peracetic acid in aqueous solutions at 25, 35, 40 and 45 °C. The decompositon of peracetic acid is a first-order reaction. The decomposition rate constants are between 1.71x10-3 h -1 for 25 °C and 9.64x10-3 h-1 for 45 °C. The decomposition rate constant is affected by temperature according to the Arrhenius equation, and the activation energy for the decomposition of peracetic acid in aqueous solutions prepared from the commercial formulation used in this work is 66.20 kJ/mol.

  16. The influence of temperature on the decomposition kinetics of peracetic acid in solutions

    OpenAIRE

    Kunigk L.; Gomes D.R.; Forte F.; Vidal K.P.; Gomes L.F.; Sousa P.F.

    2001-01-01

    Peracetic acid is a powerful sanitizer that has only recently been introduced in the Brazilian food industry. The main disadvantage of this sanitizer is its decomposition rate. The main purpose of this paper is to present results obtained in experiments carried out to study the decomposition kinetics of peracetic acid in aqueous solutions at 25, 35, 40 and 45 °C. The decompositon of peracetic acid is a first-order reaction. The decomposition rate constants are between 1.71x10-3 h -1 for 25 °C...

  17. Thermal decomposition kinetics of titanium hydride and Al alloy melt foaming process

    Institute of Scientific and Technical Information of China (English)

    YANG; Donghui; HE; Deping; YANG; Shangrun

    2004-01-01

    A temperature programmed decomposition (TPD) apparatus with metal tube structure, in which Ar is used as the carrier gas, is established and the TPD spectrum of titanium hydride is acquired. Using consulting table method (CTM), spectrum superposition method (SSM) and differential spectrum technique, TPD spectrum of titanium hydride is separated and a set of thermal decomposition kinetics equations are acquired. According to these equations, the relationship between decomposition quantity and time for titanium hydride at the temperature of 940 K is obtained and the result well coincides with the Al alloy melt foaming process.

  18. Isothermal decomposition kinetics in the Cu-9%Al-4%Ag alloy

    Energy Technology Data Exchange (ETDEWEB)

    Adorno, A.T.; Silva, R.A.G

    2004-07-28

    The influence of 4 wt.%Ag addition on the isothermal decomposition kinetics of the {beta}' phase in the Cu-9 wt.%Al alloy was studied by microhardness measurements, optical and scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, and X-ray diffractometry. The results showed that the presence of Ag decreases the {beta}'{yields}({alpha}+{gamma}{sub 1}) decomposition reaction rate in the Cu-9%Al-4%Ag alloy, an effect that may be associated to the {gamma}{sub 1} phase which catalyses the Ag precipitation, making it faster than the decomposition reaction, and thus, stabilizing the martensitic phase.

  19. Thermal Characterization and Decomposition Kinetics of Free Anthraquinones from Rhubarb

    Institute of Scientific and Technical Information of China (English)

    Li Ming ZHANG; Xia LI; Yu Jie DAI

    2006-01-01

    The thermal behaviour of aloe-emodin, chrysophanol and physcion and their kinetics have been investigated under non-isothermal conditions by means of differential thermal analysis (DTA) and thermogravimetry (TG). The thermal characteristics have been determined using the DTA and TG-DTG curves. The non-isothermal kinetic data were analyzed by means of the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method. The possible reaction mechanisms have been investigated by comparing the kinetic parameters. The kinetic equation for aloe-emodin, chrysophanol and physcion can be expressed as dα/dt=Aexp(-E/RT)1/3(1-α)[-In(1-α)]-2. The activation energy E (kJ mol-1) of the three free anthraquinones are 78.09, 89.54,and 107.5 and their lnA/s-1 are 22.98, 36.85 and 43.60, respectively.

  20. KINETIC ANALYSIS OF THE CATALYTIC DECOMPOSITION OF HYDRAZINE

    Directory of Open Access Journals (Sweden)

    J.E. de MEDEIROS

    1998-06-01

    Full Text Available The bond-order conservation method was used to study the catalytic decomposition of N2H4. Variation in the activation energy, E, of the most relevant steps was calculated as a function of the enthalpy of adsorption of N, QN, between 0 and 1250 kJmol-1. Results suggest that below QN = 520 kJmol-1 the catalytic decomposition of N2H4 produces mostly N2 and H2. Above QN = 520 kJmol-1, NH3 and N2 are the main products. Near QN = 520 kJmol-1 N2, H2 and NH3 are obtained, in agreement with experimental results on different metals.

  1. Influence of vermicomposting on solid wastes decomposition kinetics in soils

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The effect of vermicomposting on kinetic behavior of the products is not well recognized. An incubation study was conducted to investigate C mineralization kinetics of cow manure, sugarcane filter cake and their vermicomposts. Two different soils were treated with the four solid wastes at a rate of 0.5 g solid waste C per kg soil with three replications. Soils were incubated for 56 d. The CO2-C respired was monitored periodically and a first-order kinetic model was used to calculate the kinetic parameters of C mineralization. Results indicated that the percentage of C mineralized during the incubation period ranged from 31.9% to 41.8% and 55.9% to 73.4% in the calcareous and acidic soils, respectively. The potentially mineralizable C (C0) of the treated soils was lower in the solid waste composts compared to their starting materials. Overall, it can be concluded that decomposable fraction of solid wastes has decreased due to vermicomposting.

  2. Application of vacuum stability test to determine thermal decomposition kinetics of nitramines bonded by polyurethane matrix

    Science.gov (United States)

    Elbeih, Ahmed; Abd-Elghany, Mohamed; Elshenawy, Tamer

    2017-03-01

    Vacuum stability test (VST) is mainly used to study compatibility and stability of energetic materials. In this work, VST has been investigated to study thermal decomposition kinetics of four cyclic nitramines, 1,3,5-trinitro-1,3,5-triazinane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ε-HNIW, CL-20), bonded by polyurethane matrix based on hydroxyl terminated polybutadiene (HTPB). Model fitting and model free (isoconversional) methods have been applied to determine the decomposition kinetics from VST results. For comparison, the decomposition kinetics were determined isothermally by ignition delay technique and non-isothermally by Advanced Kinetics and Technology Solution (AKTS) software. The activation energies for thermolysis obtained by isoconversional method based on VST technique of RDX/HTPB, HMX/HTPB, BCHMX/HTPB and CL20/HTPB were 157.1, 203.1, 190.0 and 176.8 kJ mol-1 respectively. Model fitting method proved that the mechanism of thermal decomposition of BCHMX/HTPB is controlled by the nucleation model while all the other studied PBXs are controlled by the diffusion models. A linear relationship between the ignition temperatures and the activation energies was observed. BCHMX/HTPB is interesting new PBX in the research stage.

  3. Structural effects and thermal decomposition kinetics of chalcones under non-isothermal conditions

    Directory of Open Access Journals (Sweden)

    G. Manikandan

    2016-09-01

    Full Text Available Two chalcones namely, 1,5-bis(4-hydroxy-3-methoxyphenylpentan-1,4-dien-3-one (BHMPD and 2,5-bis(4-hydroxy-3-methoxybenzylidenecyclopentanone (BHMBC have been synthesised and characterized by microanalysis, FT-IR, mass spectra and NMR (1H and 13C techniques. The thermal decomposition of these compounds was studied by TGA and DTA under dynamic nitrogen atmosphere at different heating rates of 10, 15 and 20 K min−1. The kinetic parameters were calculated using model-fitting (Coats–Redfern, CR and model-free methods (Friedman, Kissinger–Akahira–Sunose, KAS and Flynn–Wall–Ozawa, FWO. The decomposition process of BHMPD and BHMBC followed a single step mechanism as evidenced from the data. Existence of compensation effect was noticed for the decomposition of these compounds. Invariant kinetic parameters are consistent with the average values obtained by Friedman and KAS isoconversional method in both compounds.

  4. Thermal Decomposition and Dehydration Kinetics of Tetra(piperidinium)Octamolybdate Tetrahydrate in Air

    Institute of Scientific and Technical Information of China (English)

    KU Zong-Jun; ZHANG Zhong-Hai; ZHANG Zhi-Guo; WANG Li-Na; ZHANG Ke-Li

    2008-01-01

    Thermal decomposition of tetra(piperidinium)octamolybdate tetrahydrate,[CsH10NH2]4[Mo8O26]·4H2O,was investigated in air by means of TG-DTG/DTA.DSC,TG-IR and SEM.TG-DTG/DTA curves showed that the decomposition proceeded through three well-defined steps with DTA peaks closely corresponding to mass loss obtained.Kinetics analysis of its dehydration step Was performed under non-isothermal conditions.The dehydrationactivation energy was calculated through Friedman and Flynn-Wall-Ozawa(FWO)methods,and the best-fit dehydration kinetic model function was estimated through the multiple linear regression method.The activation energy for the dehydration step of[C5H10NH2]4[MosO26]·4H2O was 139.7 kJ/mol.The solid particles became smaller accompanied by the thermal decomposition of the title compound.

  5. Kinetics of thermal decomposition of CeO2 nanocrystalline precursor prepared by precipitation method

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The thermal decomposition of CeO2 nanocrystalline precursor prepared by chemical precipitation method was investigated using thermo-gravimetric/differential scanning calorimetry (TG/DSC) and X-ray powder diffraction (XRD).In particular,the differential thermal analysis curves for the decomposition of CeO2 nanocrystalline precursor were measured at different heating rates in air by a thermal analyzer (NETZSCH STA 449C,Germany).The kinetic parameters of the thermal decomposition of CeO2 nanocrystalline precursor were calculated using the Kissinger method and the Coats-Redfern method.Results show that the apparent active energy E of the reaction is 105.51 kJ/mol,the frequency factor lnA is 3.602 and the reaction order n is 2.This thermal decomposition process can be described by the anti-Jander equation and a threedimensional diffusion mechanism.

  6. Kinetics of radiolytic decomposition of tri-n-butylphosphate

    Energy Technology Data Exchange (ETDEWEB)

    Vladimirova, M.V.; Kulikov, I.A.

    1986-09-01

    This paper studies the kinetics of the formation of the products of radiolysis of tri-n-butylphosphate (TBP). From a comparison of the calculations presented and experimental data previously obtained it follows that the accepted mechanisms of radiolysis of TBP and the kinetic scheme are satisfactorily described by the experimental data on the variation of TBP and DBPA with D = 10/sup 3/-10/sup 6/ Gy, but they do not satisfactorily described the data on the variation of MBPA and H/sub 3/PO/sub 4/. For D = 10/sup 3/-10/sup 6/ Gy, the instantaneous values of TBP and DBPA for fixed absorbed dose, irradiation dose rate, and time can be calculated using the formulas presented in this work.

  7. The Kinetics of Formation and Decomposition of Austenite in Relation to Carbide Morphology

    Science.gov (United States)

    Alvarenga, Henrique Duarte; Van Steenberge, Nele; Sietsma, Jilt; Terryn, Herman

    2017-02-01

    The effect of the carbide morphology on the kinetics of austenite formation and its decomposition was investigated by a combination of measurements of austenite fraction by dilatometry and metallography. These measurements show that coarse carbide morphology is generated by fast cooling through the early stages of eutectoid transformation, enabling fast precipitation of pro-eutectoid ferrite, followed by slow cooling during the final stages of transformation, during the precipitation of carbides. Additionally, a strong influence of the morphology of carbides on the kinetics of austenite formation is observed. The presence of coarse carbides can determine the rate of austenite formation during intercritical annealing as a result of its slow dissolution kinetics.

  8. The Refinement of The Preliminary Genetic Decomposition of Group

    Science.gov (United States)

    Wijayanti, K.

    2017-04-01

    Mathematics proof is one of the characteristics of advanced mathematics thinking, and proof plays an important role in learning the abstract algebra included group theory. The depth and complexity of individual’s understanding of a concept depend on his/her ability to establish connections among the mental structure that constitute it. One of the cognitive styles is field dependent/independent. Field independent (FI) and field dependent (FD) learners have different characteristics. Our research question is (1)How is the proposed refinement of preliminary genetic decomposition of group that is designed with a preliminary study of the learning with APOS works; (2) What understanding about group that is generated by student (Field Independent, Field Neutral, and Field Dependent) when learning through designed material. This study was a descriptive qualitative. The participants of this study were nine (9) undergraduate students who were taking Introduction of Algebraic Structure 1, which included group, in the even semester of academic year 2015/2016 at Universitas Negeri Semarang. Each of type of cognitive styles consisted of 3 participants. There were two instruments used to gather data: written examination in the course and a set of the interview. The FD and FN participants generated Action for a binary operation. The FI participant generated Action and Process for a binary operation. The FD, FN and FI participants generated Action, Process, Object, and Scheme for the set. The FD and FN participant did not generate mental structure for axiom. The FI participant generated Scheme for axiom. The FD, FN and FI participants tend to have no Coherence of Scheme of the group. Not all mental structure on the refinement of the preliminary genetic decomposition can be constructed by participants so well that there are still obstacles in the process of proving.

  9. Effects of compositional changes on reactivity continuum and decomposition kinetics of lake dissolved organic matter

    Science.gov (United States)

    Mostovaya, Alina; Koehler, Birgit; Guillemette, François; Brunberg, Anna-Kristina; Tranvik, Lars J.

    2016-07-01

    To address the link between the composition and decomposition of freshwater dissolved organic matter (DOM), we manipulated the DOM from three boreal lakes using preincubations with UV light to cleave large aromatic molecules and polyvinylpyrrolidone (PVP) to remove colored phenolic compounds. Subsequently, we monitored the dissolved organic carbon (DOC) loss over 4 months of microbial degradation in the dark to assess how compositional changes in DOM affected different aspects of the reactivity continuum, including the distribution of the apparent decay coefficients. We observed profound effects on decomposition kinetics, with pronounced shifts in the relative share of rapidly and more slowly decomposing fractions of the DOM. In the UV-exposed treatment initial apparent decay coefficient k0 was almost threefold higher than in the control. Significantly higher relative DOC loss in the UV-exposed treatment was sustained for 2 months of incubation, after which decay coefficients converged with those in the control. The PVP removed compounds with absorbance and fluorescence characteristics representative of aromatic compounds, which led to slower decomposition, compared to that in the control. Our results demonstrate the reactivity continuum underlying the decomposition of DOM in freshwaters and highlight the importance of intrinsic properties of DOM in determining its decomposition kinetics.

  10. Benzoxyl radical decomposition kinetics: formation of benzaldehyde + H, phenyl + CH2O, and benzene + HCO.

    Science.gov (United States)

    da Silva, Gabriel; Bozzelli, Joseph W

    2009-06-25

    The kinetics of benzoxyl radical decomposition was studied using ab initio computational chemistry and RRKM rate theory. The benzoxyl radical is an important but short-lived intermediate in the combustion of toluene and other alkylated aromatic hydrocarbons. A theoretical study of the thermochemistry and kinetics to products over a range of temperatures and pressures for benzoxyl decomposition is reported. Ab initio calculations with the G3X theoretical method reveal low-energy pathways from the benzoxyl radical to benzaldehyde + H and the phenyl radical + formaldehyde (CH(2)O), as well as a novel mechanism to benzene + the formyl radical (HC(*)O). RRKM simulations were performed for benzoxyl decomposition as a function of temperature and pressure. Benzaldehyde formation constitutes more than 80% of the total reaction products at temperatures below 1000 K, decreasing to around 50% at 2000 K. Formation of benzene + HC(*)O and phenyl + CH(2)O is of similar importance, each accounting for 5-10% of the decomposition products at around 1000 K, increasing to 20-30% at 2000 K. The results presented here should lead to improved kinetic models for the oxidation of alkylated aromatic hydrocarbons, particularly for the formation of benzene as a direct oxidation product of toluene. Re-evaluation of the phenyl radical heat of formation leads us to suggest a benzene C-H bond dissociation energy in the range of 113.5-114.5 kcal mol(-1).

  11. Kinetics and mechanism of the thermal decomposition of unsaturated aldehydes: benzaldehyde, 2-butenal, and 2-furaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Grela, M.A.; Colussi, A.J.

    1986-01-30

    The thermal unimolecular decomposition of benzaldehyde (BA), crotonaldehyde (CA), and furfural (FA) have been investigated in a flow reactor at very low pressures by modulated beam mass spectrometry above 1040 K. Each reaction proceeds by a different mechanism. Whereas BA decomposes by C(O)-H bond fission CA readily undergoes decarbonylation to propene via a three-center transition-state reaction. FA decomposition into vinylketene and CO involves ring opening followed by H-atom transfer in the resulting biradical. Overall high-pressure Arrhenius parameters for the three reactions are derived from kinetic data. 26 references, 4 figures, 1 table.

  12. Non-isothermal decomposition kinetics of magnesite Decomposição não isotérmica de magnesita

    OpenAIRE

    Maitra, S; Mukherjee, S.; Saha, N; Pramanik, J

    2007-01-01

    Kinetics of thermal decomposition of Indian magnesite was studied by thermo-gravimetric analysis under non-isothermal condition. Coats and Redfern Integral approximation method was used to determine the kinetic parameters. Using the kinetic parameters different kinetic functions were analyzed with the experimental data to ascertain the decomposition mechanism of magnesium carbonate and it was observed that the decomposition reaction followed a contracting sphere kinetic mechanism.A cinética d...

  13. Kinetics and Mechanism of the Exothermic First-stage Decomposition Reaction of Dinitroglycoluril

    Institute of Scientific and Technical Information of China (English)

    ZHAO,Feng-Qi(赵凤起); HU,Rong-Zu(胡荣祖); CHEN,Pei(陈沛); LUO,Yang(罗阳); GAO,Sheng-Li(高胜利); SONG,Ji-Rong(宋纪蓉); SHI,Qi-Zhen(史启祯)

    2004-01-01

    Under linear temperature increase condition, the thermal behavior, mechanism and kinetic parameters of the exothermic decomposition reaction of the title compound have been studied by means of DSC and IR. The initial stage of the mechanism was proposed. The empirical kinetic model function in differential form, apparent activation energy and pre-exponential constant of the exothermic decomposition reaction are α 0.526, 207.0 kJ·mol-1 and 1018.49 s-1, respectively. The critical temperature of thermal explosion of the compound is 252.87 ℃. The values of △S≠, △H≠ and △G≠ of the reaction are 128.4 J·mol-1·K-1, 218.9 kJ·mol-1 and 152.7 kJ·mol-1, respectively.

  14. Study on the thermal decomposition kinetics of nano-sized calcium carbonate

    Institute of Scientific and Technical Information of China (English)

    李代禧; 史鸿运; 邓洁; 徐元植

    2003-01-01

    This study of the thermal decomposition kinetics of various average diameter nano-particles of calcium carbonate by means of TG-DTA(thermogravimetry and differential thermal analysis) showed that the thermal decomposition kinetic mechanisms of the same crystal type of calcium carbonate samples do not vary with decreasing of their average diameters; their pseudo-active energy Ea; and that the top-temperature of decomposition Tp decreases gently in the scope of micron-sized diameter, but decreases sharply when the average diameter decreases from micron region to nanometer region. The extraordinary properties of nano-particles were explored by comparing the varying regularity of the mechanisms and kinetic parameters of the solid-phase reactions as well as their structural characterization with the variation of average diameters of particles. These show that the aggregation, surface effect as well as internal aberrance and stress of the nano-particles are the main reason causing both Ea and Tp to decline sharply with the decrease of the average diameter of nano-particles.

  15. Kinetic and chemical characterization of thermal decomposition of dicumylperoxide in cumene.

    Science.gov (United States)

    Di Somma, Ilaria; Marotta, Raffaele; Andreozzi, Roberto; Caprio, Vincenzo

    2011-03-15

    Dicumylperoxide (DCP) is one of the most used peroxides in the polymer industry. It has been reported that its thermal decomposition can result in runaway phenomena and thermal explosions with significant economic losses and injuries to people. In the present paper thermal behaviour of dicumylperoxide in cumene was investigated over the temperature range of 393-433 K under aerated and de-aerated conditions. The results indicated that when oxygen was present, the decomposition rate did not follow a simple pseudo-first order kinetic as previously reported in literature. A satisfactory fit of the experimental data was, in this case, achieved by means of kinetic expression derived under the assumption of an autocatalytic scheme of reaction. The reaction rate was, on the contrary, correctly described by a pseudo-first order kinetic in absence of oxygen. Under both aerated and de-aerated conditions, chemical analysis showed that the decomposition mainly resulted in the formation of acetophenone and dimethylphenylcarbinol with minor occurrence of 2,3-dimethyl-2,3-diphenylbutane. The formation of methane and ethane was also invariably observed while the appearance of cumylhydroperoxide as a reaction intermediate was detected under only aerated conditions. Therefore, two reaction schemes were proposed to explain system behaviour in the presence of oxygen and after its purging. Copyright © 2011 Elsevier B.V. All rights reserved.

  16. Kinetic analysis for non-isothermal decomposition of unirradiated and γ-irradiated indium acetyl acetonate

    Directory of Open Access Journals (Sweden)

    Refaat Mohammed Mahfouz

    2011-03-01

    Full Text Available Kinetic studies for the non-isothermal decomposition of un-irradiated and γ-irradiated indium acetyl acetonate In(acac3 with 10² kGy total γ-ray dose were carried out in static air. The results showed that the decomposition proceeds in one major step in the temperature range of 150-250 °C with the formation of In2O3 as solid residue. The non-isothermal data for un-irradiated and γ-irradiated In(acac3 were analysed using linear Flynn-Wall-Ozawa (FWO and nonlinear Vyazovkin (VYZ iso-conversional methods. The results of application of these free models on the investigated data showed a systematic dependence of Ea on α indicating a simple decomposition process. No significant changes were observed in both decomposition behaviour and (Eα-α dependency between unirradiated and γ-irradiated In(acac3. Calcination of In(acac3 at 400 °C for 5 hours led to the formation of In2O3 monodispersed nanoparticles. X-ray diffraction, FTIR and SEM techniques were employed for characterization of the synthesised nanoparticles. This is the first attempt to prepare In2O3 nanoparticles by solid state thermal decomposition of In(acac3.

  17. Decomposition kinetics of dimethyl methylphospate(chemical agent simulant) by supercritical water oxidation

    Institute of Scientific and Technical Information of China (English)

    Bambang VERIANSYAH; Jae-Duck KIM; Youn-Woo LEE

    2006-01-01

    Supercritical water oxidation (SCWO) has been drawing much attention due to effectively destroy a large variety of high-risk wastes resulting from munitions demilitarization and complex industrial chemical. An important design consideration in the development of supercritical water oxidation is the information of decomposition rate. In this paper, the decomposition rate of dimethyl methylphosphonate(DMMP), which is similar to the nerve agent VX and GB(Sarin) in its structure, was investigated under SCWO conditions. The experiments were performed in an isothermal tubular reactor with a H2O2 as an oxidant. The reaction temperatures were ranged from 398 to 633 ℃ at a fixed pressure of 24 MPa. The conversion of DMMP was monitored by analyzing total organic carbon (TOC) on the liquid effluent samples. It is found that the oxidative decomposition of DMMP proceeded rapidly and a high TOC decomposition up to 99.99% was obtained within 11 s at 555℃. On the basis of data derived from experiments, a global kinetic equation for the decomposition of DMMP was developed. The model predictions agreed well with the experimental data.

  18. Kinetic studies of the thermal decomposition of KDNBF, a primer for explosives

    Energy Technology Data Exchange (ETDEWEB)

    Jones, D.E.G.; Feng, H.T.; Fouchard, R.C. [Natural Resources Canada, CANMET Canadian Explosives Research Laboratory, Ottawa, ON (Canada)

    2000-07-01

    The potassium salt of 4,6-dinitrobenzofuroxan (KDNBF) is used in primary explosive and propellant compositions, although very little is known about its thermal properties. This paper described an extensive thermal hazard assessment conducted using differential scanning calorimetry (DSC), thermal gravimetry (TG), accelerating rate calorimetry (ARC) and heat flux calorimetry (HFC) measurements. Dynamic and isothermal methods were used to determine kinetic parameters and activation energies. Results of the analyses indicated that KDNBF decomposed during a multi-step exothermic process that proceeded directly from the solid state. Decomposition was autocatalytic in a closed system. The decomposition process was not influenced by the surrounding atmosphere or gas environment except during the final stages of the TG decomposition in air, when remaining carbonaceous materials were converted into carbon dioxide (CO{sub 2}). The initial stage of decomposition was rapid enough for ignition to occur when too large a sample was used. The activation energy determined from the HFC analysis was lower than results obtained for the TG and ARC studies. It was concluded that mass to free volume ratios used in the HFC studies were more than double than the ratios used in the ARC measurements. It was concluded that higher pressures and an enhanced autocatalytic effect was observed in the gaseous decomposition products used in the HFC system. 9 refs., 1 tab., 13 figs.

  19. Thermal Decomposition Behavior and Kinetics of Composites from Coal and Polyethylene

    Institute of Scientific and Technical Information of China (English)

    YANG Fu-sheng; QU Jian-lin; YANG Zhi-yuan; ZHOU An-ning

    2007-01-01

    A thermogravimetric analysis (TG) was conducted to study the thermal decomposition behavior and kinetics of composites from coal and high density polyethylene (HDPE), linear low density polyethylene (LLDPE) or low density polyethylene (LDPE). The results show that coal facilitates melting of the polyethylene before temperatures reach 700 K in nitrogen due to the exothermic effect of coal. Above 700 K, adding coal into the polyethylene will result in smaller maximum rates of mass loss and higher initial mass loss temperatures of the composites. Hence, some chemical interactions, occurring between liquid compounds released in the pyrolysis of the coal and polymer, depend on several factors, such as coal rank and the molecular structure of polymers. Synergetic effects in coal and polymers were also found. Both chemical interactions and synergetic effects control the entire thermal decomposition behavior of composites. The larger the amount of coal in the composites, the greater the decomposition temperature spans and the higher the maximum decomposition temperature, the smaller the devolatilization rates. The effect of coal on the thermal stability of composites lies in the hydrogen acceptor effect of the coals. Thermal decomposition of the coals, the polymers and related composites can be modelled via first order parallel reactions between 563 K and 763 K.

  20. Kinetic Study of anti-HIV drugs by Thermal Decomposition Analysis: A Multilayer Artificial Neural Network Propose

    CERN Document Server

    Ferreira, B D L; Sebastião, R C O; Yoshida, M I; Mussel, W N; Fialho, S L; Barbosa, J

    2016-01-01

    Kinetic study by thermal decomposition of antiretroviral drugs, Efavirenz (EFV) and Lamivudine (3TC), usually present in the HIV cocktail, can be done by individual adjustment of the solid decomposition models. However, in some cases unacceptable errors are found using this methodology. To circumvent this problem, here is proposed to use a multilayer perceptron neural network (MLP), with an appropriate algorithm, which constitutes a linearization of the network by setting weights between the input layer and the intermediate one and the use of Kinetic models as activation functions of neurons in the hidden layer. The interconnection weights between that intermediate layer and output layer determines the contribution of each model in the overall fit of the experimental data. Thus, the decomposition is assumed to be a phenomenon that can occur following different kinetic processes. In the investigated data, the kinetic thermal decomposition process was best described by R1 and D4 model for all temperatures to EF...

  1. Monnte Carlo Simulation of Kinetics of Ammonia Oxidative Decomposition over the Commercial Propylene Ammoxidation Catalyst(Mo-Bi)

    Institute of Scientific and Technical Information of China (English)

    罗正鸿; 詹晓力; 等

    2003-01-01

    Monte Carlo method is applied to investigate the kinetics of ammonia oxidative decomposition over the commercial propylene ammoxidation catalyst(Mo-Bi).The simulation is quite in agreement with experimetal results.Monte Carlo simulation proves that the process of ammonia oxidation decomposition is a two-step reaction.

  2. Synthesis and Thermal Decomposition Kinetics of La(Ⅲ) Complex with Unsymmetrical Schiff Base Zwitterion Ligand

    Institute of Scientific and Technical Information of China (English)

    Bi Caifeng; Xiao Yan; Fan Yuhua; Xie Sitan; Xu Jiakun

    2007-01-01

    A new unsymmetrical solid Schiff base (LLi) was synthesized using L-lysine. o-vanillin and 2-hydroxy-l-naph-thaldehyde. Solid La (Ⅲ) complex of this ligand [LaL(NO3)](NO3)·2H2O was prepared and characterized by elemental analyses, IR, UV and molar conductance. The thermal decomposition kinetics of the complex for the second stage were studied under non-isothermal condition by TG and DTG methods. The kinetic equation may be expressed as: dα/dt=A·e-E/RT·(1-α)2. The kinetic parameters (E, A), activation entropy ΔS≠ and activation free-energy ΔG≠ were also gained.

  3. Flowing afterglow spectroscopy: an ultrasensitive probe into solid-phase decomposition kinetics. [TATB and NQ

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, G.W.; Andrews, G.H. Jr.

    1979-01-01

    The thermal-decomposition kinetics of high explosives are important to manufacturers and these dangerous materials from the standpoint of processing and storage. Low-temperature kinetics (20 to 200/sup 0/C) are difficult to obtain. Either extremely sensitive analytical techniques must be employed or very large amounts of material must be tested by less sensitive methods. The latter technique has the disadvantage that when sensitive explosives or propellants are so tested, catastrophic reaction can result in the destruction of expensive equipment, and the time involved in testing may be extremely long. The flowing-afterglow method, proposed here, utilizes small explosive samples and an ultra-sensitive analytical approach. The paper describes the technique in detail and summarizes our recent efforts to elucidate the low-temperature kinetics of trinitrotriaminobenzene (TATB) and nitroguanidine (NQ).

  4. CP: AN INVESTIGATION OF COEFFICIENT OF THERMAL EXPANSION, DECOMPOSITION KINETICS, AND REACTION TO VARIOUS STIMULI

    Energy Technology Data Exchange (ETDEWEB)

    Weese, R K; Burnham, A K; Fontes, A T

    2005-03-23

    The properties of pentaamine (5-cyano-2H-tetrazolato-N2) cobalt (III) perchlorate (CP), which was first synthesized in 1968, continues to be of interest for predicting behavior in handling, shipping, aging, and thermal cook-off situations. We report coefficient of thermal expansion (CTE) values over four specific temperature ranges, decomposition kinetics using linear heating rates, and the reaction to three different types of stimuli: impact, spark, and friction. The CTE was measured using a Thermal Mechanical Analyzer (TMA) for samples that were uniaxially compressed at 10,000 psi and analyzed over a dynamic temperature range of -20 C to 70 C. Using differential scanning calorimetry, DSC, CP was decomposed at linear heating rates of 1, 3, and 7 C/min and the kinetic triplet calculated using the LLNL code Kinetics05. Values are also reported for spark, friction, and impact sensitivity.

  5. Chemical kinetics on thermal decompositions of cumene hydroperoxide in cumene studied by calorimetry: An overview

    Energy Technology Data Exchange (ETDEWEB)

    Duh, Yih-Shing, E-mail: yihshingduh@yahoo.com.tw [Department of Occupation Safety and Health, Jen-Teh Junior College of Medicine, Nursing and Management, Miaoli, 35664, Taiwan, ROC (China); Department of Safety, Health and Environmental Engineering, National United University, No. 1 Lien-Da, Miaoli, 36052, Taiwan, ROC (China)

    2016-08-10

    Highlights: • Chemical kinetics on thermal decompositions of CHP are conducted and summarized. • Kinetics agrees well between data from DSC and adiabatic calorimetry. • Ea is determined to be about 120 kJ mol{sup −1} by various calorimetry. • LogA (A in s{sup −1}) is determined to be about 11.8 by various calorimetry. - Abstract: Study on chemical kinetics related to the thermal decomposition of cumene hydoperoxide (CHP) in cumene is summarized in this work. It is of great importance to gather and compare the differences between these kinetic parameters for further substantial applications in the chemical industry and process safety. CHP has been verified to possess an autocatalytic behavior by using microcalorimetry (such as TAM and C-80) operated at isothermal mode in the temperature range from 70 °C to 120 °C. However, it exhibits a reaction of n-th order detected by non-isothermal DSC scanning and adiabatic calorimeter. By the isothermal aging tests, activation energy and frequency factor in logA(s{sup −1}) were averaged to be (117.3 ± 5.9) kJ mol{sup −1}and (11.4 ± 0.3), respectively. Kinetic parameters acquired from data of interlaboratories by using heat-flow calorimetry, the averaged activation energy and frequency factor in logA(s{sup −1}) were (119.3 ± 11.3) kJ mol{sup −1}and (12.0 ± 0.2), respectively. On the analogy of results from adiabatic calorimetry, the activation energy and frequency factor in logA(s{sup −1}) were respectively averaged to be (122.4 ± 9.2) kJ mol{sup −1}and (11.8 ± 0.8). Five sets of kinetic models in relation to autocatalytic reactions are collected and discussed as well.

  6. Hydrothermal decomposition of industrial jarosite in alkaline media: The rate determining step of the process kinetics

    Directory of Open Access Journals (Sweden)

    González-Ibarra A.A.

    2016-01-01

    Full Text Available This work examines the role of NaOH and Ca(OH2 on the hydrothermal decomposition of industrial jarosite deposited by a Mexican company in a tailings dam. The industrial jarosite is mainly composed by natrojarosite and contains 150 g Ag/t, showing a narrow particle size distribution, as revealed by XRD, fire assay, SEM-EDS and laser-diffraction analysis. The effect of the pH, when using NaOH or Ca(OH2 as alkalinizing agent was studied by carrying out decomposition experiments at different pH values and 60°C in a homogeneous size particle system (pH = 8, 9, 10 and 11 and in a heterogeneous size particle system (pH = 11. Also, the kinetic study of the process and the controlling step of the decomposition reaction when NaOH and Ca(OH2 are used was determined by fitting the data obtained to the shrinking core model for spherical particles of constant size. These results, supported by chemical (EDS, morphological (SEM and mapping of elements (EDS analysis of a partially reacted jarosite particle allowed to conclude that when NaOH is used, the process kinetics is controlled by the chemical reaction and when Ca(OH2 is used, the rate determining step is changed to a diffusion control through a layer of solid products.

  7. Kinetics and Mechanism of Decomposition of Nano-sized Calcium Carbonate under Non-isothermal Condition

    Institute of Scientific and Technical Information of China (English)

    刘润静; 陈建峰; 郭奋; 吉米; 沈志刚

    2003-01-01

    Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern''s equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃ lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151 kJ·mo1-1 while the literature value for normal calcite was approximately 200 kJ ·mol-1. The order of magnitude of Dre-exvonential factors was estimated to be 109 s-1.

  8. Comparative decomposition kinetics of neutral monosaccharides by microwave and induction heating treatments.

    Science.gov (United States)

    Tsubaki, Shuntaro; Oono, Kiriyo; Onda, Ayumu; Yanagisawa, Kazumichi; Azuma, Jun-ichi

    2013-06-28

    The stabilities of five neutral monosaccharides (glucose, galactose, mannose, arabinose, and xylose) were kinetically compared after the molecules were submitted to microwave heating (internal heating) and induction heating (external heating) under completely identical thermal histories by employing PID (proportional, integral, and derivative) temperature controlled ovens and homogeneous mixing. By heating in water at 200°C, the rate constants for the decomposition reactions varied from 2.13×10(-4) to 3.87×10(-4)s(-1) for microwave heating; however, the values increased by 1.1- to 1.5-fold for induction heating. Similarly, in a dilute (0.8%) sulfuric acid solution, the decomposition rate constants varied from 0.61×10(-3) to 2.00×10(-3)s(-1) for microwave heating; however, the values increased by 1.5- to 2.2-fold for induction heating. The results show that microwave heating imparts greater stability to neutral monosaccharides than does induction heating. The undesirable decomposition of monosaccharides at the surface boundary of reactor walls may have increased the probability of monosaccharide decomposition during induction heating.

  9. The response of the HMX-based material PBXN-9 to thermal insults: thermal decomposition kinetics and morphological changes

    Energy Technology Data Exchange (ETDEWEB)

    Glascoe, E A; Hsu, P C; Springer, H K; DeHaven, M R; Tan, N; Turner, H C

    2010-12-10

    PBXN-9, an HMX-formulation, is thermally damaged and thermally decomposed in order to determine the morphological changes and decomposition kinetics that occur in the material after mild to moderate heating. The material and its constituents were decomposed using standard thermal analysis techniques (DSC and TGA) and the decomposition kinetics are reported using different kinetic models. Pressed parts and prill were thermally damaged, i.e. heated to temperatures that resulted in material changes but did not result in significant decomposition or explosion, and analyzed. In general, the thermally damaged samples showed a significant increase in porosity and decrease in density and a small amount of weight loss. These PBXN-9 samples appear to sustain more thermal damage than similar HMX-Viton A formulations and the most likely reasons are the decomposition/evaporation of a volatile plasticizer and a polymorphic transition of the HMX from {beta} to {delta} phase.

  10. Kinetics of gas phase formic acid decomposition on platinum single crystal and polycrystalline surfaces

    Science.gov (United States)

    Detwiler, Michael D.; Milligan, Cory A.; Zemlyanov, Dmitry Y.; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-06-01

    Formic acid dehydrogenation turnover rates (TORs) were measured on Pt(111), Pt(100), and polycrystalline Pt foil surfaces at a total pressure of 800 Torr between 413 and 513 K in a batch reactor connected to an ultra-high vacuum (UHV) system. The TORs, apparent activation energies, and reaction orders are not sensitive to the structure of the Pt surface, within the precision of the measurements. CO introduced into the batch reactor depressed the formic acid dehydrogenation TOR and increased the reaction's apparent activation energies on Pt(111) and Pt(100), consistent with behavior predicted by the Temkin equation. Two reaction mechanisms were explored which explain the formic acid decomposition mechanism on Pt, both of which include dissociative adsorption of formic acid, rate limiting formate decomposition, and quasi-equilibrated hydrogen recombination and CO adsorption. No evidence was found that catalytic supports used in previous studies altered the reaction kinetics or mechanism.

  11. Decomposition kinetics study of zirconium hydride by interrupted thermal desorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Mingwang; Liang, Li; Tang, Binghua; Xiang, Wei; Wang, Yuan; Cheng, Yanlin; Tan, Xiaohua, E-mail: caepiee@163.com

    2015-10-05

    Highlights: • Interrupted TDS was applied to investigate the mechanism of ZrH{sub 2} decomposition. • The activation energies for the five desorption peaks were determined. • The origins of the five desorption peaks were identified. • The γZrH phase was observed at ambient conditions. - Abstract: Thermal desorption kinetics of zirconium hydride powder were studied using thermogravimetry and simultaneous thermal desorption spectroscopy. The activation energies for observed desorption peaks were estimated according to Kissinger relation. The intermediate phase composition was studied using X-ray diffraction by rapid cooling on different stages of heating. The origins of the peaks were described as the equilibrium hydrogen pressure of a number of consecutive phase regions that decomposition reaction passed through. The zirconium monohydride γZrH was observed for extended periods of time at ambient conditions, which has been supposed to be metastable for a long time.

  12. PROPERTIES OF CP: COEFFICIENT OF THERMAL EXPANSION, DECOMPOSITION KINETICS, AND REACTION TO SPARK, FRICTION AND IMPACT

    Energy Technology Data Exchange (ETDEWEB)

    Weese, R K; Burnham, A K

    2005-09-28

    The properties of pentaamine (5-cyano-2H-tetrazolato-N2) cobalt (III) perchlorate (CP), which was first synthesized in 1968, continues to be of interest for predicting behavior in handling, shipping, aging, and thermal cook-off situations. We report coefficient of thermal expansion (CTE) values over four specific temperature ranges, decomposition kinetics using linear and isothermal heating, and the reaction to three different types of stimuli: impact, spark, and friction. The CTE was measured using a Thermal Mechanical Analyzer (TMA) for samples that were uniaxially compressed at 10,000 psi and analyzed over a dynamic temperature range of -20 C to 70 C. Differential scanning calorimetry, DSC, was used to monitor CP decomposition at linear heating rates of 1-7 C min{sup -1} in perforated pans and of 0.1-1.0 C min{sup -1} in sealed pans. The kinetic triplet was calculated using the LLNL code Kinetics05, and predictions for 210 and 240 C are compared to isothermal thermogravimetric analysis (TGA) experiments. Values are also reported for spark, friction, and impact sensitivity.

  13. Thermochemical Properties and Non-isothermal Decomposition Reaction Kinetics of N-Guanylurea Dinitramide (GUDN)

    Institute of Scientific and Technical Information of China (English)

    ZHAO, Feng-Qi(赵凤起); CHEN, Pei(陈沛); YUAN, Hong-An(袁宏安); GAO, Sheng-Li(高胜利); HU, Rong-Zu(胡荣祖); SHI, Qi-Zhen(史启祯)

    2004-01-01

    The constant-volume combustion energy,(△) cU(GUDN, s, 298.15 K), enthalpy of solution in acetic ether,(△)solHm(I) and kinetic behavior of the exothermic decomposition reaction of the title compound (GUDN) are determined by a precise rotating bomb calorimeter, a Calvet microcalorimeter and DSC, respectively. Its standard enthalpy of combustion,(△)cHm(I) (GUDN, s, 298.15 K), standard enthalpy of formation,(△)fHm(I) (GUDN, s, 298.15 K) and kinetic parameters of the exothermic main decomposition reaction in a temperature-programmed mode [the apparent activation energy (Ea) and pre-exponential factor (A)] are calculated. The values of (△)cU(GUDN, s, 298.15 K), (△)cHm(I)(GUDN, s, 298.15 K),(△)fHm(I) (GUDN, s, 298.15 K) and (△)solHm(I)of GUDN are (-7068.64±2.37) J·g-1, (-1467.66±0.50) kJ·mol-1, (-319.76±0.58) kJ·mol-1 and (165.737±0.013) kJ·mol-1, respectively. The kinetic model function in integral form and the value of and A of the exothermic main decomposition reaction of GUDN are 220.20 kJ·mol-1 and 1021.18 s-1, respectively. The critical temperature of thermal explosion of GUDN is 217.6 ℃

  14. Thermal Behavior,Nonisothermal Decomposition Reaction Kinetics of Mixed Ester Double-base Gun Propellants

    Institute of Scientific and Technical Information of China (English)

    YI Jian-hua; ZHAO Feng-qi; XU Si-yu; GAO Hong-xu; HU Rong-zu

    2008-01-01

    The thermal decomposition behavior and nonisothermal reaction kinetics of the double-base gun propellants containing the mixed ester of triethyleneglycol dinitrate(TEGDN) and nitroglycerin(NG) were investigated by thermogravimetry(TG) and differential thermogravimetry(DTG),and differential scanning calorimetry(DSC) under the high-pressure dynamic ambience.The results show that the thermal decomposition processes of the mixed nitric ester gun propellants have two mass-loss stages.Nitric ester evaporates and decomposes in the first stage,and nitrocellulose and centralite Ⅱ(C2) decompose in the second stage.The mass loss,the DTG peak points,and the terminated temperatures of the two stages are changeable with the difference of the mass ratio of TEGDN to NG.There is only one obvious exothermic peak in the DSC curves under the different pressures.With the increase in the furnace pressure,the peak temperature decreases,and the decomposition heat increases.With the increase in the content of TEGDN,the decomposition heat decreases at 0.1 Mpa and rises at high pressure.The variety of mass ratio of TEGDN to NG makes few effect on the exothermic peak temperatures in the DSC curves at different pressures.The kinetic equation of the main exothermal decomposition reaction of the gun propellant TG0601 was determined as:da/dt-=1021.59(1-a)3e-2.60×104/T The reaction mechanism of the process can be classified as chemical reaction.The critical temperatures of the thermal explosion(Tbe and Tbp) obtained from the onset temperature(Te) and the peak temperature(Tp) are 456.46 and 473.40 K,respectively.△S≠,△H≠,and △G≠of the decomposition reaction are 163.57 J·mol-1·K-1,209.54 kJ·mol-1,and 133.55kJ·mol-1,respectively.

  15. Thermodynamic properties, decomposition kinetics and reaction models of BCHMX and its Formex bonded explosive

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Qi-Long, E-mail: terry.well@163.com [Institute of Energetic Materials, Faculty of Chemical technology, University of Pardubice, 532 10 Pardubice (Czech Republic); Zeman, Svatopluk, E-mail: svatopluk.zeman@upce.cz [Institute of Energetic Materials, Faculty of Chemical technology, University of Pardubice, 532 10 Pardubice (Czech Republic); Svoboda, Roman [Department of Physical Chemistry, Faculty of Chemical technology, University of Pardubice, 532 10 Pardubice (Czech Republic); Elbeih, Ahmed [Military Technical College, Cairo (Egypt)

    2012-11-10

    As an attractive new energetic material, cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX) and its polymer bonded explosive (PBX) with styrene-butadiene rubber (SBR) binder (Formex type) have been investigated with regard to its thermal decomposition kinetics and reaction models by using DSC, TG and SEM techniques. It was found that the decomposition of BCHMX in dynamic nitrogen could be divided into two steps, while there is only one step for its Formex bonded explosive. The activation energy for decomposition of BCHMX/Formex was obtained to be 221.7 {+-} 4.99 kJ mol{sup -1} by modified KAS method, while the mean activation energies for pure BCHMX are calculated as 233.0 {+-} 2.1 kJ mol{sup -1} for first step and 186.0 {+-} 0.92 kJ mol{sup -1} for the second step. It was further proved that the first decomposition step of BCHMX is autocatalytic, during which the crystal of BCHMX could dissolve in the liquid phase of its thermolysis products on the surface. Besides, the JMA and AC models were found to be appropriate to interpret the two-step decomposition of pure BCHMX and JMA model for BCHMX/Formex, the parameterized reaction models for BCHMX could be established as f({alpha}) = {alpha}{sup 0.45}(1 - {alpha}){sup 1.51} and f({alpha}) = 2.33 Multiplication-Sign (1 - {alpha})[-ln(1 - {alpha})]{sup 0.57}, while for BCHMX/Formex as f({alpha}) = 2 Multiplication-Sign (1 - {alpha})[-ln(1 - {alpha})]{sup 1/2}.

  16. Kinetics of the First Order Autocatalytic Decomposition Reaction of Nitrocellulose (13.86% N)

    Institute of Scientific and Technical Information of China (English)

    GUO,Peng-Jiang(郭鹏江); HU,Rong-Zu(胡荣祖); NING,Bin-Ke(宁斌科); YANG,Zheng-Quan(杨正权); SONG,Ji-Rong(宋纪蓉); SHI,Qi-Zhen(史启祯); LU,Gui-E(路桂娥); JIANG,Jin-You(江劲勇)

    2004-01-01

    The kinetics of the first order autocatalytic decomposition reaction of nitrocellulose (NC, 13.86% N) was studied by using DSC. The results show that the DSC curve for the initial 50% of conversion degree of NC can be described by the first order autocatalytic equation dy/dt=-1016.3exp(-181860/RT)y-1016.7exp(-173050)y(1-y) and that for the latter 50% conversion degree of NC described by the reaction equations dy/dt=-1016.4exp(-154820/RT)y(n=1) and dy/dt=-1016.9exp(-155270/RT)y2.80(n≠1).

  17. Numerical solution of point kinetic equations by matrix decomposition and T series expansions

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Jeronimo J.A.; Alvim, Antonio C.M., E-mail: shaolin.jr@gmail.com, E-mail: alvim@nuclear.ufrj.br [Coordenacao dos Programas de Pos-Graduacao de Engenharia (COPPE/UFRJ), Rio de Janeiro, RJ (Brazil); Vilhena, Marco T.M.B., E-mail: vilhena@pq.cnpq.br [Universidade Federal do Rio Grande do Sul (PROMEC/UFRGS), Porto Alegre, RS (Brazil). Programa de Pos-Graduacao em Engenharia Mecanica

    2013-07-01

    Recently, an analytical solution of the Point Kinetics equations free from stiffness problems has been presented. The equations, cast in matrix form are split into diagonal plus off-diagonal matrices and a series expansion of neutron density and precursor concentrations is done, producing a recurrent system which is then solved analytically. In this paper, a numerical finite differences equivalent of this decomposition plus expansion method is derived and applied to the same problems tested in the analytical case. As a result, the number of terms in the expansions needed for holding steady state is obtained, as well as results for the transient cases, with good agreement between solutions. (author)

  18. Kinetics of thermal decomposition of hydrated minerals associated with hematite ore in a fluidized bed reactor

    Science.gov (United States)

    Beuria, P. C.; Biswal, S. K.; Mishra, B. K.; Roy, G. G.

    2017-03-01

    The kinetics of removal of loss on ignition (LOI) by thermal decomposition of hydrated minerals present in natural iron ores (i.e., kaolinite, gibbsite, and goethite) was investigated in a laboratory-scale vertical fluidized bed reactor (FBR) using isothermal methods of kinetic analysis. Experiments in the FBR in batch processes were carried out at different temperatures (300 to 1200°C) and residence time (1 to 30 min) for four different iron ore samples with various LOIs (2.34wt% to 9.83wt%). The operating velocity was maintained in the range from 1.2 to 1.4 times the minimum fluidization velocity ( U mf). We observed that, below a certain critical temperature, the FBR did not effectively reduce the LOI to a desired level even with increased residence time. The results of this study indicate that the LOI level could be reduced by 90% within 1 min of residence time at 1100°C. The kinetics for low-LOI samples (reaction mechanisms in two temperature regimes. At lower temperatures (300 to 700°C), the kinetics is characterized by a lower activation energy (diffusion-controlled physical moisture removal), followed by a higher activation energy (chemically controlled removal of LOI). In the case of high-LOI samples, three different kinetics mechanisms prevail at different temperature regimes. At temperature up to 450°C, diffusion kinetics prevails (removal of physical moisture); at temperature from 450 to 650°C, chemical kinetics dominates during removal of matrix moisture. At temperatures greater than 650°C, nucleation and growth begins to influence the rate of removal of LOI.

  19. Thermal Decomposition Kinetics of High Impact Polystyrene/ Organo Fe-montmorillonite Nanocomposites

    Institute of Scientific and Technical Information of China (English)

    刘宏; 孔庆红; 程宇和; 曹功源

    2012-01-01

    In this article, high impact polystyrene/organo Fe-montmorillonite (HIPS/Fe-OMT) nanocomposites were prepared by melting intercalation. The thermal stability of HIPS/Fe-OMT nanocomposites increased significantly compared to that of HIPS examined in thermal degradation conditions. Kinetic evaluations were performed by Kissinger, Flynn-Wall-Ozawa, Friedman methods and multivariate nonlinear regression. Apparent kinetic parameters for the overall degradation were determined. The resuRs showed that the activation energy of HIPS/Fe-OMT nanocomposites was higher than that of HIPS. A very good agreement between experimental and simulated curves was observed in dynamic conditions. Their decomposition reaction model was a single-step process of an nth-order reaction

  20. Thermal decomposition of wood in oxidizing atmosphere: A kinetic study from non-isothermal TG experiments

    Energy Technology Data Exchange (ETDEWEB)

    Cordero, T.; Rodriguez-Maroto, F.G.; Rodriguez, J.J. (Univ. of Malaga (Spain))

    1991-11-22

    The kinetics of thermal decomposition of four wood species in oxygen-bearing atmospheres of 5, 10 and 20% molar O{sub 2} concentrations have been studied from temperature-programmed experiments carried out at 5, 10 and 20 K min{sup {minus}1} heating rate. Devolatilization as well as combustion of the reamining solid have been considered to analyze the weight loss curves. The homogeneous volume reaction (VR) model has been used to describe devolatilization, whereas for solid combustion the grain model has been also checked. A two-stage approach has been used to fit the conversion-time curves and to derive the corresponding apparent kinetic parameters. The VR/VR (pyrolysis/combustion) combination provided a better description of the experimental {alpha}-t curves than the VR/grain combination. Holm oak and cork oak showed very close reactivities, whereas some differences were observed for aleppo pine and eucalyptus. 6 figs. 8 tabs., 20 refs.

  1. Q-bosonization of the quantum group GL$_{q}$(2) based on the Gauss decomposition

    CERN Document Server

    Damaskinsky, E V; Damaskinsky, E V; Sokolov, M A

    1995-01-01

    The new method of q-bosonization for quantum groups based on the Gauss decomposition of a transfer matrix of generators is suggested. The simplest example of the quantum group GL_q(2) is considered in some details.

  2. Kinetics of hydrate formation and decomposition of methane in silica sand

    Energy Technology Data Exchange (ETDEWEB)

    Nam, S.C. [Korea Inst. of Energy Reserch, Daejeon (Korea, Republic of). Dept. of Energy Conversion Research; Linga, P.; Haligva, C.; Englezos, P. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical and Biological Engineering; Ripmeester, J.A. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences

    2008-07-01

    The kinetics of hydrate formation and the decomposition behaviour of methane hydrates formed in a bed of silica sand particles were investigated. An experimental apparatus was used to study hydrate formation at temperatures of 7.0, 4.0, and 1.0 degrees C. Thermocouples were used to obtain temperature profiles during the experiments. Data obtained from the experiments were then used to determine formation gas uptake measurement curves and gas release decomposition measurement curves. Results of the study showed that the percentage of water converted to hydrates was higher when the temperature was 1.0 degrees C. Multiple nucleation points occurred during formation experiments conducted at 4.0 and 1.0 degrees C. A thermal stimulation approach was used to recover methane from the hydrates. The study showed that methane recovery occurred during 2 stages of the decomposition process. It was concluded that methane recovery rates of between 95 and 98 per cent were achieved using the method. 35 refs., 6 figs.

  3. In situ oxidation remediation technologies: kinetic of hydrogen peroxide decomposition on soil organic matter.

    Science.gov (United States)

    Romero, Arturo; Santos, Aurora; Vicente, Fernando; Rodriguez, Sergio; Lafuente, A Lopez

    2009-10-30

    Rates of hydrogen peroxide decomposition were investigated in soils slurries. The interaction soil-hydrogen peroxide was studied using a slurry system at 20 degrees C and pH 7. To determine the role of soil organic matter (SOM) in the decomposition of hydrogen peroxide, several experiments were carried out with two soils with different SOM content (S1=15.1%, S2=10%). The influence of the oxidant dosage ([H2O2](o) from 10 to 30 g L(-1) and soil weight to liquid phase volume ratio=500 g L(-1)) was investigated using the two calcareous loamy sand soil samples. The results showed a rate dependency on both SOM and hydrogen peroxide concentration being the H2O2 decomposition rate over soil surface described by a second-order kinetic expression r(H2O2) = -dn(H2O2) / W(SOM) dt = kC(H2O2) C(SOM). Thermogravimetric analysis (TGA) was used to evaluate the effect caused by the application of this oxidant on the SOM content. It was found a slightly increase of SOM content after treatment with hydrogen peroxide, probably due to the incorporation of oxygen from the oxidant (hydrogen peroxide).

  4. 肌醇热分解动力学%Thermal Decomposition Kinetics of Inositol

    Institute of Scientific and Technical Information of China (English)

    刘中平; 吕淑琛; 周彩荣

    2013-01-01

      采用热重分析法(DTA-TGA)对肌醇的热分解行为及其动力学规律进行了研究。得到氮气气氛升温速率分别为5、10、15、20、25℃⋅min−1下肌醇样品的TGA-DTA曲线。运用Flynn-Wall-Ozawa积分法、Kissinger最大速率法和Šatava-Šesták积分法对实验所得的数据进行处理,计算出肌醇热分解反应的表观活化能为208.03 kJ⋅mol−1;指前因子的对数值lgA=16.76。确定了热分解反应的机理为化学反应,并得到热分解机理函数的积分式G(α)=(1−α)−1−1。%  The thermal decomposition characteristics and kinetics of inositol were studied by DTA-TGA techniques. The curves of TGA and DTA of inositol at different heating rates (5, 10, 15, 20, 25℃⋅min−1) were acquired in nitrogen atmosphere. The kinetic parameters including the activation energy and pre-exponential factor of the thermal decomposition process for inositol were calculated by Flynn-Wall-Ozawa (FWO), Kissinger andŠatava-Šesták method, respectively. Moreover, the thermal decomposition mechanism of inositol was also studied. Results of this study show that the activation energy was found to be 208.03 kJ⋅mol−1, and logarithmic value of the pre-exponential factor logA was given to be 16.76. According toŠatava-Šesták method, the thermal decomposition mechanism of inositol was thought to be chemical reaction. Integral form of the most probable mechanism function of the decomposition process was obtained to be G(α)=(1−α)−1−1.

  5. Thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates of BTATz-CMDB propellant.

    Science.gov (United States)

    Yi, Jian-Hua; Zhao, Feng-Qi; Wang, Bo-Zhou; Liu, Qian; Zhou, Cheng; Hu, Rong-Zu; Ren, Ying-Hui; Xu, Si-Yu; Xu, Kang-Zhen; Ren, Xiao-Ning

    2010-09-15

    The composite modified double base (CMDB) propellants (nos. RB0601 and RB0602) containing 3,6-bis (1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) without and with the ballistic modifier were prepared and their thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates were investigated. The results show that there are three mass-loss stages in TG curve and two exothermic peaks in DSC curve for the BTATz-CMDB propellant. The first two mass-loss stages occur in succession and the temperature ranges are near apart, and the decomposition peaks of the two stages overlap each other, inducing only one visible exothermic peak appear in DSC curve during 350-550 K. The reaction mechanisms of the main exothermal decomposition processes of RB0601 and RB0602 are all classified as chemical reaction, the mechanism functions are f(alpha)=(1-alpha)(2), and the kinetic equations are dalpha/dt = 10(19.24)(1-alpha)(2)e(-2.32x10(4)/T) and dalpha/dt = 10(20.32)(1-alpha)(2)e(-2.32x10(4)/T). The thermal safety evaluation on the BTATz-CMDB propellants was obtained. With the substitution of 26% RDX by BTATz and with the help of the ballistic modifier in the CMDB propellant formulation, the burning rate can be improved by 89.0% at 8 MPa and 47.1% at 22 MPa, the pressure exponent can be reduced to 0.353 at 14-20 MPa.

  6. Thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates of BTATz-CMDB propellant

    Energy Technology Data Exchange (ETDEWEB)

    Yi Jianhua [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China); Zhao Fengqi, E-mail: yiren@nwu.edu.cn [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China); Wang Bozhou; Liu Qian; Zhou Cheng; Hu Rongzu [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China); Ren Yinghui [School of Chemical Engineering, Northwest University, Xi' an 710069 (China); Xu Siyu [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China); Xu, Kang-Zhen [School of Chemical Engineering, Northwest University, Xi' an 710069 (China); Ren Xiaoning [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China)

    2010-09-15

    The composite modified double base (CMDB) propellants (nos. RB0601 and RB0602) containing 3,6-bis (1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) without and with the ballistic modifier were prepared and their thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates were investigated. The results show that there are three mass-loss stages in TG curve and two exothermic peaks in DSC curve for the BTATz-CMDB propellant. The first two mass-loss stages occur in succession and the temperature ranges are near apart, and the decomposition peaks of the two stages overlap each other, inducing only one visible exothermic peak appear in DSC curve during 350-550 K. The reaction mechanisms of the main exothermal decomposition processes of RB0601 and RB0602 are all classified as chemical reaction, the mechanism functions are f({alpha}) = (1 - {alpha}){sup 2}, and the kinetic equations are d{alpha}/dt=10{sup 19.24}(1-{alpha}){sup 2}e{sup -2.32x10{sup 4/T}} and d{alpha}/dt=10{sup 20.32}(1-{alpha}){sup 2}e{sup -2.43x10{sup 4/T}}. The thermal safety evaluation on the BTATz-CMDB propellants was obtained. With the substitution of 26% RDX by BTATz and with the help of the ballistic modifier in the CMDB propellant formulation, the burning rate can be improved by 89.0% at 8 MPa and 47.1% at 22 MPa, the pressure exponent can be reduced to 0.353 at 14-20 MPa.

  7. Mechanism and Kinetics of Thermal Decomposition of MgCl2 × 6H2O

    Science.gov (United States)

    Huang, Qiong-Zhu; Lu, Gui-Min; Wang, Jin; Yu, Jian-Guo

    2010-10-01

    The reaction mechanism and kinetic behavior of thermal decomposition of MgCl2 × 6H2O were studied by thermal gravimetric analysis. The results showed that the thermal decomposition process of MgCl2 × 6H2O could be divided into six stages. In the first two stages, four crystalline waters were lost. The dehydration and hydrolysis coexisted during the third and fourth stages. The fifth stage corresponded to the evaporation of 0.3 crystalline waters, and one molecular hydrogen chloride was eliminated in the last stage. The kinetic analysis of the thermal decomposition process was performed using the Doyle, Coats-Redfern, and Malek methods. The results suggested that the mechanisms of six stages were two-dimensional phase boundary mechanism, three-dimensional phase boundary mechanism, nucleation and nuclei growth mechanism (Avrami-Erofeev equation n = 3), two-dimensional phase boundary mechanism, three-dimensional diffusion mechanism (cylinder and G-B equation), and nucleation and nuclei growth mechanism (Avrami-Erofeev equation n = 1), respectively. The apparent active energies of six stages were 66.8 kJ × mol-1, 138.0 kJ × mol-1, 77.2 kJ × mol-1, 135.6 kJ × mol-1, 77.4 kJ × mol-1, and 92.2 kJ × mol-1, respectively. The frequency factors were 3.6 × 109 s-1, 8.8 × 1017 s-1, 4.6 × 109 s-1, 3.0 × 1014 s-1, 78.6 s-1, and 1.2 × 103 s-1, respectively.

  8. Thermal decomposition and kinetics of plastic bonded explosives based on mixture of HMX and TATB with polymer matrices

    Directory of Open Access Journals (Sweden)

    Arjun Singh

    2017-02-01

    Full Text Available This work describes thermal decomposition behaviour of plastic bonded explosives (PBXs based on mixture of l,3,5,7-tetranitro- 1,3,5,7-tetrazocane (HMX and 2,4,6- triamino-1,3,5-trinitrobenzene (TATB with Viton A as polymer binder. Thermal decomposition of PBXs was undertaken by applying simultaneous thermal analysis (STA and differential scanning calorimetry (DSC to investigate influence of the HMX amount on thermal behavior and its kinetics. Thermogravimetric analysis (TGA indicated that the thermal decomposition of PBXs based on mixture of HMX and TATB was occurred in a three-steps. The first step was mainly due to decomposition of HMX. The second step was ascribed due to decomposition of TATB, while the third step was occurred due to decomposition of the polymer matrices. The thermal decomposition % was increased with increasing HMX amount. The kinetics related to thermal decomposition were investigated under non-isothermal for a single heating rate measurement. The variation in the activation energy of PBXs based on mixture of HMX and TATB was observed with varying the HMX amount. The kinetics from the results of TGA data at various heating rates under non-isothermal conditions were also calculated by Flynn–Wall–Ozawa (FWO and Kissinger-Akahira-Sunose (KAS methods. The activation energies calculated by employing FWO method were very close to those obtained by KAS method. The mean activation energy calculated by FWO and KAS methods was also a good agreement with the activation energy obtained from single heating rate measurement in the first step decomposition.

  9. Decomposition mechanisms and non-isothermal kinetics of LiHC_2O_4·H_2O

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The thermal decomposition process of LiHC2O4·H2O from 30 to 600 ℃ was investigated by the thermogravimetric and differential scanning calorimetry (TG-DSC). The phases decomposited at different temperature were characterized by X-ray diffraction (XRD), which indicated the decompositions at 150, 170, and 420℃, relating to LiHC2O4, Li2C2O4, Li2C2O4, and Li2CO3, respectively. Reaction mechanisms in the whole sintering process were determined, and the model fitting kinetic approaches were applied to data for non...

  10. Thermal decomposition mechanism and non-isothermal kinetics of the polyoxometalate of ciprofloxacin with 12-tungstoboric acid

    Institute of Scientific and Technical Information of China (English)

    WANG Dunjia; FANG Zhengdong; HAN Deyan

    2005-01-01

    The polyoxometalate complex (CPFX·HCl)4H5BW12O40·12H2O was prepared in aqueous solution for the first time, and characterized by elemental analysis, IR spectrum, and TG-DTG. The TG-DTG curves showed that its thermal decomposition was a our-step process consisting of the simultaneous collapse of Keggin anion. The intermediate and residue of the decomposition were identified by mean of TG-DTG, IR, and XRD technique. The non-isothermal kinetic data were analyzed by the Achar method and Coats-Redfern method. The apparent activation energy (E) and the pre-exponential factor (ln A) of each decomposition were obtained. The most probable thermal decomposition reaction mechanisms were proposed by comparison of the kinetic parameters. The kinetic equation for both the second stage and the third stage can be expressed as dα/dt = Ae-EIRT·(1 - α)2, and the fourth stage dα/dt = Ae-EIRT·( 1 - α). And their athematic expressions of the kinetic compensation effects of thermal decomposition reaction were also determined.

  11. Estimation of the kinetic parameters for thermal decomposition of HNIW and its adiabatic time-to-explosion by Kooij formula

    Institute of Scientific and Technical Information of China (English)

    Hong-xu GAO; Feng-qi ZHAO; Rong-zu HU; Hong-an ZHAO; Hai ZHANG

    2014-01-01

    A differential/integral method to estimate the kinetic parameters (apparent activation energy Ea and pre-exponential factor A) for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane (HNIW) by analyzing nonisothermal DSC curve data. The apparent activation energy (Ea) obtained by the in-tegral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion (Tb) and adiabatic time-to-explosion (tTIad) based on Kooij formula are used to calculate the values of Tb and tTIad to evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of Ea and A of decomposition reaction of HNIW are 3(1 ? a)[?ln(1 ? a)]2/3, 152.73 kJ mol?1 and 1011.97 s?1, respectively, and the values of self-accelerating decomposition temperature (TSADT), Tb and tTIad are 486.55 K, 493.11 K and 52.01 s, respectively.

  12. Kinetic Model of Resin-Catalyzed Decomposition of Acetone Cyanohydrin in Organic Solvent

    Institute of Scientific and Technical Information of China (English)

    章亭洲; 杨立荣; 朱自强; 吴坚平

    2003-01-01

    Decomposition of acetone cyanohydrin is the first-step reaction for preparing (S)-α-cyano-3-phenoxybenzyl alcohol (CPBA) by the one-pot method in organic media. Considering the compatibility of biocatalysts with chemical catalysts and the successive operation in the bioreactor, anion exchange resin (D301) was used as catalyst for this reaction. External diffusion limitation was excluded by raising rotational speed to higher than 190r·min-1 in both solvents. Internal diffusion limitation was verified to be insignificant in this reaction system. The effect of acetone cyanohydrin concentration on the reaction was also investigated. An intrinsic kinetic model was proposed when the mass transfer limitation was excluded, and the average deviation of the model is 10.5%.

  13. Kinetics and thermal decomposition of Tetrahydrazine lanthanum 2-hydroxy-1- naphthoate

    Directory of Open Access Journals (Sweden)

    Karuppannan Parimalagandhi

    2014-12-01

    Full Text Available Tetrahydrazine lanthanum 2-hydroxy-1-naphthoate [La2(NA3L4] (where NA and L indicate C10H6(2-O(1-COO and N2H4 respectively was synthesised and characterised by micro elemental analysis, IR spectroscopy, simultaneous TG-DTA and X-ray diffraction (XRD analysis. The results indicate that the compound loses hydrazine molecules in the temperature range 65 - 150 °C and decomposes to La2O3 at 675 °C through different intermediates, [La2O(CO32], [La2O2CO3] at 426 °C and 580 °C respectively. The intermediates of thermal decomposition and final product were confirmed by IR and X-ray diffraction. Coats and Redfern method has been implemented for the estimation of various kinetic parameters viz. energy of activation (E, pre-exponential factor (A,order of decomposition (n.The thermodynamic parameters like enthalpy of activation (ΔH entropy of activation (ΔS and free energy of activation (ΔG have been calculated by using thermogravimetric data.

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

    Science.gov (United States)

    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.

  15. Kinetics and Mechanism of the Thermal Decomposition Reaction of 3,3-Bis(azidomethyl)oxetane/Tetrahydrofuran Copolymer

    Institute of Scientific and Technical Information of China (English)

    LUO, Yang(罗阳); CHEN, Pei(陈沛); ZHAO, Feng-Qi(赵凤起); HU, Rong-Zu(胡劳祖); LI, Shang-Wen(李上文); GAO, Yin(高茵)

    2004-01-01

    The thermal behavior, mechanism and kinetic parameters of the exothermic decomposition reaction of 3,3-bis(azidomethyl)oxetane/tetrahydrofuran (BAMO/THF) copolymer in a temperature-programmed mode have been investigated by means of DSC, TG-DTG, fast and lower thermolysis/FTIR and TG-MS. The reaction mechanism was proposed. The apparent activation energy and pre-exponential constant of exothermic decomposition reaction of the compound at 0.1 MPa are 167.04 kJ·mol-1 and 1014.41 s-1, respectively. The corresponding critical temperatures of thermal explosion obtained from the onset temperature Te and the peak temperature Tp are 223.20 and 245.78 ℃, respectively. The kinetic equation of the exothermic decomposition process of BAMO/THF at 0.1 MPa could be expressed as:dα/dT= 1015.19 [-ln(1-α)]2/3e-2.009×104/T

  16. Kinetics of the Exothermic Decomposition Reaction of N-Methyl-N-nitro-2,2,2- trinitroethanamine

    Institute of Scientific and Technical Information of China (English)

    陈三平; 胡荣祖; 宋纪蓉; 杨得琐; 高胜利; 赵宏安; 史启祯

    2003-01-01

    The thermal behavior and kinetic parameters of the exothermic decomposition reaction of N-methyl-N-nitro-2,2,2-trinitroethanamine in a temperature-programmed mode have been investigated by means of differential scanning calorimetry (DSC).The kinetic equation of the exothermic decomposition process of the compound is proposed. The values of the apparent activation energy (Ea), pre-exponential factor (A), entropy of activation (ΔS≠ ), enthalpy of activation (ΔH≠ ), and free energy of activation (ΔG≠ ) of this reaction and the critical temperature of thermal explosion of the compound are reported. Information is obtained on the mechanism of the initial stage of the thermal decomposition of the compound.

  17. Pyrolysis kinetics and thermal decomposition behavior of polycarbonate - a TGA-FTIR study

    Directory of Open Access Journals (Sweden)

    Apaydin-Varol Esin

    2014-01-01

    Full Text Available This study covers the thermal degradation of polycarbonate by means of Thermogravimetric Analyzer coupled with Fourier transform infrared spectrometer (TGA-FTIR. Thermogravimetric analysis of polycarbonate was carried out at four different heating rates of 5, 10, 15, and 20°C per minute from 25°C to 1000°C under nitrogen atmosphere. The results indicated that polycarbonate was decomposed in the temperature range of 425-600°C. The kinetic parameters, such as activation energy, pre-exponential factor and reaction order were determined using five different kinetic models; namely Coast-Redfern, Friedman, Kissinger, Flynn-Wall-Ozawa (FWO, and Kissinger-Akahira-Sunose (KAS. Overall decomposition reaction order was determined by Coats-Redfern method as 1.5. Average activation energy was calculated as 150.42, 230.76, 216.97, and 218.56 kJ/mol by using Kissinger, Friedman, FWO, and KAS models, respectively. Furthermore, the main gases released during the pyrolysis of polycarbonate were determined as CO2, CH4, CO, H2O, and other lower molecular weight hydrocarbons such as aldehydes, ketones and carbonyls by using thermogravimetric analyzer coupled with Fourier transform infrared spectrometer.

  18. Symmetry Groups for the Decomposition of Reversible Computers, Quantum Computers, and Computers in between

    Directory of Open Access Journals (Sweden)

    Alexis De Vos

    2011-06-01

    Full Text Available Whereas quantum computing circuits follow the symmetries of the unitary Lie group, classical reversible computation circuits follow the symmetries of a finite group, i.e., the symmetric group. We confront the decomposition of an arbitrary classical reversible circuit with w bits and the decomposition of an arbitrary quantum circuit with w qubits. Both decompositions use the control gate as building block, i.e., a circuit transforming only one (qubit, the transformation being controlled by the other w−1 (qubits. We explain why the former circuit can be decomposed into 2w − 1 control gates, whereas the latter circuit needs 2w − 1 control gates. We investigate whether computer circuits, not based on the full unitary group but instead on a subgroup of the unitary group, may be decomposable either into 2w − 1 or into 2w − 1 control gates.

  19. On submodule characterization and decomposition of modules over group rings

    Science.gov (United States)

    Uc, Mehmet; Alkan, Mustafa

    2017-07-01

    In this paper, for a commutative unity ring R and a finite group G, we characterize some submodule properties of RG- module MG introduced in [8]. Our aim is to decompose MG into RG-submodules by defining an idempotent in EndRG MG and to verify the relation between the quotient of group module and the quotient of related module.

  20. Kinetics of drug decomposition. Part 60. Thermal decomposition of the mixture of aminophenazone, allobarbital and adiphenine hydrochloride in the solid state.

    Science.gov (United States)

    Pawełczyk, E; Marciniec, B

    1981-01-01

    Kinetics of decomposition of a mixture of aminophenazone, allobarbital and adiphenine hydrochloride has been examined using accelerated testing at elevated temperatures (333-353 K). The reaction order, rate constants and activation parameters (Q10 degrees, EA, delta H#, delta S#, delta G) have been determined and compared for each component, in the presence of each component of the mixture and in the presence of two components of the mixture. The effect of individual components of the mixture on the rate of decomposition of the other components has been observed, the value of this effect has been determined using the rate constants obtained. The rate constants and times t10% for room temperature were calculated. The "shelf-life time" (t10%) was calculated from accelerated testing data at elevated temperature and compared with that obtained for Vegantalgin ragées in the mixture studied at 293 K.

  1. Estimation of the kinetic parameters for thermal decomposition of HNIW and its adiabatic time-to-explosion by Kooij formula

    Directory of Open Access Journals (Sweden)

    Hong-xu Gao

    2014-03-01

    Full Text Available A differential/integral method to estimate the kinetic parameters (apparent activation energy Ea and pre-exponential factor A for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane (HNIW by analyzing nonisothermal DSC curve data. The apparent activation energy (Ea obtained by the integral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion (Tb and adiabatic time-to-explosion (tTIad based on Kooij formula are used to calculate the values of Tb and tTIad to evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of Ea and A of decomposition reaction of HNIW are 3(1 − α[−ln(1 − α]2/3, 152.73 kJ mol−1 and 1011.97 s−1, respectively, and the values of self-accelerating decomposition temperature (TSADT, Tb and tTIad are 486.55 K, 493.11 K and 52.01 s, respectively.

  2. Renormalization group improved Higgs inflation with a running kinetic term

    Science.gov (United States)

    Takahashi, Fuminobu; Takahashi, Ryo

    2016-09-01

    We study a Higgs inflation model with a running kinetic term, taking account of the renormalization group evolution of relevant coupling constants. Specifically we study two types of the running kinetic Higgs inflation, where the inflaton potential is given by the quadratic or linear term potential in a frame where the Higgs field is canonically normalized. We solve the renormalization group equations at two-loop level and calculate the scalar spectral index and the tensor-to-scalar ratio. We find that, even if the renormalization group effects are included, the quadratic inflation is ruled out by the CMB observations, while the linear one is still allowed.

  3. Thermal Decomposition Kinetics of APT%APT热分解动力学的研究

    Institute of Scientific and Technical Information of China (English)

    蒋涛; 李军夏; 刘建华; 肖利; 刘永

    2014-01-01

    研究采用热重分析法,获得等速升温条件下APT失重变化与温度变化及反应时间的关系TG曲线。据APT的失重率,绘出DTG曲线,并以TG和DTG曲线为基础,采用非等温动力学的基本方程,对试验数据进行线性回归,建立了APT热分解动力学的数学模型。失重曲线表明APT的热分解是四个阶段进行,第一阶段为126.2℃左右时脱水,第二阶段为209.4℃左右时分解成无定型铵钨青铜(AATB),第三阶段为310.5℃左右时结晶成铵钨青铜(ATB),第四阶段为482.3℃左右时分解成“蓝钨”。试验结果表明:在不同的升温速率条件下,APT热分解的指前因子是随着热解温度的升高而逐渐减小。活化能在第二阶段达到最大值。反应级数在第一、二阶段在0.6~0.76,第三阶段在0.9~1.37,第四阶段为1.0左右。生产中宜采取三段控温,其他阶段控速的方式,提高生产效率,减少能耗。%The TG curve of APT weightlessness and the change of temperature and reaction time under the condition of a constant heating rate were obtained by thermo gravimetric analysis. According to the weight loss rate of APT, the DTG curve was drawn based on the TG and DTG curves. A dynamic model of the thermal decomposition of APT was practiced by using differential method. A linear regression of the experimental data was performed based on the basic equations of the non isothermal kinetics. The weightless curves showed that the thermal decomposition of APT consists of four main stages ,the first dehydration about 126.2 ℃, the second around into amorphous ammonium tungsten bronze(AATB) about 209.4℃, the third crystallized into ammonium tungsten bronze(ATB) about 310.5℃, and the last decomposed into WO3"blue tungsten"about 482.3℃. At each stage of the heating rate respectively is 2 ℃/min, 3 ℃/min and 8 ℃/min conditions. The pre exponential factors of the thermal decomposition of APT

  4. Investigation of Thermal Decomposition of Ascorbic Acid by TG-FTIR and Thermal Kinetics Analysis Shi Jingyan

    Institute of Scientific and Technical Information of China (English)

    史竞艳; LIU; Yuwen; WANG; Zhiyong; WANG; Cunxin

    2014-01-01

    The thermal behavior of dry solid ascorbic acid in nitrogen atmosphere in the temperature range of 25800℃was investigated by TG-FTIR.During the thermal decomposition process,five evolved gaseous species,including H2O,CO2,CO,CH4 and HCOOH,were identified and monitored,in which HCOOH was detected for the first time.The results indicated that ascorbic acid began to decompose at 191℃.Its decomposition process consisted of three stages,and dehydration and decarboxylation to form furfural were the possible principal mechanism.The kinetic analysis for the first decomposition stage was also carried out by the isoconversional method and the master plots method.The results indicated that this process can be described by the model of 1st order reaction.

  5. Kinetics of the decomposition and the estimation of the stability of 10% aqueous and non-aqueous hydrogen peroxide solutions

    Directory of Open Access Journals (Sweden)

    Zun Maria

    2014-12-01

    Full Text Available In this study, the stability of 10% hydrogen peroxide aqueous and non-aqueous solutions with the addition of 6% (w/w of urea was evaluated. The solutions were stored at 20°C, 30°C and 40°C, and the decomposition of hydrogen peroxide proceeded according to first-order kinetics. With the addition of the urea in the solutions, the decomposition rate constant increased and the activation energy decreased. The temperature of storage also affected the decomposition of substance, however, 10% hydrogen peroxide solutions prepared in PEG-300, and stabilized with the addition of 6% (w/w of urea had the best constancy.

  6. Non-isothermal decomposition kinetics and lifetime ofTb2(O-MBA)6(PHEN)2

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jianjun; BAI Jihai; WANG Ruifen; WANG Shuping; LI Jibiao

    2003-01-01

    The thermal decomposition of Tb2(O-MBA)6(PHEN)2 (O-MBA: o-methylbenzoate; PHEN: 1,10-phenanthroline)and its kinetics were studied under the non-isothermal condition by thermogravimetry-derivafive thermogravimetry (TG-DTG) techniques. Kinetic parameters were obtained from analysis of TG-DTG curves by the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method. The most probable mechanism function was suggested by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as dα/dt = Aexp(-E/RT) @ 3(1 - α)2/3. The lifetime equation at mass loss of 10% was deduced as lnτ= -28.7429 + 19797.795/T by isothermal thermogravimetric analysis.

  7. Kinetics of the thermal decomposition of tetramethylsilane behind the reflected shock waves between 1058 and 1194 K

    Indian Academy of Sciences (India)

    A Parandaman; B Rajakumar

    2016-04-01

    Thermal decomposition of tetramethylsilane (TMS) diluted in argon was studied behind the reflected shock waves in a single pulse shock tube (SPST) in the temperature range of 1058–1194 K. The major products formed in the decomposition are methane (CH4) and ethylene (C2H4); whereas ethane and propylene were detected in lower concentrations. The decomposition of TMS seems to be initiated via Si-C bond cission by forming methyl radicals (CH3) and trimethylsilyl radicals ((CH3)3Si). The total rate coefficients obtained for the decomposition of TMS were fit to Arrhenius equation in two different temperature regions 1058–1130K and 1130–1194 K. The temperature dependent rate coefficients obtained are ktotal (1058–1130 K) = (4.61 ± 0.70) × 1018 exp (−(79.9 kcal mol−1 ± 3.5)/RT) −1, ktotal (1130-1194 K) = (1.33 ± 0.19) × 106 exp (−(15.3 kcal mol−1 ± 3.5)/RT) −1. The rate coefficient for the formation of CH4 is obtained to be methane (1058–1194 K) = (4.36 ± 1.23) × 1014 exp (−(61.9 kcal mol−1±4.9)/RT) s−1. A kinetic scheme containing 21 species and 38 elementary reactions was proposed and simulations were carried out to explain the formation of all the products in the decomposition of tetramethylsilane.

  8. Prediction of biodegradation kinetics using a nonlinear group contribution method

    Energy Technology Data Exchange (ETDEWEB)

    Tabak, H.H. (Environmental Protection Agency, Cincinnati, OH (United States)); Govind, R. (Univ. of Cincinnati, OH (United States))

    1993-02-01

    The fate of organic chemicals in the environment depends on their susceptibility to biodegradation. Hence, development of regulations concerning their manufacture and use requires information on the extent and rate of biodegradation. Recent studies have attempted to correlate the kinetics of biodegradation with the molecular structure of the compound. This has led to the development of structure-biodegradation relationships (SBRs) using the group contribution approach. Each defined group present in the chemical structure of the compound is assigned a unique numerical contribution toward the calculation of the biodegradation kinetic constants. In this paper, a nonlinear group contribution method has been developed using neural networks; it is trained using literature data on the first-order biodegradation kinetic rate constant for a number of priority pollutants. The trained neural network is then used to predict the biodegradation kinetic constant for a new list of compounds, and results have been compared with the experimental values and the predictions obtained from a linear group contribution method. It has been shown that the nonlinear group contribution method using neural networks is able to provide a superior fit to the training set data and test data set and produce a lower prediction error than the previous linear method.

  9. Solution for the nuclear reactor point-kinetics problem via decomposition method; Solucao via metodo da decomposicao do problema de cinetica puntual de um reator nuclear

    Energy Technology Data Exchange (ETDEWEB)

    Vargas, Rubem Mario Figueiro [Pontificia Univ. Catolica do Rio Grande do Sul, Porto Alegre, RS (Brazil). Faculdade de Engenharia. Dept. de Engenharia Quimica]. E-mail: rvargas@pucrs.br; Vilhena, Marco Tullio de [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Matematica]. E-mail: vilhena@mat.ufrgs.br; Cardona, Augusto Vieira [Pontificia Univ. Catolica do Rio Grande do Sul, Porto Alegre, RS (Brazil). Faculdade de Matematica]. E-mail: acardona@pucrs.br

    2005-07-01

    The decomposition method is a mathematical technique, usually, applied to solve nonlinear problems, but can be an effective procedure for analytical solution of linear problems presenting advantages when compared with others techniques. In this work, an analytical solution for the nuclear reactor point-kinetics equations is developed using the decomposition method. (author)

  10. Thermodynamics and kinetics of NaAlH4 nanocluster decomposition.

    Science.gov (United States)

    Bhakta, Raghunandan K; Maharrey, Sean; Stavila, Vitalie; Highley, Aaron; Alam, Todd; Majzoub, Eric; Allendorf, Mark

    2012-06-14

    Reactive nanoparticles are of great interest for applications ranging from catalysis to energy storage. However, efforts to relate cluster size to thermodynamic stability and chemical reactivity are hampered by broad pore size distributions and poorly characterized chemical environments in many microporous templates. Metal hydrides are an important example of this problem. Theoretical calculations suggest that reducing their critical dimension to the nanoscale can in some cases considerably destabilize these materials and there is clear experimental evidence for accelerated kinetics, making hydrogen storage applications more attractive in some cases. However, quantitative measurements establishing the influence of size on thermodynamics are lacking, primarily because carbon aerogels often used as supports provide inadequate control over size and pore chemistry. Here, we employ the nanoporous metal-organic framework (MOF) Cu-BTC (also known as HKUST-1) as a template to synthesize and confine the complex hydride NaAlH(4). The well-defined crystalline structure and monodisperse pore dimensions of this MOF allow detailed, quantitative probing of the thermodynamics and kinetics of H(2) desorption from 1-nm NaAlH(4) clusters (NaAlH(4)@Cu-BTC) without the ambiguity associated with amorphous templates. Hydrogen evolution rates were measured as a function of time and temperature using the Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry method, in which sample mass changes are correlated with a complete analysis of evolved gases. NaAlH(4)@Cu-BTC undergoes a single-step dehydrogenation reaction in which the Na(3)AlH(6) intermediate formed during decomposition of the bulk hydride is not observed. Comparison of the thermodynamically controlled quasi-equilibrium reaction pathways in the bulk and nanoscale materials shows that the nanoclusters are slightly stabilized by confinement, having an H(2) desorption enthalpy that is 7 kJ (mol H(2))(-1) higher than the

  11. Facile synthesis of hydrotalcite and its thermal decomposition kinetics mechanism study with masterplots method

    Energy Technology Data Exchange (ETDEWEB)

    Long, Qiwei; Xia, Yao [Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004 (China); Liao, Sen, E-mail: liaosen@gxu.edu.cn [Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004 (China); Li, Yu; Wu, Wenwei [Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004 (China); Huang, Yingheng [Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004 (China); School of Materials Science and Engineering, Guangxi University, Nanning, Guangxi 530004 (China)

    2014-03-01

    Graphical abstract: - Highlights: • The values of E{sub α} were determined with advanced isoconversional procedure. • Masterplots and nonlinear methods were used to study the mechanisms. • Mechanism equations obtained from the two methods are the same. • Nonlinear method is more efficient than Masterplots method. - Abstract: The hydrotalcite, Mg{sub 4}Al{sub 2}(OH){sub 12}CO{sub 3}·3H{sub 2}O, was synthesized via low-heating solid-state reaction at 80 °C. The thermal decomposition of Mg{sub 4}Al{sub 2}(OH){sub 12}CO{sub 3}·3H{sub 2}O experienced two stages. The apparent activation energy E{sub a} was estimated with Vyazovkin procedure. The average values of E{sub a} associated with the two stages were determined to be 110.9 ± 10.3, 140.3 ± 4.2 kJ mol{sup −1}, respectively, which the two stages are single-step kinetic processes. Masterplots and nonlinear methods were used to define the most probable reaction mechanisms of the two stages. The results show that the reaction mechanism functions of the two stages are as follows: (i) g(α) = (1 − α){sup −2} − 1, (ii) g(α) = (1 − α){sup −1/2} − 1, respectively. The values of pre-exponential factor A for the two stages were obtained on the basis of E{sub a} and g(α). Besides, some thermodynamic functions (ΔS{sup #}, ΔH{sup #} and ΔG{sup #}) of the transition state complexes for the two stages were also calculated.

  12. A STUDY OF THE PROPERTIES OF CP: COEFFICIENT OF THERMAL EXPANSION, DECOMPOSITION KINETICS AND REACTION TO SPARK, FRICTION AND IMPACT

    Energy Technology Data Exchange (ETDEWEB)

    Weese, R K; Burnham, A K; Fontes, A T

    2005-03-30

    The properties of pentaamine (5-cyano-2H-tetrazolato-N2) cobalt (III) perchlorate (CP), which was first synthesized in 1968, continues to be of interest for predicting behavior in handling, shipping, aging, and thermal cook-off situations. We report coefficient of thermal expansion (CTE) values over four specific temperature ranges, decomposition kinetics using linear heating rates, and the reaction to three different types of stimuli: impact, spark, and friction. The CTE was measured using a Thermal Mechanical Analyzer (TMA) for samples that were uniaxially compressed at 10,000 psi and analyzed over a dynamic temperature range of -20 C to 70 C. Using differential scanning calorimetry, DSC, CP was decomposed at linear heating rates of 1, 3, and 7 C/min and the kinetic triplet calculated using the LLNL code Kinetics05. Values are also reported for spark, friction, and impact sensitivity.

  13. Mechanistic and Kinetic Analysis of Na2SO4-Modified Laterite Decomposition by Thermogravimetry Coupled with Mass Spectrometry.

    Directory of Open Access Journals (Sweden)

    Song Yang

    Full Text Available Nickel laterites cannot be effectively used in physical methods because of their poor crystallinity and fine grain size. Na2SO4 is the most efficient additive for grade enrichment and Ni recovery. However, how Na2SO4 affects the selective reduction of laterite ores has not been clearly investigated. This study investigated the decomposition of laterite with and without the addition of Na2SO4 in an argon atmosphere using thermogravimetry coupled with mass spectrometry (TG-MS. Approximately 25 mg of samples with 20 wt% Na2SO4 was pyrolyzed under a 100 ml/min Ar flow at a heating rate of 10°C/min from room temperature to 1300°C. The kinetic study was based on derivative thermogravimetric (DTG curves. The evolution of the pyrolysis gas composition was detected by mass spectrometry, and the decomposition products were analyzed by X-ray diffraction (XRD. The decomposition behavior of laterite with the addition of Na2SO4 was similar to that of pure laterite below 800°C during the first three stages. However, in the fourth stage, the dolomite decomposed at 897°C, which is approximately 200°C lower than the decomposition of pure laterite. In the last stage, the laterite decomposed and emitted SO2 in the presence of Na2SO4 with an activation energy of 91.37 kJ/mol. The decomposition of laterite with and without the addition of Na2SO4 can be described by one first-order reaction. Moreover, the use of Na2SO4 as the modification agent can reduce the activation energy of laterite decomposition; thus, the reaction rate can be accelerated, and the reaction temperature can be markedly reduced.

  14. The Iwasava decomposition and intermediate subgroups of the Steinberg groups over the field of fractions of a principal ideal ring

    Institute of Scientific and Technical Information of China (English)

    MOISEENKOVA; T.; V.; NUZHIN; Ya.; N.

    2009-01-01

    The Iwasava decomposition is proved for the Steinberg groups of types 2A2l-1, 2Dl, 2E6, 3D4 over the field of fractions of a principal ideal ring. By using this decomposition, it is described that subgroups exist between the Steinberg groups over the rings D and K under some restrictions on the ring D.

  15. Preparation, non-isothermal decomposition kinetics, heat capacity and adiabatic time-to-explosion of NTOxDNAZ.

    Science.gov (United States)

    Ma, Haixia; Yan, Biao; Li, Zhaona; Guan, Yulei; Song, Jirong; Xu, Kangzhen; Hu, Rongzu

    2009-09-30

    NTOxDNAZ was prepared by mixing 3,3-dinitroazetidine (DNAZ) and 3-nitro-1,2,4-triazol-5-one (NTO) in ethanol solution. The thermal behavior of the title compound was studied under a non-isothermal condition by DSC and TG/DTG methods. The kinetic parameters were obtained from analysis of the DSC and TG/DTG curves by Kissinger method, Ozawa method, the differential method and the integral method. The main exothermic decomposition reaction mechanism of NTOxDNAZ is classified as chemical reaction, and the kinetic parameters of the reaction are E(a)=149.68 kJ mol(-1) and A=10(15.81)s(-1). The specific heat capacity of the title compound was determined with continuous C(p) mode of microcalorimeter. The standard mole specific heat capacity of NTOxDNAZ was 352.56 J mol(-1)K(-1) in 298.15K. Using the relationship between C(p) and T and the thermal decomposition parameters, the time of the thermal decomposition from initialization to thermal explosion (adiabatic time-to-explosion) was obtained.

  16. Thermal decomposition behavior of amino groups modified bimodal mesoporous silicas as aspirin carrier.

    Science.gov (United States)

    Gao, Lin; Sun, Jihong; Zhang, Li; Li, Yuzhen; Ren, Bo

    2011-12-01

    Two kinds of amino groups were employed to functionalize bimodal mesoporous silicas and related drug carriers were prepared. The characterization results of XRD, N2 adsorption and desorption, FT-IR and TG all confirmed the structural integrity of the bimodal mesopore architecture after introduction treatment of functional groups and the successful adsorption of aspirin. In order to investigate the interaction among the mesoporous structure, the functional groups grafted onto the mesoporous surface and the existential microenvironment of the drug molecules inside the mesoporous channels, the thermal decomposition behaviors of amino groups modified and aspirin loaded carriers were studied based on the thermogravimetric analysis in details. According to the thermogravimetry and derivative thermogravimetry results, the apparent activation energies E(a) of thermal decomposition for all related samples have been evaluated by Kissinger and Flynn-Wall-Ozawa methods. Meanwhile, their thermal decomposition mechanisms have been suggested by using Coats and Redfern methods. All these featured consequence could provide a deeper understanding for large loading capacity and controlled release of drug-carriers in the pharmaceutical application.

  17. Syntheses, Crystal Structures and Kinetic Mechanisms of Thermal Decomposition of Rare Earth Complexes with Schiff Base Derived from o-Vanillin and p-Toluidine

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Three complexes, [Pr(NO3)3(HL)2] (1), [Nd(NO3)3(HL)2] (2) and [Er(NO3)3(HL)2] ·0.5H2O (3),were synthesized from the reaction of a Schiff base ligand 2-[ (4-methylphenylimino)methyl ]-6-methoxyphenol (C15 H15 mental analysis, molar conductance, FT-IR, UV-Vis, 1H NMR and thermal analysis shows the title complexes are neutral molecules where the central Ln( Ⅲ ) ion is ten-coordinated in biapical anti-hexahedron prism geometry, with four oxygen atoms of the phenolic hydroxy and methoxy groups in the two bidentate Schiff base ligands and six oxygen atoms provided by the three bidentate NO3- anions. Additionally, the kinetic mechanism of thermal decomposition of complex 3 was determined with a TG-DTG curves by both integral and differential methods. The functions of thermal decomposition reaction mechanism and the equation of kinetic compensation effect were obtained.

  18. Synthesis and Thermal Decomposition Kinetics of the Complex of Samarium p-Methylbenzoate with 1 ,1O-Phenanthroline

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Jian-Jun; REN,Ning; XU,Su

    2007-01-01

    The complex [Sm(p-MBA)3phen]2 (p-MBA, p-methylbenzoate; phen, 1,10-phenanthroline) was prepared and characterized by elemental analysis, IR and UV spectra. The thermal decomposition process of [Sm(p-MBA)3phen]2 was studied under a static air atmosphere by TG-DTG and IR techniques. Thermal decomposition kinetics was investigated employing a newly proposed method, together with the integral isoconversional non-linear method. Meanwhile, the thermodynamic parameters (△H≠, AG≠ and △S≠) were also calculated. The lifetime equation at mass-loss of 10% was deduced as lnτ= -24.7825+18070.43/T by isothermal thermogravimetric analysis.

  19. Thermal decomposition and kinetic evaluation of decanted 2,4,6-trinitrotoluene (TNT) for reutilization as composite material

    Science.gov (United States)

    Ahmed, M. F.; Hussain, A.; Malik, A. Q.

    2016-08-01

    Use of energetic materials has long been considered for only military purposes. However, it is very recent that their practical applications in wide range of commercial fields such as mining, road building, under water blasting and rocket propulsion system have been considered. About 5mg of 2,4,6-trinitrotoluene (TNT) in serviceable (Svc) as well as unserviceable (Unsvc) form were used for their thermal decomposition and kinetic parameters investigation. Thermogravimetric/ differential thermal analysis (TG/DTA), X-ray diffraction (XRD) and Scanning electron microscope (SEM) were used to characterize two types of TNT. Arrhenius kinetic parameters like activation energy (E) and enthalpy (AH) of both TNT samples were determined using TG curves with the help of Horowitz and Metzger method. Simultaneously, thermal decomposition range was evaluated from DTA curves. Distinct diffraction peaks showing crystalline nature were obtained from XRD analysis. SEM results indicated that Unsvc TNT contained a variety of defects like cracks and porosity. Similarly, it is observed that thermal as well as kinetic behavior of both TNT samples vary to a great extent. Likewise, a prominent change in the activation energies (E) of both samples is observed. This in-depth study provides a way forward in finding solutions for the safe reutilization of decanted TNT.

  20. Experimental investigation on the heterogeneous kinetic process of the low thermal decomposition of ammonium perchlorate particles

    Energy Technology Data Exchange (ETDEWEB)

    Longuet, Baptiste [Laboratoire Energetique Explosions et Structures Universite d' Orleans (Germany); Gillard, Philippe [Laboratoire Energetic Explosions et Structures, Universite d' Orleans, Bourges (France)

    2009-02-15

    The thermal decomposition of ammonium perchlorate has been extensively studied in the past. Nevertheless, the various results published illustrate, on the one hand, significant differences regarding the influence of different parameters on the decomposition and on the other hand, a lack of useful quantitative laws to predict the thermal behaviour of this crystal under a range of conditions (temperature, duration of exposure, presence of confinement). (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  1. Kinetics of Thermal Decomposition for Complex [Zn(C16H18FN3O3)2(NO3)2]*2H2O

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The thermal decomposition reaction of the [Zn(NFA)2(NO3)2]*2H2O(NFA=C16H18FN3O3,norfloxacin) was studied in a static atmosphere using TG-DTG and DTA methods. The thermal decomposition processes of the complex were determined and its kinetics was investigated. The kinetic parameters were obtained from analysis of the TG-DTG curves by differential and integral methods. The most pro- bable mechanism for the second stage was suggested by comparision of the kinetic parameters.

  2. LES and Proper Orthogonal Decomposition analysis of vertical entrainment of kinetic energy in large wind farms (Invited)

    Science.gov (United States)

    Meneveau, C. V.; VerHulst, C.

    2013-12-01

    Vertical entrainment of kinetic energy has been shown to be an important limiting factor in the performance of very large wind turbine arrays. Given high Reynolds numbers and domain sizes on the order of kilometers, we rely on wall-modeled Large Eddy Simulation (LES) to predict flow within large wind farm. We use Proper Orthogonal Decomposition (POD) to identify energetically important large-scale structures in the flow. The primary large-scale structures are found to be streamwise counter-rotating vortices located above the height of the wind turbines. The contribution of each flow structure to the kinetic energy entrainment is quantified. Surprisingly, fewer flow structures (POD modes) contribute to the vertical kinetic energy flux than to the kinetic energy in the flow, for which the POD analysis is optimal. While the general characteristics of the flow structures are robust, the net kinetic energy entrainment to the turbines depends on the orientation of the wind turbines in the array. The various modes' contributions to variability and intermittency is also quantified. The POD analysis is performed for aligned and staggered wind turbine arrays as well as for atmospheric flow without wind turbines. This research is supported by a NSF Graduate Fellowship and by the WINDINSPIRE project, funded through NSF-OISE 1243482.

  3. Interactive plant functional group and water table effects on decomposition and extracellular enzyme activity in Sphagnum peatlands

    Science.gov (United States)

    Magdalena M. Wiedermann; Evan S. Kane; Lynette R. Potvin; Erik A. Lilleskov

    2017-01-01

    Peatland decomposition may be altered by hydrology and plant functional groups (PFGs), but exactly how the latter influences decomposition is unclear, as are potential interactions of these factors.We used a factorial mesocosm experiment with intact 1 m3 peat monoliths to explore how PFGs (sedges vs Ericaceae) and water table level individually...

  4. Active space decomposition with multiple sites: Density matrix renormalization group algorithm

    CERN Document Server

    Parker, Shane M

    2014-01-01

    We extend the active space decomposition method, recently developed by us, to more than two active sites using the density matrix renormalization group algorithm. The fragment wave functions are described by complete or restricted active-space wave functions. Numerical results are shown on a benzene pentamer and a perylene diimide trimer. It is found that the truncation errors in our method decrease almost exponentially with respect to the number of renormalization states M, allowing for numerically exact calculations (to a few {\\mu}Eh or less) with M = 128 in both cases, which is in contrast to conventional ab initio density matrix renormalization group.

  5. Kinetics of phycocyanine bilin groups destruction by peroxyl radicals.

    Science.gov (United States)

    Lissi, E A; Pizarro, M; Aspee, A; Romay, C

    2000-04-01

    Bilin groups in c-phycocyanine are readily bleached by peroxyl radicals produced in the thermolysis of 2, 2'-azobis(2-amidinopropane). From an evaluation of the bilin groups destroyed per radical that interacts with the protein, it is concluded that the bilin moiety is the main target of the radicals. Kinetic expressions are derived that allows an estimation of the substrate reactivity from the analysis of the rate of bilin group modification as a function of the protein concentration. From this analysis it is concluded that micromolar concentrations of c-phycocyanine are able to reduce the steady state concentration of the peroxyl radicals by one half, indicating a high antioxidant activity for this compound. This conclusion is confirmed by measuring the capacity of the protein to protect 1-naphthol from modification by peroxyl radicals. The results obtained show that the bilin groups have, on a molar basis, an antioxidant activity similar to that of potent antioxidants such as catechin.

  6. Kinetic and thermodynamics studies on the decompositions of Ni{sub 3}C in different atmospheres

    Energy Technology Data Exchange (ETDEWEB)

    Leng Yonghua; Xie Lei; Liao Fuhui; Zheng Jie [Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Li Xingguo [Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); College of Engineering, Peking University, Beijing 100871 (China)], E-mail: xgli@pku.edu.cn

    2008-07-10

    The thermal decompositions (including TG and DSC) of nickel carbide were studied under different atmospheres of Ar, air and H{sub 2}. X-ray diffraction combined with element analysis indicated that nickel metal, together with solid amorphous carbon, was formed during Ni{sub 3}C decomposition in Ar atmosphere, accompanying mass invariant in this process. While in H{sub 2} atmosphere nickel metal was the only residual from reactions. The carbon component of nickel carbide reacted with H{sub 2} to form methane as the main volatile gases. Both the nickel and carbon components of Ni{sub 3}C reacted with O{sub 2} in the air to form their corresponding oxides. Moreover, we calculated the activation energy for the decomposition process and the molar enthalpy of formation of Ni{sub 3}C based on the thermal analysis.

  7. A kinetic study on decomposition of proton-bound dimer using data obtained by ion mobility spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Jazan, Elham, E-mail: jazan@iaush.ac.ir; Ghazali Khoob, Abdolhosein S.

    2014-08-17

    Graphical abstract: - Highlights: • The capability of corona discharge-IMS for easy study of kinetic properties was confirmed. • An equation for measuring the rate constant of the proton-bound dimer decomposition reaction was derived. • The effects of temperatures and sample concentration were investigated for monomer–dimer tail. - Abstract: In this study, an equation for measuring the rate constant of the proton-bound dimer decomposition reaction was derived using the data obtained by ion mobility spectrometry (IMS) technique. The ion mobility spectra of cyclohexanone (as the test compound) were obtained at various temperatures and different electric fields. The applied electric field for each temperature was varied between 375 and 500 V cm{sup −1} and the rate constant values of 188.24, 180.54, 280.64, 288.34 and 379.60 s{sup −1} were obtained at different temperatures of 463, 468, 473, 478 and 483 K, respectively. Subsequently, the activation energy and pre-exponential factor were calculated to be 69.5 kJ mol{sup −1} and 1.2 × 10{sup 10} s{sup −1}, respectively. In addition, the standard enthalpy changes were calculated for the dimer decomposition reaction of cyclohexanone at the above-mentioned temperatures.

  8. Thermal decomposition and kinetics of 2,4-dinitroimidazole: An insensitive high explosive

    Energy Technology Data Exchange (ETDEWEB)

    Anniyappan, M., E-mail: anniorganic@rediffmail.com; Sonawane, S.H.; Pawar, S.J.; Sikder, A.K.

    2015-08-20

    Highlights: • Pure 2,4-dinitroimidazole was prepared by re-crystallization from hot methanol. • A detailed thermal analysis of 2,4-DNI by DSC, TGA, GC–MS and ignition temperature. • Activation energy was calculated for thermal decomposition of 2,4-DNI • Effect of polymeric binder on thermal decomposition of 2,4-DNI were also studied. • Decomposition mechanisms of 2,4-DNI based on EI mass spectra were also described. - Abstract: 2,4-Dinitroimidazole (2,4-DNI) is a novel energetic material with much less sensitive and potential for use as a propellant/insensitive munition (IM) formulations. 2,4-DNI possess high thermal stability and less sensitivity as compared to RDX and HMX which are high explosives extensively used at present. This paper reports a detailed thermal study of 2,4-DNI using various instrumental techniques. The activation energy (E = 205 ± 15 kJ/mol) was calculated from thermal decomposition of 2,4-DNI using DSC at different heating rate. The ignition temperature of pure 2,4-DNI was measured and showed at 285 °C. The TGA experiments demonstrate that 2,4-DNI decomposes in three steps with 92% total weight lose. Moreover, the effect of thermal energy on decomposition of 2,4-DNI in presence of polymeric binders like GAP and HTPB were investigated. Further, decomposition mechanisms of 2,4-DNI based on Electron Impact mass spectra analysis were also reported along with its explosive properties.

  9. 葡萄糖酸亚锡热分解动力学%Thermal Decomposition Kinetics of Stannous Gluconate

    Institute of Scientific and Technical Information of China (English)

    曹亚蒙; 周彩荣; 刘中平

    2015-01-01

    Stannous gluconate was synthesized with D-Gluconic acid-δ-lactone and stannous oxide. It was characterized by FTIR techniques to speculate the formula ( SnC6 H10 O7 ) . The thermal decomposition and non-isothermal decomposition kinetic of stannous gluconate was investigated by the Differential Thermal Analysis and Thermogravimetric Analysis in nitrogen atmosphere. The mechanism function and kinetic parameters were obtained by the Flynn-Wall-Ozawa, Kissinger and Šstava-Šesta’ k methods. The results showed that the thermal decomposition was divided into two stages, the thermal decomposition tempera-ture range of first stage was 373 ~603 K, another was 603 ~733 K, the thermal decomposition meth-anism functions of them are Avrami-Erofeev equation, and the reaction orders ( n) are 3 and 1/3, re-spectively. Moreover, the enthalpy change, entropy change and the change of Gibbs free energy were ob-tained, which can contribute to industrial production and application of stannous gluconate.%以葡萄糖酸内酯和氧化亚锡为原料,制备葡萄糖酸亚锡并研究其热行为.用红外光谱和元素分析法对产物进行了表征,推测出该化合物的分子式是SnC6 H10 O7.用热重分析法( DTA-TGA)研究了葡萄糖酸亚锡在N2气氛中的热分解行为及动力学规律.用Flynn-Wall-Ozawa、Kissinger和Šstava-Šesta’ k法对非等温动力学数据进行了分析.结果表明,热分解过程分为2个阶段,第1阶段热分解温度范围为373~603 K,积分表达式为 g (α)=[-ln (1-α)]3;第2阶段热分解温度范围为603~733 K,积分表达式为g(α)=[-ln(1-α)]1/3,同时,得到分解过程的焓变、熵变和Gibbs自由能的变化量,为葡萄糖酸亚锡的工程设计、工业生产奠定基础.

  10. Determination of the Thermal Decomposition Kinetics of Polyurethane Foam by Guggenheim’s Method

    Science.gov (United States)

    1981-03-01

    34Nonisothermal Chemical Kinetics," Nature, 228, (1970). 11 E.L. Simmons and W.W. Wendlandt, "Nonisothermal Rate Equations," Thermochimica Acta , 3...11. E.L. Simmons and W.W. Wendlandt, "Nonisothermal Rate Equations," Thermochimica Acta , 3, 498 (1972). 12. P.D. Garn, "Nonisothermal Kinetics

  11. Non-isothermal kinetics of the first-stage decomposition reaction of the complex of samarium p-methoxybenzoate with 1,10-phenanthroline

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jianjun; REN Ning; CHAI Xingquan; WANG Yanxun

    2007-01-01

    The complex of [Sm(p-MOBA)3phen]2 (p-MOBA, p-methoxybenzoate; phen, 1,10-phenanthroline) was prepared and characterized by elemental analysis, IR, and UV spectroscopy. The thermal decomposition of the [Sm(p-MOBA)3phen]2 complex and its kinetics were studied under a static air atmosphere by TG-DTG methods. The intermediate and residue for each decomposition stage were identified from the TG curve. The kinetic parameters and mechanisms of the first decomposition stage were obtained from the analysis of the TG-DTG curves by a new method of processing the data of thermal analysis kinetics. The lifetime equation at a mass loss of 10% was deduced as lnτ= - 30.6795 +21034.56/T by isothermal thermogravimetric analysis.

  12. Communication: Active space decomposition with multiple sites: Density matrix renormalization group algorithm

    Energy Technology Data Exchange (ETDEWEB)

    Parker, Shane M.; Shiozaki, Toru [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208 (United States)

    2014-12-07

    We extend the active space decomposition method, recently developed by us, to more than two active sites using the density matrix renormalization group algorithm. The fragment wave functions are described by complete or restricted active-space wave functions. Numerical results are shown on a benzene pentamer and a perylene diimide trimer. It is found that the truncation errors in our method decrease almost exponentially with respect to the number of renormalization states M, allowing for numerically exact calculations (to a few μE{sub h} or less) with M = 128 in both cases. This rapid convergence is because the renormalization steps are used only for the interfragment electron correlation.

  13. Communication: Active space decomposition with multiple sites: density matrix renormalization group algorithm.

    Science.gov (United States)

    Parker, Shane M; Shiozaki, Toru

    2014-12-07

    We extend the active space decomposition method, recently developed by us, to more than two active sites using the density matrix renormalization group algorithm. The fragment wave functions are described by complete or restricted active-space wave functions. Numerical results are shown on a benzene pentamer and a perylene diimide trimer. It is found that the truncation errors in our method decrease almost exponentially with respect to the number of renormalization states M, allowing for numerically exact calculations (to a few μE(h) or less) with M = 128 in both cases. This rapid convergence is because the renormalization steps are used only for the interfragment electron correlation.

  14. Decomposition of spinor groups by the involution {\\sigma}' in exceptional Lie groups

    CERN Document Server

    Miyashita, Toshikazu

    2010-01-01

    The compact exceptional Lie groups F4, E6, E7 and E8 have spinor groups as a subgroup as follows: E8 \\supset Ss(16) \\supset Spin(15) \\supset Spin(14) \\supset Spin(13), E7 \\supset Spin(12) \\supset Spin(11), E6 \\supset Spin(10), F4 \\supset Spin(9) \\supset Spin(8) \\supset Spin(7) \\supset \\cdot \\cdot \\cdot \\supset Spin(1) \

  15. Thermal Decomposition of Methyl Esters in Biodiesel Fuel: Kinetics, Mechanisms and Products

    Science.gov (United States)

    Chai, Ming

    Biodiesel continues to enjoy increasing popularity. However, recent studies on carbonyl compounds emissions from biodiesel fuel are inconclusive. Emissions of carbonyl compounds from petroleum diesel fuels were compared to emissions from pure biodiesel fuels and petroleum-biodiesel blends used in a non-road diesel generator. The concentration of total carbonyl compounds was the highest when the engine was idling. The carbonyl emissions, as well as ozone formation potential, from biodiesel fuel blends were higher than those emitted from petroleum diesel fuel. The sulfur content of diesel fuel and the source of biodiesel fuel were not found to have a significant impact on emissions of carbonyl compounds. Mechanism parameters of the thermal decomposition of biodiesel-range methyl esters were obtained from the results of thermal gravimetric analysis (TGA). The overall reaction orders are between 0.49 and 0.71 and the energies of activation are between 59.9 and 101.3 kJ/mole. Methyl esters in air have lower activation energies than those in nitrogen. Methyl linoleate has the lowest activation energy, followed by methyl oleate, and methyl stearate. The pyrolysis and oxidation of the three methyl esters were investigated using a semi-isothermal tubular flow reactor. The profiles of major products versus reaction temperature are presented. In the pyrolysis of methyl stearate, the primary reaction pathway is the decarboxylic reaction at the methyl ester functional group. Methyl oleate's products indicate more reactions on its carbon-carbon double bond. Methyl linoleate shows highest reactivity among the three methyl esters, and 87 products were detected. The oxidation of three methyl esters resulted in more products in all compound classes, and 55, 114, and 127 products were detected, respectively. The oxidation of methyl esters includes decarboxylation on ester group. The methyl ester's carbon chain could be oxidized as a hydrocarbon compound and form oxidized esters and

  16. Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study

    Science.gov (United States)

    Nguyen, Thanh Lam; McCaslin, Laura; McCarthy, Michael C.; Stanton, John F.

    2016-10-01

    The thermal decomposition of syn-ethanal-oxide (syn-CH3CHOO) through vinyl hydrogen peroxide (VHP) leading to hydroxyl radical is characterized using a modification of the HEAT thermochemical protocol. The isomerization step of syn-CH3CHOO to VHP via a 1,4 H-shift, which involves a moderate barrier of 72 kJ/mol, is found to be rate determining. A two-dimensional master equation approach, in combination with semi-classical transition state theory, is employed to calculate the time evolution of various species as well as to obtain phenomenological rate coefficients. This work suggests that, under boundary layer conditions in the atmosphere, thermal unimolecular decomposition is the most important sink of syn-CH3CHOO. Thus, the title reaction should be included into atmospheric modeling. The fate of cold VHP, the intermediate stabilized by collisions with a third body, has also been investigated.

  17. Computational study on decomposition kinetics of CH3CFClO radical

    Indian Academy of Sciences (India)

    Hari Ji Singh; Bhupesh Kumar Mishra

    2011-09-01

    The present study deals with the decomposition of haloalkoxy radical (CH3CFClO) formed from 1,1-dichloro-1-fluoroethane (HCFC-141b) in the atmosphere. The sudy is performed using ab-initio quantum mechanical methods. Out of the three plausible pathways of decomposition of the titled species, the one that involved the C-C bond scission and the other occurring via Cl-atom elimination have been considered for detailed study. The geometries of the reactant, products and transition states involved in the decomposition pathways are optimized and characterized at MP2 level of theory using 6-311G(d,p) basis set. Single point energy calculations have been performed at G2(MP2) level of theory. The path involving the Cl-elimination is found to be dominant and found to occur with a barrier height of 3.6 kcal mol-1 whereas the C-C bond scission path proceeds with a barrier of 10.0 kcal mol-1. The thermal rate constants for the above two decomposition pathways are evaluated using Canonical Transition State Theory (CTST) and these are found to be 2.9 × 108 s−1 and 4.3 × 105 s−1 for Cl-elimination and C-C bond scission respectively at 298 K and 1 atm. pressure. The existence of transition states on the corresponding potential energy surface is ascertained by the occurrence of only one imaginary frequency obtained during the frequency calculation. The Intrinsic Reaction Coordinate (IRC) calculation has also been performed to confirm the smooth connection of the TS to the reactant and the products.

  18. Determination of Kinetic Parameters for Thermal Decomposition of Phenolic Ablative Materials by Multiple Heating Rate Method

    Science.gov (United States)

    1980-07-01

    the ratio method to analyze thermogravimetric data obtained for a urethane polymer. Baer, Hedges, Seader , Jayakar, and Wojcik6 heated samples of...reinforced polymers at heating rates up to 4200°C/min. The data were correlated by a numerical technique developed by Burningham and Seader .7 Friedman...Decomposition Through Thermogravimetric Analysis," Thermochimica Acta, No, 1, (1970), pp. 147-158. 6. A. D. Baer, J. H. Hedges, J. D. Seader , K. M. Jayakar

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

    Science.gov (United States)

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

    2016-09-01

    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.

  20. Chemical decomposition of 5-aza-2'-deoxycytidine (Decitabine): kinetic analyses and identification of products by NMR, HPLC, and mass spectrometry.

    Science.gov (United States)

    Rogstad, Daniel K; Herring, Jason L; Theruvathu, Jacob A; Burdzy, Artur; Perry, Christopher C; Neidigh, Jonathan W; Sowers, Lawrence C

    2009-06-01

    The nucleoside analogue 5-aza-2'-deoxycytidine (Decitabine, DAC) is one of several drugs in clinical use that inhibit DNA methyltransferases, leading to a decrease of 5-methylcytosine in newly replicated DNA and subsequent transcriptional activation of genes silenced by cytosine methylation. In addition to methyltransferase inhibition, DAC has demonstrated toxicity and potential mutagenicity, and can induce a DNA-repair response. The mechanisms accounting for these events are not well understood. DAC is chemically unstable in aqueous solutions, but there is little consensus between previous reports as to its half-life and corresponding products of decomposition at physiological temperature and pH, potentially confounding studies on its mechanism of action and long-term use in humans. Here, we have employed a battery of analytical methods to estimate kinetic rates and to characterize DAC decomposition products under conditions of physiological temperature and pH. Our results indicate that DAC decomposes into a plethora of products, formed by hydrolytic opening and deformylation of the triazine ring, in addition to anomerization and possibly other changes in the sugar ring structure. We also discuss the advantages and problems associated with each analytical method used. The results reported here will facilitate ongoing studies and clinical trials aimed at understanding the mechanisms of action, toxicity, and possible mutagenicity of DAC and related analogues.

  1. Decomposition Mechanisms and Kinetics of Novel Energetic Molecules BNFF-1 and ANFF-1: Quantum-Chemical Modeling

    Directory of Open Access Journals (Sweden)

    Maija M. Kuklja

    2013-07-01

    Full Text Available Decomposition mechanisms, activation barriers, Arrhenius parameters, and reaction kinetics of the novel explosive compounds, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl-1,2,5-oxadiazole (BNFF-1, and 3-(4-amino-1,2,5-oxadiazol-3-yl-4-(4-nitro-1,2,5-oxadiazol-3-yl-1,2,5-oxadiazole (ANFF-1 were explored by means of density functional theory with a range of functionals combined with variational transition state theory. BNFF-1 and ANFF-1 were recently suggested to be good candidates for insensitive high energy density materials. Our modeling reveals that the decomposition initiation in both BNFF-1 and ANFF-1 molecules is triggered by ring cleavage reactions while the further process is defined by a competition between two major pathways, the fast C-NO2 homolysis and slow nitro-nitrite isomerization releasing NO. We discuss insights on design of new energetic materials with targeted properties gained from our modeling.

  2. Non isothermal decomposition of lanthanum titanates precursors prepared by sol gel process: A kinetic and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Bassil, S. [Université Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de recherches sur la catalyse et l’environnement de Lyon, 2 avenue Albert Einstein, F-69626 Villeurbanne (France); Kaddouri, A., E-mail: akim.kaddouri@ircelyon.univ-lyon1.fr [Université Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de recherches sur la catalyse et l’environnement de Lyon, 2 avenue Albert Einstein, F-69626 Villeurbanne (France); Béguin, B.; Gélin, P. [Université Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de recherches sur la catalyse et l’environnement de Lyon, 2 avenue Albert Einstein, F-69626 Villeurbanne (France)

    2013-09-10

    Highlights: ► Metal-propionates is a most promising route for the preparation of La{sub 0.8}Sr{sub 0.2}TiO{sub 3+δ} (LST) at a temperature substantially lower than that used for the preparation of the same solid by traditional methods. ► Activation energy and isothermal thermodynamic parameters calculated for the decomposition process are close to those observed for metal organic compounds. ► Sol gel-prepared LST presented low propensity to coke deposition and high stability with time during the critical long term exposure to methane and steam at high temperatures. - Abstract: The single phase La{sub 0.8}Sr{sub 0.2}TiO{sub 3+δ} was prepared via the sol gel process using propionic acid. Kinetics of the thermal decomposition of the precursors has been studied using differential thermogravimetry under non-isothermal conditions in different atmospheres (air and helium). Non isothermal kinetic (A and ΔE) and thermodynamic parameters (ΔH, ΔS and Cp) were determined using different heating rates. La{sub 2}O{sub 3}, SrO and TiO{sub 2} products crystallized at temperatures of ca. 730, 960 and 470 °C respectively while pure La{sub 0.8}Sr{sub 0.2}TiO{sub 3+δ} phase was obtained at 1200 °C, temperature substantially lower than that used for the preparation of La{sub 0.8}Sr{sub 0.2}TiO{sub 3+δ} by conventional solid state method. Precursors and/or final solids were characterized by thermogravimetric analysis (TG), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction, diffuse reflectance ultraviolet–visible spectroscopy (DR-UV–vis) and methane steam reforming under water deficient conditions.

  3. Structural investigation of oxovanadium(IV) Schiff base complexes: X-ray crystallography, electrochemistry and kinetic of thermal decomposition.

    Science.gov (United States)

    Asadi, Mozaffar; Asadi, Zahra; Savaripoor, Nooshin; Dusek, Michal; Eigner, Vaclav; Shorkaei, Mohammad Ranjkesh; Sedaghat, Moslem

    2015-02-05

    A series of new VO(IV) complexes of tetradentate N2O2 Schiff base ligands (L(1)-L(4)), were synthesized and characterized by FT-IR, UV-vis and elemental analysis. The structure of the complex VOL(1)⋅DMF was also investigated by X-ray crystallography which revealed a vanadyl center with distorted octahedral coordination where the 2-aza and 2-oxo coordinating sites of the ligand were perpendicular to the "-yl" oxygen. The electrochemical properties of the vanadyl complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, showing the following trend: MeO5-H>5-Br>5-Cl. Furthermore, the kinetic parameters of thermal decomposition were calculated by using the Coats-Redfern equation. According to the Coats-Redfern plots the kinetics of thermal decomposition of studied complexes is of the first-order in all stages, the free energy of activation for each following stage is larger than the previous one and the complexes have good thermal stability. The preparation of VOL(1)⋅DMF yielded also another compound, one kind of vanadium oxide [VO]X, with different habitus of crystals, (platelet instead of prisma) and without L(1) ligand, consisting of a V10O28 cage, diaminium moiety and dimethylamonium as a counter ions. Because its crystal structure was also new, we reported it along with the targeted complex. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Kinetics of diffusive decomposition in the case of several mass transfer mechanisms

    Science.gov (United States)

    Alexandrov, D. V.

    2017-01-01

    An analytical description of the final stage of diffusive decomposition leaning upon the Slezov theory is developed for several mass transfer mechanisms. The process of formation and relaxation of the crystal size distribution function from the initial ripening stage to its final state corresponding to the universal distribution is studied. The boundary points of a transition region responsible for the tails of the distribution functions on the right of the relevant stopping points are found analytically. The explicit time-dependent analytical expressions for the distribution function and particle growth rates are derived with allowance for the plausible mechanisms of mass transfer.

  5. Characterization and Thermal Decomposition Kinetics of Kapok (Ceiba pentandra L.–Based Cellulose

    Directory of Open Access Journals (Sweden)

    Sarifah Fauziah Syed Draman

    2013-11-01

    Full Text Available nterest in using kapok (Ceiba pentandra L.–based cellulose in composite preparation is growing due to its advantages, including cost- effectiveness, light weight, non-toxicity, and biodegradability. In this study, chloroform, sodium chlorite, and sodium hydroxide were used for wax removal, delignification, and hemicellulose removal, respectively. It was observed that the air entrapment inside kapok fiber disappeared after it was treated with alkali. The structure became completely flattened and similar to a flat ribbon-like shape when examined using a vapour pressure scanning electron microscope (VPSEM. Fourier transform infrared (FTIR spectroscopy was used to characterize the untreated and treated kapok fibers. The peak at 898 cm−1, which is attributed to the glucose ring stretching in cellulose, was observed for the obtained cellulose samples. Peaks corresponding to lignin (1505 and 1597 cm−1 and hemicellulose (1737 and 1248 cm−1 disappeared. The results of differential scanning colorimetry (DSC indicated that the degradation of cellulose appeared as an exothermic peak at about 300 to 350 °C. The activation energy for thermal decomposition of kapok cellulose and its hemicelluloses was 185 kJ/mol and 110 kJ/mol, respectively. The activation energy for thermal decomposition can be used as an alternative approach to determine the purity of cellulose.

  6. Analysis of the Compounds from the BTEX Group, Emitted During Thermal Decomposition of Alkyd Resin

    Directory of Open Access Journals (Sweden)

    M. Kubecki

    2012-09-01

    Full Text Available Suitability of the given binding agent for the moulding sands preparation depends on the one hand on the estimation of technological properties of the sand and the mould made of it and the obtained casting quality and on the other hand on the assessment of this sand influence on the natural and working environment. Out of moulding sands used in the foundry industry, sands with organic binders deserve a special attention. These binders are based on synthetic resins, which ensure obtaining the proper technological properties and sound castings, however, they negatively influence the environment. If in the initial state these resins are not very dangerous for people and for the environment, thus under an influence of high temperatures they generate very harmful products, being the result of their thermal decomposition. Depending on the kind of the applied resin (phenol-formaldehyde, urea, furfuryl, urea–furfuryl, alkyd under an influence of a temperature such compounds as: furfuryl alcohol, formaldehyde, phenol, BTEX group (benzene, toluene, ethylbenzene, xylene, and also polycyclic aromatic hydrocarbons (PAH can be formed and released.The aim of the study was the development of the method, selection of analytical methods and the determination of optimal conditionsof formation compounds from the BTEX group. An emission of these components constitutes one of the basic criteria of the harmfulnessassessment of binders applied for moulding and core sands. Investigations were carried out in the specially designed set up for the thermal decomposition of organic substances in a temperature range: 5000C – 13000C at the laboratory scale. The object for testing was alkyd resin applied as a binding material for moulding sands. Within investigations the minimal amount of adsorbent necessary for the adsorption of compounds released during the decomposition of the resin sample of a mass app. 15 mg was selected. Also the minimal amount of solvent needed for

  7. Numerical simulation and decomposition of kinetic energy in the Central Mediterranean: insight on mesoscale circulation and energy conversion

    Directory of Open Access Journals (Sweden)

    R. Sorgente

    2011-08-01

    Full Text Available The spatial and temporal variability of eddy and mean kinetic energy of the Central Mediterranean region has been investigated, from January 2008 to December 2010, by mean of a numerical simulation mainly to quantify the mesoscale dynamics and their relationships with physical forcing. In order to understand the energy redistribution processes, the baroclinic energy conversion has been analysed, suggesting hypotheses about the drivers of the mesoscale activity in this area. The ocean model used is based on the Princeton Ocean Model implemented at 1/32° horizontal resolution. Surface momentum and buoyancy fluxes are interactively computed by mean of standard bulk formulae using predicted model Sea Surface Temperature and atmospheric variables provided by the European Centre for Medium Range Weather Forecast operational analyses. At its lateral boundaries the model is one-way nested within the Mediterranean Forecasting System operational products.

    The model domain has been subdivided in four sub-regions: Sardinia channel and southern Tyrrhenian Sea, Sicily channel, eastern Tunisian shelf and Libyan Sea. Temporal evolution of eddy and mean kinetic energy has been analysed, on each of the four sub-regions, showing different behaviours. On annual scales and within the first 5 m depth, the eddy kinetic energy represents approximately the 60 % of the total kinetic energy over the whole domain, confirming the strong mesoscale nature of the surface current flows in this area. The analyses show that the model well reproduces the path and the temporal behaviour of the main known sub-basin circulation features. New mesoscale structures have been also identified, from numerical results and direct observations, for the first time as the Pantelleria Vortex and the Medina Gyre.

    The classical kinetic energy decomposition (eddy and mean allowed to depict and to quantify the permanent and fluctuating parts of the circulation in the region, and

  8. Study on thermal decomposition kinetic parameters of GAP-TPE%GAP-TPE热分解动力学研究

    Institute of Scientific and Technical Information of China (English)

    左海丽; 肖乐勤; 周伟良; 徐复铭

    2011-01-01

    利用热量(TG)及微商热重(DTG),研究了GAP基含能热塑性弹性体(GAP-TPE)在氢气气氛、不同升温速率的热分解反应过程.根据GAP-TPE热解DTG曲线特点,把GAP-TPE热解过程分为3个阶段,用Kissinger法计算3个阶段的动力学参数,其活化能分别是223、235、57kJ/mol,lnA分别是52.73、49.39、8.28.用Ozawa法求得各阶段的平均活化能与Kinger法计算结果基本一致,并采用Coats-Redfen法求算了GAP-TPE热分解3个阶段可能遵循的动力学机理方程式分别为[ - ln(1 -α)]1/3、-ln(1-α)和-ln(1-α).%Based on the thermal analysis kinetics,thermogravimetric analysis(TG)and derivative thermogravimetry( DTG) were employed to evaluate the thermal decomposition behaviors of CAP-TPE in Ar atmosphere. A peak separation was performed to separate the thermal decomposition of CAP-TPE into three stages according to the characteristic of the experimental differential mass loss curve,and the kinetic parameters such as activation energy and pre-exponential were calculated and analyzed with Kissinger method. The activation energy of three stages were 223 kJ/mol ,233 kJ/mol and 57 kJ/mol, the hv4 were 52.73,49.39 and 8.28, respectively. The average activation energy was calculated with Ozawa methods in each decomposition stage is consistent with the result of Kissinger method. In addition,the mechanism functions of the three stage using the methods of Coats-Redfen were[ - ln( 1 -a) ]1/3, -ln(1-α) and - ln(1-α),respectively.

  9. Thermal Decomposition Kinetics and Mechanism of Tb(Ⅲ) m-Methylbenzoate Complex with 1,10-Phenanthroline in Static Air Atmosphere

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The thermal behavior of [Tb2(m-MBA)6(phen)2](H2O)2(m-MBA=C8H7O2, methoxybenzoate; phen=C12H8N2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al., it is defined that the kinetics model for the first-step thermal decomposition is SB(m,n).

  10. The gap of visual impairment between economic groups in Shahroud, Iran: a Blinder-Oaxaca decomposition.

    Science.gov (United States)

    Emamian, Mohammad Hassan; Zeraati, Hojjat; Majdzadeh, Reza; Shariati, Mohammad; Hashemi, Hassan; Fotouhi, Akbar

    2011-06-15

    The authors assessed the role of economic inequality in visual impairment and decomposed the gap between high and low income groups. Study data were extracted from the first phase of the Shahroud Eye Cohort Study, performed in 2009, with 5,190 participants aged between 40 and 64 years. The participants were divided into low, medium, and high economic groups according to their assets by using a principal component analysis. The gap between low and high economic groups was decomposed to its determinants by using the Blinder-Oaxaca method. The prevalence of visual impairment, a presenting vision worse than 20/40 in the better eye, was 3.57% and 11.07% in the high and low economic groups, respectively. Age and education were the major factors in the decomposition model, contributing to 41.38% of the gap. Insurance status, gender, and education of the head of the household had no effect on this gap. Economic inequality in visual impairment was noteworthy. Although part of the gap between low and high economic groups was explained by differences in age and education, the greater part (58.62%) could be due to differences in health-care access and utilization.

  11. Pursuing reliable thermal analysis techniques for energetic materials: decomposition kinetics and thermal stability of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50).

    Science.gov (United States)

    Muravyev, Nikita V; Monogarov, Konstantin A; Asachenko, Andrey F; Nechaev, Mikhail S; Ananyev, Ivan V; Fomenkov, Igor V; Kiselev, Vitaly G; Pivkina, Alla N

    2016-12-21

    Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) was studied using a number of thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate calorimetry, ARC). To obtain more comprehensive insight into the kinetics and mechanism of TKX-50 decomposition, a variety of complementary thermoanalytical experiments were performed under various conditions. Non-isothermal and isothermal kinetics were obtained at both atmospheric and low (up to 0.3 Torr) pressures. The gas products of thermolysis were detected in situ using IR spectroscopy, and the structure of solid-state decomposition products was determined by X-ray diffraction and scanning electron microscopy. Diammonium 5,5'-bistetrazole-1,1'-diolate (ABTOX) was directly identified to be the most important intermediate of the decomposition process. The important role of bistetrazole diol (BTO) in the mechanism of TKX-50 decomposition was also rationalized by thermolysis experiments with mixtures of TKX-50 and BTO. Several widely used thermoanalytical data processing techniques (Kissinger, isoconversional, formal kinetic approaches, etc.) were independently benchmarked against the ARC data, which are more germane to the real storage and application conditions of energetic materials. Our study revealed that none of the Arrhenius parameters reported before can properly describe the complex two-stage decomposition process of TKX-50. In contrast, we showed the superior performance of the isoconversional methods combined with isothermal measurements, which yielded the most reliable kinetic parameters of TKX-50 thermolysis. In contrast with the existing reports, the thermal stability of TKX-50 was determined in the ARC experiments to be lower than that of hexogen, but close to that of hexanitrohexaazaisowurtzitane (CL-20).

  12. Tourism forecasting using modified empirical mode decomposition and group method of data handling

    Science.gov (United States)

    Yahya, N. A.; Samsudin, R.; Shabri, A.

    2017-09-01

    In this study, a hybrid model using modified Empirical Mode Decomposition (EMD) and Group Method of Data Handling (GMDH) model is proposed for tourism forecasting. This approach reconstructs intrinsic mode functions (IMFs) produced by EMD using trial and error method. The new component and the remaining IMFs is then predicted respectively using GMDH model. Finally, the forecasted results for each component are aggregated to construct an ensemble forecast. The data used in this experiment are monthly time series data of tourist arrivals from China, Thailand and India to Malaysia from year 2000 to 2016. The performance of the model is evaluated using Root Mean Square Error (RMSE) and Mean Absolute Percentage Error (MAPE) where conventional GMDH model and EMD-GMDH model are used as benchmark models. Empirical results proved that the proposed model performed better forecasts than the benchmarked models.

  13. Multireference Perturbation Theory with Cholesky Decomposition for the Density Matrix Renormalization Group.

    Science.gov (United States)

    Freitag, Leon; Knecht, Stefan; Angeli, Celestino; Reiher, Markus

    2017-02-14

    We present a second-order N-electron valence state perturbation theory (NEVPT2) based on a density matrix renormalization group (DMRG) reference wave function that exploits a Cholesky decomposition of the two-electron repulsion integrals (CD-DMRG-NEVPT2). With a parameter-free multireference perturbation theory approach at hand, the latter allows us to efficiently describe static and dynamic correlation in large molecular systems. We demonstrate the applicability of CD-DMRG-NEVPT2 for spin-state energetics of spin-crossover complexes involving calculations with more than 1000 atomic basis functions. We first assess, in a study of a heme model, the accuracy of the strongly and partially contracted variant of CD-DMRG-NEVPT2 before embarking on resolving a controversy about the spin ground state of a cobalt tropocoronand complex.

  14. Multi-reference perturbation theory with Cholesky decomposition for the density matrix renormalization group

    CERN Document Server

    Freitag, Leon; Angeli, Celestino; Reiher, Markus

    2016-01-01

    We present a second-order N-electron valence state perturbation theory (NEVPT2) based on a density matrix renormalization group (DMRG) reference wave function that exploits a Cholesky decomposition of the two-electron repulsion integrals (CD-DMRG-NEVPT2). With a parameter-free multireference perturbation theory approach at hand, the latter allows us to efficiently describe static and dynamic correlation in large molecular systems. We demonstrate the applicability of CD-DMRG-NEVPT2 for spin-state energetics of spin-crossover complexes involving calculations with more than 1000 atomic basis functions. We first assess in a study of a heme model the accuracy of the strongly- and partially-contracted variant of CD-DMRG-NEVPT2 before embarking on resolving a controversy about the spin ground state of a cobalt tropocoronand complex.

  15. Kinetic study of the gum decomposition from brazilian gasoline; Estudo cinetico da decomposicao da goma oriunda de gasolina brasileira

    Energy Technology Data Exchange (ETDEWEB)

    Pivesso, Paulo Roberto; Galvao, Luzia Patricia Fernandes de Carvalho; Fernandes Junior, Valter Jose; Coutinho, Ana Carla S.L.S. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Souza, Antonio Gouveia de [Universidade Federal da Paraiba (UFPB), Joao Pessoa, PB (Brazil)

    2004-07-01

    The modern gasoline contains in your composition insatured hydrocarbons that can be degraded by the action of the air, heat and substances presenting catalytic activity. The presence of air and heat promote oxidation reactions and polymerization, which promote the gum formation, that is a product with diverse characteristics. The petroleum and l the automobile industries have been investing in researches to lessen the gum undesirable effects. Nowadays, several products are added to the gasoline, for example, the surfactant additives, with the purpose to reduce the formation of deposits in the engine. This work evaluated the influence of a polyester amine addictive, used as the main active component in Brazilian gasoline. The gums were generated evaporating the gasolines according to the ASTM D 381 method. Two types of gum were obtained; the Common Washed Gum (White Sample) and the Additive based Washed Gum (Additive Sample). Both samples were characterized for thermal analysis and submitted for a kinetic study using the model-free method proposed by Vyazovkin. This approach was applied to the final stage of the gums decomposition, supplying the corresponding relative kinetic parameters, such as energy of activation and conversion (author)

  16. Studies on the thermal decomposition kinetics of LiPF6 and LiBC4O8

    Indian Academy of Sciences (India)

    Li Shi-You; Ma Pei-Hua; Cui Xiao-Ling; Ren Qi-Du; Li Fa-Qiang

    2008-03-01

    Thermal decomposition of LiPF6 and LiBC4O8 (lithium bis(oxalate)borate, abbreviated as LiBOB) were studied using TG (thermogravimetry)-DTG (derivative thermogravimetry) method with different heating rate of 5, 10, 20 and 40°C min-1 or at different constant temperature C (109.80, 118.79, 148.41, 176.86 °C for LiPF6 and 278.51, 298.13, 317.65, 336.13 for LiBOB). From the nonisothermal kinetics we calculate that LiPF6 is 1.01, LiBOB is 1.04, LiPF6 is 91907.61 J/mol, and LiBOB is 205179.88 J/mol; from the isothermal kinetics we calculate that n for both LiPF6 and LiBOB are 1, LiPF6 is 91907.61 J/mol, LiBOB is 205179.88 J/mol, lnALiPF6 is 16.89 s-1, and lnALiBOB is 31.96 s-1. The results obtained from the two ways have minor differences and can validate each other.

  17. Non-isothermal decomposition kinetics of magnesite Decomposição não isotérmica de magnesita

    Directory of Open Access Journals (Sweden)

    S. Maitra

    2007-09-01

    Full Text Available Kinetics of thermal decomposition of Indian magnesite was studied by thermo-gravimetric analysis under non-isothermal condition. Coats and Redfern Integral approximation method was used to determine the kinetic parameters. Using the kinetic parameters different kinetic functions were analyzed with the experimental data to ascertain the decomposition mechanism of magnesium carbonate and it was observed that the decomposition reaction followed a contracting sphere kinetic mechanism.A cinética de decomposição térmica de magnesita indiana foi estudada por análise termogravimétrica sob condição não-isotérmica. O método da aproximação da integral de Coats e Redfern foi usado para determinar os parâmetros cinéticos. Usando estes parâmetros, foram analisadas diferentes funções cinéticas com os dados experimentais para avaliar o mecanismo de decomposição do carbonato de magnésio e foi observado que a reação de decomposição segue o mecanismo cinético de contração de esfera.

  18. Kinetics Model of Thermal Decomposition Reaction of Aluminum Potassim Sulphate%硫酸铝钾热分解反应动力学模型

    Institute of Scientific and Technical Information of China (English)

    张建军; 魏海玉; 任志强

    2001-01-01

    The thermal decomposition process of KAl(SO4)2·12H2O and its kinetics has been studied by TG-DTG. By Dollimore method, D3 is defined as the second step of thermal decomposition kinetic model and its kinetic equation is dα/dT=(1/β)CTm(3/2(1-a)2/3[1-(1-α)1/3]-1). At the same time, it has been found that the apparent activation energy E increases with the increases of fraction of conversion α and the absolute temperature T, and then it shows that a linear relationship with the temperature T has been obtained.

  19. Differential and Integral Isoconversional Non-linear Methods and Their Application to Energetic Materials.III.Non-isothermal Decomposition Reaction Kinetics of Benzotrifuroxan

    Institute of Scientific and Technical Information of China (English)

    GAO Hong-Xu; ZHAO Feng-Qi; HU Rong-Zu; ZHANG Hai; DONG Hai-Shan; YAO Pu; XU Zhou; HU Gang

    2008-01-01

    The thermal behaviour and decomposition reaction kinetics of benzotrifuroxan(BTF)were determined by TG and DSC techniques.The kinetic parameters of the exothermic decomposition reaction in a temperature pro-grammed mode(the apparent activation energy Ea and pre-exponential factor A)were calculated by a single non-isothermal DSC curve.The E values calculated using the Kissinger and Flynn-Wall-Ozawa equations and inte-gral isoconversional non-linear equations were used to check the validity of activation energy by a single non-isothermal DSC curve.The results show that the kinetic model function in integral form and the values of Ea respectively.The critical temperature of thermal explosion of BTF is 257.33 ℃.

  20. A total quasi-steady-state formulation of substrate uptake kinetics in complex networks and an example application to microbial litter decomposition

    Science.gov (United States)

    Tang, J. Y.; Riley, W. J.

    2013-12-01

    We demonstrate that substrate uptake kinetics in any consumer-substrate network subject to the total quasi-steady-state assumption can be formulated as an equilibrium chemistry (EC) problem. If the consumer-substrate complexes equilibrate much faster than other metabolic processes, then the relationships between consumers, substrates, and consumer-substrate complexes are in quasi-equilibrium and the change of a given total substrate (free plus consumer-bounded) is determined by the degradation of all its consumer-substrate complexes. In this EC formulation, the corresponding equilibrium reaction constants are the conventional Michaelis-Menten (MM) substrate affinity constants. When all of the elements in a given network are either consumer or substrate (but not both), we derived a first-order accurate EC approximation (ECA). The ECA kinetics is compatible with almost every existing extension of MM kinetics. In particular, for microbial organic matter decomposition modeling, ECA kinetics explicitly predicts a specific microbe's uptake for a specific substrate as a function of the microbe's affinity for the substrate, other microbes' affinity for the substrate, and the shielding effect on substrate uptake by environmental factors, such as mineral surface adsorption. By taking the EC solution as a reference, we evaluated MM and ECA kinetics for their abilities to represent several differently configured enzyme-substrate reaction networks. In applying the ECA and MM kinetics to microbial models of different complexities, we found (i) both the ECA and MM kinetics accurately reproduced the EC solution when multiple microbes are competing for a single substrate; (ii) ECA outperformed MM kinetics in reproducing the EC solution when a single microbe is feeding on multiple substrates; (iii) the MM kinetics failed, while the ECA kinetics succeeded, in reproducing the EC solution when multiple consumers (i.e., microbes and mineral surfaces) were competing for multiple

  1. A total quasi-steady-state formulation of substrate uptake kinetics in complex networks and an example application to microbial litter decomposition

    Directory of Open Access Journals (Sweden)

    J. Y. Tang

    2013-06-01

    Full Text Available We demonstrate that substrate uptake kinetics in any consumer-substrate network subject to the total quasi-steady-state assumption can be formulated as an equilibrium chemistry (EC problem. If the consumer-substrate complexes equilibrate much faster than other metabolic processes, then the relationships between consumers, substrates, and consumer-substrate complexes are in quasi-equilibrium and the change of a given total substrate (free plus consumer-bounded is determined by the degradation of all its consumer-substrate complexes. In this EC formulation, the corresponding equilibrium reaction constants are the conventional Michaelis–Menten (MM substrate affinity constants. When all of the elements in a given network are either consumer or substrate (but not both, we derived a first-order accurate EC approximation (ECA. The ECA kinetics is compatible with almost every existing extension of MM kinetics. In particular, for microbial organic matter decomposition modeling, ECA kinetics explicitly predicts a specific microbe's uptake for a specific substrate as a function of the microbe's affinity for the substrate, other microbes' affinity for the substrate, and the shielding effect on substrate uptake by environmental factors, such as mineral surface adsorption. By taking the EC solution as a reference, we evaluated MM and ECA kinetics for their abilities to represent several differently configured enzyme-substrate reaction networks. In applying the ECA and MM kinetics to microbial models of different complexities, we found (i both the ECA and MM kinetics accurately reproduced the EC solution when multiple microbes are competing for a single substrate; (ii ECA outperformed MM kinetics in reproducing the EC solution when a single microbe is feeding on multiple substrates; (iii the MM kinetics failed, while the ECA kinetics succeeded, in reproducing the EC solution when multiple consumers (i.e., microbes and mineral surfaces were competing for

  2. Experimental and Kinetic Investigation of the Influence of OH Groups on NOX Formation

    KAUST Repository

    Bohon, Myles

    2016-05-04

    measurements in premixed flames for temperature and species in high and low temperature flames. These measurements included probed thermocouple temperature measurements, extractive gas sampling for NO and intermediate hydrocarbon species, and planar Laser Induced Fluorescence (LIF) measurements for 2OH-LIF thermometry, semiquantitative CH2O LIF, and quantitative NO LIF. Additionally, the simplified nature of the burner geometries allowed for the modeling of the flames incorporating detailed reaction kinetics for fuel decomposition and NOX formation. Significant reductions in NO formation were observed in comparisons of alcohol and alkane flames, resulting in up to 50% reductions in the pollutant. Computational analyses and nitrogen flux accounting allowed for the identification of the reduction in NO formation through all the known NOX formation pathways. It was observed that all of the known pathways exhibited reductions in contributions to NO formation in the presence of OH functional groups, indicating a complex coupling of fuel and NOX chemistry.

  3. Kinetic analysis of the termal decomposition of colombian vacuum residua by termogravimetry

    Directory of Open Access Journals (Sweden)

    Fabian Andrey Diaz Mateus

    2015-12-01

    Full Text Available Five different Colombian vacuum residues were thermally decomposed in a thermogravimetric analyzer. Three heating rates were employed to heat the sample up to 650°C. The kinetic analysis was performed by the Coats-Redfern method to describe the non-isothermal pyrolysis of the residua, a reaction model where the reaction order gradually increases from first to second order is proposed and an excellent agreement of the experimental with the calculated data is presented. The results also indicate that the pyrolysis of a vacuum residue cannot be modeled by a single reaction mechanism.

  4. 2,4,6-三硝基间苯二酚钡一水化合物的热分解动力学%Thermal Decomposition Kinetics of Barium 2,4,6-trinitroresorecinate Monohydrate

    Institute of Scientific and Technical Information of China (English)

    胡荣祖; 陈三平; 高胜利; 宋纪蓉; 史启祯; 赵宏安; 姚朴; 李静

    2004-01-01

    Studies of the non-isothermal decomposition of barium 2,4,6-trinitroresorecinate monohydrate, Ba(TNR)· H2O,were carried out by means of TG-DTA, DSC and IR. The thermal decomposition mechanism and associated kinetics were investigated. The kinetic parameters were obtained from an analysis of the DSC curves by integral was suggested by comparison of the kinetic parameters.

  5. Effects of pressure and TEGDN content on decomposition reaction mechanism and kinetics of DB gun propellant containing the mixed ester of TEGDN and NG.

    Science.gov (United States)

    Yi, Jian-hua; Zhao, Feng-qi; Xu, Si-yu; Zhang, La-ying; Gao, Hong-xu; Hu, Rong-zu

    2009-06-15

    The effects of pressure and triethyleneglycol dinitrate (TEGDN) content on the decomposition reaction mechanism and kinetics of the double-base (DB) gun propellant composed of mixed ester of TEGDN and nitroglycerin (NG), and nitrocellulose (NC) were investigated by high-pressure differential scanning calorimetry (PDSC). The results show that the high pressure can decrease the DSC peak temperature, increase the decomposition heat; with the increase in the content of TEGDN, the decomposition heat decreases below 2MPa and rises at 4MPa. The high pressure can change the decomposition reaction mechanism and the kinetics of the DB gun propellant under 0.1MPa; the high TEGDN content does not change the mechanism functions, and the kinetic equation has a little difference between the sample and the control propellant; the high pressure makes the critical temperature (T(be)) of thermal explosion of the sample decrease, while the high TEGDN content make it present a increasing trend, and the DB gun propellant containing high content of TEGDN has a better thermal stability.

  6. Topological influence and excitations: decomposition formulas for calculating homotopy groups of symmetry broken phases

    CERN Document Server

    Higashikawa, Sho

    2016-01-01

    A symmetry broken phase of a system with internal degrees of freedom often features a complex order parameter, which generates a rich variety of topological excitations and topological influence between them, yet the very complexity of the order parameter makes it difficult to treat topological excitations and topological influence in a unified manner. To overcome this problem, we develop a general method to calculate homotopy groups and derive decomposition formulas which express homotopy groups of a quotient space $G/H$ in terms of those of the symmetry $G$ of the system and those of the remaining symmetry $H$ of the state. We apply these formulas to analyze a general monopole and a general three-dimensional skyrmion, and show that their textures are obtained through substitution of the corresponding $\\mathfrak{su}(2)$-subalgebra for the $\\mathfrak{su}(2)$-spin. We also show that a discrete symmetry of $H$ is necessary for the presence of topological influence and find the topological influence on a skyrmio...

  7. Discriminative Dictionary Learning With Two-Level Low Rank and Group Sparse Decomposition for Image Classification.

    Science.gov (United States)

    Wen, Zaidao; Hou, Biao; Jiao, Licheng

    2016-06-30

    Discriminative dictionary learning (DDL) framework has been widely used in image classification which aims to learn some class-specific feature vectors as well as a representative dictionary according to a set of labeled training samples. However, interclass similarities and intraclass variances among input samples and learned features will generally weaken the representability of dictionary and the discrimination of feature vectors so as to degrade the classification performance. Therefore, how to explicitly represent them becomes an important issue. In this paper, we present a novel DDL framework with two-level low rank and group sparse decomposition model. In the first level, we learn a class-shared and several class-specific dictionaries, where a low rank and a group sparse regularization are, respectively, imposed on the corresponding feature matrices. In the second level, the class-specific feature matrix will be further decomposed into a low rank and a sparse matrix so that intraclass variances can be separated to concentrate the corresponding feature vectors. Extensive experimental results demonstrate the effectiveness of our model. Compared with the other state-of-the-arts on several popular image databases, our model can achieve a competitive or better performance in terms of the classification accuracy.

  8. Ab initio Kinetics and Thermal Decomposition Mechanism of Mononitrobiuret and 1,5-Dinitrobiuret

    Science.gov (United States)

    2016-03-14

    two planar amide fragments (NH2−CO−NH) in the biuret molecule are slightly inclined at 5°33’ and trans to each other, forming an intramolecular H...isomer of NH2NO2 that has a geometry in which the OH group is trans to the NH group along the N‒N bond and trans to the N=O group along the N‒OH...substitutes. Biuret has been known to have two conformers; trans and cis, which refer to the two C=O groups that are either trans or cis to each other

  9. 高温液态水中木糖无催化分解反应动力学%Kinetics of Non-catalyzed Decomposition of D-xylose in High Temperature Liquid Water

    Institute of Scientific and Technical Information of China (English)

    荆琪; 吕秀阳

    2007-01-01

    The kinetics of non-catalyzed decompositions of xylose and its decomposition product furfural in high temperature liquid water (HTLW) was studied for temperature from 180 to 220℃ and under pressure of 10MPa.The main products of xylose decomposition were furfural and formic acid, and furfural further degraded to formic acid under HTLW condition. With the assumption of first order kinetics equation, the evaluated activation energy of xylose and furfural decomposition was 123.27kJ·mol-1 and 58.84kJ·mol-1, respectively.

  10. Ozone decomposition

    Directory of Open Access Journals (Sweden)

    Batakliev Todor

    2014-06-01

    Full Text Available 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

  11. Measurement and decomposition kinetics of residual hydrogen peroxide in the presence of commonly used excipients and preservatives.

    Science.gov (United States)

    Towne, Victoria; Oswald, C Brent; Mogg, Robin; Antonello, Joseph; Will, Mark; Gimenez, Juan; Washabaugh, Michael; Sitrin, Robert; Zhao, Qinjian

    2009-11-01

    Quantitation of residual hydrogen peroxide (H(2)O(2)) and evaluation of the impact on product stability is necessary as unwanted H(2)O(2) can potentially be introduced during the manufacturing of pharmaceuticals, biologics, and vaccines. A sensitive and convenient microplate-based method with fluorescence detection for H(2)O(2) quantitation was recently reported (Towne et al., 2004, Anal Biochem 334: 290-296). This method was found to be highly robust and reproducible, with a level of detection of 0.015 ppm and a level of quantitation of 0.025 ppm (in water). The relatively small sample requirements and amenability for automation make this assay an attractive tool for detecting residual H(2)O(2) levels. Without additional manipulation, the assay can be conducted on heterogeneous solutions with significant degree of turbidity, such as the presence of suspensions or aluminum-containing adjuvants. The quantitation of H(2)O(2) and its decomposition kinetics was also studied in presence of two common vaccine preservatives (thimerosal and phenol) and eight commonly used excipients (polyols). Over time, there is a distinct, temperature dependent decrease in H(2)O(2) recovered in thimerosal and phenol containing samples versus non-preservative containing controls. Based on the half-life of spiked H(2)O(2), the decay rates in eight polyols tested were found to be: ribose > sucrose > (glycerol, glucose, lactose, mannitol, sorbitol, and xylose).

  12. Ozone decomposition kinetics on alumina: effects of ozone partial pressure, relative humidity and repeated oxidation cycles

    Directory of Open Access Journals (Sweden)

    R. C. Sullivan

    2004-01-01

    Full Text Available The room temperature kinetics of gas-phase ozone loss via heterogeneous interactions with thin alumina films has been studied in real-time using 254nm absorption spectroscopy to monitor ozone concentrations. The films were prepared from dispersions of fine alumina powder in methanol and their surface areas were determined by an in situ procedure using adsorption of krypton at 77K. The alumina was found to lose reactivity with increasing ozone exposure. However, some of the lost reactivity could be recovered over timescales of days in an environment free of water, ozone and carbon dioxide. From multiple exposures of ozone to the same film, it was found that the number of active sites is large, greater than 1.4x1014 active sites per cm2 of surface area or comparable to the total number of surface sites. The films maintain some reactivity at this point, which is consistent with there being some degree of active site regeneration during the experiment and with ozone loss being catalytic to some degree. The initial uptake coefficients on fresh films were found to be inversely dependent on the ozone concentration, varying from roughly 10-6 for ozone concentrations of 1014 molecules/cm3 to 10-5 at 1013 molecules/cm3. The initial uptake coefficients were not dependent on the relative humidity, up to 75%, within the precision of the experiment. The reaction mechanism is discussed, as well as the implications these results have for assessing the effect of mineral dust on atmospheric oxidant levels.

  13. 可降解聚乳酸的热分解动力学研究%Study on Thermal Decomposition Kinetics of Biodegradable Poly Lactic Acid

    Institute of Scientific and Technical Information of China (English)

    韩宇辰; 黄震; 冯梅; 潘茜; 王艺儒

    2012-01-01

    Thermogravimetric analysis (TGA) was applied to investigate the thermal decomposition behavior of poly lactic acid in air with heating rates of 5, 10, 15, 20, 30 K/min and from ambient temperature up to 1250 K. The thermal decomposition features were obtained from resultant TGA curves. The results showed the main thermal decomposition was in the temperature range of 550-660 K and it was found to be the first order reaction from kinetic analysis. Activation energy and frequency factor for thermal decomposition can be estimated by using certain kinetic models.%采用热重法研究了聚乳酸在空气中的热分解过程,升温速率分别为5,10,15,20,30K/min,温度范围为室温-1250K,并利用TGA曲线分析了聚乳酸的热降解特点。结果表明,热分解反应最剧烈的温度介于550-660K之间,热分解动力学分析表明,该热分解过程为一级反应。热分解反应的活化能和频率因子可以通过动力学模型加以估算。

  14. Synthesis, Crystal Structure and Kinetic Mechanism of Thermal Decomposition of a Zinc(II) Complex with N-Salicylidene-p-toluidine

    Institute of Scientific and Technical Information of China (English)

    ZHAO Guo-Liang; WEN Yi-Hang; YU Yu-Ye

    2006-01-01

    The title complex, Zn(C14H13NO)2Cl2 1, has been synthesized by the reaction of zinc chloride with Schiff base ligand N-salicylidene-p-toluidine and its structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group Cc with a = 14.896(3), b = 12.506(2), c = 15.352(3)(A), β = 114.711(4)o, V = 2598.0(8) (A)3, C28H26ZnCl2N2O2, Mr = 558.80, Z = 4, Dc = 1.429 g/cm3, μ = 1.179 mm-1, Flack parameter = 0.027(19), F(000) = 1152, R = 0.0709 and wR = 0.1041 for 3117 observed reflections (I > 2σ(I)). In complex 1, the center Zn ion is four-coordinated by two O atoms from two Schiff base ligands and two Cl atoms in a distorted tetrahedral geometry. Additionally, the thermal decomposition of complex 1 as well as its kinetic mechanisms and equations is studied under the non-isothermal integral and differential methods in air by TG-DTG curves.

  15. Thermal Behavior, Non-isothermal Decomposition Reaction Kinetics of Copper(Ⅱ) Salt of 4-Hydroxy-3,5-dinitropyridine and Its Application in Propellant

    Institute of Scientific and Technical Information of China (English)

    CHEN Pei; ZHAO Feng-qi; LUO yang; HU Rong-zu; GAO Sheng-li; ZHENG Yu-mei; DENG Min-hi; GAO Yin

    2005-01-01

    The thermal behavior and kinetic parameters of the major exothermic decomposition reaction of the title compound in a temperature-programmed mode were studied by means of TG-DTG and DSC. The critical temperature of thermal explosion was calculated. The effect of the title compound on the combustion characteristic of composition modifier double base propellant containing RDX was explored with a strand burner. The results show that the kinetic model function in differential forms, the apparent activation energy(Ea) and the pre-exponential factor(A) of the major exothermic decomposition reaction are 3(1-α)[-ln(1-α)]2/3, 190.56 kJ/mol and 1013.39 s-1, respectively. The critical temperature of thermal explosion of the compound is 353.08 ℃. The kinetic equation of the major exothermic decomposition process of the title compound at 0.1 MPa could be expressed as dα/dT=1014.65(1-α)[-ln(1-α)]2/3 e-2.2920×104/T. As an auxiliary catalyzer, the title compound can help the main catalyzer of lead salt of 4-hydroxy-3,5-dinitropyridine to accelerate the burning rate and reduce the pressure exponent of RDX-CMDB propellant.

  16. Study on the thermal decomposition kinetics of cis/trans-[Cu(gly)2]·H2O

    Institute of Scientific and Technical Information of China (English)

    ZHANG Fengxing; LI Jun; LI Hengxin; DU Guixiang; SONG Shuqing

    2005-01-01

    The thermal decomposition reactions of the complexes cis/trans-[Cu(gly)2]· H2Owere studied by TG-DSC methods. The results showed that they have similar decomposition process, which occur in two steps. The first step is the loss of water and the second step is the decomposition of anhydrous complexes.But for cis-[Cu(gly)2]· H2O,the tempoerature of losing water is higher than that of trans-isomer. Their reaction mechanisms of the two-step decomposition were also proposed.

  17. Synthesis,Characterization,Thermal Decomposition Mechanism and Non—Isothermal Kinetics of the Pyruvic Acid—Salicylhydrazone and Its Complex of Prasseodymium(Ⅲ)

    Institute of Scientific and Technical Information of China (English)

    何水样; 刘煜; 赵建社; 赵宏安; 杨锐; 胡荣祖; 史启祯

    2003-01-01

    The pyruvic acid-salicylhydrazone and its new complex of Pr(Ⅲ) were synthesized.The formulae C10H10N2O4(mark as H3L)and [Pr2(L)2(H2O)2]·3H2O(L=the trad from of the pyruvic acid salicylhydrazone[C10H7N2O4]3-)were determined by elemental and EDTA volumetric analysis.Molar conductance,IR,UV,X-ray and 1H NMR were carried out for the characterizations of the complex and the ligand.The thermal decompositions of the ligand and the complex with the kinetic study were carried out by nonisothermal thermogravimetry.The Kissinger’s method and Ozawa’s method are used to calculate the activation energy value of the main step decomposition.The stages of the decompostions were identified by TG-DTG-DSC curve.The non-isothermal kinetic data were analyzed by means of integral and differential methods.The possible reaction mechanism and the kinetic equation were investigated by comparing the kinetic parameters.

  18. Investigations of the Temperature Influence on Formation of Compounds from the BTEX Group During the Thermal Decomposition of Furan Resin

    Directory of Open Access Journals (Sweden)

    M. Kubecki

    2013-04-01

    Full Text Available Organic binders applied in foundry plants based on synthetic resins, from the one side influence obtaining the required technological properties by the moulding sand and - in consequence - obtaining good quality castings, and on the other side are the source of volatile organic compounds (VOC. Together with synthetic resins their hardeners, which although added in very small amounts emit during their thermal decomposition substances negatively influencing the natural environment, are also used. Both, resins and hardeners only at the influence of high temperatures accompanying moulds pouring with liquid metal generate harmful volatile organic compounds including compounds from the BTEX group. Investigations of the temperature influence on the kind and amount of organic compounds formed during the thermal decomposition of selected binders and hardeners and their mixtures allow to determine temperature ranges the most favourable for emitting harmful substances as well as to compare their emission from the selected materials. The aim of this study was the determination the temperature influence on formation substances from the BTEX group, during thermal decomposition of the selected binder, its hardener and their mixture. The BTEX group emission constitutes one of the basic criteria in assessing the harmfulness of materials applied for moulding and core sands and it can undergo changes in dependence of the applied system resin-hardener. Investigations were carried out on the specially developed system for the thermal decomposition of organic substances in the temperature range: 500ºC - 1300ºC, at the laboratory scale. The investigations subject was the furan resin, its hardener and hardened furan resin. The assessment of the emission degree of the BTEX group in dependence of the system subjected to the temperature influence was performed, within the studies. The temperature range, in which maximal amounts of benzene, toluene, ethylbenzene and

  19. Characterization, non-isothermal decomposition kinetics and photocatalytic water splitting of green chemically synthesized polyoxoanions of molybdenum containing phosphorus as hetero atom

    Energy Technology Data Exchange (ETDEWEB)

    D’Cruz, Bessy [Department of Chemistry, Mar Ivanios College, Thiruvananthapuram 695015 (India); Samuel, Jadu, E-mail: jadu_samuel@yahoo.co.in [Department of Chemistry, Mar Ivanios College, Thiruvananthapuram 695015 (India); George, Leena [Catalysis and Inorganic Chemistry Division, National Chemical Laboratory, Pune 411008 (India)

    2014-11-20

    Highlights: • CPM nanorods were synthesized by applying the principles of green chemistry. • The isoconversional method was used to analyze the effective activation energy. • The appropriate reaction models of the two decomposition stages were determined. • Photocatalytic water splitting was investigated in the presence of platinum co-catalyst. - Abstract: In here, the green synthesis and thermal characterization of a novel polyoxoanions of molybdenum containing phosphorus as hetero atom are reported. The composition and morphology of the nanorods were established by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and inductively coupled plasma atomic emission spectroscopic (ICP-AES) techniques. Thermal properties of the nanoparticles were investigated by non-isothermal analysis under nitrogen atmosphere. The values activation energy of each stage of thermal decomposition for all heating rates was calculated by Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunnose (KAS) methods. Invariant kinetic parameter (IKP) method and master plot method were also used to evaluate the kinetic parameters and mechanism for the thermal decomposition of cetylpyridinium phosphomolybdate (CPM). Photocatalytic water oxidation mechanism using CPM catalyst in the presence of platinum (Pt) co-catalyst enhances the H{sub 2} evolution and was found to be 1.514 mmol/g/h.

  20. Kinetic simulation of complex decomposition as a tool for the ion chromatographic determination of elemental speciation of less inert metal ions.

    Science.gov (United States)

    Winter, Christian; Seubert, Andreas

    2016-01-15

    Species decomposition is an often occurring artefact during the chromatographic determination of elemental speciation. The decomposition follows a simple path to lower coordinated compounds. Therefore a simulation is developed for those decomposition reactions. The simulation separates the isochronal processes of the separation itself and the ongoing reaction and delivers thermodynamic and kinetic information about the species present in the original sample. This shifts the boundaries of separation based elemental speciation to less inert metal ions which are typically not analyzable by this approach. The less inert gallium monooxalato complex [GaOx](+) is used as example for testing the simulation software as this complex decomposes only to Ga(3+) and both species are retained on cation exchange columns. We extracted thermodynamic and kinetic information from flow rate experiments by the analysis of the peak areas in the chromatogram. The results show that some of our assumptions such as the irreversibility under the applied chromatographic conditions are not ultimately true, but good accordance of simulation and measured data was achieved.

  1. Kinetics of drug decomposition. Part 69: Effect of excipients on the thermal decomposition of the mixture of aminophenazone allobarbital and adiphenine hydrochloride in the solid.

    Science.gov (United States)

    Pawełczyk, E; Marciniec, B

    1981-08-01

    By the method of accelerated testing at elevated temperature, the thermal decomposition rate of the mixture of aminophenazone (AP), allobarbital (AB) and adiphenine hydrochloride (AD) and its individual components in the presence of the excipients starch (potato), agar, talcum, kaolin and magnesium stearate is studied. The individual and joint effect of the excipients on the components of the mixture AP + AB + AD as well as on the mixture as a whole is determined and compared. The theoretically predicted stability of the components is discussed and compared with the results of "self-life" tests in the presence and absence of the excipients.

  2. Kinetic Study on the Exothermic Decomposition Reaction of 2,4,6,8-Tetranitro-2,4,6,8-tetraazabicyclo[3,3,1]onan-3,7-dione

    Institute of Scientific and Technical Information of China (English)

    HU,Rong-Zu(胡荣祖); CHEN,San-Ping(陈三平); SHI,Qi-Zhen(史启祯); SONG,Ji-Rong(宋纪蓉); ZHAO,Feng-Qi(赵凤起); WANG,Bo-Zhou(王伯周); GAO,Sheng-Li(高胜利); ZHU,Chun-Hua(朱春华); CHEN,Pei(陈沛); LUO,Yang(罗阳); NING,Bin-Ke(宁斌科)

    2004-01-01

    The kinetic parameters of the exothermic decomposition reaction of the title compound in a temperature-programmed mode have been studied by means of DSC. The empirical kinetic model function in differential and 1020.21 s -1, respectively. The critical temperature of thermal explosion of the compound is 224.9 ℃.

  3. [Litter decomposition and associated macro-invertebrate functional feeding groups in a third-order stream of northern Guangdong].

    Science.gov (United States)

    Yan, Ling; Zhao, Ying; Han, Cui-xiang; Tong, Xiao-li

    2007-11-01

    By placing 5 mm- and 0.1 mm mesh bags with Dracontomelon duperreanum (Anacardiaceae) and Syzygium jambos (Myrtaceae) litters in the Hengshishui Stream, a third-order stream in northern Guangdong of China, this paper studied the decomposition of the litters and the colonization of macro-invertebrates over a 101-day period. The results showed that the decomposition rate of D. duperreanum litter in 5 mm- and 0.1 mm mesh bags was 0.0247 d(-1) and 0.0151 d(-1), while that of S. jambos litter was 0.0108 d(-1) and 0.0095 d(-1), respectively, indicating that D. duperreanum litter decomposed faster than S. jambos litter, and the decomposition rates of these two kinds of litters were higher in coarse mesh bag than in fine mesh bag. Among the colonized macro-invertebrate functional feeding groups, scraper occupied the highest proportion (36%), followed by collector (33%), predator (25%), and shredder (6%). At the middle and late stages of the experiment, the total number of individuals and the numbers and densities of dominant groups of macroinvertebrates on D. duperreanum litter were significantly higher than those on S. jambos litter. It was suggested that in the subtropical medium-size streams where shredders are few or absent, scrapers play an important role in the breakdown of litter. The low decomposition rate of S. jambos litter was mainly due to its high content of polyphenols which inhibits microbial activity and makes the litter less eatable to the macro-invertebrates.

  4. Kinetic analysis for non-isothermal decomposition of un-irradiated and gamma-irradiated anhydrous cadmium nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Culas, S.; Samuel, J. [Mar Ivanios College, Kerala (India). Dept. of Chemistry

    2014-04-01

    The thermal decomposition of untreated and γ-irradiated samples of anhydrous cadmium nitrate was performed under non-isothermal conditions at different heating rates (5, 10, 15 and 20 C min{sup -1}). The results showed that the decomposition proceeds in one major step with the formation of cadmium oxide as solid residue. The data were analysed by using both isoconversional and non-isoconversional methods. The activation energy was calculated by various model-free isoconversional methods: Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Friedman (FR) methods. Irradiation enhances the decomposition and the effect increases with the irradiation dose. The activation energy decreases on irradiation. The appropriate conversion model for the thermal decomposition process selected by means of the master-plot method agrees with phase boundary reaction with spherical symmetry (R3 mechanism) for both untreated and irradiated salts at all heating rates. (orig.)

  5. Kinetics and Mechanism of the Exothermic First-stage Decomposition Reaction for 1,5-Dimethy1-2,6-bis ( 2,2,2-trinitroethyl)-glycoluril

    Institute of Scientific and Technical Information of China (English)

    LI,Huan-Yong(李焕勇); HU,Rong-Zu(胡荣祖); YANG,De-Suo(杨得锁); ZHAO,Hong-An(赵宏安); GAO,Sheng-Li(高胜利); SHI,Qi-Zhen(史启祯)

    2002-01-01

    The thermal behavior, mechanism and kinetic parameters of the exothermic first- stage decomposition reaction of the title compound in a temperature-programmed mode have been investigated by means of DSC, TG-DTG and IR. The reaction mechanism was proposed. The enpirical kinetic model functions in differential form, apparent activation energy (Ea) and pre-exponential factor (A) of this reaction are (1 - α) -1.119,211.3 kJ/mol and 1020.2 s-1, respectively. The critical temperature of thermal explosion of the compound is 202.2 ℃. Tne values of △S≠, △H≠ and △G≠ of this reaction are 143.8 J.mol-1 .K-1, 208.7 kJ/mol and 141.7 kJ/mol, respectively.

  6. Kinetics and Mechanism of Exothermic First-stage Decomposition Reaction of 2,6-Bis (2,2,2-trinitroethyl)glycoluril

    Institute of Scientific and Technical Information of China (English)

    HU Rong-zu; YANG De-suo; GAO Sheng-li; ZHAO Feng-qi; CHEN San-ping; CHEN Pei; LUO Yang; ZHAO Hong-an; SHI Qi-zhen

    2004-01-01

    The thermal behavior, mechanism and kinetic parameters of the exothermic first-stage decomposition of the title compound in a temperature-programmed mode were investigated by means of DSC, TG-DTG and IR. The reaction mechanism was proposed. The kinetic model function in differential form, apparent activation energy(Ea) and pre-exponential factor(A) of this reaction are (3/2)(1-a)[-ln(1-a)]1/3, 185.52 kJ/mol and 1017.78 s-1, respectively. The critical temperature of the thermal explosion of the compound is 201.30 ℃. The values of ΔS≠, ΔH≠ and ΔG≠ of this reaction are 72.46 J/(mol · K), 175.1 kJ/mol and 141.50 kJ/mol, respectively.

  7. Effects of magnetic and kinetic helicities on the growth of magnetic fields in laminar and turbulent flows by helical-Fourier decomposition

    CERN Document Server

    Linkmann, Moritz; McKay, Mairi; Berera, Arjun; Biferale, Luca

    2016-01-01

    We present a numerical and analytical study of incompressible homogeneous conducting fluids using a Fourier-helical representation. We analytically study both small- and large-scale dynamo properties, as well as the inverse cascade of magnetic helicity, in the most general minimal subset of interacting velocity and magnetic fields on a closed Fourier triad. We mainly focus on the dependency of magnetic field growth as a function of the distribution of kinetic and magnetic helicities among the three interacting wavenumbers. By combining direct numerical simulations of the full magnetohydrodynamics (MHD) equations with the Fourier-helical decomposition we numerically confirm that in the kinematic dynamo regime the system develops a large-scale magnetic helicity with opposite sign compared to the small-scale kinetic helicity, a sort of triad-by-triad $\\alpha$-effect in Fourier space. Concerning the small-scale perturbations, we predict theoretically and confirm numerically that the largest instability is achived...

  8. Non-isothermal Decomposition Kinetics,Specific Heat Capacity and Adiabatic Time-to-explosion of 1-Amino-1-hydrazino-2,2-dinitroethylene (AHDNE)

    Institute of Scientific and Technical Information of China (English)

    XU,Kangzhen; ZHAO,Fengqi; SONG,Jirong; CHANG,Chunran; LI,Meng; WANG,Yaoyu; HU,Rongzu

    2009-01-01

    The thermal behavior and non-isothermal kinetics of the exothermic decomposition reaction of 1-amino-1-hydrazino-2,2-dinitroethylene (AHDNE) were studied with DSC and TG/DTG methods.The kinetic equation obtained is dα/dT=1019.29(1-α)exp(-1.88×104/T)/β.The critical temperature of thermal explosion is 98.16 ℃.The specific heat capacity of AHDNE was determined,and the standard molar specific heat capacity is 211.86 J·mol-1·K-1 at 298.15 K.The adiabatic time-to-explosion of AHDNE was also calculated to be 59.21 s.AHDNE is unstable and has much lower thermostability than 1,1-diamino-2,2-dinitroethylene (FOX-7).

  9. Kinetics of thermal decomposition of titanium hydride powder using in situ high-temperature X-ray diffraction (HTXRD

    Directory of Open Access Journals (Sweden)

    Hugo Ricardo Zschommler Sandim

    2005-09-01

    Full Text Available The thermal decomposition of titanium hydride powder (delta-phase to titanium (alpha-phase was investigated by means of thermogravimetric analysis (TGA and high-temperature X-ray diffraction (HTXRD in high vacuum. The delta-to-alpha phase transformation was followed in situ by HTXRD at temperatures varying from room temperature up to 1000 °C. The transformation was also analyzed as a function of time at isothermal conditions from 450 to 650 °C. The results of TGA show that the decomposition of the titanium hydride becomes significant at about 450 °C. Above 500 °C the decomposition is completed in times shorter than 50 minutes. The apparent activation energy for hydrogen desorption was found to be 63 ± 6 kJ.mol-1.

  10. Decomposition kinetics and thermal hazard of organic peroxides%有机过氧化物分解机理及热危害

    Institute of Scientific and Technical Information of China (English)

    孙峰; 薛岩; 谢传欣; 金满平; 黄飞

    2012-01-01

    The thermal hazard of organic peroxides should be assessed to predict and avoid runaway decomposition. In this paper, the Setaram C80 was used to investigate thermal decomposition of several organic peroxides such as cumene hydroperoxide (CHP), tert-butyl hydroperoxide (TBHP), dicumyl peroxide (DCP), di-tert-buty\\ peroxide (DTBP), benzoyl peroxide (BPO), tert-butyl peroxybenzoate ( TBPB ) , methyl ethyl ketone peroxide ( MEKP ) , 2 , 5-dimethyl-2 , 5-di (tert-butylperoxy ) hexane (DHBP) and 1, 1-di-(tert-butylperoxy)-3, 3, 5-trimethylcyclohexane (TMCH). Decomposition heat of the organic peroxides was calculated from isothermal scanning curves. The nth-order or autocatalytic reaction kinetics model was established for these organic peroxides, and self accelerating decomposition temperature (SADT) was derived by using Semenov model. The results showed that decomposition of the organic peroxides mostly followed nth-order model with approximate reaction order of 1, however, some of them preferred to autocatalytic model. The SADT of the organic peroxides calculated was in good agreement with values from literatures, demonstrating reaction kinetics fitting and SADT calculating in this paper are of scientific.%为了预防及控制有机过氧化物的分解爆炸事故,需要对其热危害进行必要的评估.利用塞塔姆C80微量热仪对不同种类的9种有机过氧化物进行热扫描测试,并分别利用n级反应模型及自催化反应模型对扫描曲线进行拟合,准确得到了这些物质的分解热及分解机理.根据反应动力学数据,采用Semenov爆炸模型及联合国H.3-等温储存试验原理,得到了9种有机过氧化物的临界温度及自加速分解温度(SADT).结果表明,大部分有机过氧化物分解遵循n级反应模型,反应级数在1左右,少部分有机过氧化物分解时有一定的自催化效应.所得的SADT数据与文献值符合较好,证明本文动力学模拟及SADT计算方法的科学性.

  11. Kinetics of Hydrolysis of Cationic Reactive Disperse Dyes Containing Quaternary Group

    Institute of Scientific and Technical Information of China (English)

    XIE Kong-liang; HOU Ai-qin

    2006-01-01

    The kinetics of hydrolysis of cationic reactive disperse dyes containing quaternary group and chemical shift(13CNMR) of the adjacent carbon atoms with pyridine-acetylamino were discussed. The results show pyridine-acetylamino reactive group had higher reactivity than chloroacetylamino and chemical shift(13CNMR) of the adjacent carbon atoms with pyridine-acetylamino moved 18.77 ppm.

  12. Estudo cinético da decomposição térmica do pentaeretritol-tetranitrado (PETN Kinetic study of the thermal decomposition of pentaerythritol-tetranitrate (PETN

    Directory of Open Access Journals (Sweden)

    Gilson da Silva

    2008-01-01

    Full Text Available The pentaerythritol-tetranitrate (PETN is a nitroether used in explosives and propellant formulations. Due to its suitable properties, PETN is used in booster manufacture. Knowing the thermal decomposition behavior of an energetic material is very important for storage and manipulation, and the purpose of this work is to study the kinetic parameters of the decomposition of PETN, compare the results with literature data and to study the decomposition activation energy differences between two crystalline forms of PETN (tetragonal and needle by means of differential scanning calorimetry (DSC. Fourier transform infrared spectroscopy (FT-IR is used to study the two crystalline forms.

  13. Decomposition kinetic and mechanism of syndiotactic polystyrene nanocomposites with MWCNTs and nanodiamonds studied by TGA and Py-GC/MS

    Energy Technology Data Exchange (ETDEWEB)

    Chrissafis, Konstantinos; Pavlidou, Eleni [Solid State Physics Section, Physics Department, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Macedonia (Greece); Vouvoudi, Evangelia [Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Macedonia (Greece); Bikiaris, Dimitrios, E-mail: dbic@chem.auth.gr [Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Macedonia (Greece)

    2014-05-01

    Graphical abstract: - Highlights: • Syndiotactic polystyrene nanocomposites containing MWCNTs and nanodiamonds were prepared for first time. • Addition of nanofillers causes a substantial improvement of sPS thermal stability. • From EGA and Py-GC/MS, it was found that sPS decomposes through a radical process. • The decomposition mechanism of sPS was not affected by the addition of nanoparticles. - Abstract: In the present work, syndiotactic polystyrene (sPS) based nanocomposites containing 3 wt% of multi-walled carbon nanotubes (MWCNTs) and nanodiamonds (NDs) were prepared using the melt-mixing technique. Transmission electron microscopy (TEM) micrographs verified a good dispersion of the nanoparticles in the polymeric matrix, which resulted in a slight improvement of the mechanical properties of the nanocomposites. The addition of MWCNTs promotes the formation of β-type crystals while in sPS and sPS/NDs α-type crystals are mainly formed. From the thermogravimetric analysis experiments a substantial enhancement of sPS thermal stability was found, caused by the addition of nanofillers, especially from NDs. The temperature corresponding to a mass loss of 0.5% was found 295 °C for sPS, 352.4 °C for sPS-MWCNTs and 370.7 °C for sPS-NDs nanocomposites. The analytical method of Py-GC/MS was also used for further characterization of the samples. The main chain fragments collected from sPS pyrolysis were styrene monomers, dimers and trimers, while the three pyrolization temperatures applied (390, 420 and 500 °C) indicated some variations in intensity of decomposition fragments. The decomposition temperature as well as the nanoparticle addition (NDs or MWCNTs) affected the intensity of the recorded fragments but did not induce a change on the decomposition mechanism of sPS.

  14. Elucidating the decomposition mechanism of energetic materials with geminal dinitro groups using 2-bromo-2-nitropropane photodissociation.

    Science.gov (United States)

    Booth, Ryan S; Lam, Chow-Shing; Brynteson, Matthew D; Wang, Lei; Butler, Laurie J

    2013-10-03

    These experiments photolytically generate two key intermediates in the decomposition mechanisms of energetic materials with nitro substituents, 2-nitropropene, and 2-nitro-2-propyl radicals. These intermediates are produced at high internal energies and access a number of competing unimolecular dissociation channels investigated herein. We use a combination of crossed laser-molecular beam scattering and velocity map imaging to study the photodissociation of 2-bromo-2-nitropropane at 193 nm and the subsequent unimolecular dissociation of the intermediates above. Our results demonstrate that 2-bromo-2-nitropropane has four primary photodissociation pathways: C-Br bond fission yielding the 2-nitro-2-propyl radical, HBr elimination yielding 2-nitropropene, C-N bond fission yielding the 2-bromo-2-propyl radical, and HONO elimination yielding 2-bromopropene. The photofragments are formed with significant internal energy and undergo many secondary dissociation events, including the exothermic dissociation of 2-nitro-2-propyl radicals to NO + acetone. Calculations at the G4//B3LYP/6-311++g(3df,2p) level show that the presence of a radical at a nitroalkyl center changes the mechanism for and substantially lowers the barrier to NO loss. This mechanism involves an intermediate with a three-center ring rather than the intermediate formed during the traditional nitro-nitrite isomerization. The observed dissociation pathways of the 2-nitro-2-propyl radical and 2-nitropropene help elucidate the decomposition mechanism of larger energetic materials with geminal dinitro groups.

  15. Estudio cinético de la descomposición catalizada de peróxido de hidrógeno sobre carbón activado Kinetic study of the catalyzed decomposition of hydrogen peroxide on activated carbon

    Directory of Open Access Journals (Sweden)

    Elihu Paternina

    2009-01-01

    Full Text Available The kinetic study of decomposition of hydrogen peroxide catalyzed by activated carbon was carried out. The effect of concentrations of reactants and temperature were experimentally studied. Kinetic data were evaluated using differential method of initial rates of reaction. When a typical kinetic law for reactions in homogeneous phase is used, first order of reaction is obtained for hydrogen peroxide and activated carbon, and activation energy of 27 kJ mol-1 for the reaction was estimated. Experimentally was observed that surface of activated carbon is chemically modified during decomposition of hydrogen peroxide, based on this result a scheme of reaction was proposed and evaluated. Experimental data fits very well to a Langmuir- Hinshelwood kinetic model and activation energy of 40 kJ mol-1 was estimated for reaction in heterogeneous phase.

  16. Kinetic analysis of the chemical processes in the decomposition of gaseous dielectrics by a non-equilibrium plasma - part 1: CF4 and CF4/O2

    Directory of Open Access Journals (Sweden)

    Bauerfeldt Glauco F.

    2000-01-01

    Full Text Available Numerical integration of the coupled differential equations which describe a chemical reacting system and sensitivity analysis are becoming increasingly important tools in chemical kinetics. In this work, a numerical modelling analysis of the chemical processes in the gas-phase decomposition of pure CF4 and CF4/O2 mixtures, in the presence of silicon, was performed. The relative importance of individual processes was analysed and the sensitivity coefficients as well as the effect of the parameters uncertainties were determined . The results were compared with experimental data from the literature to adjust the model parameters. The main etching agent in the system is the fluorine atom. The concentrations of the main species (SiF4, CO, CO2 and COF2 depend on the composition of the mixture.

  17. The effect of Al on thermal stability and kinetics of decomposition of MgH{sub 2} prepared by mechanochemical reaction at different conditions

    Energy Technology Data Exchange (ETDEWEB)

    Ershova, O.G.; Dobrovolsky, V.D., E-mail: dobersh@ipms.kiev.ua; Solonin, Y.M.; Khyzhun, O.Y.; Koval, A.Y.

    2015-07-15

    This work is directed at decreasing decomposition temperature of MgH{sub 2}. In accordance with the theoretical predictions, hydride of solid solution of Al in Mg should decompose at lower temperature compared to that of MgH{sub 2}, and numerous experiments indicate that thermodynamic stability of the hydride depends on methods and conditions of its synthesis. Therefore, the goal of this article is to study the possibility of obtaining the hydride of solid solution of aluminum in magnesium by different technological approaches. Three mechanical composite alloys derived by the different approaches are studied employing the X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermodesorption spectroscopy (TDS) methods. XRD Rietveld analysis reveals that the hydrogenation of a Mg + 10 wt% Al powder by means of reactive milling in the hydrogen atmosphere as well as hydrogenation of the powder from the gaseous phase after milling the powder for 20 h in the argon atmosphere leads to formation of aluminum-free MgH{sub 2} hydride and the Mg{sub 17}Al{sub 12} phase. Our TDS studies (at P{sub H2} = 0.1 MPa) indicate that additives of 10 wt% Al to magnesium do not lead to decreasing the decomposition temperature of MgH{sub 2} prepared by mechanochemical reaction at the different conditions. - Highlights: • Three mechanical alloys with 10% wt. Al additives to Mg have been synthesized. • Hydrogen-sorption properties and thermal stability of the alloys are studied at 1 bar H{sub 2}. • Al additives to Mg do not influence decomposition temperature of MgH{sub 2} phase of the alloys. • Al additives do not improve kinetics of process of hydrogen desorption from MgH{sub 2} phase.

  18. Kinetics of sub-2 nm TiO{sub 2} particle formation in an aerosol reactor during thermal decomposition of titanium tetraisopropoxide

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yang; Liu, Pai; Fang, Jiaxi; Wang, Wei-Ning; Biswas, Pratim, E-mail: pbiswas@wustl.edu [Washington University in St. Louis, Aerosol and Air Quality Research Laboratory, Department of Energy, Environmental & Chemical Engineering (United States)

    2015-03-15

    Particle size distribution measurements from differential mobility analyzers (DMAs) can be utilized to study particle formation mechanisms. However, knowledge on the initial stages of particle formation is incomplete, since in conventional DMAs, the Brownian broadening effect limits their ability to measure sub-2 nm-sized particles. Previous studies have demonstrated the capability of high-flow DMAs, such as the Half Mini DMAs, to measure sub-2 nm particles with significantly higher resolutions than conventional DMAs. A Half Mini DMA was applied to study the kinetics of sub-2 nm TiO{sub 2} nanoparticle formation in a furnace aerosol reactor, through the thermal decomposition of titanium tetraisopropoxide (TTIP). The influence of parameters such as reaction temperature, residence time, precursor concentration, and the introduction of bipolar charges on sub-2 nm particle size distributions were studied. A first order reaction rate derived from the dependence of size distributions on reaction temperature matched well with existing literature data. The change in precursor residence time and precursor concentration altered the size distributions correspondingly, indicating the occurrence of TTIP thermal decomposition. The introduction of bipolar charges in aerosol reactors enhanced the consumption of reactants, possibly due to ion-induced nucleation and induced dipole effects.

  19. Thermolysis, nonisothermal decomposition kinetics, specific heat capacity and adiabatic time-to-explosion of [Cu(NH3)4](DNANT)2 (DNANT= dinitroacetonitrile).

    Science.gov (United States)

    Zhang, Yu; Wu, Hao; Xu, Kangzhen; Zhang, Wantao; Ren, Zhaoyu; Song, Jirong; Zhao, Fengqi

    2014-02-20

    A new energetic copper complex of dinitroacetonitrile (DNANT), [Cu(NH3)4](DNANT)2, was first synthesized through an unexpected reaction. The thermal decomposition of [Cu(NH3)4](DNANT)2 was studied with DSC and TG/DTG methods. The gas products were analyzed through a TG-FTIR-MS method. The nonisothermal kinetic equation of the exothermic process is dα/dT = 10(10.92)/β4(1 - α)[-ln(1 - α)](3/4) exp(-1.298 × 10(5)/RT). The self-accelerating decomposition temperature and critical temperature of thermal explosion are 217.9 and 221.0 °C. The specific heat capacity of [Cu(NH3)4](DNANT)2 was determined with a micro-DSC method, and the molar heat capacity is 512.6 J mol(-1) K(-1) at 25 °C. Adiabatic time-to-explosion of Cu(NH3)4(DNANT)2 was also calculated to be about 137 s.

  20. Group-colouring, group-connectivity, claw-decompositions, and orientations in 5-edge-connected planar graphs

    DEFF Research Database (Denmark)

    Richter, R. Bruce; Thomassen, Carsten; Younger, Daniel H.

    2016-01-01

    Let G be a graph, let Γ be an Abelian group with identity 0Γ, and, for each vertex v of G, let p(v) be a prescription such that ∑v∈V(G)p(v)=0Γ. A (Γ,p)-flow consists of an orientation D of G and, for each edge e of G, a label f(e) in Γ∖{0Γ} such that, for each vertex v of G, ∑e points in to v f(e...

  1. Kinetic equation for the reaction of titanium tetrachloride with hydride functional groups of diamond

    Energy Technology Data Exchange (ETDEWEB)

    Zhidkov, A.B.; Smirnov, E.P.

    1989-02-01

    This work is devoted to the study of the kinetics of the reaction of titanium tetrachloride with the hydride functional groups of diamond. The research was performed on submicron powders of ASM 0.7/0.3 grade synthetic diamond with a specific surface area of 8.0 m/sup 2//g as measured from the adsorption of nitrogen. The reaction was carried out in a flow-through quartz reactor in a flow of dry He. The content of the titanium in the samples was determined by a photocolorimetric method. A kinetic equation for the reaction of diamond with titanium tetrachloride was found on the basis of a statistical approach.

  2. Gas Pressure Monitored Iodide-Catalyzed Decomposition Kinetics of H[subscript 2]O[subscript 2]: Initial-Rate and Integrated-Rate Methods in the General Chemistry Lab

    Science.gov (United States)

    Nyasulu, Frazier; Barlag, Rebecca

    2010-01-01

    The reaction kinetics of the iodide-catalyzed decomposition of [subscript 2]O[subscript 2] using the integrated-rate method is described. The method is based on the measurement of the total gas pressure using a datalogger and pressure sensor. This is a modification of a previously reported experiment based on the initial-rate approach. (Contains 2…

  3. Effects of magnetic and kinetic helicities on the growth of magnetic fields in laminar and turbulent flows by helical-Fourier decomposition

    Science.gov (United States)

    Linkmann, Moritz; Sahoo, Ganapati; McKay, Mairi; Berera, Arjun; Biferale, Luca

    2016-11-01

    We perform an analytical and numerical study of incompressible homogeneous conducting fluids by Fourier-helical decomposition of the equations of magnetohydrodynamics (MHD) and a subsequent reduction of the number of degrees of freedom. From the stability properties of the most general subset of interacting velocity and magnetic fields on a closed Fourier triad, we make predictions on the large-scale magnetic-field growth depending on the distribution of magnetic and kinetic helicities among the three wavenumbers. In the kinematic dynamo regime we predict the formation of a large-scale magnetic component with a magnetic helicity of opposite sign with respect to the kinetic helicity, a sort of triadic-by-triad α-effect in Fourier space, while in presence of strong small-scale magnetic helicity we predict an inverse cascade of magnetic helicity. We confirm these predictions through a series of Direct Numerical Simulations, either seeding different magnetic helical components in a strongly helical flow (turbulent/laminar) or directly injecting helical magnetic fluctuations at small scales. Our results show that important dynamical features of MHD flows can be predicted from an analytically tractable dynamical system derived directly from the MHD equations. ERC ADG NewTURB 2013.

  4. Recursive solutions for multi-group neutron kinetics diffusion equations in homogeneous three-dimensional rectangular domains with time dependent perturbations

    Energy Technology Data Exchange (ETDEWEB)

    Petersen, Claudio Z. [Universidade Federal de Pelotas, Capao do Leao (Brazil). Programa de Pos Graduacao em Modelagem Matematica; Bodmann, Bardo E.J.; Vilhena, Marco T. [Universidade Federal do Rio Grande do Sul, Porto Alegre, RS (Brazil). Programa de Pos-graduacao em Engenharia Mecanica; Barros, Ricardo C. [Universidade do Estado do Rio de Janeiro, Nova Friburgo, RJ (Brazil). Inst. Politecnico

    2014-12-15

    In the present work we solve in analytical representation the three dimensional neutron kinetic diffusion problem in rectangular Cartesian geometry for homogeneous and bounded domains for any number of energy groups and precursor concentrations. The solution in analytical representation is constructed using a hierarchical procedure, i.e. the original problem is reduced to a problem previously solved by the authors making use of a combination of the spectral method and a recursive decomposition approach. Time dependent absorption cross sections of the thermal energy group are considered with step, ramp and Chebyshev polynomial variations. For these three cases, we present numerical results and discuss convergence properties and compare our results to those available in the literature.

  5. A kinetic study of ferrocenium cation decomposition utilizing an integrated electrochemical methodology composed of cyclic voltammetry and amperometry.

    Science.gov (United States)

    Singh, Archana; Chowdhury, Debarati Roy; Paul, Amit

    2014-11-21

    A novel, easy, quick, and inexpensive integrated electrochemical methodology composed of cyclic voltammetry and amperometry has been developed for the determination of the kinetic stability of higher oxidation states for inorganic complexes. In this study, ferrocene and its derivatives have been used as model systems and the corresponding ferrocenium cations were generated in situ during the electrochemical experiments to determine their kinetic stabilities. The study found that the ferrocenium cations decompose following the first-order kinetics at 27 ± 3 °C in the presence of ambient oxygen and water. The half-lives of the ferrocenium, carboxylate ferrocenium, and decamethyl ferrocenium cations were found to be 1.27 × 10(3), 1.52 × 10(3), and ≫11.0 × 10(3) s, respectively, in acetonitrile solvent having a 0.5 M tetrabutylammonium hexafluorophosphate electrolyte. These results are in agreement with the previous reports, i.e. the ferrocenium cation is unstable whereas the decamethyl ferrocenium cation has superior stability. The new methodology has been established by performing various experiments using different concentrations of ferrocene, variable scan rates in cyclic voltammetry, different time periods for amperometry, and in situ spectroelectrochemical experiments.

  6. Ab initio Kinetics of Methylamine Radical Thermal Decomposition and H-abstraction from Monomethylhydrazine by H Atom

    Science.gov (United States)

    2014-08-01

    of Mechanical and Aerospace Engineering , Princeton University, Princeton, New Jersey 08544 Abstract Methylamine radicals (CH3NH) and amino...kcal/mol, forming CH2=NH (R4). The N―H bond fission reaction in the CH3NH radical that leads to the triplet 3CH3N radical and H atom is endothermic by...elimination from the CH3NH radical is endothermic by 13.24 kcal mol-1 (R6), but its energy barrier is quite high, 99.62 kcal mol-1, and is not kinetically

  7. An algorithm for multi-group two-dimensional neutron diffusion kinetics in nuclear reactor cores

    OpenAIRE

    Marcelo Schramm

    2016-01-01

    The objective of this thesis is to introduce a new methodology for two{dimensional multi{ group neutron diffusion kinetics in a reactor core. The presented methodology uses a polyno- mial approximation in a rectangular homogeneous domain with non{homogeneous boundary conditions. As it consists on a truncated Taylor series, its error estimates varies with the size of the rectangle. The coefficients are obtained mainly by their relations with the independent term, which is determined by the dif...

  8. Kinetics evaluation and thermal decomposition characteristics of co-pyrolysis of municipal sewage sludge and hazelnut shell.

    Science.gov (United States)

    Zhao, Bing; Xu, Xinyang; Li, Haibo; Chen, Xi; Zeng, Fanqiang

    2017-09-07

    Hazelnut shell, as novel biomass, has lower ash content and abundant hydrocarbon, which can be utilized resourcefully with municipal sewage sludge (MSS) by co-pyrolyisis to decrease total content of pollution. The co-pyrolysis of MSS and hazelnut shell blend was analyzed by a method of multi-heating rates and different blend ratios with TG-DTG-MS under N2 atmosphere. The apparent activation energy of co-pyrolysis was calculated by three iso-conversional methods. Satava-Sestak method was used to determine mechanism function G(α) of co-pyrolysis, and Lorentzian function was used to simulate multi-peaks curves. The results showed there were four thermal decomposition stages, and the biomass were cracked and evolved at different temperature ranges. The apparent activation energy increased from 123.99 to 608.15kJ/mol. The reaction mechanism of co-pyrolysis is random nucleation and nuclei growth. The apparent activation energy and mechanism function afford a theoretical groundwork for co-pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Quantum mechanical studies of the kinetics, mechanisms and thermodynamics of gas-phase thermal decomposition of ethyl dithiocarbonate (xanthate

    Directory of Open Access Journals (Sweden)

    I.A. Adejoro

    2017-09-01

    Full Text Available Theoretical studies were carried out to investigate the thermal decomposition of ethyl dithiocarbonates (xanthate using Hartree–Fock at the HF/321-G* level and the density functional method with Becke 3 Lee Yang pair DFT/(B3LYP, 6-31G*, 6-31G**, 6-31+G*, MP2 and CCSD in the ab initio method of calculation using Spartan 10. Geometric parameters, such as the bond length, bond angles, dihedral angles, heat of formation, atomic charges and vibrational frequencies, were obtained. The data were used to calculate the thermodynamics parameters, change in entropy ΔS, enthalpy change ΔH, free energy G, pre-exponential factor A, rate k at 623 K, and variation of rate k with temperatures from 498–623 K at temperature intervals of 25 K. It was observed that the values obtained are in good agreement with the experimental values for the ab initio methods, and according to Arrhenius theory, the calculated rate k increases with increasing temperature.

  10. Non-Isothermal Kinetics of Thermal Decomposition of a Novel Antitumor Agent 4- {5- [3,4-Dimethyl-5- (3,4,5-Trimethoxyphenyl) Thiophen-2-yl] -2- Methoxyphenyl} Morpholine

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The thermal decomposition of a new antitumor agent, 4-{5-[3,4-dimethyl-5-(3,4,5-trime-thoxyphenyl)thiophen-2-yl--2-methoxyphenyl} morpholine was studied by Differential Scanning Calorimetry (DSC) and Thermogravimetry (TG)/ Derivative Thermogravimetry (DTG) methods at a flow rate of nitrogen gas of 120 mL/min. The kinetic parameters were obtained from the analysis of the corresponding curves by Kissinger's method, Ozawa's method and the integral method. The results indicate that the apparent activation energy and pre-exponential constants of the decomposition reaction are 106.67 kJ/mol and 106.19 S-1, respectively.

  11. Group 4 Half-Sandwich Tris(trimethylsilylmethyl) Complexes: Thermal Decomposition and Reactivity with N,N-Dimethylamine-Borane.

    Science.gov (United States)

    Greño, Maider; Horno, Estefanía Del; Mena, Miguel; Pérez-Redondo, Adrián; Varela-Izquierdo, Víctor; Yélamos, Carlos

    2017-08-29

    The thermal decomposition of group 4 trimethylsilylmethyl derivatives [M(η(5)-C5Me5)(CH2SiMe3)3] (M = Ti (1), Zr (2), Hf (3)) in solution and their reactivity with N,N-dimethylamine-borane were investigated. Heating of hydrocarbon solutions of compounds 2 and 3 at 130-200 °C results in the elimination of SiMe4 and the clean formation of the singular alkylidene-alkylidyne zirconium and hafnium compounds [{M(η(5)-C5Me5)}3{(μ-CH)3SiMe}(μ3-CSiMe3)] (M = Zr (4), Hf (5)). The reaction of 2 and 3 with NHMe2BH3 (≥1 equiv) at room temperature affords the dialkyl(dimethylamidoborane) complexes [M(η(5)-C5Me5)(CH2SiMe3)2(NMe2BH3)] (M = Zr (6), Hf (7)). Compounds 6 and 7 are unstable in solution and decompose with formation of the alkyl(dimethylamino)borane [B(CH2SiMe3)H(NMe2)] (8), SiMe4, and other minor byproducts, including the tetranuclear zirconium(III) octahydride complex [{Zr(η(5)-C5Me5)}4(μ-H)8] (9) in the decomposition of 6. Addition of NHMe2BH3 to the titanium tris(trimethylsilylmethyl) derivative 1 gives the trinuclear mixed valence Ti(II)/Ti(III) tetrahydride complex [{Ti(η(5)-C5Me5)(μ-H)}3(μ3-H)(μ3-NMe2BH2)] (10) at 45-65 °C. While the complete conversion of 1 under argon atmosphere requires excess NHMe2BH3 (up to 15 equiv), complex 10 is readily prepared with 3 equiv of NHMe2BH3 under a hydrogen atmosphere indicating that the formation of 10 involves hydrogenolysis of 1 in the presence of (NMe2BH2)2. In absence of amine-borane, the reaction of 1 with H2 leads to the tetranuclear titanium(III) octahydride [{Ti(η(5)-C5Me5)}4(μ-H)8] (11), which upon addition of NHMe2BH3 and subsequent heating at 65 °C affords complex 10. The X-ray crystal structures of 2, 4, 5, 10, and 11 were determined.

  12. Role of epigeic earthworms on trophic group of nematodes during organic matter decomposition in litter bags under tomato cropping on ultisol

    Science.gov (United States)

    Alam, Syamsu; Lisnawati, Kilowasid, Laode Muhammad Harjoni; Darwis, Asniah, Nurmas, Andi

    2015-09-01

    Epigeic earthworms are often used to restore of soil quality. Trophic group of nematodes plays an important role in driving of decomposition rate of organic matter. Ultisols is characterized with the soil biological quality that is not suitable for the development of vegetable crops. The objective of this study was to analyze the effect of epigeic earthworms on the abundance of nematode trophic groups during the decomposition of organic material in litter bags under cropping of tomato (L. esculentum Mill.) on Ultisols. Epigeic species of earthworms (Lumbricus sp.) were used to modify the soil environment. The experiment treatment consisted of nine combinations of three types of organic matter and three individual levels of earthworms. The organic material consisted of litters of C. odorata, I. cylindrica and Colopogonium sp. The number of earthworms consisted of 0, 20 and 40 individuals plot-1. Each combination of each litter type and number of earthworms was repeated three times in an experimental randomized block design. Research found three trophic groups of nematodes, namely root-herbivorous, bacterivorous and predaceous in the litter bags. Abundance of root-herbivorous between combinations was significantly different at 30 days after exposure. Abundance of bacterivorous nematodes among treatments was significant at 60 days after exposure, which at the 30 and 90 days were not significant. Abundance of predaceous was differed significantly at the 60 and 90 days, and at the 30 days was not significantly different. Constant of decomposition rate of each organic matter under different number of earthworms was similar. Coefficient correlation showed that relation between the constant of decomposition rate with abundance of root-herbivorous was positive at 30 days and negative with bacterivorous at the 90 days. Research concluded that the introduction of epigeic earthworms influenced trophic group dynamics of nematodes during the decomposition of organic material

  13. Synthesis of Cubic Phase-Co Microspheres by Mechanical Solid-State Reaction-Thermal Decomposition and Research on Its Growth Kinetics

    Directory of Open Access Journals (Sweden)

    Ying Deng

    2016-01-01

    Full Text Available Cubic phase cobalt (Co, which can be used as a key component for composite materials given its excellent ductility and internal structure, is not easy to obtain at room temperature. In this study, oxalic acid and cobalt nitrate are used as raw materials to synthesize the cobalt oxalate precursor, which has a stable structure with a five-membered chelate ring. Cobalt oxalate microspheres, having a high internal energy content, were prepared by using mechanical solid-state reaction in the presence of a surfactant, which can produce spherical micelles. The thermal decomposition of the precursor was carried out by maintaining it in a nitrogen atmosphere at 450°C for 3 h. At the end of the procedure, 100 nm cubic phase-Co microspheres, stable at room temperature, were obtained. Isothermal and nonisothermal kinetic mechanisms of cobalt grain growth were investigated. The cubic-Co grain growth activation energy, Q, was calculated in this study to be 71.47 kJ/mol. The required reaction temperature was low, making the production process simple and suitable for industrial applications.

  14. Thermal decomposition of a molecular material {N(n-C4H94[FeIIFeIII(C2O43]}∞ leading to ferrite: A reaction kinetics study

    Directory of Open Access Journals (Sweden)

    Bhattacharjee Ashis

    2013-01-01

    Full Text Available A multi-step thermal decomposition of a molecular precursor, {N(n-C4H94[FeIIFeIII(C2O43}∞ has been studied using non-isothermal thermogravimetry (TG measurements in the temperature range 300 to ~800 K at multiple heating rates (5, 10 and 20 K min-1. The thermal decomposition of the oxalate-based complex proceeds stepwise through a series of intermediate reactions. Two different isoconversional methods, namely, improved iterative method and model-free method are employed to evaluate the kinetic parameters: activation energy and rate of reaction, and the most probable reaction mechanism of thermal decomposition is also determined. The different reaction pathways leading to different steps in the TG profile have also been explored which are supplemented by earlier experimental observations of the present authors.

  15. A Kinetics Investigation on the Nitro-Nitrite Rearrangement Mediated Thermal Decomposition of High Temperature Monoclinic Phase of 1,1-Diamino-2,2-Dinitroethylene (γ -Fox-7)

    Indian Academy of Sciences (India)

    KRANTHI CHATRAGADDA; ANUJ A VARGEESE

    2017-02-01

    1,1-Diamino-2,2-dinitroethylene (DADNE), commonly known as FOX-7, is one of the novel high energy density molecules recently developed along with CL-20, TNAZ and ADN. DADNE is well-known for its insensitive nature and this has motivated the research in understanding the thermal and explosive decompositionbehaviour of DADNE. We have studied the thermal decomposition kinetics of DADNE employing two isoconversional methods viz., Friedman’s differential method and Vyazovkin’s non-linear integral method. For the study, Differential Scanning Calorimetry as well as Thermogravimetry data collected at lower heatingrates (<5◦C/min) were used. This study indicated a four stage decomposition behaviour of DADNE, where each stage is characterised by different activation energy. Computed activation energy values have been usedto understand the thermal decomposition mechanism of DADNE.

  16. Kinetics of thermal decomposition of typical waste materials%典型垃圾材料的热分解动力学

    Institute of Scientific and Technical Information of China (English)

    李新跃; 彭庆法; 张浩; 谢超鸣

    2011-01-01

    对垃圾材料的热分解动力学研究目的在于研究垃圾材料的热解特性,文中对典型垃圾材料聚氯乙烯(PVC)和纸进行热分解动力学研究.用综合热分析仪分别测试PVC及纸在升温速率为10,15,20,30 K/min时的TG-DSC曲线,获取PVC和纸在最大质量损失速率时的温度Tmax及其他动力学参数.然后用Kissinger法和Flynn-Wall-Ozawa法处理实验数据并且计算得出PVC和纸在最大质量损失速率温度Tmax时的活化能和指前因子.计算结果为:采用Kissinger最大质量损失速率法求得PVC的活化能E=35.98 kJ/mol,指前因子A=8.7×105;纸的活化能E=55.15 kJ/mol,指前因子A=9.5×107.用Flynn-Wall-Ozawa法求得PVC的活化能E=38.029 kJ/mol;纸的活化能E= 40.426 kJ/mol.结果表明:垃圾的成分复杂,影响其热分解的因素较多,采用单一的动力学研究方法难以得到满意的实际应用结果.%The purpose of the experiment about thermal decomposition kinetics is to study the pyrolysis characteristics of waste materials. The thermal decomposition kinetics of typical waste materials of polyvinyl chloride (PVC) and paper was studied by means of TG and DSC at different heating rates of 10, 15, 20, 30 K/min. Maximum temperature Tmax and other kinetic parameters of PVC and paper at maximum mass loss rate were obtained. Based on Kissinger's method, the activation energies and exponential factors of PVC and paper were calculated as E = 35.98 kJ/mol and A = 8.7 × 105, E =55.15 kJ/mol and A =9.5 × 107 respectively. And based on Flynn-Wall-Ozawa's method, the activation energies of PVC and paper were calculated as £ = 38.029 kj/mol and E =40.426 kj/mol respectively. The calculated results together with the complexity of the components of waste and other influence factors lead inescapably to the conclusion that it is difficult to get a good agreement with the actual application result by single dynamics research method.

  17. Ethylene Decomposition Initiated by Ultraviolet Radiation from Low Pressure Mercury Lamps: Kinetics Model Prediction and Experimental Verification.

    Science.gov (United States)

    Jozwiak, Zbigniew Boguslaw

    1995-01-01

    Ethylene is an important auto-catalytic plant growth hormone. Removal of ethylene from the atmosphere surrounding ethylene-sensitive horticultural products may be very beneficial, allowing an extended period of storage and preventing or delaying the induction of disorders. Various ethylene removal techniques have been studied and put into practice. One technique is based on using low pressure mercury ultraviolet lamps as a source of photochemical energy to initiate chemical reactions that destroy ethylene. Although previous research showed that ethylene disappeared in experiments with mercury ultraviolet lamps, the reactions were not described and the actual cause of ethylene disappearance remained unknown. Proposed causes for this disappearance were the direct action of ultraviolet rays on ethylene, reaction of ethylene with ozone (which is formed when air or gas containing molecular oxygen is exposed to radiation emitted by this type of lamp), or reactions with atomic oxygen leading to formation of ozone. The objective of the present study was to determine the set of physical and chemical actions leading to the disappearance of ethylene from artificial storage atmosphere under conditions of ultraviolet irradiation. The goal was achieved by developing a static chemical model based on the physical properties of a commercially available ultraviolet lamp, the photochemistry of gases, and the kinetics of chemical reactions. The model was used to perform computer simulations predicting time dependent concentrations of chemical species included in the model. Development of the model was accompanied by the design of a reaction chamber used for experimental verification. The model provided a good prediction of the general behavior of the species involved in the chemistry under consideration; however the model predicted lower than measured rate of ethylene disappearance. Some reasons for the model -experiment disagreement are radiation intensity averaging, the experimental

  18. Ab Initio Chemical Kinetics for the CH3 + O((3)P) Reaction and Related Isomerization-Decomposition of CH3O and CH2OH Radicals.

    Science.gov (United States)

    Xu, Z F; Raghunath, P; Lin, M C

    2015-07-16

    The kinetics and mechanism of the CH3 + O reaction and related isomerization-decomposition of CH3O and CH2OH radicals have been studied by ab initio molecular orbital theory based on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ, CCSD/aug-cc-pVDZ, and G2M//B3LYP/6-311+G(3df,2p) levels of theory. The predicted potential energy surface of the CH3 + O reaction shows that the CHO + H2 products can be directly generated from CH3O by the TS3 → LM1 → TS7 → LM2 → TS4 path, in which both LM1 and LM2 are very loose and TS7 is roaming-like. The result for the CH2O + H reaction shows that there are three low-energy barrier processes including CH2O + H → CHO + H2 via H-abstraction and CH2O + H → CH2OH and CH2O + H → CH3O by addition reactions. The predicted enthalpies of formation of the CH2OH and CH3O radicals at 0 K are in good agreement with available experimental data. Furthermore, the rate constants for the forward and some key reverse reactions have been predicted at 200-3000 K under various pressures. Based on the new reaction pathway for CH3 + O, the rate constants for the CH2O + H and CHO + H2 reactions were predicted with the microcanonical variational transition-state/Rice-Ramsperger-Kassel-Marcus (VTST/RRKM) theory. The predicted total and individual product branching ratios (i.e., CO versus CH2O) are in good agreement with experimental data. The rate constant for the hydrogen abstraction reaction of CH2O + H has been calculated by the canonical variational transition-state theory with quantum tunneling and small-curvature corrections to be k(CH2O + H → CHO + H2) = 2.28 × 10(-19) T(2.65) exp(-766.5/T) cm(3) molecule(-1) s(-1) for the 200-3000 K temperature range. The rate constants for the addition giving CH3O and CH2OH and the decomposition of the two radicals have been calculated by the microcanonical RRKM theory with the time-dependent master equation solution of the multiple quantum well system in the 200-3000 K temperature range at 1 Torr to

  19. Decomposition kinetics of alkaline earth carbonates by integral approximation method Cinética de decomposição de carbonatos de terra alcalina pelo método de aproximação integral

    Directory of Open Access Journals (Sweden)

    S. Maitra

    2008-09-01

    Full Text Available The decomposition kinetics of four synthetic alkaline earth metal carbonates (MgCO3, CaCO3, SrCO3 and BaCO3 was studied under non-isothermal conditions from thermo-gravimetric measurements as compared to. The integral approximation method of Coats and Redfern was used to determine the kinetic parameters for the decomposition processes. The decomposition reactions followed mostly first order kinetics and the activation energy of the decomposition reactions increased with the increase in the molecular mass of the carbonates. The change in enthalpy for the decomposition processes was also calculated and compared with the activation energies for the decomposition processes. The activation energy of the decomposition process for all the carbonates was higher than the enthalpy of the reaction excepting SrCO3.A cinética de decomposição de quatro carbonatos sintéticos de metais de terra alcalina (MgCO3, CaCO3, SrCO3 e BaCO3 foi estudada sob condições não isotérmicas por meio de medidas de termogravimétricas e feita sua comparação. O método de aproximação integral de Coats e Redfern foi usado para determinar os parâmetros cinéticos dos processos de decomposição. As reações de decomposição seguiram principalmente cinética de primeira ordem e a energia de ativação para as reações de decomposição aumentou com o aumento da massa molecular dos carbonatos. A variação na entalpia para os processos de decomposição foi também calculada e comparada com as energias de ativação. A energia de ativação dos processos de decomposição de todos os carbonatos foi maior que a entalpia da reação excepto para SrCO3.

  20. Estimation of the Kinetic Parameters and the Critical Rate of Temperature Rise in the Thermal Explosion from the Exothermic Autocatalytic Decomposition of 3,4-Bis(4′-nitrofurazan-3′-yl)-2-oxofurazan (BNFOF) Using Non-isothermal Differential Scanning Calorimetry

    Institute of Scientific and Technical Information of China (English)

    ZHAO Feng-Qi; ZHOU Yan-Shui; ZHAO Hong-An; GAO Sheng-Li; SHI Qi-Zhen; LU Gui-E; JIANG Jin-Yong; GUO Peng-Jiang; HU Rong-Zu; ZHANG Hai; XIA Zhi-Ming; GAO Hong-Xu; CHEN Pei; LUO Yang; ZHANG Zhi-Zhong

    2006-01-01

    A method of estimating the kinetic parameters and the critical rate of temperature rise in the thermal explosion for the autocatalytic decomposition of 3,4-bis(4′-nitrofurazan-3′-yl)-2-oxofurazan (BNFOF) with non-isothermal differential scanning calorimetry (DSC) was presented. The rate equation for the decomposition of BNFOF was established, and information was obtained on the rate of temperature increase in BNFOF when the empiric-order autocatalytic decomposition was converted into thermal explosion.

  1. Kinetic behaviour of two-species-group aggregation process with complete annihilation

    Institute of Scientific and Technical Information of China (English)

    柯见洪; 林振权; 王向红

    2003-01-01

    We propose a two-species-group aggregation-annihilation model in which an irreversible aggregation reaction occurs between any two clusters of the same species, and an irreversible joint annihilation reaction occurs between two distinct species groups. Based on the mean-field theory, we have investigated the rate equations of the process with constant reaction rates to obtain the asymptotic descriptions of the cluster-mass distributions. The results indicate that for the symmetrical initial cases the kinetic behaviour of the system depends crucially on the ratio of the equivalent aggregation rate to the annihilation rate. The cluster-mass distribution of each species always obeys a conventional or modified scaling law in each individual case. Moreover, all the species cannot finally survive except for the cases in which at least one equivalent aggregation rate is less than twice the annihilation rate.

  2. Mo-Bi系丙烯氨氧化催化剂上氨分解反应动力学的Monte Carlo模拟%Monte Carlo Simulation of Kinetics of Ammonia Oxidative Decomposition over the Commercial Propylene Ammoxidation Catalyst (Mo-Bi)

    Institute of Scientific and Technical Information of China (English)

    罗正鸿; 詹晓力; 陈丰秋; 阳永荣

    2003-01-01

    Monte Carlo method is applied to investigate the kinetics of ammonia oxidative decomposition overthe commercial propylene ammoxidation catalyst(Mo-Bi). The simulation is quite in agreement with experimentalresults. Monte Carlo simulation proves that the process of ammonia oxidation decomposition is a two-step reaction.

  3. Kinetics Study of the Effect of Oxygen on Ammonia Decomposition on Ru%Ru上有氧条件下氨分解的动力学研究

    Institute of Scientific and Technical Information of China (English)

    李忠来; 梁长海; 王德峥; 李灿

    2004-01-01

    @@ It has been shown that Ru is valid for the synthesis and decomposition of ammonia[1,2]. Further study of ammonia adsorption and its decomposition products desorption on Ru will be important. Previous studies of ammonia adsorption on Ru mainly focused on the ammonia synthesis and hydrogen production in the absence of oxygen[3], only a few investigations on ammonia decomposition in the presence of oxygen have been reported[4,5], and the effect of adsorbed oxygen on the rates of ammonia decomposition and product formation on Ru are still not well understood. In this paper, NH3 decomposition on Ru/SiO2 was investigated in the presence of oxygen using a temporal analysis of products (TAP) reactor.

  4. Decomposition kinetics of gaseous ozone in peanuts Cinética da decomposição do gás ozônio em amendoim

    Directory of Open Access Journals (Sweden)

    Ernandes R. de Alencar

    2011-10-01

    Full Text Available This study was conducted to evaluate the decomposition kinetics of gaseous ozone in peanut grains. This evaluation was made with 1-kg peanut samples, moisture contents being 7.1 and 10.5% wet basis (w.b., placed in 3-liter glass containers. The peanut grains were ozonated at the concentration of 450 µg L-1, at 25 and 35 ºC, with gas flow rates of 1.0 and 3.0 L min-1. Time of saturation was determined by quantifying the residual concentration of ozone after the gas passed through the grains to constant mass. The decomposition kinetics of ozone was evaluated after the grain mass was ozone-saturated. For the peanut grains whose moisture content was 7.1% (w.b., at 25 and 35ºC and with flow rates of 1.0 and 3.0 L min-1, the values obtained for time of saturation of gaseous ozone ranged between 173 and 192 min; the concentration of saturation was approximately 260 µg L-1. For the grains whose moisture content was 10.5% (w.b., a higher residual concentration of gaseous ozone was obtained at 25 ºC, that of 190 µg L-1. As regards the half-life of ozone, the highest value obtained was equivalent to 7.7 min for grains ozonated at 25 ºC, while for those with moisture content of 10.5% at 35 ºC, half-life was 3.2 min. In the process of ozone decomposition in peanut grains, temperature was concluded to be the key factor. An increase of 10 ºC in the temperature of the grains results in a decrease of at least 43% in the half-life of ozone.Este trabalho foi desenvolvido com o objetivo de avaliar a cinética de decomposição do ozônio em grãos de amendoim. Para avaliar a cinética de decomposição do gás, utilizaram-se amostras de 1 kg de amendoim, com teores de água de 7,1 e 10,5% base úmida (b.u., acondicionadas em recipientes de vidro com capacidade de 3 L. Os grãos de amendoim foram ozonizados na concentração de 450 µg L-1, nas temperaturas de 25 e 35 ºC, e vazões do gás de 1,0 e 3,0 L min-1. Determinou-se o tempo de satura

  5. Effect of bioceramic functional groups on drug binding and release kinetics

    Science.gov (United States)

    Trujillo, Christopher

    Bioceramics have been studied extensively as drug delivery systems (DDS). Those studies have aimed to tailor the drug binding and release kinetics to successfully treat infections and other diseases. This research suggests that the drug binding and release kinetics are predominantly driven by the functional groups available on the surface of a bioceramic. The goal of the present study is to explain the role of silicate and phosphate functional groups in drug binding to and release kinetics from bioceramics. alpha-cristobalite (Cris; SiO2) particles (90-150 microm) were prepared and doped with 0 microg (P-0), 39.1 microg (P-39.1), 78.2 microg (P-78.2), 165.5 microg (P-165.5) or 331 microg (P-331) of P 2O5 per gram Cris, using 85% orthophosphoric (H3PO 4) acid and thermal treatment. The material structure was analyzed using X-ray diffraction (XRD) with Rietveld Refinement and Fourier Transform Infrared (FTIR) spectroscopy with Gaussian fitting. XRD demonstrated an increase from sample P-0 (170.5373 A3) to P-331 (170.6466 A 3) in the unit cell volume as the P2O5 concentration increased in the material confirming phosphate silicate substitution in Cris. Moreover, FTIR showed the characteristic bands of phosphate functional groups of nu4 PO4/O-P-O bending, P-O-P stretching, P-O-P bending, P=O stretching, and P-O-H bending in doped Cris indicating phosphate incorporation in the silicate structure. Furthermore, FTIR showed that the nu4 PO4/O-P-O bending band around 557.6 cm-1 and P=O stretching band around 1343.9 cm-1 increased in area for samples P-39.1 to P-331 from 3.5 to 10.5 and from 10.1 to 22.4, respectively due to phosphate doping. In conjunction with the increase of the nu4 PO4/O-P-O bending band and P=O stretching band, a decrease in area of the O-Si-O bending bands around 488.1 and 629.8 cm-1 was noticed for samples P-39.1 to P-331 from 5 to 2 and from 11.8 to 5.4, respectively. Furthermore, Cris samples (200 mg, n=5 for each sample) were immersed separately in

  6. STUDY OF THERMAL-DECOMPOSITION KINETICS OF Mg-Fe AND Mg-Al HYDROTALCITE WITH THE METHOD OF TEMPERATURE PROGRAMMED CALCINATION%程序升温焙烧技术研究水滑石热分解动力学

    Institute of Scientific and Technical Information of China (English)

    张维光; 葛欣; 沈俭一

    1999-01-01

    Mg-Fe and Mg-Al Hydrotalcite were prepared by the conprecipitation method. A new technique of temperature programmed calcination (TPC) is designed to investigate the thermal decomposition of the hydrotalcites. The kinetic equation of thermal decomposition ln(h/S)=lnA-Ea/RT is derived from TPC graph, and then the thermal decomposition kinetics parameters of Mg-Fe and Mg-Al hydrotalcite can be obtained. Experimental results show that this method is more definite, convenient and sensitive for characterizing the thermal decomposition process of Mg-Fe and Mg-Al Hydrotalcite. The active energy Ea of decomposition of Mg-Fe and Mg-Al hydrotalcite is about 83~48 kJ·mol-1.

  7. Effect of dysprosium on the kinetics and structural transformations during the decomposition of the supersaturated solid solution in magnesium-samarium alloys

    Science.gov (United States)

    Rokhlin, L. L.; Luk'yanova, E. A.; Tabachkova, N. Yu.; Dobatkina, T. V.; Tarytina, I. E.; Korol'kova, I. G.

    2017-03-01

    The effect of dysprosium added in the amounts such that it does not form an individual phase in equilibrium with solid magnesium on the decomposition of the supersaturated magnesium solid solution in Mg-Sm alloys is studied. The presence of dysprosium in Mg-Sm alloys is found to retard the decomposition of the supersaturated magnesium solid solution and to increase the hardening effect upon aging. When these alloys are aged, dysprosium is partly retained in the magnesium solid solution and partly enters into the compositions of the phases that form during the decomposition of the solid solution and are characteristic of Mg-Sm alloys.

  8. R and G color component competition of RGB image decomposition as a criterion to register RBC agglutinates for blood group typing.

    Science.gov (United States)

    Doubrovski, Valeri A; Ganilova, Yuliya A; Zabenkov, Igor V

    2014-03-01

    A new approach of the criterion assignment for registration of erythrocyte agglutinates to instrumentally determine blood group type is suggested. The criterion is based on comparison of R and G components of RGB decomposition of microscopy digital image taken for the blood-serum mixture sample. For the chosen experimental conditions, the minimal size (area) of RBC agglutinate to be registered by the criterion suggested is estimated theoretically. The proposed method was tested experimentally on the example of monitoring agglutinates in flow. The encouraging experimental results were obtained for improvement of the resolving power of the method; the optimal experimental conditions were revealed for maximum resolution. Though the suggested method was realized for dynamic (flow) blood group determination, it could also be applied for diagnostics in a stationary environment. This approach increases the reliability of RBC agglutinates registration and, hence, blood group typing. The results may be used to develop the apparatus for automated determination of human blood group.

  9. Particle-Size-Grouping Model of Precipitation Kinetics in Microalloyed Steels

    Science.gov (United States)

    Xu, Kun; Thomas, Brian G.

    2012-03-01

    The formation, growth, and size distribution of precipitates greatly affects the microstructure and properties of microalloyed steels. Computational particle-size-grouping (PSG) kinetic models based on population balances are developed to simulate precipitate particle growth resulting from collision and diffusion mechanisms. First, the generalized PSG method for collision is explained clearly and verified. Then, a new PSG method is proposed to model diffusion-controlled precipitate nucleation, growth, and coarsening with complete mass conservation and no fitting parameters. Compared with the original population-balance models, this PSG method saves significant computation and preserves enough accuracy to model a realistic range of particle sizes. Finally, the new PSG method is combined with an equilibrium phase fraction model for plain carbon steels and is applied to simulate the precipitated fraction of aluminum nitride and the size distribution of niobium carbide during isothermal aging processes. Good matches are found with experimental measurements, suggesting that the new PSG method offers a promising framework for the future development of realistic models of precipitation.

  10. 纳米碳酸钙在非等温条件下热分解动力学及机理研究%Kinetics and Mechanism of Decomposition of Nano-sized Calcium Carbonate under Non-isothermal Condition

    Institute of Scientific and Technical Information of China (English)

    刘润静; 陈建峰; 郭奋; 吉米; 沈志刚

    2003-01-01

    Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20 K@min-1). The Coats andRedfern's equation was used to determine the apparent activation energy and the pre-exponential factors. Themechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and thekinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonatewas different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanismof one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate wasestimated to be 151kJ@mol-1 while the literature value for normal calcite was approximately 200kJ@mol-1. Theorder of magnitude of pre-exponential factors was estimated to be 109 s-1.

  11. A kinetic study of the decomposition of the cubic perovskite-type oxide Ba(x)Sr(1-x)Co(0.8)Fe(0.2)O(3-delta) (BSCF) (x = 0.1 and 0.5).

    Science.gov (United States)

    Mueller, David N; De Souza, Roger A; Weirich, Thomas E; Roehrens, Daniel; Mayer, Joachim; Martin, Manfred

    2010-09-21

    The decomposition of the cubic perovskite-type oxide Ba(x)Sr(1-x)Co(0.8)Fe(0.2)O(3-delta) (BSCF) into hexagonal and cubic perovskite-type phases has been examined by means of Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Selected Area Electron Diffraction (SAED) and X-Ray Diffraction (XRD). SEM and TEM measurements reveal that the new hexagonal phase grows predominantly at the grain boundaries of BSCF ceramics and that the cation composition of the newly formed hexagonal phase differs from that of the starting material. An orientational relationship between the hexagonal and the parent cubic phase was also observed. By means of ex situ XRD the phase fraction of the hexagonal phase was determined as a function of annealing time. A kinetic analysis of the data, based on Avrami-type kinetics, indicates that the decomposition is independent of the initial A-site composition, and the obtained reaction order supports the conclusion that the hexagonal phase grows at the grain boundaries in dense ceramic samples.

  12. Thermal decomposition kinetics of novel monomolecular P-N intumescent flame retardant%新型单组份磷-氮膨胀型阻燃剂的热分解动力学

    Institute of Scientific and Technical Information of China (English)

    刘颖杰; 王晓

    2013-01-01

    T he thermal decomposition kinetics of the novel monomolecular P-N intumescent flame retardant hexalis-(4-DOPO-hydroxymethyl-phenoxy )-cyclotriphosphazene (DOPOM PC ) were studied by TG-DTG techniques at different heating rates in streams of N2 and air .The ki-netic parameters ,including the activation energy and frequency factor of the decomposition process for the DOPOMPC were calculated by the Kissinger and Flynn-Wall-Ozawa(FWO) methods .%利用热重分析法研究了在不同升温速率下新型单组份磷-氮膨胀型阻燃剂六(4-(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)-羟甲基苯氧基)环三磷腈(DOPOMPC)在氮气气氛和空气气氛中的热分解动力学。采用Kis-singer和Flynn-Wall-Ozawa(FWO)法分别计算出DOPOMPC在相应气氛下的活化能和指前因子。

  13. Causal hydrodynamics from kinetic theory by doublet scheme in renormalization-group method

    Science.gov (United States)

    Tsumura, Kyosuke; Kikuchi, Yuta; Kunihiro, Teiji

    2016-12-01

    We develop a general framework in the renormalization-group (RG) method for extracting a mesoscopic dynamics from an evolution equation by incorporating some excited (fast) modes as additional components to the invariant manifold spanned by zero modes. We call this framework the doublet scheme. The validity of the doublet scheme is first tested and demonstrated by taking the Lorenz model as a simple three-dimensional dynamical system; it is shown that the two-dimensional reduced dynamics on the attractive manifold composed of the would-be zero and a fast modes are successfully obtained in a natural way. We then apply the doublet scheme to construct causal hydrodynamics as a mesoscopic dynamics of kinetic theory, i.e., the Boltzmann equation, in a systematic manner with no ad-hoc assumption. It is found that our equation has the same form as Grad's thirteen-moment causal hydrodynamic equation, but the microscopic formulae of the transport coefficients and relaxation times are different. In fact, in contrast to the Grad equation, our equation leads to the same expressions for the transport coefficients as given by the Chapman-Enskog expansion method and suggests novel formulae of the relaxation times expressed in terms of relaxation functions which allow a natural physical interpretation of the relaxation times. Furthermore, our theory nicely gives the explicit forms of the distribution function and the thirteen hydrodynamic variables in terms of the linearized collision operator, which in turn clearly suggest the proper ansatz forms of them to be adopted in the method of moments.

  14. Thermal Decomposition Mechanism and Non-isothermal Kinetics of the Complex Eu2 (p-ClC6H4COO)6(C12H8N2)2%Eu2(p-C1C6H4COO)6(C12H8N2)2配合物热分解机理及非等温动力学

    Institute of Scientific and Technical Information of China (English)

    张建军; 王瑞芬; 王淑萍

    2001-01-01

    The thermal decomposition behaviour of europium p-chlorobenzoate complex with 1, 10-phenanthroline and its kinetics were studied in nitrogen by non-isothermal thermogravimetry. Its thermal decomposition occurs mainly in three steps. The intermediate and residue for each step of decomposition were identified from TG curve. The kinetic parameters were obtained from analysis of the TG-DTG curves by the Achar method、 the Madhusudanan-Krishnan-Ninan(MKN) method and Ozawa method respectively. The most probable mechanisms function for the first and second stage were suggested by comparing the kinetic parameters.

  15. Investigation of thermal decomposition as the kinetic process that causes the loss of crystalline structure in sucrose using a chemical analysis approach (part II).

    Science.gov (United States)

    Lee, Joo Won; Thomas, Leonard C; Jerrell, John; Feng, Hao; Cadwallader, Keith R; Schmidt, Shelly J

    2011-01-26

    High performance liquid chromatography (HPLC) on a calcium form cation exchange column with refractive index and photodiode array detection was used to investigate thermal decomposition as the cause of the loss of crystalline structure in sucrose. Crystalline sucrose structure was removed using a standard differential scanning calorimetry (SDSC) method (fast heating method) and a quasi-isothermal modulated differential scanning calorimetry (MDSC) method (slow heating method). In the fast heating method, initial decomposition components, glucose (0.365%) and 5-HMF (0.003%), were found in the sucrose sample coincident with the onset temperature of the first endothermic peak. In the slow heating method, glucose (0.411%) and 5-HMF (0.003%) were found in the sucrose sample coincident with the holding time (50 min) at which the reversing heat capacity began to increase. In both methods, even before the crystalline structure in sucrose was completely removed, unidentified thermal decomposition components were formed. These results prove not only that the loss of crystalline structure in sucrose is caused by thermal decomposition, but also that it is achieved via a time-temperature combination process. This knowledge is important for quality assurance purposes and for developing new sugar based food and pharmaceutical products. In addition, this research provides new insights into the caramelization process, showing that caramelization can occur under low temperature (significantly below the literature reported melting temperature), albeit longer time, conditions.

  16. A compendium of temperature responses of Rubisco kinetic traits: variability among and within photosynthetic groups and impacts on photosynthesis modeling.

    Science.gov (United States)

    Galmés, Jeroni; Hermida-Carrera, Carmen; Laanisto, Lauri; Niinemets, Ülo

    2016-09-01

    The present study provides a synthesis of the in vitro and in vivo temperature responses of Rubisco Michaelis-Menten constants for CO2 (Kc) and O2 (Ko), specificity factor (Sc,o) and maximum carboxylase turnover rate (kcatc) for 49 species from all the main photosynthetic kingdoms of life. Novel correction routines were developed for in vitro data to remove the effects of study-to-study differences in Rubisco assays. The compilation revealed differences in the energy of activation (∆Ha) of Rubisco kinetics between higher plants and other photosynthetic groups, although photosynthetic bacteria and algae were under-represented and very few species have been investigated so far. Within plants, the variation in Rubisco temperature responses was related to species' climate and photosynthetic mechanism, with differences in ∆Ha for kcatc among C3 plants from cool and warm environments, and in ∆Ha for kcatc and Kc among C3 and C4 plants. A negative correlation was observed among ∆Ha for Sc/o and species' growth temperature for all data pooled, supporting the convergent adjustment of the temperature sensitivity of Rubisco kinetics to species' thermal history. Simulations of the influence of varying temperature dependences of Rubisco kinetics on Rubisco-limited photosynthesis suggested improved photosynthetic performance of C3 plants from cool habitats at lower temperatures, and C3 plants from warm habitats at higher temperatures, especially at higher CO2 concentration. Thus, variation in Rubisco kinetics for different groups of photosynthetic organisms might need consideration to improve prediction of photosynthesis in future climates. Comparisons between in vitro and in vivo data revealed common trends, but also highlighted a large variability among both types of Rubisco kinetics currently used to simulate photosynthesis, emphasizing the need for more experimental work to fill in the gaps in Rubisco datasets and improve scaling from enzyme kinetics to realized

  17. Thermal decomposition kinetics and lifetime prediction of expanded polystyrene foam%膨胀聚苯乙烯热分解动力学分析和寿命预测

    Institute of Scientific and Technical Information of China (English)

    亓延军; 崔嵛; 张和平; 陈彦伟; 邓蕾

    2012-01-01

    Concerning the fire protection problems of existing polystyrene foam exterior wall insulation systems, the thermo- gravimetric studies on the commercial grade non-retardant and retardant expanded polystyrene foam (EPS) were carried )ut un- der air and nitrogen atmosphere from ambient temperature to 800℃ at heating rates of 10℃/min, 20℃/min, 40℃/min and 50℃/min. The dependence of the activation energy on the conversion degree was evaluated by using the isoconversional meth- ods (FWO method). The multivariate non-linear regression method was applied for investigation of the kinetic model and the corresponding kinetic parameters. The obtained kinetics parameters reveal that the hexahromocyclododecane (HBCD) flame re- tardant can enhance the thermal stability of EPS. It can be conclude that the decomposition processes of EPS undergo a single step reaction in both air and nitrogen atmosphere. The decomposition of non-retardant EPS under air and nitrogen atmosphere can be described by nth-order reaction with autoeatalysis (Cn) kinetic model. For the retardant EPS, the decomposition process can be accurately describe by the Cn and Fn (nth-order reaction) kinetic model under air and nitrogen atmosphere, respectively. Based on the kinetics parameters and the kinetic models, the lifetime of EPS at different temperatures was predicted.%针对既有聚苯乙烯泡沫类外墙外保温系统的防火问题,在空气和氮气气氛下对非阻燃和阻燃型膨胀聚苯乙烯泡沫进行了热重分析。样品由10℃/min、20℃/min、40℃/min和50℃/min四个升温速率从室温加热至800℃。热分解动力学参数由Flynn-Wall-Ozawa(FWO)等转化率方法和多参数非线性回归方法(multivariate non-linear re-gression method)计算,结果表明六溴环十二烷(HBCD)阻燃剂可一定程度上提高EPS的热稳定性。EPS在空气和氮气气氛下热解可认为是单步反应。非阻燃聚苯乙烯泡沫在空气和氮气气氛下

  18. Laboratory simulations of prebiotic molecule stability in the jarosite mineral group; end member evaluation of detection and decomposition behavior related to Mars sample return

    Energy Technology Data Exchange (ETDEWEB)

    J. Michelle Kotler; Nancy W. Hinman; C. Doc Richardson; Andrew G. Conly; Jill R. Scott

    2009-10-01

    Recently, the prebiotic amino acid glycine has been found associated with natural jarosite samples from various locations around the world. Since the discovery of jarosite on Mars, extensive research focuses on linking this mineral group with possible detection of biosignatures in the geologic record on Earth and Mars. Multiple analytical methods, including extraction and mass spectrometry techniques have identified glycine and other biomolecules in jarosite samples. The jarosite end members jarosite (sensu stricto-potassium jarosite), natrojarosite (sodium jarosite), and ammoniojarosite (ammonium jarosite) have different thermodynamic stabilities, decompose at different rates, and have potentially different susceptibilities to substitution. Planetary protection issues have led to the suggestion that samples returned from Mars would need to be heat-treated before they could be analyzed on Earth. Although heat treatment of the samples would in theory destroy any potential biosignatures, valuable information can be obtained during thermal treatment by employing gravimetric techniques. The relationship between the thermodynamic stability of the jarosite end members and the effect that glycine has on the thermal decomposition behavior of each end member was investigated using thermal gravimetric analysis. Thermal gravimetric analysis has been suggested as a method capable of providing the heat treatment necessary to provide planetary protection while still providing useful information about the original state and composition of the potentially returned materials. Introducing glycine into the synthesis procedure of the potassium, sodium and ammonium jarosite end-member has elucidated the effects that glycine has on the thermal stability of the mineral group. Potassium jarosite appears to be the least susceptible to the effects of glycine, with the sodium and ammonium end members showing marked changes in thermal decomposition behavior and decomposition rates. In

  19. Meddling with middle modalities: a decomposition approach to mental health inequalities between intersectional gender and economic middle groups in northern Sweden

    Directory of Open Access Journals (Sweden)

    Per E. Gustafsson

    2016-11-01

    Full Text Available Background: Intersectionality has received increased interest within population health research in recent years, as a concept and framework to understand entangled dimensions of health inequalities, such as gender and socioeconomic inequalities in health. However, little attention has been paid to the intersectional middle groups, referring to those occupying positions of mixed advantage and disadvantage. Objective: This article aimed to 1 examine mental health inequalities between intersectional groups reflecting structural positions of gender and economic affluence and 2 decompose any observed health inequalities, among middle groups, into contributions from experiences and conditions representing processes of privilege and oppression. Design: Participants (N=25,585 came from the cross-sectional ‘Health on Equal Terms’ survey covering 16- to 84-year-olds in the four northernmost counties of Sweden. Six intersectional positions were constructed from gender (woman vs. men and tertiles (low vs. medium vs. high of disposable income. Mental health was measured through the General Health Questionnaire-12. Explanatory variables covered areas of material conditions, job relations, violence, domestic burden, and healthcare contacts. Analysis of variance (Aim 1 and Blinder-Oaxaca decomposition analysis (Aim 2 were used. Results: Significant mental health inequalities were found between dominant (high-income women and middle-income men and subordinate (middle-income women and low-income men middle groups. The health inequalities between adjacent middle groups were mostly explained by violence (mid-income women vs. men comparison; material conditions (mid- vs. low-income men comparison; and material needs, job relations, and unmet medical needs (high- vs. mid-income women comparison. Conclusions: The study suggests complex processes whereby dominant middle groups in the intersectional space of economic affluence and gender can leverage strategic

  20. Decomposition kinetics of AgO cathode material for silver oxide/aluminum battery%铝氧化银电池正极材料AgO的分解动力学研究

    Institute of Scientific and Technical Information of China (English)

    吕霖娜; 林沛; 韩雪荣

    2011-01-01

    The instability of silver (Ⅱ). Oxide electrodes used in silver oxide/aluminum reserve batteries is the well-known cause of capacity loss and the delayed activation in reserve batteries after stored in the dry and inactivated state for the extended periods of time. The decomposition kinetics of the thermodynamically unstable AgO component of silver oxide cathodes used in silver/aluminum reverse batteries was determined by a rapid and accelerated-aging thermogravimetry (TG) technique. The calculated decomposition rates of AgO could be used to predict the storage life time of primary, and reserve silver oxide/aluminum reserve batteries.%氧化银的不稳定性是导致铝氧化银贮备电池在于态、未激活的状态下长期储存容量减少、激活时间延长的主要原因.通过加速老化实验测得电化学方法制备的氧化银的分解动力学参数,并通过建立模型计算氧化银的分解速率,以此来预测铝氧化银贮备电池中氧化银电极的储存寿命.

  1. Synthesis, spectroscopic characterization, and thermal decomposition kinetics of some lanthanide(Ⅲ) nitrate complexes of 2-(N-o-hydroxyacetophenone) amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene

    Institute of Scientific and Technical Information of China (English)

    K.Mohanan; M.Thankamony; B.Sindhu Kumari

    2008-01-01

    Complexes of La(Ⅲ), Ce(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), Dy(Ⅲ), Yb(Ⅲ), and Lu(Ⅲ) with 2-(N-o- hydroxyacetophenone)amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene (HAAT) formed by the condensation of o-hydroxyacetophenone and 2-amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene were synthesized and characterized on the basis of elemental analyses, molar conductance measurements, magnetic susceptibility data, UV-Visible, IR, and NMR spectral studies. The spectral data revealed that the ligand acted as a neutral tridentate coordinating to the metal ion through ONO donor sequence. A coordination number nine was proposed for the complexes. Thermal decomposition studies of the ligand and lanthanum(Ⅲ) complex were carried out and kinetic parameters were calculated using Coats-Redfern equation. The decomposition reactions followed random nucleation mechanism with one nucleus on each particle.

  2. Critical analysis of nitramine decomposition data: Activation energies and frequency factors for HMX and RDX decomposition

    Science.gov (United States)

    Schroeder, M. A.

    1980-01-01

    A summary of a literature review on thermal decomposition of HMX and RDX is presented. The decomposition apparently fits first order kinetics. Recommended values for Arrhenius parameters for HMX and RDX decomposition in the gaseous and liquid phases and for decomposition of RDX in solution in TNT are given. The apparent importance of autocatalysis is pointed out, as are some possible complications that may be encountered in interpreting extending or extrapolating kinetic data for these compounds from measurements carried out below their melting points to the higher temperatures and pressure characteristic of combustion.

  3. Atmospheric chemistry of CF3C(O)O2 radicals. Kinetics of their reaction with NO2 and kinetics of the thermal decomposition of the product CF3C(O)O2NO2

    DEFF Research Database (Denmark)

    Wallington, T.J.; Sehested, J.; Nielsen, O.J.

    1994-01-01

    A pulse radiolysis technique has been used to measure a rate constant of (6.6 +/- 1.3) x 10(-12) cm3 molecule-1 s-1 for the association reaction between CF3C(O)O2 radicals and NO2 at 295 K and one atmosphere total pressure of SF6 diluent. A FTIR/smog chamber system was used to study the thermal...... decomposition CF3C(O)O2NO2. The rate of decomposition of CF3C(O)O2NO2 was independent of the total pressure of N2 diluent over the range 100-700 Torr and was fit by the expression k-1 = (1.9(-1.5)+7.6) x 10(16) exp[(-14000 +/- 480)/T] s-1. Implications for the atmospheric chemistry of CFC replacements...

  4. Approximate Solution of the Point Reactor Kinetic Equations of Average One-Group of Delayed Neutrons for Step Reactivity Insertion

    Directory of Open Access Journals (Sweden)

    S. Yamoah

    2012-04-01

    Full Text Available The understanding of the time-dependent behaviour of the neutron population in a nuclear reactor in response to either a planned or unplanned change in the reactor conditions is of great importance to the safe and reliable operation of the reactor. In this study two analytical methods have been presented to solve the point kinetic equations of average one-group of delayed neutrons. These methods which are both approximate solution of the point reactor kinetic equations are compared with a numerical solution using the Euler’s first order method. To obtain accurate solution for the Euler method, a relatively small time step was chosen for the numerical solution. These methods are applied to different types of reactivity to check the validity of the analytical method by comparing the analytical results with the numerical results. From the results, it is observed that the analytical solution agrees well with the numerical solution.

  5. 热分析法研究冬凌草甲素的热稳定性和分解动力学%Thermal Stability and Decomposition Kinetics of Oridonin by Thermal Analysis Method

    Institute of Scientific and Technical Information of China (English)

    刘建群; 高俊博; 刘小红

    2015-01-01

    研究加热条件下冬凌草甲素的热稳定性、分解动力学和贮存期. 利用热重-微商热重( TG-DTG)和差热-微商差热( DTA-DDTA)分析技术,测得冬凌草甲素在氮气气氛中不同升温速率(β)下的热分解曲线,结合使用Kissinger 法、Ozawa 法、Coats-Redfern 法和Achar 法进行动力学分析,根据热分解的表观活化能( Ea )和指前因子( A)计算推断冬凌草甲素的贮存期. 结果显示:随着升温速率的提高,冬凌草甲素的热分解温度逐渐升高,冬凌草甲素失重分两阶段:1)206. 4~493. 0 ℃,失重率为84. 8%;2)493. 0~669. 6 ℃,失重率为15. 2%. DTA和DDTA 曲线249 ℃出现一个主要吸热峰,675 ℃出现一个主要放热峰. 冬凌草甲素的第一阶段热分解机制是三维扩散控制,对应的函数名称是Zhuralev-Lesokin-Tempelman 方程. 测得平均Ea 为145. 95 kJ/mol,A为4. 87 × 1010 min-1;根据第一步热分解的Ea 和A推断,在室温25℃下,冬凌草甲素的理论贮存期为4~5年.%Thermal decomposing curves of oridonin at different heating speeds were obtained in the nitrogen atmosphere by TG-DTG and DTA-DDTA techniques to study the thermal stability,decomposition kinetics,and shelflife of oridonin under the heat condition. Four thermal analysis kinetic methods ( Kissinger, Ozawa, Coats-Redfern and Achar ) were used to speculate the probable mechanism of thermal decomposing reaction and the kinetic parameters including activation energy Ea and pre-exponential factor A. The shelflife of oridonin at room temperature ( 25℃) was calculated by the kinetic parameters of the first stage. With the increase of the heating rate, thermal decomposing tempreture of oridonin rose. The TG curve showed the decomposition of oridonin could be divided into two steps. The first weight loss rate was 84. 8% from 206. 4 ℃ to 493. 0 ℃ and the second weight loss rate was 15. 2% from 493. 0 ℃ to 669. 6 ℃. The DTA and DDTA curves showed an endothermic peak at about

  6. Synthesis, Characterization, Crystal Structure and Kinetics of Thermal Decomposition of Zn(Ⅱ) Complex%金刚乙胺水杨醛Schiff碱锌(Ⅱ)配合物的合成、表征、晶体结构和热分解动力学研究

    Institute of Scientific and Technical Information of China (English)

    赵国良; 冯云龙; 刘幸海

    2005-01-01

    A Zinc(Ⅱ) complex [ZnCl2(HL)2] with Schiff base HL derived from rimantadine and salicylaldehyde was synthesized and characterized by elemental analysis, infrared spectra, 1H NMR spectra,molar conductance, ultraviolet and visible spectra, thermal analysis. Its structure was determined by single crystal X-ray diffraction method. The complex, C38H50C12N2O2Zn, crystallizes in the orthorhombic system, space group A ba2 with a=1.381 7(3),b=2.275 0(5), c=1.145 0(2) nm, V=3.599(1) nm3, Z=4, Mr=653.79, F(000)=I 496, Dc=l.301 kg·m-3,μMo Kα)=0.866mm-1. The kinetic parameters were obtained from the analysis of TG curve by integral methods. The functions of thermal decomposition reaction mechanismtion lnA=0.019 1E-0.1427. CCDC: 253297.are: F(α)=[1-(1-α)1/3]2, and kinetic compensation effect equa-tion InA=0.019 1E-0.1427. CCDC: 253297.

  7. Nonisothermal Thermal Decomposition Reaction Kinetics of Double-base Propellant Catalyzed with Lanthanum Citrate%柠檬酸镧催化双基推进剂的非等温热分解反应动力学

    Institute of Scientific and Technical Information of China (English)

    仪建华; 赵凤起; 徐司雨; 高红旭; 胡荣祖; 郝海霞; 裴庆; 高茵

    2007-01-01

    采用TG-DTG和DSC技术研究了含二缩三乙二醇二硝酸酯(TEGDN)和硝化甘油(NG)的混合酯、硝化棉(NC)和用作燃烧催化剂的柠檬酸镧组成的双基推进剂在常压和流动态氮气气氛下的非等温热分解反应动力学.结果表明,该双基推进剂的热分解过程存在2个失重阶段:第Ⅰ失重阶段为混合酯的挥发分解过程;第Ⅱ失重阶段为主放热分解反应,机理服从三级化学反应,减速型α-t曲线,动力学参数:Ea=31.14 kJ·mol-1,A=1023.29 s-1,动力学方程为dα/dt=1022.99(1-α)3e-2.78×104 /T.由外推起始点温度(Te)和峰顶温度(Tp)计算得出该双基推进剂的热爆炸临界温度值分别为Tbe=463.62 K,Tbp=477.88 K.反应的活化熵(ΔS≠)、活化焓(ΔH≠)和活化能(ΔG≠)分别为219.75J·mol-1·K-1,239.23 kJ·mol-1和135.96kJ·mol-1.%The decomposition reaction kinetics of the double-base (DB) rocket propellant composed of the mixed ester of triethyleneglycol dinitrate (TEGDN) and nitroglycerin (NG), and nitrocellulose (NC) with lanthanum citrate as a combustion catalyst was investigated by thermogravimetry and differential thermogravimetry (TG-DTG), and differential scanning calorimetry (DSC) under atmospheric pressure and flowing nitrogen gas conditions. The results showed that the thermal decomposition processes of DB propellant had two mass loss stages: volatilization and decomposition of the mixed ester in the first-stage and exothermic decomposition reaction in the second-stage. The exothermic decomposition reaction mechanism obeyed the third-order chemical reaction rule. The kinetic parameters The critical temperatures of the thermal explosion of the DB propellant obtained from the onset temperature (Te) and the peak temperature (Tp) were: Tbe=463.62 K, Tbp=477.88 K. The entropy of activation (ΔS≠), enthalpy of activation (ΔH≠), and free energy of activation (ΔG≠) of the reaction were 219.75 J·mol-1·K-1, 239.23 kJ·mol-1, and 135.96 kJ·mol-1

  8. Study on thermal decomposition kinetics of limestone with large particle size%大粒径石灰石热分解动力学研究

    Institute of Scientific and Technical Information of China (English)

    陈海; 张世红; 杨海平; 李攀; 陈汉平; 曾军

    2013-01-01

    主要研究大粒径石灰石的煅烧特性,采用热重分析仪研究了5种不同粒径石灰石的煅烧过程.石灰石粒径分布在0.5~10 mm,煅烧温度在900~1 050℃.研究结果表明,粒径越小温度越高石灰石分解速率越快,而且粒径和煅烧温度对石灰石热分解机理也有明显的影响.粒径小温度高时反应符合随机成核和随后生长机理模型,粒径大温度低时反应符合相界面反应机理.当粒径为0.5~1 mm时反应活化能很小,随着粒径的增大反应活化能有所增加,粒径在1~5 mm时活化能变化不大,粒径继续增大(5~10 mm)活化能增大了1倍.%Thermal decomposition experiments of limestone with five different particle sizes were conducted through thermo gravimetric analyzer to study its calcined characteristics with large particle size.The limestone particle sizes were distributed in the range of 0.5~10 mm,and the temperature was controlled at 900~1 050 ℃ during the experiments.Rresults revealed that the smaller the particle size,the higher the temperature and the faster the decomposition.And the particle size and calcining temperature made an obvious influence on the thermal decomposition mechanism.When the particle size was small and the temperature was high,the reaction was in accordance with the randomly nucleating and nucleus growth model,but in contrast,reaction was in accordance with the phase interface mechanism.When the particle size was at 0.5~ 1 mm,reaction activation energy was very small,and with the increase of particle size,reaction activation energy increased,while in the range of 1~5 mm,activation energy fluctuated,with the continuous increase of particle size to 5~10 mm,the activation energy doubled.

  9. Estudos sobre a cinética de decomposição térmica do poli(sulfeto de fenileno Kinetic studies of thermal decomposition of poly(phenylene sulfide

    Directory of Open Access Journals (Sweden)

    Laércio G. Lage

    1999-12-01

    Full Text Available A cinética de decomposição térmica do poli(sulfeto de fenileno (PPS foi estudada através da termogravimetria (TG. Duas amostras comerciais de PPS foram utilizadas neste trabalho: Ryton, da Philips Petroleum, e Fortron, da Hoechst-Celanese. Os parâmetros cinéticos, isto é, a energia de ativação e o fator pré-exponencial de Arrhenius, foram calculados através de três métodos diferentes. Os resultados aqui apresentados concordaram com os dados da literatura. A estimativa do tempo de meia-vida do polímero também foi feita, mostrando que o Fortron é mais estável termicamente que o Ryton.The kinetics of thermal decomposition of poly(phenylene sulfide (PPS has been studied by means of thermogravimetry (TG. Two commercial samples of PPS have been used in this work: Ryton, from Philips Petroleum, and Fortron, from Hoechst-Celanese. The kinetic parameters, i.e. activation energy and Arrhenius' pre-exponential factor have been calculated by using three different methods. The results reported here agreed with the literature data. The estimation of polymer half-lifetime was also made, showing that Fortron is more thermally stable than Ryton.

  10. A total quasi-steady-state formulation of substrate uptake kinetics in complex networks and an example application to microbial litter decomposition

    OpenAIRE

    Tang, J Y; Riley, W.J.

    2013-01-01

    We demonstrate that substrate uptake kinetics in any consumer–substrate network subject to the total quasi-steady-state assumption can be formulated as an equilibrium chemistry (EC) problem. If the consumer-substrate complexes equilibrate much faster than other metabolic processes, then the relationships between consumers, substrates, and consumer-substrate complexes are in quasi-equilibrium and the change of a given total substrate (free plus consumer-bounded) is determined...

  11. A total quasi-steady-state formulation of substrate uptake kinetics in complex networks and an example application to microbial litter decomposition

    OpenAIRE

    Tang, J Y; Riley, W.J.

    2013-01-01

    We demonstrate that substrate uptake kinetics in any consumer-substrate network subject to the total quasi-steady-state assumption can be formulated as an equilibrium chemistry (EC) problem. If the consumer-substrate complexes equilibrate much faster than other metabolic processes, then the relationships between consumers, substrates, and consumer-substrate complexes are in quasi-equilibrium and the change of a given total substrate (free plus consumer-bounded) is determined by the deg...

  12. Kinetic analysis of the chemical processes in the decomposition of gaseous dielectrics by a non-equilibrium plasma - part 2: SF6 and SF6/O2

    Directory of Open Access Journals (Sweden)

    Bauerfeldt Glauco F.

    2000-01-01

    Full Text Available In this work, a numerical modelling analysis of the gas-phase decomposition of pure SF6 and SF6/O2 mixtures, in the presence of silicon was performed. The relative rate of individual processes, the effect of the parameters uncertainties and the sensitivity coefficients were determined. The results were compared with literature experimental data for the plasma etching of silicon and with previous simulated results to adjust the model parameters. As in the CF4 system, the main etching agent is atomic fluorine and the concentration of the major species depends on the composition of the mixture. The shape of the sensitivity curves follows the general shape of the individual rate curves and the ratio between the calculated sensitivity coefficients is closely related to the contribution of each reaction.

  13. Raman study of the photopolymer formation in the {Pt(dbdtc)2}·C60 fullerene complex and the decomposition kinetics of the photo-oligomers

    Science.gov (United States)

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

    2017-08-01

    The photopolymer formation in the fullerene layers of the C60 complex with platinum dibenzyldithiocarbamate is reported for the first time. The photo-oligomer peaks appear in the Raman spectra near the Ag(2) mode of the C60 molecule upon sample illumination with various laser wavelengths. The photo-oligomers are unstable upon heating and revert back to the C60 monomeric state. The activation energy of the thermal decomposition, obtained from the Arrhenius dependence of the decay time constant on temperature, is (1.12 ± 0.11) eV and the photo-oligomers decompose at ∼130 °C, being more fragile than the crystalline polymers of C60.

  14. Application of Littlewood-Paley decomposition to the regularity of Boltzmann type kinetic equations; Application de la decomposition de Littlewood-Paley a la regularite pour des equations cinetiques de type Boltzmann

    Energy Technology Data Exchange (ETDEWEB)

    EL Safadi, M

    2007-03-15

    We study the regularity of kinetic equations of Boltzmann type.We use essentially Littlewood-Paley method from harmonic analysis, consisting mainly in working with dyadics annulus. We shall mainly concern with the homogeneous case, where the solution f(t,x,v) depends only on the time t and on the velocities v, while working with realistic and singular cross-sections (non cutoff). In the first part, we study the particular case of Maxwellian molecules. Under this hypothesis, the structure of the Boltzmann operator and his Fourier transform write in a simple form. We show a global C{sup {infinity}} regularity. Then, we deal with the case of general cross-sections with 'hard potential'. We are interested in the Landau equation which is limit equation to the Boltzmann equation, taking in account grazing collisions. We prove that any weak solution belongs to Schwartz space S. We demonstrate also a similar regularity for the case of Boltzmann equation. Let us note that our method applies directly for all dimensions, and proofs are often simpler compared to other previous ones. Finally, we finish with Boltzmann-Dirac equation. In particular, we adapt the result of regularity obtained in Alexandre, Desvillettes, Wennberg and Villani work, using the dissipation rate connected with Boltzmann-Dirac equation. (author)

  15. Kinetics of the Thermo-Oxidative Decomposition of Expanded Polystyrene Foam%膨胀聚苯乙烯泡沫热氧化分解动力学研究

    Institute of Scientific and Technical Information of China (English)

    崔嵛; 程旭东; 龚伦伦; 丁延伟; 亓延军; 张和平

    2011-01-01

    用非等温热重分析方法对膨胀聚苯乙烯泡沫的热氧化分解特性进行了研究.样品在空气气氛下由10℃/min、20 ℃/min、40℃/min和50℃/min共4个升温速率从室温加热至800℃.分别使用积分等转化率方法中的Flynn-Wall-Ozawa(FWO)和Kissinger-Akahir-Sunose(KAS)方法以及基于动力学补偿效应的恒定动力学参数方法(invariant kinetic parameter method,IKP)计算膨胀聚苯乙烯非等温热氧化分解的动力学参数.由等转化率方法得到的结果可认为膨胀聚苯乙烯泡沫在空气气氛下主要为一步反应.FWO方法和KAS方法得到的平均活化能与IKP方法得到的活化能具有较好的一致性.由IKP方法和常用固相反应机理函数在不同升温速率下动力学参数的对应准则可确定膨胀聚苯乙烯泡沫热氧化分解过程可由成核和核生长控制的机理函数(Avrami Eroféev方程)A1.7描述.%The thermo-oxidative decomposition of expanded polystyrene foam (EPS) was studied using non-isothermal thermogravimetric analysis at the heating rates of 10 ℃/min, 20 ℃/min, 40 ℃/min and 50 ℃/min under the air atmosphere within the temperature range from room temperature to 800 ℃, respectively. The kinetic parameters were calculated by the isoconversional methods (I.e. Flynn-Wall-Ozawa (FWO) and Kissinger-Akahir-Sunose (KAS)) and the invariant kinetic parameter method (IKP) which is based on the kinetic compensation effect. The results obtained from the isoconversional methods show that the EPS primarily decomposes in a single step. The values of invariant activation energy are in good agreement with those determined by the isoconversional methods. With the aim of determining the kinetic model, the IKP method was associated with the criterion of coincidence of the kinetic parameters of the known solid-state conversion functions for all heating rates. Finally, the nucleation and nuclei growth (Avrami Erofeev equation) A 1.7 mechanism was obtained

  16. Synthesis, Characterization, Structure and Kinetics of Thermal Decomposition of K2[Co(Dipc)2]·7H2O%异核配合物K2[Co(Dipc)2]·7H2O的合成、性质、结构和热分解动力学研究

    Institute of Scientific and Technical Information of China (English)

    张淑华; 蒋毅民; 肖瑜

    2003-01-01

    A heteronuclear compound, K2 [ Co (Dipc) 2 ] @ 7H2O (Dipc = pyridine-2, 6-dicarboxylic acid) has been synthesized and characterized by IR, elemental analysis, and X-ray diffraction. Crystal data: orthorhombic system withspace group Pnna and unite cell parameters: a =2. 0645(3) nm, b = 1. 3484(2) nm, c =0. 8204(1) nm; V=2.2838(6) nm3, Z=4, Dca1d=1.726g@cm-3, μ=1.193mm-1, F(000)=1212, Gof=1.045, △ρ=339~ -348 e @ nm-3, the final R is 0. 0295. In the molecule of the complex, Co (Ⅱ) ion is six-coordinate to form a dis-torted octahedron. The N atom and the carboxyl group of pyridine-2, 6-dicarboxylic acid are coordinated with thecentral ions. One of the carboxyl groups of the pyridine-2, 6-dicarboxylic acid connect K (Ⅰ) and Co (Ⅱ). The com-pound possesses approximate C2 symmetry. The compounds form a three-dimensional network of infinite lengthconnection with crystal waters, potassium ions and hydrogen bonds. The result of kinetics of thermal decompositionindicated that the compound decomposition takes place in two steps.

  17. An investigation on thermal decomposition of DNTF-CMDB propellants

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Wei; Wang, Jiangning; Ren, Xiaoning; Zhang, Laying; Zhou, Yanshui [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China)

    2007-12-15

    The thermal decomposition of DNTF-CMDB propellants was investigated by pressure differential scanning calorimetry (PDSC) and thermogravimetry (TG). The results show that there is only one decomposition peak on DSC curves, because the decomposition peak of DNTF cannot be separated from that of the NC/NG binder. The decomposition of DNTF can be obviously accelerated by the decomposition products of the NC/NG binder. The kinetic parameters of thermal decompositions for four DNTF-CMDB propellants at 6 MPa were obtained by the Kissinger method. It is found that the reaction rate decreases with increasing content of DNTF. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  18. Chemical modification and pH dependence of kinetic parameters to identify functional groups in a glucosyltransferase from Strep. Mutans

    Energy Technology Data Exchange (ETDEWEB)

    Bell, J.E.; Leone, A.; Bell, E.T.

    1986-05-01

    A glucosyltransferase, forming a predominantly al-6 linked glucan, was partially purified from the culture filtrate of S. mutans GS-5. The kinetic properties of the enzyme, assessed using the transfer of /sup 14/C glucose from sucrose into total glucan, were studied at pH values from pH 3.5 to 6.5. From the dependence of km on pH, a group with pKa = 5.5 must be protonated to maximize substrate binding. From plots of V/sub max/ vs pH two groups, with pKa's of 4.5 and 5.5 were indicated. The results suggest the involvement of either two carboxyl groups (one protonated, one unprotonated in the native enzyme) or a carboxyl group (unprotonated) and some other protonated group such as histidine, cysteine. Chemical modification studies showed that Diethylyrocarbonate (histidine specific) had no effect on enzyme activity while modification with p-phydroxy-mercuribenzoate or iodoacetic acid (sulfhydryl reactive) and carbodimide reagents (carboxyl specific) resulted in almost complete inactivation. Activity loss was dependent upon time of incubation and reagent concentration. The disaccharide lylose, (shown to be an inhibitor of the enzyme with similar affinity to sucrose) offers no protection against modification by the sulfhydryl reactive reagents.

  19. Kinetic mechanism and energetics of binding of phosphoryl group acceptors to Mycobacterium tuberculosis cytidine monophosphate kinase.

    Science.gov (United States)

    Jaskulski, Léia; Rosado, Leonardo A; Rostirolla, Diana C; Timmers, Luis F S M; de Souza, Osmar N; Santos, Diogenes S; Basso, Luiz A

    2013-08-01

    Cytidine monophosphate kinase from Mycobacterium tuberculosis (MtCMK) likely plays a role in supplying precursors for nucleic acid synthesis. MtCMK catalyzes the ATP-dependent phosphoryl group transfer preferentially to CMP and dCMP. Initial velocity studies and Isothermal titration calorimetry (ITC) measurements showed that MtCMK follows a random-order mechanism of substrate (CMP and ATP) binding, and an ordered mechanism for product release, in which ADP is released first followed by CDP. The thermodynamic signatures of CMP and CDP binding to MtCMK showed favorable enthalpy and unfavorable entropy, and ATP binding was characterized by favorable changes in enthalpy and entropy. The contribution of linked protonation events to the energetics of MtCMK:phosphoryl group acceptor binary complex formation suggested a net gain of protons. Values for the pKa of a likely chemical group involved in proton exchange and for the intrinsic binding enthalpy were calculated. The Asp187 side chain of MtCMK is suggested as the likely candidate for the protonation event. Data on thermodynamics of binary complex formation were collected to evaluate the contribution of 2'-OH group to intermolecular interactions. The data are discussed in light of functional and structural comparisons between CMP/dCMP kinases and UMP/CMP ones.

  20. Kinetic modeling and experimental studies of hydrogen production by non-equilibrium plasma discharge decomposition of methane and other hydrogen-containing species

    Energy Technology Data Exchange (ETDEWEB)

    Boutot, T.; Liu, Z. [Atlantic Hydrogen Inc., Fredericton, NB (Canada); Whidden, T.K.; Yang, Y. [New Brunswick Univ., Fredericton, NB (Canada)

    2007-07-01

    Hydrogen as an energy source is an option that is being explored in order to reduce anthropogenic greenhouse gas (GHG) emissions. In particular, proton exchange membrane (PEM) fuel cells using hydrogen and emitting no GHGs are under global development. The long-term production process of choice is hydrogen derived directly from water. However, hydrogen from electrolysis is not economically viable and bridging technologies for green hydrogen production must be found. Any new technology for hydrogen production should also accommodate the fact that no infrastructure for the widespread distribution of pure hydrogen exists. Hydrogen production technologies that leverage existing infrastructure for delivery will therefore have a significant economic advantage. This paper described the anaerobic high frequency pulsed plasma pyrolysis of methane using a proprietary reactor system. The paper discussed modeling studies and progress in scaling this reactor to pilot scale operation. It also discussed several experiments on using the system for the dissociation of another hydrogen source, hydrogen sulphide (H2{sub S}). Hydrogen and solid carbon were produced for methane or natural gas as the feedstock. The prototype bench-scale process was scaled to near pilot-scale, treating significant flows of natural gas. Long term data on system performance at conversions producing 20 per cent hydrogen in natural gas as the product were presented. Chemical kinetic models for the dissociation process and characterizational data for the solid carbon product were presented. 48 refs., 2 tabs., 9 figs.

  1. 生物质与聚乳酸共热解行为及其动力学研究%Thermal decomposition and kinetics of mixtures of polylactic acid and biomass during copyrolysis

    Institute of Scientific and Technical Information of China (English)

    王刚; 李爱民

    2008-01-01

    Thermal decomposition of polylactic acid (PLA) was studied in the presence of pine wood sawdust (PS), walnut shell (WS), corncob (CC) in order to understand the pyrolytic behavior of these components occurring in waste. A thermogravimetric analyzer (TGA) was applied for monitoring the mass loss profiles under heating rate of 10℃·min-1. Results obtained from this comprehensive investigation indicated that PLA was decomposed in the temperature range 300-372℃, whereas the thermal degradation temperature of biomass is 183-462℃. The difference of mass loss (△W) between experimental and theoretical ones, calculated as algebraic sums of those from each separated component, is about 17% 46% at 300-400℃. These experimental results indicated a significant syner-gistic effect during PLA and biomass copyrolysis. Moreover, a kinetic analysis was performed to fit thermogravimetric data, the global processes being considered as one to two consecutive reactions. A reasonable fit to the experimental data was obtained for all materials and their blends.

  2. 硝化棉(11.92%N)的一级自催化分解反应动力学%Kinetics of the First Order Autocatalytic Decomposition Reaction of Nitrocellulose(11.92%N)

    Institute of Scientific and Technical Information of China (English)

    胡荣祖; 宁斌科; 杨正权; 宋纪蓉; 高胜利; 史启祯; 路桂娥; 江劲勇

    2004-01-01

    The kinetics of the first order autocatalytic decomposition reaction of nitrocellulose (NC, 11.92%N) was studied by using DSC. The results show that the DSC curve for the initial 50% of conversion degree of NC can be described by the first order autocatalytic equation(dy)/(dt)=-1016.4exp-(210380)/(RT)y-1016.7exp-(171500)/(RT)y(1-y)and that for the latter 50% conversion degree of NC described by the reaction equations(dy)/(dt)=-1016.3exp-(174280)/(RT)y(n=1)and(dy)/(dt)=-1016.8exp-(171300)/(RT)y2.71(n≠1)%用DSC研究了硝化棉(NC,11.92%N)的一级自催化分解反应动力学.结果表明:50%转化率前的DSC曲线可用一级自催化方程描述:(dy)/(dt)=-1016.4exp-(210380)/(RT)y-1016.7exp-(171500)/(RT)y(1-y)50%转化率后的DSC曲线可用如下反应动力学方程描述:(dy)/(dt)=-1016.3exp-(174280)/(RT)y (n=1)和 (dy)/(dt)=-1016.8exp-(171300)/(RT)y2.71(n≠1)

  3. A coupled transport and solid mechanics formulation with improved reaction kinetics parameters for modeling oxidation and decomposition in a uranium hydride bed.

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher N.; Shugard, Andrew D.; Kanouff, Michael P.; Gharagozloo, Patricia E.

    2013-03-01

    Modeling of reacting flows in porous media has become particularly important with the increased interest in hydrogen solid-storage beds. An advanced type of storage bed has been proposed that utilizes oxidation of uranium hydride to heat and decompose the hydride, releasing the hydrogen. To reduce the cost and time required to develop these systems experimentally, a valid computational model is required that simulates the reaction of uranium hydride and oxygen gas in a hydrogen storage bed using multiphysics finite element modeling. This SAND report discusses the advancements made in FY12 (since our last SAND report SAND2011-6939) to the model developed as a part of an ASC-P&EM project to address the shortcomings of the previous model. The model considers chemical reactions, heat transport, and mass transport within a hydride bed. Previously, the time-varying permeability and porosity were considered uniform. This led to discrepancies between the simulated results and experimental measurements. In this work, the effects of non-uniform changes in permeability and porosity due to phase and thermal expansion are accounted for. These expansions result in mechanical stresses that lead to bed deformation. To describe this, a simplified solid mechanics model for the local variation of permeability and porosity as a function of the local bed deformation is developed. By using this solid mechanics model, the agreement between our reacting bed model and the experimental data is improved. Additionally, more accurate uranium hydride oxidation kinetics parameters are obtained by fitting the experimental results from a pure uranium hydride oxidation measurement to the ones obtained from the coupled transport-solid mechanics model. Finally, the coupled transport-solid mechanics model governing equations and boundary conditions are summarized and recommendations are made for further development of ARIA and other Sandia codes in order for them to sufficiently implement the model.

  4. 钐-邻硝基苯甲酸与1,10-邻菲咯啉配合物的热分解动力学%Thermal Decomposition Kinetics of Sm(Ⅲ) Complex with o-Nitrobenzoate and 1,10-phenanthroline

    Institute of Scientific and Technical Information of China (English)

    任宁; 张建军; 张存英; 宿素玲; 张海燕; 田靓

    2007-01-01

    The complex of Sm2(o-NBA)6(PHEN)2 (o-NBA, o-Nitrobenzoate; PHEN, 1,10-phenanthroline) was prepared and characterized by elemental analysis, IR and UV spectraoscopy. The thermal decomposition mechanism of Sm2(o-NBA)6(PHEN)2 was studied under a static air atmosphere by TG-DTG. The thermal decomposition kinetics of the complex for the first stage was studied under non-isothermal condition. The most probable mechanism functions of the thermal decomposition reaction for the first stage are: G(α)=[-ln(1-α)]1/2,f(α)=2(1-α)[-ln(1-α)]1/2. The activation at weight-loss of 10% was deduced as ln( )=-36.70+27 572.12/T by isothermal thermogravimetric analysis.

  5. Thermal Behavior and Decomposition Kinetics of the Complexes of CuX2 (X=NO3, Br, Cl and ClO4) with 3,3′-Dimethyl-1-(1 H-1,2,4-triazol-1-yl)-2-butanone

    Institute of Scientific and Technical Information of China (English)

    LU,Zhen-Rong(陆振荣); DING,Yuan-Chen(丁元晨); XU,Ying(徐颖); LI,Bao-Long(李宝龙); ZHANG,Yong(张勇)

    2004-01-01

    The thermal behaviors of the complexes of Cu(DMTZB)4X2 (DMTZB =3,3′-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, X=NO3 or ClO4) and Cu(DMTZB)2X2 (X = Br or C1) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC, EDS and elemental analysis techniques. The results showed that their decomposition proceeded in three different ways mainly depending on the anions in the molecules. The heat effect associated with the decomposition step of DMTZB molecules was also different. The decomposition mechanisms and the kinetic parameters of DMTZB were determined and calculated by jointly using four methods, which showed that its pyrolysis was controlled by D3 mechanism but with different activation energies and pre-exponential factors for different complexes.

  6. Composition decomposition

    DEFF Research Database (Denmark)

    Dyson, Mark

    2003-01-01

    This PhD is based on constructing and resolving a set of modular problems. Each problem exists as a separate entity. Each has its own characteristics, yet when combined with other, related problems, provides a dimension to a story. The relationships and order between problems has priority over....... Not only have design tools changed character, but also the processes associated with them. Today, the composition of problems and their decomposition into parcels of information, calls for a new paradigm. This paradigm builds on the networking of agents and specialisations, and the paths of communication...... that are necessary to make sense out of any design situation. The hypothesis of this project, is that Design organisation, communication and CAD-information processes must be jointly reengineered to create the dynamic structures needed for the forward projection of design knowledge into this expanding Design network....

  7. Parametric Representation of Rank d Tensorial Group Field Theory: Abelian Models with Kinetic Term $\\sum_{s}|p_s| + \\mu$

    CERN Document Server

    Geloun, Joseph Ben

    2014-01-01

    We consider the parametric representation of the amplitudes of Abelian models in the so-called framework of rank $d$ Tensorial Group Field Theory. These models are called Abelian because their fields live on $U(1)^D$. We concentrate on the case when these models are endowed with particular kinetic terms involving a linear power in momenta. New dimensional regularization and renormalization schemes are introduced for particular models in this class: a rank 3 tensor model, an infinite tower of matrix models $\\phi^{2n}$ over $U(1)$, and a matrix model over $U(1)^2$. For all divergent amplitudes, we identify a domain of meromorphicity in a strip determined by the real part of the group dimension $D$. From this point, the ordinary subtraction program is applied and leads to convergent and analytic renormalized integrals. Furthermore, we identify and study in depth the Symanzik polynomials provided by the parametric amplitudes of generic rank $d$ Abelian models. We find that these polynomials do not satisfy the ord...

  8. Parametric representation of rank d tensorial group field theory: Abelian models with kinetic term ∑ s|ps| + μ

    Science.gov (United States)

    Ben Geloun, Joseph; Toriumi, Reiko

    2015-09-01

    We consider the parametric representation of the amplitudes of Abelian models in the so-called framework of rank d tensorial group field theory. These models are called Abelian because their fields live on copies of U(1)D. We concentrate on the case when these models are endowed with particular kinetic terms involving a linear power in momenta. A new dimensional regularization is introduced for particular models in this class: a rank 3 tensor model, an infinite tower of matrix models ϕ2n over U(1), and a matrix model over U(1)2. We prove that all divergent amplitudes are meromorphic functions in the complexified group dimension D ∈ ℂ. From this point, a standard subtraction program yielding analytic renormalized integrals could be applied. Furthermore, we identify and study in depth the Symanzik polynomials provided by the parametric amplitudes of generic rank d Abelian models. We find that these polynomials do not satisfy the ordinary Tutte's rules (contraction/deletion). By scrutinizing the "face"-structure of these polynomials, we find a generalized polynomial which turns out to be stable only under contraction.

  9. Interaction between DNA and Drugs Having Protonable Basic Groups: Characterization through Affinity Constants, Drug Release Kinetics, and Conformational Changes.

    Science.gov (United States)

    Alarcón, Liliana P; Baena, Yolima; Manzo, Rubén H

    2017-01-04

    This paper reports the in vitro characterization of the interaction between the phosphate groups of DNA and the protonated species of drugs with basic groups through the determination of the affinity constants, the reversibility of the interaction, and the effect on the secondary structure of the macromolecule. Affinity constants of the counterionic condensation DNA-drug were in the order of 10⁶. The negative electrokinetic potential of DNA decreased with the increase of the proportion of loading drugs. The drugs were slowly released from the DNA-drug complexes and had release kinetics consistent with the high degree of counterionic condensation. The circular dichroism profile of DNA was not modified by complexation with atenolol, lidocaine, or timolol, but was significantly altered by the more lipophilic drugs benzydamine and propranolol, revealing modifications in the secondary structure of the DNA. The in vitro characterization of such interactions provides a physicochemical basis that would contribute to identify the effects of this kind of drugs in cellular cultures, as well as side effects observed under their clinical use. Moreover, this methodology could also be projected to the fields of intracellular DNA transfection and the use of DNA as a carrier of active drugs.

  10. Interaction between DNA and Drugs Having Protonable Basic Groups: Characterization through Affinity Constants, Drug Release Kinetics, and Conformational Changes

    Directory of Open Access Journals (Sweden)

    Liliana P. Alarcón

    2017-01-01

    Full Text Available This paper reports the in vitro characterization of the interaction between the phosphate groups of DNA and the protonated species of drugs with basic groups through the determination of the affinity constants, the reversibility of the interaction, and the effect on the secondary structure of the macromolecule. Affinity constants of the counterionic condensation DNA–drug were in the order of 106. The negative electrokinetic potential of DNA decreased with the increase of the proportion of loading drugs. The drugs were slowly released from the DNA–drug complexes and had release kinetics consistent with the high degree of counterionic condensation. The circular dichroism profile of DNA was not modified by complexation with atenolol, lidocaine, or timolol, but was significantly altered by the more lipophilic drugs benzydamine and propranolol, revealing modifications in the secondary structure of the DNA. The in vitro characterization of such interactions provides a physicochemical basis that would contribute to identify the effects of this kind of drugs in cellular cultures, as well as side effects observed under their clinical use. Moreover, this methodology could also be projected to the fields of intracellular DNA transfection and the use of DNA as a carrier of active drugs.

  11. Fenton氧化水中间氯硝基苯的动力学与机制研究%Decomposition kinetic and mechanism of meta-chloronitrobenzene by Fenton oxidation in aqueous solution

    Institute of Scientific and Technical Information of China (English)

    李炳智

    2013-01-01

    In combination with a Fenton reaction kinetic model,influencing factors and degradation mechanism of meta-chloronitrobenzene (m-ClNB) by Fenton oxidation in aqueous solution were investigated.The experimental resuits showed that initial pH,the concentrations of H2O2,Fe2+,m-ClNB,and temperature exhibited great influences on m-ClNB decomposition,and a better decomposition performance was observed at pH3.5,H2O221.55mmol/L,Fe2+0.054 mmol/L,m-ClNB0.444mmol/L and (25±1)℃.The established pseudo first order kinetic model fitted well with the m-ClNB degradation data in Fenton oxidation process,an empirical Arrhenius expression of m-ClNB degradation was derived base on the reaction rate constants (kap) at different temperature,the activation energy for its degradation was 36.51 kJ/mol.According to GC/MS and HPLC/MS analyses,the main intermediates were glycolic acid,oxalic acid,succinic acid,malonic acid,6-chlorohexanoic acid,glyoxalic acid,mesoxalic acid and 2-ethyl malonic acid,4-chloro-2-nitrophenol and its isomer.%结合Fenton氧化反应动力学模型研究了Fenton氧化水中间氯硝基苯(m-ClNB)的影响因素和降解机制.结果表明:(1)反应初始pH、H2O2浓度、Fe2+浓度、污染物初始浓度和反应温度对m-ClNB的降解均有明显影响.在反应初始pH为3.5、m-ClNB初始摩尔浓度为0.444mmol/L、H2O2摩尔浓度为21.55mmol/L、Fe2+摩尔浓度为0.054mmol/L、反应温度为(25土1)℃的条件下,m-ClNB的去除效果较好.(2)建立了Fenton氧化m-ClNB的准一级反应动力学模型,且m-ClNB的降解与该模型拟合良好.基于不同反应温度时的准一级反应速率常数(kap),得到了m-ClNB降解的阿累尼乌斯公式,且活化能为36.51kJ/mol.(3)气相色谱(GC)/质谱(MS)和高效液相色谱(HPLC)/MS分析表明,Fenton氧化m-ClNB的主要产物有4-氯-2-硝基苯酚及其同分异构体、羟基乙酸、草酸、丁二酸、丙二酸、6-氯己酸、乙醛酸、2,2-二羟基丙二酸和2-乙基丙二酸等.

  12. Kinetic Analysis of Thermal Decomposition of Flame-Retarded Polyester/Natural Brucite Composites%阻燃聚酯树脂/天然水镁石复合材料热分解动力学

    Institute of Scientific and Technical Information of China (English)

    李鑫; 于洪浩

    2016-01-01

    以不饱和聚酯树脂和天然水镁石为原料,采用直接成型技术制备了阻燃聚酯树脂/天然水镁石复合材料。利用锥形量热仪和热重分析仪分析了复合材料的燃烧特性和热分解行为,通过 Flynn–Wall–Ozawa 动力学方法研究了聚酯树脂及其和天然水镁石复合材料的降解活化能。结果表明:添加质量分数为50%的天然水镁石,可使聚酯树脂的热释放速率降低75%,在促进聚酯树脂分解成炭和改善聚酯树脂热氧稳定性方面具有明显的作用。降解活化能分析表明:转化率在0.1~0.3范围时,聚酯材料的活化能随着水镁石的加入而提高,说明在分解起始阶段水镁石对聚酯树脂分解过程起到阻碍作用;转化率在0.4~0.6范围时,聚酯材料的活化能随着水镁石的加入而下降,说明在分解中间阶段,水镁石和聚酯树脂存在双重分解控制的化学反应,改变了降解模式。%Flame–retarded unsaturated polyester resins filled with brucite powders were prepared by direct molding technique. The flammability properties and the thermal oxidative degradation behaviour were studied by cone calorimetric test (CCT) and thermogravimetric analysis (TGA). The Flynn–Wall–Ozawa model–free kinetic method was applied to determine the apparent activation energy (E) for the degradation of pristine polyester and flame–retardant polyester composites. The CCT indicated that the heat release rate (HRR) values decreased 75% when the brucite loading of about 50% of the whole mass. The results of TGA showed that the addition of brucite increased char formation and improved the thermal oxidative stability of polyester resins in air. An incorporation of the brucite powder resulted in a noticeable increase in the activation energy of the obtained composites in the conversion (α) range of 0.1–0.3, which suggested the brucite powder played a hindering role in decomposition of polyester network

  13. Catalytic activity of carbons for methane decomposition reaction

    Energy Technology Data Exchange (ETDEWEB)

    Muradov, Nazim; Smith, Franklyn; T-Raissi, Ali [Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Road, Cocoa, FL 32922 (United States)

    2005-05-15

    Catalytic decomposition of methane is an environmentally attractive approach to CO{sub 2}-free production of hydrogen. The objective of this work is to evaluate catalytic activity of a wide range of carbon materials for methane decomposition reaction and determine major factors governing their activity. It was demonstrated that the catalytic activity of carbon materials for methane decomposition is mostly determined by their structural and surface properties. Kinetics of methane decomposition reaction over disordered (amorphous) carbons such as carbon black and activated carbon were determined. The mechanism of carbon-catalyzed methane decomposition reaction and the nature of active sites on the carbon surface are discussed in this paper.

  14. Linking temperature sensitivity of soil organic matter decomposition to its molecular structure, accessibility, and microbial physiology.

    Science.gov (United States)

    Wagai, Rota; Kishimoto-Mo, Ayaka W; Yonemura, Seiichiro; Shirato, Yasuhito; Hiradate, Syuntaro; Yagasaki, Yasumi

    2013-04-01

    Temperature sensitivity of soil organic matter (SOM) decomposition may have a significant impact on global warming. Enzyme-kinetic hypothesis suggests that decomposition of low-quality substrate (recalcitrant molecular structure) requires higher activation energy and thus has greater temperature sensitivity than that of high-quality, labile substrate. Supporting evidence, however, relies largely on indirect indices of substrate quality. Furthermore, the enzyme-substrate reactions that drive decomposition may be regulated by microbial physiology and/or constrained by protective effects of soil mineral matrix. We thus tested the kinetic hypothesis by directly assessing the carbon molecular structure of low-density fraction (LF) which represents readily accessible, mineral-free SOM pool. Using five mineral soil samples of contrasting SOM concentrations, we conducted 30-days incubations (15, 25, and 35 °C) to measure microbial respiration and quantified easily soluble C as well as microbial biomass C pools before and after the incubations. Carbon structure of LFs (soil was measured by solid-state (13) C-NMR. Decomposition Q10 was significantly correlated with the abundance of aromatic plus alkyl-C relative to O-alkyl-C groups in LFs but not in bulk soil fraction or with the indirect C quality indices based on microbial respiration or biomass. The warming did not significantly change the concentration of biomass C or the three types of soluble C despite two- to three-fold increase in respiration. Thus, enhanced microbial maintenance respiration (reduced C-use efficiency) especially in the soils rich in recalcitrant LF might lead to the apparent equilibrium between SOM solubilization and microbial C uptake. Our results showed physical fractionation coupled with direct assessment of molecular structure as an effective approach and supported the enzyme-kinetic interpretation of widely observed C quality-temperature relationship for short-term decomposition. Factors

  15. The Influence of Grain Size on Decomposition Reaction of Limestone in Dispersing State

    Institute of Scientific and Technical Information of China (English)

    XU De-long; WEI Hon-gen; LUO Yong-qin

    2004-01-01

    The thermal behavior and kinetic parameters of decomposition reaction of limestone in a temperature-programmed mode were investigated by means of TG. The experimental results show that the kinetic model functions in different forms for the thermal decomposition reactions of different limestone grain sizes in dispersing state under the atmosphere of static air are 4(1-α)3/4 for small size limestone and (1-α) for large size limestone. Information was obtained on the relationship among the decomposition temperature, decomposition time, decomposition fraction, decomposition reaction rate constant and grain size of limestone.

  16. Pick-up of early visual information to guide kinetics and kinematics within a group of highly skilled baseball batters.

    Science.gov (United States)

    MüLler, Sean; Lalović, Alex; Dempsey, Alasdair R; Rosalie, Simon M; Harbaugh, Allen G

    2014-10-01

    This pilot study integrated sport expertise and biomechanics methodologies within a baseball batting task. Purpose was to examine differences within a highly skilled group of baseball batters to use visual information to guide weight transfer and bat movements. One batter who played at Major League Baseball (MLB) level was compared to five batters who played at Australian Baseball League (ABL) level in a case-control design. Batters faced pitchers in a simulated competition and attempted to hit pitches, while vision was temporally occluded during ball flight or not occluded. Time of weight transfer (kinetics), as well as bat downswing initiation and duration (kinematics) from the point of ball release, were compared between the MLB batter and ABL batters. Results indicated that the MLB batter coordinated his striking pattern by completing his weight transfer earlier than the ABL batters. His bat downswing was also initiated earlier than some ABL batters, but there was no difference in duration of bat downswing between batters. All batters initiated bat downswing prior to completion of weight transfer. Understanding of motor expertise is furthered using a novel methodology.

  17. Bis(í-oxo)dicopper in Cu-ZSM-5 and Its Role in the Decomposition of NO: A Combined in Situ XAFS, UV-Vis-Near-IR, and Kinetic Study

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Groothaert, M.H.; Bokhoven, J.A. van; Battiston, A.A.; Schoonheydt, R.A.

    2003-01-01

    In situ XAFS combined with UV-vis-near-IR spectroscopy are used to identify the active site in copper-loaded ZSM-5 responsible for the catalytic decomposition of NO. Cu-ZSM-5 was probed with in situ XAFS (i) after O2 activation and (ii) while catalyzing the direct decomposition of NO into N2 and O2.

  18. Hydrogen peroxide decomposition kinetics in aquaculture water

    DEFF Research Database (Denmark)

    Arvin, Erik; Pedersen, Lars-Flemming

    2015-01-01

    Hydrogen peroxide (HP) is used in aquaculture systems where preventive or curative water treatments occasionally are required. Use of chemical agents can be challenging in recirculating aquaculture systems (RAS) due to extended water retention time and because the agents must not damage the fish...... facilitated by microbial enzyme activity. The model describes how the hydrogen peroxide removal declines and eventually stops at relatively low chemical oxygen demand (COD) concentrations. It is hypothesized that this is due to an enzyme deficit because it is destructed due to the reactive radicals created...

  19. The Thermal Decomposition of Calcium Carbonate

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The thermogravimetry(TG) and derivative thermogravimetry(DTG) curves of the thermal decomposition reaction of calcium carbonate have been measured at five different heating rates. The kinetic parameters and the reaction mechanism of the reaction were evaluated from analysis of the TG and DTG curves by using the Ozawa method, the combined integral and differential methods and the reduced equations derived by us.

  20. Adjusting the surface areal density of click-reactive azide groups by kinetic control of the azide substitution reaction on bromine-functional SAMs.

    Science.gov (United States)

    Zhang, Shuo; Maidenberg, Yanir; Luo, Kai; Koberstein, Jeffrey T

    2014-06-03

    Azide-alkyne click chemistry has emerged as an important and versatile means for tethering a wide variety of guest molecules to virtually any substrate. In many of these applications, it is important to exercise control over the areal density of surface functional groups to achieve a desired areal density of the tethered guest molecule of interest. We demonstrate herein that the areal density of surface azide groups on flat germanium surfaces and nanoparticle substrates (silica and iron oxide) can be controlled kinetically by appropriately timed quenching of the S(N)2 substitution reaction of bromo-alkane-silane monolayers induced by the addition of sodium azide. The kinetics of the azide substitution reaction on monolayers formed on flat Ge substrates, determined by attenuated total reflection infrared spectroscopy (ATR-IR), are found to be identical to those for monolayers formed on both silica and iron oxide nanoparticles, the latter determined by transmission infrared spectroscopy. To validate the method, the percentages of surface bromine groups converted to azide groups after various reaction times were measured by quenching the S(N)2 reaction followed by analysis with ATR-IR (for Ge) and thermogravimetric analysis (after a subsequent click reaction with an alkyne-terminal polymer) for the nanoparticle substrates. The conversions found after quenching agree well with those expected from the standard kinetic curves. The latter result suggests that the kinetic method for the control of azide group areal density is a versatile means for functionalizing substrates with a prescribed areal density of azide groups for subsequent click reactions, and that the method is universal for any substrate, flat or nanoparticle, that can be modified with bromo-alkane-silane monolayers. Regardless of the surface geometry, we find that the azide substitution reaction is complete within 2-3 h, in sharp contrast to previous reports that indicate times of 48-60 h required for

  1. Kinetics and Catalysis Demonstrations.

    Science.gov (United States)

    Falconer, John L.; Britten, Jerald A.

    1984-01-01

    Eleven videotaped kinetics and catalysis demonstrations are described. Demonstrations include the clock reaction, oscillating reaction, hydrogen oxidation in air, hydrogen-oxygen explosion, acid-base properties of solids, high- and low-temperature zeolite reactivity, copper catalysis of ammonia oxidation and sodium peroxide decomposition, ammonia…

  2. 3,5-二硝基水杨酸铈的制备、热分解机理及非等温反应动力学%Preparation,Thermal Behavior and Nonisothermal Decomposition Reaction Kinetics of Cerium 3,5-dinitrosalicylate(CeDNS)

    Institute of Scientific and Technical Information of China (English)

    张衡; 赵凤起; 仪建华; 张晓宏; 胡荣祖; 徐司雨

    2009-01-01

    用3,5-二硝基水杨酸和硝酸铈为原料,制备了3,5-二硝基水杨酸铈(CeDNS),采用元素分析、X射线荧光光谱和FTIR对其进行了表征.用TG和DSC以及变温固相原位反应池/傅立叶变换红外光谱(RS-FTIR)联用技术研究了3.5-二硝基水杨酸铈的热分解机理,对主放热反应的DSC峰进行了数学处理.计算得到了动力学参数和动力学方程.结果表明,3,5-二硝基水杨酸铈的分解反应共有3个阶段,其中包括一个脱水吸热过程和一个主放热过程,主分解反应发生在第2阶段,主分解反应的表观活化能E.与指前因子A分别为:159.17 Kj·mol-1和1011.33s-1,主分解阶段的反应机理服从Avrami-Erofeev方程(n=1/4),主分解反应的动力学方程为:da/dt=1011.33×4(1-α)[-In(1-α)]3/4 e-1.92×104/T.%Cerium 3,5-dinitrosalicylate(CeDNS)was synthesized by using 3,5-dinitrosalicylic acid,sodium hydroxide and cerium nitrate as raw materials,and was characterized by elementary analysis,X·ray fluorescence and FTIRspectraoscopy.The thermal decomposition mechanism and kinetm parameters of the decomposition reaction ofCeDNS were investigated by means of TG/DSC and in situ condensed phase thermolysis/FHR(RS-FTIR).The kineticequation of decomposition reaction was obtained.The results show that the decomposition process of CeDNS hasthree stages and the main exothermie decomposition reaction Occurs in the second process.The kinetic parameters ofthe main exothermie decomposition reaction fire:Ea=159.17 kJ·mol-1,A=1011.33 s-1.The kinetic equation can be expressed as:dα/dt=1011.33×4(1-α)[-1n(1-α)]3/4 e -1.92×104/T.

  3. Thermal Decomposition of Dicyclopentadienylarylvanadium Compounds

    NARCIS (Netherlands)

    Boekel, C.P.; Jelsma, A.; Teuben, J.H.; Liefde Meijer, H.J. de

    1977-01-01

    The thermolysis of compounds of the type Cp2VR (R = aryl) in the solid state has been studied. A distinct increase in thermal stability is observed upon substitution of the ortho-position of the aryl group. Thermal decomposition occurs with formation of RH, Cp2V, a vanadocene homologue with the

  4. The photochemical decomposition of Indol in an aqueous solution; Descomposicion fotoquimica de Indol en solucion acuosa

    Energy Technology Data Exchange (ETDEWEB)

    Ibarz, A.; Tejero, J.M.; Panades, R.

    1998-06-01

    The photo decomposition of Indol at different pH has been studied. The Indol photo decomposition rate in aqueous solution a maximum at pH 10. By means of a simple mechanism in three steps, it is possible to explain the kinetics behavior of the Indol photo decomposition in aqueous solution. (Author) 6 refs.

  5. The coupled effects of carbon and nitrogen on soil decomposition: A theoretical model

    Science.gov (United States)

    Darby, B.; Finzi, A.

    2013-12-01

    Soil organic matter (SOM) plays a crucial role in the carbon (C) cycle, holding 2.5 times more carbon than plant biomass. Ecosystem models predict that climate warming will stimulate decomposition of soil carbon stocks, in turn leading to positive feedbacks on warming. Recent empirical studies and modeling work has revealed the importance of microbial physiology and exoenzyme kinetics in driving SOM decomposition. Existing mathematical models describe the microbial processes and biophysics involved in the decomposition. However, although decomposition by nitrogen-degrading enzymes is included in some models, nitrogen (N) does not drive model behavior and there are no reaction kinetics associated with the depolymerization or uptake of N. Additionally, very few empirically measured kinetic values exist for N-degrading enzymes or the uptake of N by microbes. This study proposes a theoretical model of SOM decomposition based on the principles of exoenzyme kinetics and microbial biophysics that explicitly links C and N through microbial uptake and SOM decomposition kinetics and by placing stoichiometric constraints on microbial growth and exoenzyme production. After constructing the model framework, the model was then used to test soil-carbon responses to warming, and to explore the importance of N uptake and depolymerization kinetics in driving decomposition. The model predictions suggest that the response of kinetics to temperature are more important than microbial responses in determining decomposition rates. Additionally, variations in the kinetics of N depolymerization affected decomposition rates, whereas N uptake kinetics and their effect on enzyme production had almost no effect. The model outputs were also compared to a C-only model framework in order to assess the effects of N on model behavior. The incorporation of N into a SOM decomposition model produced different, and in some cases, contradictory results as compared to a C-only model. Overall, these

  6. Soil C and N availability determine the priming effect: microbial N mining and stoichiometric decomposition theories

    Science.gov (United States)

    Chen, Ruirui; Senbayram, Mehmet; Blagodatsky, Sergey; Dittert, Klaus; Lin, Xiangui; Blagodatskaya, Evgenia; Kuzyakov, Yakov

    2014-05-01

    The increasing input of anthropogenically derived nitrogen (N) to ecosystems raises a crucial question: how does available N modify the decomposer community and thus affects the mineralization of soil organic matter (SOM). Moreover, N input modifies the priming effect (PE), that is, the effect of fresh organics on the microbial decomposition of SOM. We studied the interactive effects of C and N on SOM mineralization (by natural 13C labelling adding C4-sucrose or C4-maize straw to C3-soil) in relation to microbial growth kinetics and to the activities of five hydrolytic enzymes. This encompasses the groups of parameters governing two mechanisms of priming effects - microbial N mining and stoichiometric decomposition theories. In sole C treatments, positive PE was accompanied by a decrease in specific microbial growth rates, confirming a greater contribution of K-strategists to the decomposition of native SOM. Sucrose addition with N significantly accelerated mineralization of native SOM, whereas mineral N added with plant residues accelerated decomposition of plant residues. This supports the microbial mining theory in terms of N limitation. Sucrose addition with N was accompanied by accelerated microbial growth, increased activities of β-glucosidase and cellobiohydrolase, and decreased activities of xylanase and leucine amino peptidase. This indicated an increased contribution of r-strategists to the PE and to decomposition of cellulose but the decreased hemicellulolytic and proteolytic activities. Thus, the acceleration of the C cycle was primed by exogenous organic C and was controlled by N. This confirms the stoichiometric decomposition theory. Both K- and r-strategists were beneficial for priming effects, with an increasing contribution of K-selected species under N limitation. Thus, the priming phenomenon described in 'microbial N mining' theory can be ascribed to K-strategists. In contrast, 'stoichiometric decomposition' theory, that is, accelerated OM

  7. Spectral Decomposition Algorithm (SDA)

    Data.gov (United States)

    National Aeronautics and Space Administration — Spectral Decomposition Algorithm (SDA) is an unsupervised feature extraction technique similar to PCA that was developed to better distinguish spectral features in...

  8. A DECOMPOSITION METHOD OF STRUCTURAL DECOMPOSITION ANALYSIS

    Institute of Scientific and Technical Information of China (English)

    LI Jinghua

    2005-01-01

    Over the past two decades,structural decomposition analysis(SDA)has developed into a major analytical tool in the field of input-output(IO)techniques,but the method was found to suffer from one or more of the following problems.The decomposition forms,which are used to measure the contribution of a specific determinant,are not unique due to the existence of a multitude of equivalent forms,irrational due to the weights of different determinants not matching,inexact due to the existence of large interaction terms.In this paper,a decomposition method is derived to overcome these deficiencies,and we prove that the result of this approach is equal to the Shapley value in cooperative games,and so some properties of the method are obtained.Beyond that,the two approaches that have been used predominantly in the literature have been proved to be the approximate solutions of the method.

  9. Multiresolution signal decomposition schemes

    NARCIS (Netherlands)

    J. Goutsias (John); H.J.A.M. Heijmans (Henk)

    1998-01-01

    textabstract[PNA-R9810] Interest in multiresolution techniques for signal processing and analysis is increasing steadily. An important instance of such a technique is the so-called pyramid decomposition scheme. This report proposes a general axiomatic pyramid decomposition scheme for signal analysis

  10. Multiresolution signal decomposition schemes

    NARCIS (Netherlands)

    Goutsias, J.; Heijmans, H.J.A.M.

    1998-01-01

    [PNA-R9810] Interest in multiresolution techniques for signal processing and analysis is increasing steadily. An important instance of such a technique is the so-called pyramid decomposition scheme. This report proposes a general axiomatic pyramid decomposition scheme for signal analysis and synthes

  11. Quantum chemical aided prediction of the thermal decomposition mechanisms and temperatures of ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Kroon, Maaike C. [Physical Chemistry and Molecular Thermodynamics, Department of Chemical Technology, Faculty of Applied Sciences, Delft University of Technology, Julianalaan 136, 2628 BL Delft (Netherlands); Process Equipment, Department of Process and Energy, Faculty of Mechanical, Maritime and Materials Engineering, Delft University of Technology, Leeghwaterstraat 44, 2628 CA Delft (Netherlands)], E-mail: maaike.kroon@gmail.com; Buijs, Wim [Catalysis Engineering, Department of Chemical Technology, Faculty of Applied Sciences, Delft University of Technology, Julianalaan 136, 2628 BL Delft (Netherlands); Peters, Cor J. [Physical Chemistry and Molecular Thermodynamics, Department of Chemical Technology, Faculty of Applied Sciences, Delft University of Technology, Julianalaan 136, 2628 BL Delft (Netherlands); Witkamp, Geert-Jan [Process Equipment, Department of Process and Energy, Faculty of Mechanical, Maritime and Materials Engineering, Delft University of Technology, Leeghwaterstraat 44, 2628 CA Delft (Netherlands)], E-mail: G.J.Witkamp@3me.tudelft.nl

    2007-12-15

    The long-term thermal stability of ionic liquids is of utmost importance for their industrial application. Although the thermal decomposition temperatures of various ionic liquids have been measured previously, experimental data on the thermal decomposition mechanisms and kinetics are scarce. It is desirable to develop quantitative chemical tools that can predict thermal decomposition mechanisms and temperatures (kinetics) of ionic liquids. In this work ab initio quantum chemical calculations (DFT-B3LYP) have been used to predict thermal decomposition mechanisms, temperatures and the activation energies of the thermal breakdown reactions. These quantum chemical calculations proved to be an excellent method to predict the thermal stability of various ionic liquids.

  12. 非等温TG-DTG法确定2,2'-联吡啶-对甲氧基苯甲酸铕(Ⅲ)热分解反应的机理函数和动力学参数%Determination of Mechanism Function and Kinetic Parameters of Thermal Decomposition of the 2,2'-Dipyridine-tris(p-methoxybenzoate) Europium(Ⅲ) with Non-isothermal TG and DTG Curves

    Institute of Scientific and Technical Information of China (English)

    张建军; 王瑞芬; 翟学良; 赵建路; 杨惠芳; 默丽萍

    2000-01-01

    The thermal decomposition of the 2,2'-dipyridine-tris(p-methoxybenzoats) europium (Ⅲ) and its kinetics were studied under the non-isothermal condition in air by TG-DTG and DTA methods. The intermediate and residue for each decomposition were identified from TG curve. The non-isothermal kinetic data were analyzed by means of integral and differential methods. The possible reaction mechanisms were investigated by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as dα/dt =Aexp(-E/RT)2(1-α)1/2.%采用TG-DTG和DTA技术研究了2,2'-联吡啶-对甲氧基苯甲酸铕(Ⅲ)在静态空气中的非等温热分解过程及动力学,根据TG曲线确定了热分解过程中的中间产物及最终产物,运用微分法与积分法对非等温动力学数据进行分析,推断出第一步的动力学方程为dα/dt=Aexp(-E/RT)2(1-α)1/2.

  13. A global HMX decomposition model

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, M.L.

    1996-12-01

    HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) decomposes by competing reaction pathways to form various condensed and gas-phase intermediate and final products. Gas formation is related to the development of nonuniform porosity and high specific surface areas prior to ignition in cookoff events. Such thermal damage enhances shock sensitivity and favors self-supported accelerated burning. The extent of HMX decomposition in highly confined cookoff experiments remains a major unsolved experimental and modeling problem. The present work is directed at determination of global HMX kinetics useful for predicting the elapsed time to thermal runaway (ignition) and the extent of decomposition at ignition. Kinetic rate constants for a six step engineering based global mechanism were obtained using gas formation rates measured by Behrens at Sandia National Laboratories with his Simultaneous Modulated Beam Mass Spectrometer (STMBMS) experimental apparatus. The six step global mechanism includes competition between light gas (H[sub 2]Awe, HCN, CO, H[sub 2]CO, NO, N[sub 2]Awe) and heavy gas (C[sub 2]H[sub 6]N[sub 2]Awe and C[sub 4]H[sub 10]N0[sub 2]) formation with zero order sublimation of HMX and the mononitroso analog of HMX (mn-HMX), C[sub 4]H[sub 8]N[sub 8]Awe[sub 7]. The global mechanism was applied to the highly confined, One Dimensional Time to eXplosion (ODTX) experiment and hot cell experiments by suppressing the sublimation of HMX and mn-HMX. An additional gas-phase reaction was also included to account for the gas-phase reaction of N[sub 2]Awe with H[sub 2]CO. Predictions compare adequately to the STMBMS data, ODTX data, and hot cell data. Deficiencies in the model and future directions are discussed.

  14. A Lagrangian Dynamic Mode Decomposition

    CERN Document Server

    Sesterhenn, Jörn

    2016-01-01

    Temporal or spatial structures are readily extracted from complex data by modal decompositions like POD or DMD. Subspaces of that decompositions serve as reduced order models and define spatial structures in time or temporal structures in space. Convecting phenomena pose a major problem to those decompositions. A structure travelling with a certain group velocity will be perceived as a plethora of modes in time or space respectively. This manifests itself for example in poorly decaying Singular Values when using a POD. The poor decay is very counter-intuitive, since we expect a single structure to be represented by a few modes. The intuition proves to be correct and we show that in a properly chosen reference frame along the characteristic defined by the group velocity, a POD or DMD reduces moving structures to a few modes, as expected. Beyond serving as a reduced model, the re- sulting entity can be used to define a constant or minimally changing structure in turbulent flows. This can be interpreted as an em...

  15. 3,4-双(3',5'-二硝基苯-1'-基)氧化呋咱的热 行为和非等温热分解动力学研究%Thermal behavior and non-isothermal decomposition kinetics of 3,4-bis ( 3' ,5'-dinitrophenyl-1 '-yl ) furoxan

    Institute of Scientific and Technical Information of China (English)

    张腊莹; 朱欣华; 卿辉; 霍欢; 仪建华; 白娟; 丁黎

    2011-01-01

    为了评价含能材料3,4-双(3',5 '-二硝基苯-l'-基)氧化呋咱(BDPF)的热稳定性和安全性,采用DSC、PDSC和'G/DTG方法对其进行了热行为及非等温热分解动力学研究.通过Kissinger和Ozawa's法得到常压下热分解反应的动力学参数(Ea和A)为180.46 kJ·mol-1和1015.29 s-1,其热分解反应动力学方程为:dα/dT=1015.38/β(1-α)[-㏑(1-α)]1/4 exp(-2.173 0×104/T);临界爆炸温度为510.6 K.%In order to evaluate the thermal stability and safety of energetic material 3,4-bis(3',5'-dinitrophenyl-1 '-yl) furoxan (BDPF),the thermal behavior and non-isothermal decomposition kinetics were investigated by means of DSC,PDSC and TG/DTG methods under non-isothermal conditions.The results indicate that its thermolysis apparent activation energy ( Ea),pre-exponent parameters (A),obtained by Kissinger and Ozawa's methods,are 180.46 kJ · mol-1 and 1015.29 s-1,respectively.The kinetic equation of thermal decomposition for BDPF at 0.1 Mpa can be expressed as dα/dT=1015.38/β(1-α)[-㏑(1-α)]1/4 exp(-2.1730)× 104/T),and its critical temperature of thermal explosion is 510.6 K.

  16. Decompositions of manifolds

    CERN Document Server

    Daverman, Robert J

    2007-01-01

    Decomposition theory studies decompositions, or partitions, of manifolds into simple pieces, usually cell-like sets. Since its inception in 1929, the subject has become an important tool in geometric topology. The main goal of the book is to help students interested in geometric topology to bridge the gap between entry-level graduate courses and research at the frontier as well as to demonstrate interrelations of decomposition theory with other parts of geometric topology. With numerous exercises and problems, many of them quite challenging, the book continues to be strongly recommended to eve

  17. Algorithm of Parallel Oscillation Suppression Based on Dual Decomposition of Hidden Groups%基于隐性群体双模分解的并行振荡抑制算法

    Institute of Scientific and Technical Information of China (English)

    姚曙光

    2014-01-01

    The reality of the communication network composed of multiple network, complex network structure with multi task allocation, in task processing will produce parallel oscillation, the oscillation in complex networks is an important fac-tor to improve the inhibition of complex network parallel processing. Parallel oscillation by using the traditional method of singular value decomposition to reduce the dimensionality of the matching algorithm, the memory requirement and the time loss a lot of in the face of large-scale complex task is solved. This paper proposes a parallel oscillation suppression algo-rithm based on dual decomposition of hidden groups, first carries on the complex network of multi dimension business paral-lel processing model design, the index system of multi dimension business parameters of complex network parallel process-ing model, implicit parallel feature matching method to realize the double feature matching parallel processing. Simulation results show that, the parallel feature matching by using the algorithm of hidden groups of complex network, to realize the parallel processing and serial processing, the least square singular value decomposition time cost and space cost is reduced greatly, improve the speedup of 2 times, effectively inhibit the network oscillations. Algorithm in the complex network of multi task parallel processing in the number, it has the superior performance of delay and energy efficiency.%现实的通信网络由多重网络组成,构成具有多维任务分配的复杂网络结构,在任务处理中会产生并行振荡,对复杂网络中的振荡抑制是提高复杂网络并行处理的重要因素。传统的并行振荡方法采用奇异值分解降维的特征匹配算法,在面对大规模复杂任务求解时产生大量的内存需求和时间损耗。提出一种基于隐性群体双模分解的并行振荡抑制算法,首先进行复杂网络多维业务并行处理模型设计,得到了复杂网

  18. Analyzing stability of neutron point kinetics equations with nine photo-neutron groups using Lyapunov exponent method

    Directory of Open Access Journals (Sweden)

    M Seidi

    2016-12-01

    Full Text Available Lyapunov exponent method is one of the best tools for investigating the range of stability and the transient behavior of the dynamical systems. In beryllium-moderated and heavy water-moderated reactors, photo-neutron plays an important role in dynamic behavior of the reactor. Therefore, stability analysis for changes in the control parameters of the reactor in order to guarantee safety and control nuclear reactor is important. In this work, the range of stability has been investigated using Lyapunov exponent method in response to step, ramp and sinusoidal external reactivities regarding six groups of delayed neutrons plus nine groups of photo-neutrons. The qualitative results are in good agreement with quantitative results of other works

  19. Dominant modal decomposition method

    Science.gov (United States)

    Dombovari, Zoltan

    2017-03-01

    The paper deals with the automatic decomposition of experimental frequency response functions (FRF's) of mechanical structures. The decomposition of FRF's is based on the Green function representation of free vibratory systems. After the determination of the impulse dynamic subspace, the system matrix is formulated and the poles are calculated directly. By means of the corresponding eigenvectors, the contribution of each element of the impulse dynamic subspace is determined and the sufficient decomposition of the corresponding FRF is carried out. With the presented dominant modal decomposition (DMD) method, the mode shapes, the modal participation vectors and the modal scaling factors are identified using the decomposed FRF's. Analytical example is presented along with experimental case studies taken from machine tool industry.

  20. Litter Decomposition Rates, 2015

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This data set contains decomposition rates for litter of Salicornia pacifica, Distichlis spicata, and Deschampsia cespitosa buried at 7 tidal marsh sites in 2015....

  1. Spectral proper orthogonal decomposition

    CERN Document Server

    Sieber, Moritz; Paschereit, Christian Oliver

    2015-01-01

    The identification of coherent structures from experimental or numerical data is an essential task when conducting research in fluid dynamics. This typically involves the construction of an empirical mode base that appropriately captures the dominant flow structures. The most prominent candidates are the energy-ranked proper orthogonal decomposition (POD) and the frequency ranked Fourier decomposition and dynamic mode decomposition (DMD). However, these methods fail when the relevant coherent structures occur at low energies or at multiple frequencies, which is often the case. To overcome the deficit of these "rigid" approaches, we propose a new method termed Spectral Proper Orthogonal Decomposition (SPOD). It is based on classical POD and it can be applied to spatially and temporally resolved data. The new method involves an additional temporal constraint that enables a clear separation of phenomena that occur at multiple frequencies and energies. SPOD allows for a continuous shifting from the energetically ...

  2. Decomposition of Polynomials

    CERN Document Server

    Blankertz, Raoul

    2011-01-01

    This diploma thesis is concerned with functional decomposition $f = g \\circ h$ of polynomials. First an algorithm is described which computes decompositions in polynomial time. This algorithm was originally proposed by Zippel (1991). A bound for the number of minimal collisions is derived. Finally a proof of a conjecture in von zur Gathen, Giesbrecht & Ziegler (2010) is given, which states a classification for a special class of decomposable polynomials.

  3. Plant identity influences decomposition through more than one mechanism.

    Directory of Open Access Journals (Sweden)

    Jennie R McLaren

    Full Text Available Plant litter decomposition is a critical ecosystem process representing a major pathway for carbon flux, but little is known about how it is affected by changes in plant composition and diversity. Single plant functional groups (graminoids, legumes, non-leguminous forbs were removed from a grassland in northern Canada to examine the impacts of functional group identity on decomposition. Removals were conducted within two different environmental contexts (fertilization and fungicide application to examine the context-dependency of these identity effects. We examined two different mechanisms by which the loss of plant functional groups may impact decomposition: effects of the living plant community on the decomposition microenvironment, and changes in the species composition of the decomposing litter, as well as the interaction between these mechanisms. We show that the identity of the plant functional group removed affects decomposition through both mechanisms. Removal of both graminoids and forbs slowed decomposition through changes in the decomposition microenvironment. We found non-additive effects of litter mixing, with both the direction and identity of the functional group responsible depending on year; in 2004 graminoids positively influenced decomposition whereas in 2006 forbs negatively influenced decomposition rate. Although these two mechanisms act independently, their effects may be additive if both mechanisms are considered simultaneously. It is essential to understand the variety of mechanisms through which even a single ecosystem property is affected if we are to predict the future consequences of biodiversity loss.

  4. Synthesis and characterization of norfloxacin-transition metal complexes (group 11, IB): Spectroscopic, thermal, kinetic measurements and biological activity

    Science.gov (United States)

    Refat, Moamen S.

    2007-12-01

    The investigation of the new structures of Ag(I), Cu(II) and Au(III) complexes, [Ag 2(Nor) 2](NO 3) 2, [Cu(Nor) 2(H 2O) 2]SO 4·5H 2O and [Au(Nor) 2 (H 2O) 2]Cl 3 (where, Nor = norfloxacin) was done during the reaction of silver(I), copper(II) and gold(III) ions with norfloxacin drug ligand. Elemental analysis of CHN, infrared, electronic, 1H NMR and mass spectra, as well as thermo gravimetric analysis (TG and DTG) and conductivity measurements have been used to characterize the isolated complexes. The powder XRD studies confirm the amorphous nature of the complexes. The norfloxacin ligand is coordinated to Ag(I) and Au(III) ions as a neutral monodentate chelating through the N atom of piperidyl ring, but the copper(II) complex is coordinated through the carbonyl oxygen atom (quinolone group) and the oxygen atom of the carboxylic group. The norfloxacin and their metal complexes have been biologically tested, which resulted in norfloxacin complexes showing moderate activity against the gram positive and gram negative bacteria as well as against fungi.

  5. Geometric decompositions of collective motion

    Science.gov (United States)

    Mischiati, Matteo; Krishnaprasad, P. S.

    2017-04-01

    Collective motion in nature is a captivating phenomenon. Revealing the underlying mechanisms, which are of biological and theoretical interest, will require empirical data, modelling and analysis techniques. Here, we contribute a geometric viewpoint, yielding a novel method of analysing movement. Snapshots of collective motion are portrayed as tangent vectors on configuration space, with length determined by the total kinetic energy. Using the geometry of fibre bundles and connections, this portrait is split into orthogonal components each tangential to a lower dimensional manifold derived from configuration space. The resulting decomposition, when interleaved with classical shape space construction, is categorized into a family of kinematic modes-including rigid translations, rigid rotations, inertia tensor transformations, expansions and compressions. Snapshots of empirical data from natural collectives can be allocated to these modes and weighted by fractions of total kinetic energy. Such quantitative measures can provide insight into the variation of the driving goals of a collective, as illustrated by applying these methods to a publicly available dataset of pigeon flocking. The geometric framework may also be profitably employed in the control of artificial systems of interacting agents such as robots.

  6. An alternative approach to Michaelis-Menten kinetics that is based on the Renormalization Group: Comparison with the perturbation expansion beyond the sQSSA

    CERN Document Server

    Coluzzi, Barbara; Bersani, Enrico

    2016-01-01

    We recall the perturbation expansion for Michaelis-Menten kinetics, beyond the standard quasi-steady-state approximation (sQSSA). Against this background, we are able to appropriately apply the alternative approach to the study of singularly perturbed differential equations that is based on the renormalization group (SPDERG), by clarifying similarities and differences. In the present demanding situation, we directly renormalize the bare initial condition value for the substrate. Our main results are: i) the 2nd order SPDERG uniform approximations to the correct solutions contain, up to 1st order, the same outer components as the known perturbation expansion ones; ii) the differential equation to be solved for the derivation of the 1st order outer substrate component is simpler within the SPDERG approach; iii) the approximations better reproduce the numerical solutions of the original problem in a region encompassing the matching one, because of the 2nd order terms in the inner components, calculated here for ...

  7. Kinetic Model of Resin-Catalyzed Decomposition of Acetone Cyanohydrin in Organic Solvent%有机溶剂中树脂催化丙酮氰醇分解反应的动力学模型

    Institute of Scientific and Technical Information of China (English)

    章亭洲; 杨立荣; 朱自强; 吴坚平

    2003-01-01

    Decomposition of acetone cyanohydrin is the first-step reaction for preparing (S)-α-cyano-3-phenoxybenzyl alcohol (CPBA) by the one-pot method in organic media. Considering the compatibility of bio-catalysts with chemical catalysts and the successive operation in the bioreactor, anion exchange resin (D301) wasused as catalyst for this reaction. External diffusion limitation was excluded by raising rotational speed to higherthan 190r@min-1 in both solvents. Internal diffusion limitation was verified to be insignificant in this reactionsystem. The effect of acetone cyanohydrin concentration on the reaction was also investigated. An intrinsic kineticmodel was proposed when the mass transfer limitation was excluded, and the average deviation of the model is10.5%.

  8. Kinetic modelling of hydro-treatment reactions by study of different chemical groups; Modelisation cinetique des reactions d`hydrotraitement par regroupement en familles chimiques

    Energy Technology Data Exchange (ETDEWEB)

    Bonnardot, J.

    1998-11-19

    Hydro-treatment of petroleum shortcuts permits elimination of unwanted components in order to increase combustion in engine and to decrease atmospheric pollution. Hydro-desulfurization (HDS), Hydro-denitrogenation (HDN) and Hydrogenation of aromatics (HDA) of a LCO (Light Cycle Oil)-Type gas oil have been studied using a new pilot at a fixed temperature with a NiMo/Al{sub 2}O{sub 3} catalyst. A hydrodynamic study showed that reactions occurring in the up-flow fixed bed reactor that has been used during the experiments, were governed exclusively by chemical reaction rates and not by diffusion. Through detailed chemical analysis, height chemical groups have been considered: three aromatics groups, one sulfided group, one nitrogenized and NH{sub 3}, H{sub 2}S, H{sub 2}. Two Langmuir-Hinshelwood-type kinetic models with either one or two types of sites have been established. The model with two types of site - one site of hydrogenation and one site of hydrogenolysis - showed a better fit in the modeling of the experimental results. This model enables to forecast the influence of partial pressure of H{sub 2}S and partial pressure of H{sub 2} on hydro-treatment reactions of a LCO-type gas oil. (author) 119 refs.

  9. Modeling decomposition of rigid polyurethane foam

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, M.L.

    1998-01-01

    Rigid polyurethane foams are used as encapsulants to isolate and support thermally sensitive components within weapon systems. When exposed to abnormal thermal environments, such as fire, the polyurethane foam decomposes to form products having a wide distribution of molecular weights and can dominate the overall thermal response of the system. Decomposing foams have either been ignored by assuming the foam is not present, or have been empirically modeled by changing physical properties, such as thermal conductivity or emissivity, based on a prescribed decomposition temperature. The hypothesis addressed in the current work is that improved predictions of polyurethane foam degradation can be realized by using a more fundamental decomposition model based on chemical structure and vapor-liquid equilibrium, rather than merely fitting the data by changing physical properties at a prescribed decomposition temperature. The polyurethane decomposition model is founded on bond breaking of the primary polymer and formation of a secondary polymer which subsequently decomposes at high temperature. The bond breaking scheme is resolved using percolation theory to describe evolving polymer fragments. The polymer fragments vaporize according to individual vapor pressures. Kinetic parameters for the model were obtained from Thermal Gravimetric Analysis (TGA) from a single nonisothermal experiment with a heating rate of 20 C/min. Model predictions compare reasonably well with a separate nonisothermal TGA weight loss experiment with a heating rate of 200 C/min.

  10. A contribution to the knowledge of HMX decomposition and application of results. [at atmospheric pressure

    Science.gov (United States)

    Kraeutle, K. J.

    1980-01-01

    The decomposition of cyclotramethylenetetranitramine (HMX) in the solid and liquid phase was studied by isothermal and nonisothermal heating at atmospheric pressure. Decomposition rates of solid HMX changed with sample size and gaseous environment. Kinetic parameters were obtained from weight loss measurements in the temperature range 229 C - 269 C. These tests also yielded highly porous solid residues. Qualitative aspects of solid and liquid phase decomposition of HMX with additives were also investigated in isothermal and nonisothermal tests.

  11. A Reaction-Based River/Stream Water Quality Model: Reaction Network Decomposition and Model Application

    OpenAIRE

    2012-01-01

    This paper describes details of an automatic matrix decomposition approach for a reaction-based stream water quality model. The method yields a set of equilibrium equations, a set of kinetic-variable transport equations involving kinetic reactions only, and a set of component transport equations involving no reactions. Partial decomposition of the system of water quality constituent transport equations is performed via Gauss-Jordan column reduction of the reaction network by pivoting on equil...

  12. Decomposing Nekrasov Decomposition

    CERN Document Server

    Morozov, A

    2015-01-01

    AGT relations imply that the four-point conformal block admits a decomposition into a sum over pairs of Young diagrams of essentially rational Nekrasov functions - this is immediately seen when conformal block is represented in the form of a matrix model. However, the q-deformation of the same block has a deeper decomposition - into a sum over a quadruple of Young diagrams of a product of four topological vertices. We analyze the interplay between these two decompositions, their properties and their generalization to multi-point conformal blocks. In the latter case we explain how Dotsenko-Fateev all-with-all (star) pair "interaction" is reduced to the quiver model nearest-neighbor (chain) one. We give new identities for q-Selberg averages of pairs of generalized Macdonald polynomials. We also translate the slicing invariance of refined topological strings into the language of conformal blocks and interpret it as abelianization of generalized Macdonald polynomials.

  13. Decomposing Nekrasov decomposition

    Science.gov (United States)

    Morozov, A.; Zenkevich, Y.

    2016-02-01

    AGT relations imply that the four-point conformal block admits a decomposition into a sum over pairs of Young diagrams of essentially rational Nekrasov functions — this is immediately seen when conformal block is represented in the form of a matrix model. However, the q-deformation of the same block has a deeper decomposition — into a sum over a quadruple of Young diagrams of a product of four topological vertices. We analyze the interplay between these two decompositions, their properties and their generalization to multi-point conformal blocks. In the latter case we explain how Dotsenko-Fateev all-with-all (star) pair "interaction" is reduced to the quiver model nearest-neighbor (chain) one. We give new identities for q-Selberg averages of pairs of generalized Macdonald polynomials. We also translate the slicing invariance of refined topological strings into the language of conformal blocks and interpret it as abelianization of generalized Macdonald polynomials.

  14. Symmetric tensor decomposition

    CERN Document Server

    Brachat, Jerome; Mourrain, Bernard; Tsigaridas, Elias

    2009-01-01

    We present an algorithm for decomposing a symmetric tensor, of dimension n and order d as a sum of rank-1 symmetric tensors, extending the algorithm of Sylvester devised in 1886 for binary forms. We recall the correspondence between the decomposition of a homogeneous polynomial in n variables of total degree d as a sum of powers of linear forms (Waring's problem), incidence properties on secant varieties of the Veronese Variety and the representation of linear forms as a linear combination of evaluations at distinct points. Then we reformulate Sylvester's approach from the dual point of view. Exploiting this duality, we propose necessary and sufficient conditions for the existence of such a decomposition of a given rank, using the properties of Hankel (and quasi-Hankel) matrices, derived from multivariate polynomials and normal form computations. This leads to the resolution of polynomial equations of small degree in non-generic cases. We propose a new algorithm for symmetric tensor decomposition, based on th...

  15. Energy Diagram for the Catalytic Decomposition of Hydrogen Peroxide

    Science.gov (United States)

    Tatsuoka, Tomoyuki; Koga, Nobuyoshi

    2013-01-01

    Drawing a schematic energy diagram for the decomposition of H[subscript 2]O[subscript 2] catalyzed by MnO[subscript 2] through a simple thermometric measurement outlined in this study is intended to integrate students' understanding of thermochemistry and kinetics of chemical reactions. The reaction enthalpy, delta[subscript r]H, is…

  16. Mueller matrix differential decomposition.

    Science.gov (United States)

    Ortega-Quijano, Noé; Arce-Diego, José Luis

    2011-05-15

    We present a Mueller matrix decomposition based on the differential formulation of the Mueller calculus. The differential Mueller matrix is obtained from the macroscopic matrix through an eigenanalysis. It is subsequently resolved into the complete set of 16 differential matrices that correspond to the basic types of optical behavior for depolarizing anisotropic media. The method is successfully applied to the polarimetric analysis of several samples. The differential parameters enable one to perform an exhaustive characterization of anisotropy and depolarization. This decomposition is particularly appropriate for studying media in which several polarization effects take place simultaneously. © 2011 Optical Society of America

  17. Decomposition of residue currents

    OpenAIRE

    Andersson, Mats; Wulcan, Elizabeth

    2007-01-01

    Given a submodule $J\\subset \\mathcal O_0^{\\oplus r}$ and a free resolution of $J$ one can define a certain vector valued residue current whose annihilator is $J$. We make a decomposition of the current with respect to Ass$(J)$ that correspond to a primary decomposition of $J$. As a tool we introduce a class of currents that includes usual residue and principal value currents; in particular these currents admit a certain type of restriction to analytic varieties and more generally to construct...

  18. Hydrogen peroxide deposition and decomposition in rain and dew waters

    Science.gov (United States)

    Ortiz, Vicky; Angélica Rubio, M.; Lissi, Eduardo A.

    Peroxides and hydrogen peroxide were determined by a fluorometric method in dew and rain collected in the atmosphere of Santiago of Chile city. The measured peroxides comprise hydrogen peroxide (the main component) and peroxides not decomposed by catalase. The collected natural peroxides readily decompose in the natural matrix, rendering difficult an estimation of the values present in real-time. In order to establish the kinetics of the process and the factors that condition their decomposition, the kinetics of the decay at several pHs and/or the presence of metal chelators were followed. The kinetics of hydrogen peroxide decomposition in the water matrix was evaluated employing the natural peroxides or hydrogen peroxide externally added. First-order kinetics was followed, with half decay times ranging from 80 to 2300 min. The addition of Fe(II) in the micromolar range increases the decomposition rate, while lowering the pH (<3) notably reduces the rate of the process. The contribution of metals to the decomposition of the peroxides in the natural waters was confirmed by the reduction in decomposition rate elicited by its treatment with Chelex-100. Dew and rain waters were collected in pre-acidified collectors, rendering values considerably higher than those measured in non-treated collectors. This indicates that acidification can be proposed as an easy procedure to stabilize the samples, reducing its decomposition during collection time and the time elapsed between collection and analysis. The weighted average concentration for total peroxides measured in pre-treated collectors was 5.4 μM in rains and 2.2 μM in dews.

  19. Spinodal decomposition and precipitation in Cu–Cr nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Sheibani, S., E-mail: ssheibani@ut.ac.ir [School of Metallurgy and Materials Engineering, University of Tehran, Tehran (Iran, Islamic Republic of); Heshmati-Manesh, S.; Ataie, A. [School of Metallurgy and Materials Engineering, University of Tehran, Tehran (Iran, Islamic Republic of); Caballero, A.; Criado, J.M. [Instituto de Ciencia de Materiales de Sevilla and Departamento de Quimica Inorganica, CSIC – Universidad de Sevilla (Spain)

    2014-02-25

    Highlights: • Precipitation mechanism of supersaturated Cu-Cr solid solutions was investigated. • Precipitation begins with spinodal decomposition and ends with nucleation and growth. • Kinetics of decomposition is faster in presence of Al{sub 2}O{sub 3} nano-particles. -- Abstract: In this study, spinodal decomposition and precipitation mechanism of mechanically alloyed supersaturated Cu–3wt.%Cr and Cu–5wt.%Cr solid solutions was investigated under nonisothermal aging. Decomposition mechanism and kinetics were studied using differential scanning calorimetry (DSC) and X-ray diffraction (XRD) techniques. Also, the microstructure was characterized by transmission electron microscopy (TEM). Effect of Al{sub 2}O{sub 3} reinforcement on the aging kinetics was also evaluated. It was found that Cu–3wt.%Cr and Cu–5wt.%Cr solid solutions undergo spinodal decomposition at initial stages of ageing. However, decomposition mechanism was changed to nucleation and growth by the aging progress. The aging kinetics for the Cu–Cr/Al{sub 2}O{sub 3} composition appeared to be slightly faster than that for Cu–Cr, since the ageing activation energy is decreased in presence of Al{sub 2}O{sub 3} nano-particles. This behavior is probably due to the higher dislocation density and other structural defects previously produced during ball milling. A detailed comparison of the DSC results with those obtained by TEM, showing good consistency, has been presented. The average size of Cr-rich precipitates was about 10 nm in the copper matrix.

  20. Ozone Decomposition on the Surface of Metal Oxide Catalyst

    Directory of Open Access Journals (Sweden)

    Batakliev Todor Todorov

    2014-12-01

    Full Text Available The catalytic decomposition of ozone to molecular oxygen over catalytic mixture containing manganese, copper and nickel oxides was investigated in the present work. The catalytic activity was evaluated on the basis of the decomposition coefficient which is proportional to ozone decomposition rate, and it has been already used in other studies for catalytic activity estimation. The reaction was studied in the presence of thermally modified catalytic samples operating at different temperatures and ozone flow rates. The catalyst changes were followed by kinetic methods, surface measurements, temperature programmed reduction and IR-spectroscopy. The phase composition of the metal oxide catalyst was determined by X-ray diffraction. The catalyst mixture has shown high activity in ozone decomposition at wet and dry O3/O2 gas mixtures. The mechanism of catalytic ozone degradation was suggested.

  1. Analytical Solution of the Point Reactor Kinetics Equations for One-Group of Delayed Neutrons for a Discontinuous Linear Reactivity Insertion

    Directory of Open Access Journals (Sweden)

    S. Yamoah

    2012-11-01

    Full Text Available The understanding of the time-dependent behaviour of the neutron population in a nuclear reactor in response to either a planned or unplanned change in the reactor conditions is of great importance to the safe and reliable operation of the reactor. It is therefore important to understand the response of the neutron density and how it relates to the speed of lifting control rods. In this study, an analytical solution of point reactor kinetic equations for one-group of delayed neutrons is developed to calculate the change in neutron density when reactivity is linearly introduced discontinuously. The formulation presented in this study is validated with numerical solution using the Euler method. It is observed that for higher speed, r = 0.0005 the Euler method predicted higher values than the method presented in this study. However with r = 0.0001, the Euler method predicted lower values than the method presented in this study except for t = 1.0 s and 5.0 s. The results obtained have shown to be compatible with the numerical method.

  2. Two Notes on Discrimination and Decomposition

    DEFF Research Database (Denmark)

    Nielsen, Helena Skyt

    1998-01-01

    1. It turns out that the Oaxaca-Blinder wage decomposition is inadequate when it comes to calculation of separate contributions for indicator variables. The contributions are not robust against a change of reference group. I extend the Oaxaca-Blinder decomposition to handle this problem. 2. The p....... The paper suggests how to use the logit model to decompose the gender difference in the probability of an occurrence. The technique is illustrated by an analysis of discrimination in child labor in rural Zambia....

  3. Two Notes on Discrimination and Decomposition

    DEFF Research Database (Denmark)

    Nielsen, Helena Skyt

    1998-01-01

    1. It turns out that the Oaxaca-Blinder wage decomposition is inadequate when it comes to calculation of separate contributions for indicator variables. The contributions are not robust against a change of reference group. I extend the Oaxaca-Blinder decomposition to handle this problem. 2. The p....... The paper suggests how to use the logit model to decompose the gender difference in the probability of an occurrence. The technique is illustrated by an analysis of discrimination in child labor in rural Zambia....

  4. An analytical representation for the solution of neutron kinetic transport equation in slab-geometry multigroup discrete ordinates formulation

    Energy Technology Data Exchange (ETDEWEB)

    Tomaschewski, Fernanda K.; Segatto, Cynthia F., E-mail: fernandasls_89@hotmail.com, E-mail: cynthia.segatto@ufrgs.br [Universidade Federal do Rio Grande do Sul (UFRS), Porto Alegre, RS (Brazil). Programa de Pos-Graduacao em Matematica Aplicada; Barros, Ricardo C., E-mail: rcbarros@pq.cnpq.br [Universidade do Estado do Rio de Janeiro (UERJ), Nova Friburgo, RJ (Brazil). Departamento de Modelagem Computacional

    2015-07-01

    Presented here is a decomposition method based on series representation of the group angular fluxes and delayed neutron precursors in smoothly continuous functions for energy multigroups, slab-geometry discrete ordinates kinetics equations supplemented with a prescribed number of delayed neutron precursors. Numerical results to a non-reflected sub-critical slab stabilized by steady-state sources are given to illustrate the accuracy and efficiency of the o offered method. (author)

  5. Tree decompositions with small cost

    NARCIS (Netherlands)

    Bodlaender, H.L.; Fomin, F.V.

    2002-01-01

    The f-cost of a tree decomposition ({Xi | i e I}, T = (I;F)) for a function f : N -> R+ is defined as EieI f(|Xi|). This measure associates with the running time or memory use of some algorithms that use the tree decomposition. In this paper we investigate the problem to find tree decompositions

  6. Modeling Decomposition of Unconfined Rigid Polyurethane Foam

    Energy Technology Data Exchange (ETDEWEB)

    HOBBS,MICHAEL L.; ERICKSON,KENNETH L.; CHU,TZE YAO

    1999-11-08

    The decomposition of unconfined rigid polyurethane foam has been modeled by a kinetic bond-breaking scheme describing degradation of a primary polymer and formation of a thermally stable secondary polymer. The bond-breaking scheme is resolved using percolation theory to describe evolving polymer fragments. The polymer fragments vaporize according to individual vapor pressures. Kinetic parameters for the model were obtained from Thermal Gravimetric Analysis (TGA). The chemical structure of the foam was determined from the preparation techniques and ingredients used to synthesize the foam. Scale-up effects were investigated by simulating the response of an incident heat flux of 25 W/cm{sup 2} on a partially confined 8.8-cm diameter by 15-cm long right circular cylinder of foam that contained an encapsulated component. Predictions of center, midradial, and component temperatures, as well as regression of the foam surface, were in agreement with measurements using thermocouples and X-ray imaging.

  7. Modeling Decomposition of Unconfined Rigid Polyurethane Foam

    Energy Technology Data Exchange (ETDEWEB)

    CHU,TZE YAO; ERICKSON,KENNETH L.; HOBBS,MICHAEL L.

    1999-11-01

    The decomposition of unconfined rigid polyurethane foam has been modeled by a kinetic bond-breaking scheme describing degradation of a primary polymer and formation of a thermally stable secondary polymer. The bond-breaking scheme is resolved using percolation theory to describe evolving polymer fragments. The polymer fragments vaporize according to individual vapor pressures. Kinetic parameters for the model were obtained from Thermal Gravimetric Analysis (TGA). The chemical structure of the foam was determined from the preparation techniques and ingredients used to synthesize the foam. Scale-up effects were investigated by simulating the response of an incident heat flux of 25 W/cm{sup 2} on a partially confined 8.8-cm diameter by 15-cm long right circular cylinder of foam which contained an encapsulated component. Predictions of center, midradial, and component temperatures, as well as regression of the foam surface, were in agreement with measurements using thermocouples and X-ray imaging.

  8. Unimolecular thermal decomposition of dimethoxybenzenes

    Science.gov (United States)

    Robichaud, David J.; Scheer, Adam M.; Mukarakate, Calvin; Ormond, Thomas K.; Buckingham, Grant T.; Ellison, G. Barney; Nimlos, Mark R.

    2014-06-01

    The unimolecular thermal decomposition mechanisms of o-, m-, and p-dimethoxybenzene (CH3O-C6H4-OCH3) have been studied using a high temperature, microtubular (μtubular) SiC reactor with a residence time of 100 μs. Product detection was carried out using single photon ionization (SPI, 10.487 eV) and resonance enhanced multiphoton ionization (REMPI) time-of-flight mass spectrometry and matrix infrared absorption spectroscopy from 400 K to 1600 K. The initial pyrolytic step for each isomer is methoxy bond homolysis to eliminate methyl radical. Subsequent thermolysis is unique for each isomer. In the case of o-CH3O-C6H4-OCH3, intramolecular H-transfer dominates leading to the formation of o-hydroxybenzaldehyde (o-HO-C6H4-CHO) and phenol (C6H5OH). Para-CH3O-C6H4-OCH3 immediately breaks the second methoxy bond to form p-benzoquinone, which decomposes further to cyclopentadienone (C5H4=O). Finally, the m-CH3O-C6H4-OCH3 isomer will predominantly follow a ring-reduction/CO-elimination mechanism to form C5H4=O. Electronic structure calculations and transition state theory are used to confirm mechanisms and comment on kinetics. Implications for lignin pyrolysis are discussed.

  9. Thermal Decomposition of New and Aged LX-04 and PBX 9501

    Energy Technology Data Exchange (ETDEWEB)

    Tran, T D; Tarver, C; Idar, D J; Rodin, W A

    2002-04-09

    One-Dimensional-Time-To-Explosion (ODTX) experiments were conducted to study the thermal decomposition of new and aged LX-04, PBX 9501, HMX class 1 and class 2, Estane and EstaneBDNPA-F (PBX 950 1 plasticized-binder) materials. New and aged LX-04 showed comparable decomposition kinetics. The data for aged PBX 9501 showed slightly longer explosion times at equivalent temperatures. Analysis of the error in time measurement is complicated by several experimental factors but the small time change appears to be experimentally significant. The results suggest that aged PBX 9501 is slightly more thermally stable. The thermal decomposition of these materials were modeled using a coupled thermal and heat transport code (chemical TOPAZ) using separate kinetics for HMX and binder decomposition. The current kinetic models describe the longer explosion times by the loss of plasticizer-binder constituent, which was more thermally reactive.

  10. Decomposition of semigroup algebras

    CERN Document Server

    Boehm, Janko; Nitsche, Max Joachim

    2011-01-01

    Let A \\subseteq B be cancellative abelian semigroups, and let R be an integral domain. We show that the semigroup ring R[B] can be decomposed, as an R[A]-module, into a direct sum of R[A]-submodules of the quotient ring of R[A]. In the case of a finite extension of positive affine semigroup rings we obtain an algorithm computing the decomposition. When R[A] is a polynomial ring over a field we explain how to compute many ring-theoretic properties of R[B] in terms of this decomposition. In particular we obtain a fast algorithm to compute the Castelnuovo-Mumford regularity of homogeneous semigroup rings. As an application we confirm the Eisenbud-Goto conjecture in a range of new cases. Our algorithms are implemented in the Macaulay2 package MonomialAlgebras.

  11. Physico-Geometrical Kinetics of Solid-State Reactions in an Undergraduate Thermal Analysis Laboratory

    Science.gov (United States)

    Koga, Nobuyoshi; Goshi, Yuri; Yoshikawa, Masahiro; Tatsuoka, Tomoyuki

    2014-01-01

    An undergraduate kinetic experiment of the thermal decomposition of solids by microscopic observation and thermal analysis was developed by investigating a suitable reaction, applicable techniques of thermal analysis and microscopic observation, and a reliable kinetic calculation method. The thermal decomposition of sodium hydrogen carbonate is…

  12. Physico-Geometrical Kinetics of Solid-State Reactions in an Undergraduate Thermal Analysis Laboratory

    Science.gov (United States)

    Koga, Nobuyoshi; Goshi, Yuri; Yoshikawa, Masahiro; Tatsuoka, Tomoyuki

    2014-01-01

    An undergraduate kinetic experiment of the thermal decomposition of solids by microscopic observation and thermal analysis was developed by investigating a suitable reaction, applicable techniques of thermal analysis and microscopic observation, and a reliable kinetic calculation method. The thermal decomposition of sodium hydrogen carbonate is…

  13. Photon kinetics in plasmas

    Directory of Open Access Journals (Sweden)

    V.G. Morozov

    2009-01-01

    Full Text Available We present a kinetic theory of radiative processes in many-component plasmas with relativistic electrons and nonrelativistic heavy particles. Using the non-equilibrium Green's function technique in many-particle QED, we show that the transverse field correlation functions can be naturally decomposed into sharply peaked (non-Lorentzian parts that describe resonant (propagating photons and off-shell parts corresponding to virtual photons in the medium. Analogous decompositions are obtained for the longitudinal field correlation functions and the correlation functions of relativistic electrons. We derive a kinetic equation for the resonant photons with a finite spectral width and show that the off-shell parts of the particle and field correlation functions are essential to calculate the local radiating power in plasmas and recover the results of vacuum QED. The plasma effects on radiative processes are discussed.

  14. Thermal decomposition of dolomite under CO2-air atmosphere

    Science.gov (United States)

    Subagjo, Wulandari, Winny; Adinata, Pratitis Mega; Fajrin, Anita

    2017-01-01

    This paper reports a study on thermal decomposition of dolomite under CO2-air. Calcination was carried out non-isothermally by using thermogravimetry analysis-differential scanning calorimetry (TGA-DSC) with a heating rate of 10°C/minute in an air atmosphere as well as 10 vol% CO2 and 90 vol% air atmosphere from 25 to 950°C. In addition, a thermodynamic modeling was also carried out to simulate dolomite calcination in different level of CO2-air atmosphere by using FactSage® 7.0. The the main constituents of typical dolomite from Gresik, East Java include MgCO3 (magnesite), CaCO3 (calcite), Ca(OH)2, CaO, MgO, and less than 1% of metal impurities. Based on the kinetics analysis from TGA results, it is found that non-isothermal dolomite calcination in 10 vol% CO2 atmosphere is occurred in a two-stage reaction; the first stage is the decomposition of magnesite at 650-740 °C with activation energy of 161.23 kJ/mol, and the second stage is the decomposition of calcite at 775-820 °C with activation energy of 162.46 kJ/mol. The magnesite decomposition is found to follow nucleation reaction mechanism of Avrami Eroveyef (A3), while calcite decomposition follows second order chemical reaction equation. Thermodynamic modeling supports these kinetic analyses. The results of this research give insight to the kinetics of dolomite decomposition in CO2-air atmosphere.

  15. Kinetic features of breunnerite decarbonization

    Science.gov (United States)

    Vusikhis, A. S.; Gulyaeva, R. I.; Leont'ev, L. I.; Ovchinnikova, L. A.; Selivanov, E. N.

    2016-09-01

    The decarbonization of breunnerite from talc waste is analyzed by thermogravimetry. The temperatures of thermal effects are determined, and kinetic models for the process are proposed to describe the mechanism of breunnerite decomposition. The unit cell parameters of breunnerite (Mg x Fe1- x )CO3 and the product of its decomposition, iron-magnesium oxide (Mg,Fe)O, are calculated. The apparent activation energies E a of the decomposition are calculated using the Ozawa-Flynn-Wall and Kissenger model-free methods and the Avrami-Erofeev one-step model. Depending on the chosen model, the values of E a range within 180-185 kJ/mol. The conditions of breunnerite roasting for the subsequent use of the obtained material in metallurgical processes are substantiated.

  16. Thermal decomposition studies of CuInS2

    Institute of Scientific and Technical Information of China (English)

    Sunil H. CHAKI

    2008-01-01

    Single crystals of copper indium disulphide (CuInS2) have been successfully grown by the chemical vapour transport (CVT) technique using iodine as the transporting agent. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were carried out for the CVT grown CuInS2 single crystals. It was revealed that the crystals are thermally stable between the ambient temperature (300 K) and 845 K and that the decomposi-tion occurs sequentially in three steps. The kinetic para-meters, e.g., activation energy, order of reaction, and frequency factor were evaluated using non-mechanistic equations for thermal decomposition.

  17. 纳米结晶体Ni0.5Zn0.5Fe2O4对高氯酸铵热行为及分解反应动力学的影响%Effect of Nanocrystal Ni0.5Zn0.5Fe2O4 on Thermal Behavior and Decomposition Reaction Kinetics of Ammonium Perchlorate

    Institute of Scientific and Technical Information of China (English)

    仪建华; 赵凤起; 胡荣祖; Gurdip Singh

    2008-01-01

    采用差示扫描量热法(DSC)、热重和微分热重(TG-DTG)及固相原位反应池/快速扫描傅立叶变换红外联用技术(hyphenated in situ thermolysis/RSFTIR)研究了纳米结晶体Ni0.5Zn0.5Fe2O4与高氯酸铵(AP)组成的混合物的热行为和分解反应动力学.结果表明:Ni0.5Zn0.5Fe2O4使得AP的低、高温分解放热峰温分别提前17.44 K和27.74 K,并使得对应的分解热分别增加3.7 J·g-1和193.7 J·g-1.Ni0.5Zn0.5Fe2O4并不影响AP的晶转温度和晶转热.Ni0.5Zn0.5Fe2O4使得AP的TG曲线出现3个阶段,并使得后2个失重阶段的初始和终止温度都有所提前.凝聚相分解产物分析表明Ni0.5Zn0.5Fe2O4加速了凝聚相AP的分解及氨气的释放.含Ni0.5Zn0.5Fe2O4的AP的高温分解反应的动力学参数Ea=238.88 kJ·mol-1,A=1018.59 s-1,动力学方程可表示为dα/dt=1018.99(1-α)[-ln(1-α)]3/5e-2.87.始点温度(Te)和峰顶温度(Tp)计算得出AP的热爆炸临界温度值分别为:574.83 K和595.41 K.分解反应的活化熵(△S≠)、活化焓(△H≠)和活化能(△G≠)分别为:109.61 J·mol-1·K-1、236.49 kJ·mol-1及172.58 kJ·mol-1.%The thermal behavior and non-isothermal decomposition reaction kinetics of the mixture of the nanocrystal Ni0.5Zn0.5Fe2O4 and ammonium perchlorate (AP) were investigated by differential scanning calorimetry(DSC), thermogravimetry and differential thermogravimetry (TG-DTG), and the hyphenated technique of in situ thermolysis cell with rapid-scan Fourier transform infrared spectroscopy (in situ thermolysis/RSFTIR). The results show that Ni0.5Zn0.5Fe2O4 can decrease the low-temperature and the high-temperature exothermic peak temperatures of AP by 17.44 K and 27.74 K, respectively, and increase the decomposition heats of the two exothermic peaks by of AP. Ni0.5Zn0.5Fe2O4 makes AP shown three mass-loss processes, and it can decrease the initial and terminated temperatures of the last two mass-loss stages. The condensed phase decomposition product

  18. Decomposition of aquatic macrophytes from Cantá stream (Roraima, Brazil: kinetics approach Decomposição de macrófitas aquáticas do Igarapé do Cantá (Roraima, Brasil: aspectos cinéticos

    Directory of Open Access Journals (Sweden)

    Marcela Bianchessi da Cunha-Santino

    2010-06-01

    Full Text Available AIM: This study aimed at describing and comparing the kinetics of aerobic and anaerobic decomposition of Eleocharis interstincta, Nymphaea sp. and Montrichardia arborescens; METHODS: The samples of aquatic macrophytes and water were collected in the Cantá Stream (02° 49' 11" N and 60° 40' 24" W, Cantá, Roraima, Brazil. The plant material was dried and triturated and for each experimental condition (aerobic and anaerobic mineralization chambers were prepared with plant fragments and stream water. The volume of evolved gases in anaerobic mineralization was monitored during 78 days, while the oxygen consumption was measured for 121 days; RESULTS: The results of aerobic and anaerobic decomposition were fitted to first-order kinetics model. The oxygen consumption varied from 195.36 mg g-1 (DM for E. interstincta to 629.46 mg g-1 (DM for Nymphaea sp. The deoxygenation rate derived from mineralization of M. arborescens was higher (kD: 0.049 day-1, followed by E. interstincta (kD: 0.038 day-1 and Nymphaea sp. (kD: 0.027 day-1. For the anaerobic condition the evolution of gases presented two phases: the consumption and formation. According to temporal variations of mineralized carbon, the anaerobic decomposition of M. arborescens presents the higher mineralization coefficient (0.0047 day-1; followed by Nymphaea sp. (0.0035 d-1 and E. interstincta (0.0017 day-1; CONCLUSION: Based on these results we conclude that during the aerobic decomposition of these macrophytes, the Nymphaea sp. was responsible for the higher oxygen demand and M. arborescens generated the highest amounts of gases during the anaerobic mineralization. On average, the aerobic decay processes were 11-fold faster than anaerobic. Regarding to the materials fluxes in freshwater ecosystems, low rate of decomposition observed in anaerobic process when comparing to aerobic rates reflect that the sediment represent a very efficient sink of carbon in the organic matter cycling

  19. Kinetic Atom.

    Science.gov (United States)

    Wilson, David B.

    1981-01-01

    Surveys the research of scientists like Joule, Kelvin, Maxwell, Clausius, and Boltzmann as it comments on the basic conceptual issues involved in the development of a more precise kinetic theory and the idea of a kinetic atom. (Author/SK)

  20. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia

    2014-01-01

    After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images.......After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....

  1. Adaptive Integrand Decomposition

    CERN Document Server

    Mastrolia, Pierpaolo; Primo, Amedeo; Bobadilla, William J Torres

    2016-01-01

    We present a simplified variant of the integrand reduction algorithm for multiloop scattering amplitudes in $d = 4 - 2\\epsilon$ dimensions, which exploits the decomposition of the integration momenta in parallel and orthogonal subspaces, $d=d_\\parallel+d_\\perp$, where $d_\\parallel$ is the dimension of the space spanned by the legs of the diagrams. We discuss the advantages of a lighter polynomial division algorithm and how the orthogonality relations for Gegenbauer polynomilas can be suitably used for carrying out the integration of the irreducible monomials, which eliminates spurious integrals. Applications to one- and two-loop integrals, for arbitrary kinematics, are discussed.

  2. Clustering via Kernel Decomposition

    DEFF Research Database (Denmark)

    Have, Anna Szynkowiak; Girolami, Mark A.; Larsen, Jan

    2006-01-01

    Methods for spectral clustering have been proposed recently which rely on the eigenvalue decomposition of an affinity matrix. In this work it is proposed that the affinity matrix is created based on the elements of a non-parametric density estimator. This matrix is then decomposed to obtain...... posterior probabilities of class membership using an appropriate form of nonnegative matrix factorization. The troublesome selection of hyperparameters such as kernel width and number of clusters can be obtained using standard cross-validation methods as is demonstrated on a number of diverse data sets....

  3. Symmetric Tensor Decomposition

    DEFF Research Database (Denmark)

    Brachat, Jerome; Comon, Pierre; Mourrain, Bernard

    2010-01-01

    of polynomial equations of small degree in non-generic cases. We propose a new algorithm for symmetric tensor decomposition, based on this characterization and on linear algebra computations with Hankel matrices. The impact of this contribution is two-fold. First it permits an efficient computation...... of total degree d as a sum of powers of linear forms (Waring’s problem), incidence properties on secant varieties of the Veronese variety and the representation of linear forms as a linear combination of evaluations at distinct points. Then we reformulate Sylvester’s approach from the dual point of view...

  4. Mode decomposition evolution equations.

    Science.gov (United States)

    Wang, Yang; Wei, Guo-Wei; Yang, Siyang

    2012-03-01

    Partial differential equation (PDE) based methods have become some of the most powerful tools for exploring the fundamental problems in signal processing, image processing, computer vision, machine vision and artificial intelligence in the past two decades. The advantages of PDE based approaches are that they can be made fully automatic, robust for the analysis of images, videos and high dimensional data. A fundamental question is whether one can use PDEs to perform all the basic tasks in the image processing. If one can devise PDEs to perform full-scale mode decomposition for signals and images, the modes thus generated would be very useful for secondary processing to meet the needs in various types of signal and image processing. Despite of great progress in PDE based image analysis in the past two decades, the basic roles of PDEs in image/signal analysis are only limited to PDE based low-pass filters, and their applications to noise removal, edge detection, segmentation, etc. At present, it is not clear how to construct PDE based methods for full-scale mode decomposition. The above-mentioned limitation of most current PDE based image/signal processing methods is addressed in the proposed work, in which we introduce a family of mode decomposition evolution equations (MoDEEs) for a vast variety of applications. The MoDEEs are constructed as an extension of a PDE based high-pass filter (Europhys. Lett., 59(6): 814, 2002) by using arbitrarily high order PDE based low-pass filters introduced by Wei (IEEE Signal Process. Lett., 6(7): 165, 1999). The use of arbitrarily high order PDEs is essential to the frequency localization in the mode decomposition. Similar to the wavelet transform, the present MoDEEs have a controllable time-frequency localization and allow a perfect reconstruction of the original function. Therefore, the MoDEE operation is also called a PDE transform. However, modes generated from the present approach are in the spatial or time domain and can be

  5. Hydrogen peroxide catalytic decomposition

    Science.gov (United States)

    Parrish, Clyde F. (Inventor)

    2010-01-01

    Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated through the use of concentrated hydrogen peroxide fed as a monopropellant into a catalyzed thruster assembly. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50%-70% by volume, and may be increased in concentration in a continuous process preceding decomposition in the thruster assembly. The exhaust of the thruster assembly, rich in hydroxyl and/or hydroperoxy radicals, may be fed into a stream containing oxidizable components, such as nitric oxide, to facilitate their oxidation.

  6. Spectral Tensor-Train Decomposition

    DEFF Research Database (Denmark)

    Bigoni, Daniele; Engsig-Karup, Allan Peter; Marzouk, Youssef M.

    2016-01-01

    The accurate approximation of high-dimensional functions is an essential task in uncertainty quantification and many other fields. We propose a new function approximation scheme based on a spectral extension of the tensor-train (TT) decomposition. We first define a functional version of the TT.......e., the “cores”) comprising the functional TT decomposition. This result motivates an approximation scheme employing polynomial approximations of the cores. For functions with appropriate regularity, the resulting spectral tensor-train decomposition combines the favorable dimension-scaling of the TT...... decomposition with the spectral convergence rate of polynomial approximations, yielding efficient and accurate surrogates for high-dimensional functions. To construct these decompositions, we use the sampling algorithm \\tt TT-DMRG-cross to obtain the TT decomposition of tensors resulting from suitable...

  7. MACH: Fast Randomized Tensor Decompositions

    CERN Document Server

    Tsourakakis, Charalampos E

    2009-01-01

    Tensors naturally model many real world processes which generate multi-aspect data. Such processes appear in many different research disciplines, e.g, chemometrics, computer vision, psychometrics and neuroimaging analysis. Tensor decompositions such as the Tucker decomposition are used to analyze multi-aspect data and extract latent factors, which capture the multilinear data structure. Such decompositions are powerful mining tools, for extracting patterns from large data volumes. However, most frequently used algorithms for such decompositions involve the computationally expensive Singular Value Decomposition. In this paper we propose MACH, a new sampling algorithm to compute such decompositions. Our method is of significant practical value for tensor streams, such as environmental monitoring systems, IP traffic matrices over time, where large amounts of data are accumulated and the analysis is computationally intensive but also in "post-mortem" data analysis cases where the tensor does not fit in the availa...

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

    Energy Technology Data Exchange (ETDEWEB)

    Miehe, Gerhard; Lauterbach, Stefan; Kleebe, Hans-Joachim [Technische Universitaet Darmstadt, Fachbereich Material- und Geowissenschaften, Petersenstr. 23, 64287 Darmstadt (Germany); Gurlo, Aleksander, E-mail: gurlo@materials.tu-darmstadt.de [Technische Universitaet Darmstadt, Fachbereich Material- und Geowissenschaften, Petersenstr. 23, 64287 Darmstadt (Germany)

    2013-02-15

    nuclei with a constant growth rate. The structural transformation path in reconstructive decomposition of c-In(OH){sub 3} to c-In{sub 2}O{sub 3} is discussed in terms of (i) the displacement of hydrogen atoms that lead to breaking the hydrogen bond between OH groups of [In(OH){sub 6}] octahedra and finally to their destabilization and (ii) transformation of the vertices-shared indium-oxygen octahedra in c-In(OH){sub 3} to vertices- and edge-shared octahedra in c-In{sub 2}O{sub 3}. - Graphical abstract: Frame-by-frame analysis of video sequences recorded of HR-TEM images reveals that a single cube-shaped In(OH){sub 3} nanocrystal with {l_brace}100{r_brace} morphology decomposes into bixbyite-type In{sub 2}O{sub 3} domains while being imaged. The mechanism of this decomposition is evaluated through the analysis of the structural relationship between initial (c-In(OH){sub 3}) and transformed (c-In{sub 2}O{sub 3}) phases and though the kinetics of the decomposition followed via the time-resolved shrinkage of the initial crystal of indium hydroxide. Highlights: Black-Right-Pointing-Pointer In-situ time-resolved High Resolution Transmission Electron Microscopy. Black-Right-Pointing-Pointer Crystallographic transformation path. Black-Right-Pointing-Pointer Kinetics of the decomposition in one nanocrystal.

  9. Unimolecular thermal decomposition of dimethoxybenzenes

    Energy Technology Data Exchange (ETDEWEB)

    Robichaud, David J., E-mail: david.robichaud@nrel.gov; Mukarakate, Calvin; Nimlos, Mark R. [National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401 (United States); Scheer, Adam M.; Ormond, Thomas K.; Buckingham, Grant T. [National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401 (United States); Department of Chemistry and Biochemistry, University of Colorado-Boulder, Boulder, Colorado 80309-0215 (United States); Ellison, G. Barney [Department of Chemistry and Biochemistry, University of Colorado-Boulder, Boulder, Colorado 80309-0215 (United States)

    2014-06-21

    The unimolecular thermal decomposition mechanisms of o-, m-, and p-dimethoxybenzene (CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3}) have been studied using a high temperature, microtubular (μtubular) SiC reactor with a residence time of 100 μs. Product detection was carried out using single photon ionization (SPI, 10.487 eV) and resonance enhanced multiphoton ionization (REMPI) time-of-flight mass spectrometry and matrix infrared absorption spectroscopy from 400 K to 1600 K. The initial pyrolytic step for each isomer is methoxy bond homolysis to eliminate methyl radical. Subsequent thermolysis is unique for each isomer. In the case of o-CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3}, intramolecular H-transfer dominates leading to the formation of o-hydroxybenzaldehyde (o-HO-C{sub 6}H{sub 4}-CHO) and phenol (C{sub 6}H{sub 5}OH). Para-CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3} immediately breaks the second methoxy bond to form p-benzoquinone, which decomposes further to cyclopentadienone (C{sub 5}H{sub 4}=O). Finally, the m-CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3} isomer will predominantly follow a ring-reduction/CO-elimination mechanism to form C{sub 5}H{sub 4}=O. Electronic structure calculations and transition state theory are used to confirm mechanisms and comment on kinetics. Implications for lignin pyrolysis are discussed.

  10. Typical Lignocellulose-degrading Enzymes: a Synthesis of Kinetic Properties

    Science.gov (United States)

    Wang, G.; Post, W. M.; Mayes, M. A.; Frerichs, J.; Jagadamma, S.

    2011-12-01

    While soil enzymes have been explicitly included in the soil organic carbon (SOC) decomposition models, there are big concerns on the model parameterization. Our object is to study the kinetic parameters of five typical lignocellulose-degrading enzymes through literature research and data synthesis. The kinetic parameters refer to the maximum specific enzyme activity (Vmax) and half-saturation constant (Km) in the Michaelis-Menton equation. The Activation energy (Ea) and the pH optimum and sensitivity (pHopt and pHsen) were also analyzed. pHsen was estimated by curve fitting of an exponential-quadratic function. The Vmax values in different units under various conditions were converted into the same units at a reference temperature (20°C) and optimum pH. The scaling issue on Vmax and Km and the effects of soil temperature, pH, and SWC were discussed later. Major findings are summarized as follows. (i) Both Vmax and Km are log-normal distributed. (ii) No significant difference in Vmax is found between groups (ligninases and cellulases). The one-standard-deviation interval of Vmax falls within 10-1000 (mean ≈ 100) mg C mg^-1 Enz h^-1. However, there is significant difference in Km between groups. (iii) Significant difference in activation energy, i.e., 53±17 and 37±15 kJ mol^-1 is found for ligninases and cellulases, respectively. (iv) Both ligninases and cellulases prefer to acid environment. The average ratio of pHsen to pHopt ranges 0.3-0.4 and the optimum pH for ligninases is significantly lower than pHopt for cellulases. (v) A preliminary analysis of Vmax indicates a scaling factor 0.01-0.1 for transforming the Vmax from lab measurements to SOC decomposition models. This study provides useful information for the parameterization of enzyme-driven SOC decomposition models.

  11. SIMULATION OF THERMAL DECOMPOSITION OF MINERAL INSULATING OIL

    Directory of Open Access Journals (Sweden)

    V. G. M. Cruz

    2015-09-01

    Full Text Available AbstractDissolved gas analysis (DGA has been applied for decades as the main predictive maintenance technique for diagnosing incipient faults in power transformers since the decomposition of the mineral insulating oil (MIO produces gases that remain dissolved in the liquid phase. Nevertheless, the most known diagnostic methods are based on findings of simplified thermodynamic and compositional models for the thermal decomposition of MIO, in addition to empirical data. The simulation results obtained from these models do not satisfactorily reproduce the empirical data. This paper proposes a flexible thermodynamic model enhanced with a kinetic approach and selects, among four compositional models, the one offering the best performance for the simulation of thermal decomposition of MIO. The simulation results obtained from the proposed model showed better adequacy to reported data than the results obtained from the classical models. The proposed models may be applied in the development of a phenomenologically-based diagnostic method.

  12. Martensite decomposition in Cu–Al–Mn–Ag alloys

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Camila Maria Andrade dos, E-mail: camilaandr@gmail.com [Departamento de Físico-Química, Instituto de Química, UNESP, Caixa Postal 355, 14801-970 Araraquara, SP (Brazil); Adorno, Antonio Tallarico [Departamento de Físico-Química, Instituto de Química, UNESP, Caixa Postal 355, 14801-970 Araraquara, SP (Brazil); Galdino da Silva, Ricardo Alexandre [Departamento de Ciências Exatas e da Terra, UNIFESP, 09972-270 Diadema, SP (Brazil); Carvalho, Thaisa Mary [Departamento de Físico-Química, Instituto de Química, UNESP, Caixa Postal 355, 14801-970 Araraquara, SP (Brazil)

    2014-12-05

    Highlights: • Martensite decomposition in Cu–Al–Mn–Ag alloys is mainly influenced by Mn. • Interaction between Cu–Mn atomic pairs increases activation energy. • Cu diffusion is disturbed by the interaction between Cu–Mn atomic pairs. - Abstract: The influence of Mn and Ag additions on the isothermal kinetics of martensite decomposition in the Cu–9wt.%Al alloy was studied using X-ray diffractometry (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDXS) and microhardness changes measurements with temperature and time. The results indicated that the reaction is disturbed by the increase of Mn, an effect associated with the increase in the Al–Mn and Cu–Mn atomic pairs, which disturbs Cu diffusion and increases the activation energy for the martensite decomposition reaction.

  13. Estudio Cinético de la Descomposición Térmica de Tres Derivados del Pirano (C5H6O Kinetic Study of the Thermal Decomposition of Three Derived from the Pyran (C5H6O

    Directory of Open Access Journals (Sweden)

    Jennifer J Lafont

    2009-01-01

    Full Text Available El artículo presenta el estudio cinético de descomposición térmica de tres compuestos derivados del pirano que no han sido reportados en la literatura. Estos compuestos son ampliamente utilizados en farmacología y en la obtención de importantes productos a nivel tecnológico e industrial. Los compuestos 2,6-dietoxitetrahidro-2H-pirano; 2-etoxi-6-propoxitetrahidro-2H-pirano y 2-etoxi-6-butoxi-tetrahidro-2H-pirano se escogieron variando el sustituyente ubicado en la posición 6 del núcleo. Cada experimento cinético fue realizado a cinco temperaturas con intervalos de 10 grados en un rango entre 333 a 373 K, utilizando un sistema de reacción a microescala. Se obtuvieron los productos 2-etoxi-6-hidroxi-tetrahidro-2H-pirano y etileno, propeno, o buteno para cada caso, fueron identificados mediante la técnica de cromatografía de gases acoplada a masas. Las reacciones resultaron ser unimoleculares homogéneas y de primer orden. Teniendo en cuenta los parámetros cinéticos y termodinámicos obtenidos, se puede decir que la reacción es compatible con un estado de transición cíclico de seis miembros, concertado y semipolar.The article presents a kinetic study of the thermal decomposition of three compounds derived from pyran that have not been reported in the literature. These compounds are widely used in pharmacology to obtain important products of technological and industrial interest. The compound (2,6-dietoxitetrahydro-2H-pyran; 2-etoxi-6-propoxytetrahydro-2H-pyran and 2-etoxi-6-butoxytetra-hydro-2H-pyran were chosen by varying the substituent located in the 6 position of the nucleus. Each experiment was done at five temperature with intervals of 10 degrees in a range between 333 and 373 K, using a microscale reaction system. The products obtained, 2-etoxy-6-hydroxy-tetrahydro-2H-pyran and ethylene, propene, or butene for each case, were identified using gas chromatography connected to masses. The reactions turned out to be unimolecular

  14. Decomposition of Cellulose by Continuous Near-Critical Water Reactions

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A pilot-scale apparatus for continuous supercritical and near-critical water reaction was set up. A high- pressure slurry supplying system was developed to feed the solid material-water slurries. The apparatus features temperature up to 600℃, pressure up to 40MPa, residence time from 24s to 15min, maximum amount of slurry supply of 2.4 L.h-1, maximum solid content of slurry up to 10%(by mass) for cellulose from Merck, and resistance to corrosion. Long-time runs of decomposition of cellulose were carried out and steady runs were confirmed. Kinetics of cellulose decomposition was studied. The apparent activation energy evaluated was 147kJ·mol-1. In addition, a new three-step pathway for cellulose hydrolysis was proposed. The derived kinetic equation is in good agreement with the experimental data.

  15. A Detailed Chemical Kinetic Reaction Mechanism for Oxidation of Four Small Alkyl Esters in Laminar Premixed Flames

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Westmoreland, P R; Dryer, F L; Chaos, M; Osswald, P; Kohse-Hoinghaus, K; Cool, T A; Wang, J; Yang, B; Hansen, N; Kasper, T

    2008-02-08

    A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions in each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.

  16. Plasma Catalysis of Methane Decomposition in Pulse Microwave Discharge

    Science.gov (United States)

    Potapkin, B.; Rusanov, V.; Jivotov, V.; Babaritski, A.; Potechin, S.; Etievant, C.

    1997-10-01

    Investigation of plasma catalysis effects in various chemical reactions, such as SO2 and hydrocarbons oxidation, ammonia and nitrogen oxides synthesis, has been of interest for many decades. Present work describes the first experimental observation and theoretical analysis of plasma catalysis effects in the case of endothermic methane decomposition into molecular hydrogen and carbon black. Process energy requirements are coverd mainly by low potential gas thermal energy while plasma is used for acceleration of chemical reactions via active species generation. The experiments were done as follows: (i) methane was preheated in a conventional heat exchanger up to about 40-65 ^oC where thermal methane decomposition is limited by process kinetics, (ii) methane was passed through a non-equilibrium pulse microwave discharge (9.04 GHz, pulse duration 1 μs). Experiments have shown a strong catalytic effect of plasma on methane decomposition. The degree of conversion after discharge increased drastically, despite gas cooling, because of heat absorption in the methane decomposition reaction. Theoretical analysis of process kinetics and energy balance gave clear evidence of the catalytic effect of plasma under experimental conditions. The estimated chain length was about 300. The possible mechanism of plasma catalysis, the ion-molecular chain Winchester mechanism, is proposed and described.

  17. Memory Effect and Fast Spinodal Decomposition

    OpenAIRE

    Koide, T.; Krein, Gastão Inácio [UNESP; Ramos, Rudnei O.

    2007-01-01

    We consider the modification of the Cahn-Hilliard equation when a time delay process through a memory function is taken into account. We then study the process of spinodal decomposition in fast phase transitions associated with a conserved order parameter. The introduced memory effect plays an important role to obtain a finite group velocity. Then, we discuss the constraint for the parameters to satisfy causality. The memory effect is seen to affect the dynamics of phase transition at short t...

  18. Fischer decomposition in symplectic harmonic analysis

    OpenAIRE

    Brackx, Fred; De Schepper, Hennie; Eelbode, David; Lávička, Roman; Soucek, Vladimir

    2014-01-01

    In the framework of quaternionic Clifford analysis in Euclidean space , which constitutes a refinement of Euclidean and Hermitian Clifford analysis, the Fischer decomposition of the space of complex valued polynomials is obtained in terms of spaces of so-called (adjoint) symplectic spherical harmonics, which are irreducible modules for the symplectic group Sp. Its Howe dual partner is determined to be sl(2, C) circle plus sl(2, C) = so(4, C).

  19. Autonomous Gaussian Decomposition

    CERN Document Server

    Lindner, Robert R; Murray, Claire E; Stanimirović, Snežana; Babler, Brian L; Heiles, Carl; Hennebelle, Patrick; Goss, W M; Dickey, John

    2014-01-01

    We present a new algorithm, named Autonomous Gaussian Decomposition (AGD), for automatically decomposing spectra into Gaussian components. AGD uses derivative spectroscopy and machine learning to provide optimized guesses for the number of Gaussian components in the data, and also their locations, widths, and amplitudes. We test AGD and find that it produces results comparable to human-derived solutions on 21cm absorption spectra from the 21cm SPectral line Observations of Neutral Gas with the EVLA (21-SPONGE) survey. We use AGD with Monte Carlo methods to derive the HI line completeness as a function of peak optical depth and velocity width for the 21-SPONGE data, and also show that the results of AGD are stable against varying observational noise intensity. The autonomy and computational efficiency of the method over traditional manual Gaussian fits allow for truly unbiased comparisons between observations and simulations, and for the ability to scale up and interpret the very large data volumes from the up...

  20. Differentially Private Spatial Decompositions

    CERN Document Server

    Cormode, Graham; Shen, Entong; Srivastava, Divesh; Yu, Ting

    2011-01-01

    Differential privacy has recently emerged as the de facto standard for private data release. This makes it possible to provide strong theoretical guarantees on the privacy and utility of released data. While it is well-known how to release data based on counts and simple functions under this guarantee, it remains to provide general purpose techniques to release different kinds of data. In this paper, we focus on spatial data such as locations and more generally any data that can be indexed by a tree structure. Directly applying existing differential privacy methods to this type of data simply generates noise. Instead, we introduce a new class of "private spatial decompositions": these adapt standard spatial indexing methods such as quadtrees and kd-trees to provide a private description of the data distribution. Equipping such structures with differential privacy requires several steps to ensure that they provide meaningful privacy guarantees. Various primitives, such as choosing splitting points and describi...

  1. Single Photon Initiated Decomposition Rearrangement Reactions (spidrr) of Organic Molecules Mediated by the Ni+ Cation

    Science.gov (United States)

    Bellert, Darrin; Mansell, Adam; Theis, Zachary; Gutierrez, Michael

    2016-06-01

    The Bellert group at Baylor University has developed a novel method for performing single photon initiated decomposition rearrangement reactions (SPIDRR) of organic molecules mediated by a transition metal cation. The advantage that SPIDRR affords is the direct measurement of first order microcanonical rate constants, k(E), determined at resolved internal energies. Furthermore, the SPIDRR technique measures kinetic details of exothermic reactions where product production is limited only by submerged activation barriers (kinetic barriers that are at energies below the separated reactant limit). Thus, such reactions approach unit efficiency, are thermodynamically driven, and are of greater relevance to catalytic research. Direct measurements of k(E) values extend to isotopically labelled species that provide direct measurement of the kinetic isotope effect (KIE), furnishing unique insight into the mechanistic details of a reaction. This talk presents results from the visible photon initiated, Ni+ induced decarbonylation reaction of propionaldehyde. Here a rather unique energy dependent behavior of the measured rate constants was observed and attributed to a dynamic competition between parallel reaction coordinates available to the photo-excited precursor. RRKM calculations in concert with high level DFT is used to support and further experimental results.

  2. Why is metallic Pt the best catalyst for methoxy decomposition?

    Institute of Scientific and Technical Information of China (English)

    Ruipeng Ren; Cuiyu Niu; Shaoyue Bu; Yuhua Zhou; Yongkang Lu; Guichang Wang

    2011-01-01

    The decomposition of methoxy on Cu(111),Ag(111),Au(111),Ni(111),Pt(111),Pd(111),and Rh(111)has been studied in detail by the density functional theory calculations.The calculated activation barriers were successfully correlated with the coupling matrix element V2ad and the d-band center(εd)for the group IB metals and group Ⅷ metals,respectively.By comparison of the activation energy barriers of the methoxy decomposition on different metals,it was found that Pt is the best catalyst for methoxy decomposition.The possible reason why the metallic Pt is the best catalyst has been analyzed from both the energetic data and the electronic structure information,that is,methoxy decomposition on Pt(111)has the largest exothermic behavior due to the closest p-band center of the CH3O among all metals after the adsorption.

  3. Numerical analysis of phase decomposition in A-B binary alloys using Cahn-Hilliard equations

    Directory of Open Access Journals (Sweden)

    Susana Lezama-Alvarez

    2013-01-01

    Full Text Available The analysis of phase decomposition was carried out using the nonlinear and linear Cahn-Hilliard equations in a hypothetical A-B alloy system with a miscibility gap. These equations were solved by the explicit finite difference method assuming a regular solution model. The supersaturated solid solution and decomposed phases were considered to have an fcc structure. Different aging temperatures and thermodynamic interaction parameters ΩA-B were used to simulate different alloy systems. The numerical simulation results showed that the growth kinetics of phase decomposition in the alloy with 30at.% A was slower than that of 50 at.% A. Additionally, the start time and modulation wavelength of phase decomposition are strongly affected by the thermodynamic interaction parameter ΩA-B value. The numerical simulation results showed that the growth kinetics of phase decomposition with the linear equation is slower than that with the nonlinear one.

  4. The two steps thermal decomposition of titanium hydride and two steps foaming of Al alloy

    Institute of Scientific and Technical Information of China (English)

    SHANG Jintang; HE Deping

    2005-01-01

    Two steps foaming (TSF) technique was proposed to prepare shaped Al alloy foam. Based on the thermal decomposition kinetics equation of titanium hydride, the relationship between two steps thermal decomposition kinetics of titanium hydride and two steps foaming Al alloy melt was studied. Two steps thermal decomposition curve of titanium hydride under increasing and constant temperature was calculated respectively. The hydrogen mass needed in the second foaming step was also calculated. Results showed that the hydrogen mass of the second thermal decomposition of titanium hydride is enough for the second foaming step in the condition of as-received Al melt foaming. Experimental and theoretical results indicate that two steps foaming technique can be used to prepare Al alloy foam with high porosity, shaped components and sandwich with Al alloy foam core.

  5. Photocatalytic decomposition of cortisone acetate in aqueous solution.

    Science.gov (United States)

    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. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Radiation induced decomposition of a refractory cefathiamidine intermediate

    Institute of Scientific and Technical Information of China (English)

    Qiburi Bao; Lujun Chen; Jianlong Wang

    2014-01-01

    Diisopropylthiourea (DPT),an intermediate of a widely used cephalosporin,has been found to be one of the most refractory components in cephalosporin synthesis wastewater.This compound cannot be completely removed by conventional biological processes due to its antimicrobial property.Ionizing radiation has been applied in the decomposition of refractory pollutants in recent years and has proved effective.Therefore,the decomposition of DPT by γ-irradiation was studied.The compound was irradiated at the dose of 150-2000 Gy before a change of concentration and UV absorption of the solutions was detected.Furthermore,the decomposition kinetics and radiation yield (G-value) of DPT was investigated.The results of radiation experiments on DPT-containing aqueous showed that the DPT can be effectively degraded by γ-radiation.DPT concentration decreased with increasing absorbed doses.G-values of radiolytic decomposition for DPT (20 mg/L) were 1.04 and 0.47 for absorbed doses of 150 and 2000 Gy,respectively.The initial concentration and pH of the solutions affected the degradation.As the concentration of substrate increased,the decomposition was reduced.The decrease of removal rate and radiation efficacy under alkaline condition suggested that lower pH values benefit the γ-induced degradation.UV absorption from 190 to 250 nm decreased after radiation while that from 250 to 300 nm increased,indicating the formation of by-products.

  7. Synthesis, structural investigation and kinetic studies of uranyl(VI) unsymmetrical Schiff base complexes

    Indian Academy of Sciences (India)

    Zahra Asadi; Mozaffar Asadi; Azade Zeinali; Mohammad Ranjkeshshorkaei; Karla Fejfarova; Vaclav Eigner; Michal Dusek; Aliakbar Dehnokhalaji

    2014-11-01

    Uranyl(VI) complexes with unsymmetrical N2O2 Schiff base ligands were synthesized and characterized. Their characterization was performed using UV-Vis, 1H NMR, cyclic voltammetry, single-crystal X-ray crystallography, IR, TG and C.H.N. techniques. X-ray crystallography of the complexes show that beside coordination of the tetradentate Schiff base, one DMF molecule is also coordinated. In order to investigate the effect of the substitutional groups of the Schiff base on the oxidation and reduction potentials, we used the cyclic voltammetry method. Electrochemistry of these complexes showed that the presence of electron releasing groups accelerates oxidation of the complexes. The kinetics of thermal decomposition was studied using thermal gravimetric method (TG) and Coats-Redfern equation. According to Coats-Redfern plots, the kinetics of thermal decomposition of the studied complexes is first-order in all stages. Also the kinetics and mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was carried out in solution, using spectrophotometric method. As a result, the second order rate constants at four temperatures and the activation parameters were calculated showing an associative mechanism for all corresponding complexes. It was concluded that the steric and the electronic properties of the complexes influence the reaction rate significantly.

  8. Solid state thermochemical decomposition of neat 1,3,5,5-tetranitrohexahydropyrimidine (DNNC) and its DNNC-d{sub 6} perdeuterio-labeled analogue

    Energy Technology Data Exchange (ETDEWEB)

    Hendrickson, Scott A. [Department of Chemistry, Pt. Loma Nazarene University, San Diego, CA 92106-2899 (United States); Shackelford, Scott A. [Air Force Research Laboratory, Propellants Branch (AFRL/PRSP), 10 East Saturn Drive, Edwards AFB, CA 93524-7680 (United States)]. E-mail: scott.shackelford@edwards.af.mil

    2006-01-15

    The solid state thermochemical decomposition kinetics and activation energy of neat 1,3,5,5-tetranitrohexahydropyrimidine (DNNC) and its DNNC-d{sub 6} deuterium labeled analogue were obtained by isothermal differential scanning calorimetry (IDSC) at 142, 145, and 148 deg. C. Global rate constants and kinetic deuterium isotope effect (KDIE) data from the exothermic decomposition process suggest that homolytic C-H bond rupture, in one or both types of chemically non-equivalent methylene (-CH{sub 2}) groups of the DNNC ring structure, constitutes the exothermic rate-controlling step. A DNNC-d{sub 6} energy of activation equal to 115 kJ/mol was determined for this initial autocatalytic exothermic energy release from which a 106 kJ/mol activation energy was calculated for unlabeled DNNC. This exothermic autocatalytic decomposition process follows an extended endothermic induction period for DNNC which shows a higher 128 kJ/mol activation energy during which a catalytic initiating species may form by a rate-controlling step different from C-H bond rupture.

  9. Analysis of spinodal decomposition in Fe-32 and 40 at.% Cr alloys using phase field method based on linear and nonlinear Cahn-Hilliard equations

    Directory of Open Access Journals (Sweden)

    Orlando Soriano-Vargas

    2016-12-01

    Full Text Available Spinodal decomposition was studied during aging of Fe-Cr alloys by means of the numerical solution of the linear and nonlinear Cahn-Hilliard differential partial equations using the explicit finite difference method. Results of the numerical simulation permitted to describe appropriately the mechanism, morphology and kinetics of phase decomposition during the isothermal aging of these alloys. The growth kinetics of phase decomposition was observed to occur very slowly during the early stages of aging and it increased considerably as the aging progressed. The nonlinear equation was observed to be more suitable for describing the early stages of spinodal decomposition than the linear one.

  10. Plant diversity effects on root decomposition in grasslands

    Science.gov (United States)

    Chen, Hongmei; Mommer, Liesje; van Ruijven, Jasper; de Kroon, Hans; Gessler, Arthur; Scherer-Lorenzen, Michael; Wirth, Christian; Weigelt, Alexandra

    2016-04-01

    Loss of plant diversity impairs ecosystem functioning. Compared to other well-studied processes, we know little about whether and how plant diversity affects root decomposition, which is limiting our knowledge on biodiversity-carbon cycling relationships in the soil. Plant diversity potentially affects root decomposition via two non-exclusive mechanisms: by providing roots of different substrate quality and/or by altering the soil decomposition environment. To disentangle these two mechanisms, three decomposition experiments using a litter-bag approach were conducted on experimental grassland plots differing in plant species richness, functional group richness and functional group composition (e.g. presence/absence of grasses, legumes, small herbs and tall herbs, the Jena Experiment). We studied: 1) root substrate quality effects by decomposing roots collected from the different experimental plant communities in one common plot; 2) soil decomposition environment effects by decomposing standard roots in all experimental plots; and 3) the overall plant diversity effects by decomposing community roots in their 'home' plots. Litter bags were installed in April 2014 and retrieved after 1, 2 and 4 months to determine the mass loss. We found that mass loss decreased with increasing plant species richness, but not with functional group richness in the three experiments. However, functional group presence significantly affected mass loss with primarily negative effects of the presence of grasses and positive effects of the presence of legumes and small herbs. Our results thus provide clear evidence that species richness has a strong negative effect on root decomposition via effects on both root substrate quality and soil decomposition environment. This negative plant diversity-root decomposition relationship may partly account for the positive effect of plant diversity on soil C stocks by reducing C loss in addition to increasing primary root productivity. However, to fully

  11. Sensitivity analysis of six soil organic matter models applied to the decomposition of animal manures and crop residues

    Directory of Open Access Journals (Sweden)

    Daniele Cavalli

    2016-09-01

    Full Text Available Two features distinguishing soil organic matter simulation models are the type of kinetics used to calculate pool decomposition rates, and the algorithm used to handle the effects of nitrogen (N shortage on carbon (C decomposition. Compared to widely used first-order kinetics, Monod kinetics more realistically represent organic matter decomposition, because they relate decomposition to both substrate and decomposer size. Most models impose a fixed C to N ratio for microbial biomass. When N required by microbial biomass to decompose a given amount of substrate-C is larger than soil available N, carbon decomposition rates are limited proportionally to N deficit (N inhibition hypothesis. Alternatively, C-overflow was proposed as a way of getting rid of excess C, by allocating it to a storage pool of polysaccharides. We built six models to compare the combinations of three decomposition kinetics (first-order, Monod, and reverse Monod, and two ways to simulate the effect of N shortage on C decomposition (N inhibition and C-overflow. We conducted sensitivity analysis to identify model parameters that mostly affected CO2 emissions and soil mineral N during a simulated 189-day laboratory incubation assuming constant water content and temperature. We evaluated model outputs sensitivity at different stages of organic matter decomposition in a soil amended with three inputs of increasing C to N ratio: liquid manure, solid manure, and low-N crop residue. Only few model parameters and their interactions were responsible for consistent variations of CO2 and soil mineral N. These parameters were mostly related to microbial biomass and to the partitioning of applied C among input pools, as well as their decomposition constants. In addition, in models with Monod kinetics, CO2 was also sensitive to a variation of the half-saturation constants. C-overflow enhanced pool decomposition compared to N inhibition hypothesis when N shortage occurred. Accumulated C in the

  12. Study on the decomposition kinetics of FOX-7 and HNF

    NARCIS (Netherlands)

    Klerk, W.P.C. de; Popescu, C.; Heijden, A.E.D.M. van der

    2003-01-01

    At TNO Prins Maurits Laboratory the characterisation and application of energetic materials is one of the main research topics. In this respect, the activities are focussed on using thermal analysis techniques such as TG/DTA and DSC. Standard DSC and TG/DTA techniques usually apply a linear temperat

  13. The Effect of Simulated Welding Conditions on Austenite Decomposition Kinetics.

    Science.gov (United States)

    1981-07-01

    Departamento de Metalurgia, . Facultad de Ciencias Quimicas , Universidad Complutense, Madrid, Spain 1981 .. 2 1982 A Approved for Public Release...Development London England London England CONTRACT NUMBER DAJA 37-80-C-0298 Departamento de Metalurgia, Facultad de Ciencias Quimicas , Universidad...Complu -nse, Madrid, Spain 19h1 Approved for Public Release, Distribution unlimited E~flA: Departameflto de Metalurgia. Facultad de Ciencias Quimicas

  14. Study on the decomposition kinetics of FOX-7 and HNF

    NARCIS (Netherlands)

    Klerk, W.P.C. de; Popescu, C.; Heijden, A.E.D.M. van der

    2003-01-01

    At TNO Prins Maurits Laboratory the characterisation and application of energetic materials is one of the main research topics. In this respect, the activities are focussed on using thermal analysis techniques such as TG/DTA and DSC. Standard DSC and TG/DTA techniques usually apply a linear

  15. Decomposition methods for unsupervised learning

    DEFF Research Database (Denmark)

    Mørup, Morten

    2008-01-01

    This thesis presents the application and development of decomposition methods for Unsupervised Learning. It covers topics from classical factor analysis based decomposition and its variants such as Independent Component Analysis, Non-negative Matrix Factorization and Sparse Coding to their genera......This thesis presents the application and development of decomposition methods for Unsupervised Learning. It covers topics from classical factor analysis based decomposition and its variants such as Independent Component Analysis, Non-negative Matrix Factorization and Sparse Coding...... methods and clustering problems is derived both in terms of classical point clustering but also in terms of community detection in complex networks. A guiding principle throughout this thesis is the principle of parsimony. Hence, the goal of Unsupervised Learning is here posed as striving for simplicity...... in the decompositions. Thus, it is demonstrated how a wide range of decomposition methods explicitly or implicitly strive to attain this goal. Applications of the derived decompositions are given ranging from multi-media analysis of image and sound data, analysis of biomedical data such as electroencephalography...

  16. 基于 Kissinger 方法的3,4-双(4-硝基呋咱-3-基)氧化呋咱的热分解反应动力学参数和热稳定性研究%Study on Kinetic Parameters of Thermal Decomposition Reaction and Thermal Stability of 3,4-Bis(3-nitrofurazan-4-yl)furoxan Based on Kissinger Method

    Institute of Scientific and Technical Information of China (English)

    李鹤群; 安崇伟; 杜梦远; 温晓沐; 王晶禹

    2016-01-01

    The thermal decomposition characteristics of DNTF and 2 ,4 ,6‐trinitrotoluene (TNT) were investigated by means of differential scanning calorimetry at different heating rates .The kinetic parameters of thermal decomposition reaction ,critical tem‐perature of thermal explosion and thermodynamic parameters were calculated ,contrasted and analyzed by Kissinger methed .The results show that the thermal decomposition process of DNTF is different with TNT ,it occurs in two stages and the first acts as the major part .The activation energy of DNTF is 168 .85kJ/mol ,which is about 58kJ/mol higher than that of TNT ,revealing that DNTF has a good thermal stability at low temperature .However ,all the other thermodynamic parameters of DNTF are higher than those of TNT except the free energy of activation .The decomposition peak temperatures and critical temperature of thermal explosion of DNTF are lower than those of TNT .So ,the thermal stability of DNTF is poorer than that of TNT .%采用差示扫描量热法研究了 DNTF和TNT在不同升温速率下的热分解特性;利用Kissinger方法计算和对比分析了DNTF和TNT的热分解反应动力学参数、热爆炸临界温度和热力学参数。结果表明,DNTF的热分解过程不同于TNT ,DNTF的热分解经历了两个阶段,其中第1阶段为主要部分。DNTF的活化能为168.85kJ/mol ,比TNT高约58 kJ/mol ,表明DNTF在低温下有良好的热稳定性。然而,除自由活化能外,DNTF的其他热力学参数均比TNT高。DNTF的热分解峰温和热爆炸临界温度都比 TNT小。因此,与TNT相比,DNTF的热稳定性差。

  17. Decomposition of energetic chemicals contaminated with iron or stainless steel.

    Science.gov (United States)

    Chervin, Sima; Bodman, Glenn T; Barnhart, Richard W

    2006-03-17

    Contamination of chemicals or reaction mixtures with iron or stainless steel is likely to take place during chemical processing. If energetic and thermally unstable chemicals are involved in a manufacturing process, contamination with iron or stainless steel can impact the decomposition characteristics of these chemicals and, subsequently, the safety of the processes, and should be investigated. The goal of this project was to undertake a systematic approach to study the impact of iron or stainless steel contamination on the decomposition characteristics of different chemical classes. Differential scanning calorimetry (DSC) was used to study the decomposition reaction by testing each chemical pure, and in mixtures with iron and stainless steel. The following classes of energetic chemicals were investigated: nitrobenzenes, tetrazoles, hydrazines, hydroxylamines and oximes, sulfonic acid derivatives and monomers. The following non-energetic groups were investigated for contributing effects: halogens, hydroxyls, amines, amides, nitriles, sulfonic acid esters, carbonyl halides and salts of hydrochloric acid. Based on the results obtained, conclusions were drawn regarding the sensitivity of the decomposition reaction to contamination with iron and stainless steel for the chemical classes listed above. It was demonstrated that the most sensitive classes are hydrazines and hydroxylamines/oximes. Contamination of these chemicals with iron or stainless steel not only destabilizes them, leading to decomposition at significantly lower temperatures, but also sometimes causes increased severity of the decomposition. The sensitivity of nitrobenzenes to contamination with iron or stainless steel depended upon the presence of other contributing groups: the presence of such groups as acid chlorides or chlorine/fluorine significantly increased the effect of contamination on decomposition characteristics of nitrobenzenes. The decomposition of sulfonic acid derivatives and tetrazoles

  18. Preparation and Kinetics of Thermal Decomposition of Silver Peroxide Decorated Diatomite-Based Porous Ceramic Composite%AgO修饰硅藻土基多孔陶瓷复合材料的制备及热分解非等温动力学

    Institute of Scientific and Technical Information of China (English)

    冯拉俊; 沈文宁; 冯慧; 郭美娟

    2011-01-01

    Silver peroxide decorated diatomite-based porous ceramic composite was prepared by chemical oxidation method using potassium persulfate as oxidant and characterized by X-ray diffraction, X-ray photo electron spectroscopy and mercury injection apparatus. The process and kinetic behavior of thermal decomposition of the composite prepared were studied by means of thermogravimetry and linear temperature theory. The results show that the silver peroxide decorated diatomite-based porous ceramic composite prepared has crystal structure and is mainly made up of tetragonal christobalite and monoclinic silver peroxide. And the average pore diameter, median pore diameter, apparent density and porosity of the composite are 3.862 |xm, 0.354 μm, 1.794 g-mL-1 and 57.985% respectively. Silver peroxide in the composite decomposes at 158 °C along with the formation of silver oxide followed by decomposing into silver at higher temperature. The mechanism of decomposition reaction is random nucleation and subsequent growth (Al), and the apparent activation energy and reaction frequency factor are 136.94 kJ-mol-1 and 2.48 xl014 s-1, respectively. Compared with reference silver peroxide powders, the thermal stability of silver peroxide in the composite rises.%采用化学氧化法,以过硫酸钾为氧化剂制备了AgO修饰硅藻土基多孔陶瓷复合材料,用XRD、XPS、压汞仪对制备的复合材料进行表征,借助热重法和线性升温理论对复合材料的热分解过程和热分解动力学进行研究.结果表明,AgO修饰硅藻土基多孔陶瓷复合材料具有晶体结构,主要由正方晶系方石英和单斜晶系AgO组成;复合材料平均孔直径为3.862 μm,中值孔直径为0.354 μm,表观密度为1.794 g·mL-1,孔隙率为57.985%;复合材料中AgO的分解分两步,在158℃开始分解成Ag2O,更高温度时进一步分解成Ag;AgO分解服从核生成和核成长机理,其表观活化能为136.94 kJ·mol-1,反应频率因子为2.48×1014 s

  19. Kinetics study on biomass pyrolysis for fuel gas production

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Kinetic knowledge is of great importance in achieving good control of the pyrolysis and gasification process and optimising system design. An overall kinetic pyrolysis scheme is therefore addressed here. The kinetic modelling incorporates the following basic steps: the degradation of the virgin biomass materials into primary products (tar, gas and semi-char), the decomposition of primary tar into secondary products and the continuous interaction between primary gas and char. The last step is disregarded completely by models in the literature. Analysis and comparison of predicted results from different kinetic schemes and experimental data on our fixed bed pyrolyser yielded very positive evidence to support our kinetic scheme.

  20. Kinetics study on biomass pyrolysis for fuel gas production

    Institute of Scientific and Technical Information of China (English)

    陈冠益; 方梦祥; ANDRIES,J.; 骆仲泱; SPLIETHOFF,H.; 岑可法

    2003-01-01

    Kinetic knowledge is of great importance in achieving good control of the pyrolysis and gasification process and optimising system design. An overall kinetic pyrolysis scheme is therefore addressed here. The ki-netic modelling incorporates the following basic steps: the degradation of the virgin biomass materials into pri-mary products ( tar, gas and semi-char), the decomposition of primary tar into secondary products and the continuous interaction between primary gas and char. The last step is disregarded completely by models in the literature. Analysis and comparison of predicted results from different kinetic schemes and experimental data on our fixed bed pyrolyser yielded very positive evidence to support our kinetic scheme.

  1. Thermal decomposition of lutetium propionate

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude

    2010-01-01

    The thermal decomposition of lutetium(III) propionate monohydrate (Lu(C2H5CO2)3·H2O) in argon was studied by means of thermogravimetry, differential thermal analysis, IR-spectroscopy and X-ray diffraction. Dehydration takes place around 90 °C. It is followed by the decomposition of the anhydrous ...... of the oxycarbonate to the rare-earth oxide proceeds in a different way, which is here reminiscent of the thermal decomposition path of Lu(C3H5O2)·2CO(NH2)2·2H2O...

  2. AUTONOMOUS GAUSSIAN DECOMPOSITION

    Energy Technology Data Exchange (ETDEWEB)

    Lindner, Robert R.; Vera-Ciro, Carlos; Murray, Claire E.; Stanimirović, Snežana; Babler, Brian [Department of Astronomy, University of Wisconsin, 475 North Charter Street, Madison, WI 53706 (United States); Heiles, Carl [Radio Astronomy Lab, UC Berkeley, 601 Campbell Hall, Berkeley, CA 94720 (United States); Hennebelle, Patrick [Laboratoire AIM, Paris-Saclay, CEA/IRFU/SAp-CNRS-Université Paris Diderot, F-91191 Gif-sur Yvette Cedex (France); Goss, W. M. [National Radio Astronomy Observatory, P.O. Box O, 1003 Lopezville, Socorro, NM 87801 (United States); Dickey, John, E-mail: rlindner@astro.wisc.edu [University of Tasmania, School of Maths and Physics, Private Bag 37, Hobart, TAS 7001 (Australia)

    2015-04-15

    We present a new algorithm, named Autonomous Gaussian Decomposition (AGD), for automatically decomposing spectra into Gaussian components. AGD uses derivative spectroscopy and machine learning to provide optimized guesses for the number of Gaussian components in the data, and also their locations, widths, and amplitudes. We test AGD and find that it produces results comparable to human-derived solutions on 21 cm absorption spectra from the 21 cm SPectral line Observations of Neutral Gas with the EVLA (21-SPONGE) survey. We use AGD with Monte Carlo methods to derive the H i line completeness as a function of peak optical depth and velocity width for the 21-SPONGE data, and also show that the results of AGD are stable against varying observational noise intensity. The autonomy and computational efficiency of the method over traditional manual Gaussian fits allow for truly unbiased comparisons between observations and simulations, and for the ability to scale up and interpret the very large data volumes from the upcoming Square Kilometer Array and pathfinder telescopes.

  3. Modeling N2O Reduction and Decomposition in a Circulating Fluidized bed Boiler

    DEFF Research Database (Denmark)

    Johnsson, Jan Erik; Åmand, Lars-Erik; Dam-Johansen, Kim;

    1996-01-01

    The N2O concentration was measured in a circulating fluidized bed boiler of commercial size. Kinetics for N2O reduction by char and catalytic reduction and decomposition over bed material from the combustor were determined in a laboratory fixed bed reactor. The destruction rate of N2O in the comb......The N2O concentration was measured in a circulating fluidized bed boiler of commercial size. Kinetics for N2O reduction by char and catalytic reduction and decomposition over bed material from the combustor were determined in a laboratory fixed bed reactor. The destruction rate of N2O...

  4. Theoretical study of the thermal decomposition of dimethyl disulfide.

    Science.gov (United States)

    Vandeputte, Aäron G; Reyniers, Marie-Françoise; Marin, Guy B

    2010-10-07

    Despite its use in a wide variety of industrially important thermochemical processes, little is known about the thermal decomposition mechanism of dimethyl disulfide (DMDS). To obtain more insight, the radical decomposition mechanism of DMDS is studied theoretically and a kinetic model is developed accounting for the formation of all the decomposition products observed in the experimental studies available in literature. Thermochemical data and rate coefficients are obtained using the high-level CBS-QB3 composite method. Among five methods tested (BMK/6-311G(2d,d,p), MPW1PW91/6-311G(2d,d,p), G3, G3B3, and CBS-QB3), the CBS-QB3 method was found to reproduce most accurately the experimental standard enthalpies of formation for a set of 17 small organosulfur compounds and the bond dissociation energies for a set of 10 sulfur bonds. Enthalpies of formation were predicted within 4 kJ mol(-1) while the mean absolute deviation on the bond dissociation enthalpies amounts to 7 kJ mol(-1). From the theoretical study, a new reaction path is identified for the formation of carbon disulfide via dithiirane (CH(2)S(2)). A reaction mechanism was constructed containing 36 reactions among 25 species accounting for the formation of all the decomposition products reported in literature. High-pressure limit rate coefficients for the 36 reactions in the reaction mechanism are presented. The kinetic model is able to grasp the experimental observations. With the recombination of thiyl radicals treated as being in the low-pressure limit, the experimentally reported first-order rate coefficients for the decomposition of DMDS are reproduced within 1 order of magnitude, while the observed product selectivities of most compounds are reproduced satisfactory. Simulations indicate that at high conversions most of the carbon disulfide forms according to the newly identified reaction path involving the formation of dithiirane.

  5. DIADECOMP: A new approach to analyze decompositions from projection spectroscopy

    Science.gov (United States)

    Fredriksson, Jonas; de Paula, Viviane S.; Valente, Ana Paula; Almeida, Fabio C. L.; Billeter, Martin

    2016-12-01

    We demonstrate for the first time a complete small protein characterization with the projection-decomposition approach, including full assignments as well as determination of the 3D fold. In TOCSY- and NOESY-type 4D experiments, pairing of signals from hydrogens and from their respective heavy atoms in decompositions represents a new problem. An approach, referred to as "DIADECOMP" (diagonal decomposition), is introduced to solve this problem; it consists of two separate decompositions of the input projections, differing in a 45° rotation of the spectral axes. While DIADECOMP requires a somewhat complex formulation, in practice it results in observing signals in the rotated decompositions that correspond to sums or differences of frequencies. When applied to a small protein, human defensin β6, the analysis of a HCC(CO)NH-TOCSY with DIADECOMP results in largely unambiguous assignments of the aliphatic side chain groups. Furthermore, DIADECOMP applied to a 15N-HSQC-NOESY-15N-HSQC provides all expected short distances between amide groups (defined as all HN-HN distances assignments and a backbone fold with a RMSD of the non-flexible structure of 0.6 Å. Uniqueness of decompositions specifically from TOCSY- and NOESY-type 4D experiments is discussed.

  6. Some nonlinear space decomposition algorithms

    Energy Technology Data Exchange (ETDEWEB)

    Tai, Xue-Cheng; Espedal, M. [Univ. of Bergen (Norway)

    1996-12-31

    Convergence of a space decomposition method is proved for a general convex programming problem. The space decomposition refers to methods that decompose a space into sums of subspaces, which could be a domain decomposition or a multigrid method for partial differential equations. Two algorithms are proposed. Both can be used for linear as well as nonlinear elliptic problems and they reduce to the standard additive and multiplicative Schwarz methods for linear elliptic problems. Two {open_quotes}hybrid{close_quotes} algorithms are also presented. They converge faster than the additive one and have better parallelism than the multiplicative method. Numerical tests with a two level domain decomposition for linear, nonlinear and interface elliptic problems are presented for the proposed algorithms.

  7. Decomposition of indwelling EMG signals

    OpenAIRE

    2008-01-01

    Decomposition of indwelling electromyographic (EMG) signals is challenging in view of the complex and often unpredictable behaviors and interactions of the action potential trains of different motor units that constitute the indwelling EMG signal. These phenomena create a myriad of problem situations that a decomposition technique needs to address to attain completeness and accuracy levels required for various scientific and clinical applications. Starting with the maximum a posteriori probab...

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

    Science.gov (United States)

    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.

  9. TREE DECOMPOSITIONS OF MULTIGRAPHS

    Institute of Scientific and Technical Information of China (English)

    SHI Minyong

    1999-01-01

    For a graph G, ifE(G) can be partitioned into several pairwise disjointsets as { E1, E2,……,El} such thatthe subgraph induced by Ei is a tree of orderki, (i=1,2, ……, l), then G is said to have a {k1,k2,……, kl}-tree-decomposition, denoted by {k1,k2,……, kl}∈G.For k≥1 and l≥0, a collection(G)(k,l) is the setof multigraphs such that G∈(G)(k,l) if and only if ε(G) = k(|G|-1)-l and ε(H)≤max{(k-1)(|H|-1), k(|H|-1)-l} for any subgraph H of G.We prove that (1) If k≥2, 0≤l≤3 and G∈(G)(k,l) of order n≥l+1, then {n,n,……, n-l}∈ G. (2) If k≥2 and G∈(G)(k,2) oforder n≥3, then {n,n,……, n,n-2}∈G and {n,n,……, n,n-1,n-1}∈G. (3) If k3 and G∈(G)(k,3) oforder n≥4, then {n,n,……, n,n-3}∈G ,{ n,n,……, n,n-1,n-2}∈ G and {n,n, ……, n,n-1,n-1,n-1}∈G.

  10. Decomposition of indwelling EMG signals.

    Science.gov (United States)

    Nawab, S Hamid; Wotiz, Robert P; De Luca, Carlo J

    2008-08-01

    Decomposition of indwelling electromyographic (EMG) signals is challenging in view of the complex and often unpredictable behaviors and interactions of the action potential trains of different motor units that constitute the indwelling EMG signal. These phenomena create a myriad of problem situations that a decomposition technique needs to address to attain completeness and accuracy levels required for various scientific and clinical applications. Starting with the maximum a posteriori probability classifier adapted from the original precision decomposition system (PD I) of LeFever and De Luca (25, 26), an artificial intelligence approach has been used to develop a multiclassifier system (PD II) for addressing some of the experimentally identified problem situations. On a database of indwelling EMG signals reflecting such conditions, the fully automatic PD II system is found to achieve a decomposition accuracy of 86.0% despite the fact that its results include low-amplitude action potential trains that are not decomposable at all via systems such as PD I. Accuracy was established by comparing the decompositions of indwelling EMG signals obtained from two sensors. At the end of the automatic PD II decomposition procedure, the accuracy may be enhanced to nearly 100% via an interactive editor, a particularly significant fact for the previously indecomposable trains.

  11. Nonlinear vibrating system identification via Hilbert decomposition

    Science.gov (United States)

    Feldman, Michael; Braun, Simon

    2017-02-01

    This paper deals with the identification of nonlinear vibration systems, based on measured signals for free and forced vibration regimes. Two categories of time domain signal are analyzed, one of a fast inter-modulation signal and a second as composed of several mono-components. To some extent, this attempts to imitate analytic studies of such systems, with its two major analysis groups - the perturbation and the harmonic balance methods. Two appropriate signal processing methods are then investigated, one based on demodulation and the other on signal decomposition. The Hilbert Transform (HT) has been shown to enable effective and simple methods of analysis. We show that precise identification of the nonlinear parameters can be obtained, contrary to other average HT based methods where only approximation parameters are obtained. The effectiveness of the proposed methods is demonstrated for the precise nonlinear system identification, using both the signal demodulation and the signal decomposition methods. Following the exposition of the tools used, both the signal demodulation as well as decomposition are applied to classical examples of nonlinear systems. Cases of nonlinear stiffness and damping forces are analyzed. These include, among other, an asymmetric Helmholtz oscillator, a backlash with nonlinear turbulent square friction, and a Duffing oscillator with dry friction.

  12. Kinetic Interface

    DEFF Research Database (Denmark)

    2009-01-01

    A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises.......A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises....

  13. DECOMPOSITION STUDY OF CALCIUM CARBONATE IN COCKLE SHELL

    Directory of Open Access Journals (Sweden)

    MUSTAKIMAH MOHAMED

    2012-02-01

    Full Text Available Calcium oxide (CaO is recognized as an efficient carbon dioxide (CO2 adsorbent and separation of CO2 from gas stream using CaO based adsorbent is widely applied in gas purification process especially at high temperature reaction. CaO is normally been produced via thermal decomposition of calcium carbonate (CaCO3 sources such as limestone which is obtained through mining and quarrying limestone hill. Yet, this study able to exploit the vast availability of waste resources in Malaysia which is cockle shell, as the potential biomass resources for CaCO3 and CaO. In addition, effect of particle size towards decomposition process is put under study using four particle sizes which are 0.125-0.25 mm, 0.25-0.5 mm, 1-2 mm, and 2-4 mm. Decomposition reactivity is conducted using Thermal Gravimetric Analyzer (TGA at heating rate of 20°C/minutes in inert (Nitrogen atmosphere. Chemical property analysis using x-ray fluorescence (XRF, shows cockle shell is made up of 97% Calcium (Ca element and CaO is produced after decomposition is conducted, as been analyzed by x-ray diffusivity (XRD analyzer. Besides, smallest particle size exhibits the highest decomposition rate and the process was observed to follow first order kinetics. Activation energy, E, of the process was found to vary from 179.38 to 232.67 kJ/mol. From Arrhenius plot, E increased when the particle size is larger. To conclude, cockle shell is a promising source for CaO and based on four different particles sizes used, sample at 0.125-0.25 mm offers the highest decomposition rate.

  14. Kinetics of TEOS surface reactions on SiO{sub 2} between 765 K and 1200 K studied with FTIR

    Energy Technology Data Exchange (ETDEWEB)

    Bartram, M.E.; Moffat, H.K.

    1993-12-31

    To improve process reliability and methods for deposition, it is important to understand the rate-limiting step in TEOS-based (tetraethyl orthosilicate) SiO{sub 2} CVD and its dependence on process conditions. We have used FTIR and isotopically labeled silanols to measure intrinsic kinetics of TEOS reactions on SiO{sub 2}. These measurements were carried out in a cold-wall research reactor under controlled conditions that pertain to TEOS-based CVD processes (10 to 100 mTorr between 765 and 1200 K). We have determined that the E{sub a} for the initial chemisorption step is only 6 kcal/mol between 900 and 1200 K. The initial chemisorption probability is 3 {times} 10{sup {minus}3} and decreases to lower values as the reaction proceeds. In addition, there is a continuous build-up of ethoxy, groups on the surface. This shows that the rate of ethoxy decomposition to SiO{sub 2} and silanols can not keep up with the rate of TEOS chemisorption. It follows that the ethoxy build-up may be responsible for the observed decrease in the TEOS chemisorption probability. If so, this would indicate that ethoxy decomposition is the overall rate-limiting step in SiO{sub 2} CVD. Results also show that silanols are consumed by TEOS surface reactions at CVD temperatures and yet their concentration remains nearly constant as a result of ethoxy decomposition. Therefore, ethoxy decomposition is a key step in TEOS-based SiO{sub 2} CVD since surface ethoxy groups limit the chemisorption probability and also yield the silanols necessary for further TEOS chemisorption. This suggests CVD conditions that alter the ethoxy decomposition rate or decomposition pathway win have an adverse effect on the deposition of conformal films.

  15. The thermal decomposition behavior of ammonium perchlorate and of an ammonium-perchlorate-based composite propellant

    Energy Technology Data Exchange (ETDEWEB)

    Behrens, R.; Minier, L.

    1998-03-24

    The thermal decomposition of ammonium perchlorate (AP) and ammonium-perchlorate-based composite propellants is studied using the simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) technique. The main objective of the present work is to evaluate whether the STMBMS can provide new data on these materials that will have sufficient detail on the reaction mechanisms and associated reaction kinetics to permit creation of a detailed model of the thermal decomposition process. Such a model is a necessary ingredient to engineering models of ignition and slow-cookoff for these AP-based composite propellants. Results show that the decomposition of pure AP is controlled by two processes. One occurs at lower temperatures (240 to 270 C), produces mainly H{sub 2}O, O{sub 2}, Cl{sub 2}, N{sub 2}O and HCl, and is shown to occur in the solid phase within the AP particles. 200{micro} diameter AP particles undergo 25% decomposition in the solid phase, whereas 20{micro} diameter AP particles undergo only 13% decomposition. The second process is dissociative sublimation of AP to NH{sub 3} + HClO{sub 4} followed by the decomposition of, and reaction between, these two products in the gas phase. The dissociative sublimation process occurs over the entire temperature range of AP decomposition, but only becomes dominant at temperatures above those for the solid-phase decomposition. AP-based composite propellants are used extensively in both small tactical rocket motors and large strategic rocket systems.

  16. Real interest parity decomposition

    Directory of Open Access Journals (Sweden)

    Alex Luiz Ferreira

    2009-09-01

    Full Text Available The aim of this paper is to investigate the general causes of real interest rate differentials (rids for a sample of emerging markets for the period of January 1996 to August 2007. To this end, two methods are applied. The first consists of breaking the variance of rids down into relative purchasing power pariety and uncovered interest rate parity and shows that inflation differentials are the main source of rids variation; while the second method breaks down the rids and nominal interest rate differentials (nids into nominal and real shocks. Bivariate autoregressive models are estimated under particular identification conditions, having been adequately treated for the identified structural breaks. Impulse response functions and error variance decomposition result in real shocks as being the likely cause of rids.O objetivo deste artigo é investigar as causas gerais dos diferenciais da taxa de juros real (rids para um conjunto de países emergentes, para o período de janeiro de 1996 a agosto de 2007. Para tanto, duas metodologias são aplicadas. A primeira consiste em decompor a variância dos rids entre a paridade do poder de compra relativa e a paridade de juros a descoberto e mostra que os diferenciais de inflação são a fonte predominante da variabilidade dos rids; a segunda decompõe os rids e os diferenciais de juros nominais (nids em choques nominais e reais. Sob certas condições de identificação, modelos autorregressivos bivariados são estimados com tratamento adequado para as quebras estruturais identificadas e as funções de resposta ao impulso e a decomposição da variância dos erros de previsão são obtidas, resultando em evidências favoráveis a que os choques reais são a causa mais provável dos rids.

  17. NDMA formation by chloramination of ranitidine: Kinetics and mechanism

    KAUST Repository

    Le Roux, Julien

    2012-10-16

    The kinetics of decomposition of the pharmaceutical ranitidine (a major precursor of NDMA) during chloramination was investigated and some decomposition byproducts were identified by using high performance liquid chromatography coupled with mass spectrometry (HPLC-MS). The reaction between monochloramine and ranitidine followed second order kinetics and was acid-catalyzed. Decomposition of ranitidine formed different byproducts depending on the applied monochloramine concentration. Most identified products were chlorinated and hydroxylated analogues of ranitidine. In excess of monochloramine, nucleophilic substitution between ranitidine and monochloramine led to byproducts that are critical intermediates involved in the formation of NDMA, for example, a carbocation formed from the decomposition of the methylfuran moiety of ranitidine. A complete mechanism is proposed to explain the high formation yield of NDMA from chloramination of ranitidine. These results are of great importance to understand the formation of NDMA by chloramination of tertiary amines. © 2012 American Chemical Society.

  18. Modeling of the structure-specific kinetics of abiotic, dark reduction of Hg(II) complexed by O/N and S functional groups in humic acids while accounting for time-dependent structural rearrangement

    Science.gov (United States)

    Jiang, Tao; Skyllberg, Ulf; Wei, Shiqiang; Wang, Dingyong; Lu, Song; Jiang, Zhenmao; Flanagan, Dennis C.

    2015-04-01

    Dark reduction of Hg(II) to Hg(0) in deep waters, soils and sediments accounts for a large part of legacy Hg recycling back to the atmosphere. Natural organic matter (NOM) plays a dual role in the process, acting as an electron donor and complexation agent of Hg(II). Experimental determination of rates of dark Hg(II) reduction is complicated by the simultaneously ongoing kinetics of Hg(II) rearrangement from the abundant, relatively weakly bonding RO/N (carboxyl, amino) groups in NOM to the much stronger bonding RSH (thiol) group. In this study, kinetics of the rearrangement are accounted for and we report rates of dark Hg(II) reduction for two molecular structures in presence of humic acids (HA) extracted from three different sources. Values on the pseudo first-order rate constant for the proposed structure Hg(OR)2 (kredHg(OR)2) were 0.18, 0.22 and 0.35 h-1 for Peat, Coal and Soil HA, respectively, and values on the constant for the proposed structure RSHgOR (kred RSHgOR) were 0.003 and 0.006 h-1 for Peat and Soil HA, respectively. The Hg(SR)2 structure is the thermodynamically most stable, but the limited time of the experiment (53 h) did not allow for a determination of the rate of the very slow reduction of Hg(II) in this structure. For two out of three HA samples the concentration of RSH groups optimized by the kinetic model (0.6 × 10-3 RSH groups per C atoms) was in good agreement with independent estimates provided by sulfur X-ray absorption near-edge spectroscopy (S XANES). Experiments conducted at varying concentrations of Hg(II) and HA demonstrated a positive relationship between Hg(II) reduction and concentrations of specific Hg(II) structures and electron donor groups, suggesting first order in each of these two components. The limitation of the Hg(II) reduction by electron donating groups of HA, as represented by the native reducing capacity (NRC), was demonstrated for the Coal HA sample. Normalization to NRC resulted in pseudo second-order rate

  19. Piecewise-adaptive decomposition methods

    Energy Technology Data Exchange (ETDEWEB)

    Ramos, J.I. [Room I-320-D, E.T.S. Ingenieros Industriales, Universidad de Malaga, Plaza El Ejido, s/n, 29013 Malaga (Spain)], E-mail: jirs@lcc.uma.es

    2009-05-30

    Piecewise-adaptive decomposition methods are developed for the solution of nonlinear ordinary differential equations. These methods are based on some theorems that show that Adomian's decomposition method is a homotopy perturbation technique and coincides with Taylor's series expansions for autonomous ordinary differential equations. Piecewise-decomposition methods provide series solutions in intervals which are subject to continuity conditions at the end points of each interval, and their adaption is based on the use of either a fixed number of approximants and a variable step size, a variable number of approximants and a fixed step size or a variable number of approximants and a variable step size. It is shown that the appearance of noise terms in the decomposition method is related to both the differential equation and the manner in which the homotopy parameter is introduced, especially for the Lane-Emden equation. It is also shown that, in order to avoid the use of numerical quadrature, there is a simple way of introducing the homotopy parameter in the two first-order ordinary differential equations that correspond to the second-order Thomas-Fermi equation. It is also shown that the piecewise homotopy perturbation methods presented here provide more accurate results than a modified Adomian decomposition technique which makes use of Pade approximants and the homotopy analysis method, for the Thomas-Fermi equation.

  20. Memory Effect and Fast Spinodal Decomposition

    CERN Document Server

    Koide, T; Ramos, Rudnei O

    2007-01-01

    We consider the modification of the Cahn-Hilliard equation when a time delay process through a memory function is taken into account. We then study the process of spinodal decomposition in fast phase transitions associated with a conserved order parameter. The introduced memory effect plays an important role to obtain a finite group velocity. Then, we discuss the constraint for the parameters to satisfy causality. The memory effect is seen to affect the dynamics of phase transition at short times and has the effect of delaying, in a significant way, the process of rapid growth of the order parameter that follows a quench into the spinodal region.

  1. Kinetics and

    Directory of Open Access Journals (Sweden)

    Mojtaba Ahmadi

    2016-11-01

    Full Text Available The aqueous degradation of Reactive Yellow 84 (RY84 by potassium peroxydisulfate (K2S2O8 has been studied in laboratory scale experiments. The effect of the initial concentrations of potassium peroxydisulfate and RY84, pH and temperature on RY84 degradation were also examined. Experimental data were analyzed using first and second-order kinetics. The degradation kinetics of RY84 of the potassium peroxydisulfate process followed the second-order reaction kinetics. These rate constants have an extreme values similar to of 9.493 mM−1min−1 at a peroxydisulfate dose of 4 mmol/L. Thermodynamic parameters such as activation (Ea and Gibbs free energy (ΔG° were also evaluated. The negative value of ΔGo and Ea shows the spontaneous reaction natural conditions and exothermic nature.

  2. Investigation on the thermal decomposition of aged La2O3

    Institute of Scientific and Technical Information of China (English)

    Qifeng Shu; Jianhua Liu; Jiayun Zhang; Mei Zhang

    2006-01-01

    The thermal decomposition process of air-aged La2O3 in argon atmosphere was studied using nonisothermal TG-DSC. X-ray diffraction and TG-DSC analysis showed that the aged powder was composed of La(OH)3 with small amounts of oxycarbonate. The decomposition process of air-aged La2O3 involves the two-step decomposition of La(OH)3 and the decomposition of oxycarbonate. The kinetic analysis of the two-step decomposition of La(OH)3 was carried out using Coats-Redfern and isoconversion (Ozawa) methods.The kinetics of the two-step decomposition can be described in terms of the nucleation and growth model A (m=1.5, m is the model parameter) and A (m=2.5), respectively. The apparent activation energy for the first step is 136-144 (Coats-Redfern) and 137-164kJ/mol (isoconversion). The apparent activation energy for the second step is 191-194 (Coats-Redfern) and 186-213 kJ/mol (isoconversion).

  3. Non-Isothermal Decomposion Kinetics of Supermolecule Compound [Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O

    Institute of Scientific and Technical Information of China (English)

    YANG, Rui; HE, Shui-Yang; WU, Wang-Ting; CHEN, Feng-Ying; HU, Rong-Zu

    2006-01-01

    Europium(Ⅲ) compound with 2-oxopropionic acid salicyloyl hydrazone (C10H10N2O4, H3L) and 1,10-phenanthroline (C12HsN2, phen) has been prepared. A yellow prismatic crystal of the compound was obtained, and the molecule crystallized in the triclinic space group P-1. There are two 9-coordinated complex molecules in every structure unit, where every Eu atom is coordinated by three water molecules and two tridentate C10H10N2O4 ligands,forming two stable pentacycles. The coordination polyhedron around Eu3+ was described as a single cap square antiprism. In the crystal cell, there are one free 1,10-phenanthroline and four water molecules. The thermal decomposition of the compound and its kinetics were studied by non-isothermal thermogravimetry. The Kissinger's method and Ozawa's method were used to calculate the activation energy value of the first-step decomposition. The stages of the decompositions were identified by TG-DTG-DSC curve. The non-isothermal kinetic data were analyzed by means of integral and differential methods. The possible reaction mechanism and the kinetic equations were investigated by comparing the kinetic parameters.

  4. Thermochemical decomposition and isomerization of polysilacyclodialkynes and thermochemical and photochemical decomposition of cyclopolysilylketenes

    Energy Technology Data Exchange (ETDEWEB)

    Altman, Leon Berthold [Iowa State Univ., Ames, IA (United States)

    1994-05-10

    Kinetic data for elimination of silylene supports formation of a ``tighter`` transition state, indicating a silacyclopropene intermediate. This extends the silacyclopropene mechanism to the cyclicdialkyne system and validates the consistency of the mechanism for silylakynes, in general. Investigation into the other possible silacyclopropene product established the instability of the product. The work with silylketenes proved that an inherent difference exists between reactivity of monosilyl-substituted ketenes and polysilyl-substituted ketenes. Although the mechanism for thermal decomposition of bis(silyl)ketenes can be modified to account for the unexpected silylene elimination products, reasons for the difference are limited to speculation. The photochemistry of silylketenes has not been previously studied, so a model system does not exist for comparison with our polysilylketene work. The photochemical experimentation suggests that the photochemistry and thermochemistry of polysilylketenes is not the same. A more extensive study of the mechanism of the systems covered in this research as well as with monosilyl-substituted systems is needed.

  5. Investigation of thermal decomposition behavior of hazelnut shell

    Energy Technology Data Exchange (ETDEWEB)

    Can Celebi, Mustafa; Karatepe, Nilgun [Istanbul Technical University, Energy Institute (Turkey)], email: mcan.celebi@gmail.com, email: kmnilgun@itu.edu.tr

    2011-07-01

    The energy industry world-wide is faced with the double challenge of huge capacity power plant installations and the global warming threat. These two problems will become more acute in the future due to population growth and demands for better human well-being. A solution for reducing carbon dioxide emissions from power plants is needed. Agricultural bio-wastes include a mass of energy. The most important part of the energy conversion processes is the thermochemical conversion. The kinetic parameters of the fuels utilized depend on the carbonization process and could be used to inform the design of thermochemical conversion equipment. The purpose of this study is to examine the thermal decomposition behavior of hazelnut shells through dynamic thermogravimetry (TG) under N2 atmosphere. Various experiments were performed to investigate the impacts of heating rate and gas flow rate on the thermal decomposition.

  6. Distributed k-Core Decomposition

    CERN Document Server

    Montresor, Alberto; Miorandi, Daniele

    2011-01-01

    Among the novel metrics used to study the relative importance of nodes in complex networks, k-core decomposition has found a number of applications in areas as diverse as sociology, proteinomics, graph visualization, and distributed system analysis and design. This paper proposes new distributed algorithms for the computation of the k-core decomposition of a network, with the purpose of (i) enabling the run-time computation of k-cores in "live" distributed systems and (ii) allowing the decomposition, over a set of connected machines, of very large graphs, that cannot be hosted in a single machine. Lower bounds on the algorithms complexity are given, and an exhaustive experimental analysis on real-world graphs is provided.

  7. Thermal decomposition of ammonium hexachloroosmate

    DEFF Research Database (Denmark)

    Asanova, T I; Kantor, Innokenty; Asanov, I. P.

    2016-01-01

    Structural changes of (NH4)2[OsCl6] occurring during thermal decomposition in a reduction atmosphere have been studied in situ using combined energy-dispersive X-ray absorption spectroscopy (ED-XAFS) and powder X-ray diffraction (PXRD). According to PXRD, (NH4)2[OsCl6] transforms directly...... to metallic Os without the formation of any crystalline intermediates but through a plateau where no reactions occur. XANES and EXAFS data by means of Multivariate Curve Resolution (MCR) analysis show that thermal decomposition occurs with the formation of an amorphous intermediate {OsCl4}x with a possible...... polymeric structure. Being revealed for the first time the intermediate was subjected to determine the local atomic structure around osmium. The thermal decomposition of hexachloroosmate is much more complex and occurs within a minimum two-step process, which has never been observed before....

  8. Ozone decomposition under the irradiation of 253.7 nm in the presence of methyl bromide

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    In this paper the mechanism and kinetic of ozone decomposition under the irradiation of 253.7 nm UV-light were studied.The quantum yield of the ozone depletion in the presence of methyl bromide is further determined and a reaction model is provided to explain the experimental fact.

  9. The pressure-amorphized state in zirconium tungstate: a precursor to decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Arora, Akhilesh K [Materials Science Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Sastry, V S [Materials Science Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Sahu, P Ch [Materials Science Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Mary, T A [Department of Materials Science, California Institute of Technology, Pasadena, CA 91125 (United States)

    2004-02-25

    In contrast to widely accepted view that pressure-induced amorphization arises due to kinetic hindrance of equilibrium phase transitions, here we provide evidence that the metastable pressure-amorphized state in zirconium tungstate is a precursor to decomposition of the compound into a mixture of simple oxides. This is from the volume collapse {delta}V across amorphization, which is obtained for the first time by measuring linear dimensions of irreversibly amorphized samples during their recovery to the original cubic phase upon isochronal annealing up to 1000 K. The anomalously large {delta}V of 25.7 {+-} 1.2% being the same as that expected for the decomposition indicates that this amorphous state is probably a precursor to kinetically hindered decomposition. A P-T diagram of the compound is also proposed.

  10. Liquid state thermochemical decomposition of neat 1,3,5,5-tetranitrohexahydropyrimidine (DNNC) and its DNNC-d{sub 2}, DNNC-d{sub 4}, DNNC-d{sub 6} structural isotopomers: Mechanistic entrance into the DNNC molecule

    Energy Technology Data Exchange (ETDEWEB)

    Shackelford, S.A. [Air Force Research Laboratory, Propellants Branch (AFRL/PRSP), 10 East Saturn Blvd., Edwards AFB, CA 93524-7680 (United States); Directorate of Chemical Sciences, FJSRL, USAF Academy CO (United States)], E-mail: scott.shackelford@edwards.af.mil; Menapace, J.A. [Directorate of Chemical Sciences, FJSRL, USAF Academy CO (United States); Goldman, J.F. [Department of Chemistry, USAF Academy, CO (United States)

    2007-11-25

    Global kinetics for the liquid state thermochemical decomposition of neat 1,3,5,5-tetranitrohexahydropyrimidine (DNNC), perdeuterio-labeled DNNC-d{sub 6}, and partially deuterium-labeled DNNC-d{sub 2} and DNNC-d{sub 4} isotopomers were obtained by isothermal differential scanning calorimetry (IDSC). Molecular kinetic deuterium isotope effect (KDIE) values obtained with DNNC and DNNC-d{sub 6} from 174 to 194 deg. C revealed that C-H bond rupture regulates both an endothermic catalytic initiation and the exothermic propagation of the liquid thermochemical decomposition process. Using IDSC-based KDIE comparisons with the DNNC-d{sub 2}, DNNC-d{sub 4}, and DNNC-d{sub 6} isotopomers, a more detailed chemical structure/mechanistic relationship emerged by entering the interior of the DNNC molecule. Here structural kinetic KDIE results showed the rate-controlling C-H bond rupture has its origin at the non-equivalent C-2 methylene group sandwiched between the two nitrated DNNC nitrogen ring atoms, versus at the chemically equivalent C-4 and C-6 methylene ring positions located elsewhere in the DNNC molecule. Elucidation of such mechanistic features should aid in the structural design of new high-energy compounds with improved thermochemical properties. A 170.0 kJ/mol activation energy appeared for the endothermic induction period, and a lower 104.2 kJ/mol activation energy was determined for the exothermic acceleratory portion of the DNNC decomposition process. The global liquid and solid state thermochemical decomposition processes for DNNC are compared.

  11. Rank-based decompositions of morphological templates.

    Science.gov (United States)

    Sussner, P; Ritter, G X

    2000-01-01

    Methods for matrix decomposition have found numerous applications in image processing, in particular for the problem of template decomposition. Since existing matrix decomposition techniques are mainly concerned with the linear domain, we consider it timely to investigate matrix decomposition techniques in the nonlinear domain with applications in image processing. The mathematical basis for these investigations is the new theory of rank within minimax algebra. Thus far, only minimax decompositions of rank 1 and rank 2 matrices into outer product expansions are known to the image processing community. We derive a heuristic algorithm for the decomposition of matrices having arbitrary rank.

  12. Kinetics of Cyclohexanone Ammoximation over Titanium Silicate Molecular Sieves

    Institute of Scientific and Technical Information of China (English)

    李永祥; 吴巍; 闵恩泽

    2005-01-01

    An intrinsic kinetics of cyclohexanone ammoximation in the liquid phase over titanium silicate molecular sieves is investigated in an isothermal slurry reactor at different initial reactant concentrations, catalyst loading,and reaction temperature. The rate equations are developed by analyzing data of kinetic measurements. More than 10 side reactions were found. H202 decomposition reaction Inust be considered and other side reactions can be neglected in the kinetic modeling. The predicted values of reaction rates based on the kinetic models are almost consistent with experimental ones. The models have guidance to the selection of reactor types and they are useful to the design and operation of reactor used.

  13. Thermal Behavior and Decomposition Kinetics of Unsymmetrical Dithiolene Metal (Cd, Zn) Complexes of 1, 3-Dithiole-2-thione-4, 5-dithiolate%1,3-二硫杂环戊烯-2-硫酮-4,5-二巯基的不对称二硫纶金属(Cd,Zn) 配合物的热行为和热分解反应动力学

    Institute of Scientific and Technical Information of China (English)

    陆振荣; 丁元晨; 徐颖; 戴洁

    2003-01-01

    TA study on two unsymmetrical dithiolene dithiolene metal(Cd,Zn)complexes of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) was carried out using a simultaneous TG-DTG-DTA technique in a dynamic nitrogen atmosphere and at various heating rates.Supplemented by using both EDS and elemental analysis methods ,their thermal behavior and the composition of their intermadiate products were examined and discussed in connection with their molecular structure.Four thermal analysis kinetic methods were joinly employed to calculate the non-isothermal kinetic parameters and to determine the most probable decomposition mechanisms.%用TG-DTG-DTA联用技术研究了两种1,3-二硫杂环戊烯-2-硫酮-4,5-二巯基的不对称二硫纶金属(Cd,Zn)配合物在动态氮气气氛中的热行为,通过应用EDS技术和元素分析方法对热分解过程中各步反应中间体的组成进行了探索,并结合其物质结构进行了讨论.协同使用四种热分析动力学方法获得了各步反应的热分解动力学参数,并推断了它们的最可能分解反应机理.

  14. The kinetics of acylation and deacylation of penicillin acylase from Escherichia coli ATCC 11105: evidence for lowered pKa values of groups near the catalytic centre.

    Science.gov (United States)

    Morillas, M; Goble, M L; Virden, R

    1999-01-01

    Penicillin G acylase catalysed the hydrolysis of 4-nitrophenyl acetate with a kcat of 0.8 s-1 and a Km of 10 microM at pH 7.5 and 20 degreesC. Results from stopped-flow experiments fitted a dissociation constant of 0.16 mM for the Michaelis complex, formation of an acetyl enzyme with a rate constant of 32 s-1 and a subsequent deacylation step with a rate constant of 0.81 s-1. Non-linear Van't Hoff and Arrhenius plots for these parameters, measured at pH 7.5, may be partly explained by a conformational transition affecting catalytic groups, but a linear Arrhenius plot for the ratio of the rate constant for acylation relative to KS was consistent with energy-compensation between the binding of the substrate and catalysis of the formation of the transition state. At 20 degreesC, the pH-dependence of kcat was similar to that of kcat/Km, indicating that formation of the acyl-enzyme did not affect the pKa values (6.5 and 9.0) of an acidic and basic group in the active enzyme. The heats of ionization deduced from values of pKa for kcat, which measures the rate of deacylation, are consistent with alpha-amino and guanidinium groups whose pKa values are decreased in a non-polar environment. It is proposed that, for catalytic activity, the alpha-amino group of the catalytic SerB1 and the guanidinium group of ArgB263 are required in neutral and protonated states respectively. PMID:9931321

  15. Catalytic effects of inorganic acids on the decomposition of ammonium nitrate.

    Science.gov (United States)

    Sun, Jinhua; Sun, Zhanhui; Wang, Qingsong; Ding, Hui; Wang, Tong; Jiang, Chuansheng

    2005-12-09

    In order to evaluate the catalytic effects of inorganic acids on the decomposition of ammonium nitrate (AN), the heat releases of decomposition or reaction of pure AN and its mixtures with inorganic acids were analyzed by a heat flux calorimeter C80. Through the experiments, the different reaction mechanisms of AN and its mixtures were analyzed. The chemical reaction kinetic parameters such as reaction order, activation energy and frequency factor were calculated with the C80 experimental results for different samples. Based on these parameters and the thermal runaway models (Semenov and Frank-Kamenestkii model), the self-accelerating decomposition temperatures (SADTs) of AN and its mixtures were calculated and compared. The results show that the mixtures of AN with acid are more unsteady than pure AN. The AN decomposition reaction is catalyzed by acid. The calculated SADTs of AN mixtures with acid are much lower than that of pure AN.

  16. The Influence of Magnesium Hydride on the Thermal Decomposition Properties of Nitrocellulose

    Science.gov (United States)

    Jin, Limei; Du, Ping; Yao, Miao

    2014-05-01

    Magnesium hydride is a kind of attractive hydrogen storage material. In this article, the thermal decomposition characteristic of the pure nitrocellulose and the mixture of nitrocellulose with 5% MgH2 was investigated using an accelerating rate calorimeter. The kinetic parameters such as activation energy, Ea; preexponential factor, A; and self-accelerating decomposition temperature, TSADT, were also calculated. We easily showed that the decomposition reaction could be accelerated by adding MgH2, which indicated that MgH2 has an obvious catalytic influence on the decomposition of nitrocellulose. On the other hand, the calculated values of Ea and TSADT showed a decrease in thermal sensitivity with the addition of MgH2. These results were in accordance with our objectives. Therefore, MgH2 is very likely to be an important additive in propellants.

  17. Modeling of ferric sulfate decomposition and sulfation of potassium chloride during grate‐firing of biomass

    DEFF Research Database (Denmark)

    Wu, Hao; Jespersen, Jacob Boll; Jappe Frandsen, Flemming

    2013-01-01

    Ferric sulfate is used as an additive in biomass combustion to convert the released potassium chloride to the less harmful potassium sulfate. The decomposition of ferric sulfate is studied in a fast heating rate thermogravimetric analyzer and a volumetric reaction model is proposed to describe...... the process. The yields of sulfur oxides from ferric sulfate decomposition under boiler conditions are investigated experimentally, revealing a distribution of approximately 40% SO3 and 60% SO2. The ferric sulfate decomposition model is combined with a detailed kinetic model of gas‐phase KCl sulfation...... and a model of K2SO4 condensation to simulate the sulfation of KCl by ferric sulfate addition. The simulation results show good agreements with experiments conducted in a biomass grate‐firing reactor. The results indicate that the SO3 released from ferric sulfate decomposition is the main contributor to KCl...

  18. Shock tube study on the thermal decomposition of n-butanol.

    Science.gov (United States)

    Rosado-Reyes, Claudette M; Tsang, Wing

    2012-10-11

    Dilute concentrations of normal-butanol has been decomposed in single pulse shock tube studies in the presence of large quantities of a chemical inhibitor that suppresses contributions from chain decomposition. Reaction temperatures and pressures are in the range of [1126-1231] K and [1.3-6.5] bar. Ethylene and 1-butene are the only products. The mechanism of the initial decomposition steps involves direct elimination of water and C-C bond cleavage. The fundamental high pressure unimolecular decomposition rate expressions are k(C(4)H(9)OH → CH(3) + CH(2)CH(2)CH(2)OH) = 10(16.4±0.4) exp(42410 ± 800 [K]/T) s(-1); k(C(4)H(9)OH → CH(3)CH(2) + CH(2)CH(2)OH) = 10(16.4±0.4) exp(-41150 ± 800 [K]/T) s(-1); k(C(4)H(9)OH → CH(3)CH(2)CH(2) + CH(2)OH) = 10(16.4±0.4) exp(-41150 ± 800 [K]/T) s(-1); and k(C(4)H(9)OH → CH(3)CH(2)CH═CH(2) + H(2)O) = 10(14.0±0.4) exp(-35089 ± 800 [K]/T) s(-1), where the rate expressions for C-C bond cleavage are based on assumptions regarding the relative rates of the three processes derived from earlier studies on the effect of an OH group on rate expressions. All reactions are in the high pressure limit and suggest that the step size down in the presence of argon is at least 1300 cm(-1). These rate expressions are consistent with the following H-C bond dissociation energies: BDE(H-CH(2)CH(2)CH(2)OH) = 417.2 ± 7 kJ/mol, BDE(H-CH(2)CH(2)OH) = 419.2 ± 7 kJ/mol, and BDE(H-CH(2)OH) = 401.7 ± 9 kJ/mol, with an estimated uncertainty of 6 kJ/mol. The kinetics and thermodynamic results are compared with estimates used in the building of combustion kinetics databases.

  19. Interdiffusion and Spinodal Decomposition in Electrically Conducting Polymer Blends

    Directory of Open Access Journals (Sweden)

    Antti Takala

    2015-08-01

    Full Text Available The impact of phase morphology in electrically conducting polymer composites has become essential for the efficiency of the various functional applications, in which the continuity of the electroactive paths in multicomponent systems is essential. For instance in bulk heterojunction organic solar cells, where the light-induced electron transfer through photon absorption creating excitons (electron-hole pairs, the control of diffusion of the spatially localized excitons and their dissociation at the interface and the effective collection of holes and electrons, all depend on the surface area, domain sizes, and connectivity in these organic semiconductor blends. We have used a model semiconductor polymer blend with defined miscibility to investigate the phase separation kinetics and the formation of connected pathways. Temperature jump experiments were applied from a miscible region of semiconducting poly(alkylthiophene (PAT blends with ethylenevinylacetate-elastomers (EVA and the kinetics at the early stages of phase separation were evaluated in order to establish bicontinuous phase morphology via spinodal decomposition. The diffusion in the blend was followed by two methods: first during a miscible phase separating into two phases: from the measurement of the spinodal decomposition. Secondly the diffusion was measured by monitoring the interdiffusion of PAT film into the EVA film at elected temperatures and eventually compared the temperature dependent diffusion characteristics. With this first quantitative evaluation of the spinodal decomposition as well as the interdiffusion in conducting polymer blends, we show that a systematic control of the phase separation kinetics in a polymer blend with one of the components being electrically conducting polymer can be used to optimize the morphology.

  20. Lumley decomposition of turbulent boundary layer at high Reynolds numbers

    Science.gov (United States)

    Tutkun, Murat; George, William K.

    2017-02-01

    The decomposition proposed by Lumley in 1966 is applied to a high Reynolds number turbulent boundary layer. The experimental database was created by a hot-wire rake of 143 probes in the Laboratoire de Mécanique de Lille wind tunnel. The Reynolds numbers based on momentum thickness (Reθ) are 9800 and 19 100. Three-dimensional decomposition is performed, namely, proper orthogonal decomposition (POD) in the inhomogeneous and bounded wall-normal direction, Fourier decomposition in the homogeneous spanwise direction, and Fourier decomposition in time. The first POD modes in both cases carry nearly 50% of turbulence kinetic energy when the energy is integrated over Fourier dimensions. The eigenspectra always peak near zero frequency and most of the large scale, energy carrying features are found at the low end of the spectra. The spanwise Fourier mode which has the largest amount of energy is the first spanwise mode and its symmetrical pair. Pre-multiplied eigenspectra have only one distinct peak and it matches the secondary peak observed in the log-layer of pre-multiplied velocity spectra. Energy carrying modes obtained from the POD scale with outer scaling parameters. Full or partial reconstruction of turbulent velocity signal based only on energetic modes or non-energetic modes revealed the behaviour of urms in distinct regions across the boundary layer. When urms is based on energetic reconstruction, there exists (a) an exponential decay from near wall to log-layer, (b) a constant layer through the log-layer, and (c) another exponential decay in the outer region. The non-energetic reconstruction reveals that urms has (a) an exponential decay from the near-wall to the end of log-layer and (b) a constant layer in the outer region. Scaling of urms using the outer parameters is best when both energetic and non-energetic profiles are combined.

  1. On the de Rham-Wu decomposition for Riemannian and Lorentzian manifolds

    CERN Document Server

    Galaev, Anton S

    2016-01-01

    It is explained how to find the de~Rham decomposition of a Riemannian manifold and the Wu decomposition of a Lorentzian manifold. For that it is enough to find parallel symmetric bilinear forms on the manifold, and do some linear algebra. This result will allow to compute the connected holonomy group of an arbitrary Riemannian or Lorentzian manifold.

  2. The ecology of carrion decomposition

    Science.gov (United States)

    Carrion, or the remains of dead animals, is something that most people would like to avoid. It is visually unpleasant, emits foul odors, and may be the source of numerous pathogens. Decomposition of carrion, however, provides a unique opportunity for scientists to investigate how nutrients cycle t...

  3. Microbial interactions during carrion decomposition

    Science.gov (United States)

    This addresses the microbial ecology of carrion decomposition in the age of metagenomics. It describes what is known about the microbial communities on carrion, including a brief synopsis about the communities on other organic matter sources. It provides a description of studies using state-of-the...

  4. Wavefront reconstruction by modal decomposition

    CSIR Research Space (South Africa)

    Schulze, C

    2012-08-01

    Full Text Available We propose a new method to determine the wavefront of a laser beam based on modal decomposition by computer-generated holograms. The hologram is encoded with a transmission function suitable for measuring the amplitudes and phases of the modes...

  5. Stepwise decomposition in controlpath synthesis

    NARCIS (Netherlands)

    Berg, ten A.J.W.M.

    1990-01-01

    A method is presented for the synthesis of the microarchitecture of controlpaths. This method is called stepwise decomposition. It focuses primarily on controlpaths of instruction set processors, however it is also applicable for more general Finite State Machine synthesis. Many of the current contr

  6. Stepwise decomposition in controlpath synthesis

    NARCIS (Netherlands)

    ten Berg, A.J.W.M.; ten Berg, A.J.W.M.

    1990-01-01

    A method is presented for the synthesis of the microarchitecture of controlpaths. This method is called stepwise decomposition. It focuses primarily on controlpaths of instruction set processors, however it is also applicable for more general Finite State Machine synthesis. Many of the current contr

  7. Modular Decomposition of Boolean Functions

    NARCIS (Netherlands)

    J.C. Bioch (Cor)

    2002-01-01

    textabstractModular decomposition is a thoroughly investigated topic in many areas such as switching theory, reliability theory, game theory and graph theory. Most appli- cations can be formulated in the framework of Boolean functions. In this paper we give a uni_ed treatment of modular decompositio

  8. Modular Decomposition of Boolean Functions

    NARCIS (Netherlands)

    J.C. Bioch (Cor)

    2002-01-01

    textabstractModular decomposition is a thoroughly investigated topic in many areas such as switching theory, reliability theory, game theory and graph theory. Most appli- cations can be formulated in the framework of Boolean functions. In this paper we give a uni_ed treatment of modular

  9. Multiple Descriptions Using Sparse Decompositions

    DEFF Research Database (Denmark)

    Jensen, Tobias Lindstrøm; Østergaard, Jan; Dahl, Joachim

    2010-01-01

    In this paper, we consider the design of multiple descriptions (MDs) using sparse decompositions. In a description erasure channel only a subset of the transmitted descriptions is received. The MD problem concerns the design of the descriptions such that they individually approximate the source...

  10. Enhanced decomposition of reactive blue 19 dye in ultrasound assisted electrochemical reactor.

    Science.gov (United States)

    Siddique, Maria; Farooq, Robina; Khan, Zahid Mehmood; Khan, Zarsher; Shaukat, S F

    2011-01-01

    Textile industry effluents contain reactive dyes that may harm our receiving waters. A typical reactive blue (RB) 19 dye is frequently detected in significant concentrations in textile industry effluents. Such dyes have generally shown resistance to decomposition and tend to persist in the environment for long periods and multiply the impacts to water and environment. Therefore, the present investigation focused on high-rate decomposition of a typical reactive dye RB 19 under various ultrasound and electrochemical process conditions. The decomposition of un-hydrolyzed and hydrolyzed forms of reactive blue (RB) 19 dye by ultrasound assisted electrochemical process was investigated using various parameters including dye concentration, pH, ultrasonic frequency and reaction time. Reaction kinetics, organic carbon and mechanism for dye decomposition were determined using UV-Visible spectrophotometry, TOC (total organic carbon) analysis and gas chromatography-mass spectrometry (GC-MS). Almost complete 90% color removal and a maximum of 56% TOC removal for 50 mg L(-1) dye concentration of un-hydrolyzed RB 19 dye was achieved at an ultrasonic frequency of 80 kHz, pH of 8 after 120 min. GC-MS analysis showed that a sonoelectrochemical treatment of un-hydrolyzed RB 19 dye for 30 min resulted in the formation of products e.g. acetic acid, benzoic acid etc. with the complete removal of dye. For hydrolyzed dye, a treatment of 10 min was enough and the results were comparable with 30 min treatment of un-hydrolyzed dye. Kinetics of ultrasound assisted electrolysis showed that the dye decomposition followed 1st order. The ultrasound assisted electrolysis for dye decomposition and hence decolorization proved to be more effective and the total energy consumption reduced to half as compared with simple electrolysis/sonochemical decomposition. Therefore, ultrasound assisted electrolysis was found to be more effective technique for dye decomposition of an otherwise environmentally

  11. Nanoconfinement effects: glucose oxidase reaction kinetics in nanofluidics.

    Science.gov (United States)

    Wang, Chen; Sheng, Zhen-Huan; Ouyang, Jun; Xu, Jing-Juan; Chen, Hong-Yuan; Xia, Xing-Hua

    2012-02-01

    Size-tunable nanofluidic devices coupled to an electrochemical detector have been designed and then used to study glucose oxidase (GOx) reaction kinetics confined in nanospaces. The devices are fabricated via a photochemical decomposition reaction, which forms nanochannels covered with carboxyl groups. The generated carboxyl groups enable us to chemically pattern biological molecules on the polymer surfaces via covalent bonding. With this approach, the activity of the immobilized biological molecules confined in nanospaces with different sizes has been investigated. GOx species are chemically immobilized on the surface of the nanochannels, catalyzing the oxidation of substrate glucose as it flows through the channels. The enzyme reaction product, hydrogen peroxide, passing through the nanochannels, reaches an electrochemical detector, giving rise to an increase in anodic current. This steady-state electrochemical current, which responds to various glucose concentrations, can be used to evaluate the GOx activity under confinement conditions. The results show significant nanoconfinement effects that are dependent on the channel size where the reaction occurs, demonstrating the importance of spatial confinement on the GOx reaction kinetics. The present approach provides an effective method for the study of enzyme activity and other bioassay systems, such as cell assays, drug discovery, and clinical diagnosis. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A Reaction-Based River/Stream Water Quality Model: Reaction Network Decomposition and Model Application

    Directory of Open Access Journals (Sweden)

    Fan Zhang

    2012-01-01

    Full Text Available This paper describes details of an automatic matrix decomposition approach for a reaction-based stream water quality model. The method yields a set of equilibrium equations, a set of kinetic-variable transport equations involving kinetic reactions only, and a set of component transport equations involving no reactions. Partial decomposition of the system of water quality constituent transport equations is performed via Gauss-Jordan column reduction of the reaction network by pivoting on equilibrium reactions to decouple equilibrium and kinetic reactions. This approach minimizes the number of partial differential advective-dispersive transport equations and enables robust numerical integration. Complete matrix decomposition by further pivoting on linearly independent kinetic reactions allows some rate equations to be formulated individually and explicitly enforces conservation of component species when component transport equations are solved. The methodology is demonstrated for a case study involving eutrophication reactions in the Des Moines River in Iowa, USA and for two hypothetical examples to illustrate the ability of the model to simulate sediment and chemical transport with both mobile and immobile water phases and with complex reaction networks involving both kinetic and equilibrium reactions.

  13. Simple compactifications and polar decomposition of homogeneous real spherical spaces

    DEFF Research Database (Denmark)

    Knop, Friedrich; Krötz, Bernhard; Sayag, Eitan

    2015-01-01

    Let Z be an algebraic homogeneous space Z = G/H attached to real reductive Lie group G. We assume that Z is real spherical, i.e., minimal parabolic subgroups have open orbits on Z. For such spaces, we investigate their large scale geometry and provide a polar decomposition. This is obtained from...

  14. A Detailed Chemical Kinetic Model for TNT

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbrook, C K

    2005-01-13

    A detailed chemical kinetic mechanism for 2,4,6-tri-nitrotoluene (TNT) has been developed to explore problems of explosive performance and soot formation during the destruction of munitions. The TNT mechanism treats only gas-phase reactions. Reactions for the decomposition of TNT and for the consumption of intermediate products formed from TNT are assembled based on information from the literature and on current understanding of aromatic chemistry. Thermodynamic properties of intermediate and radical species are estimated by group additivity. Reaction paths are developed based on similar paths for aromatic hydrocarbons. Reaction-rate constant expressions are estimated from the literature and from analogous reactions where the rate constants are available. The detailed reaction mechanism for TNT is added to existing reaction mechanisms for RDX and for hydrocarbons. Computed results show the effect of oxygen concentration on the amount of soot precursors that are formed in the combustion of RDX and TNT mixtures in N{sub 2}/O{sub 2} mixtures.

  15. Studies of initial stage in coal liquefaction. Effect of decomposition of oxygen-functional groups on coal liquefaction; Ekika hanno no shoki katei ni kansuru kenkyu. 3. Gansanso kannoki no bunkai kyodo to ekika hanno eno eikyo

    Energy Technology Data Exchange (ETDEWEB)

    Komeiji, A.; Kaneko, T.; Shimazaki, K. [Nippon Brown Coal Liquefaction Co. Ltd., Tokyo (Japan)

    1996-10-28

    Pretreatment of brown coal in oil was conducted using 1-methyl naphthalene or mixture of tetralin and 1-methyl naphthalene as solvent at temperatures ranging from 300 to 430{degree}C under nitrogen atmosphere. Effects of the solvent properties on the structural change of oxygen-functional groups (OFG) and coal liquefaction were investigated by means of quantitative analysis of OFG and solid state {sup 13}C-NMR measurement. When hydrogen transfer from solvent was insufficient, it was suggested that brown coal molecules loose their hydrogen to be aromatized. While, at lower temperatures ranging from 300 to 350{degree}C, hydrogen contained in brown coal molecules was consumed for the stabilization of pyrolytic radicals, and the deterioration of liquefaction was not observed. When hydrogen transfer from solvent was insufficient at higher temperatures above 400{degree}C in nitrogen atmosphere during pretreatment in oil, crosslinking like benzofuran type was formed by dehydration condensation of hydroxyl group in brown coal, to deteriorate the liquefaction, remarkably. The addition of donor solvent like tetralin decreased the formation of crosslinking like benzofuran type, which suppressed the deterioration of liquefaction. 8 refs., 5 figs.

  16. Functionality Decomposition by Compositional Correctness Preserving Transformation

    NARCIS (Netherlands)

    Brinksma, Hendrik; Langerak, Romanus

    1995-01-01

    We present an algorithm for the decomposition of processes in a process algebraic framework. Decomposition, or the refinement of process substructure, is an important design principle in the top-down development of concurrent systems. In the approach that we follow the decomposition is based on a

  17. Physisorption kinetics

    CERN Document Server

    Kreuzer, Hans Jürgen

    1986-01-01

    This monograph deals with the kinetics of adsorption and desorption of molecules physisorbed on solid surfaces. Although frequent and detailed reference is made to experiment, it is mainly concerned with the theory of the subject. In this, we have attempted to present a unified picture based on the master equation approach. Physisorption kinetics is by no means a closed and mature subject; rather, in writing this monograph we intended to survey a field very much in flux, to assess its achievements so far, and to give a reasonable basis from which further developments can take off. For this reason we have included many papers in the bibliography that are not referred to in the text but are of relevance to physisorption. To keep this monograph to a reasonable size, and also to allow for some unity in the presentation of the material, we had to omit a number of topics related to physisorption kinetics. We have not covered to any extent the equilibrium properties of physisorbed layers such as structures, phase tr...

  18. Kinetic Biochemistry

    Directory of Open Access Journals (Sweden)

    Lorentz JÄNTSCHI

    2003-03-01

    Full Text Available Mathematics and computer programming have a major contribution to chemistry. Two directions can be identified: one that searches and tries (rich to explain the structural binding and shape of the chemical compounds [1] with major applications in QSPR/QSAR studies [2], and applied sciences such as engineering of materials or agriculture [3]; the second direction is to models the kinetic processes that are involved in chemical reactions [4]. Many such models are available here. The present paper describes three variants of well the known kinetic models and presents the mathematical equations associated with them. The differential equations are numerically solved and fitted with MathCad program. [1] Diudea M., Gutman I., Jäntschi L., Molecular Topology, Nova Science, Huntington, New York, 332 p., 2001, 2002. [2] Diudea M. V., Ed., QSPR / QSAR Studies by Molecular Descriptors, Nova Science, Huntington, New York, 438 p., 2001. [3] Jäntschi L., Microbiology and Toxicology. Phytochemistry Studies (in Romanian, Amici, Cluj-Napoca, 184 p., 2003. [4] Jäntschi L., Unguresan M., Physical Chemistry. Molecular Kinetic and Dynamic (in Romanian, Mediamira, Cluj-Napoca, 159 p., 2001.

  19. Microbial community assembly and metabolic function during mammalian corpse decomposition

    Science.gov (United States)

    Metcalf, Jessica L; Xu, Zhenjiang Zech; Weiss, Sophie; Lax, Simon; Van Treuren, Will; Hyde, Embriette R.; Song, Se Jin; Amir, Amnon; Larsen, Peter; Sangwan, Naseer; Haarmann, Daniel; Humphrey, Greg C; Ackermann, Gail; Thompson, Luke R; Lauber, Christian; Bibat, Alexander; Nicholas, Catherine; Gebert, Matthew J; Petrosino, Joseph F; Reed, Sasha C.; Gilbert, Jack A; Lynne, Aaron M; Bucheli, Sibyl R; Carter, David O; Knight, Rob

    2016-01-01

    Vertebrate corpse decomposition provides an important stage in nutrient cycling in most terrestrial habitats, yet microbially mediated processes are poorly understood. Here we combine deep microbial community characterization, community-level metabolic reconstruction, and soil biogeochemical assessment to understand the principles governing microbial community assembly during decomposition of mouse and human corpses on different soil substrates. We find a suite of bacterial and fungal groups that contribute to nitrogen cycling and a reproducible network of decomposers that emerge on predictable time scales. Our results show that this decomposer community is derived primarily from bulk soil, but key decomposers are ubiquitous in low abundance. Soil type was not a dominant factor driving community development, and the process of decomposition is sufficiently reproducible to offer new opportunities for forensic investigations.

  20. Univariate and Bivariate Empirical Mode Decomposition for Postural Stability Analysis

    Directory of Open Access Journals (Sweden)

    Jacques Duchêne

    2008-05-01

    Full Text Available The aim of this paper was to compare empirical mode decomposition (EMD and two new extended methods of  EMD named complex empirical mode decomposition (complex-EMD and bivariate empirical mode decomposition (bivariate-EMD. All methods were used to analyze stabilogram center of pressure (COP time series. The two new methods are suitable to be applied to complex time series to extract complex intrinsic mode functions (IMFs before the Hilbert transform is subsequently applied on the IMFs. The trace of the analytic IMF in the complex plane has a circular form, with each IMF having its own rotation frequency. The area of the circle and the average rotation frequency of IMFs represent efficient indicators of the postural stability status of subjects. Experimental results show the effectiveness of these indicators to identify differences in standing posture between groups.

  1. Microbial community assembly and metabolic function during mammalian corpse decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Metcalf, J. L.; Xu, Z. Z.; Weiss, S.; Lax, S.; Van Treuren, W.; Hyde, E. R.; Song, S. J.; Amir, A.; Larsen, P.; Sangwan, N.; Haarmann, D.; Humphrey, G. C.; Ackermann, G.; Thompson, L. R.; Lauber, C.; Bibat, A.; Nicholas, C.; Gebert, M. J.; Petrosino, J. F.; Reed, S. C.; Gilbert, J. A.; Lynne, A. M.; Bucheli, S. R.; Carter, D. O.; Knight, R.

    2015-12-10

    Vertebrate corpse decomposition provides an important stage in nutrient cycling in most terrestrial habitats, yet microbially mediated processes are poorly understood. Here we combine deep microbial community characterization, community-level metabolic reconstruction, and soil biogeochemical assessment to understand the principles governing microbial community assembly during decomposition of mouse and human corpses on different soil substrates. We find a suite of bacterial and fungal groups that contribute to nitrogen cycling and a reproducible network of decomposers that emerge on predictable time scales. Our results show that this decomposer community is derived primarily from bulk soil, but key decomposers are ubiquitous in low abundance. Soil type was not a dominant factor driving community development, and the process of decomposition is sufficiently reproducible to offer new opportunities for forensic investigations.

  2. Nonlinear mode decomposition: A noise-robust, adaptive decomposition method

    Science.gov (United States)

    Iatsenko, Dmytro; McClintock, Peter V. E.; Stefanovska, Aneta

    2015-09-01

    The signals emanating from complex systems are usually composed of a mixture of different oscillations which, for a reliable analysis, should be separated from each other and from the inevitable background of noise. Here we introduce an adaptive decomposition tool—nonlinear mode decomposition (NMD)—which decomposes a given signal into a set of physically meaningful oscillations for any wave form, simultaneously removing the noise. NMD is based on the powerful combination of time-frequency analysis techniques—which, together with the adaptive choice of their parameters, make it extremely noise robust—and surrogate data tests used to identify interdependent oscillations and to distinguish deterministic from random activity. We illustrate the application of NMD to both simulated and real signals and demonstrate its qualitative and quantitative superiority over other approaches, such as (ensemble) empirical mode decomposition, Karhunen-Loève expansion, and independent component analysis. We point out that NMD is likely to be applicable and useful in many different areas of research, such as geophysics, finance, and the life sciences. The necessary matlab codes for running NMD are freely available for download.

  3. Nonlinear mode decomposition: a noise-robust, adaptive decomposition method.

    Science.gov (United States)

    Iatsenko, Dmytro; McClintock, Peter V E; Stefanovska, Aneta

    2015-09-01

    The signals emanating from complex systems are usually composed of a mixture of different oscillations which, for a reliable analysis, should be separated from each other and from the inevitable background of noise. Here we introduce an adaptive decomposition tool-nonlinear mode decomposition (NMD)-which decomposes a given signal into a set of physically meaningful oscillations for any wave form, simultaneously removing the noise. NMD is based on the powerful combination of time-frequency analysis techniques-which, together with the adaptive choice of their parameters, make it extremely noise robust-and surrogate data tests used to identify interdependent oscillations and to distinguish deterministic from random activity. We illustrate the application of NMD to both simulated and real signals and demonstrate its qualitative and quantitative superiority over other approaches, such as (ensemble) empirical mode decomposition, Karhunen-Loève expansion, and independent component analysis. We point out that NMD is likely to be applicable and useful in many different areas of research, such as geophysics, finance, and the life sciences. The necessary matlab codes for running NMD are freely available for download.

  4. Leaf Litter Decomposition of Different Species of Photosynthetic Functional Plant Groups in Karst Area of Central Guizhou%黔中喀斯特区不同光合功能群树种凋落叶分解特性研究

    Institute of Scientific and Technical Information of China (English)

    汪舒雅; 喻理飞; 黄宗胜

    2014-01-01

    通过2013年在黔中喀斯特区采用网袋法进行植物凋落叶的分解实验,比较不同光合功能群树种凋落叶的残留率、分解速率、有机碳释放速率的差异。结果表明,研究区广光耐荫功能群树种(I)、窄光耐荫功能群树种(II)、广光喜光功能群树种(III)、窄光喜光功能群树种(IV)4种功能群树种凋落物在1年的分解过程中,残留率变化趋势分第1~4月、第5~9月、第10~12月3阶段,呈快-慢-快的规律;各光合功能群树种凋落叶分解速率为 III>IV>I>II。有机碳释放速率为 IV>II>III>I。凋落叶分解过程残留率与其有机碳释放速率均呈极显著负相关关系。喜光树种比耐荫树种凋落叶更易分解。%In 2013 by using the litter-bag method,the researchers carried out the plant leaf litter decompo-sition experiment in central Guizhou Karst area,in order to compare differences between residual rates of different photosynthetic functional plant groups’littered leaves,the leaf litter decomposition rates and the organic carbon release rates.There were four species of photosynthetic functional plant groups analyzed in the study area,which were wide-light shade tolerant species (I), narrow-light shade tolerant species (II),wide-light bright light species (III),narrow-light bright light species (IV).Based on analysis of the leaf litter decomposition process in one year,the results showed that tendency of the residual rates presented the fast-slow-fast changes during different periods of time from January to April,May to Sep-tember,and October to December respectively.The leaf litter decomposition rate was III>IV>I>II. The organic carbon release rate was IV>II>III>I.There were negative correlation between the residual rates and the organic carbon release rates.The bright light species were more easier to be decomposed.

  5. Decomposition of Ethanol and Dimethyl Ether during Chemical Vapor Deposition Synthesis of Single-Walled Carbon Nanotubes

    Science.gov (United States)

    Hou, Bo; Xiang, Rong; Inoue, Taiki; Einarsson, Erik; Chiashi, Shohei; Shiomi, Junichiro; Miyoshi, Akira; Maruyama, Shigeo

    2011-06-01

    In this study, we investigated carbon feedstock decomposition conditions on the synthesis of single-walled carbon nanotubes (SWNTs) by chemical vapor deposition. We simulated gas-phase thermal decomposition of ethanol and dimethyl ether (DME) at typical SWNT growth conditions using the chemical kinetic model, and confirmed the reaction trends and primary products using Fourier transform infrared (FT-IR) spectroscopy. Molar fractions were correlated against residence time in the reactor by adjusting the volumetric gas flow rate, and concentration profiles of reaction species were compared to the predicted decomposition mechanism. Signature peak intensities indicated concentrations of both ethanol and DME.

  6. Kinetics of antibody-secreting cell and fecal IgA responses after oral cholera vaccination in different age groups in a cholera endemic country.

    Science.gov (United States)

    Akhtar, Marjahan; Qadri, Firdausi; Bhuiyan, Taufiqur R; Akter, Sarmin; Rafique, Tanzeem A; Khan, Arifuzzaman; Islam, Laila N; Saha, Amit; Svennerholm, Ann-Mari; Lundgren, Anna

    2017-01-05

    Immune responses to oral enteric vaccines in children and infants may be influenced by factors such as age, previous priming with related microorganisms and breast feeding. In this study, we aimed to determine optimal time points to assess immune responses to oral enteric vaccines in different clinical specimens. This was done by investigating antibody secreting cell (ASC) and fecal antibody responses on different days after vaccination using the licensed oral cholera vaccine Dukoral, containing cholera toxin B-subunit (rCTB) and inactivated Vibrio cholerae bacteria, as a model vaccine. Two vaccine doses were given 2weeks apart to infants (6-11months), young children (12-18months), toddlers (19months-5years) and adults in a cholera endemic country (Bangladesh). IgA ASC responses, as determined by the antibodies in lymphocyte supernatant (ALS) assay, plasma IgA and IgG responses and secretory IgA (SIgA) responses in extracts of fecal samples were evaluated 4/5 and 7days after each vaccination. After the first vaccine dose, anti-CTB ALS IgA responses in adults and toddlers were high and comparable on day 5 and 7, while responses were low and infrequent in young children. After the second dose, highest ALS responses were detected on day 5 among the time points studied in all age groups and the responses declined until day 7. In contrast, plasma IgA and IgG anti-CTB responses were high both on day 5 and 7 after the second dose. Fecal SIgA responses in young children and infants were highest on day 7 after the second dose. Our results suggest that ASC/ALS responses to two doses of the oral cholera vaccine Dukoral and related oral vaccines should be analyzed earlier than previously recommended (day 7) at all ages. Fecal antibody responses should preferably be analyzed later than ASC/ALS responses to detect the highest antibody responses.

  7. Variance decomposition in stochastic simulators

    KAUST Repository

    Le Maître, O. P.

    2015-06-28

    This work aims at the development of a mathematical and computational approach that enables quantification of the inherent sources of stochasticity and of the corresponding sensitivities in stochastic simulations of chemical reaction networks. The approach is based on reformulating the system dynamics as being generated by independent standardized Poisson processes. This reformulation affords a straightforward identification of individual realizations for the stochastic dynamics of each reaction channel, and consequently a quantitative characterization of the inherent sources of stochasticity in the system. By relying on the Sobol-Hoeffding decomposition, the reformulation enables us to perform an orthogonal decomposition of the solution variance. Thus, by judiciously exploiting the inherent stochasticity of the system, one is able to quantify the variance-based sensitivities associated with individual reaction channels, as well as the importance of channel interactions. Implementation of the algorithms is illustrated in light of simulations of simplified systems, including the birth-death, Schlögl, and Michaelis-Menten models.

  8. Variance decomposition in stochastic simulators.

    Science.gov (United States)

    Le Maître, O P; Knio, O M; Moraes, A

    2015-06-28

    This work aims at the development of a mathematical and computational approach that enables quantification of the inherent sources of stochasticity and of the corresponding sensitivities in stochastic simulations of chemical reaction networks. The approach is based on reformulating the system dynamics as being generated by independent standardized Poisson processes. This reformulation affords a straightforward identification of individual realizations for the stochastic dynamics of each reaction channel, and consequently a quantitative characterization of the inherent sources of stochasticity in the system. By relying on the Sobol-Hoeffding decomposition, the reformulation enables us to perform an orthogonal decomposition of the solution variance. Thus, by judiciously exploiting the inherent stochasticity of the system, one is able to quantify the variance-based sensitivities associated with individual reaction channels, as well as the importance of channel interactions. Implementation of the algorithms is illustrated in light of simulations of simplified systems, including the birth-death, Schlögl, and Michaelis-Menten models.

  9. Variance decomposition in stochastic simulators

    Science.gov (United States)

    Le Maître, O. P.; Knio, O. M.; Moraes, A.

    2015-06-01

    This work aims at the development of a mathematical and computational approach that enables quantification of the inherent sources of stochasticity and of the corresponding sensitivities in stochastic simulations of chemical reaction networks. The approach is based on reformulating the system dynamics as being generated by independent standardized Poisson processes. This reformulation affords a straightforward identification of individual realizations for the stochastic dynamics of each reaction channel, and consequently a quantitative characterization of the inherent sources of stochasticity in the system. By relying on the Sobol-Hoeffding decomposition, the reformulation enables us to perform an orthogonal decomposition of the solution variance. Thus, by judiciously exploiting the inherent stochasticity of the system, one is able to quantify the variance-based sensitivities associated with individual reaction channels, as well as the importance of channel interactions. Implementation of the algorithms is illustrated in light of simulations of simplified systems, including the birth-death, Schlögl, and Michaelis-Menten models.

  10. Catalytic decomposition of hydrogen peroxide on anthraquinonecyanine and phthalocyanine metal complexes in acid and alkaline electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Pobedinskiy, S.N.; Trofimenko, A.A.; Zharnikova, M.A.

    1985-12-01

    A study of octaoxyanthraquinonecyanines (OOATsM) and phthalocyanines (FTs) of cobalt, iron, and manganese determined their catalytic activity in the hydrogen peroxide decomposition reaction. Hydrogen peroxide decomposition on OOATsM and FTs of the metals studied follows the kinetic mechanisms of a reaction of the first order regardless of the central ion of the metal. Complexes with a central atom of iron are most active in decomposition of hydrogen peroxide. Catalytic activity of FTsFe exceeds that of FTsCo more than 10-fold. FTs are 10-fold greater than OOATsM in catalytic activity. Change from an acid to an alkali medium did not affect the kinetic mechanisms of the decomposition reaction but the reaction rate on both a carrier and on metal complexes is higher in an alkaline medium than in an acid medium. The affect of an alkaline medium on the hydrogen peroxide decomposition rate is greater for FTS complexes than for anthraquinone-cyanines. 5 references, 2 figures.

  11. Thermal Decomposition of New and Aged LX-04 and PBX 9501

    Energy Technology Data Exchange (ETDEWEB)

    Tran, T D; Tarver, C; Idar, D J

    2002-03-25

    One-Dimensional-Time-To-Explosion (ODTX) experiments were conducted to study the thermal decomposition of aged LX-04, aged PBX 9501, HMX class 1 and class 2, Estane and Estane/BDNPA-F (PBX 950 1 plasticized-binder) materials. The tests involved heating 12.7 mm diameter spherical samples in pre-heated aluminum anvils until explosion. The times to explosion at different heating temperatures were compared to historical data on new LX-04 and PBX 9501 compounds to study any changes to their thermal stability. New and aged LX-04 showed comparable decomposition kinetics. The data for aged PBX 9501 showed slightly longer explosion times at equivalent temperatures. Analysis of the error in time measurement is limited and complicated by several experimental factors but the small time change appears to be experimentally significant. The thermal decomposition of these PBXs were modeled using a coupled thermal and heat transport code (chemical TOPAZ) using separate kinetics for HMX and binder decomposition. Separate decomposition models were developed for HMX and the reactive PBX 9501 binder component (1:1 Estane:BDNPA/F) based on the measured explosion times. Thermal aging models can describe longer explosion times by the loss of plasticizer-binder constituent which was more thermally reactive.

  12. Electrochemical decomposition of chlorinated hydrocarbons

    OpenAIRE

    McGee, Gerard Anthony

    1993-01-01

    This work involves the characterisation of the electrochemical decomposition of chlorinated hydrocarbons. A variety of methods were employed involving the use of catalytic reagents to enhance the rate at which chlorinated organic compounds are reduced. The first reagent used was oxygen which was electrochemically reduced to superoxide in nonaqueous solvents. Superoxide is a reactive intermediate and decomposes chlorinated hydrocarbons. However it was found that since the rate of reaction betw...

  13. Effect of particle size on thermal decomposition of alkali metal picrates

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Rui; Zhang, Tonglai, E-mail: ztlbit@bit.edu.cn; Yang, Li; Zhou, Zunning

    2014-05-01

    Graphical abstract: The smaller-sized picrate has greater gas emission than do its larger counterpart. The small size effect reduces the thermal decomposition activation energy, accelerates the reaction rate, and promotes the reaction activity. - Highlights: • Picrates were prepared into three micron sizes by microemulsion synthesis. • Thermal decomposition kinetics and thermodynamics were studied by DPTA and DSC. • Smaller-sized picrate has higher activity and faster reaction rate. • Particle size effect on thermal decomposition kinetics and thermodynamics was revealed. - Abstract: Three alkali metal picrates, KPA, RbPA and CsPA, were prepared into three micron sizes by microemulsion synthesis, and their thermal decomposition behaviors were investigated by DPTA at different temperatures and by DSC at different heating rates. The smaller-sized picrate has greater gas emission and smaller kinetic and thermodynamic parameters than do its larger counterpart. It can be attributed to the decreasing particle size which leads to the high surface energy, the fast mass and heat transfer, and the increasing active sites on the reaction interface. The small size effect and surface effect cause the autocatalysis which reduces the activation energy and promotes the reaction activity. The particle size does not affect the reaction mechanism. However, the picrates with different central alkali metals exhibit different reaction mechanisms even though they are of the same size. This is because the central metal determines the bond energy and consequently affects the stability of picrate.

  14. Ab initio modeling of decomposition in iron based alloys

    Science.gov (United States)

    Gorbatov, O. I.; Gornostyrev, Yu. N.; Korzhavyi, P. A.; Ruban, A. V.

    2016-12-01

    This paper reviews recent progress in the field of ab initio based simulations of structure and properties of Fe-based alloys. We focus on thermodynamics of these alloys, their decomposition kinetics, and microstructure formation taking into account disorder of magnetic moments with temperature. We review modern theoretical tools which allow a consistent description of the electronic structure and energetics of random alloys with local magnetic moments that become totally or partially disordered when temperature increases. This approach gives a basis for an accurate finite-temperature description of alloys by calculating all the relevant contributions to the Gibbs energy from first-principles, including a configurational part as well as terms due to electronic, vibrational, and magnetic excitations. Applications of these theoretical approaches to the calculations of thermodynamics parameters at elevated temperatures (solution energies and effective interatomic interactions) are discussed including atomistic modeling of decomposition/clustering in Fe-based alloys. It provides a solid basis for understanding experimental data and for developing new steels for modern applications. The precipitation in Fe-Cu based alloys, the decomposition in Fe-Cr, and the short-range order formation in iron alloys with s-p elements are considered as examples.

  15. In situ spectroscopic studies on vapor phase catalytic decomposition of dimethyl oxalate.

    Science.gov (United States)

    Hegde, Shweta; Tharpa, Kalsang; Akuri, Satyanarayana Reddy; K, Rakesh; Kumar, Ajay; Deshpande, Raj; Nair, Sreejit A

    2017-03-15

    Dimethyl Oxalate (DMO) has recently gained prominence as a valuable intermediate for the production of compounds of commercial importance. The stability of DMO is poor and hence this can result in the decomposition of DMO under reaction conditions. The mechanism of DMO decomposition is however not reported and more so on catalytic surfaces. Insights into the mechanism of decomposition would help in designing catalysts for its effective molecular transformation. It is well known that DMO is sensitive to moisture, which can also be a factor contributing to its decomposition. The present work reports the results of decomposition of DMO on various catalytic materials. The materials studied consist of acidic (γ-Al2O3), basic (MgO), weakly acidic (ZnAl2O4) and neutral surfaces such as α-Al2O3 and mesoporous precipitated SiO2. Infrared spectroscopy is used to identify the nature of adsorption of the molecule on the various surfaces. The spectroscopy study is done at a temperature of 200 °C, which is the onset of gas phase decomposition of DMO. The results indicate that the stability of DMO is lower than the corresponding acid, i.e. oxalic acid. It is also one of the products of decomposition. Spectroscopic data suggest that DMO decomposition is related to surface acidity and the extent of decomposition depends on the number of surface hydroxyl groups. Decomposition was also observed on α-Al2O3, which was attributed to the residual surface hydroxyl groups. DMO decomposition to oxalic acid was not observed on the basic surface (MgO).

  16. Thermal decomposition of natural dolomite

    Indian Academy of Sciences (India)

    S Gunasekaran; G Anbalagan

    2007-08-01

    Thermal decomposition behaviour of dolomite sample has been studied by thermogravimetric (TG) measurements. Differential thermal analysis (DTA) curve of dolomite shows two peaks at 777.8°C and 834°C. The two endothermic peaks observed in dolomite are essentially due to decarbonation of dolomite and calcite, respectively. The TG data of the decomposition steps have also been analysed using various differential, difference-differential and integral methods, viz. Freeman–Carroll, Horowitz–Metzger, Coats–Redfern methods. Values of activation entropy, Arrhenius factor, and order of reaction have been approximated and compared. Measured activation energies vary between 97 and 147 kJ mol-1. The large fluctuation in activation energy is attributed to the presence of impurities such as SiO2, Al2O3, Fe2O3, Cl- etc in the samples. FTIR and XRD analyses confirm the decomposition reaction. SEM observation of the heat-treated samples at 950°C shows cluster of grains, indicating the structural transformation.

  17. The thermal decomposition of nitrocellulose

    Energy Technology Data Exchange (ETDEWEB)

    Jones, D. E. G.; Turcotte, R.; Acheson, B.; Kwok, Q. S. M.; Vachon, M. [Natural Resources Canada, CANMET Canadian Explosives Research Laboratory, Ottawa, ON (Canada)

    2003-03-01

    In the past, the thermal decomposition of nitrocellulose, the main high-energy component of explosives and solid rocket propellant compositions, was studied using DSC, thermogravimetry and accelerating rate calorimetry. This paper discusses new results obtained by accelerating rate calorimetry (ARC), heat flux calorimetry (HFC), simultaneous thermogravimetry (TG) and differential thermal analysis (DTA) coupled to FTIR and mass spectrometry (MS). Experiments with ARC showed that both the onset temperature and the activation energy for the thermal decomposition depend on sample mass. Evaluating the thermal decomposition of nitrocellulose using HFC at various pressures of argon between ambient and 27 MPa showed that the true onset temperature and the width of the corresponding exotherms are a strong function of the initial pressure. Also presented are the results of investigations conducted using TG-DTA-FTIR-MS in air and in helium. Corresponding to the sharp exotherm observed in helium, many gaseous product species were detected in a narrow band in FTIR and MS spectra. The main species observed by FTIR were carbon dioxide, formic acid, carbon monoxide and trace amounts of formaldehyde, nitrous oxide and water. In comparison, the products detected in air were found to occur in a much wider temperature range. Absorbances of carbon dioxide, nitrogen dioxide and water were observed to have been strongly enhanced in air, while organic species such as formic acid and formaldehyde were significantly depressed. 13 refs., 1 tab., 8 figs.

  18. Characteristics and kinetics study of simultaneous pyrolysis of microalgae Chlorella vulgaris, wood and polypropylene through TGA.

    Science.gov (United States)

    Azizi, Kolsoom; Keshavarz Moraveji, Mostafa; Abedini Najafabadi, Hamed

    2017-11-01

    Thermal decomposition behavior and kinetics of microalgae Chlorella vulgaris, wood and polypropylene were investigated using thermogravimetric analysis (TGA). Experiments were carried out at heating rates of 10, 20 and 40°C/min from ambient temperature to 600°C. The results show that pyrolysis process of C. vulgaris and wood can be divided into three stages while pyrolysis of polypropylene occurs almost totally in one step. It is shown that wood can delay the pyrolysis of microalgae while microalgae can accelerate the pyrolysis of wood. The existence of polymer during the pyrolysis of microalgae or wood will lead to two divided groups of peaks in DTG curve of mixtures. The results showed that interaction is inhibitive rather than synergistic during the decomposition process of materials. Kinetics of process is studied by the Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO). The average E values obtained from FWO and KAS methods were 131.228 and 142.678kJ/mol, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Structural convergence of maize and wheat straw during two-year decomposition under different climate conditions.

    Science.gov (United States)

    Wang, Xiaoyue; Sun, Bo; Mao, Jingdong; Sui, Yueyu; Cao, Xiaoyan

    2012-07-03

    Straw decomposition plays an important role in soil carbon sequestration. Litter quality and climate condition are considered to be key factors that regulate straw decomposition. This study investigated the decomposition characteristics of wheat and maize straw under cold temperate, warm temperate, and midsubtropic climate conditions, and examined whether the chemical structures of straw residues became similar during decomposition under different climate conditions. Straws were put in 0.074-mm-mesh size litter bags to exclude soil fauna and buried in black soil plots at three experimental stations located in the aforementioned climate regions to rule out the impact of soil type. The decomposition rate constants of wheat straw and maize straw increased linearly with temperature, and the former was more sensitive to temperature. Climate conditions and straw quality had marked effects on the residual material structure in the first half year of decomposition, but then decreased. Wheat and maize straw showed common decomposition characteristics with a decrease of O/N-alkyl carbons and di-O-alkyls, and a simultaneous increase of alkyl carbons, aromatic carbons, aromatic C-O groups, and COO/N-C ═ O groups. Overall, the results indicated that the chemical compositions of the two types of straw became similar after 2-year decomposition under different climate conditions.

  20. THERMAL DECOMPOSITION REACTION IN ETHANOL SOLUTION OF DEUTERATED ACETONE CYCLIC DIPEROXIDE AND ACETONE DIPEROXIDE. SECONDARY INVERSE ISOTOPIC EFFECT

    Directory of Open Access Journals (Sweden)

    Karina Nesprias

    Full Text Available The characterization by mass spectrometry and the kinetic study of the thermal decomposition reaction of deuterated acetone diperoxide (dACDP was studied in ethanol in the 140-165 ºC temperature range. The comparison with the non deuterated species (ACDP was also made. The kinetic behavior observed for both compounds follows a pseudo first order kinetic law up to at least 86 % peroxide conversions. It could be observed that under the established experimental conditions, the dACDP decomposes ca. 1.2 times faster than the ACDP. The activation parameters were calculated for both peroxides and allowed to postulate a single process initial step, the unimolecular thermal decomposition through the O-O bond cleavage to form an intermediate biradical. The products of the acetone derived peroxides thermal decomposition support a radical-based decomposition mechanism. The changes in kinetic parameters between dACDP and ACDP were justified attending to differences in ring substituents sizes. A secondary inverse kinetic isotope effect is observed (kH/kD <1.

  1. Synergistic kinetic inhibition of natural gas hydrate formation

    DEFF Research Database (Denmark)

    Daraboina, Nagu; Malmos, Christine; von Solms, Nicolas

    2013-01-01

    Rocking cells were used to investigate the natural gas hydrate formation and decomposition in the presence of kinetic inhibitor, Luvicap. In addition, the influence of poly ethylene oxide (PEO) and NaCl on the performance of Luvicap was investigated using temperature ramping and isothermal...

  2. Hydroxylamine nitrate self-catalytic kinetics study with adiabatic calorimetry.

    Science.gov (United States)

    Liu, Lijun; Wei, Chunyang; Guo, Yuyan; Rogers, William J; Sam Mannan, M

    2009-03-15

    Hydroxylamine nitrate (HAN) is an important member of the hydroxylamine compound family with applications that include equipment decontamination in the nuclear industry and aqueous or solid propellants. Due to its instability and autocatalytic behavior, HAN has been involved in several incidents at the Hanford and Savannah River Site (SRS) [Technical Report on Hydroxylamine Nitrate, US Department of Energy, 1998]. Much research has been conducted on HAN in different areas, such as combustion mechanism, decomposition mechanism, and runaway behavior. However, the autocatalytic decomposition behavior of HAN at runaway stage has not been fully addressed due to its highly exothermic and rapid decomposition behavior. This work is focused on extracting HAN autocatalytic kinetics and analyzing HAN critical behavior from adiabatic calorimetry measurements. A lumped autocatalytic kinetic model for HAN and associated model parameters are determined. Also the storage and handling critical conditions of diluted HAN solution without metal presence are quantified.

  3. Decomposition reactions as general Poisson processes: Theory and an experimental example

    Science.gov (United States)

    Rydén, Tobias; Wernersson, Mikael

    1995-10-01

    The classical theory of decomposition reaction kinetics depends on a ``large scale'' assumption. In this paper we show how this assumption can be replaced by the assumption that the nucleation process is a space-time Poisson process. This framework is unifying in the sense that it includes many earlier formulas as special cases, and it naturally takes boundary effects into account. We consider the conversion of a sphere in detail, and fit the parameters of this model to gypsum decomposition experimental data. The so obtained model shows, for this particular reaction, that the boundary effects decrease with temperature.

  4. Preparation, X-ray crystallography, and thermal decomposition of some transition metal perchlorate complexes of hexamethylenetetramine.

    Science.gov (United States)

    Singh, Gurdip; Baranwal, B P; Kapoor, I P S; Kumar, Dinesh; Fröhlich, Roland

    2007-12-20

    The perchlorate complexes of manganese, nickel, and zinc with hexamethylenetetramine (HMTA) of the general formula [M(H2O-HMTA-H2O)2(H2O-ClO4)2(H2O)2] (where M=Mn, Ni, and Zn) have been prepared and characterized by X-ray crystallography. Thermal studies were undertaken using thermogravimetry (TG), differential thermal analysis (DTA), and explosion delay (DE) measurements. The kinetics of thermal decomposition of these complexes was investigated using isothermal TG data by applying isoconversional method. The decomposition pathways of the complexes have also been proposed. These were found to explode when subjected to higher temperatures.

  5. Buprenorphine kinetics.

    Science.gov (United States)

    Bullingham, R E; McQuay, H J; Moore, A; Bennett, M R

    1980-11-01

    Buprenorphine kinetics was determined in surgical patients using radioimmunoassay. Buprenorphine was measured in the plasma of 24 patients who had received 0.3 mg buprenorphine intraoperatively. After 3 hr 10 of these patients then received a further 0.3 mg buprenorphine intravenously for postoperative pain relief, and 11 patients were given 0.3 mg intramuscularly; again, plasma levels were measured for 3 hr. The data fitted closely to a triexponential decay curve. There was a very fast initial phase, with a half-life (t1/2) of 2 min. The terminal t1/2 was slow, approximately 3 hr. Comparison of the kinetics of the same patient, awake and anesthetized, showed that the clearance was significantly lower in the anesthetized state. A notable feature of the drug given intramuscularly is rapid systemic availability, so that peaks are obtained in 2 to 5 min, and in 10 min the resulting levels are the same as for the intravenous and intramuscular routes.

  6. Monte Carlo simulation of spinodal decomposition in a ternary alloy within a three-phases field: comparison to phase transformation of ferrite in duplex stainless steels

    Science.gov (United States)

    Emo, Jonathan; Pareige, Cristelle; Saillet, Sébastien; Domain, Christophe; Pareige, Philippe

    2014-06-01

    This work proposes to model phase transformations occurring in duplex stainless steels using atomistic kinetic Monte Carlo in a ternary model alloy. Kinetics are simulated in the three-phase field of a ternary system. Influence of the precipitation of the third phase on the kinetic of spinodal decomposition between the two other phases is studied in order to understand the synergy between spinodal decomposition and G-phase precipitation which exists in duplex stainless steels. Simulation results are compared to experimental data obtained with atom probe tomography.

  7. Adsorption and photocatalytic decomposition of roxarsone by TiO₂ and its mechanism.

    Science.gov (United States)

    Lu, Donglei; Ji, Feng; Wang, Feng; Yuan, Shoujun; Hu, Zhen-Hu; Chen, Tianhu

    2014-01-01

    Roxarsone (3-nitro-4-hydroxyphenylarsonic acid) has been widely used as organic arsenic additive in animal industry. In this study, the adsorption of roxarsone on TiO₂ under dark conditions, the photocatalytic decomposition of roxarsone under UV/TiO₂, and the possible photocatalytic pathway were investigated. At the initial concentration of 5-35 mg/L, the adsorption of roxarsone fitted well with the pseudo-second-order kinetics. The isotherms analysis showed that the Langmuir model was better than the Freundlich and Dubinin–Radushkevich models for describing the adsorption process. After 7 h of photocatalytic decomposition, a complete disappearance of roxarsone was achieved. The pH value has a significant effect on both adsorption and photocatalytic decomposition of roxarsone. The results of high-performance liquid chromatography-hydride generation-atomic fluorescence spectrometry (HPLC-HG-AFS) and gas chromatography-mass spectrometry (GC/MS) analyses proved the cleavage of the As-C bond during the photocatalytic decomposition process by TiO2 and the intermediates of the decomposition. Based on the results, a possible photocatalytic decomposition pathway was proposed.

  8. Photocatalytic decomposition of cortisone acetate in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Romão, Joana Sobral; Hamdy, Mohamed S.; Mul, Guido, E-mail: g.mul@utwente.nl; Baltrusaitis, Jonas, E-mail: j.baltrusaitis@utwente.nl

    2015-01-23

    Graphical abstract: - Highlights: • Most efficient photocatalysts for cortisone 21-acetate (CA) degradation were ZnO and TiO{sub 2} (P25). • The decomposition rate increased at low CA concentrations. • No pH dependence was observed allowing CA photocatalytic degradation at native pH. • Synergistic CA degradation effects between TiO{sub 2} and S{sub 2}O{sub 8}{sup 2−} were found. • LC–MS confirmed a decrease in CA concentration, but no intermediate products were detected. - Abstract: 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{sup −1} min{sup −1} at 10 mg L{sup −1} concentration, using the following heterogeneous photocatalysts in decreasing order of their catalytic activity: ZnO > Evonik TiO{sub 2} P25 > Hombikat TiO{sub 2} > WO{sub 3}. Due to the lack of ZnO stability in aqueous solutions, TiO{sub 2} 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{sup −1}, lower than that obtained for TiO{sub 2} P25 (0.040 min{sup −1}). The highest photocatalytic degradation rate constant was obtained combining both TiO{sub 2} P25 and S{sub 2}O{sub 8}{sup 2−} (0.071 min{sup −1}) showing a synergistic effect. No reactive intermediates were detected using LC–MS showing fast photocatalytic decomposition kinetics of CA.

  9. Kinetics of Formic Acid-autocatalyzed Preparation of Performic Acid in Aqueous Phase

    Institute of Scientific and Technical Information of China (English)

    孙晓英; 赵雪冰; 杜伟; 刘德华

    2011-01-01

    Performic acid (PFA) is an oxidant used in chemical processing, synthesis and bleaching. The macro kinetic models of synthesis, hydrolysis and decomposition of PFA were investigated via formic acid-autocatalyzed reaction. It was found that the intrinsic activation energies of PFA synthesis and hydrolysis were 75.2 kJ·mol^-1 and 40.4 kJ·mol^-1 respectively. The observed activation energy of PFA decomposition was 95.4 kJ·mol^-1. The experi-mental results indicated that the decomposition of PFA was liable to occur even at the ambient temperature. Both the spontaneous decomposition and the radical-introduced decomposition contributed to the decomposition of PFA.

  10. Kinetic buffers.

    Science.gov (United States)

    Alibrandi, Giuseppe; Fabbrizzi, Luigi; Licchelli, Maurizio; Puglisi, Antonio

    2015-01-12

    This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH-sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH-t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di-copper(II) bistren complex in a single run, in a completely automatic experiment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. The Effect of Clothing on the Rate of Decomposition and Diptera Colonization on Sus scrofa Carcasses.

    Science.gov (United States)

    Card, Allison; Cross, Peter; Moffatt, Colin; Simmons, Tal

    2015-07-01

    Twenty Sus scrofa carcasses were used to study the effect the presence of clothing had on decomposition rate and colonization locations of Diptera species; 10 unclothed control carcasses were compared to 10 clothed experimental carcasses over 58 days. Data collection occurred at regular accumulated degree day intervals; the level of decomposition as Total Body Score (TBSsurf ), pattern of decomposition, and Diptera present was documented. Results indicated a statistically significant difference in the rate of decomposition, (t427  = 2.59, p = 0.010), with unclothed carcasses decomposing faster than clothed carcasses. However, the overall decomposition rates from each carcass group are too similar to separate when applying a 95% CI, which means that, although statistically significant, from a practical forensic point of view they are not sufficiently dissimilar as to warrant the application of different formulae to estimate the postmortem interval. Further results demonstrated clothing provided blow flies with additional colonization locations.

  12. Texture Segmentation by Contractive Decomposition and Planar Grouping

    DEFF Research Database (Denmark)

    Dahl, Anders Lindbjerg; Bogunovich, Peter; Shokoufandeh, Ali

    2009-01-01

    Image segmentation has long been an important problem in the computer vision community. In our recent work we have addressed the problem of texture segmentation, where we combined top-down and bottom-up views of the image into a unified procedure. In this paper we extend our work by proposing...

  13. Modelling volatility by variance decomposition

    DEFF Research Database (Denmark)

    Amado, Cristina; Teräsvirta, Timo

    on the multiplicative decomposition of the variance is developed. It is heavily dependent on Lagrange multiplier type misspecification tests. Finite-sample properties of the strategy and tests are examined by simulation. An empirical application to daily stock returns and another one to daily exchange rate returns...... illustrate the functioning and properties of our modelling strategy in practice. The results show that the long memory type behaviour of the sample autocorrelation functions of the absolute returns can also be explained by deterministic changes in the unconditional variance....

  14. Azimuthal decomposition of optical modes

    CSIR Research Space (South Africa)

    Dudley, Angela L

    2012-07-01

    Full Text Available of Optical Modes Angela Dudley1, Igor Litvin1, Filippus S. Roux1 and Andrew Forbes1,2,3 1 CSIR National Laser Centre, Pretoria, South Africa 2 School of Physics, University of KwaZulu-Natal, Durban, South Africa 3 Laser Research Institute, University... of Stellenbosch, Stellenbosch, South Africa Presented at the 2012 South African Institute of Physics Conference University of Pretoria Pretoria, South Africa 12 July 2012 To decompose the azimuthal modes we need two steps: generation and decomposition...

  15. Highly Scalable Matching Pursuit Signal Decomposition Algorithm

    Data.gov (United States)

    National Aeronautics and Space Administration — In this research, we propose a variant of the classical Matching Pursuit Decomposition (MPD) algorithm with significantly improved scalability and computational...

  16. On Schubert decompositions of quiver Grassmannians

    Science.gov (United States)

    Lorscheid, Oliver

    2014-02-01

    In this paper, we introduce Schubert decompositions for quiver Grassmannians and investigate certain classes of quiver Grassmannians with a Schubert decomposition into affine spaces. The main theorem puts the cells of a Schubert decomposition into relation to the cells of a certain simpler quiver Grassmannian. This allows us to extend known examples of Schubert decompositions into affine spaces to a larger class of quiver Grassmannians. This includes exceptional representations of the Kronecker quiver as well as representations of forests with block matrices of the form (0100). Finally, we draw conclusions on the Euler characteristics and the cohomology of quiver Grassmannians.

  17. Direct observation of nanowire growth and decomposition

    DEFF Research Database (Denmark)

    Rackauskas, Simas; Shandakov, Sergey D; Jiang, Hua

    2017-01-01

    knowledge, so far this has been only postulated, but never observed at the atomic level. By means of in situ environmental transmission electron microscopy we monitored and examined the atomic layer transformation at the conditions of the crystal growth and its decomposition using CuO nanowires selected...... as a model object. The atomic layer growth/decomposition was studied by varying an O2 partial pressure. Three distinct regimes of the atomic layer evolution were experimentally observed: growth, transition and decomposition. The transition regime, at which atomic layer growth/decomposition switch takes place...

  18. PROCESS STUDY ON DEPHENOLIZATION OF BPA-PHENOL ADDUCT BY SOLID DECOMPOSITION REACTION%双酚A-苯酚加合物固相分解反应脱酚的工艺研究

    Institute of Scientific and Technical Information of China (English)

    刘宗章; 张敏华; 李传兆; 钱胜华; 谈遒

    1999-01-01

    The process condition of dephenolization of bisphenol A-phenol adduct is studied,by using the solid decomposition reaction on the basis of thermodynamic property of bisphenol A-phenol and the kinetics of solid decomposition reaction.The process condition is proposed with high quality bisphenol A product.A new method of dephenolization in the production of bisphenol A is developed.

  19. Decomposition methods in turbulence research

    Directory of Open Access Journals (Sweden)

    Uruba Václav

    2012-04-01

    Full Text Available Nowadays we have the dynamical velocity vector field of turbulent flow at our disposal coming thanks advances of either mathematical simulation (DNS or of experiment (time-resolved PIV. Unfortunately there is no standard method for analysis of such data describing complicated extended dynamical systems, which is characterized by excessive number of degrees of freedom. An overview of candidate methods convenient to spatiotemporal analysis for such systems is to be presented. Special attention will be paid to energetic methods including Proper Orthogonal Decomposition (POD in regular and snapshot variants as well as the Bi-Orthogonal Decomposition (BOD for joint space-time analysis. Then, stability analysis using Principal Oscillation Patterns (POPs will be introduced. Finally, the Independent Component Analysis (ICA method will be proposed for detection of coherent structures in turbulent flow-field defined by time-dependent velocity vector field. Principle and some practical aspects of the methods are to be shown. Special attention is to be paid to physical interpretation of outputs of the methods listed above.

  20. Thermal decomposition of mercuric sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Leckey, J.H.; Nulf, L.E.

    1994-10-28

    The rate of thermal decomposition of mercuric sulfide (HgS) has been measured at temperatures from 265 to 345 C. These data have been analyzed using a first-order chemical reaction model for the time dependence of the reaction and the Arrhenius equation for the temperature dependence of the rate constant. Using this information, the activation energy for the reaction was found to be 55 kcal/mol. Significant reaction vessel surface effects obscured the functional form of the time dependence of the initial portion of the reaction. The data and the resulting time-temperature reaction-rate model were used to predict the decomposition rate of HgS as a function of time and temperature in thermal treatment systems. Data from large-scale thermal treatment studies already completed were interpreted in terms of the results of this study. While the data from the large-scale thermal treatment studies were consistent with the data from this report, mass transport effects may have contributed to the residual amount of mercury which remained in the soil after most of the large-scale runs.