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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. Decomposition kinetics of plutonium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Haschke, J.M.; Stakebake, J.L.

    1979-01-01

    Kinetic data for decomposition of PuH/sub 1/ /sub 95/ provides insight into a possible mechanism for the hydriding and dehydriding reactions of plutonium. The fact that the rate of the hydriding reaction, K/sub H/, is proportional to P/sup 1/2/ and the rate of the dehydriding process, K/sub D/, is inversely proportional to P/sup 1/2/ suggests that the forward and reverse reactions proceed by opposite paths of the same mechanism. The P/sup 1/2/ dependence of hydrogen solubility in metals is characteristic of the dissociative absorption of hydrogen; i.e., the reactive species is atomic hydrogen. It is reasonable to assume that the rates of the forward and reverse reactions are controlled by the surface concentration of atomic hydrogen, (H/sub s/), that K/sub H/ = c'(H/sub s/), and that K/sub D/ = c/(H/sub s/), where c' and c are proportionality constants. For this surface model, the pressure dependence of K/sub D/ is related to (H/sub s/) by the reaction (H/sub s/) reversible 1/2H/sub 2/(g) and by its equilibrium constant K/sub e/ = (H/sub 2/)/sup 1/2//(H/sub s/). In the pressure range of ideal gas behavior, (H/sub s/) = K/sub e//sup -1/(RT)/sup -1/2/ and the decomposition rate is given by K/sub D/ = cK/sub e/(RT)/sup -1/2/P/sup 1/2/. For an analogous treatment of the hydriding process with this model, it can be readily shown that K/sub H/ = c'K/sub e//sup -1/(RT)/sup -1/2/P/sup 1/2/. The inverse pressure dependence and direct temperature dependence of the decomposition rate are correctly predicted by this mechanism which is most consistent with the observed behavior of the Pu--H system.

  3. 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.

  4. Thermal decomposition kinetics of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    Kim, E.H.; Park, J.J.; Park, J.H.; Chang, I.S.; Choi, C.S.; Kim, S.D.

    1994-01-01

    The thermal decomposition kinetics of AUC [ammonium uranyl carbonate; (NH 4 ) 4 UO 2 (CO 3 ) 3 [ in an isothermal thermogravimetric (TG) reactor under N 2 atmosphere has been determined. The kinetic data can be represented by the two-dimensional nucleation and growth model. The reaction rate increases and activation energy decreases with increasing particle size and precipitation time which appears in the particle size larger than 30 μm in the mechano-chemical phenomena. (orig.)

  5. Kinetics of hydrogen peroxide decomposition by catalase: hydroxylic solvent effects.

    Science.gov (United States)

    Raducan, Adina; Cantemir, Anca Ruxandra; Puiu, Mihaela; Oancea, Dumitru

    2012-11-01

    The effect of water-alcohol (methanol, ethanol, propan-1-ol, propan-2-ol, ethane-1,2-diol and propane-1,2,3-triol) binary mixtures on the kinetics of hydrogen peroxide decomposition in the presence of bovine liver catalase is investigated. In all solvents, the activity of catalase is smaller than in water. The results are discussed on the basis of a simple kinetic model. The kinetic constants for product formation through enzyme-substrate complex decomposition and for inactivation of catalase are estimated. The organic solvents are characterized by several physical properties: dielectric constant (D), hydrophobicity (log P), concentration of hydroxyl groups ([OH]), polarizability (α), Kamlet-Taft parameter (β) and Kosower parameter (Z). The relationships between the initial rate, kinetic constants and medium properties are analyzed by linear and multiple linear regression.

  6. Hydrogen peroxide decomposition kinetics in aquaculture water

    DEFF Research Database (Denmark)

    Arvin, Erik; Pedersen, Lars-Flemming

    2015-01-01

    during the HP decomposition. The model assumes that the enzyme decay is controlled by an inactivation stoichiometry related to the HP decomposition. In order to make the model easily applicable, it is furthermore assumed that the COD is a proxy of the active biomass concentration of the water and thereby......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...... reared or the nitrifying bacteria in the biofilters at concentrations required to eliminating pathogens. This calls for quantitative insight into the fate of the disinfectant residuals during water treatment. This paper presents a kinetic model that describes the HP decomposition in aquaculture water...

  7. Detailed Chemical Kinetic Modeling of Hydrazine Decomposition

    Science.gov (United States)

    Meagher, Nancy E.; Bates, Kami R.

    2000-01-01

    The purpose of this research project is to develop and validate a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. Hydrazine is used extensively in aerospace propulsion, and although liquid hydrazine is not considered detonable, many fuel handling systems create multiphase mixtures of fuels and fuel vapors during their operation. Therefore, a thorough knowledge of the decomposition chemistry of hydrazine under a variety of conditions can be of value in assessing potential operational hazards in hydrazine fuel systems. To gain such knowledge, a reasonable starting point is the development and validation of a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. A reasonably complete mechanism was published in 1996, however, many of the elementary steps included had outdated rate expressions and a thorough investigation of the behavior of the mechanism under a variety of conditions was not presented. The current work has included substantial revision of the previously published mechanism, along with a more extensive examination of the decomposition behavior of hydrazine. An attempt to validate the mechanism against the limited experimental data available has been made and was moderately successful. Further computational and experimental research into the chemistry of this fuel needs to be completed.

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

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Nasrollahi, R.; Dušek, Michal; Fejfarová, Karla; Ranjkeshshorkaei, M.; Firuzabadi, F.D.

    2016-01-01

    Roč. 13, č. 5 (2016), 913-924 ISSN 1735-207X R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : Schiff base complex * kinetic study * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.407, year: 2016

  9. Investigation into kinetics of decomposition of nitrates

    International Nuclear Information System (INIS)

    Belov, B.A.; Gorozhankin, Eh.V.; Efremov, V.N.; Sal'nikova, N.S.; Suris, A.L.

    1985-01-01

    Using the method of thermogravimetry, the decomposition of nitrates, Cd(NO 3 ) 2 x4H 2 O, La(NO 3 ) 2 x6H 2 O, Sr(NO 3 ) 2 , ZrO(NO 3 ) 2 x2H 2 O, Y(NO 3 ) 3 x6H 2 O, in particular, is studied in the 20-1000 deg C range. It is shown, that gaseous pyrolysis, products, remaining in the material, hamper greatly the heat transfer required for the decomposition which reduces the reaction order. An effective activation energy of the process is in a satisfactory agreement with the characteristic temperature of the last endotherm. Kinetic parameters are calculated by the minimization method using a computer

  10. Decomposition kinetics of aminoborane in aqueous solutions

    International Nuclear Information System (INIS)

    Shvets, I.B.; Erusalimchik, I.G.

    1984-01-01

    Kinetics of aminoborane hydrolysis has been studied using the method of polarization galvanostatical curves on a platinum electrode in buffer solutions at pH 3; 5; 7. The supposition that the reaction of aminoborane hydrolysis is the reaction of the first order by aminoborane is proved. The rate constant of aminoborane decomposition in the solution with pH 5 is equal to: K=2.5x10 -5 s -1 and with pH 3 it equals K=1.12x10 -4 s -1

  11. Renormalization-group theory of spinodal decomposition

    International Nuclear Information System (INIS)

    Mazenko, G.F.; Valls, O.T.; Zhang, F.C.

    1985-01-01

    Renormalization-group (RG) methods developed previously for the study of the growth of order in unstable systems are extended to treat the spinodal decomposition of the two-dimensional spin-exchange kinetic Ising model. The conservation of the order parameter and fixed-length sum rule are properly preserved in the theory. Various correlation functions in both coordinate and momentum space are calculated as functions of time. The scaling function for the structure factor is extracted. We compare our results with direct Monte Carlo (MC) simulations and find them in good agreement. The time rescaling parameter entering the RG analysis is temperature dependent, as was determined in previous work through a RG analysis of MC simulations. The results exhibit a long-time logarithmic growth law for the typical domain size, both analytically and numerically. In the time region where MC simulations have previously been performed, the logarithmic growth law can be fitted to a power law with an effective exponent. This exponent is found to be in excellent agreement with the result of MC simulations. The logarithmic growth law agrees with a physical model of interfacial motion which involves an interplay between the local curvature and an activated jump across the interface

  12. Kinetic study of lithium-cadmium ternary amalgam decomposition

    International Nuclear Information System (INIS)

    Cordova, M.H.; Andrade, C.E.

    1992-01-01

    The effect of metals, which form stable lithium phase in binary alloys, on the formation of intermetallic species in ternary amalgams and their effect on thermal decomposition in contact with water is analyzed. Cd is selected as ternary metal, based on general experimental selection criteria. Cd (Hg) binary amalgams are prepared by direct contact Cd-Hg, whereas Li is formed by electrolysis of Li OH aq using a liquid Cd (Hg) cathodic well. The decomposition kinetic of Li C(Hg) in contact with 0.6 M Li OH is studied in function of ageing and temperature, and these results are compared with the binary amalgam Li (Hg) decomposition. The decomposition rate is constant during one hour for binary and ternary systems. Ageing does not affect the binary systems but increases the decomposition activation energy of ternary systems. A reaction mechanism that considers an intermetallic specie participating in the activated complex is proposed and a kinetic law is suggested. (author)

  13. LLNL Chemical Kinetics Modeling Group

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbrook, C K; Mehl, M; Herbinet, O; Curran, H J; Silke, E J

    2008-09-24

    The LLNL chemical kinetics modeling group has been responsible for much progress in the development of chemical kinetic models for practical fuels. The group began its work in the early 1970s, developing chemical kinetic models for methane, ethane, ethanol and halogenated inhibitors. Most recently, it has been developing chemical kinetic models for large n-alkanes, cycloalkanes, hexenes, and large methyl esters. These component models are needed to represent gasoline, diesel, jet, and oil-sand-derived fuels.

  14. 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.

  15. 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...

  16. Basic dye decomposition kinetics in a photocatalytic slurry reactor

    International Nuclear Information System (INIS)

    Wu, C.-H.; Chang, H.-W.; Chern, J.-M.

    2006-01-01

    Wastewater effluent from textile plants using various dyes is one of the major water pollutants to the environment. Traditional chemical, physical and biological processes for treating textile dye wastewaters have disadvantages such as high cost, energy waste and generating secondary pollution during the treatment process. The photocatalytic process using TiO 2 semiconductor particles under UV light illumination has been shown to be potentially advantageous and applicable in the treatment of wastewater pollutants. In this study, the dye decomposition kinetics by nano-size TiO 2 suspension at natural solution pH was experimentally studied by varying the agitation speed (50-200 rpm), TiO 2 suspension concentration (0.25-1.71 g/L), initial dye concentration (10-50 ppm), temperature (10-50 deg. C), and UV power intensity (0-96 W). The experimental results show the agitation speed, varying from 50 to 200 rpm, has a slight influence on the dye decomposition rate and the pH history; the dye decomposition rate increases with the TiO 2 suspension concentration up to 0.98 g/L, then decrease with increasing TiO 2 suspension concentration; the initial dye decomposition rate increases with the initial dye concentration up to a certain value depending upon the temperature, then decreases with increasing initial dye concentration; the dye decomposition rate increases with the UV power intensity up to 64 W to reach a plateau. Kinetic models have been developed to fit the experimental kinetic data well

  17. Kinetic study and thermal decomposition behavior of viscoelastic memory foam

    International Nuclear Information System (INIS)

    Garrido, María A.; Font, Rafael; Conesa, Juan A.

    2016-01-01

    Highlights: • The thermal degradation has been studied under three different atmospheres. • Pyrolysis and combustion kinetic models have been proposed. • Evolved products under different atmospheres have been analyzed by TG-FTIR and TG-MS. - Abstract: A systematic investigation of the thermal decomposition of viscoelastic memory foam (VMF) was performed using thermogravimetric analysis (TGA) to obtain the kinetic parameters, and thermogravimetric analysis coupled to Fourier Transformed Infrared Spectrometry (TGA-FTIR) and thermogravimetric analysis coupled to Mass Spectrometry (TGA-MS) to obtain detailed information of evolved products on pyrolysis and oxidative degradations. Two consecutive nth-order reactions were employed to correlate the experimental data from dynamic and isothermal runs performed at three different heating rates (5, 10 and 20 K/min) under an inert atmosphere. On the other hand, for the kinetic study of the oxidative decomposition, the data from combustion (synthetic air) and poor oxygen combustion (N_2:O_2 = 9:1) runs, at three heating rates and under dynamic and isothermal conditions, were correlated simultaneously. A kinetic model consisting of three consecutive reactions presented a really good correlation in all runs. TGA-FTIR analysis showed that the main gases released during the pyrolysis of VMF were determined as ether and aliphatic hydrocarbons, whereas in combustion apart from the previous gases, aldehydes, amines and CO_2 have also been detected as the main gases. These results were confirmed by the TGA-MS.

  18. Kinetics of the thermal decomposition of nickel iodide

    International Nuclear Information System (INIS)

    Nakajima, Hayato; Shimizu, Saburo; Onuki, Kaoru; Ikezoe, Yasumasa; Sato, Shoichi

    1984-01-01

    Thermal decomposition kinetics of NiI 2 under constant I 2 partial pressure was studied by thermogravimetry. The reaction is considered as a reaction step of the thermochemical hydrogen production process in the Ni-I-S system. At temperatures from 775K to 869K and under I 2 pressures from 0 to 960Pa, the decomposition started at the NiI 2 pellet surface and the reactant-product interface moved interior at a constant rate until the decomposed fraction, α, reached 0.6. The overall reaction rate at a constant temperature can be expressed as the difference of the constant decomposition (forward) rate, which is proportional to the equilibrium dissociation pressure of NiI 2 , and the iodide formation (backward) rate, which is proportional to the I 2 pressure. The apparent activation energy of the decomposition was 147 kJ.mol -1 , which is very close to the heat of reaction, 152 kJ.mol -1 calculated from the equilibrium dissociation pressure. The electron microscopic observations, revealed that the reaction product obtained by decomposing NiI 2 under pure He atomosphere was composed of relatively well grown cubic Ni crystals. Whereas, the decomposed product obtained under I 2 -He mixture was composed of larger but disordered crystals. (author)

  19. 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.

  20. Ozone disintegration kinetics in the reactor for tyres decomposition

    International Nuclear Information System (INIS)

    Golota, V.I.; Manujlenko, O.V.; Taran, G.V.; Pis'menetskij, A.S.; Zamuriev, A.A.

    2010-01-01

    The results of theoretical and experimental research of ozone disintegration kinetics in the chemical reactor which is developed for decomposition of tyres in the ozone-air environment are presented. Analytical expression for dependence of ozone concentration in the reactor from time and from parameters of the task, such as volume speed of ozone-air mixture feed on a reactor input, concentration of ozone on the input to the reactor, volume speed of output of the used mixture, reactor size, and square of its internal surface is obtained. It is shown that at the same speed of ozone-air mixture pro rolling through the reactor, with growth of ozone concentration on the input, value of stationary concentration in the reactor grows, remaining always less than concentration on the input. It is also shown that at the same ozone concentration on the input, with growth of speed of ozone-air mixture pro rolling through the reactor, value of stationary ozone concentration in the reactor also grows, remaining always less than ozone concentration on the input. The ozone disintegration kinetics in the reactor in a wide range of speed of ozone-air mixture pro rolling through the reactor (0.15, 0.30, 0.45, 0.60 m3/hour) and various ozone concentration on the input (5, 10, 15, 20 g/m3) is experimentally studied. It is shown that experimental results with good accuracy coincide with the theoretical. Direct experiment showed the essential influence of the internal surface of the reactor on the ozone disintegration kinetics.

  1. Kinetics of thermal decomposition of aluminium hydride: I-non-isothermal decomposition under vacuum and in inert atmosphere (argon)

    International Nuclear Information System (INIS)

    Ismail, I.M.K.; Hawkins, T.

    2005-01-01

    Recently, interest in aluminium hydride (alane) as a rocket propulsion ingredient has been renewed due to improvements in its manufacturing process and an increase in thermal stability. When alane is added to solid propellant formulations, rocket performance is enhanced and the specific impulse increases. Preliminary work was performed at AFRL on the characterization and evaluation of two alane samples. Decomposition kinetics were determined from gravimetric TGA data and volumetric vacuum thermal stability (VTS) results. Chemical analysis showed the samples had 88.30% (by weight) aluminium and 9.96% hydrogen. The average density, as measured by helium pycnometery, was 1.486 g/cc. Scanning electron microscopy showed that the particles were mostly composed of sharp edged crystallographic polyhedral such as simple cubes, cubic octahedrons and hexagonal prisms. Thermogravimetric analysis was utilized to investigate the decomposition kinetics of alane in argon atmosphere and to shed light on the mechanism of alane decomposition. Two kinetic models were successfully developed and used to propose a mechanism for the complete decomposition of alane and to predict its shelf-life during storage. Alane decomposes in two steps. The slowest (rate-determining) step is solely controlled by solid state nucleation of aluminium crystals; the fastest step is due to growth of the crystals. Thus, during decomposition, hydrogen gas is liberated and the initial polyhedral AlH 3 crystals yield a final mix of amorphous aluminium and aluminium crystals. After establishing the kinetic model, prediction calculations indicated that alane can be stored in inert atmosphere at temperatures below 10 deg. C for long periods of time (e.g., 15 years) without significant decomposition. After 15 years of storage, the kinetic model predicts ∼0.1% decomposition, but storage at higher temperatures (e.g. 30 deg. C) is not recommended

  2. 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.

  3. 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.

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

    Science.gov (United States)

    Dhyani, Vaibhav; Kumar, Jitendra; Bhaskar, Thallada

    2017-12-01

    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.

  5. Effect of urea additive on the thermal decomposition kinetics of flame retardant greige cotton nonwoven fabric

    Science.gov (United States)

    Sunghyun Nam; Brian D. Condon; Robert H. White; Qi Zhao; Fei Yao; Michael Santiago Cintrón

    2012-01-01

    Urea is well known to have a synergistic action with phosphorus-based flame retardants (FRs) in enhancing the FR performance of cellulosic materials, but the effect of urea on the thermal decomposition kinetics has not been thoroughly studied. In this study, the activation energy (Ea) for the thermal decomposition of greige...

  6. 3.6. The kinetics of sulfuric acid decomposition of calcined concentrate of borosilicate ore

    International Nuclear Information System (INIS)

    Mirsaidov, U.M.; Kurbonov, A.S.; Mamatov, E.D.

    2015-01-01

    Present article is devoted to kinetics of sulfuric acid decomposition of calcined concentrate of borosilicate ore. The experimental data of kinetics of extraction of boron oxide from danburite at sulfuric acid decomposition were obtained at 20-90 deg C temperature range and process duration 15-90 minutes. The flowsheet of obtaining of boric acid from borosilicate ores of Ak-Arkhar Deposit by sulfuric acid method was proposed.

  7. Influence of ammonium nitrate on kinetics and mechanism of thermal decomposition of ammonium polyuranates

    International Nuclear Information System (INIS)

    Karelin, A.I.; Lobas, O.P.; Zhiganov, A.N.; Vasil'ev, K.F.; Zhiganova, A.A.

    1988-01-01

    The influence of ammonium nitrate on the mechanism and kinetics of dehydration and thermal decomposition of ammonium polyuranates was studied. An appreciable influence of the nitrate ion content in the samples of ammonium polyuranates on the development of thermal stability has been noted. The kinetic parameters of the thermal decomposition of ammonium polyuranates have been evaluated. A mechanism of the dehydration and thermal decomposition of ammonium polyuranates in the presence of ammonium nitrate has been proposed. It was shown that increase in the content of ammonium nitrate in the precipitate of ammonium polyuranates leads to a decrease in the specific surface of uranoso-uranic oxide

  8. Investigation of ammonium nitrate effect on kinetics and mechanism of thermal decomposition of ammonium polyuranates

    International Nuclear Information System (INIS)

    Karelin, A.I.; Lobas, O.P.; Zhiganov, A.N.; Vasil'ev, K.F.; Zhiganova, A.A.

    1987-01-01

    A study was made on ammonium nitrate effect on the mechanism and kinetics of dehydration and thermal decomposition of ammonium polyuranates. Sufficient effect of nitrate ion content in ammonium polyuranate samples on their thermal stability was noted. Kinetic parameters of thermal decomposition of ammonium polyuranates were evaluated. Mechanism of dehydration and thermal decomposition of ammonium polyuranates in the presence of ammonium nitrate was suggested. It was shown that increase of ammonium nitrate content in ammonium polyuranate precipitate resulted to reduction of the specific surface of prepared uranium mixed oxide

  9. Optimization and kinetics decomposition of monazite using NaOH

    International Nuclear Information System (INIS)

    MV Purwani; Suyanti; Deddy Husnurrofiq

    2015-01-01

    Decomposition of monazite with NaOH has been done. Decomposition performed at high temperature on furnace. The parameters studied were the comparison NaOH / monazite, temperature and time decomposition. From the research decomposition for 100 grams of monazite with NaOH, it can be concluded that the greater the ratio of NaOH / monazite, the greater the conversion. In the temperature influences decomposition 400 - 700°C, the greater the reaction rate constant with increasing temperature greater decomposition. Comparison NaOH / monazite optimum was 1.5 and the optimum time of 3 hours. Relations ratio NaOH / monazite with conversion (x) following the polynomial equation y = 0.1579x 2 – 0.2855x + 0.8301 (y = conversion and x = ratio of NaOH/monazite). Decomposition reaction of monazite with NaOH was second orde reaction, the relationship between temperature (T) with a reaction rate constant (k), k = 6.106.e - 1006.8 /T or ln k = - 1006.8/T + 6.106, frequency factor A = 448.541, activation energy E = 8.371 kJ/mol. (author)

  10. Kinetic analysis of the thermal decomposition of Li4Ti5O12 pellets

    Directory of Open Access Journals (Sweden)

    Hugo A. Mosqueda

    2011-12-01

    Full Text Available A single dynamic kinetic analysis, describing the surface decomposition of Li4Ti5O12 pellets, has been performed. Samples were analyzed by X-ray diffraction and scanning electron microscopy. The analyses were performed between 1000 and 1100°C and different times, perceiving the Li4Ti5O12 decomposition to Li2Ti3O7, with a loss of lithium. As expected, more rapid decomposition behaviour was found at higher temperatures. Finally, the activation energy for this decomposition of Li4Ti5O12 to Li2Ti3O7 was estimated to be equal to 383 kJ/mol.

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

    KAUST Repository

    Alabbad, Mohammed

    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.

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

    KAUST Repository

    Alabbad, Mohammed; Giri, Binod; Szőri, Milan; Viskolcz, Bé la; Farooq, Aamir

    2017-01-01

    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.

  13. 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.

  14. 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.

  15. Tensor renormalization group with randomized singular value decomposition

    Science.gov (United States)

    Morita, Satoshi; Igarashi, Ryo; Zhao, Hui-Hai; Kawashima, Naoki

    2018-03-01

    An algorithm of the tensor renormalization group is proposed based on a randomized algorithm for singular value decomposition. Our algorithm is applicable to a broad range of two-dimensional classical models. In the case of a square lattice, its computational complexity and memory usage are proportional to the fifth and the third power of the bond dimension, respectively, whereas those of the conventional implementation are of the sixth and the fourth power. The oversampling parameter larger than the bond dimension is sufficient to reproduce the same result as full singular value decomposition even at the critical point of the two-dimensional Ising model.

  16. 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

  17. Kinetics of Roasting Decomposition of the Rare Earth Elements by CaO and Coal

    Directory of Open Access Journals (Sweden)

    Shuai Yuan

    2017-06-01

    Full Text Available The roasting method of magnetic tailing mixed with CaO and coal was used to recycle the rare earth elements (REE in magnetic tailing. The phase transformation and decomposition process were researched during the roasting processes. The results showed that the decomposition processes of REE in magnetic tailing were divided into two steps. The first step from 380 to 431 °C mainly entailed the decomposition of bastnaesite (REFCO3. The second step from 605 to 716 °C mainly included the decomposition of monazite (REPO4. The decomposition products were primarily RE2O3, Ce0.75Nd0.25O1.875, CeO2, Ca5F(PO43, and CaF2. Adding CaO could reduce the decomposition temperature of REFCO3 and REPO4. Meanwhile, the decomposition effect of CaO on bastnaesite and monazite was significant. Besides, the effects of the roasting time, roasting temperature, and CaO addition level on the decomposition rate were studied. The optimum technological conditions were a roasting time of 60 min; roasting temperature of 750 °C; and CaO addition level of 20% (w/w. The maximum decomposition rate of REFCO3 and REPO4 was 99.87%. The roasting time and temperature were the major factors influencing the decomposition rate. The kinetics process of the decomposition of REFCO3 and REPO4 accorded with the interfacial reaction kinetics model. The reaction rate controlling steps were divided into two steps. The first step (at low temperature was controlled by a chemical reaction with an activation energy of 52.67 kJ/mol. The second step (at high temperature was controlled by diffusion with an activation energy of 8.5 kJ/mol.

  18. Kinetic mechanism of the decomposition of dimethyltin dichloride

    NARCIS (Netherlands)

    Mol, van A.M.B.; Croon, de M.H.J.M.; Spee, C.I.M.A.; Schouten, J.C.

    1999-01-01

    Results are reported of a study of the intrinsic kinetics of gas phase reactions. For this purpose a reactor system is designed in such a way that concentration and temperature variations throughout the reactor can be neglected enabling investigation of intrinsic reaction kinetics. The gas phase

  19. Model-free method for isothermal and non-isothermal decomposition kinetics analysis of PET sample

    International Nuclear Information System (INIS)

    Saha, B.; Maiti, A.K.; Ghoshal, A.K.

    2006-01-01

    Pyrolysis, one possible alternative to recover valuable products from waste plastics, has recently been the subject of renewed interest. In the present study, the isoconversion methods, i.e., Vyazovkin model-free approach is applied to study non-isothermal decomposition kinetics of waste PET samples using various temperature integral approximations such as Coats and Redfern, Gorbachev, and Agrawal and Sivasubramanian approximation and direct integration (recursive adaptive Simpson quadrature scheme) to analyze the decomposition kinetics. The results show that activation energy (E α ) is a weak but increasing function of conversion (α) in case of non-isothermal decomposition and strong and decreasing function of conversion in case of isothermal decomposition. This indicates possible existence of nucleation, nuclei growth and gas diffusion mechanism during non-isothermal pyrolysis and nucleation and gas diffusion mechanism during isothermal pyrolysis. Optimum E α dependencies on α obtained for non-isothermal data showed similar nature for all the types of temperature integral approximations

  20. 1.6. The kinetics of hydrochloric acid decomposition of argillite of Chashma-Sang Deposit

    International Nuclear Information System (INIS)

    Mirsaidov, U.M.; Mirzoev, D.Kh.; Boboev, Kh.E.

    2016-01-01

    Present article of book is devoted to kinetics of hydrochloric acid decomposition of argillite of Chashma-Sang Deposit. It was defined that with temperature increasing the extraction rate of Al_2O_3 and Fe_2O_3 increases. The dependence of extraction rate of Al_2O_3 and Fe_2O_3 on process duration at hydrochloric acid decomposition of argillite was studied. The activation energy of the process was defined.

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

    Directory of Open Access Journals (Sweden)

    Kunigk L.

    2001-01-01

    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.

  2. 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...

  3. Thermal decomposition of gaseous ammonium nitrate at low pressure: kinetic modeling of product formation and heterogeneous decomposition of nitric acid.

    Science.gov (United States)

    Park, J; Lin, M C

    2009-12-03

    The thermal decomposition of ammonium nitrate, NH(4)NO(3) (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH(4)NO(3) at 423 K was proposed to produce equal amounts of NH(3) and HNO(3), followed by the decomposition reaction of HNO(3), HNO(3) + M --> OH + NO(2) + M (where M = third-body and reactor surface). The absolute yields of N(2), N(2)O, H(2)O, and NH(3), which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH(3)-NO(2) (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO(3) itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO(3) in our kinetic modeling. The heterogeneous decomposition rate of HNO(3), HNO(3) + (B(2)O(3)/SiO(2)) --> OH + NO(2) + (B(2)O(3)/SiO(2)), was determined by varying its rate to match the modeled result to the measured concentrations of NH(3) and H(2)O; the rate could be represented by k(2b) = 7.91 x 10(7) exp(-12 600/T) s(-1), which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO(3) decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

  4. Thermal Decomposition of Gaseous Ammonium Nitrate at Low Pressure: Kinetic Modeling of Product Formation and Heterogeneous Decomposition of Nitric Acid

    Science.gov (United States)

    Park, J.; Lin, M. C.

    2009-10-01

    The thermal decomposition of ammonium nitrate, NH4NO3 (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH4NO3 at 423 K was proposed to produce equal amounts of NH3 and HNO3, followed by the decomposition reaction of HNO3, HNO3 + M → OH + NO2 + M (where M = third-body and reactor surface). The absolute yields of N2, N2O, H2O, and NH3, which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH3-NO2 (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO3 itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO3 in our kinetic modeling. The heterogeneous decomposition rate of HNO3, HNO3 + (B2O3/SiO2) → OH + NO2 + (B2O3/SiO2), was determined by varying its rate to match the modeled result to the measured concentrations of NH3 and H2O; the rate could be represented by k2b = 7.91 × 107 exp(-12 600/T) s-1, which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO3 decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

  5. Thermal decomposition kinetics of antimony oxychloride in air

    Institute of Scientific and Technical Information of China (English)

    阳卫军; 唐谟堂; 金胜明

    2002-01-01

    The DTA and XRD techniques were employed to study thermal decomposition mechanism of antimony oxychloride SbOCl in the air. The thermal decomposition reaction occurs in four steps, and the former three steps as: SbOCl(s)→Sb4O5Cl2(s)+SbCl3(g)→Sb8O11Cl2(s)+SbCl3(g)→Sb2O3(s)+SbCl3(g). The forth step is the oxidation of Sb2O3 by air, Sb2O3(s)+O2→Sb2O4(s). The activation energy and the order of the thermal decomposition reaction of antimony oxychloride in three steps presented in DTA curves were calculated according to Kinssinger methods from DTA curves. The values of activation energy and the order are respectively 91.97kJ/mol, 0.73 in the first step, 131.14kJ/mol, 0.63 in the second step and 146.94kJ/mol, 1.58 in the third step.

  6. Kinetics and mechanism of thermal processes of nonreversible decomposition of the system N2O4-NO

    International Nuclear Information System (INIS)

    Nesterenko, V.B.; Nichipor, G.V.

    1989-01-01

    Consideration is given to kinetics and mechanism of decomposition of nitrogen oxide in gaseous phase at devated pressures and temperature, decomposition of N 2 O 4 -NO system under flow conditions, as well as to kinetics and mechanism of formation of nitrons oxide. 37 refs.; 13 figs.; 13 tabs

  7. Thermal decomposition kinetics of strontium permanganate trihydrate, cadmium permanganate hexahydrate and calcium permanganate pentahydrate crystals

    International Nuclear Information System (INIS)

    Sakurai, K.R.; Schaeffer, D.A.; Herley, P.J.

    1978-01-01

    A thermogravimetric study of the kinetics of thermal nuclei formation and growth has been carried out for the dehydration and decomposition of single crystal strontium permanganate trihydrate, cadmium permanganate hexahydrate, and calcium permanganate pentahydrate. The isothermal dehydration of strontium parmanganate trihydrate occurs in two stages between 50 and 100 0 C. The dehydration kinetics suggest that the two dehydration stages are based on a single-step nucleation process followed by a growth process without nuclei overlap. The resulting activation energies are consistent with the proposed nucleation theory. For the dehydration kinetics of cadmium permanganate hexahydrate, an overlapping nucleation growth mechanism appears to be operating between 30 and 60 0 C. The results are irreproducible for the dehydration of calcium permanganate pentahydrate at 100 0 C. The thermal decomposition studies indicate that the data of the sigmoidal, isothermal fractional decomposition vs. time curves are reproducible for whole and ground crystals of each dehydrated permanganate. All of the data plots contain an induction or slow rate period, an acceleratory and a decay period. The induction period can be shortened by irradiation with 60 Co γ-rays prior to decomposition. Activation energies obtained for all three materials for the various thermal decomposition periods are found to be similar to those published previously on other alkali and alkaline-earth permanganates. (Auth.)

  8. Further insights into the kinetics of thermal decomposition during continuous cooling.

    Science.gov (United States)

    Liavitskaya, Tatsiana; Guigo, Nathanaël; Sbirrazzuoli, Nicolas; Vyazovkin, Sergey

    2017-07-26

    Following the previous work (Phys. Chem. Chem. Phys., 2016, 18, 32021), this study continues to investigate the intriguing phenomenon of thermal decomposition during continuous cooling. The phenomenon can be detected and its kinetics can be measured by means of thermogravimetric analysis (TGA). The kinetics of the thermal decomposition of ammonium nitrate (NH 4 NO 3 ), nickel oxalate (NiC 2 O 4 ), and lithium sulfate monohydrate (Li 2 SO 4 ·H 2 O) have been measured upon heating and cooling and analyzed by means of the isoconversional methodology. The results have confirmed the hypothesis that the respective kinetics should be similar for single-step processes (NH 4 NO 3 decomposition) but different for multi-step ones (NiC 2 O 4 decomposition and Li 2 SO 4 ·H 2 O dehydration). It has been discovered that the differences in the kinetics can be either quantitative or qualitative. Physical insights into the nature of the differences have been proposed.

  9. Effect of pre-heating on the thermal decomposition kinetics of cotton

    Science.gov (United States)

    The effect of pre-heating at low temperatures (160-280°C) on the thermal decomposition kinetics of scoured cotton fabrics was investigated by thermogravimetric analysis under nonisothermal conditions. Isoconversional methods were used to calculate the activation energies for the pyrolysis after one-...

  10. Kinetics of thermal decomposition of γ-irradiated and unirradiated complexes of mandelhydroxamic acid

    International Nuclear Information System (INIS)

    Hassan, R.M.; Farid, T.; El-Bellihi, A.A.

    1992-01-01

    The thermal decomposition of γ-irradiated and unirradiated complexes of mandelhydroxamic acid (HMA), Co (HMA) 2 .1/2H 2 O, Mn (HMA) 2 .2H 2 O, Ba (HMA) 2 .2H 2 O and Cd (HMA) 2 .2H 2 O have been studied thermogravimetrically (under isothermal conditions). The thermal dehydration of each complex occured in one step, while the decomposition of dehydrated complexes occured in two steps. The kinetic parameters for dehydration were computed by different models. The thermal dehydration is regulated by random nucleation A 3 for Co-, Mn-, and Cd-complexes and by phase-boundary (R 3 ) for Ba-complex. The effect of γ-irradiation on the kinetic parameters of thermal decomposition is discussed. Radiation did not modify the mechanism of the reaction but accelarated the dehydration steps in the case of Mn- and Co-complexes. (author) 7 refs.; 1 fig.; 4 tabs

  11. Kinetics study of thermal decomposition of calcium carboxylate salts

    International Nuclear Information System (INIS)

    Landoll, Michael P.; Holtzapple, Mark T.

    2013-01-01

    The MixAlco™ process ferments lignocellulosic biomass to carboxylate salts that are thermally decomposed into ketones, which are then chemically converted to a wide variety of chemicals and fuels. To perform these decompositions, suitable reaction models are necessary to properly design, scale, and optimize commercial reactors. For three salt types (calcium acetate, and two types of mixed calcium carboxylate salts), activation energy was determined using three isoconversional methods that employed TGA curves at different heating rates. For all three salt types, activation energy varied significantly with conversion. The average activation energy for calcium acetate was 556.75 kJ mol −1 , and the activation energies for the two mixed calcium carboxylate salts were 232.87, and 176.55 kJ mol −1 . In addition, three functions of conversion were employed to see which one best modeled the experimental data. The Sestak–Berggren model provides the best universal fit for all three salt types. -- Highlights: •Calcium carboxylate salts from fermentation broth thermally decompose to ketones. •Activation energy varies with conversion for all three salt types. •Sestak–Berggren model provides best fit overall for all three salt types

  12. Kinetics study of thermal decomposition of sodium carboxylate salts

    International Nuclear Information System (INIS)

    Landoll, Michael P.; Holtzapple, Mark T.

    2012-01-01

    The MixAlco™ process ferments lignocellulosic biomass to carboxylate salts that are thermally decomposed into ketones, which are then chemically converted to a wide variety of chemicals and fuels. To perform these decompositions, suitable reaction models are necessary to properly design, scale, and optimize commercial reactors. For three salt types (sodium acetate, and two types of mixed sodium carboxylate salts), activation energy was determined using three isoconversional methods that employed TGA curves at different heating rates. For all three salt types, activation energy varied significantly with conversion. The average activation energy for sodium acetate was 226.65 kJ/mol, and the activation energies for the two mixed sodium carboxylate salts were 195.61, and 218.18 kJ/mol. In addition, three functions of conversion were employed to see which one best modeled the experimental data. The Sestak-Berggren model fits all three salt types best. -- Highlights: ► Sodium carboxylate salts from fermentation broth thermally decompose to ketones. ► Activation energy varies with conversion for all three salt types. ► Sestak-Berggren model provides best fit for all three salt types.

  13. The non-isothermal kinetics of decomposition of manganese carbonate ore

    Directory of Open Access Journals (Sweden)

    Kenan Yıldız

    2012-06-01

    Full Text Available The non-isothermal kinetics of decomposition of manganese carbonate ore from Denizli – Tavas region was studied. The ore decomposed according to a serie of reaction, MnCO3 ;#8594;(400-600°C MnO2 ;#8594;(;600 Mn2O3. By using of Kissenger equation, the activation energies for the decomposition of MnCO3 to MnO2 and the transformation of MnO2 to Mn2O3 were calculated as 185,7 kJ/mol and 217,3 kJ/mol, respectively.

  14. Kinetic study of hydrogen peroxide decomposition by catalase in a flow-mix microcalorimetric system

    International Nuclear Information System (INIS)

    Fidaleo, Marcello; Lavecchia, Roberto

    2003-01-01

    The kinetics of hydrogen peroxide decomposition by the enzyme catalase was studied at pH 7.4 in the temperature range 10-30 deg. C. Experiments were performed by the LKB-2277 Thermal Activity Monitor equipped with a flow-mix cylinder. The calorimetric reaction unit was schematised as a tubular reactor operating under plug-flow conditions. A first-order kinetic expression, with respect to both the substrate and the enzyme, was used to describe the rate of hydrogen peroxide decomposition. Regression analysis of calorimetric data provided a molar reaction enthalpy of -87.55 kJ mol -1 and an activation energy of 11 kJ mol -1 . Analysis of model residuals and the normal probability plot indicated that the results obtained were statistically significant

  15. Generalized first-order kinetic model for biosolids decomposition and oxidation during hydrothermal treatment.

    Science.gov (United States)

    Shanableh, A

    2005-01-01

    The main objective of this study was to develop generalized first-order kinetic models to represent hydrothermal decomposition and oxidation of biosolids within a wide range of temperatures (200-450 degrees C). A lumping approach was used in which oxidation of the various organic ingredients was characterized by the chemical oxygen demand (COD), and decomposition was characterized by the particulate (i.e., nonfilterable) chemical oxygen demand (PCOD). Using the Arrhenius equation (k = k(o)e(-Ea/RT)), activation energy (Ea) levels were derived from 42 continuous-flow hydrothermal treatment experiments conducted at temperatures in the range of 200-450 degrees C. Using predetermined values for k(o) in the Arrhenius equation, the activation energies of the various organic ingredients were separated into 42 values for oxidation and a similar number for decomposition. The activation energy values were then classified into levels representing the relative ease at which the organic ingredients of the biosolids were oxidized or decomposed. The resulting simple first-order kinetic models adequately represented, within the experimental data range, hydrothermal decomposition of the organic particles as measured by PCOD and oxidation of the organic content as measured by COD. The modeling approach presented in the paper provide a simple and general framework suitable for assessing the relative reaction rates of the various organic ingredients of biosolids.

  16. Kinetics of methanol decomposition on Cu/ZnO/ZrO2 catalysts

    International Nuclear Information System (INIS)

    Grabowski, R.; Kozlowska, A.

    2004-01-01

    Interaction of methanol with Cu/ZnO/ZrO 2 (with different copper content) has been investigated by gravimetric and TPD methods. The TPD measurements of methanol adsorption on these catalysis show that it forms the complexes of two types. The first complex (I) decomposes at low temperature (453 K) yielding H 2 and CO 2 and second (II) decomposes at temperature (573 K) giving CO and H 2 . In the process of decomposition of the complex (I) takes part water which is adsorbed on the surface of the catalyst and the decomposition of the complex (II) occurs without participation of adsorbed water. Gravimetric measurements of methanol and that an increase of copper content leads to the changes in the kinetics of methanol adsorption and its decomposition. On the basis of gravimetric measurements a model of methanol adsorption and decomposition on Cu/ZnO/ZrO 2 catalyst has been proposed and the rate constants of methanol adsorption (k a ) and decomposition with and without participation of water (k 1 and k 2 ) have been determined. (author)

  17. Group-kinetic theory of turbulence

    Science.gov (United States)

    Tchen, C. M.

    1986-01-01

    The two phases are governed by two coupled systems of Navier-Stokes equations. The couplings are nonlinear. These equations describe the microdynamical state of turbulence, and are transformed into a master equation. By scaling, a kinetic hierarchy is generated in the form of groups, representing the spectral evolution, the diffusivity and the relaxation. The loss of memory in formulating the relaxation yields the closure. The network of sub-distributions that participates in the relaxation is simulated by a self-consistent porous medium, so that the average effect on the diffusivity is to make it approach equilibrium. The kinetic equation of turbulence is derived. The method of moments reverts it to the continuum. The equation of spectral evolution is obtained and the transport properties are calculated. In inertia turbulence, the Kolmogoroff law for weak coupling and the spectrum for the strong coupling are found. As the fluid analog, the nonlinear Schrodinger equation has a driving force in the form of emission of solitons by velocity fluctuations, and is used to describe the microdynamical state of turbulence. In order for the emission together with the modulation to participate in the transport processes, the non-homogeneous Schrodinger equation is transformed into a homogeneous master equation. By group-scaling, the master equation is decomposed into a system of transport equations, replacing the Bogoliubov system of equations of many-particle distributions. It is in the relaxation that the memory is lost when the ensemble of higher-order distributions is simulated by an effective porous medium. The closure is thus found. The kinetic equation is derived and transformed into the equation of spectral flow.

  18. Synthesis and thermal decomposition kinetics of Th(IV) complex with unsymmetrical Schiff base ligand

    International Nuclear Information System (INIS)

    Fan Yuhua; Bi Caifeng; Liu Siquan; Yang Lirong; Liu Feng; Ai Xiaokang

    2006-01-01

    A new unsymmetrical Schiff base ligand (H 2 LLi) was synthesized using L-lysine, o-vanillin and salicylaladyde. Thorium(IV) complex of this ligand [Th(H 2 L)(NO 3 )](NO 3 ) 2 x 3H 2 O have been prepared and characterized by elemental analyses, IR, UV and molar conductance. The thermal decomposition kinetics of the complex for the second stage was studied under non-isothermal condition by TG and DTG methods. The kinetic equation may be expressed as: dα/dt = A x e -E/RT x 1/2 (1-α) x [-ln(1-α)] -1 . The kinetic parameters (E, A), activation entropy ΔS ≠ and activation free-energy ΔG ≠ were also calculated. (author)

  19. 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.

  20. Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite

    International Nuclear Information System (INIS)

    Gunawan, Richard; Zhang Dongke

    2009-01-01

    The interaction between ammonium nitrate based industrial explosives and pyrite-rich minerals in mining operations can lead to the occurrence of spontaneous explosion of the explosives. In an effort to provide a scientific basis for safe applications of industrial explosives in reactive mining grounds containing pyrite, ammonium nitrate decomposition, with and without the presence of pyrite, was studied using a simultaneous Differential Scanning Calorimetry and Thermogravimetric Analyser (DSC-TGA) and a gas-sealed isothermal reactor, respectively. The activation energy and the pre-exponential factor of ammonium nitrate decomposition were determined to be 102.6 kJ mol -1 and 4.55 x 10 7 s -1 without the presence of pyrite and 101.8 kJ mol -1 and 2.57 x 10 9 s -1 with the presence of pyrite. The kinetics of ammonium nitrate decomposition was then used to calculate the critical temperatures for ammonium nitrate decomposition with and without the presence of pyrite, based on the Frank-Kamenetskii model of thermal explosion. It was shown that the presence of pyrite reduces the temperature for, and accelerates the rate of, decomposition of ammonium nitrate. It was further shown that pyrite can significantly reduce the critical temperature of ammonium nitrate decomposition, causing undesired premature detonation of the explosives. The critical temperature also decreases with increasing diameter of the blast holes charged with the explosive. The concept of using the critical temperature as indication of the thermal stability of the explosives to evaluate the risk of spontaneous explosion was verified in the gas-sealed isothermal reactor experiments.

  1. Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite.

    Science.gov (United States)

    Gunawan, Richard; Zhang, Dongke

    2009-06-15

    The interaction between ammonium nitrate based industrial explosives and pyrite-rich minerals in mining operations can lead to the occurrence of spontaneous explosion of the explosives. In an effort to provide a scientific basis for safe applications of industrial explosives in reactive mining grounds containing pyrite, ammonium nitrate decomposition, with and without the presence of pyrite, was studied using a simultaneous Differential Scanning Calorimetry and Thermogravimetric Analyser (DSC-TGA) and a gas-sealed isothermal reactor, respectively. The activation energy and the pre-exponential factor of ammonium nitrate decomposition were determined to be 102.6 kJ mol(-1) and 4.55 x 10(7)s(-1) without the presence of pyrite and 101.8 kJ mol(-1) and 2.57 x 10(9)s(-1) with the presence of pyrite. The kinetics of ammonium nitrate decomposition was then used to calculate the critical temperatures for ammonium nitrate decomposition with and without the presence of pyrite, based on the Frank-Kamenetskii model of thermal explosion. It was shown that the presence of pyrite reduces the temperature for, and accelerates the rate of, decomposition of ammonium nitrate. It was further shown that pyrite can significantly reduce the critical temperature of ammonium nitrate decomposition, causing undesired premature detonation of the explosives. The critical temperature also decreases with increasing diameter of the blast holes charged with the explosive. The concept of using the critical temperature as indication of the thermal stability of the explosives to evaluate the risk of spontaneous explosion was verified in the gas-sealed isothermal reactor experiments.

  2. 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.

  3. Fructose decomposition kinetics in organic acids-enriched high temperature liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yinghua; Lu, Xiuyang; Yuan, Lei; Liu, Xin [Department of Chemical and Biochemical Engineering, Zhejiang University, Zheda Road 38, Hangzhou 310027, Zhejiang (China)

    2009-09-15

    Biomass continues to be an important candidate as a renewable resource for energy, chemicals, and feedstock. Decomposition of biomass in high temperature liquid water is a promising technique for producing industrially important chemicals such as 5-hydroxymethylfurfural (5-HMF), furfural, levulinic acid with high efficiency. Hexose, which is the hydrolysis product of cellulose, will be one of the most important starting chemicals in the coming society that is highly dependent on biomass. Taking fructose as a model compound, its decomposition kinetics in organic acids-enriched high temperature liquid water was studied in the temperature range from 180 C to 220 C under the pressure of 10 MPa to further improve reaction rate and selectivity of the decomposition reactions. The results showed that the reaction rate is greatly enhanced with the addition of organic acids, especially formic acid. The effects of temperature, residence time, organic acids and their concentrations on the conversion of fructose and yield of 5-HMF were investigated. The evaluated apparent activation energies of fructose decomposition are 126.8 {+-} 3.3 kJ mol{sup -1} without any catalyst, 112.0 {+-} 13.7 kJ mol{sup -1} catalyzed with formic acid, and 125.6 {+-} 3.8 kJ mol{sup -1} catalyzed with acetic acid, respectively, which shows no significant difference. (author)

  4. Kinetics of thermal decomposition and kinetics of substitution reaction of nano uranyl Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Zeinali, A.; Dušek, Michal; Eigner, Václav

    2014-01-01

    Roč. 46, č. 12 (2014), s. 718-729 ISSN 0538-8066 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl * Schiff base * kinetics * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.517, year: 2014

  5. Using decomposition kinetics to model the removal of mine water pollutants in constructed wetlands

    Energy Technology Data Exchange (ETDEWEB)

    Tarutis, W J; Unz, R F [Pennsylvania State University, University Park, PA (United States)

    1994-01-01

    Although numerous mathematical models have been used to describe decomposition, few, if any, have been used to model the removal of pollutants in constructed wetlands. A steady state method based on decomposition kinetics and reaction stoichiometry has been developed which simulates the removal of ferrous iron entering wetlands constructed for mine drainage treatment. Input variables for the model include organic matter concentration, reaction rate coefficient, porosity and dry density, and hydraulic detection time. Application of the model assumes complete anaerobic conditions within the entire substrate profile, constant temperature, no additional organic matter input, and subsurface flow only. For these ideal conditions, model simulations indicate that wetlands constructed with readily decomposable substrates rich in organic carbon are initially capable of removing far greater amounts of iron than wetlands built with less biodegradable substrates. However, after three to five years of operation this difference becomes negligible. For acceptable long-term treatment performance, therefore, periodic additions of decomposable organic matter will be required.

  6. Determination of Kinetic Parameters for the Thermal Decomposition of Parthenium hysterophorus

    Directory of Open Access Journals (Sweden)

    Dhaundiyal Alok

    2018-02-01

    Full Text Available A kinetic study of pyrolysis process of Parthenium hysterophorous is carried out by using thermogravimetric analysis (TGA equipment. The present study investigates the thermal degradation and determination of the kinetic parameters such as activation E and the frequency factor A using model-free methods given by Flynn Wall and Ozawa (FWO, Kissinger-Akahira-Sonuse (KAS and Kissinger, and model-fitting (Coats Redfern. The results derived from thermal decomposition process demarcate decomposition of Parthenium hysterophorous among the three main stages, such as dehydration, active and passive pyrolysis. It is shown through DTG thermograms that the increase in the heating rate caused temperature peaks at maximum weight loss rate to shift towards higher temperature regime. The results are compared with Coats Redfern (Integral method and experimental results have shown that values of kinetic parameters obtained from model-free methods are in good agreement. Whereas the results obtained through Coats Redfern model at different heating rates are not promising, however, the diffusion models provided the good fitting with the experimental data.

  7. Mechanistic approach for the kinetics of the decomposition of nitrous oxide over calcined hydrotalcites

    Energy Technology Data Exchange (ETDEWEB)

    Dandl, H.; Emig, G. [Lehrstuhl fuer Technische Chemie I, Erlangen (Germany)

    1998-03-27

    A highly active catalyst for the decomposition of N{sub 2}O was prepared by the thermal treatment of CoLaAl-hydrotalcite. For this catalyst the reaction rate was determined at various partial pressures of N{sub 2}O, O{sub 2} and H{sub 2}O in a temperature range from 573K to 823K. The kinetic simulation resulted in a mechanistic model. The energies of activation and rate coefficients are estimated for the main steps of the reaction

  8. Kinetics of the isothermal decomposition of zirconium hydride: terminal solid solubility for precipitation and dissolution

    Science.gov (United States)

    Denisov, E. A.; Kompaniets, T. N.; Voyt, A. P.

    2018-05-01

    The hydrogen permeation technique in the surface-limited regime (SLR) was first used to study the isothermal decomposition of zirconium hydride. It is shown that under isothermal conditions, the hydrogen terminal solid solubility in the α-phase for hydride precipitation (TSSp) and dissolution (TSSd) differ only by 6%, in contrast to the 20-30% indicated in the available literature. It is demonstrated that even the minimum heating/cooling rate (1 C/min) used in the traditional methods of studying TSSp and TSSd is too high to exclude the effect of kinetics on the results obtained.

  9. Decomposition of clofibric acid in aqueous media by advance oxidation techniques: kinetics study and degradation pathway

    International Nuclear Information System (INIS)

    Syed, M.; Khan, A.M.; Khan, R.A.

    2016-01-01

    This study investigates the decomposition of clofibric acid (CLF) by different advanced oxidation processes (AOPs), such as UV (254 nm), VUV (185 nm), UV / TiO/sub 2/ and VUV / TiO/sub 2/. The removal efficiencies of applied AOPs were compared in the presence and absence of dissolved oxygen. The removal efficiency of the studied AOPs towards degradation of CLF were found in the order of VUV / TiO/sub 2/ + O/sub 2/ > VUV/TiO/sub 2/ + N/sub 2/ > VUV alone > UV / TiO/sub 2/ + O/sub 2/ > UV / TiO/sub 2/ +N/sub 2/ > UV alone. The decomposition kinetics of CLF was found to follow pseudo-first order rate law. VUV / TiO2 process was found to be most cheap and effective one for decomposition of CLF as compared to other applied AOPs in terms of electrical energy per order. Degradation products resulting from the degradation processes were also investigated using UPLC-MS /MS, accordingly degradation pathway was proposed. (author)

  10. Kinetics of irreversible thermal decomposition of dissociating nitrogen dioxide with nitrogen oxide or oxygen additions

    International Nuclear Information System (INIS)

    Gvozdev, A.A.

    1987-01-01

    The effect of NO or O 2 admixtures on kinetics of the irreversible thermal decomposition of nitrogen dioxide at temperatures 460-520 deg C and pressures 4-7 MPa has been studied. It follows from experimental data that the rate of N 2 O 4 formation reduces with the increase of partial pressure of oxygen or decrease of partial pressure of nitrogen oxide. The same regularity is seen for the rate of nitrogen formation. The rate constants of N 2 O formation in dissociating nitrogen tetroxide with oxygen or nitrogen oxide additions agree satisfactorily with previously published results, obtained in stoichiometric mixtures. The appreciable discrepancy at 520 deg C is bind with considerable degree of nitrogen oxide transformation which constitutes approximately 14%. It is determined that the kinetics of formation of the products of irreversible N 2 O and N 2 decomposition in stoichiometric and non-stoichiometric 2NO 2 ↔ 2NO+O 2 mixtures is described by identical 3NO → N 2 O+NO 2 and N 2 O+NO → N 2 +NO 2 reactions

  11. 4.2. The kinetics of nitric acid decomposition of calcined borosilicate raw material of Ak-Arkhar Deposit

    International Nuclear Information System (INIS)

    Mirsaidov, U.M.; Kurbonov, A.S.; Mamatov, E.D.

    2015-01-01

    Present article is devoted to kinetics of nitric acid decomposition of calcined borosilicate raw material of Ak-Arkhar Deposit. The dependence of nitric acid decomposition of calcined boric raw material for extraction of boron oxide on temperature (20-100 deg C) and process duration (15-60 minutes) was defined. It was defined that at temperature increasing the extraction rate of boron oxide increases from 20.8 to 78.6%.

  12. 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...

  13. Determination of kinetic parameters during the thermal decomposition of epoxy/carbon fiber composite material

    International Nuclear Information System (INIS)

    Lee, Jae Hun; Kim, Kwang Seok; Kim, Hyo

    2013-01-01

    An in-depth study to determine the thermal decomposition kinetics parameters such as the activation energy E_a, the reaction order n, and the pre-exponential factor A of epoxy/carbon fiber composite material has been conducted. We employ not only the modified peak property method that is proposed here, but also the conventional method in analyzing the experimental data, and compare the results to show the performance of the proposed model. The pyrolysis tests for the epoxy/carbon fiber composite materials are conducted by using thermogravimetric analyser at various heating rates. As a result, the best prediction to the experimental data can be obtained by the modified peak property method. Besides, among the methods applied here, the modified peak property method provides most convenient way to recover the parameters: it does not require a curve fitting of the data nor a long iterative computation

  14. 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%.

  15. Pyrolytic and kinetic characteristics of the thermal decomposition of Perilla frutescens polysaccharide.

    Directory of Open Access Journals (Sweden)

    Quancheng Zhou

    Full Text Available The thermal decomposition of Perilla frutescens polysaccharide was examined by thermogravimetry, differential thermogravimetry, and differential thermal analysis. The results showed that the mass loss of the substance proceeded in three steps. The first stage can be attributed to the expulsion of the water from ambient temperature to 182°C. The second stage corresponded to devolatilization from 182°C to 439°C. The residue slowly degraded in the third stage. The weight loss in air is faster than that in nitrogen, because the oxygen in air accelerated the pyrolytic reaction speed reaction. The heating rate significantly affected the pyrolysis of the sample. Similar activation energies of the degradation process (210-211 kJ mol⁻¹ were obtained by the FWO, KAS, and Popescu techniques. According to Popescu mechanism functions, the possible kinetic model was estimated to be Avrami-Erofeev 20 g(α = [-ln(1-α]⁴.

  16. Thermodynamics and kinetics of thermal decomposition of dibutylalkyl and dipentylalkyl phosphonate-nitric acid systems

    International Nuclear Information System (INIS)

    Chandran, K.; Brahmananda, C.V.S.; Anthonysamy, S.; Srinivasan, T.G.; Ganesan, V.

    2013-01-01

    Tributyl phosphate (TBP) is used in the reprocessing industry for the separation of uranium and plutonium from the spent nuclear fuels by PUREX process. A variety of dialkylalky/phosphonates were synthesised and their extraction behaviour on actinides was studied in this laboratory. The superior extraction characteristics of phosphonates make them useful for several metal recovery applications in the nuclear fuel cycle. However, higher solubility of phosphonates in aqueous phase as compared to TBP, introduces higher chances of the formation of thermally active 'red oil' like substances during the evaporation of aqueous streams. Thermal stability of neat and nitric acid solvated homologues of four dibutylalkyl phosphonates namely, dibutylpropyl phosphonate (DBPrP), dibutylbutyl phosphonate (DBBP), dibutylpentyl phosphonate (DBPP), dibutylhexyl phosphonate (DBHeP), and two dipentylalkyl phosphonates viz. dipentylbutyl phosphonate (DPBP), dipentylhexyl phosphonate (DPHeP) were studied. Experiments were conducted using an adiabatic calorimeter in heat-wait-search mode. Various stoichiometry of nitric acid-solvated DBalP and DPalP were prepared by equilibrating the respective organic with 4-15.6 M nitric acid followed by separation. Neat DBalP and DPalP are stable up to the temperature of ∼ 555 K while their acid-solvates decomposed in the temperature range 380-403 K. The results also indicated that the presence of nitric acid accelerated the decomposition of phosphonates. Decomposition of these acid solvated phosphonates is found to be exothermic and follows first order kinetics. The onset temperature, adiabatic temperature rise, pressure rise, decomposition enthalpy and activation energy were found to strongly depend on the nitric acid content of the acid-solvates. The studies also indicate that dibutylalkyl and dipentylalkyl phosphonates are also prone to form 'red oil' like substances under extreme conditions and can lead to run-away reactions

  17. Thermogravimetric and kinetic analysis of thermal decomposition characteristics of low-lipid microalgae.

    Science.gov (United States)

    Gai, Chao; Zhang, Yuanhui; Chen, Wan-Ting; Zhang, Peng; Dong, Yuping

    2013-12-01

    The thermal decomposition behavior of two microalgae, Chlorella pyrenoidosa (CP) and Spirulina platensis (SP), were investigated on a thermogravimetric analyzer under non-isothermal conditions. Iso-conversional Vyazovkin approach was used to calculate the kinetic parameters, and the universal integral method was applied to evaluate the most probable mechanisms for thermal degradation of the two feedstocks. The differential equations deduced from the models were compared with experimental data. For the range of conversion fraction investigated (20-80%), the thermal decomposition process of CP could be described by the reaction order model (F3), which can be calculated by the integral equation of G(α) = [(1 - α)(-2) - 1]/2. And the apparent activation energy was in the range of 58.85-114.5 kJ/mol. As for SP, it can be described by the reaction order model (F2), which can be calculated by the integral equation of G(α) = (1 - α)(-1) - 1, and the range of apparent activation energy was 74.35-140.1 kJ/mol. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Lipid oxidation. Part. 1. Effect of free carboxyl group on the decomposition of lipid hydroperoxide.

    Science.gov (United States)

    Pokorný, J; Rzepa, J; Janícek, G

    1976-01-01

    Hydroperoxido butyl oleate was decomposed by heating in excess palmitic acid at 60-120 degrees C. The decomposition followed the kinetics of a first order reaction with formation of both monomeric and oligomeric secondary products. The proportions of oligomers slightly increased with increasing reaction temperature and decreased with increasing concentration of hydroperoxide. The activation energy was 70.4 kJ/mol +/- 4.7 kJ/mol. The decomposition of hydroperoxides proceeded partially by monomolecular cleavage, partially by formation of esters with palmitic acid.

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

    Czech Academy of Sciences Publication Activity Database

    Asadi, M.; Asadi, Z.; Savaripoor, N.; Dušek, Michal; Eigner, Václav; Shorkaei, M.R.; Sedaghat, M.

    2015-01-01

    Roč. 136, Feb (2015), 625-634 ISSN 1386-1425 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : Oxovanadium(IV) complexes * Schiff base * Kinetic s of thermal decomposition * Electrochemistry Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.653, year: 2015

  20. Evidence for a kinetic bias towards antisite formation in SiC nano-decomposition

    International Nuclear Information System (INIS)

    Roma, G.; Crocombette, J.-P.

    2010-01-01

    This paper is devoted to the investigation of the mechanisms of Frenkel pair recombination in cubic silicon carbide. We use first principles calculations in the framework of Density Functional Theory (DFT) and we explore a variety of possible recombination paths using constrained relaxations and the Nudged-Elastic-Band (NEB) method for various possible neutral Frenkel pairs, including those formed by defects on different sublattices (carbon and silicon). We detect several metastable configurations, some of which have not been described previously. We also consider that silicon vacancies can assume the form of carbon antisite-carbon vacancy complexes and, as such, their recombination with interstitials can occur along specific paths. In particular, in this case, we find that the recombination with silicon interstitials would probably produce antisite pairs. Finally, we use our calculated recombination barriers for a simplified kinetic model which shows that, under certain hypotheses, the annealing of irradiation defects can lead to the build up of a non negligible concentration of antisites, i.e., to a nanoscale decomposition of the material driven by a kinetic bias.

  1. KINETIC STUDY FOR THE THERMAL DECOMPOSITION OF HEMICELLULOSE ISOLATED FROM CORN STALK

    Directory of Open Access Journals (Sweden)

    Gao-Jin Lv

    2010-04-01

    Full Text Available In order to study the thermal decomposition characteristics of hemicellulose, a highly efficient procedure was carried out to extract hemicellulose from corn stalk. Several different sugar units were observed by 13C NMR spectra to show the presence and species of hemicellulose. Following isolation of the hemicellulose, experimental research on its thermal behavior were carried out with a thermogravimetric analyzer under inert atmosphere at heating rates ranging from 10 to 50°C/min, and the kinetic parameters were calculated by the Kissinger and Ozawa methods, respectively. It was found that the thermal degradation of hemicellulose mainly occurred in the temperature range 180-340°C with a final residue yield of 24% at 700°C. An increase of the heating rate could slightly increase both the temperatures at which the peak weight loss rate was observed and the maximum value of weight loss rate. The activation energy (E and the pre-exponential factor (lnA obtained by the Kissinger and Ozawa methods were 213.3kJ mol-1, 211.6kJ mol-1 and 46.2min-1, 45.9min-1, respectively. Even though the data showed little difference, the fitting degree of the Ozawa method was better than that of the Kissinger method. The experimental results and kinetic parameters may provide useful data for effective design and improvement of thermochemical conversion units.

  2. Effect of Copper Oxide, Titanium Dioxide, and Lithium Fluoride on the Thermal Behavior and Decomposition Kinetics of Ammonium Nitrate

    Science.gov (United States)

    Vargeese, Anuj A.; Mija, S. J.; Muralidharan, Krishnamurthi

    2014-07-01

    Ammonium nitrate (AN) is crystallized along with copper oxide, titanium dioxide, and lithium fluoride. Thermal kinetic constants for the decomposition reaction of the samples were calculated by model-free (Friedman's differential and Vyzovkins nonlinear integral) and model-fitting (Coats-Redfern) methods. To determine the decomposition mechanisms, 12 solid-state mechanisms were tested using the Coats-Redfern method. The results of the Coats-Redfern method show that the decomposition mechanism for all samples is the contracting cylinder mechanism. The phase behavior of the obtained samples was evaluated by differential scanning calorimetry (DSC), and structural properties were determined by X-ray powder diffraction (XRPD). The results indicate that copper oxide modifies the phase transition behavior and can catalyze AN decomposition, whereas LiF inhibits AN decomposition, and TiO2 shows no influence on the rate of decomposition. Possible explanations for these results are discussed. Supplementary materials are available for this article. Go to the publisher's online edition of the Journal of Energetic Materials to view the free supplemental file.

  3. Classification Formula and Generation Algorithm of Cycle Decomposition Expression for Dihedral Groups

    Directory of Open Access Journals (Sweden)

    Dakun Zhang

    2013-01-01

    Full Text Available The necessary of classification research on common formula of group (dihedral group cycle decomposition expression is illustrated. It includes the reflection and rotation conversion, which derived six common formulae on cycle decomposition expressions of group; it designed the generation algorithm on the cycle decomposition expressions of group, which is based on the method of replacement conversion and the classification formula; algorithm analysis and the results of the process show that the generation algorithm which is based on the classification formula is outperformed by the general algorithm which is based on replacement conversion; it has great significance to solve the enumeration of the necklace combinational scheme, especially the structural problems of combinational scheme, by using group theory and computer.

  4. 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.

  5. On the exact solution for the multi-group kinetic neutron diffusion equation in a rectangle

    International Nuclear Information System (INIS)

    Petersen, C.Z.; Vilhena, M.T.M.B. de; Bodmann, B.E.J.

    2011-01-01

    In this work we consider the two-group bi-dimensional kinetic neutron diffusion equation. The solution procedure formalism is general with respect to the number of energy groups, neutron precursor families and regions with different chemical compositions. The fast and thermal flux and the delayed neutron precursor yields are expanded in a truncated double series in terms of eigenfunctions that, upon insertion into the kinetic equation and upon taking moments, results in a first order linear differential matrix equation with source terms. We split the matrix appearing in the transformed problem into a sum of a diagonal matrix plus the matrix containing the remaining terms and recast the transformed problem into a form that can be solved in the spirit of Adomian's recursive decomposition formalism. Convergence of the solution is guaranteed by the Cardinal Interpolation Theorem. We give numerical simulations and comparisons with available results in the literature. (author)

  6. Kinetics of thermal decomposition of ammonium perchlorate with nanocrystals of binary transition metal ferrites

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Gurdip; Kapoor, Inder Pal Singh; Dubey, Shalini [Department of Chemistry, D. D. U. Gorakhpur University, Gorakhpur (India); Siril, Prem Felix [Laboratoire de Chimie Physique (LCP), Universite de Paris Sud, Orsay (France)

    2009-02-15

    Binary transition metal ferrite (BTMF) nanocrystals of formula MFe{sub 2}O{sub 4}(M=Cu,Co,Ni) were prepared by the coprecipitation method and characterized by X-ray diffraction (XRD). XRD patterns gave average particle size by using Scherrer's equation for CuFe{sub 2}O{sub 4}(CuF), CoFe{sub 2}O{sub 4}(CoF), and NiFe{sub 2}O{sub 4} (NiF) as 39.9, 27.3, and 43.8 nm, respectively. The catalytic activity measurements on the thermal decomposition of ammonium perchlorate (AP) were carried out by using thermogravimetry (TG), differential thermal analysis (DTA), and ignition delay studies. Isothermal TG data up to a mass loss of 45% have been used to evaluate kinetic parameters by using model fitting as well as isoconversional method. The order of catalytic activity was found to be: CoFe{sub 2}O{sub 4}>NiFe{sub 2}O{sub 4}. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  7. 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.

  8. Effect of composting on the thermal decomposition behavior and kinetic parameters of pig manure-derived solid waste.

    Science.gov (United States)

    Dhyani, Vaibhav; Kumar Awasthi, Mukesh; Wang, Quan; Kumar, Jitendra; Ren, Xiuna; Zhao, Junchao; Chen, Hongyu; Wang, Meijing; Bhaskar, Thallada; Zhang, Zengqiang

    2018-03-01

    In this work, the influence of composting on the thermal decomposition behavior and decomposition kinetics of pig manure-derived solid wastes was analyzed using thermogravimetry. Wheat straw, biochar, zeolite, and wood vinegar were added to pig manure during composting. The composting was done in the 130 L PVC reactors with 100 L effective volume for 50 days. The activation energy of pyrolysis of samples before and after composting was calculated using Friedman's method, while the pre-exponential factor was calculated using Kissinger's equation. It was observed that composting decreased the volatile content of all the samples. The additives when added together in pig manure lead to a reduction in the activation energy of decomposition, advocating the presence of simpler compounds in the compost material in comparison with the complex feedstock. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Study of the decomposition of phase stabilized ammonium nitrate (PSAN) by simultaneous thermal analysis: determination of kinetic parameters

    OpenAIRE

    Simões, P. N.; Pedroso, L. M.; Portugal, A. A.; Campos, J. L.

    1998-01-01

    Ammonium nitrate (AN) has been extensively used both in explosive and propellant formulations. Unlike AN, there is a lack of information about the thermal decomposition and related kinetic analysis of phase stabilized ammonium nitrate (PSAN). Simultaneous thermal analysis (DSC-TG) has been used in the thermal characterisation of a specific type of PSAN containing 1.0% of NiO (stabilizing agent) and 0.5% of Petro (anti-caking agent) as additives. Repeated runs covering the nominal heating rate...

  10. Study of decomposition kinetics of volatile β-diketonates of yttrium, barium and copper in flow reactor

    International Nuclear Information System (INIS)

    Devyatykh, G.G.; Gavrishchuk, E.M.; Gibin, A.M.; Dadanov, A.Yu.; Dzyubenko, N.G.; Kaul', A.R.; Nichiporuk, R.V.; Snezhko, N.T.; Ul'yanov, A.A.

    1990-01-01

    Heterogeneous oxidative decomposition of adduct of yttrium acetylacetonate with o-phenanthroline, copper acetylacetonate and barium dipivaloylmethanate in a flow-type reactor was carried out. The basic kinetic characteristics of chemical precipitation processes of films of yttrium, copper and barium oxides, which are components of high-temperature superconductors, were obtained. The values of activation energy of precipitation process of yttrium, copper and barium oxides constituted 76±10, 108±15, 81±12 (t 600 deg C) respectively

  11. Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

    International Nuclear Information System (INIS)

    Faradzhev, N.S.; Perry, C.C.; Kusmierek, D.O.; Fairbrother, D.H.; Madey, T.E.

    2004-01-01

    The kinetics of decomposition and subsequent chemistry of adsorbed CF 2 Cl 2 , activated by low-energy electron irradiation, have been examined and compared with CCl 4 . These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF 2 Cl 2 and CCl 4 dissociation increase in an H 2 O (D 2 O) environment (2-3x), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H 2 O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2x10 -15 cm 2 for CF 2 Cl 2 and 2.5±0.2x10 -15 cm 2 for CCl 4 . RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl - and F - anions in the halocarbon/water films and production of H 3 O + , CO 2 , and intermediate compounds COF 2 (for CF 2 Cl 2 ) and COCl 2 , C 2 Cl 4 (for CCl 4 ) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation

  12. Mechanism and kinetics of thermal decomposition of ammoniacal complex of copper oxalate

    International Nuclear Information System (INIS)

    Prasad, R.

    2003-01-01

    A complex precursor has been synthesized by dissolving copper oxalate in liquor ammonia followed by drying. The thermal decomposition of the precursor has been studied in different atmospheres, air/nitrogen. The mechanism of decomposition of the precursor in air is not as simple one as in nitrogen. In nitrogen, it involves endothermic deammoniation followed by decomposition to finely divided elemental particles of copper. Whereas in air, decomposition and simultaneous oxidation of the residual products (oxidative decomposition), make the process complex and relatively bigger particle of cupric oxide are obtained as final product. The products of decomposition in different atmospheres have been characterized by X-ray diffraction and particle size analysis. The stoichiometric formula, Cu(NH 3 ) 2 C 2 O 4 of the precursor is established from elemental analysis and TG measurements, and it is designated as copper amino oxalate (CAO). In nitrogen atmosphere, the deammoniation and decomposition have been found to be zero and first order, respectively. The values of activation energy have been found to be 102.52 and 95.38 kJ/mol for deammoniation and decomposition, respectively

  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. Differential contribution of soil biota groups to plant litter decomposition as mediated by soil use

    Science.gov (United States)

    Falco, Liliana B.; Sandler, Rosana V.; Coviella, Carlos E.

    2015-01-01

    Plant decomposition is dependant on the activity of the soil biota and its interactions with climate, soil properties, and plant residue inputs. This work assessed the roles of different groups of the soil biota on litter decomposition, and the way they are modulated by soil use. Litterbags of different mesh sizes for the selective exclusion of soil fauna by size (macro, meso, and microfauna) were filled with standardized dried leaves and placed on the same soil under different use intensities: naturalized grasslands, recent agriculture, and intensive agriculture fields. During five months, litterbags of each mesh size were collected once a month per system with five replicates. The remaining mass was measured and decomposition rates calculated. Differences were found for the different biota groups, and they were dependant on soil use. Within systems, the results show that in the naturalized grasslands, the macrofauna had the highest contribution to decomposition. In the recent agricultural system it was the combined activity of the macro- and mesofauna, and in the intensive agricultural use it was the mesofauna activity. These results underscore the relative importance and activity of the different groups of the edaphic biota and the effects of different soil uses on soil biota activity. PMID:25780777

  15. Differential contribution of soil biota groups to plant litter decomposition as mediated by soil use

    Directory of Open Access Journals (Sweden)

    Ricardo A. Castro-Huerta

    2015-03-01

    Full Text Available Plant decomposition is dependant on the activity of the soil biota and its interactions with climate, soil properties, and plant residue inputs. This work assessed the roles of different groups of the soil biota on litter decomposition, and the way they are modulated by soil use. Litterbags of different mesh sizes for the selective exclusion of soil fauna by size (macro, meso, and microfauna were filled with standardized dried leaves and placed on the same soil under different use intensities: naturalized grasslands, recent agriculture, and intensive agriculture fields. During five months, litterbags of each mesh size were collected once a month per system with five replicates. The remaining mass was measured and decomposition rates calculated. Differences were found for the different biota groups, and they were dependant on soil use. Within systems, the results show that in the naturalized grasslands, the macrofauna had the highest contribution to decomposition. In the recent agricultural system it was the combined activity of the macro- and mesofauna, and in the intensive agricultural use it was the mesofauna activity. These results underscore the relative importance and activity of the different groups of the edaphic biota and the effects of different soil uses on soil biota activity.

  16. 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.

  17. 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.

  18. A group-kinetic theory of turbulent collective collisions

    International Nuclear Information System (INIS)

    Tchen, C.M.; Misguich, J.H.

    1983-05-01

    The main objective is the derivation of the kinetic equation of turbulence which has a memory in the turbulent collision integral. We consider the basic pair-interaction, and the interaction between a fluctuation and the organized cluster of other fluctuations in the collection systems, called the multiple interaction. By a group-scaling procedure, a fluctuation is decomposed into three groups to represent the three coupled transport processes of evolution, transport coefficient, and relaxation. The kinetic equation of the scaled singlet distribution is capable of investigating the spectrum of turbulence without the need of the knowledge of the pair distribution. The exact propagator describes the detailed trajectory in the phase space, and is fundamental to the Lagrangian-Eulerian transformation. We calculate the propagator and its scaled groups by means of a probability of retrograde transition. Thus our derivation of the kinetic equation of the distribution involves a parallel development of the kinetic equations of the propagator and the transition probability. In this way, we can avoid the assumptions of independence and normality. Our result shows that the multiple interaction contributes to a shielding and an enchancement of the collision in weak turbulence and strong turbulence, respectively. The weak turbulence is dominated by the wave resonance, and the strong turbulence is dominated by the diffusion

  19. 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.)

  20. Combined TGA-MS kinetic analysis of multistep processes. Thermal decomposition and ceramification of polysilazane and polysiloxane preceramic polymers.

    Science.gov (United States)

    García-Garrido, C; Sánchez-Jiménez, P E; Pérez-Maqueda, L A; Perejón, A; Criado, José M

    2016-10-26

    The polymer-to-ceramic transformation kinetics of two widely employed ceramic precursors, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (TTCS) and polyureamethylvinylsilazane (CERASET), have been investigated using coupled thermogravimetry and mass spectrometry (TG-MS), Raman, XRD and FTIR. The thermally induced decomposition of the pre-ceramic polymer is the critical step in the synthesis of polymer derived ceramics (PDCs) and accurate kinetic modeling is key to attaining a complete understanding of the underlying process and to attempt any behavior predictions. However, obtaining a precise kinetic description of processes of such complexity, consisting of several largely overlapping physico-chemical processes comprising the cleavage of the starting polymeric network and the release of organic moieties, is extremely difficult. Here, by using the evolved gases detected by MS as a guide it has been possible to determine the number of steps that compose the overall process, which was subsequently resolved using a semiempirical deconvolution method based on the Frasier-Suzuki function. Such a function is more appropriate that the more usual Gaussian or Lorentzian functions since it takes into account the intrinsic asymmetry of kinetic curves. Then, the kinetic parameters of each constituent step were independently determined using both model-free and model-fitting procedures, and it was found that the processes obey mostly diffusion models which can be attributed to the diffusion of the released gases through the solid matrix. The validity of the obtained kinetic parameters was tested not only by the successful reconstruction of the original experimental curves, but also by predicting the kinetic curves of the overall processes yielded by different thermal schedules and by a mixed TTCS-CERASET precursor.

  1. Hybrid subgroup decomposition method for solving fine-group eigenvalue transport problems

    International Nuclear Information System (INIS)

    Yasseri, Saam; Rahnema, Farzad

    2014-01-01

    Highlights: • An acceleration technique for solving fine-group eigenvalue transport problems. • Coarse-group quasi transport theory to solve coarse-group eigenvalue transport problems. • Consistent and inconsistent formulations for coarse-group quasi transport theory. • Computational efficiency amplified by a factor of 2 using hybrid SGD for 1D BWR problem. - Abstract: In this paper, a new hybrid method for solving fine-group eigenvalue transport problems is developed. This method extends the subgroup decomposition method to efficiently couple a new coarse-group quasi transport theory with a set of fixed-source transport decomposition sweeps to obtain the fine-group transport solution. The advantages of the quasi transport theory are its high accuracy, straight-forward implementation and numerical stability. The hybrid method is analyzed for a 1D benchmark problem characteristic of boiling water reactors (BWR). It is shown that the method reproduces the fine-group transport solution with high accuracy while increasing the computational efficiency up to 12 times compared to direct fine-group transport calculations

  2. A Raman spectroscopic determination of the kinetics of decomposition of ammonium chromate (NH 4) 2CrO 4

    Science.gov (United States)

    De Waal, D.; Heyns, A. M.; Range, K.-J.

    1989-06-01

    Raman spectroscopy was used as a method in the kinetic investigation of the thermal decomposition of solid (NH 4) 2CrO 4. Time-dependent measurements of the intensity of the totally symmetric stretching CrO mode of (NH 4) 2CrO 4 have been made between 343 and 363 K. A short initial acceleratory period is observed at lower temperatures and the decomposition reaction decelerates after the maximum decomposition rate has been reached at all temperatures. These results can be interpreted in terms of the Avrami-Erofe'ev law 1 - (χ r) {1}/{2} = kt , where χr is the fraction of reactant at time t. At 358 K, k is equal to 1.76 ± 0.01 × 10 -3 sec -1 for microcrystals and for powdered samples. Activation energies of 97 ± 10 and 49 ± 0.9 kJ mole -1 have been calculated for microcrystalline and powdered samples, respectively.

  3. The reductive decomposition of calcium sulphate I. Kinetics of the apparent solid-solid reaction

    NARCIS (Netherlands)

    Kamphuis, B.; Potma, A.W.; Prins, W.; van Swaaij, Willibrordus Petrus Maria

    1992-01-01

    The reductive decomposition of calcium sulphate by hydrogen is used for the regeneration of calcium-based atmospheric fluidized bed combustion (AFBC) SO2 sorbents. The apparent solid¿solid reaction between CaS and CaSO4, one of the steps involved in the reaction mechanism of the reductive

  4. Kinetic parameters for the thermal decomposition reactions of mixed oxides of selenium and tellurium

    International Nuclear Information System (INIS)

    Jerez, A.; Castro, A.; Pico, C.; Veiga, M.L.

    1982-01-01

    A comparative study of the thermal decomposition processes of Te 3 SeO 8 and TeSeO 4 has been carried out based on the results obtained directly by a Mettler TA 3000 apparatus and from calculations using other differential and integral methods. (orig.)

  5. 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...

  6. 2.4. The kinetics of hydrochloric-acid decomposition of calcined concentrate of boron raw material of Ak-Arkhar Deposit

    International Nuclear Information System (INIS)

    Mirsaidov, U.M.; Kurbonov, A.S.; Mamatov, E.D.

    2015-01-01

    Present article is devoted to kinetics of hydrochloric-acid decomposition of calcined concentrate of boron raw material of Ak-Arkhar Deposit. The experimental data of dependence of hydrochloric-acid decomposition of calcined boron raw material for boron oxide extraction on temperature (20-80 deg C) and process duration (15-60 min) were considered. It was defined that at temperature increasing the boron oxide extraction from borosilicate raw material increases from 24.1 till 86.8%. The constants of decomposition rate of boron raw material were calculated.

  7. Comparative evaluation of thermal oxidative decomposition for oil-plant residues via thermogravimetric analysis: Thermal conversion characteristics, kinetics, and thermodynamics.

    Science.gov (United States)

    Chen, Jianbiao; Wang, Yanhong; Lang, Xuemei; Ren, Xiu'e; Fan, Shuanshi

    2017-11-01

    Thermal oxidative decomposition characteristics, kinetics, and thermodynamics of rape straw (RS), rapeseed meal (RM), camellia seed shell (CS), and camellia seed meal (CM) were evaluated via thermogravimetric analysis (TGA). TG-DTG-DSC curves demonstrated that the combustion of oil-plant residues proceeded in three stages, including dehydration, release and combustion of organic volatiles, and chars oxidation. As revealed by combustion characteristic parameters, the ignition, burnout, and comprehensive combustion performance of residues were quite distinct from each other, and were improved by increasing heating rate. The kinetic parameters were determined by Coats-Redfern approach. The results showed that the most possible combustion mechanisms were order reaction models. The existence of kinetic compensation effect was clearly observed. The thermodynamic parameters (ΔH, ΔG, ΔS) at peak temperatures were calculated through the activated complex theory. With the combustion proceeding, the variation trends of ΔH, ΔG, and ΔS for RS (RM) similar to those for CS (CM). Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. NOx Direct Decomposition: Potentially Enhanced Thermodynamics and Kinetics on Chemically Modified Ferroelectric Surfaces

    Science.gov (United States)

    Kakekhani, Arvin; Ismail-Beigi, Sohrab

    2014-03-01

    NOx are regulated pollutants produced during automotive combustion. As part of an effort to design catalysts for NOx decomposition that operate in oxygen rich environment and permit greater fuel efficiency, we study chemistry of NOx on (001) ferroelectric surfaces. Changing the polarization at such surfaces modifies electronic properties and leads to switchable surface chemistry. Using first principles theory, our previous work has shown that addition of catalytic RuO2 monolayer on ferroelectric PbTiO3 surface makes direct decomposition of NO thermodynamically favorable for one polarization. Furthermore, the usual problem of blockage of catalytic sites by strong oxygen binding is overcome by flipping polarization that helps desorb the oxygen. We describe a thermodynamic cycle for direct NO decomposition followed by desorption of N2 and O2. We provide energy barriers and transition states for key steps of the cycle as well as describing their dependence on polarization direction. We end by pointing out how a switchable order parameter of substrate,in this case ferroelectric polarization, allows us to break away from some standard compromises for catalyst design(e.g. the Sabatier principle). This enlarges the set of potentially catalytic metals. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

  9. Group-kinetic theory and modeling of atmospheric turbulence

    Science.gov (United States)

    Tchen, C. M.

    1989-01-01

    A group kinetic method is developed for analyzing eddy transport properties and relaxation to equilibrium. The purpose is to derive the spectral structure of turbulence in incompressible and compressible media. Of particular interest are: direct and inverse cascade, boundary layer turbulence, Rossby wave turbulence, two phase turbulence; compressible turbulence, and soliton turbulence. Soliton turbulence can be found in large scale turbulence, turbulence connected with surface gravity waves and nonlinear propagation of acoustical and optical waves. By letting the pressure gradient represent the elementary interaction among fluid elements and by raising the Navier-Stokes equation to higher dimensionality, the master equation was obtained for the description of the microdynamical state of turbulence.

  10. R-102, 1 Group Space-Independent Inverse Reactor Kinetics

    International Nuclear Information System (INIS)

    Kaganove, J.J.

    1966-01-01

    1 - Description of problem or function: Given the space-independent, one energy group reactor kinetics equations and the initial conditions, this program determines the time variation of reactivity required to produce the given input of flux-time data. 2 - Method of solution: Time derivatives of neutron density are obtained by application of (a) five-point quartic, (b) three-point parabolic, (c) five-point least-mean-square cubic, (d) five-point least-mean-square parabolic, or (e) five-point least-mean-square linear formulae to the neutron density or to the natural logarithm of the neutron density. Between each data point the neutron density is assumed to be (a) exponential*(third-order polynomial), (b) exponential, or (c) linear. Changes in reactivity between data points are obtained algebraically from the kinetics equations, neutron density derivatives, and the algebraic representation of neutron density. First and second time derivatives of the reactivity are obtained by use of any of the formulae applicable to the neutron density. 3 - Restrictions on the complexity of the problem: Maxima of - 50 delay groups; 1000 data points; 99 data blocks (A data block is a sequence of input points characterized by a fixed time-interval between points, a smoothing option, and a number of repetitions of the smoothing option)

  11. Decomposition mechanisms and kinetics of novel energetic molecules BNFF-1 and ANFF-1: quantum-chemical modeling.

    Science.gov (United States)

    Tsyshevsky, Roman V; Kuklja, Maija M

    2013-07-18

    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.

  12. 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.

  13. 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.

  14. A kinetic study on the decomposition of 5-hydroxymethylfurfural into levulinic acid

    NARCIS (Netherlands)

    Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J.

    2006-01-01

    Levulinic acid (LA), accessible by the acid catalyzed degradation of biomass, is potentially a very versatile green intermediate chemical for the synthesis of various (bulk) chemicals for applications like fuel additives, polymers, and resin precursors. We report here a kinetic study on one of the

  15. Kinetics of G-phase precipitation and spinodal decomposition in very long aged ferrite of a Mo-free duplex stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Pareige, C., E-mail: cristelle.pareige@univ-rouen.fr [Groupe de Physique des Matériaux, UMR 6634 CNRS, Université et INSA de Rouen, Avenue de l' Université, BP 12, 76801 Saint Etienne du Rouvray (France); Emo, J. [Groupe de Physique des Matériaux, UMR 6634 CNRS, Université et INSA de Rouen, Avenue de l' Université, BP 12, 76801 Saint Etienne du Rouvray (France); Saillet, S.; Domain, C. [EDF R& D Département Matériaux et Mécanique des Composants, Avenue des Renardières – Ecuelles, F-77250 Moret sur Loing (France); Pareige, P. [Groupe de Physique des Matériaux, UMR 6634 CNRS, Université et INSA de Rouen, Avenue de l' Université, BP 12, 76801 Saint Etienne du Rouvray (France)

    2015-10-15

    Evolution of spinodal decomposition and G-phase precipitation in ferrite of a thermally aged Mo-free duplex stainless steel was studied by Atom Probe Tomography (APT). Kinetics was compared to kinetics observed in ferrite of some Mo-bearing steels aged in similar conditions. This paper shows that formation of the G-phase particles proceeds via at least a two-step mechanism: enrichment of α/α′ inter-domains by G-former elements followed by formation of G-phase particles. As expected, G-phase precipitation is much less intense in the Mo-free steel than in Mo-bearing steels. The kinetic synergy observed in Mo-bearing steels between spinodal decomposition and G-phase precipitation is shown to also exist in Mo-free steel. Spinodal decomposition is less developed in the ferrite of the Mo-free steel investigated than in Mo-bearing steels: both the amplitude of the decomposition and the effective time exponent of the wavelength (0.06 versus 0.16) are much lower for the Mo-free steel. Neither the temperature of homogenisation nor quench effects or Ni and Mo contents could successfully explain the low time exponent of the spinodal decomposition observed in the Mo-free steel. The diffusion mechanisms could be at the origin of the different time exponents (diffusion along α/α′ interfaces or diffusion of small clusters).

  16. 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

  17. 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)

  18. Kinetic study of the thermal decomposition of uranium metaphosphate, U(PO{sub 3}){sub 4}, into uranium pyrophosphate, UP{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hee-Chul, E-mail: nhcyang@kaeri.re.kr; Kim, Hyung-Ju; Lee, Si-Young; Yang, In-Hwan; Chung, Dong-Yong

    2017-06-15

    The thermochemical properties of uranium compounds have attracted much interest in relation to thermochemical treatments and the safe disposal of radioactive waste bearing uranium compounds. The characteristics of the thermal decomposition of uranium metaphosphate, U(PO{sub 3}){sub 4}, into uranium pyrophosphate, UP{sub 2}O{sub 7}, have been studied from the view point of reaction kinetics and acting mechanisms. A mixture of U(PO{sub 3}){sub 4} and UP{sub 2}O{sub 7} was prepared from the pyrolysis residue of uranium-bearing spent TBP. A kinetic analysis of the reaction of U(PO{sub 3}){sub 4} into UP{sub 2}O{sub 7} was conducted using an isoconversional method and a master plot method on the basis of data from a non-isothermal thermogravimetric analysis. The thermal decomposition of U(PO{sub 3}){sub 4} into UP{sub 2}O{sub 7} followed a single-step reaction with an activation energy of 175.29 ± 1.58 kJ mol{sup −1}. The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev model (A3), which describes that there are certain restrictions on nuclei growth of UP{sub 2}O{sub 7} during the solid-state decomposition of U(PO{sub 3}){sub 4}. - Highlights: •Thermal decomposition kinetics of U(PO{sub 3}){sub 4} into UP{sub 2}O{sub 7} was investigated. •The thermal decomposition followed a single-step reaction with an activation energy of 175.3 ± 1.6 kJ mol{sup −1}. •The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev (A3).

  19. Thermal decomposition of sewage sludge under N2, CO2 and air: Gas characterization and kinetic analysis.

    Science.gov (United States)

    Hernández, Ana Belén; Okonta, Felix; Freeman, Ntuli

    2017-07-01

    Thermochemical valorisation processes that allow energy to be recovered from sewage sludge, such as pyrolysis and gasification, have demonstrated great potential as convenient alternatives to conventional sewage sludge disposal technologies. Moreover, these processes may benefit from CO 2 recycling. Today, the scaling up of these technologies requires an advanced knowledge of the reactivity of sewage sludge and the characteristics of the products, specific to the thermochemical process. In this study the behaviour of sewage sludge during thermochemical conversion, under different atmospheres (N 2 , CO 2 and air), was studied, using TGA-FTIR, in order to understand the effects of different atmospheric gases on the kinetics of degradation and on the gaseous products. The different steps observed during the solid degradation were related with the production of different gaseous compounds. A higher oxidative degree of the atmosphere surrounding the sample resulted in higher reaction rates and a shift of the degradation mechanisms to lower temperatures, especially for the mechanisms taking place at temperatures above 400 °C. Finally, a multiple first-order reaction model was proposed to compare the kinetic parameters obtained under different atmospheres. Overall, the highest activation energies were obtained for combustion. This work proves that CO 2 , an intermediate oxidative atmosphere between N 2 and air, results in an intermediate behaviour (intermediate peaks in the derivative thermogravimetric curves and intermediate activation energies) during the thermochemical decomposition of sewage sludge. Overall, it can be concluded that the kinetics of these different processes require a different approach for their scaling up and specific consideration of their characteristic reaction temperatures and rates should be evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Development of a model system to study fuel autoxidation in supercritical media: decomposition kinetics of 2,2{prime}-azobis (isobutyronitrile) in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Morris, R.E.; Mera, A.E.; Brady, R.F. Jr. [Naval Research Laboratory, Washington, DC (USA)

    2000-07-01

    A high pressure reactor has been constructed and used for in situ spectroscopic measurements of reaction kinetics in supercritical fluids. The thermal decomposition of 2,2{prime}-azobis(isobutyronitrile) (AIBN) in supercritical carbon dioxide (SC-CO{sub 2}) was studied as part of an effort to characterize free-radical autoxidation of hydrocarbon fuels under supercritical conditions. The findings show that AIBN decomposes both thermally and photochemically in SC-CO{sub 2} to form the 2-cyano-2-propyl free radical which dimerizes to form tetramethylsuccinic dinitrile and dimethyl-N-(2-cyano-2-propyl) ketenimine. Examination of the decomposition kinetics of the ketenimine revealed that it was photochemically stable in the kinetic reactor, but decomposed thermally to form the dinitrile. 21 refs., 4 figs., 1 tab.

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

    Directory of Open Access Journals (Sweden)

    Fabian Andrey Diaz Mateus

    2015-09-01

    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.

  2. 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

  3. Thermal decomposition and kinetics of coal and fermented cornstalk using thermogravimetric analysis.

    Science.gov (United States)

    He, Yuyuan; Chang, Chun; Li, Pan; Han, Xiuli; Li, Hongliang; Fang, Shuqi; Chen, Junying; Ma, Xiaojian

    2018-07-01

    The thermal behavior and kinetics of Yiluo coal (YC) and the residues of fermented cornstalk (FC) were investigated in this study. The Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) methods were used for the kinetic analysis of the pyrolysis process. The results showed that the activation energy (E α ) was increased with the increase of the thermal conversion rate (α), and the average values of E α of YC, FC and the blend (m YC /m FC  = 6/4) were 304.26, 224.94 and 233.46 kJ/mol, respectively. The order reaction model function for the blend was also developed by the master-plots method. By comparing the E a and the enthalpy, it was found that the blend was favored to format activated complex due to the lower potential energy barrier. Meanwhile, the average value of Gibbs free energy of the blend was 169.83 kJ/mol, and the changes of entropies indicated that the pyrolysis process was evolved from ordered-state to disordered-state. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Continuous ammonium enrichment of a woodland stream: uptake kinetics, leaf decomposition, and nitrification

    Energy Technology Data Exchange (ETDEWEB)

    Newbold, J D; Elwood, J W; Schulze, M S; Stark, R W; Barmeier, J C

    1983-01-01

    In order to test for nitrogen limitation and examine ammonium uptake by stream sediments, ammonium hydroxide was added continuously at concentrations averaging 100 /sup +/gl/sup -1/ for 70 days to a second-order reach of Walker Branch, an undisturbed woodland stream in Tennessee. Ammonium uptake during the first 4 h of addition corresponded to adsorption kinetics rather than to first-order uptake or to Michaelis-Menten kinetics. However, the calculated adsorption partition coefficient was two to four orders of magnitude greater than values reported for physical adsorption of ammonium, suggesting that the uptake was largely biotic. Mass balance indicated that the uptake of ammonium from the water could be accounted for by increased nitrogen content in benthic organic detritus. Nitrification, inferred from longitudinal gradients in NO/sub 3/, began soon after enrichment and increased dramatically near the end of the experiment. Both ammonium and nitrate concentrations dropped quickly to near background levels when input ceased, indicating little desorption or nitrification of excess nitrogen stored in the reach. There was no evidence of nitrogen limitation as measured by weight loss, oxygen consumption, phosphorus content, and macroinvertebrate density of red oak leaf packs, or by chlorophyll content and aufwuchs biomass on plexiglass slides. A continuous phosphorus enrichment 1 year earlier had demonstrated phosphorus limitation in Walker Branch. 38 references, 6 figures, 3 tables.

  5. 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.

  6. 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.

  7. Kinetic Studies on Enzyme-Catalyzed Reactions: Oxidation of Glucose, Decomposition of Hydrogen Peroxide and Their Combination

    Science.gov (United States)

    Tao, Zhimin; Raffel, Ryan A.; Souid, Abdul-Kader; Goodisman, Jerry

    2009-01-01

    The kinetics of the glucose oxidase-catalyzed reaction of glucose with O2, which produces gluconic acid and hydrogen peroxide, and the catalase-assisted breakdown of hydrogen peroxide to generate oxygen, have been measured via the rate of O2 depletion or production. The O2 concentrations in air-saturated phosphate-buffered salt solutions were monitored by measuring the decay of phosphorescence from a Pd phosphor in solution; the decay rate was obtained by fitting the tail of the phosphorescence intensity profile to an exponential. For glucose oxidation in the presence of glucose oxidase, the rate constant determined for the rate-limiting step was k = (3.0 ± 0.7) ×104 M−1s−1 at 37°C. For catalase-catalyzed H2O2 breakdown, the reaction order in [H2O2] was somewhat greater than unity at 37°C and well above unity at 25°C, suggesting different temperature dependences of the rate constants for various steps in the reaction. The two reactions were combined in a single experiment: addition of glucose oxidase to glucose-rich cell-free media caused a rapid drop in [O2], and subsequent addition of catalase caused [O2] to rise and then decrease to zero. The best fit of [O2] to a kinetic model is obtained with the rate constants for glucose oxidation and peroxide decomposition equal to 0.116 s−1 and 0.090 s−1 respectively. Cellular respiration in the presence of glucose was found to be three times as rapid as that in glucose-deprived cells. Added NaCN inhibited O2 consumption completely, confirming that oxidation occurred in the cellular mitochondrial respiratory chain. PMID:19348778

  8. Application of Littlewood-Paley decomposition to the regularity of Boltzmann type kinetic equations

    International Nuclear Information System (INIS)

    EL Safadi, M.

    2007-03-01

    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 ∞ 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)

  9. Salt effect on sensitized photooxidations. A kinetic approch to environmental decomposition of marine contaminants

    Directory of Open Access Journals (Sweden)

    María I. Gutiérrez

    1998-09-01

    Full Text Available The salt effect on the kinetics of singlet molecular oxygen [O2(1Δg]-mediated photooxidations of sea water contaminants was investigated. Two families of photooxidizable compounds were employed in the study: anthracene derivatives and phenols. The presence of salt (NaCl in H2O and LiCl in MeCN, in both cases in the range 0-0.45 M produces changes in the photooxidation rate. For solvent-polarity-dependent reactions, this behavior can be predicted, by knowing the solvent-polarity dependence of the rate constant for chemical reaction of the substrates with O2(1Δ g in non-saline solutions (kr. For the cases of photooxidations possessing solvent-polarity-independent or scantily-dependent kr values, the photooxidation rates decrease as the salt content in the solution increases, mainly due to a predominance of the physical quenching pathway. In addition, the quantum yield for O2(1 Δg generation (ΦΔ was determined in a series of saline solutions, in the range of 0-0.45 M in water and MeCN solutions, in the presence of NaCl and LiCl respectively. The Δ values are independent, within the experimental error on the salt content.

  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. 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.

  12. Synthesis, characterization and thermal decomposition kinetics of Sm(III)complex with 2,4-dichlorobenzoate and 2,2'-bipyridine

    International Nuclear Information System (INIS)

    Zhang Haiyan; Zhang Jianjun; Ren Ning; Xu, Su-Ling; Zhang Yonghua; Tian Liang; Song Huihua

    2008-01-01

    The complex of [Sm(2,4-DClBA) 3 (bipy)] 2 (2,4-DClBA, 2,4-dichlorobenzoate; bipy, 2,2'-bipyridine) was synthesized and characterized by elemental analysis, molar conductivity, IR and UV spectra. The thermal decomposition process of the complex was studied by means of TG-DTG and IR techniques. And its thermal decomposition kinetics was investigated via the analysis of the TG-DTG curves by jointly using double equal-double steps method and nonlinear integral isoconversional method. The activation energy E, the pre-exponential factor A and the most probable mechanism functions of the first decomposition stage were obtained. Meanwhile, the thermodynamic parameters (ΔH ≠ , ΔG ≠ and ΔS ≠ ) were also calculated. The lifetime equation at weight-loss of 10% was deduced as ln τ = -35.53 + 20200/T by isothermal thermogravimetric analysis

  13. Theoretical evidence of the observed kinetic order dependence on temperature during the N(2)O decomposition over Fe-ZSM-5.

    Science.gov (United States)

    Guesmi, Hazar; Berthomieu, Dorothee; Bromley, Bryan; Coq, Bernard; Kiwi-Minsker, Lioubov

    2010-03-28

    The characterization of Fe/ZSM5 zeolite materials, the nature of Fe-sites active in N(2)O direct decomposition, as well as the rate limiting step are still a matter of debate. The mechanism of N(2)O decomposition on the binuclear oxo-hydroxo bridged extraframework iron core site [Fe(II)(mu-O)(mu-OH)Fe(II)](+) inside the ZSM-5 zeolite has been studied by combining theoretical and experimental approaches. The overall calculated path of N(2)O decomposition involves the oxidation of binuclear Fe(II) core sites by N(2)O (atomic alpha-oxygen formation) and the recombination of two surface alpha-oxygen atoms leading to the formation of molecular oxygen. Rate parameters computed using standard statistical mechanics and transition state theory reveal that elementary catalytic steps involved into N(2)O decomposition are strongly dependent on the temperature. This theoretical result was compared to the experimentally observed steady state kinetics of the N(2)O decomposition and temperature-programmed desorption (TPD) experiments. A switch of the reaction order with respect to N(2)O pressure from zero to one occurs at around 800 K suggesting a change of the rate determining step from the alpha-oxygen recombination to alpha-oxygen formation. The TPD results on the molecular oxygen desorption confirmed the mechanism proposed.

  14. Kinetic modeling of the polymer-derived ceramics route: investigation of the thermal decomposition kinetics of poly[B-(methylamino)borazine] precursors into boron nitride.

    Science.gov (United States)

    Bernard, Samuel; Fiaty, Koffi; Cornu, David; Miele, Philippe; Laurent, Pierre

    2006-05-11

    A complete kinetic modeling of the polymer-derived ceramics (PDCs) route is achieved for the first time through the investigation of the solid-state decomposition of a typical melt-spinnable poly[B-(methylamino)borazine] into boron nitride fibers at various heating rates. Through the use of the Lorentz fitting approach, it is shown that the two-step weight loss associated with the polymer-to-ceramic conversion is governed by a complex interplay of five diffusion-type transport mechanisms that are independent of the applied heating schedule. The application of the Friedman method to dynamic thermogravimetry data yields Ea and ln A values that are seen to increase with the extent of the ceramic conversion from region one (Ea = 38.73 kJ mol(-1)) to region five (Ea = 146.64 kJ mol(-1)). This fact indicates that both the mechanisms within those regions are parallel routes to the formation of the final solid-state material and their complexity increases with the conversion progress. The cross-linking process (first weight loss) of the polymer is governed by three dependent poorly energetic mechanisms. The first weight loss is activated by ammonolysis reactions that provide a modified polymer capable of undergoing condensation reactions in regions two and three to yield a highly cross-linked polymer. A large evolution of methylamine is identified during this process. Mineralization (region four) and ceramization (region five) steps are represented by two highly energetic multistep mechanisms. The mineralization step is associated with a large evolution of methylamine and occurs during the transition between the cross-linking and ceramization processes through the cleavage of the inter-ring B-N bonds. Ceramization represents the end of the polymer-to-ceramic conversion in which the planar consolidation of BN hexagons occurs through complex structural rearrangements of the borazine units (cleavage of the intraring B-N bonds) accompanied with an ammonia evolution. Finally

  15. Kinetics of the Thermal Decomposition of Tetramethylsilane behind the Reflected Shock Waves in a Single Pulse Shock Tube (SPST) and Modeling Study

    Science.gov (United States)

    Parandaman, A.; Sudhakar, G.; Rajakumar, B.

    Thermal reactions of Tetramethylsilane (TMS) diluted in argon were studied behind the reflected shock waves in a single-pulse shock tube (SPST) over the temperature range of 1085-1221 K and pressures varied between 10.6 and 22.8 atm. The stable products resulting from the decomposition of TMS were identified and quantified using gas chromatography and also verified with Fourier Transform Infrared (FTIR) spectrometer. The major reaction products are methane (CH4) and ethylene (C2H4). The minor reaction products are ethane (C2H6) and propylene (C3H6). The initiation of mechanism in the decomposition of TMS takes plays via the Si-C bond scission by ejecting the methyl radicals (CH3) and trimethylsilyl radicals ((CH3)3Si). The measured temperature dependent rate coefficient for the total decomposition of TMS was to be ktotal = 1.66 ×1015 exp (-64.46/RT) s-1 and for the formation of CH4 reaction channel was to be k = 2.20 × 1014 exp (-60.15/RT) s-1, where the activation energies are given in kcal mol-1. A kinetic scheme containing 17 species and 28 elementary reactions was used for the simulation using chemical kinetic simulator over the temperature range of 1085-1221 K. The agreement between the experimental and simulated results was satisfactory.

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

    International Nuclear Information System (INIS)

    D’Cruz, Bessy; Samuel, Jadu; George, Leena

    2014-01-01

    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 2 evolution and was found to be 1.514 mmol/g/h

  17. 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.

  18. A green approach towards adoption of chemical reaction model on 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane decomposition by differential isoconversional kinetic analysis

    Energy Technology Data Exchange (ETDEWEB)

    Das, Mitali; Shu, Chi-Min, E-mail: shucm@yuntech.edu.tw

    2016-01-15

    Highlights: • Thermally degraded DBPH products are identified. • An appropriate mathematical model was selected for decomposition study. • Differential isoconversional analysis was performed to obtain kinetic parameters. • Simulation on thermal analysis model was conducted for the best storage conditions. - Abstract: This study investigated the thermal degradation products of 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexane (DBPH), by TG/GC/MS to identify runaway reaction and thermal safety parameters. It also included the determination of time to maximum rate under adiabatic conditions (TMR{sub ad}) and self-accelerating decomposition temperature obtained through Advanced Kinetics and Technology Solutions. The apparent activation energy (E{sub a}) was calculated from differential isoconversional kinetic analysis method using differential scanning calorimetry experiments. The E{sub a} value obtained by Friedman analysis is in the range of 118.0–149.0 kJ mol{sup −1}. The TMR{sub ad} was 24.0 h with an apparent onset temperature of 82.4 °C. This study has also established an efficient benchmark for a thermal hazard assessment of DBPH that can be applied to assure safer storage conditions.

  19. Generation of a library of two-group diffusion and kinetics parameters for DYN3D

    International Nuclear Information System (INIS)

    Petkov, P.T.; Christoskov, I.D.; Kamenov, K.; Antov, A.

    2002-01-01

    A library of two-group diffusion and kinetics parameters has been generated for the neutron kinetics code DYN3D for analysis of reactivity initiated accidents for the WWER-440 reactors, based on the MAGRU approximation methodology for the diffusion and kinetics parameters. The accuracy of this methodology has been tested and the conclusion is that it is not adequate. A new approximation methodology, based on interpolation for the most widely varying parameters, i.e. the moderator temperature and density, and on approximation for all other independent parameters, is presented. The methodology of calculation of the kinetics parameters using primary data from ENDF-B/VI is described in detail (Authors)

  20. Kinetic Analysis of Isothermal Decomposition Process of Sodium Bicarbonate Using the Weibull Probability Function—Estimation of Density Distribution Functions of the Apparent Activation Energies

    Science.gov (United States)

    Janković, Bojan

    2009-10-01

    The decomposition process of sodium bicarbonate (NaHCO3) has been studied by thermogravimetry in isothermal conditions at four different operating temperatures (380 K, 400 K, 420 K, and 440 K). It was found that the experimental integral and differential conversion curves at the different operating temperatures can be successfully described by the isothermal Weibull distribution function with a unique value of the shape parameter ( β = 1.07). It was also established that the Weibull distribution parameters ( β and η) show independent behavior on the operating temperature. Using the integral and differential (Friedman) isoconversional methods, in the conversion (α) range of 0.20 ≤ α ≤ 0.80, the apparent activation energy ( E a ) value was approximately constant ( E a, int = 95.2 kJmol-1 and E a, diff = 96.6 kJmol-1, respectively). The values of E a calculated by both isoconversional methods are in good agreement with the value of E a evaluated from the Arrhenius equation (94.3 kJmol-1), which was expressed through the scale distribution parameter ( η). The Málek isothermal procedure was used for estimation of the kinetic model for the investigated decomposition process. It was found that the two-parameter Šesták-Berggren (SB) autocatalytic model best describes the NaHCO3 decomposition process with the conversion function f(α) = α0.18(1-α)1.19. It was also concluded that the calculated density distribution functions of the apparent activation energies ( ddfE a ’s) are not dependent on the operating temperature, which exhibit the highly symmetrical behavior (shape factor = 1.00). The obtained isothermal decomposition results were compared with corresponding results of the nonisothermal decomposition process of NaHCO3.

  1. Effects of Magnetic and Kinetic Helicities on the Growth of Magnetic Fields in Laminar and Turbulent Flows by Helical Fourier Decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Linkmann, Moritz; Sahoo, Ganapati; Biferale, Luca [Department of Physics and INFN, University of Rome Tor Vergata, Via della Ricerca Scientifica 1, I-00133 Rome (Italy); McKay, Mairi; Berera, Arjun [School of Physics and Astronomy, University of Edinburgh, Peter Guthrie Tait Road, EH9 3FD, Edinburgh (United Kingdom)

    2017-02-10

    We present a numerical and analytical study of incompressible homogeneous conducting fluids using a helical Fourier 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 equations with the helical Fourier 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 α -effect in Fourier space. Concerning the small-scale perturbations, we predict theoretically and confirm numerically that the largest instability is achived for the magnetic component with the same helicity of the flow, in agreement with the Stretch–Twist–Fold mechanism. Vice versa, in the presence of Lorentz feedback on the velocity, we find that the inverse cascade of magnetic helicity is mostly local if magnetic and kinetic helicities have opposite signs, while it is more nonlocal and more intense if they have the same sign, as predicted by the analytical approach. Our analytical and numerical results further demonstrate the potential of the helical Fourier decomposition to elucidate the entangled dynamics of magnetic and kinetic helicities both in fully developed turbulence and in laminar flows.

  2. Kinetics of methane decomposition to CO{sub x}-free hydrogen and carbon nanofiber over Ni-Cu/MgO catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Borghei, Maryam; Karimzadeh, Ramin [Chemical Engineering Department, Tarbiat Modares University, Tehran (Iran); Rashidi, Alimorad; Izadi, Nosrat [Research Center of Nanotechnology, Research Institute of Petroleum Industry, Tehran (Iran)

    2010-09-15

    Kinetic modeling of methane decomposition to CO{sub x}-free hydrogen and carbon nanofiber has been carried out in the temperature range 550-650 C over Ni-Cu/MgO catalyst from CH{sub 4}-H{sub 2} mixtures at atmospheric pressure. Assuming the different mechanisms of the reaction, several kinetic models were derived based on Langmuir-Hinshelwood type. The optimum value of kinetic parameters has been obtained by Genetic Algorithm and statistical analysis has been used for the model discrimination. The suggested kinetic model relates to the mechanism when the dissociative adsorption of methane molecule is the rate-determining stage and the estimated activation energy is 50.4 kJ/mol in agreement with the literature. The catalyst deactivation was found to be dependent on the time, reaction temperature, and partial pressures of methane and hydrogen. Inspection of the behavior of the catalyst activity in relation to time, led to a model of second order for catalyst deactivation. (author)

  3. Kinetics of acid leaching of ilmenite decomposed by KOH part 1: decomposition by KOH and leaching by HCl

    International Nuclear Information System (INIS)

    Nayl, A.A; Aly, H.F.

    2010-01-01

    Decomposition of ilmenite by KOH solutions, to convert titanium to potassium titanate, was first studied . This was followed by leaching titanium from the ilmenite paste using HCl solutions in the temperature range 50-150 degree C for different periods up to 3 hr. The significant factors affecting the leaching process were studied. The experimental data of the decomposition rate of ilmenite by KOH and of the formed KOH paste by HCl under the relevant operating variables were interpreted with the shrinking core model under chemically controlled process. The apparent activation energy for leaching of titanium in both cases bas been evaluated and discussed.

  4. Kinetics of thermal decomposition of some biomasses in an inert environment. An investigation of the effect of lead loaded by biosorption.

    Science.gov (United States)

    Martín-Lara, María Ángeles; Iáñez-Rodríguez, Irene; Blázquez, Gabriel; Quesada, Lucía; Pérez, Antonio; Calero, Mónica

    2017-12-01

    The thermal behavior of some types of raw and lead-polluted biomasses typical in south Spain was studied by non-isothermal thermogravimetry. Experiments were carried out in nitrogen atmosphere at three heating rates (5, 10 and 20°C/min). The results of thermogravimetric tests carried out proved that the presence of lead did not change the main degradation pathways of selected biomass (almond shell (AS) and olive pomace (OP)). However, from a point of view of mass loss, lead-polluted samples showed higher decomposition temperatures and decomposition at higher rate. The determination of activation energies was performed by isoconversional methods of Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Friedman (FR). In general, lead-polluted samples showed lower activation energies than raw ones. Then, Coast-Redfern method was applied to determine kinetic function. The kinetic function that seems to determine the mechanism of thermal degradation of main components of all samples was nth order reaction. Finally, a model based on three parallel reactions (for three pseudocomponents) that fit to nth order reactions was evaluated. This model was appropriate to predict the pyrolysis behavior of the raw and lead-polluted samples in all pyrolysis conditions studied. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. 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.

  6. 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.

  7. Decomposition techniques

    Science.gov (United States)

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

    1992-01-01

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

  8. The 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.

    2014-01-01

    The nucleoside analog 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 analogs. PMID:19480391

  9. An analytical solution for the two-group kinetic neutron diffusion equation in cylindrical geometry

    International Nuclear Information System (INIS)

    Fernandes, Julio Cesar L.; Vilhena, Marco Tullio; Bodmann, Bardo Ernst

    2011-01-01

    Recently the two-group Kinetic Neutron Diffusion Equation with six groups of delay neutron precursor in a rectangle was solved by the Laplace Transform Technique. In this work, we report on an analytical solution for this sort of problem but in cylindrical geometry, assuming a homogeneous and infinite height cylinder. The solution is obtained applying the Hankel Transform to the Kinetic Diffusion equation and solving the transformed problem by the same procedure used in the rectangle. We also present numerical simulations and comparisons against results available in literature. (author)

  10. Effects of Plant Functional Group Loss on Soil Microbial Community and Litter Decomposition in a Steppe Vegetation.

    Science.gov (United States)

    Xiao, Chunwang; Zhou, Yong; Su, Jiaqi; Yang, Fan

    2017-01-01

    Globally, many terrestrial ecosystems are experiencing a rapid loss of biodiversity. Continued improvements in our understanding of interrelationships between plant diversity and soil microbes are critical to address the concern over the consequences of the decline in biodiversity on ecosystem functioning and services. By removing forbs, or grasses, or, to an extreme scenario, both forbs and grasses in a steppe vegetation in Inner Mongolia, we studied how plant functional group (PFG) loss affects soil microbial community composition using phospholipid fatty acid analysis (PLFA) and litter decomposition using a litter-bag method. PFG loss significantly decreased above- and below-ground plant biomass, soil microbial biomass carbon (SMBC) and nitrogen (SMBN), but had no effect on the ratio of SMBC to SMBN. Although the ratio of fungal to bacterial PLFAs remained unaffected, PFG loss significantly reduced the amount of bacterial, fungal, and total PLFAs. PFG loss decreased litter monthly mass loss and decay constant, and such decrease was significant when both forbs and grasses were removed. Our results provide robust evidence that PFG loss in grassland ecosystem can lead to a rapid response of soil microbial activity which may affect litter decomposition and soil nutrient cycling, suggesting that the assessment of plant-microbe interactions in soils is an integral component of ecosystem response to biodiversity loss.

  11. An accurate solution of point reactor neutron kinetics equations of multi-group of delayed neutrons

    International Nuclear Information System (INIS)

    Yamoah, S.; Akaho, E.H.K.; Nyarko, B.J.B.

    2013-01-01

    Highlights: ► Analytical solution is proposed to solve the point reactor kinetics equations (PRKE). ► The method is based on formulating a coefficient matrix of the PRKE. ► The method was applied to solve the PRKE for six groups of delayed neutrons. ► Results shows good agreement with other traditional methods in literature. ► The method is accurate and efficient for solving the point reactor kinetics equations. - Abstract: 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, an accurate analytical solution of point reactor kinetics equations with multi-group of delayed neutrons for specified reactivity changes is proposed to calculate the change in neutron density. The method is based on formulating a coefficient matrix of the homogenous differential equations of the point reactor kinetics equations and calculating the eigenvalues and the corresponding eigenvectors of the coefficient matrix. A small time interval is chosen within which reactivity relatively stays constant. The analytical method was applied to solve the point reactor kinetics equations with six-groups delayed neutrons for a representative thermal reactor. The problems of step, ramp and temperature feedback reactivities are computed and the results compared with other traditional methods. The comparison shows that the method presented in this study is accurate and efficient for solving the point reactor kinetics equations of multi-group of delayed neutrons

  12. Numerical simulation of kinetic demixing and decomposition in a LaCoO3-δ oxygen membrane under an oxygen potential gradient

    DEFF Research Database (Denmark)

    Ta, Na; Chen, Ming; Zhang, Lijun

    2018-01-01

    A composition- and temperature-dependent mobility database of all ionic species in the LaCoO3-δ phase was developed and combined with a La-Co-O thermodynamic database to simulate kinetic demixing and partial decomposition in LaCoO3-δ oxygen membranes operated under a 0.0001/0.21 bar oxygen partial...... pressure difference at 1073 K for 1 year. Formation of La2O3, Co3O4 and CoO phases across the membrane is predicted. The kinetic demixing process can be divided into two stages, namely, establishment of the oxygen potential gradient (fast) and demixing of the cations (slow); the former is controlled...... by the mobility of oxygen ions, and the latter is determined by the higher mobility of Co ions as compared to the La ion in the ABO3-type perovskite. A drift motion of both oxide surfaces towards the high PO2 side occurs with the movement of cations....

  13. Homotopy analysis solutions of point kinetics equations with one delayed precursor group

    International Nuclear Information System (INIS)

    Zhu Qian; Luo Lei; Chen Zhiyun; Li Haofeng

    2010-01-01

    Homotopy analysis method is proposed to obtain series solutions of nonlinear differential equations. Homotopy analysis method was applied for the point kinetics equations with one delayed precursor group. Analytic solutions were obtained using homotopy analysis method, and the algorithm was analysed. The results show that the algorithm computation time and precision agree with the engineering requirements. (authors)

  14. Decomposition yields of the functional groups in gamma-radiolysis of the potassium and N,N'-dibenzylethylenediamine salts of benzylpenicillin in solid state

    International Nuclear Information System (INIS)

    Dziegielewski, J.O.

    1976-01-01

    The yields of particular groups in the potassium of benzylpenicillin and benzatine penicillin were determined by the NMR method. The total yields of groups are in agreement with the total radiation decomposition yields of the penicillin molecules, as determined by the spectrophotometric, polarimetric and iodometric methods. (author)

  15. Different faces of inequality across Asia: Decomposition of income gaps across demographic Groups

    OpenAIRE

    Hlasny, Vladimir

    2017-01-01

    Substantial evidence exists that economic inequality in Asia has been growing, but the dimensions of this inequality and its growth are far less clear. This paper evaluates inequality in household incomes per capita across various demographic groups in income surveys from six middle- and high-income countries across Asia: the People's Republic of China (PRC) (2002); India (2004); Japan (2008); Republic of Korea (2006); the Russian Federation (2004, 2007, and 2010); and Taipei,China (2005, 200...

  16. A decomposition theorem for compact groups with an application to supercompactness

    Czech Academy of Sciences Publication Activity Database

    Kubiś, Wieslaw; Turek, S.

    2011-01-01

    Roč. 9, č. 3 (2011), s. 593-602 ISSN 1895-1074 R&D Projects: GA AV ČR IAA100190901 Institutional research plan: CEZ:AV0Z10190503 Keywords : Simple compact Lie group * Supercompact space Subject RIV: BA - General Mathematics Impact factor: 0.440, year: 2011 http://www.springerlink.com/content/h86v44387542637r/

  17. Thermal conductivity of group-IV semiconductors from a kinetic-collective model.

    Science.gov (United States)

    de Tomas, C; Cantarero, A; Lopeandia, A F; Alvarez, F X

    2014-09-08

    The thermal conductivity of group-IV semiconductors (silicon, germanium, diamond and grey tin) with several isotopic compositions has been calculated from a kinetic-collective model. From this approach, significantly different to Callaway-like models in its physical interpretation, the thermal conductivity expression accounts for a transition from a kinetic (individual phonon transport) to a collective (hydrodynamic phonon transport) behaviour of the phonon field. Within the model, we confirm the theoretical proportionality between the phonon-phonon relaxation times of the group-IV semiconductors. This proportionality depends on some materials properties and it allows us to predict the thermal conductivity of the whole group of materials without the need to fit each material individually. The predictions on thermal conductivities are in good agreement with experimental data over a wide temperature range.

  18. Thermal conductivity of group-IV semiconductors from a kinetic-collective model

    Science.gov (United States)

    de Tomas, C.; Cantarero, A.; Lopeandia, A. F.; Alvarez, F. X.

    2014-01-01

    The thermal conductivity of group-IV semiconductors (silicon, germanium, diamond and grey tin) with several isotopic compositions has been calculated from a kinetic-collective model. From this approach, significantly different to Callaway-like models in its physical interpretation, the thermal conductivity expression accounts for a transition from a kinetic (individual phonon transport) to a collective (hydrodynamic phonon transport) behaviour of the phonon field. Within the model, we confirm the theoretical proportionality between the phonon–phonon relaxation times of the group-IV semiconductors. This proportionality depends on some materials properties and it allows us to predict the thermal conductivity of the whole group of materials without the need to fit each material individually. The predictions on thermal conductivities are in good agreement with experimental data over a wide temperature range. PMID:25197256

  19. 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.

  20. Small-angle x-ray scattering study of kinetics of spinodal decomposition in N-isopropylacrylamide gels

    International Nuclear Information System (INIS)

    Liao, G.; Xie, Y.; Ludwig, K.F. Jr.; Bansil, R.; Gallagher, P.; Xie, Y.; Gallagher, P.

    1999-01-01

    We present synchrotron-based time-resolved small-angle x-ray scattering (SAXS) measurements of spinodal decomposition in a covalently cross-linked N-isopropylacrylamide gel. The range of wave numbers examined is well beyond the position of the maximum in the structure factor S(q,t). The equilibrium structure factor is described by the sum of a Lorentzian and a Gaussian. Following a temperature jump into the two phase region, the scattered intensity increases with time and eventually saturates. For early times the linear Cahn-Hilliard-Cook (CHC) theory can be used to describe the time evolution of the scattered intensity. From this analysis we found that the growth rate R(q) is linearly dependent on q 2 , in agreement with mean-field theoretical predictions. However the Onsager transport coefficient Λ(q)∼q -4 , which is stronger than the q dependence predicted by the mean-field theory. We found that the growth rate R(q)>0, even though the wave numbers q probed by SAXS are greater than √ (2) q m where q m is the position of the peak of S(q,t), also in agreement with the mean-field predictions for a deep quench. We have also examined the range of validity of the linear CHC theory, and found that its breakdown occurs earlier at higher wave numbers. At later times, a pinning of the structure was observed. The relaxation to a final, microphase-separated morphology is faster and occurs earlier at the highest wave numbers, which probe length scales comparable to the average distance between crosslinks. copyright 1999 The American Physical Society

  1. Numerical solution of multi groups point kinetic equations by simulink toolbox of Matlab software

    International Nuclear Information System (INIS)

    Hadad, K.; Mohamadi, A.; Sabet, H.; Ayobian, N.; Khani, M.

    2004-01-01

    The simulink toolbox of Matlab Software was employed to solve the point kinetics equation with six group delayed neutrons. The method of Adams-Bash ford showed a good convergence in solving the system of simultaneous equations and the obtained results showed good agreements with other numerical schemes. The flexibility of the package in changing the system parameters and the user friendly interface makes this approach a reliable educational package in revealing the affects of reactivity changes on power incursions

  2. 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.

  3. 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.

  4. On the use of flux-adjoint condensed nuclear data for 1-group AGR kinetics

    International Nuclear Information System (INIS)

    Hutt, P.K.

    1979-03-01

    Following previous work on the differences between one and two neutron group AGR kinetics the possible advantages of flux-adjoint condensed lattice data over the simple flux condensation procedure are investigated. Analytic arguments are given for expecting flux-adjoint condensation to give a better representation of rod worth slopes and flux shape changes associated with partially rodded cores. These areas have previously been found to yield most of the one to two neutron group differences. The validity of these arguments is demonstrated comparing various calculations. (U.K.)

  5. A parallel algorithm for solving the multidimensional within-group discrete ordinates equations with spatial domain decomposition - 104

    International Nuclear Information System (INIS)

    Zerr, R.J.; Azmy, Y.Y.

    2010-01-01

    A spatial domain decomposition with a parallel block Jacobi solution algorithm has been developed based on the integral transport matrix formulation of the discrete ordinates approximation for solving the within-group transport equation. The new methodology abandons the typical source iteration scheme and solves directly for the fully converged scalar flux. Four matrix operators are constructed based upon the integral form of the discrete ordinates equations. A single differential mesh sweep is performed to construct these operators. The method is parallelized by decomposing the problem domain into several smaller sub-domains, each treated as an independent problem. The scalar flux of each sub-domain is solved exactly given incoming angular flux boundary conditions. Sub-domain boundary conditions are updated iteratively, and convergence is achieved when the scalar flux error in all cells meets a pre-specified convergence criterion. The method has been implemented in a computer code that was then employed for strong scaling studies of the algorithm's parallel performance via a fixed-size problem in tests ranging from one domain up to one cell per sub-domain. Results indicate that the best parallel performance compared to source iterations occurs for optically thick, highly scattering problems, the variety that is most difficult for the traditional SI scheme to solve. Moreover, the minimum execution time occurs when each sub-domain contains a total of four cells. (authors)

  6. 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

  7. Investigation of the kinetics of the change in the group composition of the anthracene fraction on heat treatment

    Energy Technology Data Exchange (ETDEWEB)

    Belkina, T.V.; Lur' e, M.V.; Stepanenko, M.A.

    1981-01-01

    In the reported experiments, an investigation has been made of the kinetics of the change in the group composition of the anthracene fraction during heat treatment under various conditions. On the basis of the results obtained, a kinetic model of the process has been developed which permits rational conditions for obtaining a heat-treated product of the necessary group composition to be found. 6 refs.

  8. 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

  9. Danburite decomposition by sulfuric acid

    International Nuclear Information System (INIS)

    Mirsaidov, U.; Mamatov, E.D.; Ashurov, N.A.

    2011-01-01

    Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by sulfuric acid. The process of decomposition of danburite concentrate by sulfuric acid was studied. The chemical nature of decomposition process of boron containing ore was determined. The influence of temperature on the rate of extraction of boron and iron oxides was defined. The dependence of decomposition of boron and iron oxides on process duration, dosage of H 2 SO 4 , acid concentration and size of danburite particles was determined. The kinetics of danburite decomposition by sulfuric acid was studied as well. The apparent activation energy of the process of danburite decomposition by sulfuric acid was calculated. The flowsheet of danburite processing by sulfuric acid was elaborated.

  10. Comparison of reactor RA-4 kinetics with simulations with Matlab-Simulink for one group and six groups of delayed neutrons

    International Nuclear Information System (INIS)

    Orso, J A

    2012-01-01

    The critical state of a nuclear reactor is an unstable equilibrium. The nuclear reactor can go from critical to subcritical state or can go from critical to hypercritical state. Although the evolution of the system in these cases is slow, it requires the intervention of an operator to correct deviations. For this reason an automatic control technique was designed, based on the kinetic point to a group of delayed neutrons, which corrects deviations automatically. In this paper we study the point kinetics models in a group and six groups of delayed neutrons for different values of reactivity using the simulations software MATLAB, Simulink. A comparison of two models with the reactor kinetic behavior is made (author)

  11. 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

  12. 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.

  13. Kinetic study of group IV nanoparticles ion beam synthesized in SiO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Bonafos, C. E-mail: bonafos@cemes.fr; Colombeau, B.; Altibelli, A.; Carrada, M.; Ben Assayag, G.; Garrido, B.; Lopez, M.; Perez-Rodriguez, A.; Morante, J.R.; Claverie, A

    2001-05-01

    Most studies concerning group IV (Si, Ge) ion beam synthesized nanocrystals in SiO{sub 2} have shown that a link exists between the observed physical properties and the characteristics of the 'populations' of nanoparticles (size-distribution, density, volume fraction). The aim of this paper is to study the influence of the initial supersaturation and annealing conditions on these characteristics. For this, experimental methods have been developed, that allow accurate statistical studies. Different transmission electron microscopy (TEM) imaging conditions have been tested and the most adequate ones have been identified for each system. An original method for the measurement of the density of precipitates embedded in an amorphous matrix has been developed and tested for Ge precipitates in SiO{sub 2} and has permitted to evidence a conservative Ostwald ripening during annealing. The kinetic behavior of Si nanoparticles has also been studied by coupling TEM measurements and 'atomistic' simulations. During annealing, the growth of these nanoparticles is very slow but their size significantly increases when increasing the initial Si excess. Simulations are in perfect agreement with experiment when taking into account interaction effects between particles.

  14. Surface reaction modification: The effect of structured overlayers of sulfur on the kinetics and mechanism of the decomposition of formic acid on Pt(111)

    Science.gov (United States)

    Abbas, N.; Madix, R. J.

    The reaction of formic acid (DCOOH) on Pt(111), Pt(111)-(2×2)S and Pt(111)-(√3×√3)R30°S surfaces was examined by temperature programmed reaction spectroscopy. On the clean surface formic acid decomposed to yield primarily carbon dioxide and the hydrogenic species (H 2, HD and D 2) at low coverages. Although the formation of water and carbon monoxide via a dehydration reaction was observed at these coverages, the yield of these products was small when compared to the other products of reaction. The evolution of CO 2 at low temperature was ascribed to the decomposition of the formate intermediate. In the presence of sulfur the amount of molecularly adsorbed formic acid decreased up to a factor of three on the (√3×√3)R30°S surface, and a decline in the reactivity of over an order of magnitude was also observed. The only products formed were the hydrogenic species and carbon dioxide. The absence of carbon monoxide indicated that the dehydration pathway was blocked by sulfur. In addition to the low temperature CO 2 peak a high temperature CO 2-producing path was also evident. It was inferred from both the stoichiometry and the coincident evolution of D 2 and CO 2 in the high temperature states that these products also evolved due to the decomposition of the formate intermediate. On increasing the sulfur coverage to one-third monolayer this intermediate was further stabilized, and a predominance of the decomposition via the high temperature path was observed. Stability of the formate intermediate was attributed to inhibition of the decomposition reaction by sulfur atoms. The activation energy for formate decomposition increased from 15 kcal/gmole on the clean surface to 24.3 kcal/gmol on the (√3×√3)R30°S overlayer.

  15. Algorithm development and verification of UASCM for multi-dimension and multi-group neutron kinetics model

    International Nuclear Information System (INIS)

    Si, S.

    2012-01-01

    The Universal Algorithm of Stiffness Confinement Method (UASCM) for neutron kinetics model of multi-dimensional and multi-group transport equations or diffusion equations has been developed. The numerical experiments based on transport theory code MGSNM and diffusion theory code MGNEM have demonstrated that the algorithm has sufficient accuracy and stability. (authors)

  16. Danburite decomposition by hydrochloric acid

    International Nuclear Information System (INIS)

    Mamatov, E.D.; Ashurov, N.A.; Mirsaidov, U.

    2011-01-01

    Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by hydrochloric acid. The interaction of boron containing ores of Ak-Arkhar Deposit of Tajikistan with mineral acids, including hydrochloric acid was studied. The optimal conditions of extraction of valuable components from danburite composition were determined. The chemical composition of danburite of Ak-Arkhar Deposit was determined as well. The kinetics of decomposition of calcined danburite by hydrochloric acid was studied. The apparent activation energy of the process of danburite decomposition by hydrochloric acid was calculated.

  17. 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

    2016-01-01

    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

  18. TG-MS analysis and kinetic study for thermal decomposition of six representative components of municipal solid waste under steam atmosphere.

    Science.gov (United States)

    Zhang, Jinzhi; Chen, Tianju; Wu, Jingli; Wu, Jinhu

    2015-09-01

    Thermal decomposition of six representative components of municipal solid waste (MSW, including lignin, printing paper, cotton, rubber, polyvinyl chloride (PVC) and cabbage) was investigated by thermogravimetric-mass spectroscopy (TG-MS) under steam atmosphere. Compared with TG and derivative thermogravimetric (DTG) curves under N2 atmosphere, thermal decomposition of MSW components under steam atmosphere was divided into pyrolysis and gasification stages. In the pyrolysis stage, the shapes of TG and DTG curves under steam atmosphere were almost the same with those under N2 atmosphere. In the gasification stage, the presence of steam led to a greater mass loss because of the steam partial oxidation of char residue. The evolution profiles of H2, CH4, CO and CO2 were well consistent with DTG curves in terms of appearance of peaks and relevant stages in the whole temperature range, and the steam partial oxidation of char residue promoted the generation of more gas products in high temperature range. The multi-Gaussian distributed activation energy model (DAEM) was proved plausible to describe thermal decomposition behaviours of MSW components under steam atmosphere. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Carboxyl group modification significantly altered the kinetic properties of purified carboxymethylcellulase from Aspergillus niger.

    Science.gov (United States)

    Siddiqui; Saqib; Rashid; Rajoka

    2000-10-01

    Carboxymethylcellulase (CMCase) from Aspergillus niger NIAB280 was purified by a combination of ammonium sulphate precipitation, ion-exchange, hydrophobic interaction and gel filtration chromatography on FPLC with 9-folds increase in specific activity. Native and subunit molecular weights were found to be 36 kDa each. The purified CMCase was modified by 1-ethyl-3(3-dimethylaminopropyl) carbodiimide (EDC) in the presence of glycinamide for 15 min (GAM15) and glycinamide plus cellobiose for 75 min (GAM75). Similarly, the enzyme was modified by EDC in the presence of ethylenediamine dihydrochloride plus cellobiose for 75 min (EDAM75). The neutralization (GAM15 and GAM75) and reversal (EDAM75) of negative charges of carboxyl groups of CMCase had profound effect on the specificity constant (k(cat)/K(m)), pH optima, pK(a)'s of the active-site residues and thermodynamic parameters of activation. The specificity constants of native, GAM15, GAM75, and EDAM75 were 143, 340, 804, and 48, respectively. The enthalpy of activation (DeltaH(#)) of Carboxymethylcellulose (CMC) hydrolysis of native (50 and 15 kJ mol(-1)) and GAM15 (41 and 16 kJ mol(-1)) were biphasic whereas those of GAM75 (43 kJ mol(-1)) and EDAM75 (41 k J mol(-1)) were monophasic. Similarly, the entropy of activation (DeltaS(#)) of CMC hydrolysis of native (-61 and -173 J mol(-1) K(-1)) and GAM15 (-91 and -171 J mol(-1) K(-1)) were biphasic whereas those of GAM75 (-82 J mol(-1) K(-1)) and EDAM75 (-106 J mol(-1) K(-1)) were monophasic. The pH optima/pK(a)'s of both acidic and basic limbs of charge neutralized CMCases increased compared with those of native enzyme. The CMCase modification in the presence of glycinamide and absence of cellobiose at different pH's periodically activated and inhibited the enzyme activity indicating conformational changes. We believe that the alteration of the surface charges resulted in gross movement of loops that surround the catalytic pocket, thereby inducing changes in the vicinity

  20. Mathematical modelling of the decomposition of explosives

    International Nuclear Information System (INIS)

    Smirnov, Lev P

    2010-01-01

    Studies on mathematical modelling of the molecular and supramolecular structures of explosives and the elementary steps and overall processes of their decomposition are analyzed. Investigations on the modelling of combustion and detonation taking into account the decomposition of explosives are also considered. It is shown that solution of problems related to the decomposition kinetics of explosives requires the use of a complex strategy based on the methods and concepts of chemical physics, solid state physics and theoretical chemistry instead of empirical approach.

  1. 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

  2. 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...

  3. Development of LMR basic design technology - Development of 3-D multi-group nodal kinetics code for liquid metal reactors

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Myung Hyun [Kyunghee University, Seoul (Korea, Republic of)

    1996-07-01

    A development project of 3-dimensional kinetics code for ALMR has three level of works. In the first level, a multi-group, nodal kinetics code for the HEX-Z geometry has been developed. A code showed very good results for the static analysis as well as for the kinetics problems. At the second level, a core thermal-hydraulic analysis code was developed for the temperature feedback calculation in ALMR transients analysis. This code is coupled with kinetics code. A sodium property table was programmed and tested to the KAERI data and thermal feedback model was developed and coupled in code. Benchmarking of T/H calculation has been performed and showed fairly good results. At the third level of research work, reactivity feedback model for structure thermal expansion is developed and added to the code. At present, basic model was studied. However, code development in now on going. Benchmarking of this model developed can not be done because of lack of data. 31 refs., 17 tabs., 38 figs. (author)

  4. 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

  5. Reaction kinetics and reaction heat on thermal decomposition of solvent containing unstable reactive hydrocarbons with nitric acid at Tomsk-7 reprocessing plant

    International Nuclear Information System (INIS)

    Nishio, Gunji; Watanabe, Kouji; Koike, Tadao; Miyato, Teijiro.

    1996-12-01

    For analyzing a cause of the Tomsk-7 accident at Russian reprocessing plant, it is necessary to determine reaction-rate constant and reaction heat for a thermal decomposition of TBP/kerosine containing unstable reactive hydrocarbons with nitric acid. In JAERI, the rate constant and reaction heat were obtained from data measured with a differential thermal analyzer (DTA) for unstable hydrocarbons such as n-butanol, n-butyl nitrate, aromatic hydrocarbons, and cyclic compounds. The safety evaluation of Tomsk tank ruptured by the reaction was carried out by heat balance calculations between heat generation and heat loss in the tank using these rate constants and reaction heats. Consequently, it is clear that the cause of the tank rupture would be due to an exothermic reaction of aromatic hydrocarbons in kerosine made by petroleum with the concentrated nitric acid of 14.2N. (author)

  6. 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)

  7. Semiempirical equations for modeling solid-state kinetics based on a Maxwell-Boltzmann distribution of activation energies: applications to a polymorphic transformation under crystallization slurry conditions and to the thermal decomposition of AgMnO4 crystals.

    Science.gov (United States)

    Skrdla, Peter J; Robertson, Rebecca T

    2005-06-02

    Many solid-state reactions and phase transformations performed under isothermal conditions give rise to asymmetric, sigmoidally shaped conversion-time (x-t) profiles. The mathematical treatment of such curves, as well as their physical interpretation, is often challenging. In this work, the functional form of a Maxwell-Boltzmann (M-B) distribution is used to describe the distribution of activation energies for the reagent solids, which, when coupled with an integrated first-order rate expression, yields a novel semiempirical equation that may offer better success in the modeling of solid-state kinetics. In this approach, the Arrhenius equation is used to relate the distribution of activation energies to a corresponding distribution of rate constants for the individual molecules in the reagent solids. This distribution of molecular rate constants is then correlated to the (observable) reaction time in the derivation of the model equation. In addition to providing a versatile treatment for asymmetric, sigmoidal reaction curves, another key advantage of our equation over other models is that the start time of conversion is uniquely defined at t = 0. We demonstrate the ability of our simple, two-parameter equation to successfully model the experimental x-t data for the polymorphic transformation of a pharmaceutical compound under crystallization slurry (i.e., heterogeneous) conditions. Additionally, we use a modification of this equation to model the kinetics of a historically significant, homogeneous solid-state reaction: the thermal decomposition of AgMnO4 crystals. The potential broad applicability of our statistical (i.e., dispersive) kinetic approach makes it a potentially attractive alternative to existing models/approaches.

  8. In situ study of glasses decomposition layer

    International Nuclear Information System (INIS)

    Zarembowitch-Deruelle, O.

    1997-01-01

    The aim of this work is to understand the involved mechanisms during the decomposition of glasses by water and the consequences on the morphology of the decomposition layer, in particular in the case of a nuclear glass: the R 7 T 7 . The chemical composition of this glass being very complicated, it is difficult to know the influence of the different elements on the decomposition kinetics and on the resulting morphology because several atoms have a same behaviour. Glasses with simplified composition (only 5 elements) have then been synthesized. The morphological and structural characteristics of these glasses have been given. They have then been decomposed by water. The leaching curves do not reflect the decomposition kinetics but the solubility of the different elements at every moment. The three steps of the leaching are: 1) de-alkalinization 2) lattice rearrangement 3) heavy elements solubilization. Two decomposition layer types have also been revealed according to the glass heavy elements rate. (O.M.)

  9. Kinetically inert lanthanide complexes as reporter groups for binding of potassium by 18-crown-6

    DEFF Research Database (Denmark)

    Junker, Anne Kathrine Ravnsborg; Tropiano, Manuel; Faulkner, Stephen

    2016-01-01

    in a copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) “click” reaction with azide-functionalized crown ethers. The resulting complexes were investigated using NMR and optical methods. Titrations with potassium chloride in methanol observing the sensititzed europium- and terbium-centered emissions were......-centered emission to report on the binding of potassium in an 18-crown-6 binding pocket. The responsive systems were made by linking a crown ether to a kinetically inert lanthanide binding pocket using a molecular building block approach. Specifically, an alkyne-appended Ln.DO3A was used as a building block...... used to investigate the response of the systems. The molecular reporters based on aliphatic crown ethers were found to have strongly inhibited binding of potassium, while the benzo-18-crown-6 derived systems had essentially the same association constants as the native crown ethers. The shape...

  10. Non-isothermal decomposition kinetics, heat capacity and thermal safety of 37.2/44/16/2.2/0.2/0.4-GAP/CL-20/Al/N-100/PCA/auxiliaries mixture

    International Nuclear Information System (INIS)

    Zhang, Jiao-Qiang; Gao, Hong-Xu; Ji, Tie-Zheng; Xu, Kang-Zhen; Hu, Rong-Zu

    2011-01-01

    Highlights: → Non-isothermal decomposition kinetics, heat capacity and thermal safety on 37.2/44/16/2.2/0.2/0.4-GAP/CL-20/Al/N-100/PCA/auxiliaries mixture. → Apparent activation energy and pre-exponential constant obtained. → Thermal explosion temperature, adiabatic time-to-explosion, 50% drop height of impact sensitivity, and critical temperature of hot-spot initiation calculated. - Abstract: The specific heat capacity (C p ) of 37.2/44/16/2.2/0.2/0.4-GAP/CL-20/Al/N-100/PCA/auxiliaries mixture was determined with the continuous C p mode of microcalorimeter. The equation of C p with temperature was obtained. The standard molar heat capacity of GAP/CL-20/Al/N-100/PCA/auxiliaries mixture was 1.225 J mol -1 K -1 at 298.15 K. With the help of the peak temperature (T p ) from the non-isothermal DTG curves of the mixture at different heating rates (β), the apparent activation energy (E k and E o ) and pre-exponential constant (A K ) of thermal decomposition reaction obtained by Kissinger's method and Ozawa's method. Using density (ρ) and thermal conductivity (λ), the decomposition heat (Q d , taking half-explosion heat), Zhang-Hu-Xie-Li's formula, the values (T e0 and T p0 ) of T e and T p corresponding to β → 0, thermal explosion temperature (T be and T bp ), adiabatic time-to-explosion (t TIad ), 50% drop height (H 50 ) of impact sensitivity, and critical temperature of hot-spot initiation (T cr,hotspot ) of thermal explosion of the mixture were calculated. The following results of evaluating the thermal safety of the mixture were obtained: T be = 441.64 K, T bp = 461.66 K, t Tlad = 78.0 s (n = 2), t Tlad = 74.87s (n = 1), t Tlad = 71.85 s (n = 0), H 50 = 21.33 cm.

  11. 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.)

  12. 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.

  13. 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.

  14. STAB: A kinetic, three-dimensional, one-group digital computer program

    International Nuclear Information System (INIS)

    Curtis, A.R.; Tyror, J.G.; Wrigley, H.E.

    1961-10-01

    A computer program for solving the one-group, time dependent, three-dimensional diffusion equation together with auxiliary equations representing heat transfer, xenon production and control rod movements, is presented. The equations and the methods of solution are discussed. (author)

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

    International Nuclear Information System (INIS)

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

    1986-01-01

    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 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

  16. Magic Coset Decompositions

    CERN Document Server

    Cacciatori, Sergio L; Marrani, Alessio

    2013-01-01

    By exploiting a "mixed" non-symmetric Freudenthal-Rozenfeld-Tits magic square, two types of coset decompositions are analyzed for the non-compact special K\\"ahler symmetric rank-3 coset E7(-25)/[(E6(-78) x U(1))/Z_3], occurring in supergravity as the vector multiplets' scalar manifold in N=2, D=4 exceptional Maxwell-Einstein theory. The first decomposition exhibits maximal manifest covariance, whereas the second (triality-symmetric) one is of Iwasawa type, with maximal SO(8) covariance. Generalizations to conformal non-compact, real forms of non-degenerate, simple groups "of type E7" are presented for both classes of coset parametrizations, and relations to rank-3 simple Euclidean Jordan algebras and normed trialities over division algebras are also discussed.

  17. Thermal decomposition of beryllium perchlorate tetrahydrate

    International Nuclear Information System (INIS)

    Berezkina, L.G.; Borisova, S.I.; Tamm, N.S.; Novoselova, A.V.

    1975-01-01

    Thermal decomposition of Be(ClO 4 ) 2 x4H 2 O was studied by the differential flow technique in the helium stream. The kinetics was followed by an exchange reaction of the perchloric acid appearing by the decomposition with potassium carbonate. The rate of CO 2 liberation in this process was recorded by a heat conductivity detector. The exchange reaction yielding CO 2 is quantitative, it is not the limiting one and it does not distort the kinetics of the process of perchlorate decomposition. The solid products of decomposition were studied by infrared and NMR spectroscopy, roentgenography, thermography and chemical analysis. A mechanism suggested for the decomposition involves intermediate formation of hydroxyperchlorate: Be(ClO 4 ) 2 x4H 2 O → Be(OH)ClO 4 +HClO 4 +3H 2 O; Be(OH)ClO 4 → BeO+HClO 4 . Decomposition is accompained by melting of the sample. The mechanism of decomposition is hydrolytic. At room temperature the hydroxyperchlorate is a thick syrup-like compound crystallizing after long storing

  18. The platinum catalysed decomposition of hydrazine in acidic media

    International Nuclear Information System (INIS)

    Ananiev, A.V.; Tananaev, I.G.; Brossard, Ph.; Broudic, J.C.

    2000-01-01

    Kinetic study of the hydrazine decomposition in the solutions of HClO 4 , H 2 SO 4 and HNO 3 in the presence of Pt/SiO 2 catalyst has been undertaken. It was shown that the kinetics of the hydrazine catalytic decomposition in HClO 4 and H 2 SO 4 are identical. The process is determined by the heterogeneous catalytic auto-decomposition of N 2 H 4 on the catalyst's surface. The platinum catalysed hydrazine decomposition in the nitric acid solutions is a complex process, including heterogeneous catalytic auto-decomposition of N 2 H 4 , reaction of hydrazine with catalytically generated nitrous acid and the catalytic oxidation of hydrazine by nitric acid. The kinetic parameters of these reactions have been determined. The contribution of each reaction in the total process is determined by the liquid phase composition and by the temperature. (authors)

  19. NDMA formation by chloramination of ranitidine: Kinetics and mechanism

    KAUST Repository

    Le Roux, Julien; Gallard, Hervé ; Croue, Jean-Philippe; Papot, Sé bastien; Deborde, Marie

    2012-01-01

    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

  20. Structural and Kinetic Evidence for an Extended Hydrogen-Bonding Network in Catalysis of Methyl Group Transfer

    International Nuclear Information System (INIS)

    Doukov, T.; Hemmi, H.; Drennan, C.; Ragsdale, S.

    2007-01-01

    The methyltetrahydrofolate (CH 3 -H 4 folate) corrinoid-ironsulfur protein (CFeSP) methyltransferase (MeTr) catalyzes transfer of the methyl group of CH3-H4folate to cob(I)amide. This key step in anaerobic CO and CO 2 fixation is similar to the first half-reaction in the mechanisms of other cobalamin-dependent methyltransferases. Methyl transfer requires electrophilic activation of the methyl group of CH 3 -H 4 folate, which includes proton transfer to the N5 group of the pterin ring and poises the methyl group for reaction with the Co(I) nucleophile. The structure of the binary CH 3 -H 4 folate/MeTr complex (revealed here) lacks any obvious proton donor near the N5 group. Instead, an Asn residue and water molecules are found within H-bonding distance of N5. Structural and kinetic experiments described here are consistent with the involvement of an extended H-bonding network in proton transfer to N5 of the folate that includes an Asn (Asn-199 in MeTr), a conserved Asp (Asp-160), and a water molecule. This situation is reminiscent of purine nucleoside phosphorylase, which involves protonation of the purine N7 in the transition state and is accomplished by an extended H-bond network that includes water molecules, a Glu residue, and an Asn residue (Kicska, G. A., Tyler, P. C., Evans, G. B., Furneaux, R. H., Shi, W., Fedorov, A., Lewandowicz, A., Cahill, S. M., Almo, S. C., and Schramm, V. L. (2002) Biochemistry 41, 14489-14498). In MeTr, the Asn residue swings from a distant position to within H-bonding distance of the N5 atom upon CH 3 -H 4 folate binding. An N199A variant exhibits only ∼20-fold weakened affinity for CH 3 -H 4 folate but a much more marked 20,000-40,000-fold effect on catalysis, suggesting that Asn-199 plays an important role in stabilizing a transition state or high energy intermediate for methyl transfer

  1. The Decomposition of Surrogate Fuel Molecules During Combustion

    National Research Council Canada - National Science Library

    Tsang, Wing; Manion, Jeffrey A

    2006-01-01

    This project is aimed at developing a chemical kinetic database consisting of the rate constants of fundamental single step reactions that describe the pyrolytic decomposition of surrogate fuels molecules...

  2. A Model for Thermal Decomposition of Hydrogen Peroxide

    National Research Council Canada - National Science Library

    Heister, S

    2004-01-01

    ..., gas-phase decomposition kinetics, droplet dynamics, and control volume conservation laws. The code is adjustable for HP percent concentration for both main and secondary flows, massflow rates for both flows, and initial temperature of each...

  3. Thermal Decomposition of Aluminium Chloride Hexahydrate

    Czech Academy of Sciences Publication Activity Database

    Hartman, Miloslav; Trnka, Otakar; Šolcová, Olga

    2005-01-01

    Roč. 44, č. 17 (2005), s. 6591-6598 ISSN 0888-5885 R&D Projects: GA ČR(CZ) GA203/02/0002 Institutional research plan: CEZ:AV0Z40720504 Keywords : aluminum chloride hexahydrate * thermal decomposition * reaction kinetics Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.504, year: 2005

  4. Decomposition and reduction of AUC in hydrogen

    International Nuclear Information System (INIS)

    Ge Qingren; Kang Shifang; Zhou Meng

    1987-01-01

    AUC (Ammonium Uranyl Carbonate) conversion processes have been adopted extensively in nuclear fuel cycle. The kinetics investigation of these processes, however, has not yet been reported in detail at the published literatures. In the present work, the decomposition kinetics of AUC in hydrogen has been determined by non-isothermal method. DSC curves are solved with computer by Ge Qingren method. The results show that the kinetics obeys Avrami-Erofeev equation within 90% conversion. The apparent activation energy and preexponent are found to be 113.0 kJ/mol and 7.11 x 10 11 s -1 respectively. The reduction kinetics of AUC decomposition product in hydrogen at the range of 450 - 600 deg C has been determined by isothermal thermogravimetric method. The results show that good linear relationship can be obtained from the plot of conversion vs time, and that the apparent activation energy is found to be 113.9 kJ/mol. The effects of particle size and partial pressure of hydrogen are examined in reduction of AUC decomposition product. The reduction mechanism and the structure of particle are discussed according to the kinetics behaviour and SEM (scanning electron microscope) photograph

  5. Kinetics of cyclopropane formation by 1,3-deoxystannylation. A kinetic isotope effect as a probe for the mechanism of neighboring group participation

    International Nuclear Information System (INIS)

    McWilliam, D.C.; Balasubramanian, T.R.; Kuivila, H.G.

    1978-01-01

    1-Aryl-3-trimethylstannyl 3,5-dinitrobenzoates, Me 3 SnCH 2 CH 2 CHAr(ODNB), 4H, undergo solvolysis in 2,2,2-trifluoroethanol to form arylcyclopropanes and trimethylstannyl dinitrobenzoate. The rates for nine substituents on Ar are correlated by sigma + with a rho value of -3.63 at 100 0 C. The rates for a series of model compounds, Me 3 CCH 2 CH 2 CHAr(ODNB), 5H (six substituents), are also correlated by sigma + with a rho value of -4.90. In each case the rate for a given 4H is greater than that for the corresponding 5H. The Winstein-Grunwald m values for 4H and 5H in aqueous acetic acid at 100 0 C are 0.41 and 0.46, respectively. Measurements of the rates of solvolyses in trifluoroethanol of the 2.2-d 2 analogues of 4H and 5H revealed kinetic isotope effects of 0.94 and 1.08, respectively. These results are taken as evidence that the mechanism for the rate acceleration observed in the 4H series is due to direct participation of the C--Sn sigma electrons in the transition state of the rate-determining step of the 1,3-elimination reaction

  6. Lie bialgebras with triangular decomposition

    International Nuclear Information System (INIS)

    Andruskiewitsch, N.; Levstein, F.

    1992-06-01

    Lie bialgebras originated in a triangular decomposition of the underlying Lie algebra are discussed. The explicit formulas for the quantization of the Heisenberg Lie algebra and some motion Lie algebras are given, as well as the algebra of rational functions on the quantum Heisenberg group and the formula for the universal R-matrix. (author). 17 refs

  7. Solid-state reaction kinetics of neodymium doped magnesium hydrogen phosphate system

    Science.gov (United States)

    Gupta, Rashmi; Slathia, Goldy; Bamzai, K. K.

    2018-05-01

    Neodymium doped magnesium hydrogen phosphate (NdMHP) crystals were grown by using gel encapsulation technique. Structural characterization of the grown crystals has been carried out by single crystal X-ray diffraction (XRD) and it revealed that NdMHP crystals crystallize in orthorhombic crystal system with space group Pbca. Kinetics of the decomposition of the grown crystals has been studied by non-isothermal analysis. The estimation of decomposition temperatures and weight loss has been made from the thermogravimetric/differential thermo analytical (TG/DTA) in conjuncture with DSC studies. The various steps involved in the thermal decomposition of the material have been analysed using Horowitz-Metzger, Coats-Redfern and Piloyan-Novikova equations for evaluating various kinetic parameters.

  8. Chemical physics of decomposition of energetic materials. Problems and prospects

    International Nuclear Information System (INIS)

    Smirnov, Lev P

    2004-01-01

    The review is concerned with analysis of the results obtained in the kinetic and mechanistic studies on decomposition of energetic materials (explosives, powders and solid propellants). It is shown that the state-of-the art in this field is inadequate to the potential of modern chemical kinetics and chemical physics. Unsolved problems are outlined and ways of their solution are proposed.

  9. 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

  10. 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...

  11. Thermal decomposition of pyrite

    International Nuclear Information System (INIS)

    Music, S.; Ristic, M.; Popovic, S.

    1992-01-01

    Thermal decomposition of natural pyrite (cubic, FeS 2 ) has been investigated using X-ray diffraction and 57 Fe Moessbauer spectroscopy. X-ray diffraction analysis of pyrite ore from different sources showed the presence of associated minerals, such as quartz, szomolnokite, stilbite or stellerite, micas and hematite. Hematite, maghemite and pyrrhotite were detected as thermal decomposition products of natural pyrite. The phase composition of the thermal decomposition products depends on the terature, time of heating and starting size of pyrite chrystals. Hematite is the end product of the thermal decomposition of natural pyrite. (author) 24 refs.; 6 figs.; 2 tabs

  12. 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

  13. Decomposition of Sodium Tetraphenylborate

    International Nuclear Information System (INIS)

    Barnes, M.J.

    1998-01-01

    The chemical decomposition of aqueous alkaline solutions of sodium tetraphenylborate (NaTPB) has been investigated. The focus of the investigation is on the determination of additives and/or variables which influence NaTBP decomposition. This document describes work aimed at providing better understanding into the relationship of copper (II), solution temperature, and solution pH to NaTPB stability

  14. Azimuthal decomposition of optical modes

    CSIR Research Space (South Africa)

    Dudley, Angela L

    2012-07-01

    Full Text Available This presentation analyses the azimuthal decomposition of optical modes. Decomposition of azimuthal modes need two steps, namely generation and decomposition. An azimuthally-varying phase (bounded by a ring-slit) placed in the spatial frequency...

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

    International Nuclear Information System (INIS)

    Kroon, Maaike C.; Buijs, Wim; Peters, Cor J.; Witkamp, Geert-Jan

    2007-01-01

    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

  16. Decomposition of aluminosilicate ores of Afghanistan by hydrochloric acid

    International Nuclear Information System (INIS)

    Mamatov, E.D.; Khomidi, A.K.

    2015-01-01

    Present article is devoted to decomposition of aluminosilicate ores of Afghanistan by hydrochloric acid. The physicochemical properties of initial aluminosilicate ores were studied by means of X-ray phase, differential-thermal analysis methods. The chemical and mineral composition of aluminosilicate ores was considered. The kinetics of acid decomposition of aluminosilicate ores composed of two stages was studied as well. The flowsheets of complex processing of aluminium comprising ores by means of chloric and acid methods were proposed.

  17. Decomposition of group-velocity-locked-vector-dissipative solitons and formation of the high-order soliton structure by the product of their recombination.

    Science.gov (United States)

    Wang, Xuan; Li, Lei; Geng, Ying; Wang, Hanxiao; Su, Lei; Zhao, Luming

    2018-02-01

    By using a polarization manipulation and projection system, we numerically decomposed the group-velocity-locked-vector-dissipative solitons (GVLVDSs) from a normal dispersion fiber laser and studied the combination of the projections of the phase-modulated components of the GVLVDS through a polarization beam splitter. Pulses with a structure similar to a high-order vector soliton could be obtained, which could be considered as a pseudo-high-order GVLVDS. It is found that, although GVLVDSs are intrinsically different from group-velocity-locked-vector solitons generated in fiber lasers operated in the anomalous dispersion regime, similar characteristics for the generation of pseudo-high-order GVLVDS are obtained. However, pulse chirp plays a significant role on the generation of pseudo-high-order GVLVDS.

  18. Cellular decomposition in vikalloys

    International Nuclear Information System (INIS)

    Belyatskaya, I.S.; Vintajkin, E.Z.; Georgieva, I.Ya.; Golikov, V.A.; Udovenko, V.A.

    1981-01-01

    Austenite decomposition in Fe-Co-V and Fe-Co-V-Ni alloys at 475-600 deg C is investigated. The cellular decomposition in ternary alloys results in the formation of bcc (ordered) and fcc structures, and in quaternary alloys - bcc (ordered) and 12R structures. The cellular 12R structure results from the emergence of stacking faults in the fcc lattice with irregular spacing in four layers. The cellular decomposition results in a high-dispersion structure and magnetic properties approaching the level of well-known vikalloys [ru

  19. 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

  20. 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

  1. Differential Decomposition Among Pig, Rabbit, and Human Remains.

    Science.gov (United States)

    Dautartas, Angela; Kenyhercz, Michael W; Vidoli, Giovanna M; Meadows Jantz, Lee; Mundorff, Amy; Steadman, Dawnie Wolfe

    2018-03-30

    While nonhuman animal remains are often utilized in forensic research to develop methods to estimate the postmortem interval, systematic studies that directly validate animals as proxies for human decomposition are lacking. The current project compared decomposition rates among pigs, rabbits, and humans at the University of Tennessee's Anthropology Research Facility across three seasonal trials that spanned nearly 2 years. The Total Body Score (TBS) method was applied to quantify decomposition changes and calculate the postmortem interval (PMI) in accumulated degree days (ADD). Decomposition trajectories were analyzed by comparing the estimated and actual ADD for each seasonal trial and by fuzzy cluster analysis. The cluster analysis demonstrated that the rabbits formed one group while pigs and humans, although more similar to each other than either to rabbits, still showed important differences in decomposition patterns. The decomposition trends show that neither nonhuman model captured the pattern, rate, and variability of human decomposition. © 2018 American Academy of Forensic Sciences.

  2. Chemical kinetics and oil shale process design

    Energy Technology Data Exchange (ETDEWEB)

    Burnham, A.K.

    1993-07-01

    Oil shale processes are reviewed with the goal of showing how chemical kinetics influences the design and operation of different processes for different types of oil shale. Reaction kinetics are presented for organic pyrolysis, carbon combustion, carbonate decomposition, and sulfur and nitrogen reactions.

  3. Real-time Kinetics of High-mobility Group Box 1 (HMGB1) Oxidation in Extracellular Fluids Studied by in Situ Protein NMR Spectroscopy*

    Science.gov (United States)

    Zandarashvili, Levani; Sahu, Debashish; Lee, Kwanbok; Lee, Yong Sun; Singh, Pomila; Rajarathnam, Krishna; Iwahara, Junji

    2013-01-01

    Some extracellular proteins are initially secreted in reduced forms via a non-canonical pathway bypassing the endoplasmic reticulum and become oxidized in the extracellular space. One such protein is HMGB1 (high-mobility group box 1). Extracellular HMGB1 has different redox states that play distinct roles in inflammation. Using a unique NMR-based approach, we have investigated the kinetics of HMGB1 oxidation and the half-lives of all-thiol and disulfide HMGB1 species in serum, saliva, and cell culture medium. In this approach, salt-free lyophilized 15N-labeled all-thiol HMGB1 was dissolved in actual extracellular fluids, and the oxidation and clearance kinetics were monitored in situ by recording a series of heteronuclear 1H-15N correlation spectra. We found that the half-life depends significantly on the extracellular environment. For example, the half-life of all-thiol HMGB1 ranged from ∼17 min (in human serum and saliva) to 3 h (in prostate cancer cell culture medium). Furthermore, the binding of ligands (glycyrrhizin and heparin) to HMGB1 significantly modulated the oxidation kinetics. Thus, the balance between the roles of all-thiol and disulfide HMGB1 proteins depends significantly on the extracellular environment and can also be artificially modulated by ligands. This is important because extracellular HMGB1 has been suggested as a therapeutic target for inflammatory diseases and cancer. Our work demonstrates that the in situ protein NMR approach is powerful for investigating the behavior of proteins in actual extracellular fluids containing an enormous number of different molecules. PMID:23447529

  4. Photochemical decomposition of catecholamines

    International Nuclear Information System (INIS)

    Mol, N.J. de; Henegouwen, G.M.J.B. van; Gerritsma, K.W.

    1979-01-01

    During photochemical decomposition (lambda=254 nm) adrenaline, isoprenaline and noradrenaline in aqueous solution were converted to the corresponding aminochrome for 65, 56 and 35% respectively. In determining this conversion, photochemical instability of the aminochromes was taken into account. Irradiations were performed in such dilute solutions that the neglect of the inner filter effect is permissible. Furthermore, quantum yields for the decomposition of the aminochromes in aqueous solution are given. (Author)

  5. Oxidative decomposition of aromatic hydrocarbons by electron beam irradiation

    Science.gov (United States)

    Han, Do-Hung; Stuchinskaya, Tatiana; Won, Yang-Soo; Park, Wan-Sik; Lim, Jae-Kyong

    2003-05-01

    Decomposition of aromatic volatile organic compounds (VOCs) under electron beam irradiation was studied in order to examine the kinetics of the process, to characterize the reaction product distribution and to develop a process of waste gas control technology. Toluene, ethylbenzene, o-, m-, p-xylenes and chlorobenzene were used as target materials. The experiments were carried out at doses ranging from 0.5 to 10 kGy, using a flow reactor utilized under electron beam irradiation. Maximum degrees of decomposition carried out at 10 kGy in air environment were 55-65% for “non-chlorinated” aromatic VOC and 85% for chlorobenzene. It was found that a combination of aromatic pollutants with chlorobenzene would considerably increase the degradation value up to nearly 50% compared to the same compounds in the absence of chlorine groups. Based on our experimental observation, the degradation mechanism of the aromatic compounds combined with chloro-compound suggests that a chlorine radical, formed from EB irradiation, induces a chain reaction, resulting in an accelerating oxidative destruction of aromatic VOCs.

  6. 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%.

  7. 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.

  8. Decomposing Nekrasov decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Morozov, A. [ITEP,25 Bolshaya Cheremushkinskaya, Moscow, 117218 (Russian Federation); Institute for Information Transmission Problems,19-1 Bolshoy Karetniy, Moscow, 127051 (Russian Federation); National Research Nuclear University MEPhI,31 Kashirskoe highway, Moscow, 115409 (Russian Federation); Zenkevich, Y. [ITEP,25 Bolshaya Cheremushkinskaya, Moscow, 117218 (Russian Federation); National Research Nuclear University MEPhI,31 Kashirskoe highway, Moscow, 115409 (Russian Federation); Institute for Nuclear Research of Russian Academy of Sciences,6a Prospekt 60-letiya Oktyabrya, Moscow, 117312 (Russian Federation)

    2016-02-16

    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.

  9. Decomposing Nekrasov decomposition

    International Nuclear Information System (INIS)

    Morozov, A.; Zenkevich, Y.

    2016-01-01

    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.

  10. Symmetric Tensor Decomposition

    DEFF Research Database (Denmark)

    Brachat, Jerome; Comon, Pierre; Mourrain, Bernard

    2010-01-01

    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 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 the decomposition of any tensor of sub-generic rank, as opposed to widely used iterative algorithms with unproved global convergence (e.g. Alternate Least Squares or gradient descents). Second, it gives tools for understanding uniqueness conditions and for detecting the rank....

  11. Thermodynamic and kinetic studies in the systems alkali chloride-zinconium (or hafnium) tetrachloride: Part I. Vapour pressure measurements over hexachloro compounds and use of vapour pressure data in fractional decomposition

    International Nuclear Information System (INIS)

    Ray, H.S.; Bhat, B.G.; Reddy, G.S.; Biswas, A.K.

    1978-01-01

    A molten tin isoteniscope has been used to measure the vapour pressures over ZrCl 4 , HfCl 4 and the hexachlore zirconates (M 2 ZrCl 6 ) and the hexachloro hafnates (M 2 HfCl 6 ) of four alkali metals (M = Na,K,Rb,Cs). The method of preparation of these compounds and the effect of small amounts of residual alkali chlorides on the their vapour pressure are discussed. The pressure-temperature plots are examined in the light of some theoretical postulates. A scheme for separation of hafnium from zirconoium by multistage fractional decomposition of the hexachlore compounds of any alkali metal is described. The scheme, which is analogous to rectification in liquid-vapour systems, employs a countercurrent flow of Zr(Hf)Cl 4 in a gas stream and a moving bed of alkali chlorides. The separation is based on the difference in the dissociation equilibrium for zirconium and hafnium compounds. Stage calculations for such a scheme and the main conclusions of a computational work are presented. (author)

  12. Solid-state reaction kinetics and optical studies of cadmium doped magnesium hydrogen phosphate crystals

    Science.gov (United States)

    Verma, Madhu; Gupta, Rashmi; Singh, Harjinder; Bamzai, K. K.

    2018-04-01

    The growth of cadmium doped magnesium hydrogen phosphate was successfully carried out by using room temperature solution technique i.e., gel encapsulation technique. Grown crystals were confirmed by single crystal X-ray diffraction (XRD). The structure of the grown crystal belongs to orthorhombic crystal system and crystallizes in centrosymmetric space group. Kinetics of the decomposition of the grown crystals were studied by non-isothermal analysis. Thermo gravimetric / differential thermo analytical (TG/DTA) studies revealed that the grown crystal is stable upto 119 °C. The various steps involved in the thermal decomposition of the material have been analysed using Horowitz-Metzger, Coats-Redfern and Piloyan-Novikova equations for evaluating various kinetic parameters. The optical studies shows that the grown crystals possess wide transmittance in the visible region and significant optical band gap of 5.5ev with cut off wavelength of 260 nm.

  13. 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…

  14. FDG decomposition products

    International Nuclear Information System (INIS)

    Macasek, F.; Buriova, E.

    2004-01-01

    In this presentation authors present the results of analysis of decomposition products of [ 18 ]fluorodexyglucose. It is concluded that the coupling of liquid chromatography - mass spectrometry with electrospray ionisation is a suitable tool for quantitative analysis of FDG radiopharmaceutical, i.e. assay of basic components (FDG, glucose), impurities (Kryptofix) and decomposition products (gluconic and glucuronic acids etc.); 2-[ 18 F]fluoro-deoxyglucose (FDG) is sufficiently stable and resistant towards autoradiolysis; the content of radiochemical impurities (2-[ 18 F]fluoro-gluconic and 2-[ 18 F]fluoro-glucuronic acids in expired FDG did not exceed 1%

  15. 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.

  16. XPS study of influence of exposure to air on thermal stability and kinetics of hydrogen decomposition of MgH{sub 2} films obtained by direct hydrogenation from gaseous phase of metallic Mg

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-15

    Highlights: • Air influence on thermal stability of MgH{sub 2} have been studied by XPS. • XPS spectra of MgH{sub 2} films obtained at different hydrogen pressures have been studied. • Changes in the chemical state of MgH{sub 2} films depending on time of exposure to air are analyzed. • Correlation exists between chemical surface condition of MgH{sub 2} films and their thermal stableness. • Process of hydrogen desorption from MgH{sub 2} films is studied using TDS for model samples. - Abstract: Mechanism of influence of exposure to air on thermal stability of MgH{sub 2} obtained by direct hydrogenation from the gas phase, the nature of the hydride sensitivity to the negative impact of air and the role of its surface chemical state have not been studied enough. The present article presents data of X-ray photoelectron spectroscopy (XPS) measurements of the Mg 2s, O 1s, C 1s core-level spectra of surface of hydride MgH{sub 2} films derived by gas phase hydrogenation of model samples of metallic Mg, and the evolution of changes in the chemical state of the surface of the hydride films depending on the time of exposure to air and formation conditions (hydrogen pressure and hydrogenation regime). Based on results of XPS, X-ray diffraction (XRD), and thermodesorption spectroscopy (TDS), the existence of a relationship (correlation) between chemical surface condition of hydride MgH{sub 2} films obtained at different hydrogen pressures (3.0 MPa and 11.5 MPa) and their thermal stableness and temperature of the beginning of hydride decomposition has been established.

  17. Strongly \\'etale difference algebras and Babbitt's decomposition

    OpenAIRE

    Tomašić, Ivan; Wibmer, Michael

    2015-01-01

    We introduce a class of strongly \\'{e}tale difference algebras, whose role in the study of difference equations is analogous to the role of \\'{e}tale algebras in the study of algebraic equations. We deduce an improved version of Babbitt's decomposition theorem and we present applications to difference algebraic groups and the compatibility problem.

  18. 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....

  19. Effect of dislocations on spinodal decomposition in Fe-Cr alloys

    International Nuclear Information System (INIS)

    Li Yongsheng; Li Shuxiao; Zhang Tongyi

    2009-01-01

    Phase-field simulations of spinodal decomposition in Fe-Cr alloys with dislocations were performed by using the Cahn-Hilliard diffusion equation. The stress field of dislocations was calculated in real space via Stroh's formalism, while the composition inhomogeneity-induced stress field and the diffusion equation were numerically calculated in Fourier space. The simulation results indicate that dislocation stress field facilitates, energetically and kinetically, spinodal decomposition, making the phase separation faster and the separated phase particles bigger at and near the dislocation core regions. A tilt grain boundary is thus a favorable place for spinodal decomposition, resulting in a special microstructure morphology, especially at the early stage of decomposition.

  20. Inverse scale space decomposition

    DEFF Research Database (Denmark)

    Schmidt, Marie Foged; Benning, Martin; Schönlieb, Carola-Bibiane

    2018-01-01

    We investigate the inverse scale space flow as a decomposition method for decomposing data into generalised singular vectors. We show that the inverse scale space flow, based on convex and even and positively one-homogeneous regularisation functionals, can decompose data represented...... by the application of a forward operator to a linear combination of generalised singular vectors into its individual singular vectors. We verify that for this decomposition to hold true, two additional conditions on the singular vectors are sufficient: orthogonality in the data space and inclusion of partial sums...... of the subgradients of the singular vectors in the subdifferential of the regularisation functional at zero. We also address the converse question of when the inverse scale space flow returns a generalised singular vector given that the initial data is arbitrary (and therefore not necessarily in the range...

  1. Thermal decomposition of potassium metaperiodate doped with trivalent ions

    Energy Technology Data Exchange (ETDEWEB)

    Muraleedharan, K., E-mail: kmuralika@gmail.com [Department of Chemistry, University of Calicut, Calicut, Kerala 673 635 (India); Kannan, M.P.; Gangadevi, T. [Department of Chemistry, University of Calicut, Calicut, Kerala 673 635 (India)

    2010-04-20

    The kinetics of isothermal decomposition of potassium metaperiodate (KIO{sub 4}), doped with phosphate and aluminium has been studied by thermogravimetry (TG). We introduced a custom-made thermobalance that is able to record weight decrease with time under pure isothermal conditions. The decomposition proceeds mainly through two stages: an acceleratory stages up to {alpha} = 0.50 and the decay stage beyond. The decomposition data for aluminium and phosphate doped KIO{sub 4} were found to be best described by the Prout-Tompkins equation. Separate kinetic analyses of the {alpha}-t data corresponding to the acceleratory region and decay region showed that the acceleratory stage gave the best fit with Prout-Tompkins equation itself whereas the decay stage fitted better to the contracting area equation. The rate of decomposition of phosphate doped KIO{sub 4} increases approximately linearly with an increase in the dopant concentration. In the case of aluminium doped KIO{sub 4}, the rate passes through a maximum with increase in the dopant concentration. The {alpha}-t data of pure and doped KIO{sub 4} were also subjected to isoconversional studies for the determination of activation energy values. Doping did not change the activation energy of the reaction. The results favour an electron-transfer mechanism for the isothermal decomposition of KIO{sub 4}, agreeing well with our earlier observations.

  2. Pollutant content in marine debris and characterization by thermal decomposition

    International Nuclear Information System (INIS)

    Iñiguez, M.E.; Conesa, J.A.; Fullana, A.

    2017-01-01

    Marine debris (MDs) produces a wide variety of negative environmental, economic, safety, health and cultural impacts. Most marine litter has a very low decomposition rate (plastics), leading to a gradual accumulation in the coastal and marine environment. Characterization of the MDs has been done in terms of their pollutant content: PAHs, ClBzs, ClPhs, BrPhs, PCDD/Fs and PCBs. The results show that MDs is not a very contaminated waste. Also, thermal decomposition of MDs materials has been studied in a thermobalance at different atmospheres and heating rates. Below 400–500 K, the atmosphere does not affect the thermal degradation of the mentioned waste. However, at temperatures between 500 and 800 K the presence of oxygen accelerates the decomposition. Also, a kinetic model is proposed for the combustion of the MDs, and the decomposition is compared with that of their main constituents, i.e., polyethylene (PE), polystyrene (PS), polypropylene (PP), nylon and polyethylene-terephthalate (PET). - Highlights: • The analysis and characterization of waste from marine environment were performed. • Its pollutant content has been determined, considering PAHs, PCDD/Fs and dl-PCBs. • Thermal decomposition of MDs was studied at different atmospheres and heating rates. • Kinetic models for the combustion of the five main plastics of MDs were proposed. • Composition of the waste is calculated using thermal behavior of different plastics.

  3. First-order hydrothermal oxidation kinetics of digested sludge compared with raw sludge.

    Science.gov (United States)

    Shanableh, A; Imteaz, M

    2008-09-01

    This article presents an assessment of the first-order hydrothermal oxidation kinetics of a selected digested sludge at subcritical ( 374 degrees C) temperatures in the range of 250-460 degrees C. Furthermore, the results were compared with reported oxidation kinetics of raw sludge treated under identical experimental conditions. In the assessment, oxidation was considered to proceed in two steps: (1) decomposition of the particulate, or non-filterable, chemical oxygen demand (PCOD); followed by (2) ultimate oxidation and removal of the total, particulate and soluble, COD. The accumulation and removal of soluble COD (SCOD) was determined from the difference between the rates of sludge decomposition and ultimate oxidation. Using results from batch and continuous-flow hydrothermal treatment experiments, the reacting organic ingredients were separated into groups according to the ease or difficulty at which they were decomposed or removed, with Arrhenius-type activation energy levels assigned to the different groups. The analysis confirmed that within the treatment range of 75% to more than 97% COD removal, the oxidation kinetics of the digested and raw sludges were nearly identical despite differences in the proportions of their original organic ingredients. The original organic ingredients were mostly removed above 75% COD removal, and the oxidation kinetics appeared to be dominated by the removal of acetic acid, an intermediate by-product which constituted 50% to more than 80% of the remaining COD. Furthermore, the oxidation kinetics of both sludge types were consistent with reported first-order oxidation kinetics of pure acetic acid solutions. The resulting kinetic models adequately represented hydrothermal oxidation of digested sludge, in terms of COD and PCOD removals, as well as accumulation and removal of the soluble SCOD.

  4. 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....

  5. 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.

  6. A kinetic study of the redox reactions of complex cyanides of iron, molybdenum and tungsten with compounds of the group VI A elements

    International Nuclear Information System (INIS)

    Dennis, C.R.

    1981-01-01

    The kinetic study arises out of the fact that few is known about redox kinetics of complex cyanides of molybdenum and tungsten. The redox kinetics of the complex cyanides of iron with organic and inorganic compounds are well known in organic chemistry. This comparitive study is done to obtain more information on redox reactions of complex cyanides of molybdenum and tungsten considering its greater applicability in organic and inorganic chemistry because of the propitious reduction potential of this complex cyanide in acidic and alkaline mediums. Various redox systems are kinetically investigated regarding the influence of the oxidising agent, reducing agent hydrogen ions and alkaline-metal ions on the reaction rate. A reaction mechanism is proposed for every system

  7. 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

  8. 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....

  9. 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...... °C. Full conversion to Lu2O3 is achieved at about 1000 °C. Whereas the temperatures and solid reaction products of the first two decomposition steps are similar to those previously reported for the thermal decomposition of lanthanum(III) propionate monohydrate, the final decomposition...... 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...

  10. Kinetics in radiation chemistry

    International Nuclear Information System (INIS)

    Hummel, A.

    1987-01-01

    In this chapter the authors first briefly review the kinetics of first- and second-order processes for continuous and pulsed irradiation, without taking the effects of nonhomogeneous formation of the species into consideration. They also discuss diffusion controlled reactions under conditions where interactions of more than two particles can be neglected, first the kinetics of the diffusion-controlled reaction of randomly generated species (homogeneous reaction) and then that of isolated pairs of reactants. The latter is often called geminate kinetics when dealing with pairs of oppositely charged species; they shall use this term for the kinetics of isolated pairs in general. In the last section they discuss briefly the kinetics of groups of more than two reactants

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

    International Nuclear Information System (INIS)

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

    2013-01-01

    decomposition of c-In(OH) 3 to c-In 2 O 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) 6 ] octahedra and finally to their destabilization and (ii) transformation of the vertices-shared indium–oxygen octahedra in c-In(OH) 3 to vertices- and edge-shared octahedra in c-In 2 O 3 . - Graphical abstract: Frame-by-frame analysis of video sequences recorded of HR-TEM images reveals that a single cube-shaped In(OH) 3 nanocrystal with {100} morphology decomposes into bixbyite-type In 2 O 3 domains while being imaged. The mechanism of this decomposition is evaluated through the analysis of the structural relationship between initial (c-In(OH) 3 ) and transformed (c-In 2 O 3 ) phases and though the kinetics of the decomposition followed via the time-resolved shrinkage of the initial crystal of indium hydroxide. Highlights: ► In-situ time-resolved High Resolution Transmission Electron Microscopy. ► Crystallographic transformation path. ► Kinetics of the decomposition in one nanocrystal.

  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. Decomposition of oxalate precipitates by photochemical reaction

    International Nuclear Information System (INIS)

    Jae-Hyung Yoo; Eung-Ho Kim

    1999-01-01

    A photo-radiation method was applied to decompose oxalate precipitates so that it can be dissolved into dilute nitric acid. This work has been studied as a part of partitioning of minor actinides. Minor actinides can be recovered from high-level wastes as oxalate precipitates, but they tend to be coprecipitated together with lanthanide oxalates. This requires another partitioning step for mutual separation of actinide and lanthanide groups. In this study, therefore, some experimental work of photochemical decomposition of oxalate was carried out to prove its feasibility as a step of partitioning process. The decomposition of oxalic acid in the presence of nitric acid was performed in advance in order to understand the mechanistic behaviour of oxalate destruction, and then the decomposition of neodymium oxalate, which was chosen as a stand-in compound representing minor actinide and lanthanide oxalates, was examined. The decomposition rate of neodymium oxalate was found as 0.003 mole/hr at the conditions of 0.5 M HNO 3 and room temperature when a mercury lamp was used as a light source. (author)

  14. Decomposition of PCBs in oils using gamma radiolysis

    International Nuclear Information System (INIS)

    Mincher, B.J.; Arbon, R.E.; Schwendiman, G.L.

    1996-01-01

    This paper investigates the radiolysis of the polychlorinated biphenyls (PCBs) in several oil matrices. The results of mechanism and kinetic studies in isooctane are presented. The decomposition of PCBs in isooctane is shown to occur by reductive dechlorination due to electron capture and to proceed with pseudo-first-order kinetics. The rate is dependent on the initial PCB concentration. Electron capture detection gas chromatograms confirm that dechlorination also occurs with commercial Aroclor PCBs in irradiated transformer and hydraulic oils. The results of a demonstration experiment involving PCB contaminated waste hydraulic oils are presented

  15. A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions.

    Science.gov (United States)

    Goerigk, Lars; Hansen, Andreas; Bauer, Christoph; Ehrlich, Stephan; Najibi, Asim; Grimme, Stefan

    2017-12-13

    We present the GMTKN55 benchmark database for general main group thermochemistry, kinetics and noncovalent interactions. Compared to its popular predecessor GMTKN30 [Goerigk and Grimme J. Chem. Theory Comput., 2011, 7, 291], it allows assessment across a larger variety of chemical problems-with 13 new benchmark sets being presented for the first time-and it also provides reference values of significantly higher quality for most sets. GMTKN55 comprises 1505 relative energies based on 2462 single-point calculations and it is accessible to the user community via a dedicated website. Herein, we demonstrate the importance of better reference values, and we re-emphasise the need for London-dispersion corrections in density functional theory (DFT) treatments of thermochemical problems, including Minnesota methods. We assessed 217 variations of dispersion-corrected and -uncorrected density functional approximations, and carried out a detailed analysis of 83 of them to identify robust and reliable approaches. Double-hybrid functionals are the most reliable approaches for thermochemistry and noncovalent interactions, and they should be used whenever technically feasible. These are, in particular, DSD-BLYP-D3(BJ), DSD-PBEP86-D3(BJ), and B2GPPLYP-D3(BJ). The best hybrids are ωB97X-V, M052X-D3(0), and ωB97X-D3, but we also recommend PW6B95-D3(BJ) as the best conventional global hybrid. At the meta-generalised-gradient (meta-GGA) level, the SCAN-D3(BJ) method can be recommended. Other meta-GGAs are outperformed by the GGA functionals revPBE-D3(BJ), B97-D3(BJ), and OLYP-D3(BJ). We note that many popular methods, such as B3LYP, are not part of our recommendations. In fact, with our results we hope to inspire a change in the user community's perception of common DFT methods. We also encourage method developers to use GMTKN55 for cross-validation studies of new methodologies.

  16. Radiation-induced decomposition of aqueous trichloroethylene solutions

    International Nuclear Information System (INIS)

    Gehringer, P.; Proksch, E.; Szinovatz, W.; Eschweiler, H.

    1988-01-01

    In air-saturated reagent grade water, 10 ppm trichloroethylene are decomposed by γ radiation in a roughly first-order reaction; the initial G-value being 5.4 molecules/100 eV. At sub-ppm concentrations the kinetics remain roughly first-order; the initial G-values decrease with decreasing concentration. The main decomposition products are Cl - , CO 2 and HCOOH. A tentative reaction scheme in accordance with these results is presented. (author)

  17. 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.

  18. Proton mass decomposition

    Science.gov (United States)

    Yang, Yi-Bo; Chen, Ying; Draper, Terrence; Liang, Jian; Liu, Keh-Fei

    2018-03-01

    We report the results on the proton mass decomposition and also on the related quark and glue momentum fractions. The results are based on overlap valence fermions on four ensembles of Nf = 2 + 1 DWF configurations with three lattice spacings and volumes, and several pion masses including the physical pion mass. With 1-loop pertur-bative calculation and proper normalization of the glue operator, we find that the u, d, and s quark masses contribute 9(2)% to the proton mass. The quark energy and glue field energy contribute 31(5)% and 37(5)% respectively in the MS scheme at µ = 2 GeV. The trace anomaly gives the remaining 23(1)% contribution. The u, d, s and glue momentum fractions in the MS scheme are consistent with the global analysis at µ = 2 GeV.

  19. Art of spin decomposition

    International Nuclear Information System (INIS)

    Chen Xiangsong; Sun Weimin; Wang Fan; Goldman, T.

    2011-01-01

    We analyze the problem of spin decomposition for an interacting system from a natural perspective of constructing angular-momentum eigenstates. We split, from the total angular-momentum operator, a proper part which can be separately conserved for a stationary state. This part commutes with the total Hamiltonian and thus specifies the quantum angular momentum. We first show how this can be done in a gauge-dependent way, by seeking a specific gauge in which part of the total angular-momentum operator vanishes identically. We then construct a gauge-invariant operator with the desired property. Our analysis clarifies what is the most pertinent choice among the various proposals for decomposing the nucleon spin. A similar analysis is performed for extracting a proper part from the total Hamiltonian to construct energy eigenstates.

  20. Influence of Family Structure on Variance Decomposition

    DEFF Research Database (Denmark)

    Edwards, Stefan McKinnon; Sarup, Pernille Merete; Sørensen, Peter

    Partitioning genetic variance by sets of randomly sampled genes for complex traits in D. melanogaster and B. taurus, has revealed that population structure can affect variance decomposition. In fruit flies, we found that a high likelihood ratio is correlated with a high proportion of explained ge...... capturing pure noise. Therefore it is necessary to use both criteria, high likelihood ratio in favor of a more complex genetic model and proportion of genetic variance explained, to identify biologically important gene groups...

  1. 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...... in the combustion chamber and the cyclone was calculated taking three mechanisms into account: Reduction by char, catalytic decomposition over bed material and thermal decomposition. The calculated destruction rate was in good agreement with the measured destruction of N2O injected at different levels in the boiler...

  2. 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...... 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...

  3. Wood decomposition as influenced by invertebrates.

    Science.gov (United States)

    Ulyshen, Michael D

    2016-02-01

    The diversity and habitat requirements of invertebrates associated with dead wood have been the subjects of hundreds of studies in recent years but we still know very little about the ecological or economic importance of these organisms. The purpose of this review is to examine whether, how and to what extent invertebrates affect wood decomposition in terrestrial ecosystems. Three broad conclusions can be reached from the available literature. First, wood decomposition is largely driven by microbial activity but invertebrates also play a significant role in both temperate and tropical environments. Primary mechanisms include enzymatic digestion (involving both endogenous enzymes and those produced by endo- and ectosymbionts), substrate alteration (tunnelling and fragmentation), biotic interactions and nitrogen fertilization (i.e. promoting nitrogen fixation by endosymbiotic and free-living bacteria). Second, the effects of individual invertebrate taxa or functional groups can be accelerative or inhibitory but the cumulative effect of the entire community is generally to accelerate wood decomposition, at least during the early stages of the process (most studies are limited to the first 2-3 years). Although methodological differences and design limitations preclude meta-analysis, studies aimed at quantifying the contributions of invertebrates to wood decomposition commonly attribute 10-20% of wood loss to these organisms. Finally, some taxa appear to be particularly influential with respect to promoting wood decomposition. These include large wood-boring beetles (Coleoptera) and termites (Termitoidae), especially fungus-farming macrotermitines. The presence or absence of these species may be more consequential than species richness and the influence of invertebrates is likely to vary biogeographically. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.

  4. Physical kinetics

    International Nuclear Information System (INIS)

    Lifschitz, E.M.; Pitajewski, L.P.

    1983-01-01

    The textbook covers the subject under the following headings: kinetic gas theory, diffusion approximation, collisionless plasma, collisions within the plasma, plasma in the magnetic field, theory of instabilities, dielectrics, quantum fluids, metals, diagram technique for nonequilibrium systems, superconductors, and kinetics of phase transformations

  5. LEAF RESIDUE DECOMPOSITION OF SELECTED ATLANTIC FOREST TREE SPECIES

    Directory of Open Access Journals (Sweden)

    Helga Dias Arato

    2018-02-01

    Full Text Available ABSTRACT Biogeochemical cycling is essential to establish and maintain plant and animal communities. Litter is one of main compartments of this cycle, and the kinetics of leaf decomposition in forest litter depend on the chemical composition and environmental conditions. This study evaluated the effect of leaf composition and environmental conditions on leaf decomposition of native Atlantic Forest trees. The following species were analyzed: Mabea fistulifera Mart., Bauhinia forficata Link., Aegiphila sellowiana Cham., Zeyheria tuberculosa (Vell, Luehea grandiflora Mart. et. Zucc., Croton floribundus Spreng., Trema micrantha (L Blume, Cassia ferruginea (Schrad Schrad ex DC, Senna macranthera (DC ex Collad. H. S. Irwin and Barney and Schinus terebinthifolius Raddi (Anacardiaceae. For each species, litter bags were distributed on and fixed to the soil surface of soil-filled pots (in a greenhouse, or directly to the surface of the same soil type in a natural forest (field. Every 30 days, the dry weight and soil basal respiration in both environments were determined. The cumulative decomposition of leaves varied according to the species, leaf nutrient content and environment. In general, the decomposition rate was lowest for Aegiphila sellowiana and fastest for Bauhinia forficate and Schinus terebinthifolius. This trend was similar under the controlled conditions of a greenhouse and in the field. The selection of species with a differentiated decomposition pattern, suited for different stages of the recovery process, can help improve soil restoration.

  6. Reaction mechanism of reductive decomposition of FGD gypsum with anthracite

    International Nuclear Information System (INIS)

    Zheng, Da; Lu, Hailin; Sun, Xiuyun; Liu, Xiaodong; Han, Weiqing; Wang, Lianjun

    2013-01-01

    Highlights: • The reaction mechanism was different if the molar ratio of C/CaSO 4 was different. • The yield of CaO rises with an increase in temperature. • The optimal ratio of C/CaSO 4 = 1.2:1. • The decomposition process is mainly apparent solid–solid reaction with liquid-phase involved. - Abstract: The process of decomposition reaction between flue gas desulfurization (FGD) gypsum and anthracite is complex, which depends on the reaction conditions and atmosphere. In this study, thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA-FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and the experiment in a tubular reactor were used to characterize the decomposition reaction in a nitrogen atmosphere under different conditions. The reaction mechanism analysis showed that the decomposition reaction process and mechanism were different when the molar proportion of C/CaSO 4 was changed. The experiment results showed that appropriate increase in the C/CaSO 4 proportion and higher temperatures were suitable for the formation of the main production of CaO, which can help us to understand the solid state reaction mechanism better. Via kinetic analysis of the reaction between anthracite and FGD gypsum under the optimal molar ratio of C/CaSO 4 , the mechanism model of the reaction was confirmed and the decomposition process was a two-step reaction which was in accordance with apparent solid–solid reaction

  7. Heparin kinetics

    International Nuclear Information System (INIS)

    Swart, C.A.M. de.

    1983-01-01

    The author has studied the kinetics of heparin and heparin fractions after intravenous administration in humans and in this thesis the results of this study are reported. Basic knowledge about the physico-chemical properties of heparin and its interactions with proteins resulting in anticoagulant and lipolytic effects are discussed in a review (chapter II), which also comprises some clinical aspects of heparin therapy. In chapter III the kinetics of the anticoagulant effect are described after intravenous administration of five commercial heparin preparations. A mathematical model is presented that fits best to these kinetics. The kinetics of the anticoagulant and lipolytic effects after intravenous injection of various 35 S-radiolabelled heparin fractions and their relationship with the disappearance of the radiolabel are described in chapter IV. Chapter V gives a description of the kinetics of two radiolabels after injection of in vitro formed complexes consisting of purified, 125 I-radiolabelled antithrombin III and various 35 S-radiolabelled heparin fractions. (Auth.)

  8. Low temperature kinetics of In-Cd solid solution decomposition

    Czech Academy of Sciences Publication Activity Database

    Pal-Val, P.P.; Pal-Val, L.N.; Ostapovets, A.A.; Vaněk, Přemysl

    2008-01-01

    Roč. 137, - (2008), s. 35-42 ISSN 1012-0394 Institutional research plan: CEZ:AV0Z10100520 Keywords : low temperatures * In-based alloys * solid solutions * isothermal structure instability * Young's modulus * electrical resistivity * phase diagrams Subject RIV: BM - Solid Matter Physics ; Magnetism http://www.scientific.net/3-908451-53-1/35/

  9. 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

  10. 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.

  11. Decomposition of pre calcined aluminium silicate ores of Afghanistan by hydrochloric acid

    International Nuclear Information System (INIS)

    Khomidi, A.K.; Mamatov, E.D.

    2015-01-01

    Present article is devoted to decomposition of pre calcined aluminium silicate ores of Afghanistan by hydrochloric acid. The physicochemical properties of initial aluminium silicate ores were studied by means of X-ray phase, differential thermal and silicate analysis. The chemical composition of aluminium containing ores was determined. The optimal conditions of interaction of initial and pre calcined siallites with hydrochloric acid were defined. The kinetics of acid decomposition of aluminium silicate ores was studied as well.

  12. 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

  13. Impacts of Different Functional Groups on the Kinetic Rates of α-Amine Ketoximesilanes Hydrolysis in the Preparation of Room Temperature Vulcanized Silicone Rubber.

    Science.gov (United States)

    Xu, Huihui; Liu, Zihou; Liu, Qingyang; Bei, Yiling; Zhu, Qingzeng

    2018-05-13

    α-Amine ketoximesilanes are proven to be effective crosslinkers in the preparation of ketone-oxime one-component room temperature vulcanized (RTV) silicone rubber without the use of toxic metal catalyst. This work aimed to investigate the hydrolysis kinetic of α-amine ketoximesilanes, which is vitally important for the preparation of RTV silicone rubber. Five kinds of α-amine ketoximesilanes, namely α-(N,N-diethyl)aminomethyltri(methylethylketoxime)silane (DEMOS), α-(N,N-di-n-butyl)aminomethyltri(methylethylketoxime)silane (DBMOS), α-(N-n-butyl)aminomethyltri(methylethylketoxime)silane (n-BMOS), α-(N-cyclohexyl)aminomethyltri(methylethylketoxime)silane (CMOS) and α-(β-aminomethyl)aminomethyltri(methylethylketoxime)silane (AEMOS), were successfully obtained and confirmed using Fourier transform infrared spectrometer (FT-IR) and hydrogen-1 nuclear magnetic resonance ( ¹H NMR). Kinetics of hydrolysis reactions were measured by FT-IR and conductivity. Our results illustrated that the kinetic constant rates ranged from 12.2 × 10 −4 s −1 to 7.6 × 10 −4 s −1 , with the decreasing order of DEMOS > n-BMOS > DBMOS > CMOS > AEMOS at the given temperature and humidity. Better performances of thermal stability could be achieved when using the α-amine ketoximesilanes as crosslinkers in the preparation of RTV silicon rubber than that of RTV silicone rubber with the use of methyltri(methylethylketoxime)silane (MOS) as a crosslinker and organic tin as a catalyst.

  14. 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.

  15. AUTONOMOUS GAUSSIAN DECOMPOSITION

    International Nuclear Information System (INIS)

    Lindner, Robert R.; Vera-Ciro, Carlos; Murray, Claire E.; Stanimirović, Snežana; Babler, Brian; Heiles, Carl; Hennebelle, Patrick; Goss, W. M.; Dickey, John

    2015-01-01

    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 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

  16. Decomposition of lake phytoplankton. 2

    International Nuclear Information System (INIS)

    Hansen, L.; Krog, G.F.; Soendergaard, M.

    1986-01-01

    The lysis process of phytoplankton was followed in 24 h incubations in three Danish lakes. By means of gel-chromatography it was shown that the dissolved carbon leaching from different algal groups differed in molecular weight composition. Three distinct molecular weight classes (>10,000; 700 to 10,000 and < 700 Daltons) leached from blue-green algae in almost equal proportion. The lysis products of spring-bloom diatoms included only the two smaller size classes, and the molecules between 700 and 10,000 Daltons dominated. Measurements of cell content during decomposition of the diatoms revealed polysaccharides and low molecular weight compounds to dominate the lysis products. No proteins were leached during the first 24 h after cell death. By incubating the dead algae in natural lake water, it was possible to detect a high bacterial affinity towards molecules between 700 and 10,000 Daltons, although the other size classes were also utilized. Bacterial transformation of small molecules to larger molecules could be demonstrated. (author)

  17. 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....

  18. NRSA enzyme decomposition model data

    Data.gov (United States)

    U.S. Environmental Protection Agency — Microbial enzyme activities measured at more than 2000 US streams and rivers. These enzyme data were then used to predict organic matter decomposition and microbial...

  19. 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.

  20. 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.

  1. Decomposition of oxalate precipitates by photochemical reaction

    International Nuclear Information System (INIS)

    Yoo, J.H.; Kim, E.H.

    1998-01-01

    A photo-radiation method was applied to decompose oxalate precipitates so that it can be dissolved into dilute nitric acid. This work has been studied as a part of partitioning of minor actinides. Minor actinides can be recovered from high-level wastes as oxalate precipitates, but they tend to be coprecipitated together with lanthanide oxalates. This requires another partitioning step for mutual separation of actinide and lanthanide groups. In this study, therefore, the photochemical decomposition mechanism of oxalates in the presence of nitric acid was elucidated by experimental work. The decomposition of oxalates was proved to be dominated by the reaction with hydroxyl radical generated from the nitric acid, rather than with nitrite ion also formed from nitrate ion. The decomposition rate of neodymium oxalate, which was chosen as a stand-in compound representing minor actinide and lanthanide oxalates, was found to be 0.003 M/hr at the conditions of 0.5 M HNO 3 and room temperature when a mercury lamp was used as a light source. (author)

  2. 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.

  3. 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.

  4. Kinetic, stereochemical, and molecular association factors in the hydralumination of group IV subtituted alkynes. The role of p/sub π/-d/sub π/ conjugation in the addition of diisobutylaluminum hydride to trimethyl(phenylethynyl)silane

    International Nuclear Information System (INIS)

    Eisch, J.J.; Rhee, S.G.

    1975-01-01

    The kinetic, stereochemistry, and molecular association factors for the addition of diisobutylaluminum hydride to trimethyl(phenylethynyl)silane were studied in the temperature range of -10 to 38 0 . Hydralumination was found to have a kinetic true order of essentially one in the alkyne and one-third in the hydride. Although the trans adduct is the predominating product (approximately 99 percent) after completion of the hydralumination, the variation of the proportion of cis adduct and the initial rate law are consistent with a kinetically controlled cis hydralumination by monomeric R 2 'AlH, followed by a rapid isomerization to the trans adduct. The trans adduct formed a complex with l equivalent to the hydride. This complexation had to be taken into account, in order to explain the observed rate retardation and to obtain satisfactory integrated rate expressions for hydraluminations monitored to high conversion. Since in hydralumination this silylacetylene shows a stereospecificity and regiospecificity exactly opposite that of tert-butyl(phenyl)acetylene, as well as a heightened reactivity, a critical consideration of possible p/sub π/--d/sub π/ electronic effects was undertaken. The unusually facile isomerization of the resulting silyl-substituted vinylalanes, however, does seem more persuasive evidence for a p/sub π/--d/sub π/ effect, which promotes isomerization by electrophilic attack of R 2 'AlH on the carbon α to the Me 3 Si group. (U.S.)

  5. 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.

  6. 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.

  7. 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.

  8. Pollutant content in marine debris and characterization by thermal decomposition.

    Science.gov (United States)

    Iñiguez, M E; Conesa, J A; Fullana, A

    2017-04-15

    Marine debris (MDs) produces a wide variety of negative environmental, economic, safety, health and cultural impacts. Most marine litter has a very low decomposition rate (plastics), leading to a gradual accumulation in the coastal and marine environment. Characterization of the MDs has been done in terms of their pollutant content: PAHs, ClBzs, ClPhs, BrPhs, PCDD/Fs and PCBs. The results show that MDs is not a very contaminated waste. Also, thermal decomposition of MDs materials has been studied in a thermobalance at different atmospheres and heating rates. Below 400-500K, the atmosphere does not affect the thermal degradation of the mentioned waste. However, at temperatures between 500 and 800K the presence of oxygen accelerates the decomposition. Also, a kinetic model is proposed for the combustion of the MDs, and the decomposition is compared with that of their main constituents, i.e., polyethylene (PE), polystyrene (PS), polypropylene (PP), nylon and polyethylene-terephthalate (PET). Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Granulocyte kinetics

    International Nuclear Information System (INIS)

    Peters, A.M.; Lavender, J.P.; Saverymuttu, S.H.

    1985-01-01

    By using density gradient materials enriched with autologous plasma, the authors have been able to isolate granulocutes from other cellular elements and label them with In-111 without separation from a plasma environment. The kinetic behavior of these cells suggests that phenomena attributed to granulocyte activation are greatly reduced by this labeling. Here, they review their study of granulocyte kinetics in health and disease in hope of quantifying sites of margination and identifying principal sites of destruction. The three principle headings of the paper are distribution, life-span, and destruction

  10. The catalytic performance of Cu-containing zeolites in N2O decomposition and the influence of O2, NO and H2O on recombination of oxygen

    NARCIS (Netherlands)

    Smeets, P.J.; Sels, B.F.; Teeffelen, van R.M.; Leeman, H.; Hensen, E.J.M.; Schoonheydt, R.A.

    2008-01-01

    The catalytic decomposition of N2O was studied over Cu-containing zeolites with different Cu loadings and framework topologies (MFI, MOR, FER, BEA, and FAU). The influence of NO, O2, and H2O on the rate of N2O decomposition was investigated in detail. A kinetic model was developed based on the

  11. Memory effect and fast spinodal decomposition

    International Nuclear Information System (INIS)

    Koide, T.; Krein, G.; 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 have 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. (author)

  12. Patched bimetallic surfaces are active catalysts for ammonia decomposition.

    Science.gov (United States)

    Guo, Wei; Vlachos, Dionisios G

    2015-10-07

    Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core-shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core-shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

  13. On the hadron mass decomposition

    Science.gov (United States)

    Lorcé, Cédric

    2018-02-01

    We argue that the standard decompositions of the hadron mass overlook pressure effects, and hence should be interpreted with great care. Based on the semiclassical picture, we propose a new decomposition that properly accounts for these pressure effects. Because of Lorentz covariance, we stress that the hadron mass decomposition automatically comes along with a stability constraint, which we discuss for the first time. We show also that if a hadron is seen as made of quarks and gluons, one cannot decompose its mass into more than two contributions without running into trouble with the consistency of the physical interpretation. In particular, the so-called quark mass and trace anomaly contributions appear to be purely conventional. Based on the current phenomenological values, we find that in average quarks exert a repulsive force inside nucleons, balanced exactly by the gluon attractive force.

  14. On the hadron mass decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Lorce, Cedric [Universite Paris-Saclay, Centre de Physique Theorique, Ecole Polytechnique, CNRS, Palaiseau (France)

    2018-02-15

    We argue that the standard decompositions of the hadron mass overlook pressure effects, and hence should be interpreted with great care. Based on the semiclassical picture, we propose a new decomposition that properly accounts for these pressure effects. Because of Lorentz covariance, we stress that the hadron mass decomposition automatically comes along with a stability constraint, which we discuss for the first time. We show also that if a hadron is seen as made of quarks and gluons, one cannot decompose its mass into more than two contributions without running into trouble with the consistency of the physical interpretation. In particular, the so-called quark mass and trace anomaly contributions appear to be purely conventional. Based on the current phenomenological values, we find that in average quarks exert a repulsive force inside nucleons, balanced exactly by the gluon attractive force. (orig.)

  15. Abstract decomposition theorem and applications

    CERN Document Server

    Grossberg, R; Grossberg, Rami; Lessmann, Olivier

    2005-01-01

    Let K be an Abstract Elementary Class. Under the asusmptions that K has a nicely behaved forking-like notion, regular types and existence of some prime models we establish a decomposition theorem for such classes. The decomposition implies a main gap result for the class K. The setting is general enough to cover \\aleph_0-stable first-order theories (proved by Shelah in 1982), Excellent Classes of atomic models of a first order tehory (proved Grossberg and Hart 1987) and the class of submodels of a large sequentially homogenuus \\aleph_0-stable model (which is new).

  16. Thermal decomposition of biphenyl (1963); Decomposition thermique du biphenyle (1963)

    Energy Technology Data Exchange (ETDEWEB)

    Clerc, M [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1962-06-15

    The rates of formation of the decomposition products of biphenyl; hydrogen, methane, ethane, ethylene, as well as triphenyl have been measured in the vapour and liquid phases at 460 deg. C. The study of the decomposition products of biphenyl at different temperatures between 400 and 460 deg. C has provided values of the activation energies of the reactions yielding the main products of pyrolysis in the vapour phase. Product and Activation energy: Hydrogen 73 {+-} 2 kCal/Mole; Benzene 76 {+-} 2 kCal/Mole; Meta-triphenyl 53 {+-} 2 kCal/Mole; Biphenyl decomposition 64 {+-} 2 kCal/Mole; The rate of disappearance of biphenyl is only very approximately first order. These results show the major role played at the start of the decomposition by organic impurities which are not detectable by conventional physico-chemical analysis methods and the presence of which accelerates noticeably the decomposition rate. It was possible to eliminate these impurities by zone-melting carried out until the initial gradient of the formation curves for the products became constant. The composition of the high-molecular weight products (over 250) was deduced from the mean molecular weight and the dosage of the aromatic C - H bonds by infrared spectrophotometry. As a result the existence in tars of hydrogenated tetra, penta and hexaphenyl has been demonstrated. (author) [French] Les vitesses de formation des produits de decomposition du biphenyle: hydrogene, methane, ethane, ethylene, ainsi que des triphenyles, ont ete mesurees en phase vapeur et en phase liquide a 460 deg. C. L'etude des produits de decomposition du biphenyle a differentes temperatures comprises entre 400 et 460 deg. C, a fourni les valeurs des energies d'activation des reactions conduisant aux principaux produits de la pyrolyse en phase vapeur. Produit et Energie d'activation: Hydrogene 73 {+-} 2 kcal/Mole; Benzene 76 {+-} 2 kcal/Mole; Metatriphenyle, 53 {+-} 2 kcal/Mole; Decomposition du biphenyle 64 {+-} 2 kcal/Mole; La

  17. 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.

  18. Solvation effect on decomposition rate of 10-methyl-10-phenylphenoxarsonium iodide in some alcohols and ketones

    International Nuclear Information System (INIS)

    Gavrilov, V.I.; Gumerov, N.S.; Rakhmatullin, R.R.

    1989-01-01

    By the method of conductometry decomposition kinetics of 10-methyl-10phenylphenoxarsonium iodide in methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and methyl ethyl ketone at initial concentration of the salt 0.00024-0.003 mol/l, is studied. It is shown that at the temperatures up to 80-95 deg C practically no decomposition of arsonium salt in methanol and ethanol is observed. With an increase in the length of alcohol alkyl radical the decomposition rate increases. The values of activation enrgy both for alcohols and ketone are approximately the same. At the same time, decomposition rate in alcohol proved much slower than in ketone, which is related to iodide-ion solvation in protic solvents

  19. Solvation effect on decomposition rate of 10-methyl-10-phenylphenoxarsonium iodide in some alcohols and ketones

    Energy Technology Data Exchange (ETDEWEB)

    Gavrilov, V I; Gumerov, N S; Rakhmatullin, R R [Kazanskij Khimiko-Tekhnologicheskij Inst., Kazan (USSR)

    1989-03-01

    By the method of conductometry decomposition kinetics of 10-methyl-10phenylphenoxarsonium iodide in methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and methyl ethyl ketone at initial concentration of the salt 0.00024-0.003 mol/l, is studied. It is shown that at the temperatures up to 80-95 deg C practically no decomposition of arsonium salt in methanol and ethanol is observed. With an increase in the length of alcohol alkyl radical the decomposition rate increases. The values of activation enrgy both for alcohols and ketone are approximately the same. At the same time, decomposition rate in alcohol proved much slower than in ketone, which is related to iodide-ion solvation in protic solvents.

  20. 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...

  1. 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.

  2. Nanocrystalline transition metal oxides as catalysts in the thermal decomposition of ammonium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, Inder Pal Singh; Srivastava, Pratibha; Singh, Gurdip [Department of Chemistry, DDU Gorakhpur University, Gorakhpur (India)

    2009-08-15

    Nanocrystalline transition metal oxides (NTMOs) have been successfully prepared by three different methods: novel quick precipitation method (Cr{sub 2}O{sub 3} and Fe{sub 2}O{sub 3}); surfactant mediated method (CuO), and reduction of metal complexes with hydrazine as reducing agent (Mn{sub 2}O{sub 3}). The nano particles have been characterized by X-ray diffraction (XRD) which shows an average particle diameter of 35-54 nm. Their catalytic activity was measured in the thermal decomposition of ammonium perchlorate (AP). AP decomposition undergoes a two step process where the addition of metal oxide nanocrystals led to a shifting of the high temperature decomposition peak toward lower temperature. The kinetics of the thermal decomposition of AP and catalyzed AP has also been evaluated using model fitting and isoconversional method. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  3. The combined effect of thermodynamic promoters tetrahydrofuran and cyclopentane on the kinetics of flue gas hydrate formation

    DEFF Research Database (Denmark)

    Daraboina, Nagu; von Solms, Nicolas

    2015-01-01

    ) hydrate formation using a rocking cell apparatus. Hydrate formation and decomposition kinetics were investigated by constant cooling (hydrate nucleation temperature) and isothermal (hydrate nucleation time) methods. Improved (synergistic) hydrate formation kinetics (hydrate nucleation and growth) were...... of these two promoters is favorable both thermodynamically and kinetically for hydrate formation from flue gas....

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

    Science.gov (United States)

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

    2013-02-01

    The high-resolution transmission electron microscopy (HR-TEM) is used to study, in situ, spatially resolved decomposition in individual nanocrystals of metal hydroxides and oxyhydroxides. This case study reports on the decomposition of indium hydroxide (c-In(OH)3) to bixbyite-type indium oxide (c-In2O3). The electron beam is focused onto a single cube-shaped In(OH)3 crystal of {100} morphology with ca. 35 nm edge length and a sequence of HR-TEM images was recorded during electron beam irradiation. The frame-by-frame analysis of video sequences allows for the in situ, time-resolved observation of the shape and orientation of the transformed crystals, which in turn enables the evaluation of the kinetics of c-In2O3 crystallization. Supplementary material (video of the transformation) related to this article can be found online at 10.1016/j.jssc.2012.09.022. After irradiation the shape of the parent cube-shaped crystal is preserved, however, its linear dimension (edge) is reduced by the factor 1.20. The corresponding spotted selected area electron diffraction (SAED) pattern representing zone [001] of c-In(OH)3 is transformed to a diffuse strongly textured ring-like pattern of c-In2O3 that indicates the transformed cube is no longer a single crystal but is disintegrated into individual c-In2O3 domains with the size of about 5-10 nm. The induction time of approximately 15 s is estimated from the time-resolved Fourier transforms. The volume fraction of the transformed phase (c-In2O3), calculated from the shrinkage of the parent c-In(OH)3 crystal in the recorded HR-TEM images, is used as a measure of the kinetics of c-In2O3 crystallization within the framework of Avrami-Erofeev formalism. The Avrami exponent of ˜3 is characteristic for a reaction mechanism with fast nucleation at the beginning of the reaction and subsequent three-dimensional growth of nuclei with a constant growth rate. The structural transformation path in reconstructive decomposition of c-In(OH)3 to c

  5. Decomposition of metal nitrate solutions

    International Nuclear Information System (INIS)

    Haas, P.A.; Stines, W.B.

    1982-01-01

    Oxides in powder form are obtained from aqueous solutions of one or more heavy metal nitrates (e.g. U, Pu, Th, Ce) by thermal decomposition at 300 to 800 deg C in the presence of about 50 to 500% molar concentration of ammonium nitrate to total metal. (author)

  6. Probability inequalities for decomposition integrals

    Czech Academy of Sciences Publication Activity Database

    Agahi, H.; Mesiar, Radko

    2017-01-01

    Roč. 315, č. 1 (2017), s. 240-248 ISSN 0377-0427 Institutional support: RVO:67985556 Keywords : Decomposition integral * Superdecomposition integral * Probability inequalities Subject RIV: BA - General Mathematics OBOR OECD: Statistics and probability Impact factor: 1.357, year: 2016 http://library.utia.cas.cz/separaty/2017/E/mesiar-0470959.pdf

  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 meta...

  8. Thermal decomposition of ammonium perchlorate—A TGA–FTIR–MS study: Part I

    International Nuclear Information System (INIS)

    Mallick, Lovely; Kumar, Sudarshan; Chowdhury, Arindrajit

    2015-01-01

    Highlights: • TGA–FTIR–MS study of ammonium perchlorate. • Decomposition was divided into low, intermediate, and high temperature regimes. • N 2 O and NO 2 were the major species at low and high temperature regimes, respectively. • N 2 O, NO 2 , HNO 3 , and HCl were quantified to aid kinetic evaluation. • NO was not detected as a major product at any stage. - Abstract: The thermal decomposition of ammonium perchlorate has been studied using thermogravimetric analysis (TGA), coupled with Fourier transform infrared (FTIR) spectroscopy and electron ionization (EI) mass spectrometry (MS) of the evolved gases. The thermal decomposition could be demarcated into three distinct regimes, the low temperature decomposition (LTD) regime and the high temperature decomposition (HTD) regime, with an intermediate regime between the two, named as the intermediate temperature decomposition (ITD) regime. Using FTIR spectroscopy, N 2 O was detected as the primary species during the LTD regime, followed by HCl, NO 2 , and HNO 3 , in lesser quantities. On the contrary, NO 2 was found to be the principal species, followed by almost equal concentrations of HCl, N 2 O, and HNO 3 in the HTD regime. Other important species, such as H 2 O, Cl 2 , O 2 , etc., although observed by MS, were not quantified. NO could not be identified in appreciable quantities in any of the regimes. Based on the species detected during the present work, and previous research, a reaction scheme has been proposed for AP decomposition in the LTD and the HTD regimes

  9. Mechanism of Prototropy. III. Kinetics of the Tautomerization of Benzylidene-Benzylamine. comparison of the influence of hydrogen and alkyl groups on the SE2' reaction rate

    International Nuclear Information System (INIS)

    Perez Ossorio, R.; Gamboa, J. M.; Martinez Utrilla, R.

    1961-01-01

    The rate of the proto tropic change of benzylidene-benzylamine has been determined by using azomethine 1 4C-labelled in the methylenic group and measuring the distribution of activity between benzaldehyde and benzylamine obtained by hydrolysis at different reaction times. this rate has been compared with those of tautomerization of benzylidene-α-alkyl benzylamine and α-alkyl benzylidene-benzyl amines in the same experimental conditions in order to establish ethe influence of alkyl group on this reaction. (Author) 14 refs

  10. 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...

  11. On the de Rham–Wu decomposition for Riemannian and Lorentzian manifolds

    International Nuclear Information System (INIS)

    Galaev, Anton S

    2014-01-01

    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. (paper)

  12. Investigating hydrogel dosimeter decomposition by chemical methods

    International Nuclear Information System (INIS)

    Jordan, Kevin

    2015-01-01

    The chemical oxidative decomposition of leucocrystal violet micelle hydrogel dosimeters was investigated using the reaction of ferrous ions with hydrogen peroxide or sodium bicarbonate with hydrogen peroxide. The second reaction is more effective at dye decomposition in gelatin hydrogels. Additional chemical analysis is required to determine the decomposition products

  13. Robust regularized singular value decomposition with application to mortality data

    KAUST Repository

    Zhang, Lingsong; Shen, Haipeng; Huang, Jianhua Z.

    2013-01-01

    We develop a robust regularized singular value decomposition (RobRSVD) method for analyzing two-way functional data. The research is motivated by the application of modeling human mortality as a smooth two-way function of age group and year. The Rob

  14. Stochastic kinetics

    International Nuclear Information System (INIS)

    Colombino, A.; Mosiello, R.; Norelli, F.; Jorio, V.M.; Pacilio, N.

    1975-01-01

    A nuclear system kinetics is formulated according to a stochastic approach. The detailed probability balance equations are written for the probability of finding the mixed population of neutrons and detected neutrons, i.e. detectrons, at a given level for a given instant of time. Equations are integrated in search of a probability profile: a series of cases is analyzed through a progressive criterium. It tends to take into account an increasing number of physical processes within the chosen model. The most important contribution is that solutions interpret analytically experimental conditions of equilibrium (moise analysis) and non equilibrium (pulsed neutron measurements, source drop technique, start up procedures)

  15. 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.

  16. 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.

  17. 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.

  18. Dictionary-Based Tensor Canonical Polyadic Decomposition

    Science.gov (United States)

    Cohen, Jeremy Emile; Gillis, Nicolas

    2018-04-01

    To ensure interpretability of extracted sources in tensor decomposition, we introduce in this paper a dictionary-based tensor canonical polyadic decomposition which enforces one factor to belong exactly to a known dictionary. A new formulation of sparse coding is proposed which enables high dimensional tensors dictionary-based canonical polyadic decomposition. The benefits of using a dictionary in tensor decomposition models are explored both in terms of parameter identifiability and estimation accuracy. Performances of the proposed algorithms are evaluated on the decomposition of simulated data and the unmixing of hyperspectral images.

  19. Decomposition of diesel oil by various microorganisms

    Energy Technology Data Exchange (ETDEWEB)

    Suess, A; Netzsch-Lehner, A

    1969-01-01

    Previous experiments demonstrated the decomposition of diesel oil in different soils. In this experiment the decomposition of /sup 14/C-n-Hexadecane labelled diesel oil by special microorganisms was studied. The results were as follows: (1) In the experimental soils the microorganisms Mycoccus ruber, Mycobacterium luteum and Trichoderma hamatum are responsible for the diesel oil decomposition. (2) By adding microorganisms to the soil an increase of the decomposition rate was found only in the beginning of the experiments. (3) Maximum decomposition of diesel oil was reached 2-3 weeks after incubation.

  20. 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.

  1. 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.

  2. Variance decomposition in stochastic simulators

    Energy Technology Data Exchange (ETDEWEB)

    Le Maître, O. P., E-mail: olm@limsi.fr [LIMSI-CNRS, UPR 3251, Orsay (France); Knio, O. M., E-mail: knio@duke.edu [Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708 (United States); Moraes, A., E-mail: alvaro.moraesgutierrez@kaust.edu.sa [King Abdullah University of Science and Technology, Thuwal (Saudi Arabia)

    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.

  3. Variance decomposition in stochastic simulators

    KAUST Repository

    Le Maî tre, O. P.; Knio, O. M.; Moraes, Alvaro

    2015-01-01

    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.

  4. Finite Range Decomposition of Gaussian Processes

    CERN Document Server

    Brydges, C D; Mitter, P K

    2003-01-01

    Let $D$ be the finite difference Laplacian associated to the lattice $bZ^{d}$. For dimension $dge 3$, $age 0$ and $L$ a sufficiently large positive dyadic integer, we prove that the integral kernel of the resolvent $G^{a}:=(a-D)^{-1}$ can be decomposed as an infinite sum of positive semi-definite functions $ V_{n} $ of finite range, $ V_{n} (x-y) = 0$ for $|x-y|ge O(L)^{n}$. Equivalently, the Gaussian process on the lattice with covariance $G^{a}$ admits a decomposition into independent Gaussian processes with finite range covariances. For $a=0$, $ V_{n} $ has a limiting scaling form $L^{-n(d-2)}Gamma_{ c,ast }{bigl (frac{x-y}{ L^{n}}bigr )}$ as $nrightarrow infty$. As a corollary, such decompositions also exist for fractional powers $(-D)^{-alpha/2}$, $0group on the lattice.

  5. 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.

  6. Effect of particle size on thermal decomposition of alkali metal picrates

    International Nuclear Information System (INIS)

    Liu, Rui; Zhang, Tonglai; Yang, Li; Zhou, Zunning

    2014-01-01

    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

  7. Tolrestat kinetics

    International Nuclear Information System (INIS)

    Hicks, D.R.; Kraml, M.; Cayen, M.N.; Dubuc, J.; Ryder, S.; Dvornik, D.

    1984-01-01

    The kinetics of tolrestat, a potent inhibitor of aldose reductase, were examined. Serum concentrations of tolrestat and of total 14 C were measured after dosing normal subjects and subjects with diabetes with 14 C-labeled tolrestat. In normal subjects, tolrestat was rapidly absorbed and disappearance from serum was biphasic. Distribution and elimination t 1/2s were approximately 2 and 10 to 12 hr, respectively, after single and multiple doses. Unchanged tolrestat accounted for the major portion of 14 C in serum. Radioactivity was rapidly and completely excreted in urine and feces in an approximate ratio of 2:1. Findings were much the same in subjects with diabetes. In normal subjects, the kinetics of oral tolrestat were independent of dose in the 10 to 800 mg range. Repetitive dosing did not result in unexpected cumulation. Tolrestat was more than 99% bound to serum protein; it did not compete with warfarin for binding sites but was displaced to some extent by high concentrations of tolbutamide or salicylate

  8. Excimer laser decomposition of silicone

    International Nuclear Information System (INIS)

    Laude, L.D.; Cochrane, C.; Dicara, Cl.; Dupas-Bruzek, C.; Kolev, K.

    2003-01-01

    Excimer laser irradiation of silicone foils is shown in this work to induce decomposition, ablation and activation of such materials. Thin (100 μm) laminated silicone foils are irradiated at 248 nm as a function of impacting laser fluence and number of pulsed irradiations at 1 s intervals. Above a threshold fluence of 0.7 J/cm 2 , material starts decomposing. At higher fluences, this decomposition develops and gives rise to (i) swelling of the irradiated surface and then (ii) emission of matter (ablation) at a rate that is not proportioned to the number of pulses. Taking into consideration the polymer structure and the foil lamination process, these results help defining the phenomenology of silicone ablation. The polymer decomposition results in two parts: one which is organic and volatile, and another part which is inorganic and remains, forming an ever thickening screen to light penetration as the number of light pulses increases. A mathematical model is developed that accounts successfully for this physical screening effect

  9. 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.

  10. Synthesis, structural investigation and kinetic studies of uranyl(VI) unsymmetrical Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Asadi, M.; Zeinali, A.; Ranjkeshshorkaei, M.; Fejfarová, Karla; Eigner, Václav; Dušek, Michal; Dehnokhalaji, A.

    2014-01-01

    Roč. 126, č. 6 (2014), s. 1673-1683 ISSN 0974-3626 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl schiff base complexes * kinetic study * kinetics of thermal decomposition * X-ray crystallography * cyclic voltammetry Subject RIV: CA - Inorganic Chemistry Impact factor: 1.191, year: 2014

  11. 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...

  12. Hydroxylamine nitrate self-catalytic kinetics study with adiabatic calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Liu Lijun [Mary Kay O' Connor Process Safety Center, Artie McFerrin Department of Chemical Engineering, Texas A and M University System, College Station, TX 77843-3122 (United States); Wei Chunyang [BASF Corporation, Wyandotte, MI 48192 (United States); Guo Yuyan; Rogers, William J. [Mary Kay O' Connor Process Safety Center, Artie McFerrin Department of Chemical Engineering, Texas A and M University System, College Station, TX 77843-3122 (United States); Sam Mannan, M. [Mary Kay O' Connor Process Safety Center, Artie McFerrin Department of Chemical Engineering, Texas A and M University System, College Station, TX 77843-3122 (United States)], E-mail: mannan@tamu.edu

    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.

  13. Hydroxylamine nitrate self-catalytic kinetics study with adiabatic calorimetry

    International Nuclear Information System (INIS)

    Liu Lijun; Wei Chunyang; Guo Yuyan; Rogers, William J.; Sam Mannan, M.

    2009-01-01

    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

  14. Decomposition features of a supersaturated solid solution in the Mg-3.3 wt. % Yb alloy

    International Nuclear Information System (INIS)

    Dobromyslov, A.V.; Kajgorodova, L.I.; Sukhanov, V.D.; Dobatkina, T.V.

    2007-01-01

    Methods of electron microscopy, hardness measuring and X-ray diffraction analysis are applied to study decomposition kinetics for a supersaturated solid solution in a Mg-3.3 mas. % alloy on aging within a temperature range of 150-225 deg C. The mechanism of supersaturation solid solution decomposition is revealed along with the nature of phases precipitated at various stages of aging: on incomplete and extended aging as well as at maximum hardness. The types of structural constituents responsible for changes of hardness on aging are determined [ru

  15. Thermic decomposition of biphenyl; Decomposition thermique du biphenyle

    Energy Technology Data Exchange (ETDEWEB)

    Lutz, M [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1966-03-01

    Liquid and vapour phase pyrolysis of very pure biphenyl obtained by methods described in the text was carried out at 400 C in sealed ampoules, the fraction transformed being always less than 0.1 per cent. The main products were hydrogen, benzene, terphenyls, and a deposit of polyphenyls strongly adhering to the walls. Small quantities of the lower aliphatic hydrocarbons were also found. The variation of the yields of these products with a) the pyrolysis time, b) the state (gas or liquid) of the biphenyl, and c) the pressure of the vapour was measured. Varying the area and nature of the walls showed that in the absence of a liquid phase, the pyrolytic decomposition takes place in the adsorbed layer, and that metallic walls promote the reaction more actively than do those of glass (pyrex or silica). A mechanism is proposed to explain the results pertaining to this decomposition in the adsorbed phase. The adsorption seems to obey a Langmuir isotherm, and the chemical act which determines the overall rate of decomposition is unimolecular. (author) [French] Du biphenyle tres pur, dont la purification est decrite, est pyrolyse a 400 C en phase vapeur et en phase liquide dans des ampoules scellees sous vide, a des taux de decomposition n'ayant jamais depasse 0,1 pour cent. Les produits provenant de la pyrolyse sont essentiellement: l' hydrogene, le benzene, les therphenyles, et un depot de polyphenyles adherant fortement aux parois. En plus il se forme de faibles quantites d'hydrocarbures aliphatiques gazeux. On indique la variation des rendements des differents produits avec la duree de pyrolyse, l'etat gazeux ou liquide du biphenyle, et la pression de la vapeur. Variant la superficie et la nature des parois, on montre qu'en absence de liquide la pyrolyse se fait en phase adsorbee. La pyrolyse est plus active au contact de parois metalliques que de celles de verres (pyrex ou silice). A partir des resultats experimentaux un mecanisme de degradation du biphenyle en phase

  16. Analysis of sulfur-iodine thermochemical cycle for solar hydrogen production. Part 1: decomposition of sulfuric acid

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Cunping; T-Raissi, Ali [Central Florida Univ., Florida Solar Energy Center, Cocoa, FL (United States)

    2005-05-01

    The sulfur-iodine (S-I) thermochemical water splitting cycle is one of the most studied cycles for hydrogen (H{sub 2}) production. S-I cycle consists of four sections: (I) acid production and separation and oxygen purification, (II) sulfuric acid concentration and decomposition, (III) hydroiodic acid (HI) concentration, and (IV) HI decomposition and H{sub 2} purification. Section II of the cycle is an endothermic reaction driven by the heat input from a high temperature source. Analysis of the S-I cycle in the past thirty years have been focused mostly on the utilization of nuclear power as the high temperature heat source for the sulfuric acid decomposition step. Thermodynamic as well as kinetic considerations indicate that both the extent and rate of sulfuric acid decomposition can be improved at very high temperatures (in excess of 1000 deg C) available only from solar concentrators. The beneficial effect of high temperature solar heat for decomposition of sulfuric acid in the S-I cycle is described in this paper. We used Aspen Technologies' HYSYS chemical process simulator (CPS) to develop flowsheets for sulfuric acid (H{sub 2}SO{sub 4}) decomposition that include all mass and heat balances. Based on the HYSYS analyses, two new process flowsheets were developed. These new sulfuric acid decomposition processes are simpler and more stable than previous processes and yield higher conversion efficiencies for the sulfuric acid decomposition and sulfur dioxide and oxygen formation. (Author)

  17. Prediction of spur overlap time, radical yield profiles, and decomposition of trichloroethylene induced by various pulse types of electron beam

    International Nuclear Information System (INIS)

    Kim, D.-W.; Han, K.-C.; Lee, W.-K.; Ihm, S.-K.

    1996-01-01

    A kinetic model was suggested to compute the yield profiles of primary radicals generated from water radiolysis. For various cases including pulse radiolysis and steady irradiation time of spur overlap was computed in order to ensure homogeneity over the entire system. As a result, consistency to roughly first order kinetics was resulted for decomposition of 1 ppm trichloroethylene (TCE) and slight deviation from the linear model was predicted for 10 ppm TCE. (author)

  18. Dolomite decomposition under CO2

    International Nuclear Information System (INIS)

    Guerfa, F.; Bensouici, F.; Barama, S.E.; Harabi, A.; Achour, S.

    2004-01-01

    Full text.Dolomite (MgCa (CO 3 ) 2 is one of the most abundant mineral species on the surface of the planet, it occurs in sedimentary rocks. MgO, CaO and Doloma (Phase mixture of MgO and CaO, obtained from the mineral dolomite) based materials are attractive steel-making refractories because of their potential cost effectiveness and world wide abundance more recently, MgO is also used as protective layers in plasma screen manufacture ceel. The crystal structure of dolomite was determined as rhombohedral carbonates, they are layers of Mg +2 and layers of Ca +2 ions. It dissociates depending on the temperature variations according to the following reactions: MgCa (CO 3 ) 2 → MgO + CaO + 2CO 2 .....MgCa (CO 3 ) 2 → MgO + Ca + CaCO 3 + CO 2 .....This latter reaction may be considered as a first step for MgO production. Differential thermal analysis (DTA) are used to control dolomite decomposition and the X-Ray Diffraction (XRD) was used to elucidate thermal decomposition of dolomite according to the reaction. That required samples were heated to specific temperature and holding times. The average particle size of used dolomite powders is 0.3 mm, as where, the heating temperature was 700 degree celsius, using various holding times (90 and 120 minutes). Under CO 2 dolomite decomposed directly to CaCO 3 accompanied by the formation of MgO, no evidence was offered for the MgO formation of either CaO or MgCO 3 , under air, simultaneous formation of CaCO 3 , CaO and accompanied dolomite decomposition

  19. 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...... adaptive Smolyak approach. The method is also used to approximate the solution of an elliptic PDE with random input data. The open source software and examples presented in this work are available online (http://pypi.python.org/pypi/TensorToolbox/)....

  20. Growth kinetics in multicomponent fluids

    International Nuclear Information System (INIS)

    Chen, S.; Lookman, T.

    1995-01-01

    The hydrodynamic effects on the late-stage kinetics in spinodal decomposition of multicomponent fluids are examined using a lattice Boltzmann scheme with stochastic fluctuations in the fluid and at the interface. In two dimensions, the three- and four-component immiscible fluid mixture (with a 1024 2 lattice) behaves like an off-critical binary fluid with an estimated domain growth of t 0.4 +/= 0.03 rather than t 1/3 as previously estimated, showing the significant influence of hydrodynamics. In three dimensions (with a 256 3 lattice), we estimate the growth as t 0.96 +/= 0.05 for both critical and off-critical quenches, in agreement with phenomenological theory

  1. Kosambi and Proper Orthogonal Decomposition

    Indian Academy of Sciences (India)

    any meteorological station, or process and control pa- rameters in a chemical plant. All these are .... The power spectrum of turbulent kinetic energy is usu- ally expressed in ... to have been inspired by Kelvin's tidal machine, with templates and ...

  2. Thermal decomposition of natural dolomite

    Indian Academy of Sciences (India)

    TECS

    calcite reported by Garcia Calvo et al (1990) indicates that the presence of impurities is a cause of variation of kinetic parameters obtained. The impurities could func- tion as catalysts owing to their influence in the crystalline structure. 3.3 X-ray diffraction analysis. Figure 2 depicts the powder X-ray diffraction pattern of.

  3. Decomposition of Multi-player Games

    Science.gov (United States)

    Zhao, Dengji; Schiffel, Stephan; Thielscher, Michael

    Research in General Game Playing aims at building systems that learn to play unknown games without human intervention. We contribute to this endeavour by generalising the established technique of decomposition from AI Planning to multi-player games. To this end, we present a method for the automatic decomposition of previously unknown games into independent subgames, and we show how a general game player can exploit a successful decomposition for game tree search.

  4. Constructive quantum Shannon decomposition from Cartan involutions

    International Nuclear Information System (INIS)

    Drury, Byron; Love, Peter

    2008-01-01

    The work presented here extends upon the best known universal quantum circuit, the quantum Shannon decomposition proposed by Shende et al (2006 IEEE Trans. Comput.-Aided Des. Integr. Circuits Syst. 25 1000). We obtain the basis of the circuit's design in a pair of Cartan decompositions. This insight gives a simple constructive factoring algorithm in terms of the Cartan involutions corresponding to these decompositions

  5. Constructive quantum Shannon decomposition from Cartan involutions

    Energy Technology Data Exchange (ETDEWEB)

    Drury, Byron; Love, Peter [Department of Physics, 370 Lancaster Ave., Haverford College, Haverford, PA 19041 (United States)], E-mail: plove@haverford.edu

    2008-10-03

    The work presented here extends upon the best known universal quantum circuit, the quantum Shannon decomposition proposed by Shende et al (2006 IEEE Trans. Comput.-Aided Des. Integr. Circuits Syst. 25 1000). We obtain the basis of the circuit's design in a pair of Cartan decompositions. This insight gives a simple constructive factoring algorithm in terms of the Cartan involutions corresponding to these decompositions.

  6. Decomposition in pelagic marine ecosytems

    International Nuclear Information System (INIS)

    Lucas, M.I.

    1986-01-01

    During the decomposition of plant detritus, complex microbial successions develop which are dominated in the early stages by a number of distinct bacterial morphotypes. The microheterotrophic community rapidly becomes heterogenous and may include cyanobacteria, fungi, yeasts and bactivorous protozoans. Microheterotrophs in the marine environment may have a biomass comparable to that of all other heterotrophs and their significance as a resource to higher trophic orders, and in the regeneration of nutrients, particularly nitrogen, that support 'regenerated' primary production, has aroused both attention and controversy. Numerous methods have been employed to measure heterotrophic bacterial production and activity. The most widely used involve estimates of 14 C-glucose uptake; the frequency of dividing cells; the incorporation of 3 H-thymidine and exponential population growth in predator-reduced filtrates. Recent attempts to model decomposition processes and C and N fluxes in pelagic marine ecosystems are described. This review examines the most sensitive components and predictions of the models with particular reference to estimates of bacterial production, net growth yield and predictions of N cycling determined by 15 N methodology. Directed estimates of nitrogen (and phosphorus) flux through phytoplanktonic and bacterioplanktonic communities using 15 N (and 32 P) tracer methods are likely to provide more realistic measures of nitrogen flow through planktonic communities

  7. Infrared multiphoton absorption and decomposition

    International Nuclear Information System (INIS)

    Evans, D.K.; McAlpine, R.D.

    1984-01-01

    The discovery of infrared laser induced multiphoton absorption (IRMPA) and decomposition (IRMPD) by Isenor and Richardson in 1971 generated a great deal of interest in these phenomena. This interest was increased with the discovery by Ambartzumian, Letokhov, Ryadbov and Chekalin that isotopically selective IRMPD was possible. One of the first speculations about these phenomena was that it might be possible to excite a particular mode of a molecule with the intense infrared laser beam and cause decomposition or chemical reaction by channels which do not predominate thermally, thus providing new synthetic routes for complex chemicals. The potential applications to isotope separation and novel chemistry stimulated efforts to understand the underlying physics and chemistry of these processes. At ICOMP I, in 1977 and at ICOMP II in 1980, several authors reviewed the current understandings of IRMPA and IRMPD as well as the particular aspect of isotope separation. There continues to be a great deal of effort into understanding IRMPA and IRMPD and we will briefly review some aspects of these efforts with particular emphasis on progress since ICOMP II. 31 references

  8. Decomposition of Diethylstilboestrol in Soil

    DEFF Research Database (Denmark)

    Gregers-Hansen, Birte

    1964-01-01

    The rate of decomposition of DES-monoethyl-1-C14 in soil was followed by measurement of C14O2 released. From 1.6 to 16% of the added C14 was recovered as C14O2 during 3 months. After six months as much as 12 to 28 per cent was released as C14O2.Determination of C14 in the soil samples after the e...... not inhibit the CO2 production from the soil.Experiments with γ-sterilized soil indicated that enzymes present in the soil are able to attack DES.......The rate of decomposition of DES-monoethyl-1-C14 in soil was followed by measurement of C14O2 released. From 1.6 to 16% of the added C14 was recovered as C14O2 during 3 months. After six months as much as 12 to 28 per cent was released as C14O2.Determination of C14 in the soil samples after...

  9. Reducibility of quantum representations of mapping class groups

    DEFF Research Database (Denmark)

    Andersen, Jørgen Ellegaard; Fjelstad, Jens

    2010-01-01

    that the quantum representations of all the mapping class groups built from the modular tensor category are reducible. In particular, for SU(N) we get reducibility for certain levels and ranks. For the quantum SU(2) Reshetikhin–Turaev theory we construct a decomposition for all even levels. We conjecture...... this decomposition is a complete decomposition into irreducible representations for high enough levels....

  10. Radiolytic decomposition of pesticide carbendazim in waters and wastes for environmental protection

    International Nuclear Information System (INIS)

    Bojanowska-Czajka, A.; Drzewicz, P.; Meczynska, S.; Kruszewski, M.; Zimek, Z.; Nichipor, H.; Galezowska, A.; Nalecz-Jawecki, G.; Trojanowicz, M.; Warsaw University, Warsaw

    2011-01-01

    The radiolytic degradation of widely used fungicide, carbendazim, in synthetic aqueous solutions and industrial wastewater was investigated employing γ-irradiation. The effect of the absorbed dose, initial concentration and pH of irradiated solution on the effectiveness of carbendazim decomposition were investigated. Decomposition of carbendazim in 100 μM concentration in synthetic aqueous solutions required irradiation with 600 Gy dose. The aqueous solutions of carbendazim have been irradiated in different conditions, where particular active radical species from water radiolysis predominate. The obtained data have been compared with the kinetic modeling. The reversed-phase high-performance liquid chromatography was used for the determination of carbendazim and its radiolytic decomposition products in irradiated solutions. The changes of toxicity of irradiated solutions were examined with different test organisms and human leukemia cells. (author)

  11. Structure, morphology and electrochemical behaviour of manganese oxides prepared by controlled decomposition of permanganate

    Energy Technology Data Exchange (ETDEWEB)

    Donne, S.W.; Jones, B.C. [Discipline of Chemistry, University of Newcastle, Callaghan, NSW 2308 (Australia); Hollenkamp, A.F. [CSIRO Energy Technology, Box 312, Clayton South, Vic. 3169 (Australia)

    2010-01-01

    Hydrothermal decomposition of permanganate, conducted in a range of pH-controlled solutions (from strongly acidic to strongly basic), is used to prepare manganese dioxides that are well-suited for use as supercapacitor electrode materials. While permanganate is thermodynamically unstable, the kinetics of its decomposition in an aqueous environment are very slow, until the temperature is raised to {proportional_to}200 C. Although the resultant materials are relatively crystalline and have low total pore volume, their prominent meso-porosity leads to good electrochemical performance. Best behaviour is obtained for material from permanganate decomposition in 0.01 M H{sub 2}SO{sub 4} solution, for which composite electrodes (150 {mu}m thick) yield {proportional_to}150 F g{sup -1} at 5 mV s{sup -1} in a 9 M KOH electrolyte. (author)

  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. MECHANISTIC STUDIES OF SURFACE CATALYZED H2O2 DECOMPOSITION AND CONTAMINANT DEGRADATION IN THE PRESENCE OF SAND. (R823402)

    Science.gov (United States)

    This study examined the mechanism and kinetics of surface catalyzed hydrogen peroxide decomposition and degradation of contaminants in the presence of sand collected from an aquifer and a riverbed. Batch experiments were conducted using variable sand concentrations (0.2 to 1.0&nb...

  14. Linear stability analysis of detonations via numerical computation and dynamic mode decomposition

    KAUST Repository

    Kabanov, Dmitry; Kasimov, Aslan R.

    2018-01-01

    We introduce a new method to investigate linear stability of gaseous detonations that is based on an accurate shock-fitting numerical integration of the linearized reactive Euler equations with a subsequent analysis of the computed solution via the dynamic mode decomposition. The method is applied to the detonation models based on both the standard one-step Arrhenius kinetics and two-step exothermic-endothermic reaction kinetics. Stability spectra for all cases are computed and analyzed. The new approach is shown to be a viable alternative to the traditional normal-mode analysis used in detonation theory.

  15. Linear stability analysis of detonations via numerical computation and dynamic mode decomposition

    KAUST Repository

    Kabanov, Dmitry I.

    2017-12-08

    We introduce a new method to investigate linear stability of gaseous detonations that is based on an accurate shock-fitting numerical integration of the linearized reactive Euler equations with a subsequent analysis of the computed solution via the dynamic mode decomposition. The method is applied to the detonation models based on both the standard one-step Arrhenius kinetics and two-step exothermic-endothermic reaction kinetics. Stability spectra for all cases are computed and analyzed. The new approach is shown to be a viable alternative to the traditional normal-mode analysis used in detonation theory.

  16. Linear stability analysis of detonations via numerical computation and dynamic mode decomposition

    KAUST Repository

    Kabanov, Dmitry

    2018-03-20

    We introduce a new method to investigate linear stability of gaseous detonations that is based on an accurate shock-fitting numerical integration of the linearized reactive Euler equations with a subsequent analysis of the computed solution via the dynamic mode decomposition. The method is applied to the detonation models based on both the standard one-step Arrhenius kinetics and two-step exothermic-endothermic reaction kinetics. Stability spectra for all cases are computed and analyzed. The new approach is shown to be a viable alternative to the traditional normal-mode analysis used in detonation theory.

  17. Thermal oxidative degradation kinetics of agricultural residues using distributed activation energy model and global kinetic model.

    Science.gov (United States)

    Ren, Xiu'e; Chen, Jianbiao; Li, Gang; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi

    2018-08-01

    The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol -1 and 94.86-169.18 kJ mol -1 , respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Modelling a deep water oil/gas spill under conditions of gas hydrate formation and decomposition

    International Nuclear Information System (INIS)

    Zheng, L.; Yapa, P.D.

    2000-01-01

    A model for the behavior of oil and gas spills at deepwater locations was presented. Such spills are subjected to pressures and temperatures that can convert gases to gas hydrates which are lighter than water. Knowing the state of gases as they rise with the plume is important in predicting the fate of an oil or gas plume released in deepwater. The objective of this paper was to develop a comprehensive jet/plume model which includes computational modules that simulate the gas hydrate formation/decomposition of gas bubbles. This newly developed model is based on the kinetics of hydrate formation and decomposition coupled with mass and heat transfer phenomena. The numerical model was successfully tested using results of experimental data from the Gulf of Mexico. Hydrate formation and decomposition are integrated with an earlier model by Yapa and Zheng for underwater oil or gas jets and plumes. The effects of hydrate on the behavior of an oil or gas plume was simulated to demonstrate the models capabilities. The model results indicate that in addition to thermodynamics, the kinetics of hydrate formation/decomposition should be considered when studying the behavior of oil and gas spills. It was shown that plume behavior changes significantly depending on whether or not the local conditions force the gases to form hydrates. 25 refs., 4 tabs., 12 figs

  19. High-purity Cu nanocrystal synthesis by a dynamic decomposition method

    OpenAIRE

    Jian, Xian; Cao, Yu; Chen, Guozhang; Wang, Chao; Tang, Hui; Yin, Liangjun; Luan, Chunhong; Liang, Yinglin; Jiang, Jing; Wu, Sixin; Zeng, Qing; Wang, Fei; Zhang, Chengui

    2014-01-01

    Cu nanocrystals are applied extensively in several fields, particularly in the microelectron, sensor, and catalysis. The catalytic behavior of Cu nanocrystals depends mainly on the structure and particle size. In this work, formation of high-purity Cu nanocrystals is studied using a common chemical vapor deposition precursor of cupric tartrate. This process is investigated through a combined experimental and computational approach. The decomposition kinetics is researched via differential sca...

  20. Vegetation exerts a greater control on litter decomposition than climate warming in peatlands.

    Science.gov (United States)

    Ward, Susan E; Orwin, Kate H; Ostle, Nicholas J; Briones, J I; Thomson, Bruce C; Griffiths, Robert I; Oakley, Simon; Quirk, Helen; Bardget, Richard D

    2015-01-01

    Historically, slow decomposition rates have resulted in the accumulation of large amounts of carbon in northern peatlands. Both climate warming and vegetation change can alter rates of decomposition, and hence affect rates of atmospheric CO2 exchange, with consequences for climate change feedbacks. Although warming and vegetation change are happening concurrently, little is known about their relative and interactive effects on decomposition processes. To test the effects of warming and vegetation change on decomposition rates, we placed litter of three dominant species (Calluna vulgaris, Eriophorum vaginatum, Hypnum jutlandicum) into a peatland field experiment that combined warming.with plant functional group removals, and measured mass loss over two years. To identify potential mechanisms behind effects, we also measured nutrient cycling and soil biota. We found that plant functional group removals exerted a stronger control over short-term litter decomposition than did approximately 1 degrees C warming, and that the plant removal effect depended on litter species identity. Specifically, rates of litter decomposition were faster when shrubs were removed from the plant community, and these effects were strongest for graminoid and bryophyte litter. Plant functional group removals also had strong effects on soil biota and nutrient cycling associated with decomposition, whereby shrub removal had cascading effects on soil fungal community composition, increased enchytraeid abundance, and increased rates of N mineralization. Our findings demonstrate that, in addition to litter quality, changes in vegetation composition play a significant role in regulating short-term litter decomposition and belowground communities in peatland, and that these impacts can be greater than moderate warming effects. Our findings, albeit from a relatively short-term study, highlight the need to consider both vegetation change and its impacts below ground alongside climatic effects when

  1. Spinodal decomposition in fluid mixtures

    International Nuclear Information System (INIS)

    Kawasaki, Kyozi; Koga, Tsuyoshi

    1993-01-01

    We study the late stage dynamics of spinodal decomposition in binary fluids by the computer simulation of the time-dependent Ginzburg-Landau equation. We obtain a temporary linear growth law of the characteristic length of domains in the late stage. This growth law has been observed in many real experiments of binary fluids and indicates that the domain growth proceeds by the flow caused by the surface tension of interfaces. We also find that the dynamical scaling law is satisfied in this hydrodynamic domain growth region. By comparing the scaling functions for fluids with that for the case without hydrodynamic effects, we find that the scaling functions for the two systems are different. (author)

  2. Early stage litter decomposition across biomes

    Science.gov (United States)

    Ika Djukic; Sebastian Kepfer-Rojas; Inger Kappel Schmidt; Klaus Steenberg Larsen; Claus Beier; Björn Berg; Kris Verheyen; Adriano Caliman; Alain Paquette; Alba Gutiérrez-Girón; Alberto Humber; Alejandro Valdecantos; Alessandro Petraglia; Heather Alexander; Algirdas Augustaitis; Amélie Saillard; Ana Carolina Ruiz Fernández; Ana I. Sousa; Ana I. Lillebø; Anderson da Rocha Gripp; André-Jean Francez; Andrea Fischer; Andreas Bohner; Andrey Malyshev; Andrijana Andrić; Andy Smith; Angela Stanisci; Anikó Seres; Anja Schmidt; Anna Avila; Anne Probst; Annie Ouin; Anzar A. Khuroo; Arne Verstraeten; Arely N. Palabral-Aguilera; Artur Stefanski; Aurora Gaxiola; Bart Muys; Bernard Bosman; Bernd Ahrends; Bill Parker; Birgit Sattler; Bo Yang; Bohdan Juráni; Brigitta Erschbamer; Carmen Eugenia Rodriguez Ortiz; Casper T. Christiansen; E. Carol Adair; Céline Meredieu; Cendrine Mony; Charles A. Nock; Chi-Ling Chen; Chiao-Ping Wang; Christel Baum; Christian Rixen; Christine Delire; Christophe Piscart; Christopher Andrews; Corinna Rebmann; Cristina Branquinho; Dana Polyanskaya; David Fuentes Delgado; Dirk Wundram; Diyaa Radeideh; Eduardo Ordóñez-Regil; Edward Crawford; Elena Preda; Elena Tropina; Elli Groner; Eric Lucot; Erzsébet Hornung; Esperança Gacia; Esther Lévesque; Evanilde Benedito; Evgeny A. Davydov; Evy Ampoorter; Fabio Padilha Bolzan; Felipe Varela; Ferdinand Kristöfel; Fernando T. Maestre; Florence Maunoury-Danger; Florian Hofhansl; Florian Kitz; Flurin Sutter; Francisco Cuesta; Francisco de Almeida Lobo; Franco Leandro de Souza; Frank Berninger; Franz Zehetner; Georg Wohlfahrt; George Vourlitis; Geovana Carreño-Rocabado; Gina Arena; Gisele Daiane Pinha; Grizelle González; Guylaine Canut; Hanna Lee; Hans Verbeeck; Harald Auge; Harald Pauli; Hassan Bismarck Nacro; Héctor A. Bahamonde; Heike Feldhaar; Heinke Jäger; Helena C. Serrano; Hélène Verheyden; Helge Bruelheide; Henning Meesenburg; Hermann Jungkunst; Hervé Jactel; Hideaki Shibata; Hiroko Kurokawa; Hugo López Rosas; Hugo L. Rojas Villalobos; Ian Yesilonis; Inara Melece; Inge Van Halder; Inmaculada García Quirós; Isaac Makelele; Issaka Senou; István Fekete; Ivan Mihal; Ivika Ostonen; Jana Borovská; Javier Roales; Jawad Shoqeir; Jean-Christophe Lata; Jean-Paul Theurillat; Jean-Luc Probst; Jess Zimmerman; Jeyanny Vijayanathan; Jianwu Tang; Jill Thompson; Jiří Doležal; Joan-Albert Sanchez-Cabeza; Joël Merlet; Joh Henschel; Johan Neirynck; Johannes Knops; John Loehr; Jonathan von Oppen; Jónína Sigríður Þorláksdóttir; Jörg Löffler; José-Gilberto Cardoso-Mohedano; José-Luis Benito-Alonso; Jose Marcelo Torezan; Joseph C. Morina; Juan J. Jiménez; Juan Dario Quinde; Juha Alatalo; Julia Seeber; Jutta Stadler; Kaie Kriiska; Kalifa Coulibaly; Karibu Fukuzawa; Katalin Szlavecz; Katarína Gerhátová; Kate Lajtha; Kathrin Käppeler; Katie A. Jennings; Katja Tielbörger; Kazuhiko Hoshizaki; Ken Green; Lambiénou Yé; Laryssa Helena Ribeiro Pazianoto; Laura Dienstbach; Laura Williams; Laura Yahdjian; Laurel M. Brigham; Liesbeth van den Brink; Lindsey Rustad; al. et

    2018-01-01

    Through litter decomposition enormous amounts of carbon is emitted to the atmosphere. Numerous large-scale decomposition experiments have been conducted focusing on this fundamental soil process in order to understand the controls on the terrestrial carbon transfer to the atmosphere. However, previous studies were mostly based on site-specific litter and methodologies...

  3. Nutrient Dynamics and Litter Decomposition in Leucaena ...

    African Journals Online (AJOL)

    Nutrient contents and rate of litter decomposition were investigated in Leucaena leucocephala plantation in the University of Agriculture, Abeokuta, Ogun State, Nigeria. Litter bag technique was used to study the pattern and rate of litter decomposition and nutrient release of Leucaena leucocephala. Fifty grams of oven-dried ...

  4. Climate history shapes contemporary leaf litter decomposition

    Science.gov (United States)

    Michael S. Strickland; Ashley D. Keiser; Mark A. Bradford

    2015-01-01

    Litter decomposition is mediated by multiple variables, of which climate is expected to be a dominant factor at global scales. However, like other organisms, traits of decomposers and their communities are shaped not just by the contemporary climate but also their climate history. Whether or not this affects decomposition rates is underexplored. Here we source...

  5. The decomposition of estuarine macrophytes under different ...

    African Journals Online (AJOL)

    The aim of this study was to determine the decomposition characteristics of the most dominant submerged macrophyte and macroalgal species in the Great Brak Estuary. Laboratory experiments were conducted to determine the effect of different temperature regimes on the rate of decomposition of 3 macrophyte species ...

  6. Decomposition and flame structure of hydrazinium nitroformate

    NARCIS (Netherlands)

    Louwers, J.; Parr, T.; Hanson-Parr, D.

    1999-01-01

    The decomposition of hydrazinium nitroformate (HNF) was studied in a hot quartz cell and by dropping small amounts of HNF on a hot plate. The species formed during the decomposition were identified by ultraviolet-visible absorption experiments. These experiments reveal that first HONO is formed. The

  7. Multilevel index decomposition analysis: Approaches and application

    International Nuclear Information System (INIS)

    Xu, X.Y.; Ang, B.W.

    2014-01-01

    With the growing interest in using the technique of index decomposition analysis (IDA) in energy and energy-related emission studies, such as to analyze the impacts of activity structure change or to track economy-wide energy efficiency trends, the conventional single-level IDA may not be able to meet certain needs in policy analysis. In this paper, some limitations of single-level IDA studies which can be addressed through applying multilevel decomposition analysis are discussed. We then introduce and compare two multilevel decomposition procedures, which are referred to as the multilevel-parallel (M-P) model and the multilevel-hierarchical (M-H) model. The former uses a similar decomposition procedure as in the single-level IDA, while the latter uses a stepwise decomposition procedure. Since the stepwise decomposition procedure is new in the IDA literature, the applicability of the popular IDA methods in the M-H model is discussed and cases where modifications are needed are explained. Numerical examples and application studies using the energy consumption data of the US and China are presented. - Highlights: • We discuss the limitations of single-level decomposition in IDA applied to energy study. • We introduce two multilevel decomposition models, study their features and discuss how they can address the limitations. • To extend from single-level to multilevel analysis, necessary modifications to some popular IDA methods are discussed. • We further discuss the practical significance of the multilevel models and present examples and cases to illustrate

  8. Decomposition of gender wage differentials among Portuguese top management jobs

    OpenAIRE

    Mendes, Raquel Vale

    2004-01-01

    This paper studies gender wage differentials among top managers in the Portuguese economy. The objective is to investigate whether men and women within the same occupational group, with relatively high levels of human capital, and who are evaluated basically on their performance, are treated unequally in relation to pay. The Oaxaca wage differential decomposition method is used, relying on 1999 micro data gathered by the Portuguese Ministry of Social Security and Employment. The main findings...

  9. Investigation into chromatographic decomposition of tritium labelled aminoacid racemates

    International Nuclear Information System (INIS)

    Myasoedov, N.F.; Zolotarev, Yu.A.; Penkina, V.I.; Petrenik, O.V.

    1983-01-01

    Results of investigations of ligand-exchange chromatography of amino acids racemates on asymmetric sorbent containing L-oxy-proline groups in polystyrene carcass, and filled with copper ions, are described. Conditions are chosen for ligand-exchange chromatography of amino acids with high specific radioactivity labelled with tritium providing quantitative decomposition of racemates for several hours. Sorbent on polyacryl amide carcass is synthesized, the possibility of its application for the separation of amino acid racemates is studied

  10. Multilinear operators for higher-order decompositions.

    Energy Technology Data Exchange (ETDEWEB)

    Kolda, Tamara Gibson

    2006-04-01

    We propose two new multilinear operators for expressing the matrix compositions that are needed in the Tucker and PARAFAC (CANDECOMP) decompositions. The first operator, which we call the Tucker operator, is shorthand for performing an n-mode matrix multiplication for every mode of a given tensor and can be employed to concisely express the Tucker decomposition. The second operator, which we call the Kruskal operator, is shorthand for the sum of the outer-products of the columns of N matrices and allows a divorce from a matricized representation and a very concise expression of the PARAFAC decomposition. We explore the properties of the Tucker and Kruskal operators independently of the related decompositions. Additionally, we provide a review of the matrix and tensor operations that are frequently used in the context of tensor decompositions.

  11. Management intensity alters decomposition via biological pathways

    Science.gov (United States)

    Wickings, Kyle; Grandy, A. Stuart; Reed, Sasha; Cleveland, Cory

    2011-01-01

    Current conceptual models predict that changes in plant litter chemistry during decomposition are primarily regulated by both initial litter chemistry and the stage-or extent-of mass loss. Far less is known about how variations in decomposer community structure (e.g., resulting from different ecosystem management types) could influence litter chemistry during decomposition. Given the recent agricultural intensification occurring globally and the importance of litter chemistry in regulating soil organic matter storage, our objectives were to determine the potential effects of agricultural management on plant litter chemistry and decomposition rates, and to investigate possible links between ecosystem management, litter chemistry and decomposition, and decomposer community composition and activity. We measured decomposition rates, changes in litter chemistry, extracellular enzyme activity, microarthropod communities, and bacterial versus fungal relative abundance in replicated conventional-till, no-till, and old field agricultural sites for both corn and grass litter. After one growing season, litter decomposition under conventional-till was 20% greater than in old field communities. However, decomposition rates in no-till were not significantly different from those in old field or conventional-till sites. After decomposition, grass residue in both conventional- and no-till systems was enriched in total polysaccharides relative to initial litter, while grass litter decomposed in old fields was enriched in nitrogen-bearing compounds and lipids. These differences corresponded with differences in decomposer communities, which also exhibited strong responses to both litter and management type. Overall, our results indicate that agricultural intensification can increase litter decomposition rates, alter decomposer communities, and influence litter chemistry in ways that could have important and long-term effects on soil organic matter dynamics. We suggest that future

  12. New simultaneous thermogravimetry and modulated molecular beam mass spectrometry apparatus for quantitative thermal decomposition studies

    International Nuclear Information System (INIS)

    Behrens, R. Jr.

    1987-01-01

    A new type of instrument has been designed and constructed to measure quantitatively the gas phase species evolving during thermal decompositions. These measurements can be used for understanding the kinetics of thermal decomposition, determining the heats of formation and vaporization of high-temperature materials, and analyzing sample contaminants. The new design allows measurements to be made on the same time scale as the rates of the reactions being studied, provides a universal detection technique to study a wide range of compounds, gives quantitative measurements of decomposition products, and minimizes interference from the instrument on the measurements. The instrument design is based on a unique combination of thermogravimetric analysis (TGA), differential thermal analysis (DTA), and modulated beam mass spectroscopy (MBMS) which are brought together into a symbiotic relationship through the use of differentially pumped vacuum systems, modulated molecular beam techniques, and computer control and data-acquisition systems. A data analysis technique that calculates partial pressures in the reaction cell from the simultaneous microbalance force measurements and the modulated mass spectrometry measurements has been developed. This eliminates the need to know the ionization cross section, the ion dissociation channels, the quadrupole transmission, and the ion detector sensitivity for each thermal decomposition product prior to quantifying the mass spectral data. The operation of the instrument and the data analysis technique are illustrated with the thermal decomposition of contaminants from a precipitated palladium powder

  13. Short-range clustering and decomposition in copper-nickel and copper-nickel-iron alloys

    International Nuclear Information System (INIS)

    Aalders, T.J.A.

    1982-07-01

    The thermodynamic equilibrium state of short-range clustering and the kinetics of short-range clustering and decomposition has been studied for a number of CuNi(Fe)-alloys by means of neutron scattering. The validity of the theories, which are usually applied to describe spinodal decomposition, nucleation and growth, coarsening etc., was investigated. It was shown that for the investigated substances the conventional theory of spinodal decomposition is valid for the relaxation of short-range clustering only for the case that the initial and final states do not differ too much. The dynamical scaling procedure described by Lebowitz et al. did not lead to a time-independent scaled function F(x) for the relaxation of short-range clustering, for the early stages of decomposition and for the case that an alloy, which was already decomposed at the quench temperature T 1 , was annealed at a temperature T 2 (T 1 ). For the later stages of decomposition, however, the scaling procedure was indeed successful. The coarsening of the alloys could, except for the later stages, be described by the Lifshitz-Slyozov theory. (Auth.)

  14. Decomposition of toluene in a steady-state atmospheric-pressure glow discharge

    International Nuclear Information System (INIS)

    Trushkin, A. N.; Grushin, M. E.; Kochetov, I. V.; Trushkin, N. I.; Akishev, Yu. S.

    2013-01-01

    Results are presented from experimental studies of decomposition of toluene (C 6 H 5 CH 3 ) in a polluted air flow by means of a steady-state atmospheric pressure glow discharge at different water vapor contents in the working gas. The experimental results on the degree of C 6 H 5 CH 3 removal are compared with the results of computer simulations conducted in the framework of the developed kinetic model of plasma chemical decomposition of toluene in the N 2 : O 2 : H 2 O gas mixture. A substantial influence of the gas flow humidity on toluene decomposition in the atmospheric pressure glow discharge is demonstrated. The main mechanisms of the influence of humidity on C 6 H 5 CH 3 decomposition are determined. The existence of two stages in the process of toluene removal, which differ in their duration and the intensity of plasma chemical decomposition of C 6 H 5 CH 3 is established. Based on the results of computer simulations, the composition of the products of plasma chemical reactions at the output of the reactor is analyzed as a function of the specific energy deposition and gas flow humidity. The existence of a catalytic cycle in which hydroxyl radical OH acts a catalyst and which substantially accelerates the recombination of oxygen atoms and suppression of ozone generation when the plasma-forming gas contains water vapor is established.

  15. Decomposition of toluene in a steady-state atmospheric-pressure glow discharge

    Science.gov (United States)

    Trushkin, A. N.; Grushin, M. E.; Kochetov, I. V.; Trushkin, N. I.; Akishev, Yu. S.

    2013-02-01

    Results are presented from experimental studies of decomposition of toluene (C6H5CH3) in a polluted air flow by means of a steady-state atmospheric pressure glow discharge at different water vapor contents in the working gas. The experimental results on the degree of C6H5CH3 removal are compared with the results of computer simulations conducted in the framework of the developed kinetic model of plasma chemical decomposition of toluene in the N2: O2: H2O gas mixture. A substantial influence of the gas flow humidity on toluene decomposition in the atmospheric pressure glow discharge is demonstrated. The main mechanisms of the influence of humidity on C6H5CH3 decomposition are determined. The existence of two stages in the process of toluene removal, which differ in their duration and the intensity of plasma chemical decomposition of C6H5CH3 is established. Based on the results of computer simulations, the composition of the products of plasma chemical reactions at the output of the reactor is analyzed as a function of the specific energy deposition and gas flow humidity. The existence of a catalytic cycle in which hydroxyl radical OH acts a catalyst and which substantially accelerates the recombination of oxygen atoms and suppression of ozone generation when the plasma-forming gas contains water vapor is established.

  16. Studies of combustion kinetics and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Gutman, D. [Catholic Univ. of America, Washington, DC (United States)

    1993-12-01

    The objective of the current research is to gain new quantitative knowledge of the kinetics and mechanisms of polyatomic free radicals which are important in hydrocarbon combustion processes. The special facility designed and built for these (which includes a heatable tubular reactor coupled to a photoionization mass spectrometer) is continually being improved. Where possible, these experimental studies are coupled with theoretical ones, sometimes conducted in collaboration with others, to obtain an improved understanding of the factors determining reactivity. The decomposition of acetyl radicals, isopropyl radicals, and n-propyl radicals have been studied as well as the oxidation of methylpropargyl radicals.

  17. Thermal decomposition of ammonium perchlorate—A TGA–FTIR–MS study: Part I

    Energy Technology Data Exchange (ETDEWEB)

    Mallick, Lovely; Kumar, Sudarshan [Department of Aerospace Engineering, Indian Institute of Technology, Bombay, Mumbai 400076 (India); Chowdhury, Arindrajit, E-mail: arindra@iitb.ac.in [Department of Mechanical Engineering Indian Institute of Technology, Bombay, Mumbai 400076 (India)

    2015-06-20

    Highlights: • TGA–FTIR–MS study of ammonium perchlorate. • Decomposition was divided into low, intermediate, and high temperature regimes. • N{sub 2}O and NO{sub 2} were the major species at low and high temperature regimes, respectively. • N{sub 2}O, NO{sub 2}, HNO{sub 3}, and HCl were quantified to aid kinetic evaluation. • NO was not detected as a major product at any stage. - Abstract: The thermal decomposition of ammonium perchlorate has been studied using thermogravimetric analysis (TGA), coupled with Fourier transform infrared (FTIR) spectroscopy and electron ionization (EI) mass spectrometry (MS) of the evolved gases. The thermal decomposition could be demarcated into three distinct regimes, the low temperature decomposition (LTD) regime and the high temperature decomposition (HTD) regime, with an intermediate regime between the two, named as the intermediate temperature decomposition (ITD) regime. Using FTIR spectroscopy, N{sub 2}O was detected as the primary species during the LTD regime, followed by HCl, NO{sub 2}, and HNO{sub 3}, in lesser quantities. On the contrary, NO{sub 2} was found to be the principal species, followed by almost equal concentrations of HCl, N{sub 2}O, and HNO{sub 3} in the HTD regime. Other important species, such as H{sub 2}O, Cl{sub 2}, O{sub 2}, etc., although observed by MS, were not quantified. NO could not be identified in appreciable quantities in any of the regimes. Based on the species detected during the present work, and previous research, a reaction scheme has been proposed for AP decomposition in the LTD and the HTD regimes.

  18. Decomposition of peracetic acid catalyzed by vanadium complexes

    International Nuclear Information System (INIS)

    Makarov, A.P.; Gekhman, A.E.; Moiseev, I.I.; Polotryuk, O.Y.

    1986-01-01

    This paper studies the decomposition of peracetic acid (AcOOH) in acetic acid (AcOH) catalyzed by vanadium complexes. It is shown that peractic acid in acetic acid solutions of ammonium anadate decomposes with the predominant formation of 0 2 and small amounts of CO 2 , the yield of which increases with increasing temperature and peracetic acid concentration. Both reactions proceed without the formation of free radicals in amounts detectable by ESR spectroscopy. The rate of oxygen release under conditions in which the formation of CO 2 is insignificant obeys a kinetic equation indicating the intermediate formation of a complex between V 5+ ions and peracetic acid and the slow conversion of this complex into the observed products

  19. Parallel pic plasma simulation through particle decomposition techniques

    International Nuclear Information System (INIS)

    Briguglio, S.; Vlad, G.; Di Martino, B.; Naples, Univ. 'Federico II'

    1998-02-01

    Particle-in-cell (PIC) codes are among the major candidates to yield a satisfactory description of the detail of kinetic effects, such as the resonant wave-particle interaction, relevant in determining the transport mechanism in magnetically confined plasmas. A significant improvement of the simulation performance of such codes con be expected from parallelization, e.g., by distributing the particle population among several parallel processors. Parallelization of a hybrid magnetohydrodynamic-gyrokinetic code has been accomplished within the High Performance Fortran (HPF) framework, and tested on the IBM SP2 parallel system, using a 'particle decomposition' technique. The adopted technique requires a moderate effort in porting the code in parallel form and results in intrinsic load balancing and modest inter processor communication. The performance tests obtained confirm the hypothesis of high effectiveness of the strategy, if targeted towards moderately parallel architectures. Optimal use of resources is also discussed with reference to a specific physics problem [it

  20. Radiation induced decomposition of chlorinated phenols in water

    Science.gov (United States)

    Getoff, N.; Solar, S.

    Experiments with 4-Cl-phenol as a model compound for pesticides were performed under steady-state conditions using deoxygenated solutions as well as such saturated with air, oxygen or oxygen mixed with ozone. The yield of Cl -ions serviced as an indicator for the degradation process. As main products of the first step of decomposition were identified: polyhydroxybenzenes, aldehydes and acids. The yield of aldehydes was studied as a function of the absorbed dose and substrate concentration. In the presence of ozone a chain-reaction of the oxidative pollutant degradation takes place. Transient absorption spectra and kinetics obtained by preliminary pulse radiolysis studies of 4-Cl-phenol in the presence of oxygen as well as probable reaction mechanisms are also presented.

  1. Radiation induced decomposition of chlorinated phenols in water

    International Nuclear Information System (INIS)

    Getoff, N.; Solar, S.

    1988-01-01

    Experiments with 4-Cl-phenol as a model compound for pesticides were performed under steady-state conditions using deoxygenated solutions as well as solutions saturated with air, oxygen or oxygen mixed with ozone. The yield of Cl - ions served as an indicator for the degradation process. As main products of the first step of decomposition were identified: polyhydroxybenzenes, aldehydes and acids. The yield of aldehydes was studied as a function of the absorbed dose and substrate concentration. In the presence of ozone a chain-reaction of the oxidative pollutant degradation takes place. Transient absorption spectra and kinetics obtained by preliminary pulse radiolysis studies of 4-Cl-phenol in the presence of oxygen as well as probable reaction mechanisms are also presented. (author)

  2. Gas emission from anaerobic decomposition of plant resources

    Directory of Open Access Journals (Sweden)

    Marcela Bianchessi da Cunha-Santino

    Full Text Available Abstract: Aim The aim of this study was to quantify the emission rates of gases resulting from the anaerobic decomposition of different plant resources under conditions usually found in sediments of tropical aquatic systems and drained organic soils. Methods Incubations were prepared with green leaves, bark, twigs, plant litter, sugarcane stalks and leaves, soybean leaves, grasses, forest leaves and an aquatic macrophyte (Typha domingensis. Over 10 months, the daily volume of gas evolved from decay was measured and a kinetic model was used to describe the anaerobic mineralization. Results Using the mathematical model, it can be observed that the composition of the plant resources is heterogeneous. The temporal variation of the gas rates indicated that the mineralization of the labile fractions of detritus varied, on a carbon basis, from 16.2 (bark to 100% (samples composed of leaves, grasses and sugar cane stalks. High gas emissions were observed during the mineralization of grasses, sugar cane stalks, leaves and plant litter, while low volumes of gases were measured during the mineralization of bark, twigs, forest leaves and T. domingensis, which are the most fibrous and recalcitrant resources (carbon content: 83.8, 78.2, 64.8 and 53.4%, respectively. The mineralization of labile carbon presented half-life values, which varied from 41 (twigs to 295 days (grasses. Conclusions Considering the high amount of remaining recalcitrant fraction, the anaerobic decomposition of these plant resources showed a strong trend towards accumulating organic matter in flooded soils. Despite the higher temperatures found in the tropical environment, these environments represent a sink of particulate detritus due to its slow decomposition.

  3. Decomposition of fresh and anaerobically digested plant biomass in soil

    International Nuclear Information System (INIS)

    Moorhead, K.K.; Graetz, D.A.; Reddy, K.R.

    1987-01-01

    Using water hyacinth [Eichhornia crassipes (Mart.) Solms] for waste water renovation produces biomass that must be disposed of. This biomass may be anaerobically digested to produce CH 4 or added to soil directly as an amendment. In this study, fresh and anaerobically digested water hyacinth biomass, with either low or high N tissue content, were added to soil to evaluate C and N mineralization characteristics. The plant biomass was labeled with 15 N before digestion. The fresh plant biomass and digested biomass sludge were freeze-dried and ground to pass a 0.84-mm sieve. The materials were thoroughly mixed with a Kindrick fine sand at a rate of 5 g kg -1 soil and incubated for 90 d at 27 0 C at a moisture content adjusted to 0.01 MPa. Decomposition was evaluated by CO 2 evolution and 15 N mineralization. After 90 d, approximately 20% of the added C of the digested sludges had evolved as CO 2 compared to 39 and 50% of the added C of the fresh plant biomass with a low and high N content, respectively. First-order kinetics were used to describe decomposition stages. Mineralization of organic 15 N to 15 NO 3 - -N accounted for 8% of applied N for both digested sludges at 90 d. Nitrogen mineralization accounted for 3 and 33% of the applied organic N for fresh plant biomass with a low and high N content, respectively

  4. Experimental study of decomposition of aqueous nitrosyl thiocyanate.

    Science.gov (United States)

    Rayson, Mark S; Mackie, John C; Kennedy, Eric M; Dlugogorski, Bogdan Z

    2011-08-15

    This study has examined the kinetics of the decomposition of nitrosyl thiocyanate (ONSCN) by stopped flow UV-vis spectrophotometry, with the reaction products identified and quantified by infrared spectroscopy, membrane inlet mass spectrometry, ion chromatography, and CN(-) ion selective electrode. The reaction results in the formation of nitric oxide and thiocyanogen, the latter decomposing to sulfate and hydrogen cyanide in aqueous solution. The rate of consumption of ONSCN depends strongly on the concentration of SCN(-) ions and is inhibited by nitric oxide. We have developed a reaction mechanism that comprises three parallel pathways for the decomposition of ONSCN. At high thiocyanate concentrations, two reaction pathways operate including a second order reaction to generate NO and (SCN)(2) and a reversible reaction between ONSCN and SCN(-) producing NO and (SCN)(2)(-), with the rate limiting step corresponding to the consumption of (SCN)(2)(-) by reaction with ONSCN. The third reaction pathway, which becomes significant at low thiocyanate concentrations, involves formation of a previously unreported species, ONOSCN, via a reaction between ONSCN and HOSCN, the latter constituting an intermediate in the hydrolysis of (SCN)(2). ONOSCN contributes to the formation of NO via homolysis of the O-NO bond and subsequent dimerization and hydrolysis of OSCN. Fitting the chemical reactions of the model to the experimental measurements, which covered a wide range of reactant concentrations, afforded estimation of all relevant kinetic parameters and provided an excellent match. The reaction mechanism developed in this contribution may be applied to predict the rates of NO formation from ONSCN during the synthesis of azo dyes, the gassing of explosive emulsions, or nitrosation reactions occurring in the human body. © 2011 American Chemical Society

  5. The influence of water vapor and sulfur dioxide on the catalytic decomposition of nitrous oxide

    Energy Technology Data Exchange (ETDEWEB)

    Yalamas, C.; Heinisch, R.; Barz, M. [Technische Univ. Berlin (Germany). Inst. fuer Energietechnik; Cournil, M. [Ecole Nationale Superieure des Mines, 42 - Saint-Etienne (France)

    2001-03-01

    For the nitrous oxide decomposition three groups of catalysts such as metals on support, hydrotalcites, and perovskites were studied relating to their activity in the presence of vapor or sulfur dioxide, in the temperature range from 200 to 500 C. It was found that the water vapor strongly inhibates the nitrous oxide decomposition at T=200-400 C. The sulfur dioxide poisons the catalysts, in particular the perovskites. (orig.)

  6. LMDI decomposition approach: A guide for implementation

    International Nuclear Information System (INIS)

    Ang, B.W.

    2015-01-01

    Since it was first used by researchers to analyze industrial electricity consumption in the early 1980s, index decomposition analysis (IDA) has been widely adopted in energy and emission studies. Lately its use as the analytical component of accounting frameworks for tracking economy-wide energy efficiency trends has attracted considerable attention and interest among policy makers. The last comprehensive literature review of IDA was reported in 2000 which is some years back. After giving an update and presenting the key trends in the last 15 years, this study focuses on the implementation issues of the logarithmic mean Divisia index (LMDI) decomposition methods in view of their dominance in IDA in recent years. Eight LMDI models are presented and their origin, decomposition formulae, and strengths and weaknesses are summarized. Guidelines on the choice among these models are provided to assist users in implementation. - Highlights: • Guidelines for implementing LMDI decomposition approach are provided. • Eight LMDI decomposition models are summarized and compared. • The development of the LMDI decomposition approach is presented. • The latest developments of index decomposition analysis are briefly reviewed.

  7. Do soil organisms affect aboveground litter decomposition in the semiarid Patagonian steppe, Argentina?

    Science.gov (United States)

    Araujo, Patricia I; Yahdjian, Laura; Austin, Amy T

    2012-01-01

    Surface litter decomposition in arid and semiarid ecosystems is often faster than predicted by climatic parameters such as annual precipitation or evapotranspiration, or based on standard indices of litter quality such as lignin or nitrogen concentrations. Abiotic photodegradation has been demonstrated to be an important factor controlling aboveground litter decomposition in aridland ecosystems, but soil fauna, particularly macrofauna such as termites and ants, have also been identified as key players affecting litter mass loss in warm deserts. Our objective was to quantify the importance of soil organisms on surface litter decomposition in the Patagonian steppe in the absence of photodegradative effects, to establish the relative importance of soil organisms on rates of mass loss and nitrogen release. We estimated the relative contribution of soil fauna and microbes to litter decomposition of a dominant grass using litterboxes with variable mesh sizes that excluded groups of soil fauna based on size class (10, 2, and 0.01 mm), which were placed beneath shrub canopies. We also employed chemical repellents (naphthalene and fungicide). The exclusion of macro- and mesofauna had no effect on litter mass loss over 3 years (P = 0.36), as litter decomposition was similar in all soil fauna exclusions and naphthalene-treated litter. In contrast, reduction of fungal activity significantly inhibited litter decomposition (P soil fauna have been mentioned as a key control of litter decomposition in warm deserts, biogeographic legacies and temperature limitation may constrain the importance of these organisms in temperate aridlands, particularly in the southern hemisphere.

  8. Energy transfer and kinetics in mechanochemistry.

    Science.gov (United States)

    Chen, Zhiliang; Lu, Shengyong; Mao, Qiongjing; Buekens, Alfons; Wang, Yuting; Yan, Jianhua

    2017-11-01

    Mechanochemistry (MC) exerts extraordinary degradation and decomposition effects on many chlorinated, brominated, and even fluorinated persistent organic pollutants (POPs). However, its application is still limited by inadequate study of its reaction kinetic aspects. In the present work, the ball motion and energy transfer in planetary ball mill are investigated in some detail. Almost all milling parameters are summarised in a single factor-total effective impact energy. Furthermore, the MC kinetic between calcium oxide/Al and hexachlorobenzene is well established and modelled. The results indicate that total effective impact energy and reagent ratio are the two factors sufficient for describing the MC degradation degree of POPs. The reaction rate constant only depends on the chemical properties of reactants, so it could be used as an important index to appraise the quality of MC additives. This model successfully predicts the reaction rate for different operating conditions, indicating that it could be suitably applied for conducting MC reactions in other reactors.

  9. Thermal decomposition of lanthanide and actinide tetrafluorides

    International Nuclear Information System (INIS)

    Gibson, J.K.; Haire, R.G.

    1988-01-01

    The thermal stabilities of several lanthanide/actinide tetrafluorides have been studied using mass spectrometry to monitor the gaseous decomposition products, and powder X-ray diffraction (XRD) to identify solid products. The tetrafluorides, TbF 4 , CmF 4 , and AmF 4 , have been found to thermally decompose to their respective solid trifluorides with accompanying release of fluorine, while cerium tetrafluoride has been found to be significantly more thermally stable and to congruently sublime as CeF 4 prior to appreciable decomposition. The results of these studies are discussed in relation to other relevant experimental studies and the thermodynamics of the decomposition processes. 9 refs., 3 figs

  10. Underdetermined Blind Audio Source Separation Using Modal Decomposition

    Directory of Open Access Journals (Sweden)

    Abdeldjalil Aïssa-El-Bey

    2007-03-01

    Full Text Available This paper introduces new algorithms for the blind separation of audio sources using modal decomposition. Indeed, audio signals and, in particular, musical signals can be well approximated by a sum of damped sinusoidal (modal components. Based on this representation, we propose a two-step approach consisting of a signal analysis (extraction of the modal components followed by a signal synthesis (grouping of the components belonging to the same source using vector clustering. For the signal analysis, two existing algorithms are considered and compared: namely the EMD (empirical mode decomposition algorithm and a parametric estimation algorithm using ESPRIT technique. A major advantage of the proposed method resides in its validity for both instantaneous and convolutive mixtures and its ability to separate more sources than sensors. Simulation results are given to compare and assess the performance of the proposed algorithms.

  11. Underdetermined Blind Audio Source Separation Using Modal Decomposition

    Directory of Open Access Journals (Sweden)

    Aïssa-El-Bey Abdeldjalil

    2007-01-01

    Full Text Available This paper introduces new algorithms for the blind separation of audio sources using modal decomposition. Indeed, audio signals and, in particular, musical signals can be well approximated by a sum of damped sinusoidal (modal components. Based on this representation, we propose a two-step approach consisting of a signal analysis (extraction of the modal components followed by a signal synthesis (grouping of the components belonging to the same source using vector clustering. For the signal analysis, two existing algorithms are considered and compared: namely the EMD (empirical mode decomposition algorithm and a parametric estimation algorithm using ESPRIT technique. A major advantage of the proposed method resides in its validity for both instantaneous and convolutive mixtures and its ability to separate more sources than sensors. Simulation results are given to compare and assess the performance of the proposed algorithms.

  12. Qualitative Functional Decomposition Analysis of Evolved Neuromorphic Flight Controllers

    Directory of Open Access Journals (Sweden)

    Sanjay K. Boddhu

    2012-01-01

    Full Text Available In the previous work, it was demonstrated that one can effectively employ CTRNN-EH (a neuromorphic variant of EH method methodology to evolve neuromorphic flight controllers for a flapping wing robot. This paper describes a novel frequency grouping-based analysis technique, developed to qualitatively decompose the evolved controllers into explainable functional control blocks. A summary of the previous work related to evolving flight controllers for two categories of the controller types, called autonomous and nonautonomous controllers, is provided, and the applicability of the newly developed decomposition analysis for both controller categories is demonstrated. Further, the paper concludes with appropriate discussion of ongoing work and implications for possible future work related to employing the CTRNN-EH methodology and the decomposition analysis techniques presented in this paper.

  13. Decomposition of lake phytoplankton. 1

    International Nuclear Information System (INIS)

    Hansen, L.; Krog, G.F.; Soendergaard, M.

    1986-01-01

    Short-time (24 h) and long-time (4-6 d) decomposition of phytoplankton cells were investigasted under in situ conditions in four Danish lakes. Carbon-14-labelled, dead algae were exposed to sterile or natural lake water and the dynamics of cell lysis and bacterial utilization of the leached products were followed. The lysis process was dominated by an initial fast water extraction. Within 2 to 4 h from 4 to 34% of the labelled carbon leached from the algal cells. After 24 h from 11 to 43% of the initial particulate carbon was found as dissolved carbon in the experiments with sterile lake water; after 4 to 6 d the leaching was from 67 to 78% of the initial 14 C. The leached compounds were utilized by bacteria. A comparison of the incubations using sterile and natural water showed that a mean of 71% of the lysis products was metabolized by microorganisms within 24 h. In two experiments the uptake rate equalled the leaching rate. (author)

  14. Cesium removal and kinetics equilibrium: Precipitation kinetics

    International Nuclear Information System (INIS)

    Barnes, M.J.

    1999-01-01

    This task consisted of both non-radioactive and radioactive (tracer) tests examining the influence of potentially significant variables on cesium tetraphenylborate precipitation kinetics. The work investigated the time required to reach cesium decontamination and the conditions that affect the cesium precipitation kinetics

  15. In situ study of glasses decomposition layer; Etude in situ de la couche d`alteration de verres

    Energy Technology Data Exchange (ETDEWEB)

    Zarembowitch-Deruelle, O

    1997-10-21

    The aim of this work is to understand the involved mechanisms during the decomposition of glasses by water and the consequences on the morphology of the decomposition layer, in particular in the case of a nuclear glass: the R{sub 7} T{sub 7}. The chemical composition of this glass being very complicated, it is difficult to know the influence of the different elements on the decomposition kinetics and on the resulting morphology because several atoms have a same behaviour. Glasses with simplified composition (only 5 elements) have then been synthesized. The morphological and structural characteristics of these glasses have been given. They have then been decomposed by water. The leaching curves do not reflect the decomposition kinetics but the solubility of the different elements at every moment. The three steps of the leaching are: 1) de-alkalinization 2) lattice rearrangement 3) heavy elements solubilization. Two decomposition layer types have also been revealed according to the glass heavy elements rate. (O.M.) 59 refs.

  16. An Efficient Local Correlation Matrix Decomposition Approach for the Localization Implementation of Ensemble-Based Assimilation Methods

    Science.gov (United States)

    Zhang, Hongqin; Tian, Xiangjun

    2018-04-01

    Ensemble-based data assimilation methods often use the so-called localization scheme to improve the representation of the ensemble background error covariance (Be). Extensive research has been undertaken to reduce the computational cost of these methods by using the localized ensemble samples to localize Be by means of a direct decomposition of the local correlation matrix C. However, the computational costs of the direct decomposition of the local correlation matrix C are still extremely high due to its high dimension. In this paper, we propose an efficient local correlation matrix decomposition approach based on the concept of alternating directions. This approach is intended to avoid direct decomposition of the correlation matrix. Instead, we first decompose the correlation matrix into 1-D correlation matrices in the three coordinate directions, then construct their empirical orthogonal function decomposition at low resolution. This procedure is followed by the 1-D spline interpolation process to transform the above decompositions to the high-resolution grid. Finally, an efficient correlation matrix decomposition is achieved by computing the very similar Kronecker product. We conducted a series of comparison experiments to illustrate the validity and accuracy of the proposed local correlation matrix decomposition approach. The effectiveness of the proposed correlation matrix decomposition approach and its efficient localization implementation of the nonlinear least-squares four-dimensional variational assimilation are further demonstrated by several groups of numerical experiments based on the Advanced Research Weather Research and Forecasting model.

  17. Enhanced decomposition of stable soil organic carbon and microbial catabolic potentials by long-term field warming.

    Science.gov (United States)

    Feng, Wenting; Liang, Junyi; Hale, Lauren E; Jung, Chang Gyo; Chen, Ji; Zhou, Jizhong; Xu, Minggang; Yuan, Mengting; Wu, Liyou; Bracho, Rosvel; Pegoraro, Elaine; Schuur, Edward A G; Luo, Yiqi

    2017-11-01

    Quantifying soil organic carbon (SOC) decomposition under warming is critical to predict carbon-climate feedbacks. According to the substrate regulating principle, SOC decomposition would decrease as labile SOC declines under field warming, but observations of SOC decomposition under warming do not always support this prediction. This discrepancy could result from varying changes in SOC components and soil microbial communities under warming. This study aimed to determine the decomposition of SOC components with different turnover times after subjected to long-term field warming and/or root exclusion to limit C input, and to test whether SOC decomposition is driven by substrate lability under warming. Taking advantage of a 12-year field warming experiment in a prairie, we assessed the decomposition of SOC components by incubating soils from control and warmed plots, with and without root exclusion for 3 years. We assayed SOC decomposition from these incubations by combining inverse modeling and microbial functional genes during decomposition with a metagenomic technique (GeoChip). The decomposition of SOC components with turnover times of years and decades, which contributed to 95% of total cumulative CO 2 respiration, was greater in soils from warmed plots. But the decomposition of labile SOC was similar in warmed plots compared to the control. The diversity of C-degradation microbial genes generally declined with time during the incubation in all treatments, suggesting shifts of microbial functional groups as substrate composition was changing. Compared to the control, soils from warmed plots showed significant increase in the signal intensities of microbial genes involved in degrading complex organic compounds, implying enhanced potential abilities of microbial catabolism. These are likely responsible for accelerated decomposition of SOC components with slow turnover rates. Overall, the shifted microbial community induced by long-term warming accelerates the

  18. Decomposition and particle release of a carbon nanotube/epoxy nanocomposite at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Schlagenhauf, Lukas [Empa - Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Functional Polymers (Switzerland); Kuo, Yu-Ying; Bahk, Yeon Kyoung [Empa - Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Advanced Analytical Technologies (Switzerland); Nüesch, Frank [Empa - Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Functional Polymers (Switzerland); Wang, Jing, E-mail: Jing.Wang@ifu.baug.ethz.ch [Empa - Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Advanced Analytical Technologies (Switzerland)

    2015-11-15

    Carbon nanotubes (CNTs) as fillers in nanocomposites have attracted significant attention, and one of the applications is to use the CNTs as flame retardants. For such nanocomposites, possible release of CNTs at elevated temperatures after decomposition of the polymer matrix poses potential health threats. We investigated the airborne particle release from a decomposing multi-walled carbon nanotube (MWCNT)/epoxy nanocomposite in order to measure a possible release of MWCNTs. An experimental set-up was established that allows decomposing the samples in a furnace by exposure to increasing temperatures at a constant heating rate and under ambient air or nitrogen atmosphere. The particle analysis was performed by aerosol measurement devices and by transmission electron microscopy (TEM) of collected particles. Further, by the application of a thermal denuder, it was also possible to measure non-volatile particles only. Characterization of the tested samples and the decomposition kinetics were determined by the usage of thermogravimetric analysis (TGA). The particle release of different samples was investigated, of a neat epoxy, nanocomposites with 0.1 and 1 wt% MWCNTs, and nanocomposites with functionalized MWCNTs. The results showed that the added MWCNTs had little effect on the decomposition kinetics of the investigated samples, but the weight of the remaining residues after decomposition was influenced significantly. The measurements with decomposition in different atmospheres showed a release of a higher number of particles at temperatures below 300 °C when air was used. Analysis of collected particles by TEM revealed that no detectable amount of MWCNTs was released, but micrometer-sized fibrous particles were collected.

  19. Decomposition and particle release of a carbon nanotube/epoxy nanocomposite at elevated temperatures

    International Nuclear Information System (INIS)

    Schlagenhauf, Lukas; Kuo, Yu-Ying; Bahk, Yeon Kyoung; Nüesch, Frank; Wang, Jing

    2015-01-01

    Carbon nanotubes (CNTs) as fillers in nanocomposites have attracted significant attention, and one of the applications is to use the CNTs as flame retardants. For such nanocomposites, possible release of CNTs at elevated temperatures after decomposition of the polymer matrix poses potential health threats. We investigated the airborne particle release from a decomposing multi-walled carbon nanotube (MWCNT)/epoxy nanocomposite in order to measure a possible release of MWCNTs. An experimental set-up was established that allows decomposing the samples in a furnace by exposure to increasing temperatures at a constant heating rate and under ambient air or nitrogen atmosphere. The particle analysis was performed by aerosol measurement devices and by transmission electron microscopy (TEM) of collected particles. Further, by the application of a thermal denuder, it was also possible to measure non-volatile particles only. Characterization of the tested samples and the decomposition kinetics were determined by the usage of thermogravimetric analysis (TGA). The particle release of different samples was investigated, of a neat epoxy, nanocomposites with 0.1 and 1 wt% MWCNTs, and nanocomposites with functionalized MWCNTs. The results showed that the added MWCNTs had little effect on the decomposition kinetics of the investigated samples, but the weight of the remaining residues after decomposition was influenced significantly. The measurements with decomposition in different atmospheres showed a release of a higher number of particles at temperatures below 300 °C when air was used. Analysis of collected particles by TEM revealed that no detectable amount of MWCNTs was released, but micrometer-sized fibrous particles were collected

  20. Decomposition and particle release of a carbon nanotube/epoxy nanocomposite at elevated temperatures

    Science.gov (United States)

    Schlagenhauf, Lukas; Kuo, Yu-Ying; Bahk, Yeon Kyoung; Nüesch, Frank; Wang, Jing

    2015-11-01

    Carbon nanotubes (CNTs) as fillers in nanocomposites have attracted significant attention, and one of the applications is to use the CNTs as flame retardants. For such nanocomposites, possible release of CNTs at elevated temperatures after decomposition of the polymer matrix poses potential health threats. We investigated the airborne particle release from a decomposing multi-walled carbon nanotube (MWCNT)/epoxy nanocomposite in order to measure a possible release of MWCNTs. An experimental set-up was established that allows decomposing the samples in a furnace by exposure to increasing temperatures at a constant heating rate and under ambient air or nitrogen atmosphere. The particle analysis was performed by aerosol measurement devices and by transmission electron microscopy (TEM) of collected particles. Further, by the application of a thermal denuder, it was also possible to measure non-volatile particles only. Characterization of the tested samples and the decomposition kinetics were determined by the usage of thermogravimetric analysis (TGA). The particle release of different samples was investigated, of a neat epoxy, nanocomposites with 0.1 and 1 wt% MWCNTs, and nanocomposites with functionalized MWCNTs. The results showed that the added MWCNTs had little effect on the decomposition kinetics of the investigated samples, but the weight of the remaining residues after decomposition was influenced significantly. The measurements with decomposition in different atmospheres showed a release of a higher number of particles at temperatures below 300 °C when air was used. Analysis of collected particles by TEM revealed that no detectable amount of MWCNTs was released, but micrometer-sized fibrous particles were collected.

  1. Kinetics of evaporation of barium THD precursors used for organometallic chemical vapor deposition (OMCVD) thin films

    Science.gov (United States)

    Burtman, V.; Schieber, M.; Yitzchaik, S.; Yaroslavsky, Y.

    1997-04-01

    Various methods have been used to synthesize Ba(THD) 2 and its molecular structure has been studied using nuclear magnetic resonance. Compared with Raman and infrared spectroscopy it was found that NMR is very useful to determine quantitatively the decomposition through aging of Ba(THD) 2. The transport kinetics of Ba(THD) 2 has been studied under experimental conditions of a OMCVD reactor. It has been found that the freshly prepared Ba(THD) 2 by the reaction of Ba metal with THD ligand in anhydrous conditions with subsequent crystallization from methanol transported quantitatively without decomposition. A simple model shows that the transport kinetics corresponds to a diffusion controlled process.

  2. Central limit theorems for large graphs: Method of quantum decomposition

    International Nuclear Information System (INIS)

    Hashimoto, Yukihiro; Hora, Akihito; Obata, Nobuaki

    2003-01-01

    A new method is proposed for investigating spectral distribution of the combinatorial Laplacian (adjacency matrix) of a large regular graph on the basis of quantum decomposition and quantum central limit theorem. General results are proved for Cayley graphs of discrete groups and for distance-regular graphs. The Coxeter groups and the Johnson graphs are discussed in detail by way of illustration. In particular, the limit distributions obtained from the Johnson graphs are characterized by the Meixner polynomials which form a one-parameter deformation of the Laguerre polynomials

  3. A Decomposition Theorem for Finite Automata.

    Science.gov (United States)

    Santa Coloma, Teresa L.; Tucci, Ralph P.

    1990-01-01

    Described is automata theory which is a branch of theoretical computer science. A decomposition theorem is presented that is easier than the Krohn-Rhodes theorem. Included are the definitions, the theorem, and a proof. (KR)

  4. Spatial domain decomposition for neutron transport problems

    International Nuclear Information System (INIS)

    Yavuz, M.; Larsen, E.W.

    1989-01-01

    A spatial Domain Decomposition method is proposed for modifying the Source Iteration (SI) and Diffusion Synthetic Acceleration (DSA) algorithms for solving discrete ordinates problems. The method, which consists of subdividing the spatial domain of the problem and performing the transport sweeps independently on each subdomain, has the advantage of being parallelizable because the calculations in each subdomain can be performed on separate processors. In this paper we describe the details of this spatial decomposition and study, by numerical experimentation, the effect of this decomposition on the SI and DSA algorithms. Our results show that the spatial decomposition has little effect on the convergence rates until the subdomains become optically thin (less than about a mean free path in thickness)

  5. Plasma kinetic theory

    International Nuclear Information System (INIS)

    Elliott, J.A.

    1993-01-01

    Plasma kinetic theory is discussed and a comparison made with the kinetic theory of gases. The plasma is described by a modified set of fluid equations and it is shown how these fluid equations can be derived. (UK)

  6. Chemical Kinetic Modeling of 2-Methylhexane Combustion

    KAUST Repository

    Mohamed, Samah Y.; Sarathy, Mani

    2015-01-01

    necessity, as new experiments and advanced theories show inaccuracy in certain portions of the models. This study focuses on updating thermodynamic data and kinetic model for a gasoline surrogate fuel, 2-methylhexane, with recently published group values

  7. Joint Matrices Decompositions and Blind Source Separation

    Czech Academy of Sciences Publication Activity Database

    Chabriel, G.; Kleinsteuber, M.; Moreau, E.; Shen, H.; Tichavský, Petr; Yeredor, A.

    2014-01-01

    Roč. 31, č. 3 (2014), s. 34-43 ISSN 1053-5888 R&D Projects: GA ČR GA102/09/1278 Institutional support: RVO:67985556 Keywords : joint matrices decomposition * tensor decomposition * blind source separation Subject RIV: BB - Applied Statistics, Operational Research Impact factor: 5.852, year: 2014 http://library.utia.cas.cz/separaty/2014/SI/tichavsky-0427607.pdf

  8. Review on Thermal Decomposition of Ammonium Nitrate

    Science.gov (United States)

    Chaturvedi, Shalini; Dave, Pragnesh N.

    2013-01-01

    In this review data from the literature on thermal decomposition of ammonium nitrate (AN) and the effect of additives to their thermal decomposition are summarized. The effect of additives like oxides, cations, inorganic acids, organic compounds, phase-stablized CuO, etc., is discussed. The effect of an additive mainly occurs at the exothermic peak of pure AN in a temperature range of 200°C to 140°C.

  9. Note on Symplectic SVD-Like Decomposition

    Directory of Open Access Journals (Sweden)

    AGOUJIL Said

    2016-02-01

    Full Text Available The aim of this study was to introduce a constructive method to compute a symplectic singular value decomposition (SVD-like decomposition of a 2n-by-m rectangular real matrix A, based on symplectic refectors.This approach used a canonical Schur form of skew-symmetric matrix and it allowed us to compute eigenvalues for the structured matrices as Hamiltonian matrix JAA^T.

  10. Non-isothermal kinetics of thermal degradation of chitosan

    Directory of Open Access Journals (Sweden)

    Georgieva Velyana

    2012-08-01

    Full Text Available Abstract Background Chitosan is the second most abundant nitrogen containing biopolymer in nature, obtained from the shells of crustaceans, particularly crabs, shrimp and lobsters, which are waste products of seafood processing industries. It has great potential application in the areas of biotechnology, biomedicine, food industries, and cosmetics. Chitosan is also capable of adsorbing a number of metal ions as its amino groups can serve as chelation sites. Grafted functional groups such as hydroxyl, carboxyl, sulfate, phosphate, and amino groups on the chitosan have been reported to be responsible for metal binding and sorption of dyes and pigments. The knowledge of their thermal stability and pyrolysis may help to better understand and plan their industrial processing. Results Thermogravimetric studies of chitosan in air atmosphere were carried out at six rates of linear increasing of the temperature. The kinetics and mechanism of the thermal decomposition reaction were evaluated from the TG data using recommended from ICTAC kinetics committee iso-conversional calculation procedure of Kissinger-Akahira-Sunose, as well as 27 mechanism functions. The comparison of the obtained results showed that they strongly depend on the selection of proper mechanism function for the process. Therefore, it is very important to determine the most probable mechanism function. In this respect the iso-conversional calculation procedure turned out to be the most appropriate. Conclusion Chitosan have excellent properties such as hydrophilicity, biocompatibility, biodegradability, antibacterial, non-toxicity, adsorption application. The thermal degradation of chitosan occurs in two stages. The most probable mechanism function for both stages is determined and it was best described by kinetic equations of n-th order (Fn mechanism. For the first stage, it was established that n is equal to 3.0 and for the second stage – to 1.0 respectively. The values of the

  11. Temperature influence on the malonic acid decomposition in the Belousov-Zhabotinsky reaction

    Science.gov (United States)

    Blagojević, S. M.; Anić, S. R.; Čupić, Ž. D.; Pejić, N. D.; Kolar-Anić, Lj. Z.

    2009-09-01

    The kinetic investigations of the malonic acid decomposition (8.00 × 10-3 mol dm-3 ≤ [CH2(COOH)2]0 ≤ 4.30 × 10-2 mol dm-3) in the Belousov-Zhabotinsky (BZ) system in the presence of bromate, bromide, sulfuric acid and cerium sulfate, were performed in the isothermal closed well stirred reactor at different temperatures (25.0°C ≤ T ≤ 45.0°C). The formal kinetics of the overall BZ reaction, and particularly kinetics in characteristic periods of BZ reaction, based on the analyses of the bromide oscillograms, was accomplished. The evolution as well as the rate constants and the apparent activation energies of the reactions, which exist in the preoscillatory and oscillatory periods, are also successfully calculated by numerical simulations. Simulations are based on the model including the Br2O species.

  12. A comparison of carcass decomposition and associated insect succession onto burnt and unburnt pig carcasses.

    Science.gov (United States)

    McIntosh, Craig S; Dadour, Ian R; Voss, Sasha C

    2017-05-01

    The rate of decomposition and insect succession onto decomposing pig carcasses were investigated following burning of carcasses. Ten pig carcasses (40-45 kg) were exposed to insect activity during autumn (March-April) in Western Australia. Five replicates were burnt to a degree described by the Crow-Glassman Scale (CGS) level #2, while five carcasses were left unburnt as controls. Burning carcasses greatly accelerated decomposition in contrast to unburnt carcasses. Physical modifications following burning such as skin discolouration, splitting of abdominal tissue and leathery consolidation of skin eliminated evidence of bloat and altered microambient temperatures associated with carcasses throughout decomposition. Insect species identified on carcasses were consistent between treatment groups; however, a statistically significant difference in insect succession onto remains was evident between treatments (PERMANOVA F (1, 224)  = 14.23, p < 0.01) during an 8-day period that corresponds with the wet stage of decomposition. Differences were noted in the arrival time of late colonisers (Coleoptera) and the development of colonising insects between treatment groups. Differences in the duration of decomposition stages and insect assemblages indicate that burning has an effect on both rate of decomposition and insect succession. The findings presented here provide baseline data for entomological casework involving burnt remains criminal investigations.

  13. Stopped-Flow Spectrophotometric Study of the Kinetics and Mechanism of CO2 Uptake by cis-[Cr(C2O4(BaraNH2(OH22]+ Cation and the Acid-Catalyzed Decomposition of cis-[Cr(C2O4(BaraNH2OCO2]− Anion in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Lech Chmurzyński

    2011-09-01

    Full Text Available The kinetics of CO2 uptake by the cis-[Cr(C2O4(BaraNH2(OH22]+ complex cation and the acid hydrolysis of the cis-[Cr(C2O4(BaraNH2OCO2]− complex anion (where BaraNH2 denotes methyl 3-amino-2,3-dideoxy-b-D-arabino-hexopyranoside were studied using the stopped-flow technique. The reactions under study were investigated in aqueous solution in the 288–308 K temperature range. In the case of the reaction between CO2 and cis-[Cr(C2O4(BaraNH2(OH22]+ cation variable pH values (6.82–8.91 and the constant ionic strength of solution (H+, Na+, ClO4− = 1.0 were used. Carbon dioxide was generated by the reaction between sodium pyruvate and hydrogen peroxide. The acid hydrolysis of cis-[Cr(C2O4(BaraNH2OCO2]− was investigated for varying concentrations of H+ ions (0.01–2.7 M. The obtained results enabled the determination of the number of steps of the studied reactions. Based on the kinetic equations, rate constants were determined for each step. Finally, mechanisms for both reactions were proposed and discussed. Based on the obtained results it was concluded that the carboxylation (CO2 uptake reactions of cis-[Cr(C2O4(BaraNH2(OH22]+ and the decarboxylation (acid hydrolysis of the cis-[Cr(C2O4(BaraNH2OCO2]− are the opposite of each other.

  14. Microbiological decomposition of bagasse after radiation pasteurization

    International Nuclear Information System (INIS)

    Ito, Hitoshi; Ishigaki, Isao

    1987-01-01

    Microbiological decomposition of bagasse was studied for upgrading to animal feeds after radiation pasteurization. Solid-state culture media of bagasse were prepared with addition of some amount of inorganic salts for nitrogen source, and after irradiation, fungi were infected for cultivation. In this study, many kind of cellulosic fungi such as Pleurotus ostreatus, P. flavellatus, Verticillium sp., Coprinus cinereus, Lentinus edodes, Aspergillus niger, Trichoderma koningi, T. viride were used for comparison of decomposition of crude fibers. In alkali nontreated bagasse, P. ostreatus, P. flavellatus, C. cinereus and Verticillium sp. could decompose crude fibers from 25 to 34 % after one month of cultivation, whereas other fungi such as A. niger, T. koningi, T. viride, L. edodes decomposed below 10 %. On the contrary, alkali treatment enhanced the decomposition of crude fiber by A. niger, T. koningi and T. viride to be 29 to 47 % as well as Pleurotus species or C. cinereus. Other species of mushrooms such as L. edodes had a little ability of decomposition even after alkali treatment. Radiation treatment with 10 kGy could not enhance the decomposition of bagasse compared with steam treatment, whereas higher doses of radiation treatment enhanced a little of decomposition of crude fibers by microorganisms. (author)

  15. Decomposition of tetrachloroethylene by ionizing radiation

    International Nuclear Information System (INIS)

    Hakoda, T.; Hirota, K.; Hashimoto, S.

    1998-01-01

    Decomposition of tetrachloroethylene and other chloroethenes by ionizing radiation were examined to get information on treatment of industrial off-gas. Model gases, airs containing chloroethenes, were confined in batch reactors and irradiated with electron beam and gamma ray. The G-values of decomposition were larger in the order of tetrachloro- > trichloro- > trans-dichloro- > cis-dichloro- > monochloroethylene in electron beam irradiation and tetrachloro-, trichloro-, trans-dichloro- > cis-dichloro- > monochloroethylene in gamma ray irradiation. For tetrachloro-, trichloro- and trans-dichloroethylene, G-values of decomposition in EB irradiation increased with increase of chlorine atom in a molecule, while those in gamma ray irradiation were almost kept constant. The G-value of decomposition for tetrachloroethylene in EB irradiation was the largest of those for all chloroethenes. In order to examine the effect of the initial concentration on G-value of decomposition, airs containing 300 to 1,800 ppm of tetrachloroethylene were irradiated with electron beam and gamma ray. The G-values of decomposition in both irradiation increased with the initial concentration. Those in electron beam irradiation were two times larger than those in gamma ray irradiation

  16. Microbiological decomposition of bagasse after radiation pasteurization

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Hitoshi; Ishigaki, Isao

    1987-11-01

    Microbiological decomposition of bagasse was studied for upgrading to animal feeds after radiation pasteurization. Solid-state culture media of bagasse were prepared with addition of some amount of inorganic salts for nitrogen source, and after irradiation, fungi were infected for cultivation. In this study, many kind of cellulosic fungi such as Pleurotus ostreatus, P. flavellatus, Verticillium sp., Coprinus cinereus, Lentinus edodes, Aspergillus niger, Trichoderma koningi, T. viride were used for comparison of decomposition of crude fibers. In alkali nontreated bagasse, P. ostreatus, P. flavellatus, C. cinereus and Verticillium sp. could decompose crude fibers from 25 to 34 % after one month of cultivation, whereas other fungi such as A. niger, T. koningi, T. viride, L. edodes decomposed below 10 %. On the contrary, alkali treatment enhanced the decomposition of crude fiber by A. niger, T. koningi and T. viride to be 29 to 47 % as well as Pleurotus species or C. cinereus. Other species of mushrooms such as L. edodes had a little ability of decomposition even after alkali treatment. Radiation treatment with 10 kGy could not enhance the decomposition of bagasse compared with steam treatment, whereas higher doses of radiation treatment enhanced a little of decomposition of crude fibers by microorganisms.

  17. Oxidative degradation of low and intermediate level Radioactive organic wastes 2. Acid decomposition on spent Ion-Exchange resins

    International Nuclear Information System (INIS)

    Ghattas, N.K.; Eskander, S.B.

    1995-01-01

    The present work provides a simplified, effective and economic method for the chemical decomposition of radioactively contaminated solid organic waste, especially spent ion - exchange resins. The goal is to achieve volume reduction and to avoid technical problems encountered in processes used for similar purposes (incineration, pyrolysis). Factors efficiency and kinetics of the oxidation of the ion exchange resins in acid medium using hydrogen peroxide as oxidant, namely, duration of treatment and the acid to resin ratio were studied systematically on a laboratory scale. Moreover the percent composition of the off-gas evolved during the decomposition process was analysed. 3 figs., 5 tabs

  18. Oxidative degradation of low and intermediate level Radioactive organic wastes 2. Acid decomposition on spent Ion-Exchange resins

    Energy Technology Data Exchange (ETDEWEB)

    Ghattas, N K; Eskander, S B [Radioisotope dept., atomic energy authority, (Egypt)

    1995-10-01

    The present work provides a simplified, effective and economic method for the chemical decomposition of radioactively contaminated solid organic waste, especially spent ion - exchange resins. The goal is to achieve volume reduction and to avoid technical problems encountered in processes used for similar purposes (incineration, pyrolysis). Factors efficiency and kinetics of the oxidation of the ion exchange resins in acid medium using hydrogen peroxide as oxidant, namely, duration of treatment and the acid to resin ratio were studied systematically on a laboratory scale. Moreover the percent composition of the off-gas evolved during the decomposition process was analysed. 3 figs., 5 tabs.

  19. Kinetics and hybrid kinetic-fluid models for nonequilibrium gas and plasmas

    International Nuclear Information System (INIS)

    Crouseilles, N.

    2004-12-01

    For a few decades, the application of the physics of plasmas has appeared in different fields like laser-matter interaction, astrophysics or thermonuclear fusion. In this thesis, we are interested in the modeling and the numerical study of nonequilibrium gas and plasmas. To describe such systems, two ways are usually used: the fluid description and the kinetic description. When we study a nonequilibrium system, fluid models are not sufficient and a kinetic description have to be used. However, solving a kinetic model requires the discretization of a large number of variables, which is quite expensive from a numerical point of view. The aim of this work is to propose a hybrid kinetic-fluid model thanks to a domain decomposition method in the velocity space. The derivation of the hybrid model is done in two different contexts: the rarefied gas context and the more complicated plasmas context. The derivation partly relies on Levermore's entropy minimization approach. The so-obtained model is then discretized and validated on various numerical test cases. In a second stage, a numerical study of a fully kinetic model is presented. A collisional plasma constituted of electrons and ions is considered through the Vlasov-Poisson-Fokker-Planck-Landau equation. Then, a numerical scheme which preserves total mass and total energy is presented. This discretization permits in particular a numerical study of the Landau damping. (author)

  20. An analogue of Wagner's theorem for decompositions of matrix algebras

    International Nuclear Information System (INIS)

    Ivanov, D N

    2004-01-01

    Wagner's celebrated theorem states that a finite affine plane whose collineation group is transitive on lines is a translation plane. The notion of an orthogonal decomposition (OD) of a classically semisimple associative algebra introduced by the author allows one to draw an analogy between finite affine planes of order n and ODs of the matrix algebra M n (C) into a sum of subalgebras conjugate to the diagonal subalgebra. These ODs are called WP-decompositions and are equivalent to the well-known ODs of simple Lie algebras of type A n-1 into a sum of Cartan subalgebras. In this paper we give a detailed and improved proof of the analogue of Wagner's theorem for WP-decompositions of the matrix algebra of odd non-square order an outline of which was earlier published in a short note in 'Russian Math. Surveys' in 1994. In addition, in the framework of the theory of ODs of associative algebras, based on the method of idempotent bases, we obtain an elementary proof of the well-known Kostrikin-Tiep theorem on irreducible ODs of Lie algebras of type A n-1 in the case where n is a prime-power.

  1. Operator Decomposition Framework for Perturbation Theory

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-Khalik, Hany S.; Wang, Congjian; Bang, Young Suk [North Carolina State University, Raleigh (United States)

    2012-05-15

    This summary describes a new framework for perturbation theory intended to improve its performance, in terms of the associated computational cost and the complexity of implementation, for routine reactor calculations in support of design, analysis, and regulation. Since its first introduction in reactor analysis by Winger, perturbation theory has assumed an aura of sophistication with regard to its implementation and its capabilities. Only few reactor physicists, typically mathematically proficient, have contributed to its development, with the general body of the nuclear engineering community remaining unaware of its current status, capabilities, and challenges. Given its perceived sophistication and the small body of community users, the application of perturbation theory has been limited to investigatory analyses only. It is safe to say that the nuclear community is split into two groups, a small one which understands the theory and, and a much bigger group with the perceived notion that perturbation theory is nothing but a fancy mathematical approach that has very little use in practice. Over the past three years, research has demonstrated two goals. First, reduce the computational cost of perturbation theory in order to enable its use for routine reactor calculations. Second, expose some of the myth about perturbation theory and present it in a form that is simple and relatable in order to stimulate the interest of nuclear practitioners, especially those who are currently working on the development of next generation reactor design and analysis tools. The operator decomposition approach has its roots in linear algebra and can be easily understood by code developers, especially those involved in the design of iterative numerical solution strategies

  2. Hydrogen production by the decomposition of water

    Science.gov (United States)

    Hollabaugh, C.M.; Bowman, M.G.

    A process is described for the production of hydrogen from water by a sulfuric acid process employing electrolysis and thermo-chemical decomposition. The water containing SO/sub 2/ is electrolyzed to produce H/sub 2/ at the cathode and to oxidize the SO/sub 2/ to form H/sub 2/SO/sub 4/ at the anode. After the H/sub 2/ has been separated, a compound of the type M/sub r/X/sub s/ is added to produce a water insoluble sulfate of M and a water insoluble oxide of the metal in the radical X. In the compound M/sub r/X/sub s/, M is at least one metal selected from the group consisting of Ba/sup 2 +/, Ca/sup 2 +/, Sr/sup 2 +/, La/sup 2 +/, and Pb/sup 2 +/; X is at least one radical selected from the group consisting of molybdate (MoO/sub 4//sup 2 -/), tungstate (WO/sub 4//sup 2 -/), and metaborate (BO/sub 2//sup 1 -/); and r and s are either 1, 2, or 3 depending upon the valence of M and X. The precipitated mixture is filtered and heated to a temperature sufficiently high to form SO/sub 3/ gas and to reform M/sub r/X/sub s/. The SO/sub 3/ is dissolved in a small amount of H/sub 2/O to produce concentrated H/sub 2/SO/sub 4/, and the M/sub r/X/sub s/ is recycled to the process. Alternatively, the SO/sub 3/ gas can be recycled to the beginning of the process to provide a continuous process for the production of H/sub 2/ in which only water need be added in a substantial amount. (BLM)

  3. Aridity and decomposition processes in complex landscapes

    Science.gov (United States)

    Ossola, Alessandro; Nyman, Petter

    2015-04-01

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

  4. Slow Decomposition of Silicone Rubber.

    Science.gov (United States)

    1982-09-01

    for the presence of silanol groups in the original polymer was obtained by reacting PDMS with tetraethoxysllane, yielding a substantial amount, 76 per...degree of gelatlon. 4J 8 An attempt was also made to block these OH groups by reacting POMS with hexamethyldisilazane to yield trimethylsiloxy groups in...toluene for various periods. Cold extraction, 0; hot ( Soxhlet ) extraction, A. Figure 2. Soluble fraction AS generated in a previously- extracted

  5. On a closed form solution of the point kinetics equations with reactivity feedback of temperature

    International Nuclear Information System (INIS)

    Silva, Jeronimo J.A.; Vilhena, Marco T.M.B.; Petersen, Claudio Z.; Bodmann, Bardo E.J.; Alvim, Antonio C.M.

    2011-01-01

    An analytical solution of the point kinetics equations to calculate reactivity as a function of time by the Decomposition method has recently appeared in the literature. In this paper, we go one step forward, by considering the neutron point kinetics equations together with temperature feedback effects. To accomplish that, we extended the point kinetics by a temperature perturbation, obtaining a second order nonlinear ordinary differential equation. This equation is then solved by the Decomposition Method, that is, by expanding the neutron density in a series and the nonlinear terms into Adomian Polynomials. Substituting these expansions into the nonlinear ordinary equation, we construct a recursive set of linear problems that can be solved by the methodology previously mentioned for the point kinetics equation. We also report on numerical simulations and comparisons against literature results. (author)

  6. Decomposition of forest products buried in landfills

    International Nuclear Information System (INIS)

    Wang, Xiaoming; Padgett, Jennifer M.; Powell, John S.; Barlaz, Morton A.

    2013-01-01

    Highlights: • This study tracked chemical changes of wood and paper in landfills. • A decomposition index was developed to quantify carbohydrate biodegradation. • Newsprint biodegradation as measured here is greater than previous reports. • The field results correlate well with previous laboratory measurements. - Abstract: The objective of this study was to investigate the decomposition of selected wood and paper products in landfills. The decomposition of these products under anaerobic landfill conditions results in the generation of biogenic carbon dioxide and methane, while the un-decomposed portion represents a biogenic carbon sink. Information on the decomposition of these municipal waste components is used to estimate national methane emissions inventories, for attribution of carbon storage credits, and to assess the life-cycle greenhouse gas impacts of wood and paper products. Hardwood (HW), softwood (SW), plywood (PW), oriented strand board (OSB), particleboard (PB), medium-density fiberboard (MDF), newsprint (NP), corrugated container (CC) and copy paper (CP) were buried in landfills operated with leachate recirculation, and were excavated after approximately 1.5 and 2.5 yr. Samples were analyzed for cellulose (C), hemicellulose (H), lignin (L), volatile solids (VS), and organic carbon (OC). A holocellulose decomposition index (HOD) and carbon storage factor (CSF) were calculated to evaluate the extent of solids decomposition and carbon storage. Samples of OSB made from HW exhibited cellulose plus hemicellulose (C + H) loss of up to 38%, while loss for the other wood types was 0–10% in most samples. The C + H loss was up to 81%, 95% and 96% for NP, CP and CC, respectively. The CSFs for wood and paper samples ranged from 0.34 to 0.47 and 0.02 to 0.27 g OC g −1 dry material, respectively. These results, in general, correlated well with an earlier laboratory-scale study, though NP and CC decomposition measured in this study were higher than

  7. Decomposition of forest products buried in landfills

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoming, E-mail: xwang25@ncsu.edu [Department of Civil, Construction, and Environmental Engineering, Campus Box 7908, North Carolina State University, Raleigh, NC 27695-7908 (United States); Padgett, Jennifer M. [Department of Civil, Construction, and Environmental Engineering, Campus Box 7908, North Carolina State University, Raleigh, NC 27695-7908 (United States); Powell, John S. [Department of Chemical and Biomolecular Engineering, Campus Box 7905, North Carolina State University, Raleigh, NC 27695-7905 (United States); Barlaz, Morton A. [Department of Civil, Construction, and Environmental Engineering, Campus Box 7908, North Carolina State University, Raleigh, NC 27695-7908 (United States)

    2013-11-15

    Highlights: • This study tracked chemical changes of wood and paper in landfills. • A decomposition index was developed to quantify carbohydrate biodegradation. • Newsprint biodegradation as measured here is greater than previous reports. • The field results correlate well with previous laboratory measurements. - Abstract: The objective of this study was to investigate the decomposition of selected wood and paper products in landfills. The decomposition of these products under anaerobic landfill conditions results in the generation of biogenic carbon dioxide and methane, while the un-decomposed portion represents a biogenic carbon sink. Information on the decomposition of these municipal waste components is used to estimate national methane emissions inventories, for attribution of carbon storage credits, and to assess the life-cycle greenhouse gas impacts of wood and paper products. Hardwood (HW), softwood (SW), plywood (PW), oriented strand board (OSB), particleboard (PB), medium-density fiberboard (MDF), newsprint (NP), corrugated container (CC) and copy paper (CP) were buried in landfills operated with leachate recirculation, and were excavated after approximately 1.5 and 2.5 yr. Samples were analyzed for cellulose (C), hemicellulose (H), lignin (L), volatile solids (VS), and organic carbon (OC). A holocellulose decomposition index (HOD) and carbon storage factor (CSF) were calculated to evaluate the extent of solids decomposition and carbon storage. Samples of OSB made from HW exhibited cellulose plus hemicellulose (C + H) loss of up to 38%, while loss for the other wood types was 0–10% in most samples. The C + H loss was up to 81%, 95% and 96% for NP, CP and CC, respectively. The CSFs for wood and paper samples ranged from 0.34 to 0.47 and 0.02 to 0.27 g OC g{sup −1} dry material, respectively. These results, in general, correlated well with an earlier laboratory-scale study, though NP and CC decomposition measured in this study were higher than

  8. Synthesis, X-ray crystallography, spectroscopy, electrochemistry, thermal and kinetic study of uranyl Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Golzard, F.; Eigner, Václav; Dušek, Michal

    2013-01-01

    Roč. 66, č. 20 (2013), s. 3629-3646 ISSN 0095-8972 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : X-ray crystallography * uranyl Schiff base complex * kinetics of thermal decomposition * cyclic voltammetry * kinetics and mechanism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.224, year: 2013

  9. Local Fractional Adomian Decomposition and Function Decomposition Methods for Laplace Equation within Local Fractional Operators

    Directory of Open Access Journals (Sweden)

    Sheng-Ping Yan

    2014-01-01

    Full Text Available We perform a comparison between the local fractional Adomian decomposition and local fractional function decomposition methods applied to the Laplace equation. The operators are taken in the local sense. The results illustrate the significant features of the two methods which are both very effective and straightforward for solving the differential equations with local fractional derivative.

  10. Global decomposition experiment shows soil animal impacts on decomposition are climate-dependent

    Czech Academy of Sciences Publication Activity Database

    Wall, D.H.; Bradford, M.A.; John, M.G.St.; Trofymow, J.A.; Behan-Pelletier, V.; Bignell, D.E.; Dangerfield, J.M.; Parton, W.J.; Rusek, Josef; Voigt, W.; Wolters, V.; Gardel, H.Z.; Ayuke, F. O.; Bashford, R.; Beljakova, O.I.; Bohlen, P.J.; Brauman, A.; Flemming, S.; Henschel, J.R.; Johnson, D.L.; Jones, T.H.; Kovářová, Marcela; Kranabetter, J.M.; Kutny, L.; Lin, K.-Ch.; Maryati, M.; Masse, D.; Pokarzhevskii, A.; Rahman, H.; Sabará, M.G.; Salamon, J.-A.; Swift, M.J.; Varela, A.; Vasconcelos, H.L.; White, D.; Zou, X.

    2008-01-01

    Roč. 14, č. 11 (2008), s. 2661-2677 ISSN 1354-1013 Institutional research plan: CEZ:AV0Z60660521; CEZ:AV0Z60050516 Keywords : climate decomposition index * decomposition * litter Subject RIV: EH - Ecology, Behaviour Impact factor: 5.876, year: 2008

  11. The functionalization of limonite to prepare NZVI and its application in decomposition of p-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Haibo; Chen, Tianhu, E-mail: chentianhu@hfut.edu.cn; Xie, Qiaoqin; Zou, Xuehua; Chen, Chen [Hefei University of Technology, Laboratory of Nanomineral and Environmental Material, School of Resources and Environmental Engineering (China); Frost, Ray L. [Queensland University of Technology, Science and Engineering Faculty, School of Chemistry, Physics and Mechanical Engineering (Australia)

    2015-09-15

    Nano zero valent iron (NZVI) was prepared by reducing natural limonite using hydrogen. X-ray fluorescence, thermogravimetry, X-ray diffraction, transmission electron microscope, temperature programmed reduction (TPR), field emission scanning electron microscope/energy disperse spectroscopy (FESEM/EDS) were utilized to characterize the natural limonite and reduced limonite. The ratios of Fe:O before and after reducing was determined using EDS. The reactivity of the NZVI was assessed by decomposition of p-nitrophenol (p-NP) and was compared with commercial iron powder. In this study, the results of TPR and FESEM/EDS indicated that NZVI can be prepared by reducing natural limonite using hydrogen. Most importantly, this NZVI was proved to have a good performance on decomposition of p-NP and the process of p-NP decomposition agreed well with the pseudo-first-order kinetic model. The reactivity of this NZVI for decomposition of p-NP was greatly superior to that of commercial iron powder.

  12. Time space domain decomposition methods for reactive transport - Application to CO2 geological storage

    International Nuclear Information System (INIS)

    Haeberlein, F.

    2011-01-01

    Reactive transport modelling is a basic tool to model chemical reactions and flow processes in porous media. A totally reduced multi-species reactive transport model including kinetic and equilibrium reactions is presented. A structured numerical formulation is developed and different numerical approaches are proposed. Domain decomposition methods offer the possibility to split large problems into smaller subproblems that can be treated in parallel. The class of Schwarz-type domain decomposition methods that have proved to be high-performing algorithms in many fields of applications is presented with a special emphasis on the geometrical viewpoint. Numerical issues for the realisation of geometrical domain decomposition methods and transmission conditions in the context of finite volumes are discussed. We propose and validate numerically a hybrid finite volume scheme for advection-diffusion processes that is particularly well-suited for the use in a domain decomposition context. Optimised Schwarz waveform relaxation methods are studied in detail on a theoretical and numerical level for a two species coupled reactive transport system with linear and nonlinear coupling terms. Well-posedness and convergence results are developed and the influence of the coupling term on the convergence behaviour of the Schwarz algorithm is studied. Finally, we apply a Schwarz waveform relaxation method on the presented multi-species reactive transport system. (author)

  13. Towards a paradigm shift in the modeling of soil organic carbon decomposition for earth system models

    Science.gov (United States)

    He, Yujie

    Soils are the largest terrestrial carbon pools and contain approximately 2200 Pg of carbon. Thus, the dynamics of soil carbon plays an important role in the global carbon cycle and climate system. Earth System Models are used to project future interactions between terrestrial ecosystem carbon dynamics and climate. However, these models often predict a wide range of soil carbon responses and their formulations have lagged behind recent soil science advances, omitting key biogeochemical mechanisms. In contrast, recent mechanistically-based biogeochemical models that explicitly account for microbial biomass pools and enzyme kinetics that catalyze soil carbon decomposition produce notably different results and provide a closer match to recent observations. However, a systematic evaluation of the advantages and disadvantages of the microbial models and how they differ from empirical, first-order formulations in soil decomposition models for soil organic carbon is still needed. This dissertation consists of a series of model sensitivity and uncertainty analyses and identifies dominant decomposition processes in determining soil organic carbon dynamics. Poorly constrained processes or parameters that require more experimental data integration are also identified. This dissertation also demonstrates the critical role of microbial life-history traits (e.g. microbial dormancy) in the modeling of microbial activity in soil organic matter decomposition models. Finally, this study surveys and synthesizes a number of recently published microbial models and provides suggestions for future microbial model developments.

  14. Investigation of the decomposition reaction and dust explosion characteristics of crystalline benzoyl peroxides

    International Nuclear Information System (INIS)

    Lu, K.-T.; Chen, T.-C.; Hu, K.-H.

    2009-01-01

    The benzoyl peroxide (BPO) is widely used in the chemical industry. Many catastrophes have been caused by its thermal instability or reactive incompatibility in storage or thermal decomposition reaction. Thus, its hazard characteristics have to be clearly identified. First of all, the differential scanning calorimeter (DSC) is used to measure the heat of decomposition reaction, which can contribute to understanding the reaction characteristics of benzoyl peroxide. The accelerating rate calorimeter (ARC) is used to measure the rates of temperature and pressure rises of decomposition reaction, and then the kinetics parameters are estimated. Furthermore, the MIKE 3 apparatus and the 20-l-Apparatus are used to measure and analyze the dust explosion characteristics of benzoyl peroxide under room temperature and atmospheric pressure. Finally, Semenov's thermal explosion theory is applied to investigate the critical runaway condition and the stability criterion of decomposition reaction, and to build the relationship of critical temperature, convective heat transfer coefficient, heat transfer surface area and ambient temperature. These results contribute to improving the safety in the reaction, transportation and storage processes of benzoyl peroxide

  15. Testing the Use of Pigs as Human Proxies in Decomposition Studies.

    Science.gov (United States)

    Connor, Melissa; Baigent, Christiane; Hansen, Eriek S

    2017-12-28

    Pigs are a common human analogue in taphonomic study, yet data comparing the trajectory of decomposition between the two groups are lacking. This study compared decomposition rate and gross tissue change in 17 pigs and 22 human remains placed in the Forensic Investigation Research Station in western Colorado between 2012 and 2015. Accumulated degree days (ADD) were used to assess the number of thermal units required to reach a given total body score (TBS) (1) which was used as the measure of decomposition. A comparison of slopes in linear mixed effects model indicated that decomposition rates significantly differed between human donors and pig remains χ 2 (1) = 5.662, p = 0.017. Neither the pig nor the human trajectory compared well to the TBS model. Thus, (i) pigs are not an adequate proxy for human decomposition studies, and (ii) in the semiarid environment of western Colorado, there is a need to develop a regional decomposition model. © 2017 American Academy of Forensic Sciences.

  16. Steganography based on pixel intensity value decomposition

    Science.gov (United States)

    Abdulla, Alan Anwar; Sellahewa, Harin; Jassim, Sabah A.

    2014-05-01

    This paper focuses on steganography based on pixel intensity value decomposition. A number of existing schemes such as binary, Fibonacci, Prime, Natural, Lucas, and Catalan-Fibonacci (CF) are evaluated in terms of payload capacity and stego quality. A new technique based on a specific representation is proposed to decompose pixel intensity values into 16 (virtual) bit-planes suitable for embedding purposes. The proposed decomposition has a desirable property whereby the sum of all bit-planes does not exceed the maximum pixel intensity value, i.e. 255. Experimental results demonstrate that the proposed technique offers an effective compromise between payload capacity and stego quality of existing embedding techniques based on pixel intensity value decomposition. Its capacity is equal to that of binary and Lucas, while it offers a higher capacity than Fibonacci, Prime, Natural, and CF when the secret bits are embedded in 1st Least Significant Bit (LSB). When the secret bits are embedded in higher bit-planes, i.e., 2nd LSB to 8th Most Significant Bit (MSB), the proposed scheme has more capacity than Natural numbers based embedding. However, from the 6th bit-plane onwards, the proposed scheme offers better stego quality. In general, the proposed decomposition scheme has less effect in terms of quality on pixel value when compared to most existing pixel intensity value decomposition techniques when embedding messages in higher bit-planes.

  17. Microbial Signatures of Cadaver Gravesoil During Decomposition.

    Science.gov (United States)

    Finley, Sheree J; Pechal, Jennifer L; Benbow, M Eric; Robertson, B K; Javan, Gulnaz T

    2016-04-01

    Genomic studies have estimated there are approximately 10(3)-10(6) bacterial species per gram of soil. The microbial species found in soil associated with decomposing human remains (gravesoil) have been investigated and recognized as potential molecular determinants for estimates of time since death. The nascent era of high-throughput amplicon sequencing of the conserved 16S ribosomal RNA (rRNA) gene region of gravesoil microbes is allowing research to expand beyond more subjective empirical methods used in forensic microbiology. The goal of the present study was to evaluate microbial communities and identify taxonomic signatures associated with the gravesoil human cadavers. Using 16S rRNA gene amplicon-based sequencing, soil microbial communities were surveyed from 18 cadavers placed on the surface or buried that were allowed to decompose over a range of decomposition time periods (3-303 days). Surface soil microbial communities showed a decreasing trend in taxon richness, diversity, and evenness over decomposition, while buried cadaver-soil microbial communities demonstrated increasing taxon richness, consistent diversity, and decreasing evenness. The results show that ubiquitous Proteobacteria was confirmed as the most abundant phylum in all gravesoil samples. Surface cadaver-soil communities demonstrated a decrease in Acidobacteria and an increase in Firmicutes relative abundance over decomposition, while buried soil communities were consistent in their community composition throughout decomposition. Better understanding of microbial community structure and its shifts over time may be important for advancing general knowledge of decomposition soil ecology and its potential use during forensic investigations.

  18. Thermal decomposition process of silver behenate

    International Nuclear Information System (INIS)

    Liu Xianhao; Lu Shuxia; Zhang Jingchang; Cao Weiliang

    2006-01-01

    The thermal decomposition processes of silver behenate have been studied by infrared spectroscopy (IR), X-ray diffraction (XRD), combined thermogravimetry-differential thermal analysis-mass spectrometry (TG-DTA-MS), transmission electron microscopy (TEM) and UV-vis spectroscopy. The TG-DTA and the higher temperature IR and XRD measurements indicated that complicated structural changes took place while heating silver behenate, but there were two distinct thermal transitions. During the first transition at 138 deg. C, the alkyl chains of silver behenate were transformed from an ordered into a disordered state. During the second transition at about 231 deg. C, a structural change took place for silver behenate, which was the decomposition of silver behenate. The major products of the thermal decomposition of silver behenate were metallic silver and behenic acid. Upon heating up to 500 deg. C, the final product of the thermal decomposition was metallic silver. The combined TG-MS analysis showed that the gas products of the thermal decomposition of silver behenate were carbon dioxide, water, hydrogen, acetylene and some small molecule alkenes. TEM and UV-vis spectroscopy were used to investigate the process of the formation and growth of metallic silver nanoparticles

  19. Litter quality mediated nitrogen effect on plant litter decomposition regardless of soil fauna presence.

    Science.gov (United States)

    Zhang, Weidong; Chao, Lin; Yang, Qingpeng; Wang, Qingkui; Fang, Yunting; Wang, Silong

    2016-10-01

    Nitrogen addition has been shown to affect plant litter decomposition in terrestrial ecosystems. The way that nitrogen deposition impacts the relationship between plant litter decomposition and altered soil nitrogen availability is unclear, however. This study examined 18 co-occurring litter types in a subtropical forest in China in terms of their decomposition (1 yr of exposure in the field) with nitrogen addition treatment (0, 0.4, 1.6, and 4.0 mol·N·m -2 ·yr -1 ) and soil fauna exclusion (litter bags with 0.1 and 2 cm mesh size). Results showed that the plant litter decomposition rate is significantly reduced because of nitrogen addition; the strength of the nitrogen addition effect is closely related to the nitrogen addition levels. Plant litters with diverse quality responded to nitrogen addition differently. When soil fauna was present, the nitrogen addition effect on medium-quality or high-quality plant litter decomposition rate was -26% ± 5% and -29% ± 4%, respectively; these values are significantly higher than that of low-quality plant litter decomposition. The pattern is similar when soil fauna is absent. In general, the plant litter decomposition rate is decreased by soil fauna exclusion; an average inhibition of -17% ± 1.5% was exhibited across nitrogen addition treatment and litter quality groups. However, this effect is weakly related to nitrogen addition treatment and plant litter quality. We conclude that the variations in plant litter quality, nitrogen deposition, and soil fauna are important factors of decomposition and nutrient cycling in a subtropical forest ecosystem. © 2016 by the Ecological Society of America.

  20. Ocean Models and Proper Orthogonal Decomposition

    Science.gov (United States)

    Salas-de-Leon, D. A.

    2007-05-01

    The increasing computational developments and the better understanding of mathematical and physical systems resulted in an increasing number of ocean models. Long time ago, modelers were like a secret organization and recognize each other by using secret codes and languages that only a select group of people was able to recognize and understand. The access to computational systems was reduced, on one hand equipment and the using time of computers were expensive and restricted, and on the other hand, they required an advance computational languages that not everybody wanted to learn. Now a days most college freshman own a personal computer (PC or laptop), and/or have access to more sophisticated computational systems than those available for research in the early 80's. The resource availability resulted in a mayor access to all kind models. Today computer speed and time and the algorithms does not seem to be a problem, even though some models take days to run in small computational systems. Almost every oceanographic institution has their own model, what is more, in the same institution from one office to the next there are different models for the same phenomena, developed by different research member, the results does not differ substantially since the equations are the same, and the solving algorithms are similar. The algorithms and the grids, constructed with algorithms, can be found in text books and/or over the internet. Every year more sophisticated models are constructed. The Proper Orthogonal Decomposition is a technique that allows the reduction of the number of variables to solve keeping the model properties, for which it can be a very useful tool in diminishing the processes that have to be solved using "small" computational systems, making sophisticated models available for a greater community.

  1. Categorical Cell Decomposition of Quantized Symplectic Algebraic Varieties

    OpenAIRE

    Bellamy, Gwyn; Dodd, Christopher; McGerty, Kevin; Nevins, Thomas

    2013-01-01

    We prove a new symplectic analogue of Kashiwara’s equivalence from D–module\\ud theory. As a consequence, we establish a structure theory for module categories over\\ud deformation-quantizations that mirrors, at a higher categorical level, the BiałynickiBirula\\ud stratification of a variety with an action of the multiplicative group Gm . The\\ud resulting categorical cell decomposition provides an algebrogeometric parallel to the\\ud structure of Fukaya categories of Weinstein manifolds. From it,...

  2. Catalytic activity of laminated compounds of graphite with transitions metals in decomposition of alcohols and formic acid

    International Nuclear Information System (INIS)

    Novikov, Yu.N.; Lapkina, N.D.; Vol'pin, M.E.

    1976-01-01

    The catalytic activity is studied of laminated graphite compounds with Fe, Co, Ni, Cu, Mo, W and Mn both in the reduced and oxidized forms in gas phase decomposition reactions of isopropyl, n-butyl, cyclohexyl, and 4-tret-butylcyclohexyl alcohols, and also formic acid. All the catalysts are shown to be active in the reactions where isopropyl and n-butyl alcohols undergo decomposition. The laminated compounds of graphite with Co and Ni both in the oxidized and reduction form are the most active catalysts of the selective decomposition of alcohols to aldehydes and ketones, and also formic acid to CO 2 and H 2 . The kinetics of a number of reactions is found to obey the second order equation with allowance made for the system volume

  3. Early stages of spinodal decomposition in Fe-Cr resolved by in-situ small-angle neutron scattering

    Science.gov (United States)

    Hörnqvist, M.; Thuvander, M.; Steuwer, A.; King, S.; Odqvist, J.; Hedström, P.

    2015-02-01

    In-situ, time-resolved small-angle neutron scattering (SANS) investigations of the early stages of the spinodal decomposition process in Fe-35Cr were performed at 773 and 798 K. The kinetics of the decomposition, both in terms of characteristic distance and peak intensity, followed a power-law behaviour from the start of the heat treatment (a'= 0.10-0.11 and a″ = 0.67-0.86). Furthermore, the method allows tracking of the high-Q slope, which is a sensitive measure of the early stages of decomposition. Ex-situ SANS and atom probe tomography were used to verify the results from the in-situ investigations. Finally, the in-situ measurement of the evolution of the characteristic distance at 773 K was compared with the predictions from the Cahn-Hilliard-Cook model, which showed good agreement with the experimental data (a'= 0.12-0.20 depending on the assumed mobility).

  4. Effect of oxygen on decomposition of nitrous oxide over various metal oxide catalysts

    International Nuclear Information System (INIS)

    Satsuma, Atsushi; Maeshima, Hajime; Watanabe, Kiyoshi; Hattori, Tadashi

    2001-01-01

    The inhibitory effect of oxygen on decomposition of nitrous oxide over various metal oxide catalysts was investigated. The activity of nitrous oxide decomposition significantly decreased over CuO, Co 3 O 4 , NiO, Fe 2 O 3 , SnO 2 , In 2 O 3 and Cr 2 O 3 by reversible adsorption of oxygen onto the active sites. On the contrary to this, there was no or small change in the activity of TiO 2 , Al 2 O 3 , MgO, La 2 O 3 and CaO. A good correlation was observed between the degree of inhibition and the heat of formation of metal oxides. On the basis of kinetic model, the reduction of catalytic activity in the presence of oxygen was rationalized with the strength of oxygen adsorption on the metal oxide surface. (author)

  5. Differences in SOM decomposition and temperature sensitivity among soil aggregate size classes in a temperate grasslands.

    Science.gov (United States)

    Wang, Qing; Wang, Dan; Wen, Xuefa; Yu, Guirui; He, Nianpeng; Wang, Rongfu

    2015-01-01

    The principle of enzyme kinetics suggests that the temperature sensitivity (Q10) of soil organic matter (SOM) decomposition is inversely related to organic carbon (C) quality, i.e., the C quality-temperature (CQT) hypothesis. We tested this hypothesis by performing laboratory incubation experiments with bulk soil, macroaggregates (MA, 250-2000 μm), microaggregates (MI, 53-250 μm), and mineral fractions (MF, temperature and aggregate size significantly affected on SOM decomposition, with notable interactive effects (Ptemperature in the following order: MA>MF>bulk soil >MI(P classes (P temperature is closely associated withsoil aggregation and highlights the complex responses of ecosystem C budgets to future warming scenarios.

  6. Radiolytic decomposition of 4-bromodiphenyl ether

    International Nuclear Information System (INIS)

    Tang Liang; Xu Gang; Wu Wenjing; Shi Wenyan; Liu Ning; Bai Yulei; Wu Minghong

    2010-01-01

    Polybrominated diphenyl ethers (PBDEs) spread widely in the environment are mainly removed by photochemical and anaerobic microbial degradation. In this paper, the decomposition of 4-bromodiphenyl ether (BDE -3), the PBDEs homologues, is investigated by electron beam irradiation of its ethanol/water solution (reduction system) and acetonitrile/water solution (oxidation system). The radiolytic products were determined by GC coupled with electron capture detector, and the reaction rate constant of e sol - in the reduction system was measured at 2.7 x 10 10 L · mol -1 · s -1 by pulsed radiolysis. The results show that the BDE-3 concentration affects strongly the decomposition ratio in the alkali solution, and the reduction system has a higher BDE-3 decomposition rate than the oxidation system. This indicates that the BDE-3 was reduced by effectively capturing e sol - in radiolytic process. (authors)

  7. Parallel processing for pitch splitting decomposition

    Science.gov (United States)

    Barnes, Levi; Li, Yong; Wadkins, David; Biederman, Steve; Miloslavsky, Alex; Cork, Chris

    2009-10-01

    Decomposition of an input pattern in preparation for a double patterning process is an inherently global problem in which the influence of a local decomposition decision can be felt across an entire pattern. In spite of this, a large portion of the work can be massively distributed. Here, we discuss the advantages of geometric distribution for polygon operations with limited range of influence. Further, we have found that even the naturally global "coloring" step can, in large part, be handled in a geometrically local manner. In some practical cases, up to 70% of the work can be distributed geometrically. We also describe the methods for partitioning the problem into local pieces and present scaling data up to 100 CPUs. These techniques reduce DPT decomposition runtime by orders of magnitude.

  8. Thermal Plasma decomposition of fluoriated greenhouse gases

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Soo Seok; Watanabe, Takayuki [Tokyo Institute of Technology, Yokohama (Japan); Park, Dong Wha [Inha University, Incheon (Korea, Republic of)

    2012-02-15

    Fluorinated compounds mainly used in the semiconductor industry are potent greenhouse gases. Recently, thermal plasma gas scrubbers have been gradually replacing conventional burn-wet type gas scrubbers which are based on the combustion of fossil fuels because high conversion efficiency and control of byproduct generation are achievable in chemically reactive high temperature thermal plasma. Chemical equilibrium composition at high temperature and numerical analysis on a complex thermal flow in the thermal plasma decomposition system are used to predict the process of thermal decomposition of fluorinated gas. In order to increase economic feasibility of the thermal plasma decomposition process, increase of thermal efficiency of the plasma torch and enhancement of gas mixing between the thermal plasma jet and waste gas are discussed. In addition, noble thermal plasma systems to be applied in the thermal plasma gas treatment are introduced in the present paper.

  9. Multilevel domain decomposition for electronic structure calculations

    International Nuclear Information System (INIS)

    Barrault, M.; Cances, E.; Hager, W.W.; Le Bris, C.

    2007-01-01

    We introduce a new multilevel domain decomposition method (MDD) for electronic structure calculations within semi-empirical and density functional theory (DFT) frameworks. This method iterates between local fine solvers and global coarse solvers, in the spirit of domain decomposition methods. Using this approach, calculations have been successfully performed on several linear polymer chains containing up to 40,000 atoms and 200,000 atomic orbitals. Both the computational cost and the memory requirement scale linearly with the number of atoms. Additional speed-up can easily be obtained by parallelization. We show that this domain decomposition method outperforms the density matrix minimization (DMM) method for poor initial guesses. Our method provides an efficient preconditioner for DMM and other linear scaling methods, variational in nature, such as the orbital minimization (OM) procedure

  10. KINETICS OF THE OXIDATION OF VITAMIN C

    Directory of Open Access Journals (Sweden)

    Sitti Rahmawati

    2012-12-01

    Full Text Available Vitamin C or ascorbic acid is needed by the human body but it is already damaged by the rise in temperature due to be oxidized to L-dehydroascorbic acid. This research aims to determine the kinetics of oxidation of ascorbic acid due to an increase if temperature (40-80 °C and to design an ascorbic acid oxidation reaction laboratory module to be applied in the senior high school reaction kinetics curriculum. The determination of the kinetics of the oxidation of ascorbic acid applies the integral and half-change time methods, while the concentration of the remained ascorbic acid in sixty minute intervals is determined by iodimetric titration method. Decomposition of ascorbic acid was measured at 40, 50, 60, 70 and 80 °C. The results of this research indicate that at 40, 50, 60, 70 and 80 °C the kinetics of the oxidation of ascorbic acid is a first-order reaction with rate constants of 4.55 x 10-4, 5.85 x 10-4, 8.4 x 10-4, 1.1 x 10-3 and 1.015 x 10-3 min-1, respectively. Pre-exponential factor or the frequency of collisions is a factor which is a measure of the collision rate. The activation energy and the pre-exponential factor for the oxidation of ascorbic acid were found to be 20.73 kJ.mol-1 and 1.372 min-1. The procedure used in this study was modified into a laboratory module will be applied in the teaching of reaction kinetics at the senior high school level.

  11. Expert vs. novice: Problem decomposition/recomposition in engineering design

    Science.gov (United States)

    Song, Ting

    The purpose of this research was to investigate the differences of using problem decomposition and problem recomposition among dyads of engineering experts, dyads of engineering seniors, and dyads of engineering freshmen. Fifty participants took part in this study. Ten were engineering design experts, 20 were engineering seniors, and 20 were engineering freshmen. Participants worked in dyads to complete an engineering design challenge within an hour. The entire design process was video and audio recorded. After the design session, members participated in a group interview. This study used protocol analysis as the methodology. Video and audio data were transcribed, segmented, and coded. Two coding systems including the FBS ontology and "levels of the problem" were used in this study. A series of statistical techniques were used to analyze data. Interview data and participants' design sketches also worked as supplemental data to help answer the research questions. By analyzing the quantitative and qualitative data, it was found that students used less problem decomposition and problem recomposition than engineer experts in engineering design. This result implies that engineering education should place more importance on teaching problem decomposition and problem recomposition. Students were found to spend less cognitive effort when considering the problem as a whole and interactions between subsystems than engineer experts. In addition, students were also found to spend more cognitive effort when considering details of subsystems. These results showed that students tended to use dept-first decomposition and experts tended to use breadth-first decomposition in engineering design. The use of Function (F), Behavior (B), and Structure (S) among engineering experts, engineering seniors, and engineering freshmen was compared on three levels. Level 1 represents designers consider the problem as an integral whole, Level 2 represents designers consider interactions between

  12. Fast approximate convex decomposition using relative concavity

    KAUST Repository

    Ghosh, Mukulika; Amato, Nancy M.; Lu, Yanyan; Lien, Jyh-Ming

    2013-01-01

    Approximate convex decomposition (ACD) is a technique that partitions an input object into approximately convex components. Decomposition into approximately convex pieces is both more efficient to compute than exact convex decomposition and can also generate a more manageable number of components. It can be used as a basis of divide-and-conquer algorithms for applications such as collision detection, skeleton extraction and mesh generation. In this paper, we propose a new method called Fast Approximate Convex Decomposition (FACD) that improves the quality of the decomposition and reduces the cost of computing it for both 2D and 3D models. In particular, we propose a new strategy for evaluating potential cuts that aims to reduce the relative concavity, rather than absolute concavity. As shown in our results, this leads to more natural and smaller decompositions that include components for small but important features such as toes or fingers while not decomposing larger components, such as the torso, that may have concavities due to surface texture. Second, instead of decomposing a component into two pieces at each step, as in the original ACD, we propose a new strategy that uses a dynamic programming approach to select a set of n c non-crossing (independent) cuts that can be simultaneously applied to decompose the component into n c+1 components. This reduces the depth of recursion and, together with a more efficient method for computing the concavity measure, leads to significant gains in efficiency. We provide comparative results for 2D and 3D models illustrating the improvements obtained by FACD over ACD and we compare with the segmentation methods in the Princeton Shape Benchmark by Chen et al. (2009) [31]. © 2012 Elsevier Ltd. All rights reserved.

  13. Fast approximate convex decomposition using relative concavity

    KAUST Repository

    Ghosh, Mukulika

    2013-02-01

    Approximate convex decomposition (ACD) is a technique that partitions an input object into approximately convex components. Decomposition into approximately convex pieces is both more efficient to compute than exact convex decomposition and can also generate a more manageable number of components. It can be used as a basis of divide-and-conquer algorithms for applications such as collision detection, skeleton extraction and mesh generation. In this paper, we propose a new method called Fast Approximate Convex Decomposition (FACD) that improves the quality of the decomposition and reduces the cost of computing it for both 2D and 3D models. In particular, we propose a new strategy for evaluating potential cuts that aims to reduce the relative concavity, rather than absolute concavity. As shown in our results, this leads to more natural and smaller decompositions that include components for small but important features such as toes or fingers while not decomposing larger components, such as the torso, that may have concavities due to surface texture. Second, instead of decomposing a component into two pieces at each step, as in the original ACD, we propose a new strategy that uses a dynamic programming approach to select a set of n c non-crossing (independent) cuts that can be simultaneously applied to decompose the component into n c+1 components. This reduces the depth of recursion and, together with a more efficient method for computing the concavity measure, leads to significant gains in efficiency. We provide comparative results for 2D and 3D models illustrating the improvements obtained by FACD over ACD and we compare with the segmentation methods in the Princeton Shape Benchmark by Chen et al. (2009) [31]. © 2012 Elsevier Ltd. All rights reserved.

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Garay-Reyes, C.G., E-mail: garay_820123@hotmail.com [Universidad Autónoma de San Luis Potosí, Instituto de Metalurgia, Sierra leona 550, Col. Lomas 2 sección, 78210 S.L.P. (Mexico); Hernández-Santiago, F. [Instituto Politécnico Nacional, ESIME-AZC, Av. de las Granjas 682, col. Sta. Catarina, 02550 D.F. (Mexico); Cayetano-Castro, N. [Instituto Potosino de Investigación Científica y Tecnológica, División de Materiales Avanzados, camino a la Presa San José 2055, Col Lomas 4 sección, 78216 S.L.P. (Mexico); López-Hirata, V.M. [Instituto Politécnico Nacional, ESIQIE-DIM, 118-556, D.F. (Mexico); García-Rocha, J. [Universidad Autónoma de San Luis Potosí, Instituto de Metalurgia, Sierra leona 550, Col. Lomas 2 sección, 78210 S.L.P. (Mexico); Hernández-Rivera, J.L. [Centro de Investigación de Materiales Avanzados (CIMAV), Laboratorio Nacional de Nanotecnología, Miguel de Cervantes 120, 31109 Chihuahua (Mexico); Dorantes-Rosales, H.J. [Instituto Politécnico Nacional, ESIQIE-DIM, 118-556, D.F. (Mexico); Cruz-Rivera, J.J. [Universidad Autónoma de San Luis Potosí, Instituto de Metalurgia, Sierra leona 550, Col. Lomas 2 sección, 78210 S.L.P. (Mexico)

    2013-09-15

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

  16. Solid State Thermochemical Decomposition of Neat 1,3,5,5-Tetranitrohexahydropyrimidine (DNNC) and Its DNNC-d6 Perdeuterio-Labeled Analogue (PREPRINT)

    National Research Council Canada - National Science Library

    Hendrickson, Scott A; Shackleford, Scott A

    2005-01-01

    ...) at 142, 145, and 148 oC. 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...

  17. Tensor network decompositions in the presence of a global symmetry

    International Nuclear Information System (INIS)

    Singh, Sukhwinder; Pfeifer, Robert N. C.; Vidal, Guifre

    2010-01-01

    Tensor network decompositions offer an efficient description of certain many-body states of a lattice system and are the basis of a wealth of numerical simulation algorithms. We discuss how to incorporate a global symmetry, given by a compact, completely reducible group G, in tensor network decompositions and algorithms. This is achieved by considering tensors that are invariant under the action of the group G. Each symmetric tensor decomposes into two types of tensors: degeneracy tensors, containing all the degrees of freedom, and structural tensors, which only depend on the symmetry group. In numerical calculations, the use of symmetric tensors ensures the preservation of the symmetry, allows selection of a specific symmetry sector, and significantly reduces computational costs. On the other hand, the resulting tensor network can be interpreted as a superposition of exponentially many spin networks. Spin networks are used extensively in loop quantum gravity, where they represent states of quantum geometry. Our work highlights their importance in the context of tensor network algorithms as well, thus setting the stage for cross-fertilization between these two areas of research.

  18. Analytical representation of the solution of the space kinetic diffusion equation in a one-dimensional and homogeneous domain

    Energy Technology Data Exchange (ETDEWEB)

    Tumelero, Fernanda; Bodmann, Bardo E. J.; Vilhena, Marco T. [Universidade Federal do Rio Grande do Sul (PROMEC/UFRGS), Porto Alegre, RS (Brazil). Programa de Pos Graduacao em Engenharia Mecanica; Lapa, Celso M.F., E-mail: fernanda.tumelero@yahoo.com.br, E-mail: bardo.bodmann@ufrgs.br, E-mail: mtmbvilhena@gmail.com, E-mail: lapa@ien.gov.br [Instituto de Engenharia Nuclear (IEN/CNEN-RJ), Rio de Janeiro, RJ (Brazil)

    2017-07-01

    In this work we solve the space kinetic diffusion equation in a one-dimensional geometry considering a homogeneous domain, for two energy groups and six groups of delayed neutron precursors. The proposed methodology makes use of a Taylor expansion in the space variable of the scalar neutron flux (fast and thermal) and the concentration of delayed neutron precursors, allocating the time dependence to the coefficients. Upon truncating the Taylor series at quadratic order, one obtains a set of recursive systems of ordinary differential equations, where a modified decomposition method is applied. The coefficient matrix is split into two, one constant diagonal matrix and the second one with the remaining time dependent and off-diagonal terms. Moreover, the equation system is reorganized such that the terms containing the latter matrix are treated as source terms. Note, that the homogeneous equation system has a well known solution, since the matrix is diagonal and constant. This solution plays the role of the recursion initialization of the decomposition method. The recursion scheme is set up in a fashion where the solutions of the previous recursion steps determine the source terms of the subsequent steps. A second feature of the method is the choice of the initial and boundary conditions, which are satisfied by the recursion initialization, while from the rst recursion step onward the initial and boundary conditions are homogeneous. The recursion depth is then governed by a prescribed accuracy for the solution. (author)

  19. Separable decompositions of bipartite mixed states

    Science.gov (United States)

    Li, Jun-Li; Qiao, Cong-Feng

    2018-04-01

    We present a practical scheme for the decomposition of a bipartite mixed state into a sum of direct products of local density matrices, using the technique developed in Li and Qiao (Sci. Rep. 8:1442, 2018). In the scheme, the correlation matrix which characterizes the bipartite entanglement is first decomposed into two matrices composed of the Bloch vectors of local states. Then, we show that the symmetries of Bloch vectors are consistent with that of the correlation matrix, and the magnitudes of the local Bloch vectors are lower bounded by the correlation matrix. Concrete examples for the separable decompositions of bipartite mixed states are presented for illustration.

  20. Vector domain decomposition schemes for parabolic equations

    Science.gov (United States)

    Vabishchevich, P. N.

    2017-09-01

    A new class of domain decomposition schemes for finding approximate solutions of timedependent problems for partial differential equations is proposed and studied. A boundary value problem for a second-order parabolic equation is used as a model problem. The general approach to the construction of domain decomposition schemes is based on partition of unity. Specifically, a vector problem is set up for solving problems in individual subdomains. Stability conditions for vector regionally additive schemes of first- and second-order accuracy are obtained.

  1. Gamma ray induced decomposition of lanthanide nitrates

    International Nuclear Information System (INIS)

    Joshi, N.G.; Garg, A.N.

    1992-01-01

    Gamma ray induced decomposition of the lanthanide nitrates, Ln(NO 3 ) 3 .xH 2 O where Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm and Yb has been studied at different absorbed doses up to 600 kGy. G(NO 2 - ) values depend on the absorbed dose and the nature of the outer cation. It has been observed that those lanthanides which exhibit variable valency (Ce and Eu) show lower G-values. An attempt has been made to correlate thermal and radiolytic decomposition processes. (author). 20 refs., 3 figs., 1 tab

  2. Excess Sodium Tetraphenylborate and Intermediates Decomposition Studies

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, M.J.

    1998-12-07

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

  3. Multiresolution signal decomposition transforms, subbands, and wavelets

    CERN Document Server

    Akansu, Ali N; Haddad, Paul R

    2001-01-01

    The uniqueness of this book is that it covers such important aspects of modern signal processing as block transforms from subband filter banks and wavelet transforms from a common unifying standpoint, thus demonstrating the commonality among these decomposition techniques. In addition, it covers such ""hot"" areas as signal compression and coding, including particular decomposition techniques and tables listing coefficients of subband and wavelet filters and other important properties.The field of this book (Electrical Engineering/Computer Science) is currently booming, which is, of course

  4. Basis of the biological decomposition of xenobiotica

    International Nuclear Information System (INIS)

    Mueller, R. von

    1993-01-01

    The ability of micro-organisms to decompose different molecules and to use them as a source of carbon, nitrogen, sulphur or energy is the basis for all biological processes for cleaning up contaminated soil. Therefore, the knowledge of these decomposition processes is an important precondition for judging which contamination can be treated biologically at all and which materials can be decomposed biologically. The decomposition schemes of the most important harmful material classes (aliphatic, aromatic and chlorinated hydrocarbons) are introduced and the consequences which arise for the practical application in biological cleaning up of contaminated soils are discussed. (orig.) [de

  5. Eigenvalue Decomposition-Based Modified Newton Algorithm

    Directory of Open Access Journals (Sweden)

    Wen-jun Wang

    2013-01-01

    Full Text Available When the Hessian matrix is not positive, the Newton direction may not be the descending direction. A new method named eigenvalue decomposition-based modified Newton algorithm is presented, which first takes the eigenvalue decomposition of the Hessian matrix, then replaces the negative eigenvalues with their absolute values, and finally reconstructs the Hessian matrix and modifies the searching direction. The new searching direction is always the descending direction. The convergence of the algorithm is proven and the conclusion on convergence rate is presented qualitatively. Finally, a numerical experiment is given for comparing the convergence domains of the modified algorithm and the classical algorithm.

  6. Principles of chemical kinetics

    CERN Document Server

    House, James E

    2007-01-01

    James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications. Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative rela

  7. Introduction to chemical kinetics

    CERN Document Server

    Soustelle, Michel

    2013-01-01

    This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area. Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental re

  8. Chemical Kinetic Modeling of 2-Methylhexane Combustion

    KAUST Repository

    Mohamed, Samah Y.

    2015-03-30

    Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important for investigating the combustion behavior of diesel, gasoline, and aviation fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracy in certain portions of the models. This study focuses on updating thermodynamic data and kinetic model for a gasoline surrogate fuel, 2-methylhexane, with recently published group values and rate rules. These update provides a better agreement with rapid compression machine measurements of ignition delay time, while also strengthening the fundamental basis of the model.

  9. A kinetic study on the conversion of glucose to levulinic acid

    NARCIS (Netherlands)

    Girisuta, B; Janssen, LPBM; Heeres, HJ

    Levulinic acid has been identified as a promising green. biomass derived platform chemical. A kinetic study oil one of the key steps in the conversion of biomass to levulinic acid, i.e., the acid catalysed decomposition of glucose to levulinic acid has been performed. The experiments were Performed

  10. Green chemicals : A Kinetic Study on the Conversion of Glucose to Levulinic Acid

    NARCIS (Netherlands)

    Girisuta, B.; Janssen, L.P.B.M.; Heeres, H.J.

    2006-01-01

    Levulinic acid has been identified as a promising green, biomass derived platform chemical. A kinetic study on one of the key steps in the conversion of biomass to levulinic acid, i.e., the acid catalysed decomposition of glucose to levulinic acid has been performed. The experiments were performed

  11. Determination of Kinetic Parameters of Coal Pyrolysis to Simulate the Process of Underground Coal Gasification (UCG

    Directory of Open Access Journals (Sweden)

    Beata Urych

    2014-01-01

    Originality/value: The devolatilization of a homogenous lump of coal is a complex issue. Currently, the CFD technique (Computational Fluid Dynamics is commonly used for the multi-dimensional and multiphase phenomena modelling. The mathematical models, describing the kinetics of the decomposition of coal, proposed in the article can, therefore, be an integral part of models based on numerical fluid mechanics.

  12. Thermogravimetric analysis and kinetic study of bamboo waste treated by Echinodontium taxodii using a modified three-parallel-reactions model.

    Science.gov (United States)

    Yu, Hongbo; Liu, Fang; Ke, Ming; Zhang, Xiaoyu

    2015-06-01

    In this study, the effect of pretreatment with Echinodontium taxodii on thermal decomposition characteristics and kinetics of bamboo wastes was investigated by thermogravimetric analysis. The results showed fungal pretreatment can enhance the thermal degradation of bamboo. The negative effect of extractives in bamboo on the thermal decomposition can be decreased by the pretreatment. A modified three-parallel-reactions model based on isolated lignin was firstly proposed to study pyrolysis kinetics of bamboo lignocellulose. Kinetic analysis showed that with increasing pretreatment time fungal delignification was enhanced to transform the lignin component with high activation energy into that with low activation energy and raise the cellulose content in bamboo, making the thermal decomposition easier. These results demonstrated fungal pretreatment provided a potential way to improve thermal conversion efficiency of bamboo. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Carbochlorination kinetics of tantalum and niobium pentoxides

    International Nuclear Information System (INIS)

    Allain, E.; Gaballah, I.; Garcia, F.; Ferreira, S.; Ayala, J. N.; Hernandez, A.

    1999-01-01

    The carbochlorination kinetics of pure Nb 2 O 5 and Ta 2 O 5 by gas mixture (CL 2 +CO+N 2 ) between 380 and 1,000 degree centigree is studied. A calculation of the standard free energy of the carbochlorination reactions is made. A diagram of the phases stability is drawn. The influence of the gas flow, temperature and the partial pressure of Cl 2 and Co at temperatures below 650 degree centigree on the reaction rate is studied. The apparent activation energy is approximately 75 and 110 kJ/mol for Nb 2 O 5 and Ta 2 O 5 , respectively. At temperatures above 650 degree centigree the Arrhenius diagram presents and anomaly which may be attributed to the decomposition of the COCL 2 formed in situ. The apparent reaction order of the carbochlorination of these oxides against Cl 2 +CO is approximately 2. The carbochlorination rates of these oxides are much greater than those of chlorination by Cl 2 +N 2 . The carbochlorination kinetics of tin furnace slag leaching concentrates containing tantalum and niobium compounds are also studied and compared with the carbochlorination kinetics of the pure oxides. (Author) 14 refs

  14. Treatment of polymer surfaces in plasma Part I. Kinetic model

    International Nuclear Information System (INIS)

    Tabaliov, N A; Svirachev, D M

    2006-01-01

    The surface tension of the polymer materials depends on functional groups over its surface. As a result from the plasma treatment the kind and concentration of the functional groups can be changed. In the present work, the possible kinetic reactions are defined. They describe the interaction between the plasma and the polymer surface of polyethylene terephthalate (PET). Basing on these reactions, the systems of differential kinetic equations are suggested. The solutions are obtained analytically for the system kinetic equations at defined circumstances

  15. Kinetic equation solution by inverse kinetic method

    International Nuclear Information System (INIS)

    Salas, G.

    1983-01-01

    We propose a computer program (CAMU) which permits to solve the inverse kinetic equation. The CAMU code is written in HPL language for a HP 982 A microcomputer with a peripheral interface HP 9876 A ''thermal graphic printer''. The CAMU code solves the inverse kinetic equation by taking as data entry the output of the ionization chambers and integrating the equation with the help of the Simpson method. With this program we calculate the evolution of the reactivity in time for a given disturbance

  16. Synthesis, characterization and photocatalytic activity of porous manganese oxide doped titania for toluene decomposition

    International Nuclear Information System (INIS)

    Jothiramalingam, R.; Wang, M.K.

    2007-01-01

    The present study describes the photocatalytic degradation of toluene in gas phase on different porous manganese oxide doped titanium dioxide. As synthesized birnessite and cryptomelane type porous manganese oxide were doped with titania and tested for photocatalytic decomposition of toluene in gas phase. The effects of the inlet concentration of toluene, flow rate (retention time) were examined and the relative humidity was maintained constantly. Thermal and textural characterization of manganese oxide doped titania materials were characterized by X-ray diffraction (XRD), thermogravemetry (TG), BET and TEM-EDAX studies. The aim of the present study is to synthesize the porous manganese oxide doped titania and to study its photocatalytic activity for toluene degradation in gas phase. Cryptomelane doped titania catalyst prepared in water medium [K-OMS-2 (W)] is shown the good toluene degradation with lower catalysts loading compared to commercial bulk titania in annular type photo reactor. The higher photocatalytic activity due to various factors such as catalyst preparation method, experimental conditions, catalyst loading, surface area, etc. In the present study manganese oxide OMS doped titania materials prepared by both aqueous and non-aqueous medium, aqueous medium prepared catalyst shows the good efficiency due to the presence of OH bonded groups on the surface of catalyst. The linear forms of different kinetic equations were applied to the adsorption data and their goodness of fit was evaluated based on the R 2 and standard error. The goodness to the linear fit was observed for Elovich model with high R 2 (≥0.9477) value

  17. Kinetic concepts of thermally stimulated reactions in solids

    Science.gov (United States)

    Vyazovkin, Sergey

    Historical analysis suggests that the basic kinetic concepts of reactions in solids were inherited from homogeneous kinetics. These concepts rest upon the assumption of a single-step reaction that disagrees with the multiple-step nature of solid-state processes. The inadequate concepts inspire such unjustified anticipations of kinetic analysis as evaluating constant activation energy and/or deriving a single-step reaction mechanism for the overall process. A more adequate concept is that of the effective activation energy, which may vary with temperature and extent of conversion. The adequacy of this concept is illustrated by literature data as well as by experimental data on the thermal dehydration of calcium oxalate monohydrate and thermal decomposition of calcium carbonate, ammonium nitrate and 1,3,5,7- tetranitro-1,3,5,7-tetrazocine.

  18. Non-isothermal degradation and evaluation of kinetic parameters of some Schiff base metal complexes

    International Nuclear Information System (INIS)

    Mishra, A.P.; Soni, Monika

    2008-01-01

    Thermal decomposition of VO (II)-methyl isobutyl ketone-nicotinamide, VO (II)-2-furfurylidine-3,4-dichloroaniline, Co(II)-4-dimethyl amino benzylidine-3-chloro-4-fluoroaniline, VO(II)-2-pyridine carboxylidine-4-aminobenzoic acid complexes have been carried out by thermogravimetric method. The TG curves of complexes were recorded at a uniform rate of 20 deg C/min in nitrogen. The thermogram of the three VO(II) complexes exhibit single stage decomposition whereas the Co(II) complex shows a double stage decomposition. Various kinetic parameters i. e., energy of activation (E), entropy (AS) and frequency factor (Z) have been evaluated by using Coats-Redfern and Piloyan-Novikova equations and their comparable values are reported. The order of thermal stability of first decomposition stage is as: 4=2>1>3. (author)

  19. The processing of aluminum gasarites via thermal decomposition of interstitial hydrides

    Science.gov (United States)

    Licavoli, Joseph J.

    Gasarite structures are a unique type of metallic foam containing tubular pores. The original methods for their production limited them to laboratory study despite appealing foam properties. Thermal decomposition processing of gasarites holds the potential to increase the application of gasarite foams in engineering design by removing several barriers to their industrial scale production. The following study characterized thermal decomposition gasarite processing both experimentally and theoretically. It was found that significant variation was inherent to this process therefore several modifications were necessary to produce gasarites using this method. Conventional means to increase porosity and enhance pore morphology were studied. Pore morphology was determined to be more easily replicated if pores were stabilized by alumina additions and powders were dispersed evenly. In order to better characterize processing, high temperature and high ramp rate thermal decomposition data were gathered. It was found that the high ramp rate thermal decomposition behavior of several hydrides was more rapid than hydride kinetics at low ramp rates. This data was then used to estimate the contribution of several pore formation mechanisms to the development of pore structure. It was found that gas-metal eutectic growth can only be a viable pore formation mode if non-equilibrium conditions persist. Bubble capture cannot be a dominant pore growth mode due to high bubble terminal velocities. Direct gas evolution appears to be the most likely pore formation mode due to high gas evolution rate from the decomposing particulate and microstructural pore growth trends. The overall process was evaluated for its economic viability. It was found that thermal decomposition has potential for industrialization, but further refinements are necessary in order for the process to be viable.

  20. Physicochemical aspects of decomposition of silica-alumina ores of argillites and green clays of Chashma-Sang Deposit of the Republic of Tajikistan by hydrochloric and nitric acids

    International Nuclear Information System (INIS)

    Kayumov, A.M.

    2018-01-01

    The purpose of work is to study the processes of decomposition of silica-alumina ores of argillites and green clays of Chashma-Sang Deposit of the Republic of Tajikistan by hydrochloric and nitric acids in temperature interval 20-98 deg C with the using of methods of selective extraction of valuable materials; elaboration of rational conditions of decomposition of raw material. Physicochemical properties of initial aluminium comprising ores, intermediate and final products of processing of argillites and green clays have been studied. Kinetic parameters of processes at acidic decomposition of argillites and green clays have been studied as well. The kinetic parameters of processes of decomposition of green clays and argillites by nitric and hydrochloric acids have been calculated. The flowsheet of complex processing of green clays and argillites of Chashma-Sang Deposit has been elaborated.

  1. Decomposition of jellyfish carrion in situ

    DEFF Research Database (Denmark)

    Chelsky, Ariella; Pitt, Kylie A.; Ferguson, Angus J.P.

    2016-01-01

    Jellyfish often form blooms that persist for weeks to months before they collapse en masse, resulting in the sudden release of large amounts of organic matter to the environment. This study investigated the biogeochemical and ecological effects of the decomposition of jellyfish in a shallow coast...

  2. Compactly supported frames for decomposition spaces

    DEFF Research Database (Denmark)

    Nielsen, Morten; Rasmussen, Kenneth Niemann

    2012-01-01

    In this article we study a construction of compactly supported frame expansions for decomposition spaces of Triebel-Lizorkin type and for the associated modulation spaces. This is done by showing that finite linear combinations of shifts and dilates of a single function with sufficient decay in b...

  3. Preparation, Structure Characterization and Thermal Decomposition ...

    African Journals Online (AJOL)

    NJD

    Decomposition Process of the Dysprosium(III) m-Methylbenzoate 1 ... A dinuclear complex [Dy(m-MBA)3phen]2·H2O was prepared by the reaction of DyCl3·6H2O, m-methylbenzoic acid and .... ing rate of 10 °C min–1 are illustrated in Fig. 4.

  4. A decomposition of pairwise continuity via ideals

    Directory of Open Access Journals (Sweden)

    Mahes Wari

    2016-02-01

    Full Text Available In this paper, we introduce and study the notions of (i, j - regular - ℐ -closed sets, (i, j - Aℐ -sets, (i, j - ℐ -locally closed sets, p- Aℐ -continuous functions and p- ℐ -LC-continuous functions in ideal bitopological spaces and investigate some of their properties. Also, a new decomposition of pairwise continuity is obtained using these sets.

  5. Nested grids ILU-decomposition (NGILU)

    NARCIS (Netherlands)

    Ploeg, A. van der; Botta, E.F.F.; Wubs, F.W.

    1996-01-01

    A preconditioning technique is described which shows, in many cases, grid-independent convergence. This technique only requires an ordering of the unknowns based on the different levels of multigrid, and an incomplete LU-decomposition based on a drop tolerance. The method is demonstrated on a

  6. A Martingale Decomposition of Discrete Markov Chains

    DEFF Research Database (Denmark)

    Hansen, Peter Reinhard

    We consider a multivariate time series whose increments are given from a homogeneous Markov chain. We show that the martingale component of this process can be extracted by a filtering method and establish the corresponding martingale decomposition in closed-form. This representation is useful fo...

  7. Triboluminescence and associated decomposition of solid methanol

    International Nuclear Information System (INIS)

    Trout, G.J.; Moore, D.E.; Hawke, J.G.

    1975-01-01

    The decomposition is initiated by the cooling of solid methanol through the β → α transiRon at 157.8K, producing the gases hydrogen, carbon monoxide, and methane. The passage through this lambda transition causes the breakup of large crystals of β-methanol into crystallites of α-methanol and is accompanied by light emission as well as decomposition. This triboluminescence is accompanied by, and apparently produced by, electrical discharges through methanol vapor in the vicinity of the solid. The potential differences needed to produce the electrical breakdown of the methanol vapor apparently arise from the disruption of the long hydrogen bonded chains of methanol molecules present in crystalline methanol. Charge separation following crystal deformation is a characteristic of substances which exhibit gas discharge triboluminescence; solid methanol has been found to emit such luminescence when mechanically deformed in the absence of the β → α transition The decomposition products are not produced directly by the breaking up of the solid methanol but from the vapor phase methanol by the electrical discharges. That gas phase decomposition does occur was confirmed by observing that the vapors of C 2 H 5 OH, CH 3 OD, and CD 3 OD decompose on being admitted to a vessel containing methanol undergoing the β → α phase transition. (U.S.)

  8. On Orthogonal Decomposition of a Sobolev Space

    OpenAIRE

    Lakew, Dejenie A.

    2016-01-01

    The theme of this short article is to investigate an orthogonal decomposition of a Sobolev space and look at some properties of the inner product therein and the distance defined from the inner product. We also determine the dimension of the orthogonal difference space and show the expansion of spaces as their regularity increases.

  9. TP89 - SIRZ Decomposition Spectral Estimation

    Energy Technology Data Exchange (ETDEWEB)

    Seetho, Isacc M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Azevedo, Steve [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Smith, Jerel [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Brown, William D. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Martz, Jr., Harry E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-12-08

    The primary objective of this test plan is to provide X-ray CT measurements of known materials for the purposes of generating and testing MicroCT and EDS spectral estimates. These estimates are to be used in subsequent Ze/RhoE decomposition analyses of acquired data.

  10. Methodologies in forensic and decomposition microbiology

    Science.gov (United States)

    Culturable microorganisms represent only 0.1-1% of the total microbial diversity of the biosphere. This has severely restricted the ability of scientists to study the microbial biodiversity associated with the decomposition of ephemeral resources in the past. Innovations in technology are bringing...

  11. Organic matter decomposition in simulated aquaculture ponds

    NARCIS (Netherlands)

    Torres Beristain, B.

    2005-01-01

    Different kinds of organic and inorganic compounds (e.g. formulated food, manures, fertilizers) are added to aquaculture ponds to increase fish production. However, a large part of these inputs are not utilized by the fish and are decomposed inside the pond. The microbiological decomposition of the

  12. Wood decomposition as influenced by invertebrates

    Science.gov (United States)

    Michael D. Ulyshen

    2014-01-01

    The diversity and habitat requirements of invertebrates associated with dead wood have been the subjects of hundreds of studies in recent years but we still know very little about the ecological or economic importance of these organisms. The purpose of this review is to examine whether, how and to what extent invertebrates affect wood decomposition in terrestrial...

  13. Decomposition of variance for spatial Cox processes

    DEFF Research Database (Denmark)

    Jalilian, Abdollah; Guan, Yongtao; Waagepetersen, Rasmus

    Spatial Cox point processes is a natural framework for quantifying the various sources of variation governing the spatial distribution of rain forest trees. We introduce a general criterion for variance decomposition for spatial Cox processes and apply it to specific Cox process models...

  14. Decomposition of variance for spatial Cox processes

    DEFF Research Database (Denmark)

    Jalilian, Abdollah; Guan, Yongtao; Waagepetersen, Rasmus

    2013-01-01

    Spatial Cox point processes is a natural framework for quantifying the various sources of variation governing the spatial distribution of rain forest trees. We introduce a general criterion for variance decomposition for spatial Cox processes and apply it to specific Cox process models...

  15. Decomposition of variance for spatial Cox processes

    DEFF Research Database (Denmark)

    Jalilian, Abdollah; Guan, Yongtao; Waagepetersen, Rasmus

    Spatial Cox point processes is a natural framework for quantifying the various sources of variation governing the spatial distribution of rain forest trees. We introducea general criterion for variance decomposition for spatial Cox processes and apply it to specific Cox process models with additive...

  16. Linear, Constant-rounds Bit-decomposition

    DEFF Research Database (Denmark)

    Reistad, Tord; Toft, Tomas

    2010-01-01

    When performing secure multiparty computation, tasks may often be simple or difficult depending on the representation chosen. Hence, being able to switch representation efficiently may allow more efficient protocols. We present a new protocol for bit-decomposition: converting a ring element x ∈ ℤ M...

  17. Decomposition approaches to integration without a measure

    Czech Academy of Sciences Publication Activity Database

    Greco, S.; Mesiar, Radko; Rindone, F.; Sipeky, L.

    2016-01-01

    Roč. 287, č. 1 (2016), s. 37-47 ISSN 0165-0114 Institutional support: RVO:67985556 Keywords : Choquet integral * Decision making * Decomposition integral Subject RIV: BA - General Mathematics Impact factor: 2.718, year: 2016 http://library.utia.cas.cz/separaty/2016/E/mesiar-0457408.pdf

  18. Radiolytic decomposition of dioxins in liquid wastes

    International Nuclear Information System (INIS)

    Zhao Changli; Taguchi, M.; Hirota, K.; Takigami, M.; Kojima, T.

    2006-01-01

    The dioxins including polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are some of the most toxic persistent organic pollutants. These chemicals have widely contaminated the air, water, and soil. They would accumulate in the living body through the food chains, leading to a serious public health hazard. In the present study, radiolytic decomposition of dioxins has been investigated in liquid wastes, including organic waste and waste-water. Dioxin-containing organic wastes are commonly generated in nonane or toluene. However, it was found that high radiation doses are required to completely decompose dioxins in the two solvents. The decomposition was more efficient in ethanol than in nonane or toluene. The addition of ethanol to toluene or nonane could achieve >90% decomposition of dioxins at the dose of 100 kGy. Thus, dioxin-containing organic wastes can be treated as regular organic wastes after addition of ethanol and subsequent γ-ray irradiation. On the other hand, radiolytic decomposition of dioxins easily occurred in pure-water than in waste-water, because the reaction species is largely scavenged by the dominant organic materials in waste-water. Dechlorination was not a major reaction pathway for the radiolysis of dioxin in water. In addition, radiolytic mechanism and dechlorinated pathways in liquid wastes were also discussed. (authors)

  19. Thermal decomposition of barium valerate in argon

    DEFF Research Database (Denmark)

    Torres, P.; Norby, Poul; Grivel, Jean-Claude

    2015-01-01

    The thermal decomposition of barium valerate (Ba(C4H9CO2)(2)/Ba-pentanoate) was studied in argon by means of thermogravimetry, differential thermal analysis, IR-spectroscopy, X-ray diffraction and hot-stage optical microscopy. Melting takes place in two different steps, at 200 degrees C and 280...

  20. A framework for bootstrapping morphological decomposition

    CSIR Research Space (South Africa)

    Joubert, LJ

    2004-11-01

    Full Text Available The need for a bootstrapping approach to the morphological decomposition of words in agglutinative languages such as isiZulu is motivated, and the complexities of such an approach are described. The authors then introduce a generic framework which...