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Sample records for theoretical kinetic study

  1. Theoretical study on mechanism, kinetics, and thermochemistry of ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 127; Issue 6. Theoretical study on mechanism, kinetics, and thermochemistry of the gas phase reaction of 2,2,2-trifluoroethyl butyrate with OH radicals at 298 K. Nand Kishor Gour Bhupesh Kumar Mishra Hari Ji Singh. Regular Articles Volume 127 Issue 6 June 2015 ...

  2. Electrochemical kinetics theoretical aspects

    CERN Document Server

    Vetter, Klaus J

    1967-01-01

    Electrochemical Kinetics: Theoretical Aspects focuses on the processes, methodologies, reactions, and transformations in electrochemical kinetics. The book first offers information on electrochemical thermodynamics and the theory of overvoltage. Topics include equilibrium potentials, concepts and definitions, electrical double layer and electrocapillarity, and charge-transfer, diffusion, and reaction overvoltage. Crystallization overvoltage, total overvoltage, and resistance polarization are also discussed. The text then examines the methods of determining electrochemical reaction mechanisms

  3. Theoretical Studies in Chemical Kinetics - Annual Report, 1970.

    Science.gov (United States)

    Karplus, Martin

    1970-10-01

    The research performed includes (a) Alkali-Halide, Alkali-Halide (MX, M’X’) Exchange Reactions; (b) Inversion Problem; (c) Quantum Mechanics of Scattering Processes, (d) Transition State Analysis of Classical Trajectories, (e) Differential Cross Sections from Classical Trajectories; and (f) Other Studies.

  4. An experimental and theoretical kinetic study of the reaction of OH radicals with tetrahydrofuran

    KAUST Repository

    Giri, Binod

    2016-06-24

    Tetrahydrofuran (CHO, THF) and its alkylated derivatives of the cyclic ether family are considered to be promising future biofuels. They appear as important intermediates during the low-temperature oxidation of conventional hydrocarbon fuels and of heavy biofuels such as long-chain fatty acid methyl esters. The reaction of tetrahydrofuran with OH radicals was investigated in a shock tube, over a temperature range of 800-1340 K and at pressures near 1.5 bar. Hydroxyl radicals were generated by the rapid thermal decomposition of tert-butyl hydroperoxide, and a UV laser absorption technique was used to monitor the mole fraction of OH radicals. High-level CCSD(T)/cc-pV(D,T)Z//MP2/aug-cc-pVDZ quantum chemical calculations were performed to explore the chemistry of the THF+OH reaction system. Our calculations reveal that the THF+OH (R1) reaction proceeds via either direct or indirect H-abstraction from various sites, leading to the formation of tetrahydrofuran-2-yl (THF-R2) or tetrahydrofuran-3-yl (THF-R3) radicals and water. Theoretical kinetic analysis revealed that both channels are important under conditions relevant to combustion. To our knowledge, this is the first direct experimental and theoretical kinetic study of the reaction of tetrahydrofuran with OH radicals at high temperatures. The following theoretical rate expressions (in units of cmmols) are recommended for combustion modeling in the temperature range 800-1350 K: . k1(T)=4.11×1040.16em0ex(TK)2.69exp(1316.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→Products) . k2(T)=6.930.16em0ex×10110.16em0ex(TK)0.41exp(-106.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R20.16em0ex+H2O) . k3(T)=4.120.16em0ex×1030.16em0ex(TK)3.02exp(456.90.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R30.16em0ex+H2O) . .

  5. Theoretical Kinetic Study of the Formic Acid Catalyzed Criegee Intermediate Isomerization: Multistructural Anharmonicity and Atmospheric Implications

    KAUST Repository

    Monge Palacios, Manuel

    2018-01-29

    We performed a theoretical study on the double hydrogen shift isomerization reaction of a six carbon atom Criegee intermediate (C6-CI), catalyzed by formic acid (HCOOH), to produce vinylhydroperoxide (VHP), C6-CI+HCOOH→VHP+HCOOH. This Criegee intermediate can serve as a surrogate for larger CIs derived from important volatile organic compounds like monoterpenes, whose reactivity is not well understood and are difficult to handle computationally. The reactant HCOOH exerts a pronounced catalytic effect on the studied reaction by lowering the barrier height, but the kinetic enhancement is hindered by the multistructural anharmonicity. First, the rigid ring-structure adopted by the saddle point to facilitate simultaneous transfer of two atoms does not allow formation of as many conformers as those formed by the reactant C6-CI. And second, the flexible carbon chain of C6-CI facilitates the formation of stabilizing intramolecular C–H···O hydrogen bonds; this stabilizing effect is less pronounced in the saddle point structure due to its tightness and steric effects. Thus, the contribution of the reactant C6-CI conformers to the multistructural partition function is larger than that of the saddle point conformers. The resulting low multistructural anharmonicity factor partially cancels out the catalytic effect of the carboxylic acid, yielding in a moderately large rate coefficient, k(298 K) = 4.9·10-13 cm3 molecule-1 s-1. We show that carboxylic acids may promote the conversion of stabilized Criegee intermediates into vinylhydroperoxides in the atmosphere, which generates OH radicals and leads to secondary organic aerosol, thereby affecting the oxidative capacity of the atmosphere and ultimately the climate.

  6. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: ahlaguna@ugr.es [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)

    2012-01-17

    Highlights: Black-Right-Pointing-Pointer Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. Black-Right-Pointing-Pointer Gas chromatography and computational potential energy surfaces were performed. Black-Right-Pointing-Pointer A mechanism in steps looked like the most probable mechanism. Black-Right-Pointing-Pointer A spin-orbit coupling appeared at the singlet and triple diradical open structures. Black-Right-Pointing-Pointer A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 {+-} 0.8 kcal/mol and 5.2 Multiplication-Sign 10{sup 13} s{sup -1}, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G{sup Asterisk-Operator Asterisk-Operator} level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  7. Reaction mechanism and kinetics of the degradation of terbacil initiated by OH radical - A theoretical study

    Science.gov (United States)

    Ponnusamy, S.; Sandhiya, L.; Senthilkumar, K.

    2018-02-01

    The reaction of terbacil with OH radical is studied by using electronic structure calculations. The reaction of terbacil with OH radical is found to proceed by H-atom abstraction, Cl-atom abstraction and OH addition reactions. The initially formed alkyl radical will undergo atmospheric transformation in the presence of molecular oxygen leading to the formation of peroxy radical. The reaction of peroxy radical with other atmospheric oxidants, such as HO2 and NO radicals is studied. The rate constant is calculated for the H-atom abstraction reactions over the temperature range of 200-1000 K. The results obtained from electronic structure calculations and kinetic study show that the H-atom abstraction reaction is more favorable. The calculated lifetime of terbacil is 24 h in normal atmospheric OH concentration. The rate constant calculated for H-atom abstraction reactions is 6 × 10-12, 4.4 × 10-12 and 3.2 × 10-12 cm3molecule-1s-1, respectively which is in agreement with the previous literature value of 1.9 × 10-12 cm3molecule-1s-1.

  8. A theoretical study on surfactant adsorption kinetics: effect of bubble shape on dynamic surface tension.

    Science.gov (United States)

    Yang, Ming-Wei; Wei, Hsien-Hung; Lin, Shi-Yow

    2007-12-04

    A planar or spherical fluid-liquid interface was commonly assumed on studying the surfactant adsorption kinetics for a pendant bubble in surfactant solutions. However, the shape of a pendant bubble deviates from a sphere unless the bubble's capillary constant is close to zero. Up to date, the literature has no report about the shape effect on the relaxation of surface tension due to the shape difference between a pendant bubble and a sphere. The dynamic surface tension (DST), based on the actual shape of a pendant bubble with a needle, of the diffusion-controlled process is simulated using a time-dependent finite element method in this work. The shape effect and the existence of a needle on DST are investigated. This numerical simulation resolves also the time-dependent bulk surfactant concentration. The depth of solution needed to satisfy the classical Ward-Tordai infinite-solution assumption was also studied. For a diffusion-controlled adsorption process, bubble shape and needle size are two major factors affecting the DST. The existence of a needle accelerates the bulk diffusion for a small bubble; however, the shape of a large pendant bubble decelerates the bulk diffusion. An example using this method on the DST data of C12E4 is illustrated at the end of this work.

  9. Gas-Phase Theoretical Kinetics for Astrochemistry

    Science.gov (United States)

    Klippenstein, Stephen

    2013-05-01

    We will survey a number of our applications of ab initio theoretical kinetics to reactions of importance to astrochemistry. Illustrative examples will be taken from our calculations for (i) interstellar chemistry, (ii) Titan's atmospheric chemistry, and (iii) the chemistry of extrasolar giant planets. For low temperature interstellar chemistry, careful consideration of the long-range expansion of the potential allows for quantitative predictions of the kinetics. Our recent calculations for the reactions of H3+ with O(3P) and with CO suggest an increase of the predicted destruction rate of H3+ by a factor of 2.5 to 3.0 for temperatures that are typical of dense clouds. Further consideration of the interplay between spin-orbit and multipole terms for open-shell atomic fragments allows us to predict the kinetics for a number of the reactions that have been listed as important reactions for interstellar chemical modeling [V. Wakelam, I. W. M. Smith, E. Herbst, J. Troe, W. Geppert, et al. Space Science Rev., 156, 13-72, 2010]. Our calculations for Titan's atmosphere demonstrate the importance of radiative emission as a stabilization process in the low-pressure environment of Titan's upper atmosphere. Theory has also helped to illuminate the role of various reactions in both Titan's atmosphere and in extrasolar planetary atmospheres. Comparisons between theory and experiment have provided a more detail understanding of the kinetics of PAH dimerization. High level predictions of thermochemical properties are remarkably accurate, and allow us to provide important data for studying P chemistry in planetary atmospheres. Finally, our study of O(3P) + C3 provides an example of a case where theory provides suggestive but not definitive results, and further experiments are clearly needed.

  10. Gas Phase Theoretical Kinetics for Astrochemistry

    Science.gov (United States)

    Klippenstein, Stephen J.; Georgievskii, Y.; Harding, L. B.

    2012-05-01

    We will survey a number of our applications of ab initio theoretical kinetics to reactions of importance to astrochemistry. Illustrative examples will be taken from our calculations for (i) interstellar chemistry, (ii) Titan’s atmospheric chemistry, and (iii) the chemistry of extrasolar giant planets. For low temperature interstellar chemistry, careful consideration of the long-range expansion of the potential allows for quantitative predictions of the kinetics. Our recent calculations for the reactions of H3+ with O(3P) and with CO suggest an increase of the predicted destruction rate of H3+ by a factor of 2.5 to 3.0 for temperatures that are typical of dense clouds. Further consideration of the interplay between spin-orbit and multipole terms for open-shell atomic fragments allows us to predict the kinetics for a number of the reactions that have been listed as important reactions for interstellar chemical modeling [V. Wakelam, I. W. M. Smith, E. Herbst, J. Troe, W. Geppert, et al. Space Science Rev., 156, 13-72, 2010]. Our calculations for Titan’s atmosphere demonstrate the importance of radiative emission as a stabilization process in the low-pressure environment of Titan’s upper atmosphere. Theory has also helped to illuminate the role of various reactions in both Titan’s atmosphere and in extrasolar planetary atmospheres. Comparisons between theory and experiment have provided a more detail understanding of the kinetics of PAH dimerization. High level predictions of thermochemical properties are remarkably accurate, and allow us to provide important data for studying P chemistry in planetary atmospheres. Finally, our study of O(3P) + C3 provides an example of a case where theory provides suggestive but not definitive results, and further experiments are clearly needed.

  11. Simulation and Theoretical Study of Spontaneous Excitation of Convective Cells by Kinetic Alfven Waves

    Science.gov (United States)

    Lin, Yu; Zonca, Fulvio; Chen, Liu

    2015-11-01

    It has been recently demonstrated that, generally, electrostatic (ES) and magnetostatic (MS) convective cells (CCs), or zonal flows, can be excited simultaneously by kinetic Alfven waves (KAWs). In this paper, spontaneous excitations of electrostatic as well as magnetostatic convective cells by KAWs are investigated through hybrid simulations, and the results are compared with the analytical theory based on the nonlinear gyrokinetic equations. In the hybrid simulation, ions are treated as fully kinetic particles, and electrons are treated as a massless fluid. It is found that finite ion-Larmor-radius (FILR) effects play a crucial. Furthermore, ES and MS convective cells are intrinsically coupled and must be treated on an equal footing. Excellent agreement is obtained for mode structure and generation rate of convective cells by KAW, demonstrating that ESCC and MSCC are indeed coupled, and that spontaneous CC excitation is suppressed at long wavelength, showing the crucial destabilizing role of FILR effects in the excitation via modulational instabilities. This work is supported by US DoE, NSF, ITER-CN, and NSFC grants.

  12. Kinetic Adsorption Study of Silver Nanoparticles on Natural Zeolite: Experimental and Theoretical Models

    Directory of Open Access Journals (Sweden)

    Alvaro Ruíz-Baltazar

    2015-12-01

    Full Text Available In this research, the adsorption capacity of Ag nanoparticles on natural zeolite from Oaxaca is presented. In order to describe the adsorption mechanism of silver nanoparticles on zeolite, experimental adsorption models for Ag ions and Ag nanoparticles were carried out. These experimental data obtained by the atomic absorption spectrophotometry technique were compared with theoretical models such as Lagergren first-order, pseudo-second-order, Elovich, and intraparticle diffusion. Correlation factors R2 of the order of 0.99 were observed. Analysis by transmission electron microscopy describes the distribution of the silver nanoparticles on the zeolite outer surface. Additionally, a chemical characterization of the material was carried out through a dilution process with lithium metaborate. An average value of 9.3 in the Si/Al ratio was observed. Factors such as the adsorption behavior of the silver ions and the Si/Al ratio of the zeolite are very important to support the theoretical models and establish the adsorption mechanism of Ag nanoparticles on natural zeolite.

  13. Thermochemistry and Kinetic Analysis of the Unimolecular Oxiranyl Radical Dissociation Reaction: A Theoretical Study.

    Science.gov (United States)

    Wang, Heng; Bozzelli, Joseph W

    2016-07-04

    Oxirane structures are important in organic synthesis, and they are important initial products in the oxidation reactions of alkyl radicals. The thermochemical properties (enthalpy of formation, entropy, and heat capacity) for the reaction steps of the unimolecular oxiranyl radical dissociation reaction are determined and compared with the available literature. The overall ring opening and subsequent steps involve four types of reactions: β-scission ring opening, intramolecular hydrogen transfer, β-scission hydrogen elimination, and β-scission methyl radical elimination. The enthalpies of formation of the transition states are determined and evaluated using six popular Density Functional Theory (DFT) calculation methods (B3LYP, B2PLYP, M06, M06-2X, ωB97X, ωB97XD), each combined with three different basis sets. The DFT enthalpy values are compared with five composite calculation methods (G3, G4, CBS-QB3, CBS-APNO, W1U), and by CCSD(T)/aug-cc-pVTZ. Kinetic parameters are determined versus pressure and temperature for the unimolecular dissociation pathways of an oxiranyl radical, which include the chemical activation reactions of the ring-opened oxiranyl radical relative to the ring-opening barrier. Multifrequency quantum Rice Ramsperger Kassel (QRRK) analysis is used to determine k(E) with master equation analysis for falloff. The major overall reaction pathway at lower combustion temperatures is oxiranyl radical dissociation to a methyl radical and carbon monoxide. Oxiranyl radical dissociation to a ketene and hydrogen atom is the key reaction path above 700 K. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Theoretical study of the reaction kinetics of atomic bromine with tetrahydropyran

    KAUST Repository

    Giri, Binod

    2015-02-12

    A detailed theoretical analysis of the reaction of atomic bromine with tetrahydropyran (THP, C5H10O) was performed using several ab initio methods and statistical rate theory calculations. Initial geometries of all species involved in the potential energy surface of the title reaction were obtained at the B3LYP/cc-pVTZ level of theory. These molecular geometries were reoptimized using three different meta-generalized gradient approximation (meta-GGA) functionals. Single-point energies of the stationary points were obtained by employing the coupled-cluster with single and double excitations (CCSD) and fourth-order Møller-Plesset (MP4 SDQ) levels of theory. The computed CCSD and MP4(SDQ) energies for optimized structures at various DFT functionals were found to be consistent within 2 kJ mol-1. For a more accurate energetic description, single-point calculations at the CCSD(T)/CBS level of theory were performed for the minimum structures and transition states optimized at the B3LYP/cc-pVTZ level of theory. Similar to other ether + Br reactions, it was found that the tetrahydropyran + Br reaction proceeds in an overall endothermic addition-elimination mechanism via a number of intermediates. However, the reactivity of various ethers with atomic bromine was found to vary substantially. In contrast with the 1,4-dioxane + Br reaction, the chair form of the addition complex (c-C5H10O-Br) for THP + Br does not need to undergo ring inversion to form a boat conformer (b-C4H8O2-Br) before the intramolecular H-shift can occur to eventually release HBr. Instead, a direct, yet more favorable route was mapped out on the potential energy surface of the THP + Br reaction. The rate coefficients for all relevant steps involved in the reaction mechanism were computed using the energetics of coupled cluster calculations. On the basis of the results of the CCSD(T)/CBS//B3LYP/cc-pVTZ level of theory, the calculated overall rate coefficients can be expressed as kov.,calc.(T) = 4.60 × 10

  15. Hydrogen Atom Transfer (HAT) Processes Promoted by the Quinolinimide-N-oxyl Radical. A Kinetic and Theoretical Study.

    Science.gov (United States)

    DiLabio, Gino A; Franchi, Paola; Lanzalunga, Osvaldo; Lapi, Andrea; Lucarini, Fiorella; Lucarini, Marco; Mazzonna, Marco; Prasad, Viki Kumar; Ticconi, Barbara

    2017-06-16

    A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of organic compounds to the quinolinimide-N-oxyl radical (QINO) was performed in CH3CN. The HAT rate constants are significantly higher than those observed with the phthalimide-N-oxyl radical (PINO) as a result of enthalpic and polar effects due to the presence of the N-heteroaromatic ring in QINO. The relevance of polar effects is supported by theoretical calculations conducted for the reactions of the two N-oxyl radicals with toluene, which indicate that the HAT process is characterized by a significant degree of charge transfer permitted by the π-stacking that occurs between the toluene and the N-oxyl aromatic rings in the transition state structures. An increase in the HAT reactivity of QINO was observed in the presence of 0.15 M HClO4 and 0.15 M Mg(ClO4)2 due to the protonation or complexation with the Lewis acid of the pyridine nitrogen that leads to a further decrease in the electron density in the N-oxyl radical. These results fully support the use of N-hydroxyquinolinimide as a convenient substitute for N-hydroxyphthalimide in the catalytic aerobic oxidations of aliphatic hydrocarbons characterized by relatively high C-H bond dissociation energies.

  16. A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals.

    Science.gov (United States)

    Khaled, Fethi; Giri, Binod Raj; Szőri, Milán; Mai, Tam V-T; Huynh, Lam K; Farooq, Aamir

    2017-03-08

    The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning's augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

  17. A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

    KAUST Repository

    Khaled, Fathi

    2017-02-08

    The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt\\'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning\\'s augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

  18. Theoretical and kinetic study of the hydrogen atom abstraction reactions of unsaturated C6 methyl esters with hydroxyl radical

    Science.gov (United States)

    Wang, Quan-De; Ni, Zhong-Hai

    2016-04-01

    This work reports a systematic ab initio and chemical kinetic study of the rate constants for hydrogen atom abstraction reactions by hydroxyl radical (OH) on typical isomers of unsaturated C6 methyl esters at the CBS/QB3 level of theory. The high-pressure limit rate constants at different reaction sites for all the methyl esters in the temperature range from 500 to 2000 K are calculated via transition-state theory with the Wigner method for quantum tunneling effect and fitted to the modified three parameters Arrhenius expression using least-squares regression. Further, a branching ratio analysis for each reaction site has been performed.

  19. Lewis Base Catalytic Properties of [Nb10 O28 ]6- for CO2 Fixation to Epoxide: Kinetic and Theoretical Studies.

    Science.gov (United States)

    Hayashi, Shun; Yamazoe, Seiji; Koyasu, Kiichirou; Tsukuda, Tatsuya

    2017-07-04

    The decaniobate cluster (TBA)6 [Nb10 O28 ] (TBA+ =tetrabutylammonium cation) was found to act as a Lewis base catalyst for fixation of carbon dioxide (CO2 ) to styrene oxide (SO). A kinetic study showed that the cycloaddition of CO2 adsorbed on [Nb10 O28 ]6- with SO corresponds to the rate-determining step in the Eley-Rideal mechanism. Density functional theory calculation predicted that CO2 on the corner and edge O atoms of [Nb10 O28 ]6- is negatively charged and thus activated for nucleophilic attack on SO. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Kinetic Chain Rehabilitation: A Theoretical Framework

    Directory of Open Access Journals (Sweden)

    Aaron Sciascia

    2012-01-01

    Full Text Available Sequenced physiologic muscle activations in the upper and lower extremity result in an integrated biomechanical task. This sequencing is known as the kinetic chain, and, in upper extremity dominant tasks, the energy development and output follows a proximal to distal sequencing. Impairment of one or more kinetic chain links can create dysfunctional biomechanical output leading to pain and/or injury. When deficits exist in the preceding links, they can negatively affect the shoulder. Rehabilitation of shoulder injuries should involve evaluation for and restoration of all kinetic chain deficits that may hinder kinetic chain function. Rehabilitation programs focused on eliminating kinetic chain deficits, and soreness should follow a proximal to distal rationale where lower extremity impairments are addressed in addition to the upper extremity impairments. A logical progression focusing on flexibility, strength, proprioception, and endurance with kinetic chain influence is recommended.

  1. Theoretical study of the dynamics and kinetics of the O + CS → CO + S chemical laser reaction, where CO shows a very high vibrational excitation.

    Science.gov (United States)

    Gamallo, Pablo; Francia, Rafael; Martínez, Rodrigo; Sayós, Ramón; González, Miguel

    2012-12-06

    The dynamics and kinetics of the O((3)P) + CS(X(1)Σ(+)) → CO(X(1)Σ(+)) + S((3)P) chemical laser reaction was studied theoretically in detail for the first time, as a function of collision energy (0.0388-2.0 eV) and rovibrational excitation of CS. This was made using the quasi-classical trajectory (QCT) method and employing the best ab initio analytical ground potential energy surface (1(3)A' PES) available. A broad set of properties was determined, including scalar and vector properties, and the reaction mode. The behaviors observed and the considerable formation of OCS collision complexes were interpreted from some characteristics of the PES (early barrier, shallow minimum in the exit channel, and high exoergicity (mainly channeled into CO vibration; up to ∼81% of the available energy)) and the kinematics. The QCT vibrational and rotational CO populations and the vector properties show a quite good agreement with experiments, but the QCT rate constants disagree. To better account for the kinetics, we performed CASPT2/aug-cc-pVTZ ab initio calculations on the stationary points along the minimum energy path of the ground and first excited (1(3)A'') PESs. The transition state theory, which can be satisfactorily applied here, leads to rate constants (100-2000 K) that are quite close to the measured ones, where comparison is possible (150-300 K). We expect that these results will encourage further theoretical and experimental developments.

  2. Kinetics of the Strain-Promoted Oxidation-Controlled Cycloalkyne-1,2-quinone Cycloaddition: Experimental and Theoretical Studies.

    Science.gov (United States)

    Escorihuela, Jorge; Das, Anita; Looijen, Wilhelmus J E; van Delft, Floris L; Aquino, Adelia J A; Lischka, Hans; Zuilhof, Han

    2018-01-05

    Stimulated by its success in both bioconjugation and surface modification, we studied the strain-promoted oxidation-controlled cycloalkyne-1,2-quinone cycloaddition (SPOCQ) in three ways. First, the second-order rate constants and activation parameters (ΔH⧧) were determined of various cyclooctynes reacting with 4-tert-butyl-1,2-quinone in a SPOCQ reaction, yielding values for ΔH⧧ of 4.5, 7.3, and 12.1 kcal/mol, for bicyclo[6.1.0]non-4-yne (BCN), cyclooctyne (OCT), and dibenzoazacyclooctyne (DIBAC), respectively. Second, their reaction paths were investigated in detail by a range of quantum mechanical calculations. Single-configuration theoretical methods, like various DFT and a range of MP2-based methods, typically overestimate this barrier by 3-8 kcal/mol (after inclusion of zero-point energy, thermal, and solvation corrections), whereas MP2 itself underestimates the barrier significantly. Only dispersion-corrected DFT methods like B97D (yielding 4.9, 6.4, and 12.1 kcal/mol for these three reactions) and high-level CCSD(T) and multireference multiconfiguration AQCC ab initio approaches (both yielding 8.2 kcal/mol for BCN) give good approximations of experimental data. Finally, the multireference methods show that the radical character in the TS is rather small, thus rationalizing the use of single-reference methods like B97D and SCS-MP2 as intrinsically valid approaches.

  3. Chemical, physical, and theoretical kinetics of an ultrafast folding protein.

    Science.gov (United States)

    Kubelka, Jan; Henry, Eric R; Cellmer, Troy; Hofrichter, James; Eaton, William A

    2008-12-02

    An extensive set of equilibrium and kinetic data is presented and analyzed for an ultrafast folding protein--the villin subdomain. The equilibrium data consist of the excess heat capacity, tryptophan fluorescence quantum yield, and natural circular-dichroism spectrum as a function of temperature, and the kinetic data consist of time courses of the quantum yield from nanosecond-laser temperature-jump experiments. The data are well fit with three kinds of models--a three-state chemical-kinetics model, a physical-kinetics model, and an Ising-like theoretical model that considers 10(5) possible conformations (microstates). In both the physical-kinetics and theoretical models, folding is described as diffusion on a one-dimensional free-energy surface. In the physical-kinetics model the reaction coordinate is unspecified, whereas in the theoretical model, order parameters, either the fraction of native contacts or the number of native residues, are used as reaction coordinates. The validity of these two reaction coordinates is demonstrated from calculation of the splitting probability from the rate matrix of the master equation for all 10(5) microstates. The analysis of the data on site-directed mutants using the chemical-kinetics model provides information on the structure of the transition-state ensemble; the physical-kinetics model allows an estimate of the height of the free-energy barrier separating the folded and unfolded states; and the theoretical model provides a detailed picture of the free-energy surface and a residue-by-residue description of the evolution of the folded structure, yet contains many fewer adjustable parameters than either the chemical- or physical-kinetics models.

  4. Theoretical studies on kinetics, mechanism and thermochemistry of gas-phase reactions of HFE-449mec-f with OH radicals and Cl atom.

    Science.gov (United States)

    Deka, Ramesh Chandra; Mishra, Bhupesh Kumar

    2014-09-01

    A theoretical study on the mechanism and kinetics of the gas phase reactions of CF3CHFCF2OCH2CF3 (HFE-449mec-f) with the OH radicals and Cl atom have been performed using meta-hybrid modern density functional M06-2X using 6-31+G(d,p) basis set. Two conformers have been identified for CF3CHFCF2OCH2CF3 and the most stable one is considered for detailed study. Reaction profiles for OH-initiated hydrogen abstraction are modeled including the formation of pre-reactive and post-reactive complexes at entrance and exit channels. Our calculations reveal that hydrogen abstraction from the CH2 group is thermodynamically and kinetically more facile than that from the CHF group. Using group-balanced isodesmic reactions, the standard enthalpies of formation for HFE-449mecf and radicals generated by hydrogen abstraction, are also reported. The calculated bond dissociation energies for CH bonds are in good agreement with experimental results. The rate constants of the two reactions are determined for the first time in a wide temperature range of 250-450K. The calculated rate constant values are found to be 9.10×10(-15) and 4.77×10(-17)cm(3)molecule(-1)s(-1) for reactions with OH radicals and Cl atom, respectively. At 298K, the total calculated rate coefficient for reactions with OH radical is in good agreement with the experimental results. The atmospheric life time of HFE-449mec-f is estimated to be 0.287 years. Copyright © 2014 Elsevier Inc. All rights reserved.

  5. Theoretical Mechanistic and Kinetic Studies on Homogeneous Gas-Phase Formation of Polychlorinated Naphthalene from 2-Chlorophenol as Forerunner

    Directory of Open Access Journals (Sweden)

    Fei Xu

    2015-10-01

    Full Text Available Polychlorinated naphthalenes (PCNs are dioxins-like compounds and are formed along with polychlorinated dibenzo-p-dioxins (PCDDs and polychlorinated dibenzofurans (PCDFs in thermal and combustion procedures. Chlorophenols (CPs are the most important forerunners of PCNs. A comprehensive comprehension of PCN formation procedure from CPs is a precondition for reducing the discharge of PCNs. Experiments on the formation of PCNs from CPs have been hindered by PCN toxicity and short of precise detection methods for active intermediate radicals. In this work, PCN formation mechanism in gas-phase condition from 2-chlorophenol (2-CP as forerunner was studied by quantum chemistry calculations. Numbers of energetically advantaged formation routes were proposed. The rate constants of key elementary steps were calculated over 600–1200 K using canonical variational transition-state theory (CVT with small curvature tunneling contribution (SCT method. This study illustrates formation of PCNs with one chlorine atom loss from 2-CP is preferred over that without chlorine atom loss. In comparison with formation of PCDFs from 2-CP, PCN products are less chlorinated and have lower formation potential.

  6. A kinetic and theoretical study of the borate catalysed reactions of hydrogen peroxide: the role of dioxaborirane as the catalytic intermediate for a wide range of substrates.

    Science.gov (United States)

    Deary, Michael E; Durrant, Marcus C; Davies, D Martin

    2013-01-14

    Our recent work has provided new insights into the equilibria and species that exist in aqueous solution at different pHs for the boric acid - hydrogen peroxide system, and the role of these species in oxidation reactions. Most recently, (M. C. Durrant, D. M. Davies and M. E. Deary, Org. Biomol. Chem., 2011, 9, 7249-7254), we have produced strong theoretical and experimental evidence for the existence of a previously unreported monocyclic three membered peroxide species, dioxaborirane, that is the likely catalytic species in borate mediated electrophilic reactions of hydrogen peroxide in alkaline solution. In the present paper, we extend our study of the borate-peroxide system to look at a wide range of substrates that include substituted dimethyl anilines, methyl-p-tolyl sulfoxide, halides, hydrogen sulfide anion, thiosulfate, thiocyanate, and hydrazine. The unusual selectivity-reactivity pattern of borate catalysed reactions compared with hydrogen peroxide and inorganic or organic peracids previously observed for the organic sulfides (D. M. Davies, M. E. Deary, K. Quill and R. A. Smith, Chem.-Eur. J., 2005, 11, 3552-3558) is also seen with substituted dimethyl aniline nucleophiles. This provides evidence that the pattern is not due to any latent electrophilic tendency of the organic sulfides and further supports dioxaborirane being the likely reactive intermediate, thus broadening the applicability of this catalytic system. Moreover, density functional theory calculations on our proposed mechanism involving dioxaborirane are consistent with the experimental results for these substrates. Results obtained at high concentrations of both borate and hydrogen peroxide require the inclusion the diperoxodiborate dianion in the kinetic analysis. A scheme detailing our current understanding of the borate-peroxide system is presented.

  7. An Experimental and Theoretical Study on the Kinetic Isotope Effect of C2H6 and C2D6 Reaction with OH

    KAUST Repository

    Khaled, Fathi

    2015-10-30

    We report experimental and theoretical results for the deuterated kinetic isotope effect (DKIE) of the reaction of OH with ethane (C2H6) and deuterated ethane (C2D6). The reactions were investigated behind reflected shock waves over 800–1350 K by monitoring OH radicals near 306.69 nm using laser absorption. In addition, high level CCSD(T)/cc-pV(T,Q)Z//MP2/cc-pVTZ quantum chemical and statistical rate theory calculations were performed which agreed very well with the experimental findings. The results reported herein provide the first experimental evidence that DKIE for alkanes asymptotes to a value of 1.4 at high temperatures.

  8. Kinetic and theoretical studies of novel biodegradable thermo-sensitive xerogels based on PEG/PVP/silica for sustained release of enrofloxacin

    Science.gov (United States)

    Ebadi, Azra; Rafati, Amir Abbas; Bavafa, Sadeghali; Mohammadi, Masoumah

    2017-12-01

    This study involves the synthesis of a new silica-based colloidal hybrid system. In this new hybrid system, poly (ethylene glycol) (PEG) and thermo-sensitive amphiphilic biocompatible poly (vinyl pyrrolidone) (PVP) were used to create suitable storage for hydrophobic drugs. The possibility of using variable PVP/PEG molar ratios to modulate drug release rate from silica nanoparticles was a primary goal of the current research. In addition, an investigation of the drug release kinetic was conducted. To achieve this, silica nanoparticles were synthesized in poly (ethylene glycol) (PEG) and poly (vinyl pyrrolidone) (PVP) solution incorporated with enrofloxacin (EFX) (as a model hydrophobic drug), using a simple synthetic strategy of hybrid materials which avoided waste and multi-step processes. The impacts of PVP/PEG molar ratios, temperature, and pH of the release medium on release kinetic were investigated. The physicochemical properties of the drug-loaded composites were studied by Fourier transform infrared (FT-IR) spectra, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). In vitro drug release studies demonstrated that the drug release rate, which was evaluated by analyzing the experimental data with seven kinetic models in a primarily non-Fickian diffusion-controlled process, aligned well with both Ritger-Peppas and Sahlin-Peppas equations.

  9. Energetics and kinetics of phase transition between a 2H and a 1T MoS2 monolayer-a theoretical study.

    Science.gov (United States)

    Zhao, Wen; Ding, Feng

    2017-02-09

    Phase transitions between semiconducting 2H and metallic 1T (or 1T') molybdenum disulphides (MoS2) are explored comprehensively by first-principles calculations. The nucleation of a 1T (or 1T') nucleus in a 2H MoS2 lattice, the formation of the 2H-1T (1T') interfaces and the kinetics of interface propagation during phase transition were thoroughly investigated in this study. It was found that, among various potential interface structures between the two phases, Mo-rich and two S-rich zigzag (ZZ) boundaries are energetically more preferable than others. Therefore, triangular or hexagonal 1T MoS2 domains with the three types of ZZ boundaries are expected to be the equilibrium structures of the 1T nucleus in a 2H lattice. Further exploration reveals a very high nucleation energy of the 1T phase which suggests that the nucleation may start from a defect site or the edge of the 2H phase. Besides, the kinetics of 2H-1T (1T') boundary propagation show that the growth rate of the ZZ boundaries is significantly slower than the armchair (AC) ones'. Therefore, the ZZ-boundary dominated domains are expected to be observed during the growth of the 1T phase while the rounded domains with various high-index edges are expected to be seen throughout shrinkage. This study reveals both the energetics and the kinetics of the phase transition of transition metal dichalcogenide materials and also sheds light on other 2D materials.

  10. Kinetic theory molecular dynamics and hot dense matter: theoretical foundations.

    Science.gov (United States)

    Graziani, F R; Bauer, J D; Murillo, M S

    2014-09-01

    Electrons are weakly coupled in hot, dense matter that is created in high-energy-density experiments. They are also mildly quantum mechanical and the ions associated with them are classical and may be strongly coupled. In addition, the dynamical evolution of plasmas under these hot, dense matter conditions involve a variety of transport and energy exchange processes. Quantum kinetic theory is an ideal tool for treating the electrons but it is not adequate for treating the ions. Molecular dynamics is perfectly suited to describe the classical, strongly coupled ions but not the electrons. We develop a method that combines a Wigner kinetic treatment of the electrons with classical molecular dynamics for the ions. We refer to this hybrid method as "kinetic theory molecular dynamics," or KTMD. The purpose of this paper is to derive KTMD from first principles and place it on a firm theoretical foundation. The framework that KTMD provides for simulating plasmas in the hot, dense regime is particularly useful since current computational methods are generally limited by their inability to treat the dynamical quantum evolution of the electronic component. Using the N-body von Neumann equation for the electron-proton plasma, three variations of KTMD are obtained. Each variant is determined by the physical state of the plasma (e.g., collisional versus collisionless). The first variant of KTMD yields a closed set of equations consisting of a mean-field quantum kinetic equation for the electron one-particle distribution function coupled to a classical Liouville equation for the protons. The latter equation includes both proton-proton Coulombic interactions and an effective electron-proton interaction that involves the convolution of the electron density with the electron-proton Coulomb potential. The mean-field approach is then extended to incorporate equilibrium electron-proton correlations through the Singwi-Tosi-Land-Sjolander (STLS) ansatz. This is the second variant of KTMD

  11. Theoretical and experimental study on the effects of particle size and temperature on the reaction kinetics of cubic nano-Cu2O

    Science.gov (United States)

    Tang, Huanfeng; Huang, Zaiyin; Xiao, Ming; Liang, Min; Chen, Liying; Tan, XueCai

    2017-09-01

    The activities, selectivities, and stabilities of nanoparticles in heterogeneous reactions are size-dependent. In order to investigate the influencing laws of particle size and temperature on kinetic parameters in heterogeneous reactions, cubic nano-Cu2O particles of four different sizes in the range of 40-120 nm have been controllably synthesized. In situ microcalorimetry has been used to attain thermodynamic data on the reaction of Cu2O with aqueous HNO3 and, combined with thermodynamic principles and kinetic transition-state theory, the relevant reaction kinetic parameters have been evaluated. The size dependences of the kinetic parameters are discussed in terms of the established kinetic model and the experimental results. It was found that the reaction rate constants increased with decreasing particle size. Accordingly, the apparent activation energy, pre-exponential factor, activation enthalpy, activation entropy, and activation Gibbs energy decreased with decreasing particle size. The reaction rate constants and activation Gibbs energies increased with increasing temperature. Moreover, the logarithms of the apparent activation energies, pre-exponential factors, and rate constants were found to be linearly related to the reciprocal of particle size, consistent with the kinetic models. The influence of particle size on these reaction kinetic parameters may be explained as follows: the apparent activation energy is affected by the partial molar enthalpy, the pre-exponential factor is affected by the partial molar entropy, and the reaction rate constant is affected by the partial molar Gibbs energy. [Figure not available: see fulltext.

  12. Theoretical studies on the kinetics and mechanism of the gas-phase reactions of CHF(2)OCHF (2) with OH radicals.

    Science.gov (United States)

    Chandra, Asit K

    2012-09-01

    The mechanism, kinetics and thermochemistry of the gas-phase reactions between CHF(2)OCHF(2) (HFE-134) and OH radical are investigated using the high level ab initio G2(MP2) and hybrid density functional model MPWB1K quantum chemical methods. Two relatively close in energy conformers are found for CHF(2)OCHF(2) molecule; both of them are likely to be important in the temperature range (250-1000 K) of our study. The hydrogen abstraction pathway for both the conformers with OH radical is studied and the rate constants are determined for the first time in a wide temperature range of 250 - 1000 K. The G2(MP2) calculated total rate constant value of 2.9 × 10(-15) cm(3) molecule(-1) s(-1) at 298 K is found to be in very good agreement with the reported experimental value of 2.4 × 10(-15) cm(3) molecule(-1) s(-1) at 298 K. The heats of reaction for CHF(2)OCHF(2) + OH reaction is computed to be -13.2 kcal mol(-1). The atmospheric lifetime of CHF(2)OCHF(2) is expected to be around 12 years.

  13. Kinetics, Mechanism and Theoretical Studies of Norbornene-Ethylene Alternating Copolymerization Catalyzed by Organopalladium(II Complexes Bearing Hemilabile α-Amino–pyridine

    Directory of Open Access Journals (Sweden)

    Kuo-Hsuan Yu

    2017-06-01

    Full Text Available Cationic methylpalladium complexes bearing hemilabile bidentate α-amino–pyridines can serve as effective precursors for catalytic alternating copolymerization of norbornene (N and ethylene (E, under mild conditions. The norbornyl palladium complexes in the formula of {[RHNCH2(o-C6H4N]Pd(C7H10Me(NCMe}(BF4 (R = iPr (2a, tBu (2b, Ph (2c, 2,6-Me2C6H3 (2d, 2,6-iPr2C6H3 (2e were synthesized via single insertion of norbornene into the corresponding methylpalladium complexes 1a–1e, respectively. Both square planar methyl and norbornyl palladium complexes exhibit facile equilibria of geometrical isomerization, via sterically-controlled amino decoordination–recoordination of amino–pyridine. Kinetic studies of E-insertion, N-insertion of complexes 1 and 2, and the geometric isomerization reactions have been examined by means of VT-NMR, and found in excellent agreement with the results estimated by DFT calculations. The more facile N-insertion in the cis-isomers, and ready geometric isomerization, cooperatively lead to a new mechanism that accounts for the novel catalytic formation of alternating COC.

  14. Low temperature kinetics and theoretical studies of the reaction CN + CH3NH2: a potential source of cyanamide and methyl cyanamide in the interstellar medium.

    Science.gov (United States)

    Sleiman, Chantal; El Dib, Gisèle; Rosi, Marzio; Skouteris, Dimitrios; Balucani, Nadia; Canosa, André

    2017-10-30

    The reaction between cyano radicals (which are ubiquitous in interstellar clouds) and methylamine (a molecule detected in various interstellar sources) has been investigated in a synergistic experimental and theoretical study. The reaction has been found to be very fast in the entire range of temperatures investigated (23-297 K) by using a CRESU apparatus coupled to pulsed laser photolysis - laser induced fluorescence. The global experimental rate coefficient is given by In addition, dedicated electronic structure calculations of the underlying potential energy surface have been performed, together with capture theory and RRKM calculations. The experimental data have been interpreted in the light of the theoretical calculations and the product branching ratio has been established. According to the present study, in the range of temperatures investigated the title reaction is an efficient interstellar route of formation of cyanamide, NH2CN, another interstellar species. The second most important channel is the one leading to methyl cyanamide, CH3NHCN (an isomer of aminoacetonitrile), via a CN/H exchange mechanism with a yield of 12% of the global reaction in the entire range of temperatures explored. For a possible inclusion in future astrochemical models we suggest, by referring to the usual expression the following values: α = 3.68 × 10(-12) cm(3) molec(-1) s(-1), β = -1.80, γ = 7.79 K for the channel leading to NH2CN + CH3; α = 5.05 × 10(-13) cm(3) molec(-1) s(-1), β = -1.82, γ = 7.93 K for the channel leading to CH3NHCN + H.

  15. Kinetic studies of elementary chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

  16. Kinetics of syntrophic cultures: A theoretical treatise on butyrate fermentation

    NARCIS (Netherlands)

    Kleerebezem, R.; Stams, A.J.M.

    2000-01-01

    Numerous microbial conversions in methanogenic environments proceed at (Gibbs) free energy changes close to thermodynamic equilibrium. In this paper we attempt to describe the consequences of this thermodynamic boundary condition on the kinetics of anaerobic conversions in methanogenic environments.

  17. Steering charge kinetics in photocatalysis: intersection of materials syntheses, characterization techniques and theoretical simulations.

    Science.gov (United States)

    Bai, Song; Jiang, Jun; Zhang, Qun; Xiong, Yujie

    2015-05-21

    Charge kinetics is highly critical in determining the quantum efficiency of solar-to-chemical conversion in photocatalysis, and this includes, but is not limited to, the separation of photoexcited electron-hole pairs, utilization of plasmonic hot carriers and delivery of photo-induced charges to reaction sites, as well as activation of reactants by energized charges. In this review, we highlight the recent progress on probing and steering charge kinetics toward designing highly efficient photocatalysts and elucidate the fundamentals behind the combinative use of controlled synthesis, characterization techniques (with a focus on spectroscopic characterizations) and theoretical simulations in photocatalysis studies. We first introduce the principles of various processes associated with charge kinetics that account for or may affect photocatalysis, from which a set of parameters that are critical to photocatalyst design can be summarized. We then outline the design rules for photocatalyst structures and their corresponding synthetic approaches. The implementation of characterization techniques and theoretical simulations in different steps of photocatalysis, together with the associated fundamentals and working mechanisms, are also presented. Finally, we discuss the challenges and opportunities for photocatalysis research at this unique intersection as well as the potential impact on other research fields.

  18. Field-theoretic calculation of kinetic helicity flux

    Indian Academy of Sciences (India)

    bulence and compute the fluxes of energy and kinetic helicity. The renormalized viscosity computed using RG procedure is used in the calculation. Contrast this with the arbitrary constant used in EDQNM calculation. In addition, the EDQNM calculations require numerical integration of energy equation, which is not required.

  19. Theoretical Advanced Study Institute: 2014

    Energy Technology Data Exchange (ETDEWEB)

    DeGrand, Thomas [Univ. of Colorado, Boulder, CO (United States)

    2016-08-17

    The Theoretical Advanced Study Institute (TASI) was held at the University of Colorado, Boulder, during June 2-27, 2014. The topic was "Journeys through the Precision Frontier: Amplitudes for Colliders." The organizers were Professors Lance Dixon (SLAC) and Frank Petriello (Northwestern and Argonne). There were fifty-one students. Nineteen lecturers gave sixty seventy-five minute lectures. A Proceedings was published. This TASI was unique for its large emphasis on methods for calculating amplitudes. This was embedded in a program describing recent theoretical and phenomenological developments in particle physics. Topics included introductions to the Standard Model, to QCD (both in a collider context and on the lattice), effective field theories, Higgs physics, neutrino interactions, an introduction to experimental techniques, and cosmology.

  20. Theoretical studies of combustion dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Bowman, J.M. [Emory Univ., Atlanta, GA (United States)

    1993-12-01

    The basic objectives of this research program are to develop and apply theoretical techniques to fundamental dynamical processes of importance in gas-phase combustion. There are two major areas currently supported by this grant. One is reactive scattering of diatom-diatom systems, and the other is the dynamics of complex formation and decay based on L{sup 2} methods. In all of these studies, the authors focus on systems that are of interest experimentally, and for which potential energy surfaces based, at least in part, on ab initio calculations are available.

  1. 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.

  2. A theoretical study on seasonality.

    Science.gov (United States)

    Schmal, Christoph; Myung, Jihwan; Herzel, Hanspeter; Bordyugov, Grigory

    2015-01-01

    In addition to being endogenous, a circadian system must be able to communicate with the outside world and align its rhythmicity to the environment. As a result of such alignment, external Zeitgebers can entrain the circadian system. Entrainment expresses itself in coinciding periods of the circadian oscillator and the Zeitgeber and a stationary phase difference between them. The range of period mismatches between the circadian system and the Zeitgeber that Zeitgeber can overcome to entrain the oscillator is called an entrainment range. The width of the entrainment range usually increases with increasing Zeitgeber strength, resulting in a wedge-like Arnold tongue. This classical view of entrainment does not account for the effects of photoperiod on entrainment. Zeitgebers with extremely small or large photoperiods are intuitively closer to constant environments than equinoctial Zeitgebers and hence are expected to produce a narrower entrainment range. In this paper, we present theoretical results on entrainment under different photoperiods. We find that in the photoperiod-detuning parameter plane, the entrainment zone is shaped in the form of a skewed onion. The bottom and upper points of the onion are given by the free-running periods in DD and LL, respectively. The widest entrainment range is found near photoperiods of 50%. Within the onion, we calculated the entrainment phase that varies over a range of 12 h. The results of our theoretical study explain the experimentally observed behavior of the entrainment phase in dependence on the photoperiod.

  3. THEORETICAL ASPECTS OF FILMMUSIC STUDY

    Directory of Open Access Journals (Sweden)

    Egorova Tatiana K.

    2014-04-01

    Full Text Available In this article, author analyzes the theoretical aspects of the film music study taking into account with modern realities in the development of world film-process and attempts to its scientific understanding. Need for innovation in this area is long overdue, because the existing on this topic nonfiction no longer meets the new aesthetic and art-practical achievements and innovations in the film music development at the XXI century. Related to the phenomenon of music in screen arts a number of new terms and concepts require a certain adjustment as well. Their range of action is not yet fully defined. Author of the article offered her version of their content-semantic interpretation (largely experimental designed to promote new research methods for the film music study.

  4. Experimental and Theoretical Study on the OH-Reaction Kinetics and Photochemistry of Acetyl Fluoride (CH3C(O)F), an Atmospheric Degradation Intermediate of HFC-161 (C2H5F).

    Science.gov (United States)

    Song, Xinli; Zügner, Gábor L; Farkas, Mária; Illés, Ádám; Sarzyński, Dariusz; Rozgonyi, Tamás; Wang, Baoshan; Dóbé, Sándor

    2015-07-16

    The direct reaction kinetic method of low pressure fast discharge flow (DF) with resonance fluorescence monitoring of OH (RF) has been applied to determine rate coefficients for the overall reactions OH + C2H5F (EtF) (1) and OH + CH3C(O)F (AcF) (2). Acetyl fluoride reacts slowly with the hydroxyl radical, the rate coefficient at laboratory temperature is k2(300 K) = (0.74 ± 0.05) × 10(-14) cm(3) molecule(-1) s(-1) (given with 2σ statistical uncertainty). The temperature dependence of the reaction does not obey the Arrhenius law and it is described well by the two-exponential rate expression of k2(300-410 K) = 3.60 × 10(-3) exp(-10500/T) + 1.56 × 10(-13) exp(-910/T) cm(3) molecule(-1) s(-1). The rate coefficient of k1 = (1.90 ± 0.19) × 10(-13) cm(3) molecule(-1) s(-1) has been determined for the EtF-reaction at room temperature (T = 298 K). Microscopic mechanisms for the OH + CH3C(O)F reaction have also been studied theoretically using the ab initio CBS-QB3 and G4 methods. Variational transition state theory was employed to obtain rate coefficients for the OH + CH3C(O)F reaction as a function of temperature on the basis of the ab initio data. The calculated rate coefficients are in good agreement with the experimental data. It is revealed that the reaction takes place predominantly via the indirect H-abstraction mechanism involving H-bonded prereactive complexes and forming the nascent products of H2O and the CH2CFO radical. The non-Arrhenius behavior of the rate coefficient at temperatures below 500 K is ascribed to the significant tunneling effect of the in-the-plane H-abstraction dynamic bottleneck. The production of FC(O)OH + CH3 via the addition/elimination mechanism is hardly competitive due to the significant barriers along the reaction routes. Photochemical experiments of AcF were performed at 248 nm by using exciplex lasers. The total photodissociation quantum yield for CH3C(O)F has been found significantly less than unity; among the primary

  5. Diffusion in liquids a theoretical and experimental study

    CERN Document Server

    Tyrrell, H J V

    1984-01-01

    Diffusion in Liquids: A Theoretical and Experimental Study aims to discuss the principles, applications, and advances in the field of diffusion, thermal diffusion, and thermal conduction in liquid systems. The book covers topics such as the principles of non-equilibrium thermodynamics; diffusion in binary and multicompetent systems; and experimental methods of studying diffusion processes in liquids. Also covered in the book are topics such as the theoretical interpretations of diffusion coefficients; hydrodynamic and kinetic theories; and diffusion in electrolyte systems. The text is recommen

  6. Electronic Effects versus Distortion Energies During Strain-Promoted Alkyne-Azide Cycloadditions: A Theoretical Tool to Predict Reaction Kinetics

    NARCIS (Netherlands)

    Garcia-Hartjes, J.; Dommerholt, J.; Wennekes, T.; Delft, van F.L.; Zuilhof, H.

    2013-01-01

    Second-order reaction kinetics of known strain-promoted azide–alkyne cycloaddition (SPAAC) reactions were compared with theoretical data from a range of ab initio methods. This produced both detailed insights into the factors determining the reaction rates and two straightforward theoretical tools

  7. Theoretical studies of unconventional superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Groensleth, Martin Sigurd

    2008-07-01

    This thesis presents four research papers. In the first three papers we have derived analytical results for the transport properties in unconventional superconductors and ferromagnetic systems with multiple broken symmetries. In Paper I and parts of Paper II we have studied tunneling transport between two non-unitary ferromagnetic spin-triplet superconductors, and found a novel interplay between ferromagnetism and superconductivity manifested in the Josephson effect as a spin- and charge-current in the absence of an applied voltage across the junction. The critical amplitudes of these currents can be adjusted by the relative magnetization direction on each side of the junction. Furthermore, in Paper II, we have found a way of controlling a spin-current between two ferromagnets with spin-orbit coupling. Paper III considers a junction consisting of a ferromagnet and a non-unitary ferromagnetic superconductor, and we show that the conductance spectra contains detailed information about the superconducting gaps and pairing symmetry of the Cooper-pairs. In the last paper we present a Monte Carlo study of an effective Hamiltonian describing orbital currents in the CuO2 layers of high-temperature superconductive cuprates. The model features two intrinsically anisotropic Ising models, coupled through an anisotropic next-nearest neighbor interaction, and an Ashkin-Teller nearest neighbor fourth order coupling. We have studied the specific heat anomaly, as well as the anomaly in the staggered magnetization associated with the orbital currents and its susceptibility. We have found that in a limited parameter regime, the specific heat anomaly is substantially suppressed, while the susceptibility has a non-analytical peak across the order-disorder transition. The model is therefore a candidate for describing the breakup of hidden order when crossing the pseudo-gap line on the under-doped side in the phase diagram of high-temperature superconductors. (Author) 64 refs., figs

  8. Diffusion-controlled interface kinetics-inclusive system-theoretic propagation models for molecular communication systems

    Science.gov (United States)

    Chude-Okonkwo, Uche A. K.; Malekian, Reza; Maharaj, B. T.

    2015-12-01

    Inspired by biological systems, molecular communication has been proposed as a new communication paradigm that uses biochemical signals to transfer information from one nano device to another over a short distance. The biochemical nature of the information transfer process implies that for molecular communication purposes, the development of molecular channel models should take into consideration diffusion phenomenon as well as the physical/biochemical kinetic possibilities of the process. The physical and biochemical kinetics arise at the interfaces between the diffusion channel and the transmitter/receiver units. These interfaces are herein termed molecular antennas. In this paper, we present the deterministic propagation model of the molecular communication between an immobilized nanotransmitter and nanoreceiver, where the emission and reception kinetics are taken into consideration. Specifically, we derived closed-form system-theoretic models and expressions for configurations that represent different communication systems based on the type of molecular antennas used. The antennas considered are the nanopores at the transmitter and the surface receptor proteins/enzymes at the receiver. The developed models are simulated to show the influence of parameters such as the receiver radius, surface receptor protein/enzyme concentration, and various reaction rate constants. Results show that the effective receiver surface area and the rate constants are important to the system's output performance. Assuming high rate of catalysis, the analysis of the frequency behavior of the developed propagation channels in the form of transfer functions shows significant difference introduce by the inclusion of the molecular antennas into the diffusion-only model. It is also shown that for t > > 0 and with the information molecules' concentration greater than the Michaelis-Menten kinetic constant of the systems, the inclusion of surface receptors proteins and enzymes in the models

  9. Kinetic and theoretical studies on the protonation of [Ni(2-SC6H4N){PhP(CH2CH2PPh2)2}]+: nitrogen versus sulfur as the protonation site.

    Science.gov (United States)

    Petrou, Athinoula L; Koutselos, Andreas D; Wahab, Hilal S; Clegg, William; Harrington, Ross W; Henderson, Richard A

    2011-02-07

    The complexes [Ni(4-Spy)(triphos)]BPh(4) and [Ni(2-Spy)(triphos)]BPh(4) {triphos = PhP(CH(2)CH(2)PPh(2))(2), 4-Spy = 4-pyridinethiolate, 2-Spy = 2-pyridinethiolate} have been prepared and characterized both spectroscopically and using X-ray crystallography. In both complexes the triphos is a tridentate ligand. However, [Ni(4-Spy)(triphos)](+) comprises a 4-coordinate, square-planar nickel with the 4-Spy ligand bound to the nickel through the sulfur while [Ni(2-Spy)(triphos)](+) contains a 5-coordinate, trigonal-bipyramidal nickel with a bidentate 2-Spy ligand bound to the nickel through both sulfur and nitrogen. The kinetics of the reactions of [Ni(4-Spy)(triphos)](+) and [Ni(2-Spy)(triphos)](+) with lutH(+) (lut = 2,6-dimethylpyridine) in MeCN have been studied using stopped-flow spectrophotometry, and the two complexes show very different reactivities. The reaction of [Ni(4-Spy)(triphos)](+) with lutH(+) is complete within the deadtime of the stopped-flow apparatus (2 ms) and corresponds to protonation of the nitrogen. However, upon mixing [Ni(2-Spy)(triphos)](+) and lutH(+) a reaction is observed (on the seconds time scale) to produce an equilibrium mixture. The mechanistic interpretation of the rate law has been aided by the application of MSINDO semiempirical and ADF calculations. The kinetics and calculations are consistent with the reaction between [Ni(2-Spy)(triphos)](+) and lutH(+) involving initial protonation of the sulfur followed by dissociation of the nitrogen and subsequent transfer of the proton from sulfur to nitrogen. The factors affecting the position of protonation and the coupling of the coordination state of the 2-pyridinethiolate ligand to the site of protonation are discussed.

  10. Modelling drying kinetics of thyme (Thymus vulgaris L.): theoretical and empirical models, and neural networks.

    Science.gov (United States)

    Rodríguez, J; Clemente, G; Sanjuán, N; Bon, J

    2014-01-01

    The drying kinetics of thyme was analyzed by considering different conditions: air temperature of between 40°C  and 70°C , and air velocity of 1 m/s. A theoretical diffusion model and eight different empirical models were fitted to the experimental data. From the theoretical model application, the effective diffusivity per unit area of the thyme was estimated (between 3.68 × 10(-5) and 2.12 × 10 (-4) s(-1)). The temperature dependence of the effective diffusivity was described by the Arrhenius relationship with activation energy of 49.42 kJ/mol. Eight different empirical models were fitted to the experimental data. Additionally, the dependence of the parameters of each model on the drying temperature was determined, obtaining equations that allow estimating the evolution of the moisture content at any temperature in the established range. Furthermore, artificial neural networks were developed and compared with the theoretical and empirical models using the percentage of the relative errors and the explained variance. The artificial neural networks were found to be more accurate predictors of moisture evolution with VAR ≥ 99.3% and ER ≤ 8.7%.

  11. Theoretical study of fractal growth and stability on surface

    DEFF Research Database (Denmark)

    Dick, Veronika V.; Solov'yov, Ilia; Solov'yov, Andrey V.

    2009-01-01

    We perform a theoretical study of the fractal growing process on surface by using the deposition, diffusion, aggregation method. We present a detailed analysis of the post-growth processes occurring in a nanofractal on surface. For this study we developed a method which describes the internal dyn...... dynamics of particles in a fractal and accounts for their diffusion and detachment. We demonstrate that these kinetic processes are responsible for the formation of the final shape of the islands on surface after the post-growth relaxation.......We perform a theoretical study of the fractal growing process on surface by using the deposition, diffusion, aggregation method. We present a detailed analysis of the post-growth processes occurring in a nanofractal on surface. For this study we developed a method which describes the internal...

  12. Liquefaction chemistry and kinetics: Hydrogen utilization studies

    Energy Technology Data Exchange (ETDEWEB)

    Rothenberger, K.S.; Warzinski, R.P.; Cugini, A.V. [Pittsburgh Energy Technology Center, PA (United States)] [and others

    1995-12-31

    The objectives of this project are to investigate the chemistry and kinetics that occur in the initial stages of coal liquefaction and to determine the effects of hydrogen pressure, catalyst activity, and solvent type on the quantity and quality of the products produced. The project comprises three tasks: (1) preconversion chemistry and kinetics, (2) hydrogen utilization studies, and (3) assessment of kinetic models for liquefaction. The hydrogen utilization studies work will be the main topic of this report. However, the other tasks are briefly described.

  13. Theoretical Study of the Diastereofacial Isomers of Aldrin and Dieldrin

    Directory of Open Access Journals (Sweden)

    Zoran Zdravkovski

    2006-02-01

    Full Text Available The Diels-Alder reaction of hexachlorocyclopentadiene with norbornadiene givesaldrin but theoretically three other diastereofacial isomers are possible. On oxidation theseisomers can generate eight adducts one of which is known as dieldrin. All these, as well asthe corresponding reactions with hexafluorocyclopenadiene were studied by semiempirical(AM1 and PM3 and hybrid density functional (B3LYP methods. Besides the energy levels,the transition states were calculated for the reactions leading to the diastereofacial isomers ofaldrin, which indicate that aldrin is the favored product of the reaction both fromthermodynamic and kinetic point of view.

  14. Theoretical studies of chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Schatz, G.C. [Argonne National Laboratory, IL (United States)

    1993-12-01

    This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

  15. Experimental and theoretical investigations of the kinetics and mechanism of the Cl + 4-hydroxy-4-methyl-2-pentanone reaction

    Science.gov (United States)

    Aslan, L.; Priya, A. Mano; Sleiman, C.; Zeineddine, M. N.; Coddeville, P.; Fittschen, C.; Ballesteros, B.; Canosa, A.; Senthilkumar, L.; El Dib, G.; Tomas, A.

    2017-10-01

    The reaction of 4-hydroxy-4-methyl-2-pentanone (4H4M2P) with Cl atoms was studied for the first time experimentally and theoretically. Relative kinetic measurements were carried out at room temperature and 1 bar of synthetic air/N2 in two different environmental chambers: a 300 L Teflon bag and a 16 L borosilicate glass cell. Reactants, reference compounds and products were monitored either by IR absorption or by GC-FID. Theoretical calculations were performed using the density functional theory method at BH&HLYP level of theory for twelve hydrogen abstraction pathways. The individual rate coefficients for the most favorable H-abstraction pathways were calculated by canonical variational theory using small curvature tunneling method at 298 K. An average experimental rate coefficient of (7.4 ± 0.6) × 10-11 cm3 molecule-1 s-1 was obtained at 298 K, in good agreement with the theoretical rate coefficient. The branching ratios for each reaction channel were evaluated theoretically from the individual rate coefficients of the identified channels. The H-atom abstracted on the -CH2 group appeared to be the dominant channel with a small barrier height. Formaldehyde, acetic acid, HCl, CO2 and CO were identified by IR as the major primary products. The obtained results are presented and discussed in terms of structure-reactivity relationships. A mechanism is suggested for the formation of the observed products. The atmospheric implications of the studied reaction are presented and more particularly, the lifetime of 4H4M2P towards Cl atoms is evaluated to be about 3 days.

  16. Theoretical and simulation studies of seeding methods

    Energy Technology Data Exchange (ETDEWEB)

    Pellegrini, Claudio [Univ. of California, Los Angeles, CA (United States)

    2017-12-11

    We report the theoretical and experimental studies done with the support of DOE-Grant DE-SC0009983 to increase an X-ray FEL peak power from the present level of 20 to 40 GW to one or more TW by seeding, undulator tapering and using the new concept of the Double Bunch FEL.

  17. Synthesis, crystal structure, theoretical study and luminescence ...

    Indian Academy of Sciences (India)

    Synthesis, crystal structure, theoretical study and luminescence property of a butterfly-like W/Cu/S cluster with 1,10-phenanthroline. AI-HUA CHENa,b, SU-CI MENGc,d, JIN-FANG ZHANGb,c and CHI ZHANGb,c,∗. aSchool of Chemical & Chemical Engineering, Yancheng Institute of Technology, Yancheng 224051,.

  18. EXPERIMENT AL AND THEORETICAL STUDY OF PRECAST ...

    African Journals Online (AJOL)

    EXPERIMENT AL AND THEORETICAL STUDY OF PRECAST BEAM-SLAB. CONSTRUCTION. Girma Zerayohannes and Adil Zekaria. Department of Civil Engineering. Addis Ababa University. ABSTRACT. The use of partially precast beam elements ivith shear connectors in slab construction relieves the requirement of ...

  19. Theoretical Studies of Rare Gas Halide Systems

    Science.gov (United States)

    1988-11-01

    The Journal of Chemical Physics , Vol...Mixtures of Hydrogen and Rare Gases." The Journal of Chemical Physics , Vol. 49, No. 12, pp. 5426-5437, December 1968. 6. Jacox, M.E., "Matrix Isolation...Xe+H." The Journal of Chemical Physics , Vol. 68, No. 11, pp. 4917-4929, June 1978. 8. Matcha, R.L., and Milleur, M.B., "Theoretical Studies

  20. New constraints on kinetic isotope effects during CO2(aq) hydration and hydroxylation: Revisiting theoretical and experimental data

    Science.gov (United States)

    Sade, Ziv; Halevy, Itay

    2017-10-01

    CO2 (de)hydration (i.e., CO2 hydration/HCO3- dehydration) and (de)hydroxylation (i.e., CO2 hydroxylation/HCO3- dehydroxylation) are key reactions in the dissolved inorganic carbon (DIC) system. Kinetic isotope effects (KIEs) during these reactions are likely to be expressed in the DIC and recorded in carbonate minerals formed during CO2 degassing or dissolution of gaseous CO2. Thus, a better understanding of KIEs during CO2 (de)hydration and (de)hydroxylation would improve interpretations of disequilibrium compositions in carbonate minerals. To date, the literature lacks direct experimental constraints on most of the oxygen KIEs associated with these reactions. In addition, theoretical estimates describe oxygen KIEs during separate individual reactions. The KIEs of the related reverse reactions were neither derived directly nor calculated from a link to the equilibrium fractionation. Consequently, KIE estimates of experimental and theoretical studies have been difficult to compare. Here we revisit experimental and theoretical data to provide new constraints on oxygen KIEs during CO2 (de)hydration and (de)hydroxylation. For this purpose, we provide a clearer definition of the KIEs and relate them both to isotopic rate constants and equilibrium fractionations. Such relations are well founded in studies of single isotope source/sink reactions, but they have not been established for reactions that involve dual isotopic sources/sinks, such as CO2 (de)hydration and (de)hydroxylation. We apply the new quantitative constraints on the KIEs to investigate fractionations during simultaneous CaCO3 precipitation and HCO3- dehydration far from equilibrium.

  1. Theoretical study on high order interior tomography

    Science.gov (United States)

    Yang, Jiansheng; Cong, Wenxiang; Jiang, Ming; Wang, Ge

    2013-01-01

    In this paper, we study a new type of high order interior problems characterized by high order differential phase shift measurement. This problem is encountered in local x-ray phase-contrast tomography. Here we extend our previous theoretical framework from interior CT to interior differential phase-contrast tomography, and establish the solution uniqueness in this context. We employ the analytic continuation method and high order total variation minimization which we developed in our previous work for interior CT, and prove that an image in a region of interest (ROI) can be uniquely reconstructed from truncated high order differential projection data if the image is known a priori in a sub-region of the ROI or the image is piecewise polynomial in the ROI. Preliminary numerical experiments support the theoretical finding. PMID:23324783

  2. Theoretical study on a water muffler

    Science.gov (United States)

    Du, T.; Chen, Y. W.; Miao, T. C.; Wu, D. Z.

    2016-05-01

    Theoretical computation on a previously studied water muffler is carried out in this article. Structure of the water muffler is composed of two main parts, namely, the Kevlar- reinforced rubber tube and the inner-noise-reduction structure. Rubber wall of the rubber tube is assumed to function as rigid wall lined with sound absorption material and is described by a complex radial wave number. Comparison among the results obtained from theoretical computation, FEM (finite element method) simulation and experiment of the rubber tube and that of the water muffler has been made. The theoretical results show a good accordance in general tendency with the FEM simulated and the measured results. After that, parametric study on the diameter of the inner structure and that of the rubber tube is conducted. Results show that the diameter of the left inner structure has the most significant effect on the SPL of the water muffler due to its location and its effect on the diameter ratio D2/D1.

  3. Statistical optimization and kinetic studies of enhanced ...

    African Journals Online (AJOL)

    The objectives of this study were to investigate and evaluate through Taguchi orthogonal experimental design the effects of amendment agents as well as the optimization and kinetics of enhanced bioremediation of crude oil-contaminated marine water using combined adsorption-biostimulation strategy. The amendment ...

  4. CO oxidation on gold nanoparticles: Theoretical studies

    DEFF Research Database (Denmark)

    Remediakis, Ioannis; Lopez, Nuria; Nørskov, Jens Kehlet

    2005-01-01

    We present a summary of our theoretical results regarding CO oxidation on both oxide-supported and isolated gold nanoparticles. Using Density Functional Theory we have studied the adsorption of molecules and the oxidation reaction of CO on gold clusters. Low-coordinated sites on the gold...... nanoparticles can adsorb small inorganic molecules such as O2 and CO, and the presence of these sites is the key factor for the catalytic properties of supported gold nanoclusters. Other contributions, induced by the presence of the support, can provide parallel channels for the reaction and modulate the final...

  5. Theoretical prediction of selectivity in kinetic resolution of secondary alcohols catalyzed by chiral DMAP derivatives.

    Science.gov (United States)

    Larionov, Evgeny; Mahesh, Mohan; Spivey, Alan C; Wei, Yin; Zipse, Hendrik

    2012-06-06

    The mechanism of esterification of the secondary alcohol 1-(1-naphthyl)ethanol 9 by isobutyric anhydride catalyzed by 4-pyrrolidinopyridine (PPY, 11) and a series of single enantiomer atropisomeric 4-dialkylaminopyridines 8a-g has been studied computationally at the B3LYP/6-311+G(d,p)//B3LYP/6-31G(d) level. Comparison of the levels of enantioselectivity predicted computationally with the results obtained experimentally allowed the method to be validated. The value of the approach is demonstrated by the successful prediction that a structural modification of an aryl group within the catalyst from phenyl to 3,5-dimethylphenyl would lead to improved levels of selectivity in this type of kinetic resolution (KR) reaction, as was subsequently verified following synthesis and evaluation of this catalyst (8d). Experimentally, the selectivity of this type of KR is found to exhibit a significant deuterium isotope effect (for 9 vs d(1)-9).

  6. Theoretical studies of hadrons and nuclei

    Energy Technology Data Exchange (ETDEWEB)

    COTANCH, STEPHEN R

    2007-03-20

    This report details final research results obtained during the 9 year period from June 1, 1997 through July 15, 2006. The research project, entitled Theoretical Studies of Hadrons and Nuclei , was supported by grant DE-FG02-97ER41048 between North Carolina State University [NCSU] and the U. S. Department of Energy [DOE]. In compliance with grant requirements the Principal Investigator [PI], Professor Stephen R. Cotanch, conducted a theoretical research program investigating hadrons and nuclei and devoted to this program 50% of his time during the academic year and 100% of his time in the summer. Highlights of new, significant research results are briefly summarized in the following three sections corresponding to the respective sub-programs of this project (hadron structure, probing hadrons and hadron systems electromagnetically, and many-body studies). Recent progress is also discussed in a recent renewal/supplemental grant proposal submitted to DOE. Finally, full detailed descriptions of completed work can be found in the publications listed at the end of this report.

  7. Performance enhancement by unsteady-state reactor operation: Theoretical analysis for two-sites kinetic model

    OpenAIRE

    Reshetnikov, S. I.; Ivanov, E. A.; Kiwi-Minsker, L; Renken, A.

    2003-01-01

    Theor. anal. of the reactor performance under unsteady-state conditions was carried out. The reactions are described by two kinetic models, which involve the participation in catalytic reaction of two types of active sites. The kinetic model I assumes the blocking of one of the active sites by a reactant, and the kinetic model II suggests a transformation of active sites of one type into another under the effect of the reaction temp. The unsteady-state conditions on the catalyst surface are s...

  8. Theoretical pluralism in psychoanalytic case studies

    Science.gov (United States)

    Willemsen, Jochem; Cornelis, Shana; Geerardyn, Filip M.; Desmet, Mattias; Meganck, Reitske; Inslegers, Ruth; Cauwe, Joachim M. B. D.

    2015-01-01

    The aim of this study is to provide an overview of the scientific activity of different psychoanalytic schools of thought in terms of the content and production of case studies published on ISI Web of Knowledge. Between March 2013 and November 2013, we contacted all case study authors included in the online archive of psychoanalytic and psychodynamic case studies (www.singlecasearchive.com) to inquire about their psychoanalytic orientation during their work with the patient. The response rate for this study was 45%. It appears that the two oldest psychoanalytic schools, Object-relations psychoanalysis and Ego psychology or “Classical psychoanalysis” dominate the literature of published case studies. However, most authors stated that they feel attached to two or more psychoanalytic schools of thought. This confirms that the theoretical pluralism in psychoanalysis stretches to the field of single case studies. The single case studies of each psychoanalytic school are described separately in terms of methodology, patient, therapist, or treatment features. We conclude that published case studies features are fairly similar across different psychoanalytic schools. The results of this study are not representative of all psychoanalytic schools, as some do not publish their work in ISI ranked journals. PMID:26483725

  9. Theoretical pluralism in psychoanalytic case studies.

    Science.gov (United States)

    Willemsen, Jochem; Cornelis, Shana; Geerardyn, Filip M; Desmet, Mattias; Meganck, Reitske; Inslegers, Ruth; Cauwe, Joachim M B D

    2015-01-01

    The aim of this study is to provide an overview of the scientific activity of different psychoanalytic schools of thought in terms of the content and production of case studies published on ISI Web of Knowledge. Between March 2013 and November 2013, we contacted all case study authors included in the online archive of psychoanalytic and psychodynamic case studies (www.singlecasearchive.com) to inquire about their psychoanalytic orientation during their work with the patient. The response rate for this study was 45%. It appears that the two oldest psychoanalytic schools, Object-relations psychoanalysis and Ego psychology or "Classical psychoanalysis" dominate the literature of published case studies. However, most authors stated that they feel attached to two or more psychoanalytic schools of thought. This confirms that the theoretical pluralism in psychoanalysis stretches to the field of single case studies. The single case studies of each psychoanalytic school are described separately in terms of methodology, patient, therapist, or treatment features. We conclude that published case studies features are fairly similar across different psychoanalytic schools. The results of this study are not representative of all psychoanalytic schools, as some do not publish their work in ISI ranked journals.

  10. Theoretical studies on aerosol agglomeration processes

    Energy Technology Data Exchange (ETDEWEB)

    Lehtinen, K.E.J. [VTT Energy, Espoo (Finland). Energy Use

    1997-12-31

    In this thesis, theoretical modeling of certain aerosol systems has been presented. At first, the aerosol general dynamic equation is introduced, along with a discretization routine for its numerical solution. Of the various possible phenomena affecting aerosol behaviour, this work is mostly focused on aerosol agglomeration. The fundamentals of aerosol agglomeration theory are thus briefly reviewed. The two practical applications of agglomeration studied in this thesis are flue gas cleaning using an electrical agglomerator and nanomaterial synthesis with a free jet reactor. In an electrical agglomerator the aerosol particles are charged and brought into an alternating electric field. The aim is to remove submicron particles from flue gases by collisions with larger particles before conventional gas cleaning devices that have a clear penetration window in the problematic 0.1-1{mu}m size range. A mathematical model was constructed to find out the effects of the different system parameters on the agglomerator`s performance. A crucial part of this task was finding out the collision efficiencies of particles of varying size and charge. The original idea was to use unipolar charging of the particles, and a laboratory scale apparatus was constructed for this purpose. Both theory and experiments clearly show that significant removal of submicron particles can not be achieved by such an arrangement. The theoretical analysis further shows that if the submicron particles and the large collector particles were charged with opposite polarity, significant removal of the submicron particles could be obtained. The second application of agglomeration considered in this thesis is predicting/controlling nanoparticle size in the gas-to-particle aerosol route to material synthesis. In a typical material reactor, a precursor vapor reacts to form molecules of the desired material. In a cooling environment, a particulate phase forms, the dynamics of which are determined by the rates of

  11. Coal pyrolysis: Thermogravimetric study and kinetic modelling

    Energy Technology Data Exchange (ETDEWEB)

    Coll, T.; Perales, J.F.; Arnaldos, J.; Casal, J. (Dept. of Chemical Engineering, Universidad Politecnica de Cataluna, Barcelona (Spain))

    1992-02-03

    In this experimental study on coal pyrolysis it was found that heat transfer and heating rate have an important influence on the results obtained. A model has been developed which takes into account these aspects. The kinetic parameters were determined using a differential method and the experimental data obtained at low heating rates. The agreement between the predictions of the model, for any heating rate, and the experimental values is fairly good. 8 figs., 2 tabs., 10 refs.

  12. Theoretical Investigation of Kinetic Processes in Small Radicals of Importance in Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, Millard [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Dagdigian, Paul J. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry

    2017-12-12

    Our group studies inelastic and reactive collisions of small molecules, focusing on radicals important in combustion environments. The goal is the better understanding of kinetic processes that may be difficult to access experimentally. An essential component is the accurate determination and fitting of potential energy surfaces (PESs). After fitting the ab initio points to obtain global PESs, we treat the dynamics using time-independent (close-coupling) methods. Cross sections and rate constants for collisions of are determined with our Hibridon program suite . We have studied energy transfer (rotationally, vibrationally, and/or electronically inelastic) in small hydrocarbon radicals (CH2 and CH3) and the CN radical. We have made a comparison with experimental measurements of relevant rate constants for collisions of these radicals. Also, we have calculated accurate transport properties using state-of-the-art PESs and to investigate the sensitivity to these parameters in 1-dimensional flame simulations. Of particular interest are collision pairs involving the light H atom.

  13. Studies In Theoretical High Energy Particle Physics

    Energy Technology Data Exchange (ETDEWEB)

    Keung, Wai Yee [Univ. of Illinois, Chicago, IL (United States)

    2017-07-01

    This is a final technical report for grant no. DE-SC0007948 describing research activities in theoretical high energy physics at University of Illinois at Chicago for the whole grant period from July 1, 2012 to March 31, 2017.

  14. Vibrational and theoretical study of selected diacetylenes.

    Science.gov (United States)

    Roman, Maciej; Baranska, Malgorzata

    2013-11-01

    Six commonly used disubstituted diacetylenes with short side-chains (RCCCCR, where R=CH2OH, CH2OPh, C(CH3)2OH, C(CH3)3, Si(CH3)3, and Ph) were analyzed using vibrational spectroscopy and quantum-chemical calculations to shed new light on structural and spectroscopic properties of these compounds. Prior to that the conformational analysis of diacetylenes was performed to search the Potential Energy Surface for low-energy minima. Theoretical investigations were followed by the potential energy distribution (PED) analysis to gain deeper insight into FT-Raman and FT-IR spectra that, in some cases, were recorded for the first time for the studied compounds. The analysis was focused mainly on spectral features of the diacetylene system sensitive to the substitution. Shifts of the characteristic bands and changes in bond lengths were observed when changing the substituent. Furthermore, Fermi resonance was observed in the vibrational spectra of some diacetylenes. FT-IR spectra were measured by using two methods, i.e. transmission (with KBr substrate) and Attenuated Total Reflection (ATR), showing the latter adequate and fast tool for IR measurements of diacetylenes. Additionally, Surface Enhanced Raman Spectroscopy (SERS) was applied for phenyl derivative for the first time to study its interaction with metallic nanoparticles that seems to be perpendicular. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Theoretical study on mechanism, kinetics, and thermochemistry of ...

    Indian Academy of Sciences (India)

    O)OCH2CF3) with OH rad- icals using a ... sess any chlorine atom. This shows .... energy correction, kB and h are the Boltzmann and the Planck's constants, and R represents the universal gas constant. The tunneling correction factor κ(T ) is.

  16. Electron kinetics dependence on gas pressure in laser-induced oxygen plasma experiment: Theoretical analysis

    Science.gov (United States)

    Gamal, Yosr E. E.-D.; Abdellatif, Galila

    2017-08-01

    A study is performed to investigate the dependency of threshold intensity on gas pressure observed in the measurements of the breakdown of molecular oxygen that carried out by Phuoc (2000) [1]. In this experiment, the breakdown was induced by 532 nm laser radiation of pulse width 5.5 ns and spot size of 8.5 μm, in oxygen over a wide pressure range (190-3000 Torr). The analysis aimed to explore the electron kinetic reliance on gas pressure for the separate contribution of each of the gain and loss processes encountered in this study. The investigation is based on an electron cascade model applied previously in Gamal and Omar (2001) [2] and Gaabour et al. (2013) [3]. This model solves numerically a differential equation designates the time evolution of the electron energy distribution, and a set of rate equations that describe the change of excited states population. The numerical examination of the electron energy distribution function and its parameters revealed that photo-ionization of the excited molecules plays a significant role in enhancing the electron density growth rate over the whole tested gas pressure range. This process is off set by diffusion of electrons out of the focal volume in the low-pressure regime. At atmospheric pressure electron, collisional processes dominate and act mainly to populate the excited states. Hence photo-ionization becomes efficient and compete with the encountered loss processes (electron diffusion, vibrational excitation of the ground state molecules as well as two body attachments). At high pressures ( 3000 Torr) three body attachments are found to be the primary cause of losses which deplete the electron density and hence results in the slow decrease of the threshold intensity.

  17. Theoretical study of free electron laser physics

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Jae Gwon; Cho, Sung Oh; Jeong, Young Uk; Kim, Sun Kook; Lee, Byung Cheol; Cha, Byung Heon; Lee, Jong Min [Korea Atomic Energy Research Institute, Taejeon (Korea)

    2000-04-01

    A theoretical study of free electron laser physics is presented in this report. In particular, an analysis is given of the free electron laser with a linearly polarized magnetic wiggler. We describe the basic electron dynamics and gain mechanism in a free electron laser by solving the one-body classical Lorentz force equations in the presence of a periodic magnetic field and a plane electromagnetic wave. Phase space paths for electrons analogously related to those of a simple pendulum are used to describe the laser gain and saturation, and the evolution of the electron beam energy and position distributions. We present an analysis of the single-mode problem and a self-consistent nonlinear treatment of the finite transverse dimensional effects associated with the free electron laser in a steady state. Results computed by applying an external D.C. electric field to the system are discussed for investigating efficiency enhancement of the free electron lasers. Finally optical guiding effect in small signal regime is described to investigate the possibility of amplifying radiation fields in very long wigglers for large gain and high extraction efficiency. 14 refs., 45 figs. (Author)

  18. Adsorption studies of molasse's wastewaters on activated carbon: modelling with a new fractal kinetic equation and evaluation of kinetic models.

    Science.gov (United States)

    Figaro, S; Avril, J P; Brouers, F; Ouensanga, A; Gaspard, S

    2009-01-30

    Adsorption kinetic of molasses wastewaters after anaerobic digestion (MSWD) and melanoidin respectively on activated carbon was studied at different pH. The kinetic parameters could be determined using classical kinetic equations and a recently published fractal kinetic equation. A linear form of this equation can also be used to fit adsorption data. Even with lower correlation coefficients the fractal kinetic equation gives lower normalized standard deviation values than the pseudo-second order model generally used to fit adsorption kinetic data, indicating that the fractal kinetic model is much more accurate for describing the kinetic adsorption data than the pseudo-second order kinetic model.

  19. ENZYMATIC KINETIC STUDY HYDROLASE FROM CITRUS

    Directory of Open Access Journals (Sweden)

    Israel Hernández

    2015-09-01

    Full Text Available In this paper the degrading activity of enzymes derived from orange peels (Citrus x sinensis, grapefruit (Citrus paradise and pineapple (Ananas comosus on the organic matter in wastewater is evaluated. This activity is measured indirectly by quantifying the biochemical oxygen demand (COD before and after degradation process based on a period of time using the HACH DR / 2010, and then the kinetic study was performed by the differential method and integral with the experimental data, obtaining a reaction order of 1 to pectinase (orange, and order 2 for bromelain (pineapple.

  20. Theoretical study of bone sialoprotein in bone biomineralization

    CSIR Research Space (South Africa)

    Yang

    2011-05-01

    Full Text Available -1 Cells Tissues Organs DOI: 10.1159/000324648 Theoretical Study of Bone Sialoprotein in Bone Biomineralization Yang Yanga Donald Mkhontoe Qiang Cuib Nita Sahaia, c, d a Department of Geoscience, b Department of Chemistry and Theoretical...

  1. EXPERIMENTAL AND THEORETICAL NMR STUDY OF 4-(1 ...

    African Journals Online (AJOL)

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    experimental and theoretical data have showed that the molecular geometry and the ... 1D and 2D hetero- and homonuclear NMR methods enable to ... The essence of this study is briefly to report experimental and theoretical NMR features of.

  2. Theoretical study of conjugated porphyrin polymers

    DEFF Research Database (Denmark)

    Pedersen, T.G.; Lynge, T.B.; Kristensen, P.K.

    2005-01-01

    for these applications. From a theoretical analysis of excitons in long metalloporphyrin chains, we demonstrate that the binding energy is much lower than in usual conjugated polymers. Our calculated absorption spectra are in good agreement with measurements. (c) 2004 Elsevier B.V. All rights reserved....

  3. Theoretical Studies in Elementary Particle Physics

    Energy Technology Data Exchange (ETDEWEB)

    Collins, John C.; Roiban, Radu S

    2013-04-01

    This final report summarizes work at Penn State University from June 1, 1990 to April 30, 2012. The work was in theoretical elementary particle physics. Many new results in perturbative QCD, in string theory, and in related areas were obtained, with a substantial impact on the experimental program.

  4. Theoretical study of the electron paramagnetic resonance ...

    Indian Academy of Sciences (India)

    Abstract. The electron paramagnetic resonance (EPR) parameters (the g factors, hy- perfine structure constants and the superhyperfine parameters) for the tetragonal Ir2+ centre in NaCl are theoretically investigated from the perturbation formulas of these parameters for a 5d7 ion in tetragonally elongated octahedra.

  5. Stochastic optimization-based study of dimerization kinetics

    Indian Academy of Sciences (India)

    We investigate the potential of numerical algorithms to decipher the kinetic parameters involved in multi-step chemical reactions. To this end, we study dimerization kinetics of protein as a model system. We follow the dimerization kinetics using a stochastic simulation algorithm and combine it with three different optimization ...

  6. A Kinetic Study of the Electrochemical Vapor Deposition of Solid Oxide Electrolyte Films on Porous Substrates

    NARCIS (Netherlands)

    Lin, Y.S.; de Haart, L.G.J.; de Vries, K.J.; Burggraaf, A.J.

    1990-01-01

    The electrochemical vapor deposition (EVD) method is a very promising technique for making gas-tight dense solidelectrolyte films on porous substrates. In this paper, theoretical and experimental studies on the kinetics of the depositionof dense yttria-stabilized zirconia films on porous ceramic

  7. Effects of solution composition on the theoretical prediction of ice nucleation kinetics and thermodynamics.

    Science.gov (United States)

    Karlsson, Jens O M

    2010-02-01

    Predictions by various mathematical models of intracellular ice formation (proposed by Mazur, Pitt, Toner, and Karlsson, respectively) were compared to the known thermodynamic and kinetic behavior of ice formation in supercooled aqueous systems. The older models (Mazur, Pitt, and Toner) significantly underestimated the magnitude of colligative nonequilibrium freezing point depression in response to increased concentration of solutes, such as salts or cryoprotectants. Furthermore, kinetics predicted using phenomenological models (by Mazur and Pitt) exhibited implausible temperature-dependence, with the probability of intracellular ice formation being allowed to increase even at temperatures below the glass transition point. The Toner model, on the other hand, produced invalid results at temperatures below -48 degrees C. The Karlsson model was the only model that consistently yielded realistic predictions over a wide range of temperatures and solute concentrations, especially in the presence of cryoprotectant additives. To facilitate adoption of the Karlsson model of intracellular ice nucleation, the complete set of model equations has been collected and described in detail. Copyright 2009 Elsevier Inc. All rights reserved.

  8. Novae a theoretical and observational study

    Science.gov (United States)

    Soraisam, Monika D.

    2016-02-01

    In this thesis, we present studies relating to novae that include both theoretical and ob- servational aspects. Being hosted by accreting white dwarfs (WDs), they have drawn attention in the context of the supernova Ia (SN Ia) progenitor problem. In the case of the nova explosion, the WD host is not disrupted. Instead, it continues to supply energy, even after the optical outbust, via stable nuclear burning of the remnant hydrogen envelope that survived the outburst. Accordingly, nova emission progresses toward the harder part of the electromagnetic spectrum, where it lasts longer than in the optical regime. As a consequence, novae are found to constitute the majority of the observed supersoft X-ray sources (SSSs). This is particularly well established for the galaxy M31. For high mass accretion rates in the unstable nuclear burning regime (or nova regime), there is evidence that significant mass accumulation by the WD is possible. This paved the way for SN Ia progenitor models in the single degenerate (SD) scenario involving novae. Based on the statistics of novae in M31, which is the most frequently used target for nova surveys, we investigate the role that novae may play in producing SNe Ia. Using multicycle nova evolution models and the observationally inferred nova rate in M31, we estimate the maximal SN Ia rate that novae can produce, assuming that all of the involved WDs reach the Chandrasekhar mass. Comparing this rate to the observationally inferred SN Ia rate for M31 constrains the contribution of the nova channel to the SN Ia rate to 2-7%. Additionally, we demonstrate that a more powerful diagnostic can be obtained from statistics of fast novae, which are characterized by decline times t2 10 days. Most novae resulting from a typical SD SN Ia progenitor accreting in the nova regime are fast. Specifically, as the WD in the nova grows in mass, it produces novae more frequently and with decreasing decline times. We therefore investigate how efficiently fast

  9. The Thermodynamic and Kinetic Properties of 2-Hydroxypyridine/2-Pyridone Tautomerization: A Theoretical and Computational Revisit

    Directory of Open Access Journals (Sweden)

    Safiyah A. Hejazi

    2016-11-01

    Full Text Available The gas-phase thermal tautomerization reaction between 2-hydroxypyridine (2-HPY and 2-pyridone (2-PY was investigated by applying 6-311++G** and aug-cc-pvdz basis sets incorporated into some density functional theory (DFT and coupled cluster with singles and doubles (CCSD methods. The geometrical structures, dipole moments, HOMO-LUMO energy gaps, total hyperpolarizability, kinetics and thermodynamics functions were monitored against the effects of the corrections imposed on these functionals. The small experimental energy difference between the two tautomers of 3.23 kJ/mol; was a real test of the accuracy of the applied levels of theory. M062X and CCSD methods predicted the preference of 2-HPY over 2-PY by 5–9 kJ/mol; while B3LYP functional favoured 2-PY by 1–3 kJ/mol. The CAM-B3LYP and ωB97XD functionals yielded mixed results depending on the basis set used. The source of preference of 2-HPY is the minimal steric hindrance and electrostatic repulsion that subdued the huge hyperconjugation in 2-PY. A 1,3-proton shift intramolecular gas-phase tautomerization yielded a high average activation of 137.152 kJ/mol; while the intermolecular mixed dimer interconversion gave an average barrier height of 30.844 kJ/mol. These findings are boosted by a natural bond orbital (NBO technique. The low total hyperpolarizabilities of both tautomers mark out their poor nonlinear optical (NLO behaviour. The enhancement of the total hyperpolarizability of 2-HPY over that of 2-PY is interpreted by the bond length alternation.

  10. Kinetic study of compost liquor nitrification.

    Science.gov (United States)

    Gagnaire, J; Wang, X Y; Chapon, L; Moulin, P; Marrot, B

    2011-01-01

    This study is a first kinetic approach about the compost liquor treatment by activated sludge. This industrial wastewater is highly loaded in organic and nitrogen compounds (COD≈12,000 mg L(-1) and NH(4)(+)-N≈4,000 mg L(-1)). The possibility of its treatment in an urban WWTP is studied measuring ammonia oxidation rate with non-acclimated sludge to the industrial effluent. Compost liquor appears as an inhibitor substrate. The ammonia oxidation rate can be modelled by the Haldane model: U(MAX)=0.180 d(-1), K(S)=12.0 mgN.L(-1) and K(I)=26.0 mgN.L(-1). The ammonia oxidation rate also follows for a synthetic substrate which has the same pollutant load as the real substrate. In this case, the ammonia oxidation rate can be modelled by the Monod model: U(MAX)=0.073 d(-1) and K(S)=4.3 mgN.L(-1). This result confirms that the ammonia oxidising bacteria are inhibited by the real wastewater. The following-up of nitrate production shows also the inhibition of nitrite oxidising bacteria. The compost liquor treatment seems not possible in an urban WWTP (<50,000 p.e.). That's why a specific WWTP is recommended and an acclimation step of activated sludge is essential.

  11. Experimental and theoretical study of horizontal-axis wind turbines

    OpenAIRE

    Anderson, Michael Broughton

    1981-01-01

    An experimental and theoretical study of horizontal-axis wind turbines is undertaken. The theoretical analyses cover the four major areas of aerodynamics, turbulence. aeroelasticity and blade optimisation. EXisting aerodynamic theories based on blade-element theory for predicting the loads on a wind turbine blade are reviewed and extended to include non-uniform flow, tip losses and the 'turbulent wake' state. A theoretical model based on a free vortex representation of a ...

  12. Combustion Kinetic Studies of Gasolines and Surrogates

    KAUST Repository

    Javed, Tamour

    2016-11-01

    Future thrusts for gasoline engine development can be broadly summarized into two categories: (i) efficiency improvements in conventional spark ignition engines, and (ii) development of advance compression ignition (ACI) concepts. Efficiency improvements in conventional spark ignition engines requires downsizing (and turbocharging) which may be achieved by using high octane gasolines, whereas, low octane gasolines fuels are anticipated for ACI concepts. The current work provides the essential combustion kinetic data, targeting both thrusts, that is needed to develop high fidelity gasoline surrogate mechanisms and surrogate complexity guidelines. Ignition delay times of a wide range of certified gasolines and surrogates are reported here. These measurements were performed in shock tubes and rapid compression machines over a wide range of experimental conditions (650 – 1250 K, 10 – 40 bar) relevant to internal combustion engines. Using the measured the data and chemical kinetic analyses, the surrogate complexity requirements for these gasolines in homogeneous environments are specified. For the discussions presented here, gasolines are classified into three categories: (i)\\tLow octane gasolines including Saudi Aramco’s light naphtha fuel (anti-knock index, AKI = (RON + MON)/2 = 64; Sensitivity (S) = RON – MON = 1), certified FACE (Fuels for Advanced Combustion Engines) gasoline I and J (AKI ~ 70, S = 0.7 and 3 respectively), and their Primary Reference Fuels (PRF, mixtures of n-heptane and iso-octane) and multi-component surrogates. (ii)\\t Mid octane gasolines including FACE A and C (AKI ~ 84, S ~ 0 and 1 respectively) and their PRF surrogates. Laser absorption measurements of intermediate and product species formed during gasoline/surrogate oxidation are also reported. (iii)\\t A wide range of n-heptane/iso-octane/toluene (TPRF) blends to adequately represent the octane and sensitivity requirements of high octane gasolines including FACE gasoline F and G

  13. Theoretical & Experimental Studies of Elementary Particles

    Energy Technology Data Exchange (ETDEWEB)

    McFarland, Kevin [Univ. of Rochester, NY (United States)

    2012-10-04

    Abstract High energy physics has been one of the signature research programs at the University of Rochester for over 60 years. The group has made leading contributions to experimental discoveries at accelerators and in cosmic rays and has played major roles in developing the theoretical framework that gives us our ``standard model'' of fundamental interactions today. This award from the Department of Energy funded a major portion of that research for more than 20 years. During this time, highlights of the supported work included the discovery of the top quark at the Fermilab Tevatron, the completion of a broad program of physics measurements that verified the electroweak unified theory, the measurement of three generations of neutrino flavor oscillations, and the first observation of a ``Higgs like'' boson at the Large Hadron Collider. The work has resulted in more than 2000 publications over the period of the grant. The principal investigators supported on this grant have been recognized as leaders in the field of elementary particle physics by their peers through numerous awards and leadership positions. Most notable among them is the APS W.K.H. Panofsky Prize awarded to Arie Bodek in 2004, the J.J. Sakurai Prizes awarded to Susumu Okubo and C. Richard Hagen in 2005 and 2010, respectively, the Wigner medal awarded to Susumu Okubo in 2006, and five principal investigators (Das, Demina, McFarland, Orr, Tipton) who received Department of Energy Outstanding Junior Investigator awards during the period of this grant. The University of Rochester Department of Physics and Astronomy, which houses the research group, provides primary salary support for the faculty and has waived most tuition costs for graduate students during the period of this grant. The group also benefits significantly from technical support and infrastructure available at the University which supports the work. The research work of the group has provided educational opportunities

  14. Theoretical Studies of Hydrogen Storage Alloys.

    Energy Technology Data Exchange (ETDEWEB)

    Jonsson, Hannes

    2012-03-22

    Theoretical calculations were carried out to search for lightweight alloys that can be used to reversibly store hydrogen in mobile applications, such as automobiles. Our primary focus was on magnesium based alloys. While MgH{sub 2} is in many respects a promising hydrogen storage material, there are two serious problems which need to be solved in order to make it useful: (i) the binding energy of the hydrogen atoms in the hydride is too large, causing the release temperature to be too high, and (ii) the diffusion of hydrogen through the hydride is so slow that loading of hydrogen into the metal takes much too long. In the first year of the project, we found that the addition of ca. 15% of aluminum decreases the binding energy to the hydrogen to the target value of 0.25 eV which corresponds to release of 1 bar hydrogen gas at 100 degrees C. Also, the addition of ca. 15% of transition metal atoms, such as Ti or V, reduces the formation energy of interstitial H-atoms making the diffusion of H-atoms through the hydride more than ten orders of magnitude faster at room temperature. In the second year of the project, several calculations of alloys of magnesium with various other transition metals were carried out and systematic trends in stability, hydrogen binding energy and diffusivity established. Some calculations of ternary alloys and their hydrides were also carried out, for example of Mg{sub 6}AlTiH{sub 16}. It was found that the binding energy reduction due to the addition of aluminum and increased diffusivity due to the addition of a transition metal are both effective at the same time. This material would in principle work well for hydrogen storage but it is, unfortunately, unstable with respect to phase separation. A search was made for a ternary alloy of this type where both the alloy and the corresponding hydride are stable. Promising results were obtained by including Zn in the alloy.

  15. kinetic studies of colour and phenol removal from wastewater using ...

    African Journals Online (AJOL)

    user

    Kinetic studies by batch technique were carried out using activated carbon prepared from mango seed shell for the adsorption of colour and phenol from wastewater. The data generated from the studies were used for kinetic modelling in order to determine the rate and mechanism of adsorption. The results revealed that ...

  16. Theoretical Studies of Small-System Thermodynamics in Energetic Materials

    Science.gov (United States)

    2016-01-06

    SECURITY CLASSIFICATION OF: This is a comprehensive theoretical research program to investigate the fundamental principles of small-system thermodynamics ...a.k.a. nanothermodynamics). The proposed work is motivated by our desire to better understand the fundamental dynamics and thermodynamics of...for Public Release; Distribution Unlimited Final Report: Theoretical Studies of Small-System Thermodynamics in Energetic Materials The views, opinions

  17. Kinetic studies of stress-corrosion cracking

    Science.gov (United States)

    Noronha, P. J.

    1977-01-01

    Use of time-to-failure curves for stress-corrosion cracking processes may lead to incorrect estimates of structural life, if material is strongly dependent upon prestress levels. Technique characterizes kinetics of crackgrowth rates and intermediate arrest times by load-level changes.

  18. Theoretical Study of Semiconductor Laser under Modulation

    Science.gov (United States)

    Boukari, O.; Hassine, L.; Dherbecourt, P.; Latry, O.; Ketata, M.; Bouchriha, H.

    2007-09-01

    In this paper we present a description of the chirp induced in a direct modulated DFB laser. Our study is follows two different approaches. The first approach is based on a resolution of the rate equations of laser; the second, on a simulation of a heterodyne system with the Optisystem software. This study enables us to visualize the chirp in the RF field. We also characterize it according to the injection current i(t) parameters, such as the amplitude and the frequency of the modulation. The aim of our study is to choose the appropriate values of these parameters, in order to use the direct modulated DFB laser as an optical tunable source for Coherent Optical Frequency Domain Reflectometry technique (C-OFDR). We demonstrate that the optical frequency of these lasers can be controlled via the injection current i(t) and it can be linearly swept (chirped) over some tens of gigahertz.

  19. Theoretical Studies Of Small Boson Clusters

    CERN Document Server

    Chen, Y

    2005-01-01

    This work uses the DVR method to study the vibrational states of small boson clusters. With the adiabatic hyperspherical approximation, the lower and upper bounds of the bound states of the helium trimer are calculated. The first fully converged 3-dimensional basis set variational calculation for this system is carried out using Pekeris coordinates and the Laguerre basis functions. Two bound states are found for the system, as well as a third state which might be an Efimov state. The same method is used to study the bound states and resonance states of the neon trimer using a realistic potential, and proved to be efficient and accurate.

  20. Theoretical aspects of solid state reactions in a mixed particulate ensemble and kinetics of lead zirconate formation

    Energy Technology Data Exchange (ETDEWEB)

    Chandratreya, S.S.

    1979-09-01

    A theoretical analysis was carried out to estimate the quasi-steady-state external mass transport by lattice, surface and gaseous diffusion in terms of the stereologically measurable microstructural parameters of a mixed powder compact. It was shown that the gaseous transport can be described by a single dimensionless quantity termed sublimation transport modulus. Using these equations, the relative importance of the alternate external transport modes can be evaluated. Experimental work determined the reaction isotherms for the formation of lead zirconate from yellow PbO and monoclinic zirconia between 710/sup 0/C to 810/sup 0/C for two zirconia size distributions. The larger zirconia showed diffusion controlled shrinking core kinetics up to about 90 percent reaction while the smaller zirconia indicated a diffusion controlled spherical growth of up to 85 percent reaction after an instantaneous nucleation at a limited number of sites. The difference was attributed to the differences in the mixing time and not to the particulate sizes. It was observed that for the same size range, a longer mixing operation gave a better dispersion of reactants which resulted in a higher nucleation site density required for a shrinking core type of product morphology and faster kinetics. A microprobe profile analysis of partially reacted particles confirmed that for the shorter mixing period, reaction resultedin a nucleation-growth-impingement type of morphology. The activation energy as calculated from the nucleation-growth model fit to the data was 138 Kcal/mole which is close to 131 Kcal/mole reported for Pb/sup 2 +/ diffusion in PbZrO/sub 3/. Approximate calculations show that the gaseous external mass flux of PbO was negligible compared to the lattice or surface diffusive flux.

  1. THEORETICAL STUDY OF CATALYTIC HYDROGENATION OF ...

    African Journals Online (AJOL)

    Preferred Customer

    Hydrogen. (H2). Figure 1. Drawings of molecules contained in the chemical systems studied. During the hydrogenation process of each molecule, one atom of the hydrogen molecule is turned to the oxygen atom O of the adsorbed molecule. At the beginning of process, the distance of OH between those both atoms was 10 ...

  2. Synthesis, Crystal Structure, Theoretical Study, The

    Indian Academy of Sciences (India)

    Supramolecular Isomerism in Nonmolecular Solids? A case study of Copper Pyridazine Halides J. Chem. Sci. 128 1687. 15. Chen C, Ma J F, Liu B, Yang J and Liu Y Y 2011 Two. Unusual 3D Copper(II) Coordination Polymers Con- structed by p-Sulfonated Calixarenes and Bis(triazolyl). Ligands Cryst. Growth Des. 11 4491.

  3. THEORETICAL STUDY ON ELECTRONIC STRUCTURES AND ...

    African Journals Online (AJOL)

    Preferred Customer

    Luminescent materials [1, 2] have extensive applications in medical diagnostics, molecular biology, aviation, and material science. The incorporation of boron atoms into extended organic π-systems is widely studied due to intriguing electronic and photophysical properties. These properties are commonly arisen from the ...

  4. Global Leadership Study: A Theoretical Framework

    Science.gov (United States)

    Perkins, Anne W.

    2009-01-01

    Traditional leadership theory and research courses do not adequately prepare students for cross-cultural leadership. This article notes six premises of Western theories and demonstrates the limitations of these premises in non-Western settings. A framework for the study of cross-cultural leadership, The Global Leadership-Learning Pyramid, is…

  5. Theoretical Frameworks for Studying Female Marriage Migrants

    Science.gov (United States)

    Merali, Noorfarah

    2008-01-01

    Transnational marriages account for a significant proportion of family-based immigration to North America. An increasing number of immigrant men are choosing to marry women from their countries of origin, and an increasing number of nonimmigrant men are choosing to marry women from other countries. Existing studies on the experiences of foreign…

  6. Theoretical and experimental studies on the foundation theoretical and experimental studies on the foundation of mesomechanics

    Science.gov (United States)

    Chudnovsky, A.; Wu, S.

    1992-06-01

    The report summarizes a closely coupled experimental and theoretical investigation of various stages of Fracture Process: (1) accumulation of 'damage' on submicroscopical and microscopical scales leading to crack initiation; (2) slow (subcritical) crack growth and an evolution of the damage zone; (3) transition to dynamic crack growth and the catastrophic failure. The experimental part of the program is focused on the observation and quantitative characterization of damage preceding and accompanying crack initiation and growth. A special experimental setup for studying the fracture process under variable stress field is reported in Chapter 2. A leading role of crack-damage interaction in fracture process is well documented. A new formalism for solution of crack-microcrack array interaction problem and its successful implementation in the evaluation of crack layer driving forces is presented in Chapter 3. A new model of the process zone, which generalizes the well-known Dagdale-Barenblatt model is presented in Chapter 4. A new measure for material toughness and the prediction of R-curve behavior illustrate the practical application of our model. Experimental examinations of our model under various test conditions are reported in Chapters 4, 5 and 6. The development of the constitutive equations for Crack Layer evolution and their experimental examinations under stress relaxation, fatigue and creep conditions are reported in Chapters 5 and 6. An accelerated test procedure and the formulation of crack layer instability criteria as a substitution for the conventional fracture toughness parameters are also discussed in Chapter 6.

  7. Kinetic and docking studies of the interaction of quinones with the quinone reductase active site.

    Science.gov (United States)

    Zhou, Zhigang; Fisher, Derek; Spidel, Jared; Greenfield, Jodi; Patson, Brian; Fazal, Aleem; Wigal, Carl; Moe, Owen A; Madura, Jeffry D

    2003-02-25

    NAD(P)H/quinone acceptor oxidoreductase type 1 (QR1) protects cells from cytotoxic and neoplastic effects of quinones though two-electron reduction. Kinetic experiments, docking, and binding affinity calculations were performed on a series of structurally varied quinone substrates. A good correlation between calculated and measured binding affinities from kinetic determinations was obtained. The experimental and theoretical studies independently support a model in which quinones (with one to three fused aromatic rings) bind in the QR1 active site utilizing a pi-stacking interaction with the isoalloxazine ring of the FAD cofactor.

  8. Kinetic Studies of Alkaline Phosphatase from the Liver of Agama ...

    African Journals Online (AJOL)

    ABSTRACT: Kinetic studies were carried out on alkaline phosphatase (ALP) extracted from the liver of Agama agama lizard. Incubation of ALP extract with para – nitrophenyl phosphate formed the basis for the determination of enzyme activity. Spectrophotometric method was used to assay the enzyme, and the kinetic ...

  9. KINETIC STUDIES ON THE SORPTION OF LEAD AND CADMIUM ...

    African Journals Online (AJOL)

    Kinetic investigations are necessary for determining the rate of reaction and mechanism. The kinetics of the sorption of Pb2+ and Cd2+ from aqueous solution on to the biomass of C. bicolor was studied by batch equilibrium technique. The removal of the two metal ions was found to be > 60% depending on the initial metal ...

  10. Kinetic Study of Calcination of Jakura Limestone Using Power Rate ...

    African Journals Online (AJOL)

    The current demand of hydrated lime [Ca(OH)2] worldwide has necessitated investigation into kinetics of calcinations of some large commercial deposits of limestone in Nigeria. The study is aimed at finding kinetic parameters for the purpose of energy saving, lime kiln design, modeling and simulation of lime kiln.

  11. Synthesis, structural investigation and kinetic studies of uranyl (VI ...

    Indian Academy of Sciences (India)

    Uranyl schiff base complexes; kinetic study; X-ray crystallography; kinetics of thermal decomposition; cyclic voltammetry. ... Chemistry Department, College of Sciences, Shiraz University, Shiraz 71454, I. R. Iran; Institute of Physics ASCR, v.v.i, Na Slovance 2, 182 21 Praha, Czech Republic; Department of Chemistry, Faculty ...

  12. Theoretical study of a molecular turbine.

    Science.gov (United States)

    Perez-Carrasco, R; Sancho, J M

    2013-10-01

    We present an analytic and stochastic simulation study of a molecular engine working with a flux of particles as a turbine. We focus on the physical observables of velocity, flux, power, and efficiency. The control parameters are the external conservative force and the particle densities. We revise a simpler previous study by using a more realistic model containing multiple equidistant vanes complemented by stochastic simulations of the particles and the turbine. Here we show that the effect of the thermal fluctuations into the flux and the efficiency of these nanometric devices are relevant to the working scale of the system. The stochastic simulations of the Brownian motion of the particles and turbine support the simplified analytical calculations performed.

  13. Theoretical Study of White Dwarf Double Stars

    Science.gov (United States)

    Hira, Ajit; Koetter, Ted; Rivera, Ruben; Diaz, Juan

    2015-04-01

    We continue our interest in the computational simulation of the astrophysical phenomena with a study of gravitationally-bound binary stars, composed of at least one white dwarf star. Of particular interest to astrophysicists are the conditions inside a white dwarf star in the time frame leading up to its explosive end as a Type Ia supernova, for an understanding of the massive stellar explosions. In addition, the studies of the evolution of white dwarfs could serve as promising probes of theories of gravitation. We developed FORTRAN computer programs to implement our models for white dwarfs and other stars. These codes allow for different sizes and masses of stars. Simulations were done in the mass interval from 0.1 to 2.0 solar masses. Our goal was to obtain both atmospheric and orbital parameters. The computational results thus obtained are compared with relevant observational data. The data are further analyzed to identify trends in terms of sizes and masses of stars. We hope to extend our computational studies to blue giant stars in the future. Research Supported by National Science Foundation.

  14. kinetics

    Directory of Open Access Journals (Sweden)

    D. E. Panayotounakos

    2002-01-01

    Full Text Available We present the construction of the general solutions concerning the one-dimensional (1D fully dynamic nonlinear partial differential equations (PDEs, for the erosion kinetics. After an uncoupling procedure of the above mentioned equations a second–order nonlinear PDE of the Monge type governing the porosity is derived, the general solution of which is constructed in the sense that a full complement of arbitrary functions (as many as the order is introduced. Afterwards, we specify the above solution according to convenient initial conditions.

  15. Experimental and theoretical study of reflux condensation

    Energy Technology Data Exchange (ETDEWEB)

    Bakke, Knut

    1997-12-31

    This thesis studies the separation of gas mixtures in a reflux condenser. also called a dephlegmator. Reflux condensation is separation of a gas mixture, in reflux flow with condensing liquid, under continuous heat removal. A numerical model of a dephlegmator for binary mixtures was developed. The model may readily be extended to multi-component mixtures, as the solution method is based on a matrix solver. Separation of a binary mixture in a reflux condenser test rig is demonstrated. The test facility contains a single-tube test section that was designed and built as part of the project. Test mixtures of propane and n-butane were used, and a total of 15 experiments are reported. Limited degree of separation was achieved due to limited heat transfer area and narrow boiling point range of the test mixture. The numerical model reproduces the experimental data within reasonable accuracy. Deviation between calculated and measured properties is less than 6% of the measured temperature and less than 5% of the measured flow rate. The model is based on mechanistic models of physical processes and is not calibrated or tuned to fit the experimental data. The numerical model is applied to a number of separation processes. These case studies show that the required heat transfer area increases rapidly with increments in top product composition (light component). Flooding limits the amount of reflux liquid. The dephlegmator is suitable for separation of feed mixtures that are rich in light components. The gliding temperature in the dephlegmation process enables utilization of top product as refrigerant, with subsequent energy saving as a result. 61 refs., 50 figs., 34 tabs.

  16. Theoretical Studies of Strong Correlations in Cuprates

    Science.gov (United States)

    Mistark, Peter

    This thesis presents work that has been done to describe the high temperature superconducting cuprates by going beyond first principles calculations using the Hubbard model with (pi,pi) antiferromagnetic and BCS superconducting order. The unique approach here is to fit the Hubbard model to either first principles or experimental band structure and obtain electronic structure properties by self consisting the antiferromagnetic and superconducting gaps as well as self consistently computing self energy corrections. The self energy corrections are determined through the QPGW model which correctly describes the cuprates as having intermediate coupling of electrons. These methods of modeling cuprates are used to describe the experimental results of spectroscopies such as photoemission and scanning tunneling spectroscopy. The first topic presented here studies the one, three, and four band versions of the Hubbard model. It is shown that, in the three and four band model, by fitting the tight binding parameters to first principles calculations and the antiferromagnetic gap to experimental gap measurements, cuprates should be described as charge transfer insulators instead of Mott insulators which is predicted by one band models. The one, three, and four band models with parameters fit to experiment predict a negative electronic compressibility. This phenomenon is shown to be due to a dramatic decrease in the Hubbard U with increased electron doping away from half filling. Switching focus to hole doped cuprates, the addition of superconducting order reveals a property known as Fermi surface free superconductivity. Fermi surface free superconductivity drives a topological transition from open to closed Fermi surfaces in the hole doped cuprates. STM measurements of the local density of states on hole doped cuprates show a gap filling rather than a gap closing with increased doping. A model of nanoscale phase separation in conjunction with a Coulomb gap which describes stripe

  17. Theoretical studies of the marine sulfur cycle

    Science.gov (United States)

    Toon, Owen B.; Kasting, James B.; Liu, May S.

    1985-01-01

    Several reduced sulfur compounds are produced by marine organisms and then enter the atmosphere, where they are oxidized and ultimately returned to the ocean or the land. The oceanic dimethyl sulfide (DMS) flux, in particular, represents a significant fraction of the annual global sulfur input to the atmosphere. In the atmosphere, this gas is converted to sulfur dioxide (SO2), methane sulfonic acid, and other organic acids which are relatively stable and about which little is known. SO2 is a short lived gas which, in turn, is converted to sulfuric acid and other sulfate compounds which contribute significantly to acid rain. Because of the complexity of the sulfur system, it is not well understood even in the unperturbed atmosphere. However, a number of new observations and experiments have led to a significant increase in the understanding of this system. A number of one dimensional model experiments were conducted on the gas phase part of the marine sulfur cycle. The results indicate the measured concentration of DMS and the amplitude of its diurnal cycle are in agreement with estimates of its global flux. It was also found that DMS can make a large contribution to the background SO2 concentration in the free troposphere. Estimates of CS2 concentrations in the atmosphere are inconsistent with estimated fluxes; however, measured reaction rates are consistent with the observed steep tropospheric gradient in CS2. Observations of CS2 are extremely sparse. Further study is planned.

  18. Theoretical studies of homogeneous catalysts mimicking nitrogenase.

    Science.gov (United States)

    Sgrignani, Jacopo; Franco, Duvan; Magistrato, Alessandra

    2011-01-10

    The conversion of molecular nitrogen to ammonia is a key biological and chemical process and represents one of the most challenging topics in chemistry and biology. In Nature the Mo-containing nitrogenase enzymes perform nitrogen 'fixation' via an iron molybdenum cofactor (FeMo-co) under ambient conditions. In contrast, industrially, the Haber-Bosch process reduces molecular nitrogen and hydrogen to ammonia with a heterogeneous iron catalyst under drastic conditions of temperature and pressure. This process accounts for the production of millions of tons of nitrogen compounds used for agricultural and industrial purposes, but the high temperature and pressure required result in a large energy loss, leading to several economic and environmental issues. During the last 40 years many attempts have been made to synthesize simple homogeneous catalysts that can activate dinitrogen under the same mild conditions of the nitrogenase enzymes. Several compounds, almost all containing transition metals, have been shown to bind and activate N₂ to various degrees. However, to date Mo(N₂)(HIPTN)₃N with (HIPTN)₃N= hexaisopropyl-terphenyl-triamidoamine is the only compound performing this process catalytically. In this review we describe how Density Functional Theory calculations have been of help in elucidating the reaction mechanisms of the inorganic compounds that activate or fix N₂. These studies provided important insights that rationalize and complement the experimental findings about the reaction mechanisms of known catalysts, predicting the reactivity of new potential catalysts and helping in tailoring new efficient catalytic compounds.

  19. Theoretical Studies of Homogeneous Catalysts Mimicking Nitrogenase

    Directory of Open Access Journals (Sweden)

    Alessandra Magistrato

    2011-01-01

    Full Text Available The conversion of molecular nitrogen to ammonia is a key biological and chemical process and represents one of the most challenging topics in chemistry and biology. In Nature the Mo-containing nitrogenase enzymes perform nitrogen ‘fixation’ via an iron molybdenum cofactor (FeMo-co under ambient conditions. In contrast, industrially, the Haber-Bosch process reduces molecular nitrogen and hydrogen to ammonia with a heterogeneous iron catalyst under drastic conditions of temperature and pressure. This process accounts for the production of millions of tons of nitrogen compounds used for agricultural and industrial purposes, but the high temperature and pressure required result in a large energy loss, leading to several economic and environmental issues. During the last 40 years many attempts have been made to synthesize simple homogeneous catalysts that can activate dinitrogen under the same mild conditions of the nitrogenase enzymes. Several compounds, almost all containing transition metals, have been shown to bind and activate N2 to various degrees. However, to date Mo(N2(HIPTN3N with (HIPTN3N= hexaisopropyl-terphenyl-triamidoamine is the only compound performing this process catalytically. In this review we describe how Density Functional Theory calculations have been of help in elucidating the reaction mechanisms of the inorganic compounds that activate or fix N2. These studies provided important insights that rationalize and complement the experimental findings about the reaction mechanisms of known catalysts, predicting the reactivity of new potential catalysts and helping in tailoring new efficient catalytic compounds.

  20. Theoretical study of cisplatin adsorption on silica

    Energy Technology Data Exchange (ETDEWEB)

    Simonetti, S., E-mail: ssimonet@uns.edu.ar [Departamento de Fisica and IFISUR, Universidad Nacional del Sur-CONICET, Av. Alem 1253, 8000 Bahia Blanca (Argentina); Departamentos de Ciencias Basicas e Ingenieria Mecanica, Universidad Tecnologica Nacional, 11 de Abril 461, 8000 Bahia Blanca (Argentina); Company, A. Diaz; Brizuela, G.; Juan, A. [Departamento de Fisica and IFISUR, Universidad Nacional del Sur-CONICET, Av. Alem 1253, 8000 Bahia Blanca (Argentina)

    2011-11-15

    The adsorption of cisplatin and its complexes, cis-[PtCl(NH{sub 3}){sub 2}]{sup +} and cis-[Pt(NH{sub 3}){sub 2}]{sup 2+}, on a SiO{sub 2}(1 1 1) hydrated surface has been studied by the Atom Superposition and Electron Delocalization method. The adiabatic energy curves for the adsorption of the drug and its products on the delivery system were considered. The electronic structure and bonding analysis were also performed. The molecule-surface interactions are formed at expenses of the OH surface bonds. The more important interactions are the Cl-H bond for cis-[PtCl{sub 2}(NH{sub 3}){sub 2}] and cis-[PtCl(NH{sub 3}){sub 2}]{sup +} adsorptions, and the Pt-O interaction for cis-[Pt(NH{sub 3}){sub 2}]{sup 2+} adsorption. The Cl p orbitals and Pt s, p y d orbitals of the molecule and its complexes, and the s H orbital and, the s and p orbitals of the O atoms of the hydrated surface are the main contribution to the surface bonds.

  1. A comparative study of kinetics of nuclear reactors

    Directory of Open Access Journals (Sweden)

    Obaidurrahman Khalilurrahman

    2009-01-01

    Full Text Available The paper deals with the study of reactivity initiated transients to investigate major differences in the kinetics behavior of various reactor systems under different operating conditions. The article also states guidelines to determine the safety limits on reactivity insertion rates. Three systems, light water reactors (pressurized water reactors, heavy water reactors (pressurized heavy water reactors, and fast breeder reactors are considered for the sake of analysis. The upper safe limits for reactivity insertion rate in these reactor systems are determined. The analyses of transients are performed by a point kinetics computer code, PKOK. A simple but accurate method for accounting total reactivity feedback in kinetics calculations is suggested and used. Parameters governing the kinetics behavior of the core are studied under different core states. A few guidelines are discussed to project the possible kinetics trends in the next generation reactors.

  2. Theoretical and Experimental Studies in Accelerator Physics

    Energy Technology Data Exchange (ETDEWEB)

    Rosenzweig, James [Univ. of California, Los Angeles, CA (United States). Dept. of Physics and Astronomy

    2017-03-08

    . We note also that PBPL graduates remain as close elaborators for the program after leaving UCLA. The UCLA PBPL program is a foremost developer of on-campus facilities, such as the Neptune and Pegasus Laboratories, providing a uniquely strong environment for student-based research. In addition, the PBPL is a strong user of off-campus national lab facilities, such as SLAC FACET and NLCTA, and the BNL ATF. UCLA has also vigorously participated in the development of these facilities. The dual emphases on off- and on-campus opportunities permit the PBPL to address in an agile way a wide selection of cutting-edge research topics. The topics embraced by this proposal illustrate this program aspect well. These include: GV/m dielectric wakefield acceleration/coherent Cerenkov radiation experiments at FACET (E-201) and the ATF; synergistic laser-excited dielectric accelerator and light source development; plasma wakefield (PWFA) experiments on “Trojan horse” ionization injection (FACET E-210), quasi-nonlinear PWFA at BNL and the production at Neptune high transformer ratio plasma wakes; the inauguration of a new type of RF photoinjector termed “hybrid” at UCLA, and application to PWFA; space-charge dominated beam and cathode/near cathode physics; the study of advanced IFEL systems, for very high energy gain and utilization of novel OAM modes; the physcis of inverse Compton scattering (ICS), with applications to e+ production and γγ colliders; electron diffraction; and advanced beam diagnostics using coherent imaging techniques. These subjects are addressed under the leadership of PBPL director Prof. James Rosenzweig in Task A, and Prof. Pietro Musumeci in Task J, which was initiated following his OHEP Outstanding Junior Investigator award.

  3. Theoretical Studies of Low Frequency Instabilities in the Ionosphere. Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Dimant, Y. S.

    2003-08-20

    The objective of the current project is to provide a theoretical basis for better understanding of numerous radar and rocket observations of density irregularities and related effects in the lower equatorial and high-latitude ionospheres. The research focused on: (1) continuing efforts to develop a theory of nonlinear saturation of the Farley-Buneman instability; (2) revision of the kinetic theory of electron-thermal instability at low altitudes; (3) studying the effects of strong anomalous electron heating in the high-latitude electrojet; (4) analytical and numerical studies of the combined Farley-Bunemadion-thermal instabilities in the E-region ionosphere; (5) studying the effect of dust charging in Polar Mesospheric Clouds. Revision of the kinetic theory of electron thermal instability at low altitudes.

  4. Theoretical Studies of Elementary Hydrocarbon Species and Their Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Allen, Wesley D. [Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry. Center for Computational Quantum Chemistry; Schaefer, III, Henry F. [Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry. Center for Computational Quantum Chemistry

    2015-11-14

    This is the final report of the theoretical studies of elementary hydrocarbon species and their reactions. Part A has a bibliography of publications supported by DOE from 2010 to 2016 and Part B goes into recent research highlights.

  5. A theoretical and experimental study of coplanar waveguide shunt stubs

    Science.gov (United States)

    Dib, Nihad I.; Ponchak, George E.; Katehi, Linda P. B.

    1993-01-01

    A comprehensive theoretical and experimental study of straight and bent coplanar waveguide (CPW) shunt stubs is presented. In the theoretical analysis, the CPW is assumed to be inside a cavity while, the experiments are performed on open structures. For the analysis of CPW discontinuities with air-bridges, a hybrid technique was developed which was validated through extensive theoretical and experimental comparisons. The effect of the cavity resonances on the behavior of the stubs with and without air-bridges is investigated. In addition, the encountered radiation loss due to the discontinuities is evaluated experimentally.

  6. A theoretical study of factors influencing calcium-secretion coupling in a presynaptic active zone model.

    Science.gov (United States)

    Gil, Amparo; González-Vélez, Virginia; Segura, Javier; Gutiérrez, Luis Miguel

    2014-10-01

    A theoretical analysis of some of the relevant factors influencing the calcium time course and the strength and timing of release probabilities of vesicles evoked by an action potential in a calyx-type active zone is presented in this paper. In particular, our study focus on the comparison of cooperative vs non-cooperative calcium binding by the release site and the effect of the number of Ca(2+) binding sites on the calcium sensitivity for release. Regarding the comparison of cooperative and non-cooperative kinetic schemes, our simulations show that quite different results are obtained when considering one or another: a reduction in the release probability of more than a 50% is obtained when considering the cooperative kinetic scheme. Also, a delay in the average time for release appears when using this model for the calcium sensor. Our study also shows that a non-cooperative kinetic binding scheme gives rise to a well defined average calcium level for release assuming that the same kinetic constants are considered for all the sites. Our results also suggest that the central value of the calcium sensitivity for release depends on the number of binding sites N and the dissociation constant KD with a scaling law depending on NKD.

  7. Martian weathering processes: Terrestrial analog and theoretical modeling studies

    Science.gov (United States)

    McAdam, Amy Catherine

    2008-06-01

    Understanding the role of water in the Martian near-surface, and its implications for possible habitable environments, is among the highest priorities of NASA's Mars Exploration Program. Characterization of alteration signatures in surface materials provides the best opportunity to assess the role of water on Mars. This dissertation investigates Martian alteration processes through analyses of Antarctic analogs and numerical modeling of mineral-fluid interactions. Analog work involved studying an Antarctic diabase, and associated soils, as Mars analogs to understand weathering processes in cold, dry environments. The soils are dominated by primary basaltic minerals, but also contain phyllosilicates, salts, iron oxides/oxyhydroxides, and zeolites. Soil clay minerals and zeolites, formed primarily during deuteric or hydrothermal alteration of the parent rock, were subsequently transferred to the soil by physical rock weathering. Authigenic soil iron oxides/oxyhydroxides and small amounts of poorly-ordered secondary silicates indicate some contributions from low-temperature aqueous weathering. Soil sulfates, which exhibit a sulfate- aerosol-derived mass-independent oxygen isotope signature, suggest contributions from acid aerosol-rock interactions. The complex alteration history of the Antarctic materials resulted in several similarities to Martian materials. The processes that affected the analogs, including deuteric/ hydrothermal clay formation, may be important in producing Martian surface materials. Theoretical modeling focused on investigating the alteration of Martian rocks under acidic conditions and using modeling results to interpret Martian observations. Kinetic modeling of the dissolution of plagioclase-pyroxene mineral mixtures under acidic conditions suggested that surfaces with high plagioclase/pyroxene, such as several northern regions, could have experienced some preferential dissolution of pyroxenes at a pH less than approximately 3-4. Modeling of the

  8. Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ4H7Potential Energy Surface.

    Science.gov (United States)

    Li, Yang; Klippenstein, Stephen J; Zhou, Chong-Wen; Curran, Henry J

    2017-10-12

    The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of polyunsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution toward soot formation. On the basis of our previous work on propene and the butene isomers (1-, 2-, and isobutene), it was found that the reaction kinetics of Ḣ-atom addition to the C═C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations, and flame speed measurements. In this study, the rate constants and thermodynamic properties for Ḣ-atom addition to 1,3-butadiene and related reactions on the Ċ 4 H 7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero-point energies, single-point energies, rate constants, barrier heights, and thermochemistry are systematically compared among the two quantum chemical methods. 1-Methylallyl (Ċ 4 H 7 1-3) and 3-buten-1-yl (Ċ 4 H 7 1-4) radicals and C 2 H 4 + Ċ 2 H 3 are found to be the most important channels and reactivity-promoting products, respectively. We calculated that terminal addition is dominant (>80%) compared to internal Ḣ-atom addition at all temperatures in the range 298-2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C 4 H 6 + Ḣ → products and C 2 H 4 + Ċ 2 H 3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C 4 species, the calculated thermochemical values are also in good agreement with literature data. In addition, the rate constants for H atom abstraction by Ḣ atoms have also been calculated, and it is

  9. Structural, Vibrational, and Electronic Properties of the Glucoalkaloid Strictosidine: A Combined Experimental and Theoretical Study

    Directory of Open Access Journals (Sweden)

    Renyer Alves Costa

    2016-01-01

    Full Text Available A detailed structural analysis and spectral behavior of the glucoalkaloid strictosidine, a precursor of all monoterpene indole alkaloids, are discussed. The experimental NMR, FTIR, and UV results were compared to the theoretical DFT spectra calculated by Becke using the three-parameter Lee-Yang-Parr (B3LYP function with 6-31G(d and 6-311++G(2d,p basis sets. The theoretical geometry optimization data were compared with the X-ray data for precursors and similar structures in the associated literature. The similarity between the theoretical and experimental coupling constants values made it possible to affirm the values of dihedral angles and their configuration, reinforcing findings from previous stereochemical studies. Theoretical UV analysis agreed well with the measured experimental data, with bands assigned. Calculated HOMO/LUMO gaps show low excitation energy for strictosidine, justifying its stability and reaction kinetics. The molecular electrostatic potential map shows opposite potentials regions that form hydrogen bonds that stabilize the dimeric form, which were confirmed by excellent agreement of the dimeric form theoretical wavenumbers with the experimental IR spectrum. ESI-MS/MS data revealed patterns for the fragmentation of the protonated strictosidine molecule outlined by an NBO study.

  10. An assessment of theoretical procedures for predicting the thermochemistry and kinetics of hydrogen abstraction by methyl radical from benzene.

    Science.gov (United States)

    Hemelsoet, Karen; Moran, Damian; Van Speybroeck, Veronique; Waroquier, Michel; Radom, Leo

    2006-07-20

    The reaction enthalpy (298 K), barrier (0 K), and activation energy and preexponential factor (600-800 K) have been examined computationally for the abstraction of hydrogen from benzene by the methyl radical, to assess their sensitivity to the applied level of theory. The computational methods considered include high-level composite procedures, including W1, G3-RAD, G3(MP2)-RAD, and CBS-QB3, as well as conventional ab initio and density functional theory (DFT) methods, with the latter two classes employing the 6-31G(d), 6-31+G(d,p) and/or 6-311+G(3df,2p) basis sets, and including ZPVE/thermal corrections obtained from 6-31G(d) or 6-31+G(d,p) calculations. Virtually all the theoretical procedures except UMP2 are found to give geometries that are suitable for subsequent calculation of the reaction enthalpy and barrier. For the reaction enthalpy, W1, G3-RAD, and URCCSD(T) give best agreement with experiment, while the large-basis-set DFT procedures slightly underestimate the endothermicity. The reaction barrier is slightly more sensitive to the choice of basis set and/or correlation level, with URCCSD(T) and the low-cost BMK method providing values in close agreement with the benchmark G3-RAD value. Inspection of the theoretically calculated rate parameters reveals a minor dependence on the level of theory for the preexponential factor. There is more sensitivity for the activation energy, with a reasonable agreement with experiment being obtained for the G3 methods and the hybrid functionals BMK, BB1K, and MPW1K, especially in combination with the 6-311+G(3df,2p) basis set. Overall, the high-level G3-RAD composite procedure, URCCSD(T), and the cost-effective DFT methods BMK, BB1K, and MPW1K give the best results among the methods assessed for calculating the thermochemistry and kinetics of hydrogen abstraction by the methyl radical from benzene.

  11. Study on nucleation kinetics of lysozyme crystallization

    Science.gov (United States)

    Lin, Chen; Zhang, Yang; Liu, Jing J.; Wang, Xue Z.

    2017-07-01

    The nucleation kinetics of hen egg-white lysozyme crystallization was investigated using a hot stage cooling crystallizer and a microscope to monitor the solution crystallization process in real time. Images of crystals were continuously recorded under varied precipitant and protein concentrations. The nucleation rate was found to be higher at higher precipitant concentration, and increase monotonically with protein concentration if the precipitant concentration was held constant. Attempt was made to interpret the experimental data using classical nucleation theory. It was found that the model predictions are lower than the experimental values at low supersaturations but agree well with experimental data at high supersaturations. The trends in the experimental data suggest that two nucleation mechanisms might co-exist: heterogeneous nucleation seems to be the dominant at low supersaturation while at higher supersaturation homogeneous nucleation seems to play the major role.

  12. Ab initio and kinetic modeling studies of formic acid oxidation

    DEFF Research Database (Denmark)

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...... have been compared to the experimental results of de Wilde and van Tiggelen (1968) who measured the laminar burning velocities for HOCHO flames over a range of stoichiometries and dilution ratios. The modeling predictions are generally satisfactory. The governing reaction mechanisms are outlined based...... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH reaction, as well...

  13. Theoretical and experimental studies on the atmospheric degradation of 2-bromo-3,3,3-trifluoropropene.

    Science.gov (United States)

    Chen, Weiwang; Zhou, Xiaomeng; Han, Yajun

    2015-08-28

    As a new kind of Halon replacement, 2-bromo-3,3,3-trifluoropropene (2-BTP) is finding application as a fire extinguishing agent in confined spaces. For assessing its environmental impact, it is necessary to perform kinetic and product studies of its degradation in the atmospheric environment. In this sense, five possible reaction pathways between 2-BTP and OH radicals are found by Gaussian 03. Detailed analysis shows that the main product is the CF3CBrCH2OH radical, which may produce a series of compounds by further reaction with O2, NO, etc. In order to further prove the validity of the theoretical calculations and investigate the atmospheric transformation process of 2-BTP, atmospheric degradation of 2-BTP is then studied experimentally under controlled radiation conditions. Based on the theoretical analyses and experimental results, the atmospheric degradation mechanism of 2-BTP is finally proposed and detailed information on the atmospheric chemistry of 2-BTP is provided.

  14. Kinetics of ethylcyclohexane pyrolysis and oxidation: An experimental and detailed kinetic modeling study

    KAUST Repository

    Wang, Zhandong

    2015-07-01

    Ethylcyclohexane (ECH) is a model compound for cycloalkanes with long alkyl side-chains. A preliminary investigation on ECH (Wang et al., Proc. Combust. Inst., 35, 2015, 367-375) revealed that an accurate ECH kinetic model with detailed fuel consumption mechanism and aromatic growth pathways, as well as additional ECH pyrolysis and oxidation data with detailed species concentration covering a wide pressure and temperature range are required to understand the ECH combustion kinetics. In this work, the flow reactor pyrolysis of ECH at various pressures (30, 150 and 760Torr) was studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS) and gas chromatography (GC). The mole fraction profiles of numerous major and minor species were evaluated, and good agreement was observed between the PIMS and GC data sets. Furthermore, a fuel-rich burner-stabilized laminar premixed ECH/O2/Ar flame at 30Torr was studied using synchrotron VUV PIMS. A detailed kinetic model for ECH high temperature pyrolysis and oxidation was developed and validated against the pyrolysis and flame data performed in this work. Further validation of the kinetic model is presented against literature data including species concentrations in jet-stirred reactor oxidation, ignition delay times in a shock tube, and laminar flame speeds at various pressures and equivalence ratios. The model well predicts the consumption of ECH, the growth of aromatics, and the global combustion properties. Reaction flux and sensitivity analysis were utilized to elucidate chemical kinetic features of ECH combustion under various reaction conditions. © 2015 The Combustion Institute.

  15. Threshold collision-induced dissociation and theoretical study of protonated azobenzene

    Science.gov (United States)

    Rezaee, Mohammadreza; McNary, Christopher P.; Armentrout, P. B.

    2017-10-01

    Protonated azobenzene (AB), H+(C6H5N2C6H5), has been studied using threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer. Product channels observed are C6H5N2+ + C6H6 and C6H5+ + N2 + C6H6. The experimental kinetic energy-dependent cross sections were analyzed using a statistical model that accounts for internal and kinetic energy distributions of the reactants, multiple collisions, and kinetic shifts. From this analysis, the activation energy barrier height of 2.02 ± 0.11 eV for benzene loss is measured. To identify the transition states (TSs) and intermediates (IMs) for these dissociations, relaxed potential energy surface (PES) scans were performed at the B3LYP/aug-cc-pVTZ level of theory. The PES indicates that there is a substantial activation energy along the dissociation reaction coordinate that is the rate-limiting step for benzene loss and at some levels of theory, for subsequent N2 loss as well. Relative energies of the reactant, TSs, IMs, and products were calculated at B3LYP, wB97XD, M06, PBEPBE, and MP2(full) levels of theory using both 6-311++G(2d,2p) and aug-cc-pVTZ basis sets. Comparison of the experimental results with theoretical values from various computational methods indicates how well these theoretical methods can predict thermochemical properties. In addition to these density functional theory and MP2 methods, several high accuracy multi-level calculations such as CBS-QB3, G3, G3MP2, G3B3MP2, G4, and G4MP2 were performed to determine the thermochemical properties of AB including the proton affinity and gas-phase basicity, and to compare the performance of different theoretical methods.

  16. An Activity Theoretical Approach to Social Interaction during Study Abroad

    Science.gov (United States)

    Shively, Rachel L.

    2016-01-01

    This case study examines how one study abroad student oriented to social interaction during a semester in Spain. Using an activity theoretical approach, the findings indicate that the student not only viewed social interaction with his Spanish host family and an expert-Spanish-speaking age peer as an opportunity for second language (L2) learning,…

  17. Theoretical study (ab initio and DFT methods) on acidic dissociation ...

    African Journals Online (AJOL)

    Analytical measurement of materials requires exact knowledge of their acid dissociation constant (pKa) values. In recent years, quantum mechanical calculations have been extensively used to study of acidities in the aqueous solutions and the results were compared with the experimental values. In this study, a theoretical ...

  18. Theoretical and Methodological Perspectives on Designing Video Studies of Interaction

    Directory of Open Access Journals (Sweden)

    Anna-Lena Rostvall

    2005-12-01

    Full Text Available In this article the authors discuss the theoretical basis for the methodological decisions made during the course of a Swedish research project on interaction and learning. The purpose is to discuss how different theories are applied at separate levels of the study. The study is structured on three levels, with separate sets of research questions and theoretical concepts. The levels reflect a close-up description, a systematic analysis, and an interpretation of how teachers and students act and interact. The data consist of 12 hours of video-recorded and transcribed music lessons from high school and college. Through a multidisciplinary theoretical framework, the general understanding of teaching and learning in terms of interaction can be widened. The authors also present a software tool developed to facilitate the processes of transcription and analysis of the video data.

  19. Kinetic and spectroscopic studies on nitrogenase

    Energy Technology Data Exchange (ETDEWEB)

    Gutheil, W.G.

    1989-01-01

    A detailed procedure and description of the apparatus used for the purification of sodium dithionite obtained from commercial sources is presented with yields 98+% pure material with yields of 25-35%. The effect of the purified dithionite on nitrogenase specific activities was determined and found to be insignificant. Mass spectra analysis of the P{sub i} obtained from nitrogenase catalyzed labeled ATP hydrolysis indicated that nitrogenase acts as a normal ATPase catalyzing nucleophilic attack at the {lambda} phosphorus atom of ATP. Recovered ATP was analyzed for positional isotope exchange (PIX) by {sup 31}P NMR. A numerical model to quantitatively interpret these results in terms of the currently available information on the kinetics of nitrogenase catalyzed ATP hydrolysis was developed. CD monitored titrations of the oxidized Fe protein at 360 nm with MgADP and MgATP are presented. Data were analyzed by fitting to models where cooperativity was allowed or not allowed. Analytical and numerical solutions for non cooperative and cooperative models were implemented. Statistical analysis of the data are presented and discussed as supporting non cooperative vs. cooperative behavior between the nucleotide binding sites. The thermodynamic analysis and incorporation of redox data allow a proposed model of the interactions between the ligand binding sites and the redox center of this protein to be presented. Several complete spectral titrations with various nucleotide analogs are also presented.

  20. Kinetic Uptake Studies of Powdered Materials in Solution

    Directory of Open Access Journals (Sweden)

    Mohamed H. Mohamed

    2015-06-01

    Full Text Available Challenges exist for the study of time dependent sorption processes for heterogeneous systems, especially in the case of dispersed nanomaterials in solvents or solutions because they are not well suited to conventional batch kinetic experiments. In this study, a comparison of batch versus a one-pot setup in two variable configurations was evaluated for the study of uptake kinetics in heterogeneous (solid/solution systems: (i conventional batch method; (ii one-pot system with dispersed adsorbent in solution with a semi-permeable barrier (filter paper or dialysis tubing for in situ sampling; and (iii one-pot system with an adsorbent confined in a semi-permeable barrier (dialysis tubing or filter paper barrier with ex situ sampling. The sorbent systems evaluated herein include several cyclodextrin-based polyurethane materials with two types of phenolic dyes: p-nitrophenol and phenolphthalein. The one-pot kinetics method with in situ (Method ii or ex situ (Method iii sampling described herein offers significant advantages for the study of heterogeneous sorption kinetics of highly dispersed sorbent materials with particles sizes across a range of dimensions from the micron to nanometer scale. The method described herein will contribute positively to the development of advanced studies for heterogeneous sorption processes where an assessment of the relative uptake properties is required at different experimental conditions. The results of this study will be advantageous for the study of nanomaterials with significant benefits over batch kinetic studies for a wide range of heterogeneous sorption processes.

  1. Theoretical studies of the spin-Hamiltonian parameters for the ...

    Indian Academy of Sciences (India)

    Home; Journals; Pramana – Journal of Physics; Volume 70; Issue 4. Theoretical studies of the spin-Hamiltonian parameters for the orthorhombic Pr4+ centers in Sr2CeO4 ... Author Affiliations. Wen-Lin Feng1. Department of Applied Physics, Chongqing Institute of Technology, Chongqing 400050, People Republic of China ...

  2. A theoretical study on interaction of proline with gold cluster

    Indian Academy of Sciences (India)

    Author for correspondence (harjinder.singh@iiit.ac.in) small gold clusters with xDNA base pairs (Sharma et al. 2009) have motivated us to carry out a theoretical study on interaction of proline with gold nanoparticles. Proline is unique among the natural amino acids as its side chain is cyclized to the backbone, which gives ...

  3. Trends In The Study Of Language Variation:Theoretical And ...

    African Journals Online (AJOL)

    Register study, stylistics, sociolinguistics, discourse analysis, and English for specific purposes all deal with language variation. This can be gleaned from several perspectives. In this paper, however, we have tried to look at the issue of variation from two main perspectives namely: the theoretical and the taxonomic.

  4. An experimental and theoretical study of oligo- and polyelectrolyte adsorption

    NARCIS (Netherlands)

    Schee, van der H.A.

    1984-01-01

    The purpose of this study is the description of the behaviour of a model polyelectrolyte near a model interface.

    Chapter 1 gives a general background and the outline of the investigations.

    The chapters 2 and 3 comprise the theoretical parts. Chapter 2 considers the applicability of

  5. THEORETICAL STUDY (AB INITIO AND DFT METHODS) ON ...

    African Journals Online (AJOL)

    Theoretical study on acidic dissociation constant of xylenol orange in aqueous solution. Bull. Chem. Soc. Ethiop. 2017, 31(1). 129 modeled. Hartree-Fock ab initio and density functional geometry optimizations were performed with the Gaussian 09 program. The optimizations were done using HF/6-31+G(d) method. The.

  6. Theoretical study of catalytic hydrogenation of oxirane and its methyl ...

    African Journals Online (AJOL)

    C3H6O) is its methyl derivative. Theoretical studies on catalytic hydrogenation of both compounds, in presence of aluminium chloride (AlCl3) catalyst, are carried out. The products of reactions are ethanol and propan-1-ol from oxirane and ...

  7. Theoretical study on the molecular and crystal structures of nitrogen ...

    Indian Academy of Sciences (India)

    mainly contributed by the p orbital of N atom and the valence band (HOCO) from the p orbital of F atom. Keywords. Molecular; crystal; structure; property; theoretical study. 1. Introduction ... the global search was confined to these groups only. By analyzing the simulation trajectory of molecular packing within seven space ...

  8. Piezoelectricity in quasicrystals: A group-theoretical study

    Indian Academy of Sciences (India)

    and tabulated employing a compact notation. The results of this group-theoretical study are briefly discussed. Keywords. Quasicrystals; pentagonal and icosahedral point groups; piezoelectricity; non-vanishing and independent tensor coefficients; irreducible representations; compo- sition series. PACS Nos 62.40+i; 77.60+v.

  9. Synthesis, experimental and theoretical studies of two cocrystals in 1 ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 127; Issue 11. Synthesis, experimental and theoretical studies of two cocrystals in 1:1 stoichiometric ratio from 4,4'-bithiazole-2,2'-diamine with two hydrogen acceptor molecules. Zohreh Rashidi Ranjbar Ali Morsali. Articles Volume 127 Issue 11 November 2015 pp ...

  10. Theoretical study on the optical properties of polyvinylidene fluoride crystal

    CERN Document Server

    Duan Chun Gang; Yin Wei Guo; Liu Jian Jun; Hardy, J R; Bai Meng Jun; Ducharme, S

    2003-01-01

    We report our first-principles studies on the linear and non-linear optical properties of ferroelectric polyvinylidene fluoride crystal. Calculated values of the refractive indices agree well with experiments. As regards the second-harmonic-generation coefficients, theoretical values are larger than experimental ones. Possible reasons for the discrepancy are discussed.

  11. Theoretical study of a twin-tube magnetorheological damper concept

    OpenAIRE

    Gołdasz, Janusz

    2017-01-01

    In this study, the author presents a theoretical model of a semi-active magnetorheological (MR) twin-tube damper concept. The model relies on geometric variables and material properties and can be used in engineering and research studies on damper structures. Other non-linear characteristics, namely, the fluid chamber compressibility, fluid inertia, cylinder elasticity, friction, one-way check valves are included into the model as well. The author studies the performance of the damper model a...

  12. Theoretical studies of the spin-Hamiltonian parameters for the ...

    Indian Academy of Sciences (India)

    Theoretical studies of spin-Hamiltonian (SH) parameters associated with. Pr4+ in Sr2CeO4 single crystals have been made by ... other is the perturbation theory method (PTM) [7,8]. As suggested in previous studies [7–10], the PTM ... k (θj,φj) can be obtained from the local lattice struc- tural parameters of the studied system.

  13. Drug and Alcohol Studies (Volume 2: Theoretical Studies)

    OpenAIRE

    MacGregor, S.; Thom, B

    2014-01-01

    VOLUME TWO: THEORETICAL PERSPECTIVES Excerpt from Drug, Set and Setting: The Basis for Controlled Intoxicant Use N. Zinberg Sociocultural Anthropology and Alcohol and Drug Research Geoffrey Hunt and Judith Barker Towards a Unified Theory Addiction Is a Brain Disease and It Matters Alan Leshner Drug Dependence A. Thomas McLellan et al A Chronic Mental Illness Alcohol Dependence Griffith Edwards and Milton Gross Provisional Description of a Clinical Syndrome Illicit Drugs and the Rise of Epidem...

  14. Kinetic studies of bovine liver fructose-1,6-bisphosphatase.

    Science.gov (United States)

    Casazza, J P; Stone, S R; Fromm, H J

    1979-06-10

    Initial rate kinetic studies with bovine liver fructose-1,6-bisphosphatase were carried out in both directions of the reaction to determine the sequence of product release from the enzyme. Product inhibition by fructose-6-P was found to be S-linear, I-linear noncompetitive relative to fructose-1,6-bisphosphate, whereas inorganic orthophosphate was determined to be linear competitive with respect to the substrate. The kinetics of the reverse reaction were studied by coupling the phosphatase reaction to the aldolase, triosephosphate isomerase, and glycerolphosphate dehydrogenase reactions. The kinetic results were found to be in harmony with the Uni Bi ordered and random sequential mechanisms as well as a Uni Bi ping-pong mechanism. The nomenclature is that of Cleland (Cleland, W.W. (1963) Biochim. Biophys. Acta 67, 104-137). However, nonkinetic considerations, when taken together with the kinetic results, suggest that the steady state ordered Uni Bi mechanism is the most likely possibility. There is evidence that isomerization of the binary complex of enzyme and phosphate occurs in the kinetic mechanism. Although magnesium is required for the reverse reaction, there is no evidence to suggest that the enzyme discriminates between the magnesium-associated or divalent cation-free forms of the substrates.

  15. The Influence of Complexation on Radionuclide Migration: A Theoretical Study

    DEFF Research Database (Denmark)

    Carlsen, L.; Nielsen, O.J.; Bo, P.

    1989-01-01

    -order kinetics. It is shown that as long as the rate of interconversion between the free and complexed metal ions is rapid relative to the residence time in the system studied, the two species will migrate with the same speed, controlled by an "effective retention factor." It is clearly demonstrated...... that approaching zero complexation the effective retention approaches that of the more retarded species (the free metal ion), whereas the effective retention approached that of the less retarded species (the complex) for increased complexation. The implication for the distribution of radionuclides...

  16. Theoretical Study of Structure and Synthesis Mechanism of Superheavy Nuclei

    Science.gov (United States)

    Zhou, Shan-Gui

    The study of superheavy nuclei (SHN) is on the frontier of modern nuclear physics. In recent years, we have carried out theoretical investigations of both the structure properties and the synthesis mechanism of SHN. In this contribution, we briefly review these progresses and focus on the study of potential energy surfaces and fission barriers of actinide nuclei by using the MDC-RMF model and that of the fusion mechanism by using the ImQMD model.

  17. Studies on the kinetics and intraparticle diffusivities of BOD, colour ...

    African Journals Online (AJOL)

    Therefore, this study reveals that boiler fly ash can effectively be used as an adsorbent for POME treatment and also established the kinetic and mechanisms of the sorption process. Also, the results of this study could serve as effective design parameters for a treatment plant to further reduce BOD, colour and TSS from ...

  18. Kinetics study of balanites aegyptiaca oil transesterification for the ...

    African Journals Online (AJOL)

    Kinetics study of balanites aegyptiaca oil transesterification for the production of biodiesel. ... In this study, transesterification of Balanites aegyptiaca oil employing a homogeneous catalyst (NaOH) was conducted in a reactor with methanol. The transesterification reaction at 6:1 methanol to oil ratio with 1wt% catalyst was ...

  19. Kinetic study of Mongolian coals by thermal analysis

    Directory of Open Access Journals (Sweden)

    Jargalmaa S

    2018-02-01

    Full Text Available Thermal analysis was used for the thermal characterization of the coal samples. The experiments were performed to study the pyrolysis and gasification kinetics of typical Mongolian brown coals. Low rank coals from Shivee ovoo, Ulaan ovoo, Aduun chuluun and Baganuur deposits have been investigated. Coal samples were heated in the thermogravimetric apparatus under argon at a temperature ranges of 25-1020ºC with heating rates of 10, 20, 30 and 40ºC/min. Thermogravimetry (TG and derivative thermogravimetry (DTG were performed to measure weight changes and rates of weight losses used for calculating the kinetic parameters. The activation energy (Ea was calculated from the experimental results by using an Arrhenius type kinetic model.

  20. ANALYTICAL METHODS FOR KINETIC STUDIES OF BIOLOGICAL INTERACTIONS: A REVIEW

    Science.gov (United States)

    Zheng, Xiwei; Bi, Cong; Li, Zhao; Podariu, Maria; Hage, David S.

    2015-01-01

    The rates at which biological interactions occur can provide important information concerning the mechanism and behavior of these processes in living systems. This review discusses several analytical methods that can be used to examine the kinetics of biological interactions. These techniques include common or traditional methods such as stopped-flow analysis and surface plasmon resonance spectroscopy, as well as alternative methods based on affinity chromatography and capillary electrophoresis. The general principles and theory behind these approaches are examined, and it is shown how each technique can be utilized to provide information on the kinetics of biological interactions. Examples of applications are also given for each method. In addition, a discussion is provided on the relative advantages or potential limitations of each technique regarding its use in kinetic studies. PMID:25700721

  1. Theoretical Analysis of the Relative Significance of Thermodynamic and Kinetic Dispersion in the dc and ac Voltammetry of Surface-Confined Molecules

    KAUST Repository

    Morris, Graham P.

    2015-05-05

    © 2015 American Chemical Society. Commonly, significant discrepancies are reported in theoretical and experimental comparisons of dc voltammograms derived from a monolayer or close to monolayer coverage of redox-active surface-confined molecules. For example, broader-than-predicted voltammetric wave shapes are attributed to the thermodynamic or kinetic dispersion derived from distributions in reversible potentials (E0) and electrode kinetics (k0), respectively. The recent availability of experimentally estimated distributions of E0 and k0 values derived from the analysis of data for small numbers of surface-confined modified azurin metalloprotein molecules now allows more realistic modeling to be undertaken, assuming the same distributions apply under conditions of high surface coverage relevant to voltammetric experiments. In this work, modeling based on conventional and stochastic kinetic theory is considered, and the computationally far more efficient conventional model is shown to be equivalent to the stochastic one when large numbers of molecules are present. Perhaps unexpectedly, when experimentally determined distributions of E0 and k0 are input into the model, thermodynamic dispersion is found to be unimportant and only kinetic dispersion contributes significantly to the broadening of dc voltammograms. Simulations of ac voltammetric experiments lead to the conclusion that the ac method, particularly when the analysis of kinetically very sensitive higher-order harmonics is undertaken, are far more sensitive to kinetic dispersion than the dc method. ac methods are therefore concluded to provide a potentially superior strategy for addressing the inverse problem of determining the k0 distribution that could give rise to the apparent anomalies in surface-confined voltammetry.

  2. Kinetic-energy functionals studied by surface calculations

    DEFF Research Database (Denmark)

    Vitos, Levente; Skriver, Hans Lomholt; Kollár, J.

    1998-01-01

    The self-consistent jellium model of metal surfaces is used to study the accuracy of a number of semilocal kinetic-energy functionals for independent particles. It is shown that the poor accuracy exhibited by the gradient expansion approximation and most of the semiempirical functionals in the low...... density, high gradient limit may be subtantially improved by including locally a von Weizsacker term. Based on this, we propose a simple one-parameter Pade's approximation, which reproduces the exact Kohn-Sham surface kinetic energy over the entire range of metallic densities....

  3. Theoretical study of electron transport throughout some molecular structures

    Science.gov (United States)

    Abbas, Mohammed A. A.; Hanoon, Falah H.; Al-Badry, Lafy F.

    2017-11-01

    The present work is a theoretical study of the electronic properties of some molecular structures. The system that takes into account in the study is left lead-donor-molecule-acceptor-right lead. The molecule, such as (phenyl, biphenyl, triphenyl, naphthalene, anthracene, and phenanthrene), is threaded by magnetic flux. This work contains two parts. First is computing density of states of the molecular structures as a closed system by density functional theory (DFT). Second is calculating the transmission probability and electric current of such molecular structures as an open system by steady-state theoretical model. Furthermore, the most important effects, taking into consideration are quantum interference, magnetic flux, and interface structure. Our results show that the connection of the molecule to the two leads, the number of rings, the magnetic flux, and the geometrical structure of the molecule play an important role in determining the energy gap of molecular structures.

  4. Information Theoretic Studies and Assessment of Space Object Identification

    Science.gov (United States)

    2014-03-24

    AFRL-OSR-VA-TR-2014-0119 INFORMATION THEORETIC STUDIES AND ASSESMENTS OF SPACE-OBJECT IDENTIFICATION Sudhakar Prasad UNIVERSITY OF NEW MEXICO Final... computational -imaging approach to encoding the field depth of a target using the rotation of a point-spread function based on the orbital angular momentum (OAM... Computing the statistical entropy and associated MI requires the evaluation of statistical averages of logarithms of PDs and their ratios, as we have

  5. Experimental and theoretical study on the electrospinning nanoporous fibers process

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Jianghui; Si, Na [National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou (China); Xu, Lan, E-mail: lanxu@suda.edu.cn [National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou (China); Nantong Textile Institute of Soochow University, Nantong (China); Tang, Xiaopeng; Song, Yanhua; Sun, Zhaoyang [National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou (China)

    2016-02-15

    Porous materials can be prepared by sol–gel method, hydrothermal synthesis method, electrospinning and other methods. In this paper, electrospun porous nanofibers were prepared by adjusting electrospinning parameters. And the properties of obtained porous nanofiber mats were investigated. Theoretical analysis and experiment research were carried out to research mechanical mechanism of electrospun porous nanofibers, and could be used to optimize and control the porous structure. The theoretical analysis results were further verified according to the experimental data. In addition, Bernoulli equation was used to study the electrospinning “splaying” process. We found the ratio of pore width to pore length was varied along with the variation of the internal pressure of the jet, and the internal pressure of the jet increases with the velocity of the charged jet decreases. - Highlights: • Mechanical mechanism of electrospun porous nanofibers process was studied. • A simplifying gas–liquid two-phase flow model was established. • Bernoulli equation was used to study the electrospinning “splaying” process. • The theoretical results were in good agreement with the experimental data. • The electrospinning parameters affected the surface morphology of charged jet.

  6. Sociomateriality: a theoretical framework for studying distributed medical education.

    Science.gov (United States)

    MacLeod, Anna; Kits, Olga; Whelan, Emma; Fournier, Cathy; Wilson, Keith; Power, Gregory; Mann, Karen; Tummons, Jonathan; Brown, Peggy Alexiadis

    2015-11-01

    Distributed medical education (DME) is a type of distance learning in which students participate in medical education from diverse geographic locations using Web conferencing, videoconferencing, e-learning, and similar tools. DME is becoming increasingly widespread in North America and around the world.Although relatively new to medical education, distance learning has a long history in the broader field of education and a related body of literature that speaks to the importance of engaging in rigorous and theoretically informed studies of distance learning. The existing DME literature is helpful, but it has been largely descriptive and lacks a critical "lens"-that is, a theoretical perspective from which to rigorously conceptualize and interrogate DME's social (relationships, people) and material (technologies, tools) aspects.The authors describe DME and theories about distance learning and show that such theories focus on social, pedagogical, and cognitive considerations without adequately taking into account material factors. They address this gap by proposing sociomateriality as a theoretical framework allowing researchers and educators to study DME and (1) understand and consider previously obscured actors, infrastructure, and other factors that, on the surface, seem unrelated and even unimportant; (2) see clearly how the social and material components of learning are intertwined in fluid, messy, and often uncertain ways; and (3) perhaps think differently, even in ways that disrupt traditional approaches, as they explore DME. The authors conclude that DME brings with it substantial investments of social and material resources, and therefore needs careful study, using approaches that embrace its complexity.

  7. Bench-scale Kinetics Study of Mercury Reactions in FGD Liquors

    Energy Technology Data Exchange (ETDEWEB)

    Gary Blythe; John Currie; David DeBerry

    2008-03-31

    This document is the final report for Cooperative Agreement DE-FC26-04NT42314, 'Kinetics Study of Mercury Reactions in FGD Liquors'. The project was co-funded by the U.S. DOE National Energy Technology Laboratory and EPRI. The objective of the project has been to determine the mechanisms and kinetics of the aqueous reactions of mercury absorbed by wet flue gas desulfurization (FGD) systems, and develop a kinetics model to predict mercury reactions in wet FGD systems. The model may be used to determine optimum wet FGD design and operating conditions to maximize mercury capture in wet FGD systems. Initially, a series of bench-top, liquid-phase reactor tests were conducted and mercury species concentrations were measured by UV/visible light spectroscopy to determine reactant and byproduct concentrations over time. Other measurement methods, such as atomic absorption, were used to measure concentrations of vapor-phase elemental mercury, that cannot be measured by UV/visible light spectroscopy. Next, a series of bench-scale wet FGD simulation tests were conducted. Because of the significant effects of sulfite concentration on mercury re-emission rates, new methods were developed for operating and controlling the bench-scale FGD experiments. Approximately 140 bench-scale wet FGD tests were conducted and several unusual and pertinent effects of process chemistry on mercury re-emissions were identified and characterized. These data have been used to develop an empirically adjusted, theoretically based kinetics model to predict mercury species reactions in wet FGD systems. The model has been verified in tests conducted with the bench-scale wet FGD system, where both gas-phase and liquid-phase mercury concentrations were measured to determine if the model accurately predicts the tendency for mercury re-emissions. This report presents and discusses results from the initial laboratory kinetics measurements, the bench-scale wet FGD tests, and the kinetics modeling

  8. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Energy Technology Data Exchange (ETDEWEB)

    Svelle, Stian

    2004-07-01

    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  9. Isothermal, kinetic and thermodynamic studies on basic dye sorption ...

    African Journals Online (AJOL)

    PRECIOUS

    2009-12-15

    Dec 15, 2009 ... Full Length Research Paper. Isothermal, kinetic and thermodynamic studies on ... al., 2008), castor seed shell (Oladoja et al., 2008), coffee husk (Oliveira et al., 2008), neem leaf powder (Tahir et ... length and washed with tap water to remove soil and dust and then dried overnight at 50°C. Dried wheat straw ...

  10. Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

    African Journals Online (AJOL)

    Cyclohexene was oxidized using chromium (VI) oxide (CrO3) in pure acetic acid medium. The products of oxidation were analysed using simple qualitative analysis, IR spectroscopy and Gas chromatography-Mass spectrometry (GC/MS). Kinetics studies were carried out to determine the order of reaction, rate constant and ...

  11. Kinetic models and parameters estimation study of biomass and ...

    African Journals Online (AJOL)

    The growth kinetics and modeling of ethanol production from inulin by Pichia caribbica (KC977491) were studied in a batch system. Unstructured models were proposed using the logistic equation for growth, the Luedeking-Piret equation for ethanol production and modified Leudeking-Piret model for substrate consumption.

  12. Kinetic models and parameters estimation study of biomass and ...

    African Journals Online (AJOL)

    compaq

    2017-01-11

    Jan 11, 2017 ... The growth kinetics and modeling of ethanol production from inulin by Pichia caribbica (KC977491) were studied in a batch system. Unstructured models were proposed using the logistic equation for growth, the Luedeking-Piret equation for ethanol production and modified Leudeking-Piret model for.

  13. Kinetic modelling and thermodynamic studies on purification of ...

    African Journals Online (AJOL)

    ... kinetic model suggesting that the adsorption mechanism might be a chemisorption process; thermodynamic studies showed that this process is spontaneous and endothermic. These results are very important in optimization of this purification process. Keywords: Polyvinylpyrrolidone (PVP), adsorption, activated carbon, ...

  14. Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

    African Journals Online (AJOL)

    acer

    70oC in the presence of ruthenium catalyst. N2O was equally reported to effectively oxidize cyclohexene in gaseous phase to cyclohexanone with nearly 100% selectivity. (Avdeev et al, 2003). The kinetics of the reaction by which thallium(III) acetate oxidizes cyclohexene in glacial acetic acid medium at 30°C, was studied ...

  15. Kinetic studies of alkaline phosphatase extracted from rabbit (Lepus ...

    African Journals Online (AJOL)

    user

    Studies were carried out to ascertain some kinetic properties of alkaline phosphatase (ALP) extracted from Lepus townsendii liver. Incubation of ALP extract with 4-nitrophenylphosphate (4-NPP) formed the basis for determination of enzyme activity. Spectrophotometric method was used to assay the enzyme activity, and the ...

  16. Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

    African Journals Online (AJOL)

    acer

    ABSTRACT: Cyclohexene was oxidized using chromium (VI) oxide (CrO3) in pure acetic acid medium. The products of oxidation were analysed using simple qualitative analysis, IR spectroscopy and Gas chromatography-Mass spectrometry (GC/MS). Kinetics studies were carried out to determine the order of reaction, rate ...

  17. Kinetic studies of alkaline phosphatase extracted from rabbit ( Lepus ...

    African Journals Online (AJOL)

    Studies were carried out to ascertain some kinetic properties of alkaline phosphatase (ALP) extracted from Lepus townsendii liver. Incubation of ALP extract with 4-nitrophenylphosphate (4-NPP) formed the basis for determination of enzyme activity. Spectrophotometric method was used to assay the enzyme activity, and the ...

  18. KINETIC STUDY OF LIQUID-PHASE ADSORPTIVE REMOVAL OF ...

    African Journals Online (AJOL)

    The kinetic sorption of five metal ions - Al3+, Cr6+, Zn2+, Ag+ and Mn2+ - from aqueous solution onto almond tree leaves (ATL) waste in single component system has been studied. The experimental data was analyzed in terms of intraparticle diffusion and rate of adsorption, thus comparing transport mechanism and ...

  19. A microfluidic method to study demulsification kinetics

    NARCIS (Netherlands)

    Krebs, T.; Schroën, C.G.P.H.; Boom, R.M.

    2012-01-01

    We present the results of experiments studying droplet coalescence in a dense layer of emulsion droplets using microfluidic circuits. The microfluidic structure allows direct observation of collisions and coalescence events between oil droplets dispersed in water. The coalescence rate of a flowing

  20. Kinetic Modelling and Experimental Study of Small Esters: Methyl Acetate and Ethyl Acetate

    KAUST Repository

    Ahmed, Ahfaz

    2017-12-14

    A detailed chemical kinetic mechanism comprising methyl acetate and ethyl acetate has been developed based on the previous work by Westbrook et al. [1]. The newly developed kinetic mechanism has been updated with new reaction rates from recent theoretical studies. To validate this model, shock tube experiments measuring ignition delay time have been conducted at 15 & 30 bar and equivalence ratio 0.5, 1.0 and 2.0. Another set of experiments measuring laminar burning velocity was also performed on a heat flux burner at atmospheric pressure over wide range of equivalence ratios [~0.7-1.4]. The new mechanism shows significant improvement in prediction of experimental data over earlier model across the range of experiments.

  1. Kinetics and inhibition study of tyrosinase by pressure mediated microanalysis.

    Science.gov (United States)

    Liu, Dong-Mei; Yang, Jun-Li; Ha, Wei; Chen, Juan; Shi, Yan-Ping

    2017-05-15

    In the present study, pressure mediated microanalysis (PMMA), a fast, convenient and efficient capillary electrophoresis (CE) method was developed for studying enzyme kinetics of tyrosinase and inhibition kinetics of kojic acid, a model inhibitor of tyrosinase. The enzymatic reaction conditions and CE conditions were optimized in order to obtain high enzyme activity and short analysis time. By PMMA, only the product could be detected at 475 nm, and no voltage was applied to separate the product from the reaction mixture thus greatly simplifying the optimization procedure. The spectrophotometric assay and electrophoretically mediated microanalysis (EMMA) were also performed to validate the developed method. With the present method, the Michaelis-Menten constant (Km) was calculated to be 1.347 mM for tyrosinase. The inhibition constant of kojic acid to free tyrosinase (KI) and kojic acid to tyrosinase/L-DOPA complex (KIS) were calculated to be 36.64 and 74.35 μM, respectively, and the half-maximal inhibitory concentration (IC50) was determined to be 46.64 μM for kojic acid. The developed method is fast and convenient for studying enzyme kinetics, inhibition kinetics and further screening enzyme inhibitors. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Theoretical study for solar air pretreatment collector/regenerator

    Energy Technology Data Exchange (ETDEWEB)

    Peng Donggen; Zhang Xiaosong; Yin Yonggao [School of Energy and Environment, Southeast Univ., Nanjing (China)

    2008-07-01

    A new liquid regeneration equipment - solar air pretreatment collector/regenerator for liquid desiccant cooling system is put forward in this paper, which is preferable to solution regeneration in hot and moist climate in South China. The equipment can achieve liquid regeneration in lower temperature. When the solution and the air are in ''match'' state in collector/ regenerator, a match air to salt mass ratio ASMR* is found by theoretical study in which there is the largest theoretical storage capacity SC{sub max}. After two new concepts of the effective solution proportion (EPS) and the effective storage capacity (ESC) are defined, it is found by theoretical calculation that when ESP drops from 100% to 67%, ESC raises lowly, not drops and liquid outlet concentration C{sub str} {sub sol} increases from 40% to 49% in which its increment totals to 90%. All these data explain fully that air pretreatment liquid regeneration equipment enables to improve the performance of liquid desiccant cooling system. (orig.)

  3. Study on the agglomeration kinetics of uranium peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, M.; Mojica Rodriguez, L.A. [CEA, Centre de Marcoule, Nuclear Energy Division, RadioChemistry and Process Department, 17171, Bagnols-sur-Ceze 30207 (France); Muhr, H.; Plasari, E. [Reaction and Process Engineering Laboratory, CNRS, University of Lorraine. 1 rue Grandville, BP 20451, Nancy 54001 (France); Auger, F. [Areva Mines/SEPA. 2 route de Lavaugrasse, Bessines-sur-Gartempe 87250 (France)

    2016-07-01

    Considering the previous study dealing with thermodynamic and kinetic phenomena (nucleation and crystal growth) during the uranium peroxide precipitation, this work focuses on the agglomeration mechanism. It provides the results obtained from the experiments carried out in a mixed suspension - mixed product removal (MSMPR) mixer operating at steady state. The influence of the operating parameters on the uranium peroxide agglomerates was studied in order to identify the agglomeration kernel. The method is based on the resolution of the population balance equation using the method of moments and the experimental particle size distributions. The results lead to a size-independent kernel directly proportional to the crystal growth rate. Under the stirring conditions studied, the agglomeration appears to be significantly reduced by mixing which results in a kernel inversely proportional to the average shear rate. The agglomeration kinetic law obtained in this study will be used for the process modelling in a further study. (authors)

  4. A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Chen Zhu; William E. Seyfried

    2005-01-01

    Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory-measured and field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between lab and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO{sub 2} injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the first year of the project, we have successfully developed a sample preparation method and completed three batch feldspar dissolution experiments at 200 C and 300 bars. The changes of solution chemistry as dissolution experiments progressed were monitored with on-line sampling of the aqueous phase at the constant temperature and pressure

  5. Covalent binding of aniline to humic substances. 1. Kinetic studies

    Science.gov (United States)

    Weber, E.J.; Spidle, D.L.; Thorn, K.A.

    1996-01-01

    The reaction kinetics for the covalent binding of aniline with reconstituted IHSS humic and fulvic acids, unfractionated DOM isolated from Suwannee River water, and whole samples of Suwannee River water have been investigated. The reaction kinetics in each of these systems can be adequately described by a simple second-order rate expression. The effect of varying the initial concentration of aniline on reaction kinetics suggested that approximately 10% of the covalent binding sites associated with Suwannee River fulvic acid are highly reactive sites that are quickly saturated. Based on the kinetic parameters determined for the binding of aniline with the Suwannee River fulvic and humic acid isolates, it was estimated that 50% of the aniline concentration decrease in a Suwannee River water sample could be attributed to reaction with the fulvic and humic acid components of the whole water sample. Studies with Suwannee River fulvic acid demonstrated that the rate of binding decreased with decreasing pH, which parallels the decrease in the effective concentration of the neutral form, or reactive nucleophilic species of aniline. The covalent binding of aniline with Suwannee River fulvic acid was inhibited by prior treatment of the fulvic acid with hydrogen sulfide, sodium borohydride, or hydroxylamine. These observations are consistent with a reaction pathway involving nucleophilic addition of aniline to carbonyl moieties present in the fulvic acid.

  6. Theoretical investigation of the thermodynamic structures and kinetic water-exchange reactions of aqueous Al(III)-salicylate complexes

    Science.gov (United States)

    Shi, Wenjing; Jin, Xiaoyan; Dong, Shaonan; Bi, Shuping

    2013-11-01

    Density functional theory (DFT) calculations were performed on the structures and water-exchange reactions of aqueous Al(III)-salicylate complexes. Based on the four models (gas phase (GP); polarizable continuum model (PCM), which estimates the bulk solvent effect; supermolecule model (SM), which considers the explicit solvent effect, and supermolecule-polarizable continuum model (SM-PCM), which accounts for both types of solvent effects), we systematically conducted this study by examining three different properties of the complexes. (1) The microscopic properties of the aqueous Al(III)-salicylate complexes were studied by optimizing their various structures (including the possible 1:1 mono- and bidentate complexes, cis and trans isomers of the 1:2 bidentate complexes and 1:3 bidentate complexes) at the B3LYP/6-311+G(d, p) level. (2) The 27Al and 13C NMR chemical shifts were calculated using the GIAO method at the HF/6-311+G(d, p) level. The calculation results show that the values obtained with the SM-PCM models are in good agreement with the experimental data available in the literature, indicating that the models we employed are appropriate for Al(III)-salicylate complexes. (3) The water-exchange reactions of 1:1 mono- and bidentate Al(III)-salicylate complexes were simulated using supermolecule models at the B3LYP/6-311+G(d, p) level. The logarithm of the water-exchange rate constant (log kex) of the 1:1 bidentate complex predicted using the "log kex-dAl-OH2" correlation is 4.0, which is in good agreement with the experimental value of 3.7, whereas the calculated range of log kex of the 1:1 monodentate complexes is 1.3-1.9. By effectively combining the results for the thermodynamic static structures with the simulations of the kinetic water-exchange reactions, this work promotes further understanding of the configurations and formation mechanism of Al(III)-salicylate complexes.

  7. Theoretical studies of the electronic structure of small metal clusters

    Science.gov (United States)

    Jordan, K. D.

    1982-01-01

    Theoretical studies of the electronic structure of metal clusters, in particular clusters of Group IIA and IIB atoms were conducted. Early in the project it became clear that electron correlation involving d orbitals plays a more important role in the binding of these clusters than had been previously anticipated. This necessitated that computer codes for calculating two electron integrals and for constructing the resulting CI Hamiltonions be replaced with newer, more efficient procedures. Program modification, interfacing and testing were performed. Results of both plans are reported.

  8. Theoretical studies of ionic conductivity of crosslinked chitosan membranes

    Energy Technology Data Exchange (ETDEWEB)

    Chavez, Ernesto Lopez [Programa de Ingenieria Molecular y Nuevos Materiales, Universidad Autonoma de la Ciudad de Mexico, Fray Servando Teresa de Mier 92, 1er. Piso, Col Centro, Mexico D.F. CP 06080 (Mexico); Oviedo-Roa, R.; Contreras-Perez, Gustavo; Martinez-Magadan, Jose Manuel [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas Norte 152, Col. San Bartolo Atepehuacan, CP 07730 Mexico D.F. (Mexico); Castillo-Alvarado, F.L. [Escuela Superior de Fisica y Matematicas del Instituto Politecnico Nacional, Edificio 9 de la UPALM, Colonia Lindavista, Mexico D.F. CP 07738 (Mexico)

    2010-11-15

    Ionic conductivity of crosslinked chitosan membranes was studied using techniques of molecular modeling and simulation. The COMPASS force field was used. The simulation allows the description of the mechanism of ionic conductivity along the polymer matrix. The theoretical results obtained are compared with experimental results for chitosan membranes. The analysis suggests that the conduction mechanism is portrayed by the overlapping large Polaron tunneling model. In addition, when the chitosan membrane was crosslinked with an appropriate degree of crosslinking its ionic conductivity, at room temperature, was increased by about one order of magnitude. The chitosan membranes can be used as electrolytes in solid state batteries, electric double layer capacitors and fuel cells. (author)

  9. Theoretical and experimental studies on emissions from wood combustion

    Energy Technology Data Exchange (ETDEWEB)

    Skreiberg, Oeyvind

    1997-12-31

    This thesis discusses experiments on emissions from wood log combustion and single wood particle combustion, both caused by incomplete combustion and emissions of nitric and nitrous oxide, together with empirical and kinetic NO{sub x} modelling. Experiments were performed in three different wood stoves: a traditional stove, a staged air stove and a stove equipped with a catalytic afterburner. Ideally, biomass fuel does not give a net contribution to the greenhouse effect. However, incomplete combustion was found to result in significant greenhouse gas emissions. Empirical modelling showed the excess air ratio and the combustion chamber temperature to be the most important input variables controlling the total fuel-N to NO{sub x} conversion factor. As the result of an international round robin test of a wood stove equipped with a catalytic afterburner, particle emission measurements were found to be the best method to evaluate the environmental acceptability of the tested stove, since the particle emission level was least dependent of the national standards, test procedures and calculation procedures used. In batch single wood particle combustion experiments on an electrically heated small-scale fixed bed reactor the fuel-N to NO conversion factor varied between 0.11-0.86 depending on wood species and operating conditions. A parameter study and homogeneous kinetic modelling on a plug flow reactor showed that, depending on the combustion compliance in question, there is an optimum combination of primary excess air ratio, temperature and residence time that gives a maximum conversion of fuel-N to N{sub 2}. 70 refs., 100 figs., 26 tabs.

  10. CAN WE CONFIDENTLY STUDY VO2 KINETICS IN YOUNG PEOPLE?

    Directory of Open Access Journals (Sweden)

    Samantha G. Fawkner

    2007-09-01

    Full Text Available The study of VO2 kinetics offers the potential to non-invasively examine the cardiorespiratory and metabolic response to dynamic exercise and limitations to every day physical activity. Its non-invasive nature makes it hugely attractive for use with young people, both healthy and those with disease, and yet the literature, whilst growing with respect to adults, remains confined to a cluster of studies with these special populations. It is most likely that this is partly due to the methodological difficulties involved in studying VO2 kinetics in young people which are not present, or present to a lesser degree, with adults. This article reviews these methodological issues, and explains the main procedures that might be used to overcome them

  11. A theoretical investigation on kinetics, mechanism, and thermochemistry of the gas-phase reactions of methyl fluoroacetate with OH radicals and fate of alkoxy radical.

    Science.gov (United States)

    Mishra, Bhupesh Kumar; Deka, Ramesh Chandra

    2014-09-25

    We theoretically investigated OH-initiated hydrogen abstraction reactions of methyl fluoroacetate (MFA) CH2FC(O)OCH3 at the MPWB1K level of theory in conjunction with the 6-31+G(d,p) basis set. Thermodynamic and kinetic data are computed using the comparatively accurate G2(MP2) method. Two most stable conformers of MFA are identified, and the energy difference between them is found to be only 0.32 kcal mol(-1). Both of them are considered for rate coefficient calculations, and the contribution from each of the conformers is found to be quite significant. We propose an indirect mechanism due to validation of pre- and post-reactive complexes. The rate parameters are determined using canonical transition state theory and energetics at the G2(MP2) level. The temperature dependence of the rate constant can be described by the Arrhenius expressions: k = 8.79 × 10(-13) exp[(-377.27 ± 64)/T] cm(3) molecule(-1) s(-1) over a temperature range of 250-450 K. The ΔfH°298 for CH2FC(O)OCH3, CH2FC(O)OC(•)H2, and C(•)HFC(O)OCH3 are also computed using an isodesmic procedure. The OH-driven atmospheric lifetime of MFA was estimated to be 24 days. A mechanistic study to shed light on the atmospheric degradation and the sole fate for the consumption of CH2FC(O)OCH2O(•) radical has also been reported.

  12. A theoretical and experimental study of the thermal degradation of biomass

    Energy Technology Data Exchange (ETDEWEB)

    Groenli, Morten G.

    1996-12-31

    This thesis relates to the thermal degradation of biomass covering a theoretical and experimental study in two parts. In the first part, there is presented an experimental and modeling work on the pyrolysis of biomass under regimes controlled by chemical kinetics, and the second part presents an experimental and modeling work on the pyrolysis of biomass under regimes controlled by heat and mass transfer. Five different celluloses, and hemicellulose and lignin isolated from birch and spruce have been studied by thermogravimetry. The thermo grams of wood species revealed different weight loss characteristics which can be attributed to their different chemical composition. The kinetic analysis gave activation energies between 210 and 280 kJ/mole for all the celluloses, and a model of independent parallel reactions was successfully used to describe the thermal degradation. In the second part of the thesis there is presented experimental and modeling work on the pyrolysis of biomass under regimes controlled by heat and mass transfer. The effect of heating conditions on the product yields distribution and reacted fraction was investigated. The experiments show that heat flux alters the pyrolysis products as well as the intra particle temperatures to the greatest extent. A comprehensive mathematical model which can simulate drying and pyrolysis of moist wood is presented. The simulation of thermal degradation and heat transport processes agreed well with experimental results. 198 refs., 139 figs., 68 abs.

  13. Theoretical and Experimental Study of Bimetal-Pipe Hydroforming.

    Science.gov (United States)

    Dezhi, Zeng; Kuanhai, Deng; Taihe, Shi; Yuanhua, Lin; Hongjun, Zhu; Tianlei, Li; Yongxing, Sun

    2014-12-01

    The corrosion of oil country tubular goods (OCTG) gets more and more serious especially in the acidic environment. So, it is very important to develop a perfect anticorrosion technology for exploring sour oil and gas fields economically and safely. Analysis indicates that the bimetal-pipe (BP) which consists of the base layer of low carbon steel and a corrosion resistant alloy (CRA) cladding layer is an economic and reliable anticorrosion technology and has broad application prospects in the transportation of acid medium. However, theoretical study of hydraulic expansion mechanism for BP is not enough. In this paper, the deformation compatibility condition of BP was obtained by studying the deformation rule of the (CRA) liner and the outer pipe of carbon steel in the forming process; the mechanical model which can compute the hydroforming pressure of BP has been established based on the nonlinear kinematic hardening characteristics of material; furthermore, based on the stress strain curve of inner pipe simultaneously, the calculation method of the plastic hardening stress has been proposed. Thus, the accurate method for computing the forming pressure was obtained. The experimental data show that results are consistent with results of the proposed model. It indicates that the model can be used to provide theoretical guidance for the design and production as well as use of BP.

  14. We need theoretical physics approaches to study living systems

    Science.gov (United States)

    Blagoev, Krastan B.; Shukla, Kamal; affil="3" >Herbert Levine,

    2013-08-01

    Living systems, as created initially by the transition from assemblies of large molecules to self-reproducing information-rich cells, have for centuries been studied via the empirical toolkit of biology. This has been a highly successful enterprise, bringing us from the vague non-scientific notions of vitalism to the modern appreciation of the biophysical and biochemical bases of life. Yet, the truly mind-boggling complexity of even the simplest self-sufficient cells, let alone the emergence of multicellular organisms, of brain and consciousness, and to ecological communities and human civilizations, calls out for a complementary approach. In this editorial, we propose that theoretical physics can play an essential role in making sense of living matter. When faced with a highly complex system, a physicist builds simplified models. Quoting Philip W Anderson's Nobel prize address, 'the art of model-building is the exclusion of real but irrelevant parts of the problem and entails hazards for the builder and the reader. The builder may leave out something genuinely relevant and the reader, armed with too sophisticated an experimental probe, may take literally a schematized model. Very often such a simplified model throws more light on the real working of nature....' In his formulation, the job of a theorist is to get at the crux of the system by ignoring details and yet to find a testable consequence of the resulting simple picture. This is rather different than the predilection of the applied mathematician who wants to include all the known details in the hope of a quantitative simulacrum of reality. These efforts may be practically useful, but do not usually lead to increased understanding. To illustrate how this works, we can look at a non-living example of complex behavior that was afforded by spatiotemporal patterning in the Belousov-Zhabotinsky reaction [1]. Physicists who worked on this system did not attempt to determine all the relevant chemical intermediates

  15. Kinetic study of enzymatic hydrolysis of potato starch

    Directory of Open Access Journals (Sweden)

    Óscar Fernando Castellanos Domínguez

    2004-01-01

    Full Text Available This article describes the kinetic study of potato starch enzymatic hydrolysis using soluble enzymes (Novo Nordisk. Different assays divided into four groups were used: reaction time (with which it was possible to reduce the 48-72 hour duration reported in the literature to 16 hours with comparable productivity levels; selecting the set of enzymes to be used (different types were evaluated - BAN and Termamyl as alfa-amylases during dextrinisation stage, and AMG, Promozyme and Fungamyl for sacarification reaction- identifying those presenting the best performance during hydrolysis.Reaction conditions were optimised for the process's two stages (destrinisation and sacarification. Enzyme dose, calcium cofactor concentration, pH, temperature and agitation speed were studied for the first stage. Enzyme ratio, pH and agitation speed were studied for sacarification; the latter parameter reported values having no antecedents in the literature (60 rpm and 30 rpm for first and second reactions, respectively. Michaelis Menten kinetics were calculated once conditions had been optimised, varying substrate from 10-50% P/V, obtaining km and Vmax kinetic parameters for each reaction. A kinetic model was found according to local working conditions which was able to explain potato starch conversion to glucose syrup, achieving 96 dextrose equivalents by the end of the reaction, being well within the maximum range reported in the literature (94-98.Laboratory equipment was constructed prior to carrying out assays which was able to reproduce and improve the conditions reported in the literature, making it a useful, reliable tool for use in assays returning good results.

  16. Theoretical Studies of the Surface Tension of Liquid Metal System

    Science.gov (United States)

    Stroud, D. G.; Shih, W. H.

    1985-01-01

    A major goal of this project is to understand the surface tension and other thermophysical properties of liquid metals and alloys from a fundamental viewpoint. The approach is to calculate these quantities by a first principles technique which combines the statistical-mechanical theory of the liquid state with an electronic pseudopotential theory of electrons in metals. The inhomogeneity of the surface is treated using an ionic-density-functional formalism developed with the support of NASA. Of particular interest are the variation of surface tension with temperature and impurity concentration: such variations strongly influence the types of convection which make take place in a low-gravity environment. Some progress has already been achieved in computing the reduction of surface tension due to the presence of low-surface-tension impurities, and the corresponding surface segregation of such impurities. In the coming year, it is planned to concentrate on the surface properties of materials of particular interest to the MSA program: Si, Ga and GaSn alloys. An additional goal is to gain some theoretical understanding of the high temperature thermophysical properties of liquid metals, particularly high melting point materials which have not been studied extensively from a theoretical viewpoint.

  17. THEORETICAL ANALYSIS STUDY OF FORMATION OF FUTURE LEGAL LAWYERS

    Directory of Open Access Journals (Sweden)

    Eugene Stepanovich Shevlakov

    2015-09-01

    Full Text Available The article deals with topical issues of formation of legal consciousness of future lawyers in high school. Obtained kinds of legal consciousness of future lawyers, determined its structure. Dedicated components of justice are mutually reinforcing, and provide an opportunity for further development of the personality of the future specialist, their personal growth.The purpose: to carry out theoretical analysis of the problem of formation of legal consciousness of future lawyers.The novelty is based. On the analysis of theoretical appro-aches of pedagogy, psychology, law, the notion of «lawfulness of the future of the law student», which is regarded as a form of social consciousness, which is a set of legal views and feelings, expressing the attitude to the law and legal phenomena that have regulatory in character and which includes know-ledge of legal phenomena and their evaluation from the point of view of fairness and justice, formed in the process of studying in the University.Results: this article analyzes different approaches to understanding the content and essence of the concept of legal consciousness of the legal profession. Define the types and structure of legal consciousness of future lawyers.

  18. Kinetics study on conventional and microwave pyrolysis of moso bamboo.

    Science.gov (United States)

    Dong, Qing; Xiong, Yuanquan

    2014-11-01

    A comparative study on the pyrolysis kinetics of moso bamboo has been conducted in a conventional thermogravimetric analyzer and a microwave thermogravimetric analyzer respectively. The effect of heating rate on the pyrolysis process was also discussed. The results showed that both the maximum and average reaction rates increased with the heating rate increasing. The values of activation energy increased from 58.30 to 84.22 kJ/mol with the heating rate decreasing from 135 to 60 °C/min during conventional pyrolysis. The value of activation energy was 24.5 kJ/mol for microwave pyrolysis, much lower than that for conventional pyrolysis at a similar heating rate of 160 °C/min. The pyrolysis of moso bamboo exhibited a kinetic compensation effect. The low activation energy obtained under microwave irradiation suggests that microwaves heating would be a promising method for biomass pyrolysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Adsorption of chromium onto activated alumina: kinetics and thermodynamics studies.

    Science.gov (United States)

    Marzouk, Ikhlass; Dammak, Lassaad; Hamrouni, Béchir

    2013-02-01

    In this study, the removal of chromium (VI) by adsorption on activated alumina was investigated and the results were fitted to Langmuir, Freundlich, Dubinin-Redushkevich, and Temkin adsorption models at various temperatures. The constants of each model were evaluated depending on temperature. Thermodynamic parameters for the adsorption system were determined at 10, 25 and 40 degrees C. (deltaH degrees = -21.18 kJ x mol(-1); deltaG degrees = -8.75 to -7.43 kJ x mol(-1) and deltaS degrees = -0.043 kJ x K(-1) x mol(-1)). The obtained values showed that chromium (VI) adsorption is a spontaneous and exothermic process. The kinetic process was evaluated by first-order, second-order and Elovich kinetic models.

  20. DEFLUORIDATION OF DRINKING WATER BY ELECTROCOAGULATION/ELECTROFLOTATION: KINETIC STUDY

    Directory of Open Access Journals (Sweden)

    Mounir Bennajah

    2010-01-01

    Full Text Available A variable order kinetic (VOK model derived from the langmuir-freundlish equation was applied to determine the kinetics of fluoride removal reaction by electrocoagulation (EC. Synthetic solutions were employed to elucidate the effects of the initial fluoride concentration, the applied current and the initial acidity on the simulation results of the model. The proposed model successfully describes the fluoride removal in Airlift reactor in comparison with the experimental results. In this study two EC cells with the same capacity (V = 20 L were used to carry out fluoride removal with aluminum electrodes, the first is a stirred tank reactor (STR the second is an airlift reactor (ALR. The comparison of energy consumption demonstrates that the (ALR is advantageous for carrying out the defluoridation removal process.

  1. DEFLUORIDATION OF DRINKING WATER BY ELECTROCOAGULATION/ELECTROFLOTATION - KINETIC STUDY

    Directory of Open Access Journals (Sweden)

    Bennajah Mounir

    2010-06-01

    Full Text Available A variable order kinetic (VOK model derived from the langmuir-freundlish equation was applied to determine the kinetics of fluoride removal reaction by electrocoagulation (EC. Synthetic solutions were employed to elucidate the effects of the initial fluoride concentration, the applied current and the initial acidity on the simulation results of the model. The proposed model successfully describes the fluoride removal in Airlift reactor in comparison with the experimental results. In this study two EC cells with the same capacity (V = 20 L were used to carry out fluoride removal with aluminum electrodes, the first is a stirred tank reactor (STR the second is an airlift reactor (ALR. The comparison of energy consumption demonstrates that the (ALR is advantageous for carrying out the defluoridation removal process.

  2. Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6reaction and kinetics study of rate constants and kinetic isotope effects.

    Science.gov (United States)

    Rangel, Cipriano; Espinosa-Garcia, Joaquin

    2018-02-07

    Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

  3. Kinetic study of ozonation of molasses fermentation wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Coca, M. [Departamento de Ingenieria Quimica y Tecnologia del Medio Ambiente, Universidad de Valladolid, Prado de la Magdalena s/n, 47011 Valladolid (Spain)], E-mail: monica@iq.uva.es; Pena, M.; Gonzalez, G. [Departamento de Ingenieria Quimica y Tecnologia del Medio Ambiente, Universidad de Valladolid, Prado de la Magdalena s/n, 47011 Valladolid (Spain)

    2007-10-22

    A kinetic study of molasses wastewater ozonation was carried out in a stirred tank reactor to obtain the rate constants for the decolorization reaction and the regime through which ozone is absorbed. First, fundamental mass transfer parameters such as ozone solubility, volumetric mass transfer coefficients and ozone decomposition kinetics were determined from semi-batch experiments in organic-free solutions with an ionic composition similar that of industrial wastewater. The influence of operating variables such as the stirring rate and gas flow rate on the kinetic and mass transfer parameters was also studied. The application of film theory allows to establish that the reactions between ozone and colored compounds in wastewater take place in the fast and pseudo-first-order regime, within the liquid film. The decolorization rate constants were evaluated at pH 8.7 and 25 deg. C, varying from 0.6 x 10{sup 7} to 3.8 x 10{sup 7} L mol{sup -1} s{sup -1}, depending on the stirring rate and the inlet gas flow.

  4. A Theoretical Study of Microwave Beam Absorption by a Rectenna

    Science.gov (United States)

    Ott, J. H.; Rice, J. S.; Thorn, D. C.

    1981-01-01

    The theoretical operational parameters for the workable satellite power system were examined. The system requirements for efficient transmission and reception of an environmentally benign microwave beam were determined.

  5. A comparative kinetic study of SNCR process using ammonia

    Directory of Open Access Journals (Sweden)

    M. Tayyeb Javed

    2008-03-01

    Full Text Available The paper presents comparative kinetic modelling of nitrogen oxides (NOx removal from flue gases by selective non-catalytic reduction process using ammonia as reducing agent. The computer code SENKIN is used in this study with the three published chemical kinetic mechanisms; Zanoelo, Kilpinen and Skreiberg. Kinetic modeling was performed for an isothermal plug flow reactor at atmospheric pressure so as to compare it with the experimental results. A 500 ppm NOx background in the flue gas is considered and kept constant throughout the investigation. The ammonia performance was modeled in the range of 750 to 1250 ºC using the molar ratios NH3/NOx from 0.25 to 3.0 and residence times up to 1.5 seconds. The modeling using all the mechanisms exhibits and confirms a temperature window of NOx reduction with ammonia. It was observed that 80% of NOx reduction efficiency could be achieved if the flue gas is given 300 msec to react with ammonia, while it is passing through a section within a temperature range of 910 to 1060 ºC (Kilpinen mechanism or within a temperature range of 925 to 1030 ºC (Zanoelo mechanism or within a temperature range of 890 to 1090 ºC (Skreiberg mechanism.

  6. Antioxidant activity and kinetics studies of eugenol and 6-bromoeugenol.

    Science.gov (United States)

    Mahboub, Radia; Memmou, Faiza

    2015-01-01

    In this work, we report the antioxidant and free radical scavenging activity of 6-bromoeugenol and eugenol. EC50, the concentration providing 50% inhibition, is calculated and the antioxidant activity index (AAI) is evaluated. The antioxidant activity was evaluated using 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging method. EC50 values of 6-bromoeugenol, ascorbic acid and eugenol were 34.270 μg/mL, 54.888 μg/mL and 130.485 μg/mL, respectively. 6-Bromoeugenol showed higher AAI value (1.122) followed by ascorbic acid (0.700), then by eugenol (0.295). We also investigate the kinetics of DPPH radical scavenging activity of our products to determine the useful parameter TEC50 to evaluate their antiradical efficiency (ARE). Our results have shown high ARE. This study has provided the following ARE ( × 10(-3)) order for the tested antioxidants: ascorbic acid (70.119)>6-bromoeugenol (34.842) > eugenol (21.313). Finally, we classify ascorbic acid and eugenol as fast kinetics reaction (TEC50 8.82 and 11.38 min, respectively) and 6-bromoeugenol as medium kinetics reaction (TEC50 39.24 min).

  7. Experimental and theoretical study of metal combustion in oxygen flows

    CERN Document Server

    El-Rabii, Hazem; Muller, Maryse

    2016-01-01

    The effects of oxygen flow speed and pressure on the iron and mild steel combustion are investigated experimentally and theoretically. The studied specimens are vertical cylindrical rods subjected to an axial oxygen flow and ignited at the upper end by laser irradiation. Three main stages of the combustion process have been identified experimentally: (1) Induction period, during which the rod is heated until an intensive metal oxidation begins at its upper end; (2) Static combustion, during which a laminar liquid "cap" slowly grows on the upper rod end; and, after the liquid cap detachment from the sample, (3) Dynamic combustion, which is characterized by a rapid metal consumption and turbulent liquid motions. An analytical description of these stages is given. In particular, a model of the dynamic combustion is constructed based on the turbulent oxygen transport through the liquid metal-oxide flow. This model yields a simple expression for the fraction of metal burned in the process, and allows one to calcul...

  8. Electron transport through a quantum interferometer: a theoretical study

    Science.gov (United States)

    Maiti, Santanu K.

    2010-05-01

    In the present work, we explore the properties of electron transport through a quantum interferometer attached symmetrically to two one-dimensional semi-infinite metallic electrodes, namely the source and the drain. The interferometer is made up of two sub-rings where individual sub-rings are penetrated by the Aharonov-Bohm (AB) fluxes phi1 and phi2, respectively. We adopt a simple tight-binding framework to describe the model, and all the calculations are done based on the single-particle Green's function formalism. Our exact numerical calculations describe two-terminal conductance and current as functions of the interferometer-to-electrode coupling strength, magnetic fluxes threaded by left and right sub-rings of the interferometer and the difference of these two fluxes. Our theoretical results reveal several interesting features of electron transport across the interferometer, and these aspects may be utilized to study electron transport in AB geometries.

  9. Theoretical study of disorder induced magnetoresistance in graphene

    Science.gov (United States)

    Adam, Shaffique; Ping, Jinglei; Yudhistira, Indra; Ramakrishnan, Navneeth; Cho, Sungjae; Fuhrer, Michael S.

    2014-03-01

    In this work we predict theoretically that carrier density inhomogeneity provides a new mechanism for classical magnetoresistance. For concreteness, we study the case of graphene where density inhomogeneity and carrier scattering is dominated by charged impurities, although the mechanism itself is quite general and applies to other systems in which there are large spatial fluctuations of the carrier density. Calculations using an effective medium approximation show that low-field magnetoresistance becomes a universal function of the ratio between the average carrier density and the fluctuations of the carrier density, and scales as a power-law when this ratio is large. Our finding is in excellent agreement with recent experimental results. This work is supported by the Singapore National Research Foundation NRF-NRFF2012-01.

  10. Theoretical study on alkaline hydrolysis of trinitrotoluene: later steps

    Directory of Open Access Journals (Sweden)

    Liudmyla K. Sviatenko

    2015-10-01

    Full Text Available Alkaline hydrolysis is an effective method to destroy such the pollutant as 2,4,6-trinitrotoluene (TNT in solution and in well-mixed soil. The mechanism of hydrolytic transformation of polynegative complex, which is one of the products of early stages of TNT hydrolysis, was theoretically investigated at the SMD(Pauling/M06-2X/6-31+G(d,p level under alkali condition. The studied process consists of more than twenty steps and includes a six-membered cycle cleavage and sequenced [1,3]-hydrogen migration and C-C bond rupture. The highest energy barrier is observed for interaction of nitromethanide with hydroxide. The most exothermic steps are C–C bonds breaking. As a result final products such as formate, acetate, ammonium, and nitrogen are formed.

  11. Mechanical properties of jennite: A theoretical and experimental study

    Energy Technology Data Exchange (ETDEWEB)

    Moon, Juhyuk, E-mail: juhyuk.moon@stonybrook.edu [Civil Engineering Program, Department of Mechanical Engineering, Stony Brook University, NY 11794 (United States); Yoon, Seyoon [School of Engineering, Kings College, University of Aberdeen, Aberdeen AB24 3UE (United Kingdom); Monteiro, Paulo J.M. [Department of Civil and Environmental Engineering, University of California, Berkeley, CA 94720 (United States)

    2015-05-15

    The objective of this study is to determine the mechanical properties of jennite. To date, several hypotheses have been proposed to predict the structural properties of jennite. For the first time as reported herein, the isothermal bulk modulus of jennite was measured experimentally. Synchrotron-based high-pressure x-ray diffraction experiments were performed to observe the variation of lattice parameters under pressure. First-principles calculations were applied to compare with the experimental results and predict additional structural properties. Accurately measured isothermal bulk modulus herein (K{sub 0} = 64(2) GPa) and the statistical assessment on experimental and theoretical results suggest reliable mechanical properties of shear and Young's modulus, Poisson's ratio, and elastic tensor coefficients. Determination of these fundamental structural properties is the first step toward greater understanding of calcium–silicate–hydrate, as well as provides a sound foundation for forthcoming atomic level simulations.

  12. Theoretical study of irradiation effects in close binaries

    Directory of Open Access Journals (Sweden)

    Srinivasa Rao M.

    2009-01-01

    Full Text Available The effect of irradiation is studied in a close binary system assuming that the secondary component is a point source, moving in a circular orbit. The irradiation effects are calculated on the atmosphere of the primary component in a 3-dimensional Cartesian coordinate geometry. In treating the reflection effect theoretically, the total radiation (ST is obtained as the sum of the radiation of 1 the effect of irradiation on the primary component which is calculated by using one dimensional rod model (Sr and 2 the self radiation of the primary component which is calculated by using the solution of radiative transfer equation in spherical symmetry (Ss. The radiation field is estimated along the line of sight of the observer at infinity. It is shown how the radiation field changes depending on the position of the secondary component.

  13. Theoretical Study of Irradiation Effects in Close Binaries

    Directory of Open Access Journals (Sweden)

    Srinivasa Rao, M.

    2009-06-01

    Full Text Available The effect of irradiation is studied in a close binary systemassuming that the secondary component is a point source, moving in a circularorbit. The irradiation effects are calculatedon the atmosphere of the primary component in a 3-dimensional Cartesiancoordinate geometry. In treating the reflection effect theoretically, the totalradiation $(S_mathrm{T}$ is obtained as the sum of the radiation of 1 the effect ofirradiation on the primary component which is calculated by using onedimensional rod model $(S_mathrm{r}$ and 2 the self radiation of the primarycomponent which is calculated by using the solution of radiative transferequation in spherical symmetry $(S_mathrm{s}$. The radiation field is estimated alongthe line of sight of the observer at infinity. It is shown how the radiationfield changes depending on the position of the secondary component.

  14. Theoretical and experimental study of 15N NMR protonation shifts.

    Science.gov (United States)

    Semenov, Valentin A; Samultsev, Dmitry O; Krivdin, Leonid B

    2015-06-01

    A combined theoretical and experimental study revealed that the nature of the upfield (shielding) protonation effect in 15N NMR originates in the change of the contribution of the sp(2)-hybridized nitrogen lone pair on protonation resulting in a marked shielding of nitrogen of about 100 ppm. On the contrary, for amine-type nitrogen, protonation of the nitrogen lone pair results in the deshielding protonation effect of about 25 ppm, so that the total deshielding protonation effect of about 10 ppm is due to the interplay of the contributions of adjacent natural bond orbitals. A versatile computational scheme for the calculation of 15N NMR chemical shifts of protonated nitrogen species and their neutral precursors is proposed at the density functional theory level taking into account solvent effects within the supermolecule solvation model. Copyright © 2015 John Wiley & Sons, Ltd.

  15. Theoretical and Experimental Study of Plasmonic Polymer Solar Cells

    DEFF Research Database (Denmark)

    Mirsafaei, Mina; Adam, Jost; Madsen, Morten

    The organic bulk hetero-junction solar cell has remarkable advantages such as low cost, mechanical flexibility and simple process techniques. Recently, low-band gap photoactive materials have obtained a significant attention due to their potential to absorb a wider range of the solar spectrum...... to attain higher power conversion efficiencies. Many low-band gap photoactive materials, however, still show a relatively low external quantum efficiency of less than 60% [1]. One possible approach to improve the device performance is to increase the light absorption in the active layer. This may, amongst...... other approaches, be achieved by using nano- or micro-structures that trap light at specific wavelengths [2], or by using the localized surface plasmon resonance effect of metal nanoparticles in the devices. In this work, we theoretically studied planar polymer solar cell based on finite-difference time...

  16. Theoretical study of diaquamalonatozinc (II) single crystal for ...

    Indian Academy of Sciences (India)

    The aim of the present paper is to employ theoretical methods to investigate the zero field splitting (ZFS) parameter and to investigate the position of the dopant in the host. These theoretical calculations have been compared with the empirical results. The superposition model (SPM)with themicroscopic spin-Hamiltonian ...

  17. Theoretical study of turbulent channel flow: Bulk properties, pressure fluctuations, and propagation of electromagnetic waves

    Science.gov (United States)

    Canuto, V. M.; Hartke, G. J.; Battaglia, A.; Chasnov, J.; Albrecht, G. F.

    1988-01-01

    In this paper, we apply two theoretical turbulence models, DIA and the recent GISS model, to study properties of a turbulent channel flow. Both models provide a turbulent kinetic energy spectral function E(k) as the solution of a non-linear equation; the two models employ the same source function but different closures. The source function is characterized by a rate n sub s (k) which is derived from the complex eigenvalues of the Orr--Sommerfeld (OS) equation in which the basic flow is taken to be of a Poiseuille type. The O--S equation is solved for a variety of Reynolds numbers corresponding to available experimental data. A physical argument is presented whereby the central line velocity characterizing the basic flow, U0 sup L, is not to be identified with the U0 appearing in the experimental Reynolds number. The theoretical results are compared with two types of experimental data: (1) turbulence bulk properties, and (2) properties that depend stongly on the structure of the turbulence spectrun at low wave numbers. The only existing analytical expression for Pi (k) cannot be used in the present case because it applies to the case of a flat plate, not a finite channel.

  18. Theoretical study of turbulent channel flow - Bulk properties, pressure fluctuations, and propagation of electromagnetic waves

    Science.gov (United States)

    Canuto, V. M.; Hartke, G. J.; Battaglia, A.; Chasnov, J.; Albrecht, G. F.

    1990-01-01

    In this paper, we apply two theoretical turbulence models, DIA and the recent GISS model, to study properties of a turbulent channel flow. Both models provide a turbulent kinetic energy spectral function E(k) as the solution of a non-linear equation; the two models employ the same source function but different closures. The source function is characterized by a rate n sub s (k) which is derived from the complex eigenvalues of the Orr-Sommerfeld (OS) equation in which the basic flow is taken to be of a Poiseuille type. The O-S equation is solved for a variety of Reynolds numbers corresponding to available experimental data. A physical argument is presented whereby the central line velocity characterizing the basic flow, U0 sup L, is not to be identified with the U0 appearing in the experimental Reynolds number. The theoretical results are compared with two types of experimental data: (1) turbulence bulk properties, and (2) properties that depend strongly on the structure of the turbulence spectrum at low wave numbers. The only existing analytical expression for Pi (k) cannot be used in the present case because it applies to the case of a flat plate, not a finite channel.

  19. Theoretical and experimental study on the aerodynamic characteristics of a horizontal axis wind turbine

    Energy Technology Data Exchange (ETDEWEB)

    Kishinami, K.; Suzuki, J. [Muroran Institute of Technology (Japan); Taniguchi, H. [Hokkai-Gakuen University, Sapporo (Japan); Ibano, H. [Muroran-Techno-Center, Muroran (Japan); Kazunou, T. [Hokudenn-Kogyo Ltd., Sapporo (Japan); Turuhami, M. [Toshiba Software Ltd., Musashi-dai Hutyu (Japan)

    2005-09-01

    The aerodynamic performance characteristics of a horizontal axis wind turbine (HAWT) were investigated theoretically by an analysis involving a combination of momentum, energy and blade element theory by means of the strip element method, and experimentally by the use of a subscale demonstration model. In this study, two approaches involving combination analysis are made use of, namely, the thrust-torque and the thrust-energy methods. Although both approaches yield identical results, the latter is superior for elucidating the relationship of the kinetic energy of the flows on the blades. Scale experiments are performed with three types of wing aerofoil involving different arrangements with the free stream velocity, U{sub {infinity}}=0.8-4.5 m/s, and for the open type of wind tunnel with an outlet duct diameter of 0.88 m. The experimental and theoretical characteristics of the HAWT using the different three types of the HAWT blades are discussed by reference to the power, torque and thrust coefficients, C{sub p}, C{sub T}, C{sub th}, and the tip speed ratio {lambda} from the point of view of variable pitch control and fixed pitch stall control methods for the output regulation. The aeronautical characteristics predicted by means of the present numerical approaches, for large units involving large power generation at high efficiency, are discussed, and it is clear how to obtain optimized design parameters that play a significant role in the overall performance. (author)

  20. Experimental and Theoretical Studies of Atmosphereic Inorganic Chlorine Chemistry

    Science.gov (United States)

    Sander, Stanley P.; Friedl, Randall R.

    1993-01-01

    Over the last five years substantial progress has been made in defining the realm of new chlorine chemistry in the polar stratosphere. Application of existing experimental techniques to potentially important chlorine-containing compounds has yielded quantitative kinetic and spectroscopic data as well as qualitative mechanistic insights into the relevant reactions.

  1. KINETIC STUDIES OF THE TWO LIGHT REACTIONS IN PHOTOSYNTHESIS

    Energy Technology Data Exchange (ETDEWEB)

    Kuntz Jr., I.D.; Calvin, Melvin

    1964-11-01

    The decay kinetics of the photo-induced absorbance changes in red and green algae are very sensitive to the wavelength of the actinic 11ght. A four to twofold increase in half-decay time is noted in going from short wavelength (550-650 mu) to long wavelength (> 700 mu) excitation. The slow decay ratios, produced by long wavelength light can be enhanced with a steady background of short wavelength light. A relationship between initial decay rates and 02 evolution rates is described. This relationship allows a direct correspondence between these spectroscopic studies and the 'red-drop' and 'enhancement' experiments of Emerson.

  2. Theoretical Analysis on the Kinetic Isotope Effects of Bimolecular Nucleophilic Substitution (SN2 Reactions and Their Temperature Dependence

    Directory of Open Access Journals (Sweden)

    Wan-Chen Tsai

    2013-04-01

    Full Text Available Factors affecting the kinetic isotope effects (KIEs of the gas-phase SN2 reactions and their temperature dependence have been analyzed using the ion-molecule collision theory and the transition state theory (TST. The quantum-mechanical tunneling effects were also considered using the canonical variational theory with small curvature tunneling (CVT/SCT. We have benchmarked a few ab initio and density functional theory (DFT methods for their performance in predicting the deuterium KIEs against eleven experimental values. The results showed that the MP2/aug-cc-pVDZ method gave the most accurate prediction overall. The slight inverse deuterium KIEs usually observed for the gas-phase SN2 reactions at room temperature were due to the balance of the normal rotational contribution and the significant inverse vibrational contribution. Since the vibrational contribution is a sensitive function of temperature while the rotation contribution is temperature independent, the KIEs are thus also temperature dependent. For SN2 reactions with appreciable barrier heights, the tunneling effects were predicted to contribute significantly both to the rate constants and to the carbon-13, and carbon-14 KIEs, which suggested important carbon atom tunneling at and below room temperature.

  3. Isotherm, kinetic, and thermodynamic study of ciprofloxacin sorption on sediments.

    Science.gov (United States)

    Mutavdžić Pavlović, Dragana; Ćurković, Lidija; Grčić, Ivana; Šimić, Iva; Župan, Josip

    2017-04-01

    In this study, equilibrium isotherms, kinetics and thermodynamics of ciprofloxacin on seven sediments in a batch sorption process were examined. The effects of contact time, initial ciprofloxacin concentration, temperature and ionic strength on the sorption process were studied. The K d parameter from linear sorption model was determined by linear regression analysis, while the Freundlich and Dubinin-Radushkevich (D-R) sorption models were applied to describe the equilibrium isotherms by linear and nonlinear methods. The estimated K d values varied from 171 to 37,347 mL/g. The obtained values of E (free energy estimated from D-R isotherm model) were between 3.51 and 8.64 kJ/mol, which indicated a physical nature of ciprofloxacin sorption on studied sediments. According to obtained n values as measure of intensity of sorption estimate from Freundlich isotherm model (from 0.69 to 1.442), ciprofloxacin sorption on sediments can be categorized from poor to moderately difficult sorption characteristics. Kinetics data were best fitted by the pseudo-second-order model (R 2  > 0.999). Thermodynamic parameters including the Gibbs free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were calculated to estimate the nature of ciprofloxacin sorption. Results suggested that sorption on sediments was a spontaneous exothermic process.

  4. Study of water vapour adsorption kinetics on aluminium oxide materials

    Science.gov (United States)

    Livanova, Alesya; Meshcheryakov, Evgeniy; Reshetnikov, Sergey; Kurzina, Irina

    2017-11-01

    Adsorbents on the basis of active aluminum oxide are still of demand on the adsorbent-driers market. Despite comprehensive research of alumina adsorbents, and currently is an urgent task to improve their various characteristics, and especially the task of increasing the sorption capacity. In the present work kinetics of the processes of water vapours' adsorption at room temperature on the surface of desiccant samples has been studied. It was obtained on the basis of bayerite and pseudoboehmite experimentally. The samples of pseudoboehmite modified with sodium and potassium ions were taken as study objects. The influence of an adsorbent's grain size on the kinetics of water vapours' adsorption was studied. The 0.125-0.25 mm and 0.5-1.0 mm fractions of this sample were used. It has been revealed that the saturation water vapor fine powder (0.125-0.25 mm) is almost twofold faster in comparison with the sample of fraction 0.5-1.0 mm due to the decrease in diffusion resistance in the pores of the samples when moving from the sample of larger fraction to the fine-dispersed sample. It has been established that the adsorption capacity of the pseudoboehmite samples, modified by alkaline ions, is higher by ˜40 %, than for the original samples on the basis of bayerite and pseudoboehmite.

  5. A Observational and Theoretical Study of Squall Line Evolution

    Science.gov (United States)

    Rasmussen, Erik Nels

    By utilizing a number of Doppler radar observations of ten squall lines, a certain class of squall lines is documented that is quasi-two-dimensional and has a solid leading edge at some time during the life cycle. It is found that the kinematic structure of these systems can be described as being due to a sloping zone of negative horizontal vorticity which extends across the entire squall line. Further, the evolution of these systems can be characterized by the sloping of this vorticity zone from erect to more horizontal orientations. The existence of the vorticity zone appears to be due to buoyancy gradients extending across the system. The primary difference between the systems studied is the rate at which tilting occurs. Motivated by the observations, a new theory is developed for squall line evolution. The theory allows for an environment with two layers characterized by differing shear values, and the squall line is characterized by a sloping region with a specified average vorticity. Using a circulation tendency approach, the rate of change of squall line slope is predicted based on environmental shear and cold pool strength. The predictions of the theory compare well with observations, and previously published theoretical and modelling results.

  6. Strategic Step for Environmental Rescue: A Theoretical Legal Studies

    Directory of Open Access Journals (Sweden)

    Bambang Sutrisno

    2014-01-01

    Full Text Available Indonesia is among the developing countries that are struggling to develop in the field of industrial development. The logical consequence of any development process, especially industrial development is the emergence of associated impacts that greatly affect the durability and sustainability of the environment. Developing the equitable industry in order to create public welfare is important. However, maintaining the security and preservation of the environment is also very important, because it is only with the availability of a good environment and healthy living that human beings can perform daily living. The availability of good and healthy environment is the constitutional responsibility of the government, as well as part of the human rights of all citizens which must be given by the State. Efforts to create a good environment and healthy living will be effective if controlled by State government and institutions who understand the objective conditions on the ground. In this regard, the granting of the authority on environmental control to regional government autonomously is the right, very smart policy choice. How To Cite: Sutrisno, B. (2016. Strategic Step for Environmental Rescue: A Theoretical Legal Studies. Rechtsidee, 1(1, 27-58. doi:http://dx.doi.org/10.21070/jihr.v1i1.98

  7. Theoretical studies of potential energy surfaces and computational methods

    Energy Technology Data Exchange (ETDEWEB)

    Shepard, R. [Argonne National Laboratory, IL (United States)

    1993-12-01

    This project involves the development, implementation, and application of theoretical methods for the calculation and characterization of potential energy surfaces involving molecular species that occur in hydrocarbon combustion. These potential energy surfaces require an accurate and balanced treatment of reactants, intermediates, and products. This difficult challenge is met with general multiconfiguration self-consistent-field (MCSCF) and multireference single- and double-excitation configuration interaction (MRSDCI) methods. In contrast to the more common single-reference electronic structure methods, this approach is capable of describing accurately molecular systems that are highly distorted away from their equilibrium geometries, including reactant, fragment, and transition-state geometries, and of describing regions of the potential surface that are associated with electronic wave functions of widely varying nature. The MCSCF reference wave functions are designed to be sufficiently flexible to describe qualitatively the changes in the electronic structure over the broad range of geometries of interest. The necessary mixing of ionic, covalent, and Rydberg contributions, along with the appropriate treatment of the different electron-spin components (e.g. closed shell, high-spin open-shell, low-spin open shell, radical, diradical, etc.) of the wave functions, are treated correctly at this level. Further treatment of electron correlation effects is included using large scale multireference CI wave functions, particularly including the single and double excitations relative to the MCSCF reference space. This leads to the most flexible and accurate large-scale MRSDCI wave functions that have been used to date in global PES studies.

  8. Experimental and theoretical NMR study of selected oxocarboxylic acid oximes.

    Science.gov (United States)

    Malek, Kamilla; Vala, Martin; Kozłowski, Henryk; Proniewicz, Leonard M

    2004-01-01

    1H and 13C NMR spectra of the oxocarboxylic acid oximes 2-hydroxyiminopropanoic acid (1), 2-(4-methylthiazol-2-yl)-2-(hydroxyimino)acetic acid (2) and 2-cyano-2-(hydroxyimino)acetic acid (3) were measured in DMSO-d6, D2O and acetone-d6 solutions. The data indicate the presence of hydrogen bonding in 1 and 2 and a strong electron-withdrawing effect due to the cyano group in 3. The effect of intra- and intermolecular hydrogen bonding on the hydrogen and carbon chemical shifts in these molecules was studied theoretically. Total energy calculations of the stability of various hydrogen-bonded species, in addition to equilibrium parameters and chemical shifts, were calculated using ab initio methods (RHF, MP2) and density functional theory (B3LYP), implemented in the Gaussian 98 software package. The gauge-including atomic orbital (GIAO) method was used to predict magnetic shielding constants. Chemical shift calculations for the most stable species agree fairly well with the observed data, especially for the hydroxyl protons. Substituents adjacent to the alpha-carbon show some influence of the oximic and carboxyl groups on the 13C chemical shifts, as expected for groups with different polar and anisotropic character. Copyright 2003 John Wiley & Sons, Ltd.

  9. High-level theoretical study of the reaction between hydroxyl and ammonia: Accurate rate constants from 200 to 2500 K

    Science.gov (United States)

    Nguyen, Thanh Lam; Stanton, John F.

    2017-10-01

    Hydrogen abstraction from NH3 by OH to produce H2O and NH2—an important reaction in combustion of NH3 fuel—was studied with a theoretical approach that combines high level quantum chemistry and advanced chemical kinetics methods. Thermal rate constants calculated from first principles agree well (within 5%-20%) with available experimental data over a temperature range that extends from 200 to 2500 K. Quantum mechanical tunneling effects were found to be important; they lead to a decided curvature and non-Arrhenius behavior for the rate constant.

  10. 3D studies of coarserning kinetics of individual grains

    DEFF Research Database (Denmark)

    Poulsen, Stefan Othmar

    Techniques for fast, non-destructive characterization of the microstructure of materials using synchrotron X-ray radiation have in recent years become an important tool in materials science. The non-destructive nature of the techniques allows for time-resolved characterization of three-dimensiona...... to make general predictions of the coarsening kinetics of polycrystalline, dual-phase materials, specifically the coarsening mechanism, steady state distributions of grain size and topology, and interface morphology....... grains during recrystallization, where the recrystallization kinetics of individual grains and the temperature dependence of the recrystallization rate is examined, and for a study of grain structure and grain growth, where growth predictions are put forth in terms of the grain size and topology......-dimensional microstructures, i.e. direct probing of the evolution of specific microstructural features. Synchrotron X-ray radiation techniques have in the present work been employed for experimental characterization of microstructural evolution in individual grains during isothermal annealing: For a study of individual...

  11. Adsorption kinetic and thermodynamic studies of phosphate onto tantalum hydroxide.

    Science.gov (United States)

    Yu, Shi-Hua; Dong, Xiao-Le; Gong, Hong; Jiang, Heng; Liu, Zhi-Gang

    2012-12-01

    Tantalum hydroxide exhibits the ability for the removal of phosphate from aqueous solution. The kinetic study, adsorption isotherm, thermodynamic study, desorption, and foreign anions effect were examined in batch experiments. The kinetic process was very well described by a pseudo-second-order rate model. The adsorption isotherms showed that phosphate uptake fitted with a Langmuir-type model very well, with an increase of PO4(3-) adsorption capacity from 78.5 to 97.0 mg/g when the temperature increased from 298 to 338 K. The negative values of deltaG(0) and the positive values of deltaH(0) indicated that the phosphate adsorption process was spontaneous and endothermic naturally. While the deltaS(0) values obtained were positive, indicating an increase in randomness at the solid-liquid interface during the adsorption. Foreign anions tests showed that the presence of competitive ions cause minimal interference with the adsorption of phosphate on tantalum hydroxide.

  12. A theoretical study of the isotropic cut sphere fluids

    Science.gov (United States)

    Chamoux, Antoine; Perera, Aurélien

    1998-05-01

    The cut sphere fluid is studied in the isotropic phase by the Percus Yevick (PY) and the Hypernetted Chain (HNC) integral equation techniques, as well as by the theory recently proposed which is based on a geometrical interpretation of the direct correlation function. Fluids of cut spheres with thicknesses L* ranging from 0 to 0.7 have been studied, and detailed results for L*=0.1, 0.2, and 0.3 are reported. The L*=0 case is also examined. A new simplified version of the numerical implementation of the PY and HNC closures is proposed here. The results for pressures and structural properties are compared with the available simulations results and the recent theoretical results from the authors. The important feature of the present work is to show the ability of the HNC theory to predict the cubatic phase observed in the computer simulations for thicknesses around 0.2. The nematic phase is also predicted by the HNC theory for thicknesses smaller than L*=0.12. In agreement with previously obtained results, the detailed analysis of the PY theory results show that this approximation is unable to predict an instability toward any of the orientationally ordered fluid phases. The geometrical approach shows the correct trend for an isotropic to nematic transition, but exhibits an instability toward the cubatic phase only for thicknesses above L*=0.5, thus providing an illustration of the inability of standard density functional type theories to fully describe complex fluids. This study also sheds some light on the major differences between the three approaches in the treatment of many body density correlations.

  13. Theoretical study of incoherent {phi} photoproduction on a deuteron target

    Energy Technology Data Exchange (ETDEWEB)

    Sekihara, T. [Kyoto University, Department of Physics, Graduate School of Science, Kyoto (Japan); Kyoto University, Yukawa Institute for Theoretical Physics, Kyoto (Japan); Martinez Torres, A.; Jido, D. [Kyoto University, Yukawa Institute for Theoretical Physics, Kyoto (Japan); Oset, E. [Institutos de Investigacion de Paterna, Departamento de Fisica Teorica and IFIC, Centro Mixto Universidad de Valencia-CSIC, Valencia (Spain)

    2012-01-15

    We study the photoproduction of {phi} mesons in deuteron, paying attention to the modification of the cross-section from bound protons to the free ones. For this purpose we take into account Fermi motion in single scattering and rescattering of {phi} to account for {phi} absorption on a second nucleon as well as the rescattering of the proton on the neutron. We find that the contribution of the double scattering for {phi} is much smaller than the typical cross-section of {gamma}p{yields}{phi}p in free space, which implies a very small screening of the {phi} production in deuteron. The contribution from the proton rescattering, on the other hand, is found to be not negligible compared to the cross-section of {gamma}p{yields}{phi}p in free space, and leads to a moderate reduction of the {phi} photoproduction cross-section on a deuteron at forward angles if the LEPS set-up is taken into account. The Fermi motion allows contribution of the single scattering in regions forbidden by phase-space in the free case. In particular, we find that for momentum transfer squared close to the maximum value, the Fermi motion changes drastically the shape of d{sigma}/dt, to the point that the ratio of this cross-section to the free one becomes very sensitive to the precise value of t chosen, or the size of the bin used in an experimental analysis. Hence, this particular region of t does not seem to be the most indicated to find effects of a possible {phi} absorption in the deuteron. This reaction is studied theoretically as a function of t and the results are contrasted with recent experiments at LEPS and Jefferson Lab. The effect of the experimental angular cuts at LEPS is also discussed, providing guidelines for future experimental analyses of the reaction. (orig.)

  14. Slag founding: kinetic study and election of a grinding system

    Directory of Open Access Journals (Sweden)

    Salas Vinent, M. E.

    2001-06-01

    Full Text Available Here we offer results obtained in laboratories and industry, concerning the kinetic study of steelfounding in cement manufacture. We choose the most suitable grinding system, valuing also its economical and environmental repercussion. The obtained results indicated that the kinetic method is extremely useful to solve the practical problems in the conception and design of grinding systems, and it is also a speed and the inverted bolting-rell gap almost like a Arrhenius equation.

    Se presentan resultados logrados a escala de laboratorio e industrial referidos al estudio cinético de las escorias de fundición de aceros para la producción de cementos. Se realiza la elección del sistema de molienda más adecuado, valorando además el efecto económico y medio ambiental del mismo. De los resultados obtenidos se concluye que el método cinético resulta de extrema utilidad en la solución de problemas prácticos para la concepción y diseño de sistemas de molienda, amén de que en el plano teórico resulta una novedad la correlación encontrada entre la constante de velocidad de molienda y el inverso de la abertura del tamiz de modo similar a la ecuación de Arrhenius.

  15. Pulsed laser kinetic studies of liquids under high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Eyring, E.M.

    1991-11-25

    A high pressure apparatus constructed for measuring the rates of reactions in liquids under pressures ranging from 1 atm to 2000 atm has been used to measure the complexation kinetics of molybdenum hexacarbonyl reacting with 2,2-bipyridine, 4,4{prime}-dimethyl-2-2{prime}-bipyridine and 4,4{prime}-diphenyl-2-2{prime} bipyridine in toluene. Pentacarbonyl reaction intermediates are created by a 10 nsec flash of frequency tripled Nd:YAG laser light. Measured activation volumes for chelate ligand ring closure indicate a change in mechanism from associative interchange to dissociative interchange as steric hindrance increases. A similar high pressure kinetics study of molybdenum carbonyl complexation by several substituted phenanthrolines is now well advanced that indicates that with the more rigid phenanthroline ligands steric effects from bulky substituents have less effect on the ring closure mechanism than in the case of the bipyridine ligands. An experimental concentration dependence of the fluorescence quantum yield of cresyl violet has been harmonized with previously published contradictory reports. Fluorescence of cresyl violet in various solvents and in micellar systems has also been systematically explored.

  16. Kinetic study of sulphuric acid hydrolysis of protein feathers.

    Science.gov (United States)

    Ben Hamad Bouhamed, Sana; Kechaou, Nabil

    2017-05-01

    Poultry feather keratin is the most important by-product from the poultry industry due to its abundance. Different methods have been still applied to process this by-product such as enzymatic hydrolysis which is expensive and inapplicable at the industrial level. This paper presents a study of acid hydrolysis of poultry feathers using different types of acids, sulphuric acid concentration, different temperatures and solid to liquid ratio to obtain a liquid product rich in peptides. The feathers analysis revealed a crude protein content of 88.83%. A maximum peptides production of 676 mg/g was reached using sulphuric acid, 1 molar acid concentration and 50 g/l solid to liquid ratio at a temperature of 90 °C after 300 min. A reaction scheme for protein aggregation and decomposition to polypeptides and amino acids was proposed and a kinetic model for peptides production was developed. The proposed kinetic model proved to be well adapted to the experimental data with R (2) = 0.99.

  17. Kinetic Study of Free Radicals Scavenging by Saffron Petal Extracts

    Directory of Open Access Journals (Sweden)

    T. Ardalan

    2013-01-01

    Full Text Available Saffron petal is the main by-product of saffron processing which is produced in large amounts, annually. The objectives of this study were to study the antioxidant activity and free radical-scavenging effects of saffron petal extracts. The ability of saffron petal to act as an antioxidant using the 2, 2-diphenyl-1-picrylhydrazyl (DPPH free-radical method was investigated by applying the Uv–Vis spectrometry. The Uv–Vis spectra of reaction mixtures in acetonitrile revealed that saffron petal has a considerable effect on scavenging free radical. Kinetic studies were conducted by measuring the disappearance of DPPH in acetonitrile over the wavelength range of 515-522 nm under pseudo-first-order conditions at 37oC. Furthermore, the pseudo first order rate constants were determined

  18. Studying stellar rotation and convection theoretical background and seismic diagnostics

    CERN Document Server

    Belkacem, Kévin; Neiner, Coralie; Lignières, Francois; Green, John

    2013-01-01

    This volume synthesizes the results of work carried out by several international teams of the SIROCO (Seismology for Rotation and Convection) collaboration. It provides the theoretical background required to interpret the huge quantity of high-quality observational data recently provided by space experiments such as CoRoT and Kepler. Asteroseismology allows astrophysicists to test, to model and to understand stellar structure and evolution as never before. The chapters in this book address the two groups of topics summarized as "Stellar Rotation and Associated Seismology" as well as "Stellar Convection and Associated Seismology". The book offers the reader solid theoretical background knowledge and adapted seismic diagnostic techniques.

  19. Theoretical Study of the Compound Parabolic Trough Solar Collector

    Directory of Open Access Journals (Sweden)

    Dr. Subhi S. Mahammed

    2012-06-01

    Full Text Available Theoretical design of compound parabolic trough solar collector (CPC without tracking is presented in this work. The thermal efficiency is obtained by using FORTRAN 90 program. The thermal efficiency is between (60-67% at mass flow rate between (0.02-0.03 kg/s at concentration ratio of (3.8 without need to tracking system.The total and diffused radiation is calculated for Tikrit city by using theoretical equations. Good agreement between present work and the previous work.

  20. Surface composition of materials used as catalysts for methanol steam reforming: a theoretical study.

    Science.gov (United States)

    Lim, Kok Hwa; Moskaleva, Lyudmila V; Rösch, Notker

    2006-08-11

    PdZn (1:1) alloy is assumed to be the active component of a promising catalyst for methanol steam reforming. Using density functional calculations on periodic supercell slab models, followed by atomistic thermodynamics modeling, we study the chemical composition of the surfaces PdZn(111) and, as a reference, Cu(111) in contact with water and hydrogen at conditions relevant to methanol steam reforming. For the two surfaces, we determine similar maximum adsorption energies for the dissociative adsorption of H(2), O(2), and the molecular adsorption of H(2)O. These reactions are calculated to be exothermic by about -40, -320, and -20 kJ mol(-1), respectively. Using a thermodynamic analysis based on theoretically predicted adsorption energies and vibrational frequencies, we determine the most favorable surface compositions for given pressure windows. However, surface energy plots alone cannot provide quantitative information on individual coverages in a system of coupled adsorption reactions. To overcome this limitation, we employ a kinetic model, from which equilibrium surface coverages of H, O, OH, and H(2)O are derived. We also discuss the sensitivity of our results and the ensuing conclusions with regard to the model surfaces employed and the inaccuracies of our computational method. Our kinetic model predicts surfaces of both materials, PdZn and Cu, to be essentially adsorbate-free already from very low values of the partial pressure of H(2). The model surfaces PdZn(111) and Cu(111) are predicted to be free of water-related adsorbates for a partial H(2) pressure greater than 10(-8) and 10(-5) atm, respectively.

  1. Pulsed laser kinetic studies of liquids under high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Eyring, E.M.

    1992-09-22

    A laser flash photolysis kinetic study of 2,2{prime}-bipyridine bidentate chelating ligands with one claw in the first coordination sphere of a molybdenum carbonyl complex has been completed at pressures up to 150 MPa. The reaction mechanism for thermal ring closure is found from activation volumes to change from associative interchange to dissociative interchange as substituents on the 2,2{prime}-bipyridine ligands become bulkier. In a similar study of more rigid, substituted phenanthroline bidentate ligands it was found that substituent bulkiness had little effect on the thermal ring closure mechanism. Stability constants for lithium ion complexes with crown ethers in a room temperature molten salt, fluorescence quantum yields for cresyl violet and several other dyes in solution, and the oxidation of alcohols by OsO{sub 4} have also been investigated.

  2. Kinetic study of negative dry-film photoresists

    Directory of Open Access Journals (Sweden)

    2007-10-01

    Full Text Available Thanks to the differential photocalorimetry technique DPC, characteristics of negative photoresists (Riston® PM 215 and Riston® MM 140, 1 mil or 25.4 µm thickness to be developed in nonorganic aqueous medium used in microlithography are highlighted. The photoreactivity (being evaluated by DPC of the matrix polymer involved in these Riston® is critical for ensuring good lithographic performance. The influence of temperature and irradiation intensity on kinetic parameters such as the enthalpy of reaction ΔH, the time of induction (It, the conversion rate to the maximum peak (RPM, the coefficient rate of the reaction (k, the conversion rate α, and the polymerization rate Rp were studied. All the results highlights not only the strong differences between the two Riston® studied, but also the great reactivity of Riston® PM 215 compared to Riston® MM 140.

  3. Experimental and theoretical study of magnetohydrodynamic ship models.

    Directory of Open Access Journals (Sweden)

    David Cébron

    Full Text Available Magnetohydrodynamic (MHD ships represent a clear demonstration of the Lorentz force in fluids, which explains the number of students practicals or exercises described on the web. However, the related literature is rather specific and no complete comparison between theory and typical small scale experiments is currently available. This work provides, in a self-consistent framework, a detailed presentation of the relevant theoretical equations for small MHD ships and experimental measurements for future benchmarks. Theoretical results of the literature are adapted to these simple battery/magnets powered ships moving on salt water. Comparison between theory and experiments are performed to validate each theoretical step such as the Tafel and the Kohlrausch laws, or the predicted ship speed. A successful agreement is obtained without any adjustable parameter. Finally, based on these results, an optimal design is then deduced from the theory. Therefore this work provides a solid theoretical and experimental ground for small scale MHD ships, by presenting in detail several approximations and how they affect the boat efficiency. Moreover, the theory is general enough to be adapted to other contexts, such as large scale ships or industrial flow measurement techniques.

  4. Experimental and theoretical study of magnetohydrodynamic ship models.

    Science.gov (United States)

    Cébron, David; Viroulet, Sylvain; Vidal, Jérémie; Masson, Jean-Paul; Viroulet, Philippe

    2017-01-01

    Magnetohydrodynamic (MHD) ships represent a clear demonstration of the Lorentz force in fluids, which explains the number of students practicals or exercises described on the web. However, the related literature is rather specific and no complete comparison between theory and typical small scale experiments is currently available. This work provides, in a self-consistent framework, a detailed presentation of the relevant theoretical equations for small MHD ships and experimental measurements for future benchmarks. Theoretical results of the literature are adapted to these simple battery/magnets powered ships moving on salt water. Comparison between theory and experiments are performed to validate each theoretical step such as the Tafel and the Kohlrausch laws, or the predicted ship speed. A successful agreement is obtained without any adjustable parameter. Finally, based on these results, an optimal design is then deduced from the theory. Therefore this work provides a solid theoretical and experimental ground for small scale MHD ships, by presenting in detail several approximations and how they affect the boat efficiency. Moreover, the theory is general enough to be adapted to other contexts, such as large scale ships or industrial flow measurement techniques.

  5. THEORETICAL STUDY (AB INITIO AND DFT METHODS) ON ...

    African Journals Online (AJOL)

    We considered several ionization reactions and equilibriums in water that constitute the indispensable theoretical ... of these indicators also have the typical properties of acid-base indicators and the color changes are the result of the ... acidic and basic properties of the XO molecule, which can form various complexes, the.

  6. Theoretical studies of ethylnitrolic acid using Gaussian | Nikafshar ...

    African Journals Online (AJOL)

    The tautomerism of all possible forms of ethylnitrolic acid was investigated theoretically in various environment including gas phase, ethanol, dimethyl sulfoxide (DMSO) and water. The calculations were carried out at DFT/B3LYP and MP2 of theory singly. It was found that, form of B eythynitrolic acid is the most stable isomer ...

  7. Experimental and theoretical study of precast beam-slab construction

    African Journals Online (AJOL)

    The use of partially precast beam elements with shear connectors in slab construction relieves the requirement of extensive use of soffit formwork and props and will have the advantage of faster construction. It also reduces adverse effects associated deforestation. Experimental and theoretical investigations were conducted ...

  8. Theoretical studies of mutual diffusivities and surface properties in ...

    Indian Academy of Sciences (India)

    for phenomena such as gas absorption, nucleation of gas bubbles, nucleation and growth of nonmetallic inclusions and slag/metal reactions [7]. On the other ...... for the Theoretical Physics for financial support as associate member of the Centre. References. [1] R Novakovic, D Giuranno, E Ricci and T Lanata, Surface Sci.

  9. Theoretical and computational studies in protein folding, design, and function

    Science.gov (United States)

    Morrissey, Michael Patrick

    2000-10-01

    In this work, simplified statistical models are used to understand an array of processes related to protein folding and design. In Part I, lattice models are utilized to test several theories about the statistical properties of protein-like systems. In Part II, sequence analysis and all-atom simulations are used to advance a novel theory for the behavior of a particular protein. Part I is divided into five chapters. In Chapter 2, a method of sequence design for model proteins, based on statistical mechanical first-principles, is developed. The cumulant design method uses a mean-field approximation to expand the free energy of a sequence in temperature. The method successfully designs sequences which fold to a target lattice structure at a specific temperature, a feat which was not possible using previous design methods. The next three chapters are computational studies of the double mutant cycle, which has been used experimentally to predict intra-protein interactions. Complete structure prediction is demonstrated for a model system using exhaustive, and also sub-exhaustive, double mutants. Nonadditivity of enthalpy, rather than of free energy, is proposed and demonstrated to be a superior marker for inter-residue contact. Next, a new double mutant protocol, called exchange mutation, is introduced. Although simple statistical arguments predict exchange mutation to be a more accurate contact predictor than standard mutant cycles, this hypothesis was not upheld in lattice simulations. Reasons for this inconsistency will be discussed. Finally, a multi-chain folding algorithm is introduced. Known as LINKS, this algorithm was developed to test a method of structure prediction which utilizes chain-break mutants. While structure prediction was not successful, LINKS should nevertheless be a useful tool for the study of protein-protein and protein-ligand interactions. The last chapter of Part I utilizes the lattice to explore the differences between standard folding, from

  10. Experimental study of the kinetic inductance fraction of superconducting coplanar waveguide

    Energy Technology Data Exchange (ETDEWEB)

    Gao, J. [California Institute of Technology, Pasadena, CA 91125 (United States)]. E-mail: jgao@ist.caltech.edu; Zmuidzinas, J. [California Institute of Technology, Pasadena, CA 91125 (United States); Mazin, B.A. [Jet Propulsion Lab, Pasadena, CA 91107 (United States); Day, P.K. [Jet Propulsion Lab, Pasadena, CA 91107 (United States); Leduc, H.G. [Jet Propulsion Lab, Pasadena, CA 91107 (United States)

    2006-04-15

    We have studied the kinetic inductance fraction (ratio of kinetic inductance to total inductance) of superconducting coplanar waveguides (CPWs) by measuring the resonance frequency of CPW transmission line resonators. We describe a procedure for accurately determining the kinetic inductance of transmission line geometries with small kinetic inductance fractions. In this approach, we compare the temperature dependence of the resonance frequency with that of a resonator of the same film thickness but with a large kinetic inductance fraction. We present data for 200 nm-thick Al CPWs of several geometries and compare that with our own calculations and with calculations found in literature.

  11. UV/Vis Spectroscopy Studies of the Photoisomerization Kinetics in Self-Assembled Azobenzene-Containing Adlayers.

    Science.gov (United States)

    Krekiehn, N R; Müller, M; Jung, U; Ulrich, S; Herges, R; Magnussen, O M

    2015-08-04

    Direct comparative studies of the photoisomerization of azobenzene derivatives in self-assembled adlayers on Au and as free molecules in dichloromethane solution were performed using UV/vis spectroscopy. For all studied systems a highly reversible trans-cis isomerization in the adlayer is observed. Quantitative studies of the absorbance changes and photoisomerization kinetics reveal that in azobenzenes mounted as freestanding vertical groups on the surface via triazatriangulene-based molecular platforms photoswitching is nearly uninhibited by the local environment in the adlayer. The blue-shift of the π-π* transition in adlayers of these molecules is in good agreement with theoretical studies of the effect of excitonic coupling between the molecules. In contrast, in azobenzene-containing thiol self-assembled monolayers the fraction of photoswitching molecules and the photoisomerization kinetics are significantly reduced compared to free molecules in solution.

  12. Thermogravimetric kinetic study of agricultural residue biomass pyrolysis based on combined kinetics.

    Science.gov (United States)

    Wang, Xun; Hu, Mian; Hu, Wanyong; Chen, Zhihua; Liu, Shiming; Hu, Zhiquan; Xiao, Bo

    2016-11-01

    Pyrolytic kinetic of an agricultural residue (AR) feedstock, a mixture of plants (cotton, wheat, rich, corn) stems, was investigated based on combined kinetics. The most suitable mechanism for AR one-step pyrolysis was f(α)=(1-α)(1.1816)α(-1.8428) with kinetic parameters of: apparent activation energy 221.7kJ/mol, pre-exponential factor 4.17E16s(-1). Pyrolysis of AR feedstock could not be described by one-step reaction attributes to heterogeneous features of pyrolysis processes. Combined kinetics three-parallel-reaction (CK-TPR) model fitted the pyrolysis experimental data very well. Reaction mechanisms for pseudo hemicelluloses, cellulose, lignin in CK-TPR model was f(α)=(1-α)(1.6244)α(-0.3371)[-ln(1-α)](-0.0515), f(α)=(1-α)(1.0597)α(-0.6909)[-ln(1-α)](0.9026) and f(α)=(1-α)(2.9577)α(-4.7719), respectively. Apparent activation energy of three pseudo components followed the order of Elignin(197.3kJ/mol)>Ecellulose(176.3kJ/mol)>Ehemicelluloses (151.1kJ/mol). Mechanism of hemicelluloses pyrolysis could be further expressed as f(α)=(1-α)(1.4). The pyrolytic mechanism of cellulose met the Nucleation well. However, mechanism of lignin pyrolysis was complex, which possibly was the combined effects of Nucleation, Diffusion, Geometrical contraction, and Power law. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Carbohydrate deficient transferrin (CDT) in alcoholic cirrhosis: a kinetic study

    DEFF Research Database (Denmark)

    Henriksen, Jens Henrik; Grønbaek, M; Møller, Søren

    1997-01-01

    of carbohydrate deficient transferrin in liver and kidney. METHODS/RESULTS: The median value of serum carbohydrate deficient transferrin was 16.0 U/l in patients with alcoholic cirrhosis (n = 41), and this value was not significantly different from that of a normal control group (median 17.4 U/l, n = 55, ns......BACKGROUND/AIMS: Carbohydrate deficient transferrin has been introduced as a marker of excessive alcohol intake. The present study was undertaken in order to measure the circulating level of carbohydrate deficient transferrin in patients with alcoholic cirrhosis and to assess arteriovenous kinetics......). Carbohydrate deficient transferrin was significantly higher in patients with cirrhosis and high current alcohol intake than in abstaining patients (20 vs. 14 U/l, p alcohol intake (> 50 g/day) had a significantly higher carbohydrate deficient transferrin...

  14. A study of butyl acetate synthesis. 4-reaction kinetics

    Directory of Open Access Journals (Sweden)

    Álvaro Orjuela Londoño

    2006-05-01

    Full Text Available This work was aimed at studying liquid-phase acetic acid and butyl alcohol esterification reaction (P atm =0.76 Bar,using an ion exchange resin (Lewatit K-2431 as catalyst. The effect of the absence of internal and external mass transport on catalyst particles was established in the research conditions used here. A set of assays to determine the effect of catalyst load (0.5%, 1%, 2% w/w temperature (73°C, 80°C, 87°C and molar ratio (1:2, 1:1, 2:1 acid/alcohol on reaction rate was carried out and both LHHW and pseudo-homogeneous kinetic expressions were obtained, these being in good agreement with the experimental data.

  15. An Experimental and Kinetic Modeling Study of Methyl Decanoate Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Sarathy, S M; Thomson, M J; Pitz, W J; Lu, T

    2010-02-19

    Biodiesel is typically a mixture of long chain fatty acid methyl esters for use in compression ignition engines. Improving biofuel engine performance requires understanding its fundamental combustion properties and the pathways of combustion. This research study presents new combustion data for methyl decanoate in an opposed-flow diffusion flame. An improved detailed chemical kinetic model for methyl decanoate combustion is developed, which serves as the basis for deriving a skeletal mechanism via the direct relation graph method. The novel skeletal mechanism consists of 648 species and 2998 reactions. This mechanism well predicts the methyl decanoate opposed-flow diffusion flame data. The results from the flame simulations indicate that methyl decanoate is consumed via abstraction of hydrogen atoms to produce fuel radicals, which lead to the production of alkenes. The ester moiety in methyl decanoate leads to the formation of low molecular weight oxygenated compounds such as carbon monoxide, formaldehyde, and ketene.

  16. Preliminary study on mechanics-based rainfall kinetic energy

    Directory of Open Access Journals (Sweden)

    Yuan Jiuqin Ms.

    2014-09-01

    Full Text Available A raindrop impact power observation system was employed to observe the real-time raindrop impact power during a rainfall event and to analyze the corresponding rainfall characteristics. The experiments were conducted at different simulated rainfall intensities. As rainfall intensity increased, the observed impact power increased linearly indicating the power observation system would be satisfactory for characterizing rainfall erosivity. Momentum is the product of mass and velocity (Momentum=MV, which is related to the observed impact power value. Since there is no significant difference between momentum and impact power, observed impact power can represent momentum for different rainfall intensities. The relationship between momentum and the observed impact power provides a convenient way to calculate rainfall kinetic energy. The value of rainfall kinetic energy based on the observed impact power was higher than the classic rainfall kinetic energy. The rainfall impact power based kinetic energy and the classic rainfall kinetic energy showed linear correlation, which indicates that the raindrop impact power observation system can characterize rainfall kinetic energy. The article establishes a preliminary way to calculate rainfall kinetic energy by using the real-time observed momentum, providing a foundation for replacing the traditional methods for estimating kinetic energy of rainstorms.

  17. Kinetic studies of cellulose enzymatic hydrolysis from pretreated corn cob

    Science.gov (United States)

    Stevanie, Jeannie; Kartawiria, Irvan; Abimanyu, Haznan

    2017-01-01

    Successful utilization of corn cob biomass as raw material in bioethanol production is depending on the hydrolysis process where high level of β-cellulose is converted into glucose. Enzymatic hydrolysis is the common process for this purpose. This study is focusing on the evaluation of hydrolysis of pre-treated corn cob using Novozymes Cellic ® C-Tec2 and H-Tec2 enzymes to obtain the optimum reaction condition and its general reaction kinetics. The corn cob used was pretreated using 10% of NaOH solution. Hydrolysis reactions were conducted in 250 ml Erlenmeyer flask for 72 hour using mixture of C-Tec2 and H-Tec2 enzymes at the fixed ratio of 5:1 and glucose concentration were measured using HPLC. Reaction temperature of 40°C and quantity of 0.5 ml enzyme solution per gram substrate gives the highest reaction rate (0.0123 gram of glucose/gram sample.h) with the glucose yield being 0.089 g glucose/ g substrate. Total conversion of cellulose observed was 11.91 %. Corn cob hydrolysis using C-Tec2 and H-Tec2 enzymes also result in xylose (0.0202 g/g substrate), which can also contribute to bioethanol productivity in further fermentation process. The reaction is following zero order kinetics for the first 8 hours and reaches maximum yield within 10 hours; significantly shorter compared to previous studies of cellulosic material hydrolysis that may take up to 72 hour to complete. Prolonging the hydrolysis of pre-treated corn cob more than 24 hour gives no significant increase in glucose conversion and yield. Hydrolysis temperature range of 40°C to 60°C is in accordance with the manufacturer recommendation for the purpose; however the decrease of reaction rate is observable at temperature 50°C or higher.

  18. Cross-metathesis of polynorbornene with polyoctenamer: a kinetic study.

    Science.gov (United States)

    Denisova, Yulia I; Gringolts, Maria L; Peregudov, Alexander S; Krentsel, Liya B; Litmanovich, Ekaterina A; Litmanovich, Arkadiy D; Finkelshtein, Eugene Sh; Kudryavtsev, Yaroslav V

    2015-01-01

    The cross-metathesis of polynorbornene and polyoctenamer in d-chloroform mediated by the 1(st) generation Grubbs' catalyst Cl2(PCy3)2Ru=CHPh is studied by monitoring the kinetics of carbene transformation and evolution of the dyad composition of polymer chains with in situ (1)H and ex situ (13)C NMR spectroscopy. The results are interpreted in terms of a simple kinetic two-stage model. At the first stage of the reaction all Ru-benzylidene carbenes are transformed into Ru-polyoctenamers within an hour, while the polymer molar mass is considerably decreased. The second stage actually including interpolymeric reactions proceeds much slower and takes one day or more to achieve a random copolymer of norbornene and cyclooctene. Its rate is limited by the interaction of polyoctenamer-bound carbenes with polynorbornene units, which is hampered, presumably due to steric reasons. Polynorbornene-bound carbenes are detected in very low concentrations throughout the whole process thus indicating their higher reactivity, as compared with the polyoctenamer-bound ones. Macroscopic homogeneity of the reacting media is proved by dynamic light scattering from solutions containing the polymer mixture and its components. In general, the studied process can be considered as a new way to unsaturated multiblock statistical copolymers. Their structure can be controlled by the amount of catalyst, mixture composition, and reaction time. It is remarkable that this goal can be achieved with a catalyst that is not suitable for ring-opening metathesis copolymerization of norbornene and cis-cyclooctene because of their substantially different monomer reactivities.

  19. Cross-metathesis of polynorbornene with polyoctenamer: a kinetic study

    Directory of Open Access Journals (Sweden)

    Yulia I. Denisova

    2015-10-01

    Full Text Available The cross-metathesis of polynorbornene and polyoctenamer in d-chloroform mediated by the 1st generation Grubbs’ catalyst Cl2(PCy32Ru=CHPh is studied by monitoring the kinetics of carbene transformation and evolution of the dyad composition of polymer chains with in situ 1H and ex situ 13C NMR spectroscopy. The results are interpreted in terms of a simple kinetic two-stage model. At the first stage of the reaction all Ru-benzylidene carbenes are transformed into Ru-polyoctenamers within an hour, while the polymer molar mass is considerably decreased. The second stage actually including interpolymeric reactions proceeds much slower and takes one day or more to achieve a random copolymer of norbornene and cyclooctene. Its rate is limited by the interaction of polyoctenamer-bound carbenes with polynorbornene units, which is hampered, presumably due to steric reasons. Polynorbornene-bound carbenes are detected in very low concentrations throughout the whole process thus indicating their higher reactivity, as compared with the polyoctenamer-bound ones. Macroscopic homogeneity of the reacting media is proved by dynamic light scattering from solutions containing the polymer mixture and its components. In general, the studied process can be considered as a new way to unsaturated multiblock statistical copolymers. Their structure can be controlled by the amount of catalyst, mixture composition, and reaction time. It is remarkable that this goal can be achieved with a catalyst that is not suitable for ring-opening metathesis copolymerization of norbornene and cis-cyclooctene because of their substantially different monomer reactivities.

  20. Forth-back oscillated charge carrier motion in dynamically disordered hexathienocoronene molecules: a theoretical study.

    Science.gov (United States)

    Navamani, K; Senthilkumar, K

    2015-07-21

    Electronic structure calculations were performed to investigate the charge transport properties of hexathienocoronene (HTC) based molecules. The effective displacement of the charge carrier along the π-orbital of nearby molecules is calculated by monitoring the forth and back oscillations of the charge carrier through kinetic Monte Carlo simulation. The charge transport parameters such as charge transfer rate, mobility, hopping conductivity, localized charge density, time average effective mass and degeneracy pressure are calculated and used to study the charge transport mechanism in the studied molecules. The existence of degeneracy levels facilitates the charge transfer and is analyzed through degeneracy pressure. Theoretical results show that the site energy difference in the dynamically disordered system controls the forth-back oscillation of charge carrier and facilitates the unidirectional charge transport mechanism along the sequential localized sites. The ethyl substituted HTC has good hole and electron hopping conductivity of 415 and 894 S cm(-1), respectively, whereas unsubstituted HTC has the small hole mobility of 0.06 cm(2) V(-1) s(-1) which is due to large average effective mass of 1.42 × 10(-28) kg.

  1. Spectroscopic Analysis of Neurotransmitters: A Theoretical and Experimental Raman Study

    Science.gov (United States)

    Alonzo, Matthew

    Surface-enhanced Raman spectroscopy (SERS) was applied to investigate the feasibility in the detection and monitoring of the dopamine (DA) neurotransmitter adsorbed onto silver nanoparticles (Ag NPs) at 10-11 molar, a concentration far below physiological levels. In addition, density functional theory (DFT) calculations were obtained with the Gaussian-09 analytical suite software to generate the theoretical molecular configuration of DA in its neutral, cationic, anionic, and dopaminequinone states for the conversion of computer-simulated Raman spectra. Comparison of theoretical and experimental results show good agreement and imply the presence of dopamine in all of its molecular forms in the experimental setting. The dominant dopamine Raman bands at 750 cm-1 and 795 cm-1 suggest the adsorption of dopaminequinone onto the silver nanoparticle surface. The results of this experiment give good insight into the applicability of using Raman spectroscopy for the biodetection of neurotransmitters.

  2. Theoretical Study of a Thermophysical Property of Molten Semiconductors

    Directory of Open Access Journals (Sweden)

    Fathi Aqra

    2011-01-01

    Full Text Available This paper deals with theoretical approach to surface tension of molten silicon and germanium, and contributes to this field, which is very important. A theoretical calculation for determining the surface tension of high-temperature semiconductor melts, such as molten silicon and germanium, in the temperature range 1687–1825 K and 1211–1400 K, respectively, is described. The calculated temperature-dependence surface tension data for both Si and Ge are expressed as =876−0.32(− and =571−0.074(− (mJ m−2, respectively. These values are in consistence with the reported experimental data (720–875 for Si and 560–632 mJ m−2 for Ge. The calculated surface tension for both elements decreases linearly with temperature.

  3. A theoretical study of ternary indole-cation-anion complexes.

    Science.gov (United States)

    Carrazana-García, Jorge A; Cabaleiro-Lago, Enrique M; Campo-Cacharrón, Alba; Rodríguez-Otero, Jesús

    2014-12-07

    The simultaneous interactions of an anion and a cation with a π system were investigated by MP2 and M06-2X theoretical calculations. Indole was chosen as a model π system for its relevance in biological environments. Two different orientations of the anion, interacting with the N-H and with the C-H groups of indole, were considered. The four cations (Na(+), NH4(+), C(NH2)3(+) and N(CH3)4(+)) and the four anions (Cl(-), NO3(-), HCOO(-) and BF4(-)) included in the study are of biological interest. The total interaction energy of the ternary complexes was calculated and separated into its two- and three-body components and all of them are further divided into their electrostatic, exchange, repulsion, polarization and dispersion contributions using the local molecular orbital-energy decomposition analysis (LMO-EDA) methodology. The binding energy of the indole-cation-anion complexes depends on both ions, with the cation having the strongest effect. The intense cation-anion attraction determines the geometric and energetic features in all ternary complexes. These structures, with both ions on the same side of the π system, show an anti-cooperative interaction. However, the interaction is not only determined by electrostatics, but also the polarization contribution is important. Specific interactions like the one established between the anion and the N-H group of indole or the proton transfer between an acidic cation and a basic anion play a significant role in the energetics and the structure of particular complexes. The presence of the polar solvent as modelled with the polarizable continuum model (PCM) does not seem to have a significant effect on the geometry of the ternary complexes, but drastically weakens the interaction energy. Also, the strength of the interaction is reduced at a faster rate when the anion is pushed away, compared to the results obtained in the gas phase. The combination of PCM with the addition of one water molecule indicates that the PCM

  4. Rovibrational and temperature effects in theoretical studies of NMR parameters

    DEFF Research Database (Denmark)

    Faber, Rasmus; Kaminsky, Jakub; Sauer, Stephan P. A.

    2016-01-01

    The demand for high precision calculations of NMR shieldings (or their related values, chemical shifts δ) and spin-spin coupling constants facilitating and supporting detailed interpretations of NMR spectra increases hand in hand with the development of computational techniques and hardware...... resources. Highly sophisticated calculations including even relativistic effects are nowadays possible for these properties. However, NMR parameters depend not only on molecular structure and environment but also on molecular flexibility and temperature and the apparent success of theoretical predictions...

  5. MULTIMEDIA LEARNING METHODS IN THE STUDY OF THEORETICAL MECHANICS

    Directory of Open Access Journals (Sweden)

    А.Р. Kudin

    2013-03-01

    Full Text Available This Article is dedicated to the development of the modern methodological foundation based on ICT to support the teaching process of theoretical mechanics in pedagogical universities in the "Mathematics" specialty. Proposed metodological system is based on methodological multimedia teaching complex, made of internet-capable software products. The Paper covers the methodological issues of using individual elements of the complex at various stages of the learning process.

  6. Pathways in coal thermolysis: a theoretical and experimental study with model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ekpenyong, I.A.; Virk, P.S.

    1982-01-01

    Fundamental aspects of coal thermolysis were investigated, including how the chemical structures of aromatics, hydroaromatics, and alcohols affect their reactivities as hydrogen donors and acceptors in coal processing. The susceptibilities of substructural entities in coals to fragmentation via a number of thermal pericyclic and free radical mechanisms were probed, as were the factors governing relative reactivities within series of such coal model compounds. The theoretical part of the work applied perturbation molecular orbital (PMO) and frontier orbital theories, in conjunction with ..pi..- and pseudo-..pi.. MO's, to the study of model compound reactivity. This enabled prediction of reactivity patterns of H-donors, H-acceptors and coal-like structures as functions of their ..pi..- and sigma-bond configurations, including heteroatomic effects. Experimentally, the liquid phase reactions of the coal model compound PhOCH/sub 2/Ph (Benzyl phenyl ether, BPE) were detailed for the first time in each of four hydronaphthalene H-donor solvents in the temperature range 220/sup 0/ to 300/sup 0/C. The thermolysis of BPE exhibited a pronounced dependence on solvent structure, both with respect to product selectivities and reaction kinetics. BPE thermolysis pathways were delineated as involving (a) rearrangement, leading to isomerization, (b) hydrogenations, leading ultimately to PhOH and PhCH/sub 3/ products, and (c) addition reactions, engendering heavy products. Pathways (b) and (c) are competitive and, in each, self-reactions of BPE-derivatives vie against reactions between these and the donor solvent. Of the detailed free radical and pericyclic reaction mechanisms postulated, the latter rationalized many more facets of the BPE results than the former. The theoretical and experimental results were appraised against previous coal thermolysis literature.

  7. The kinetic study of oxidation of iodine by hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Cantrel, L. [Institut de Protection et de Surete Nucleaire, IPNS, CEN Cadarache, Saint Paul lez Durance (France); Chopin, J. [Laboratoire d`Electrochimie Inorganique, ENSSPICAM, Marseille (France)

    1996-12-01

    Iodine chemistry is one of the most important subjects of research in the field of reactor safety because this element can form volatile species which represent a biological hazard for environment. As the iodine and the peroxide are both present in the sump of the containment in the event of a severe accident on a light water nuclear reactor, it can be important to improve the knowledge on the reaction of oxidation of iodine by hydrogen peroxide. The kinetics of iodine by hydrogen peroxide has been studied in acid solution using two different analytical methods. The first is a UV/Vis spectrophotometer which records the transmitted intensity at 460 nm as a function of time to follow the decrease of iodine concentration, the second is an amperometric method which permits to record the increase of iodine+1 with time thanks to the current of reduction of iodine+1 to molecular iodine. The iodine was generated by Dushman reaction and the series of investigations were made at 40{sup o}C in a continuous stirring tank reactor. The influence of the initial concentrations of iodine, iodate, hydrogen peroxide, H{sup +} ions has been determined. The kinetics curves comprise two distinct chemical phases both for molecular iodine and for iodine+1. The relative importance of the two processes is connected to the initial concentrations of [I{sub 2}], [IO{sub 3}{sup -}], [H{sub 2}O{sub 2}] and [H{sup +}]. A rate law has been determined for the two steps for molecular iodine. (author) figs., tabs., 22 refs.

  8. Cure kinetic study of methacrylate-POSS copolymers for ocular lens.

    Science.gov (United States)

    Shokrolahi, F; Zandi, M; Shokrollahi, P; Atai, M; Ghafarzadeh, E; Hanifeh, M

    2017-10-25

    The physical, mechanical and biological properties of multicomponent acrylate-based hard lenses are directly influenced by degree of conversion achieved during copolymerization. In this research, polyhedral oligomeric silsesquioxane (POSS) acrylate is introduced into the polymer backbone in combination with hydroxyethyl methacrylate, dimethyl itaconate, methyl methacrylate, 3-(trimethoxysilyl) propyl methacrylate and triethylene glycol dimethacrylate in free-radical bulk polymerization. Kinetics of curing process was investigated by two techniques: differential scanning calorimetry and FTIR spectroscopy. Reaction kinetics in free-radical bulk polymerization of the system was studied by isothermal DSC performed at 65, 75, 85, and 95 °C using different quantities of initiator. Three compounds were prepared in different concentrations (0.2, 0.4 and 0.6 mol%) of 2,2'-azobisisobutyronitrile as initiator. Conversion rate was calculated as a function of time using data obtained from DSC measurements. The kinetic parameters of the reaction such as reaction constants, reaction orders and activation energies were obtained from the isothermal DSC data according to the autocatalytic model developed by Kamal and Sourour. The results showed that the experimental values were in good agreement with theoretically estimated values and our results may suggest that the polymerization reaction of this system is well described by Kamal's model. Cytotoxicity results, performed on extracts 28 days after PBS incubation, showed no toxicity of the materials extracted from the lenses indicating that they can be considered as safe materials in ocular lens applications. The viability and proliferation of L929 fibroblast cells in extracting media were followed by 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) and they may have a great potential as ideal supporting lens in people who suffer from keratoconus disease.

  9. Kinetic Study and Thermal Decomposition Behavior of Lignite Coal

    Directory of Open Access Journals (Sweden)

    Mehran Heydari

    2015-01-01

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

  10. Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate

    KAUST Repository

    Wu, Junjun

    2017-08-03

    We report a systematic chemical kinetics study of the H-atom abstractions from ethyl formate (EF) by H, O(3P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range of 500‒2500 K by the transition state theory (TST) in conjunction with asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900‒1321 K and 1.4‒2.0 atm. Our theoretical rate constants of OH + EF → Products agree well with the experimental results within 15% over the experimental temperature range of 900‒1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.

  11. Theoretical and experimental study of carburisation and decarburisation of a meta-stable austenitic steel

    Directory of Open Access Journals (Sweden)

    Charles West

    2005-12-01

    Full Text Available Metastable austenitic stainless steels are known to undergo a partial transformation of austenite to martensite as a consequence of plastic deformation. In the case of cyclic loading, a certain level of plastic strain must be exceeded, and phase formation takes place after an incubation period, during which the necessary amount of plastic deformation is accumulated. The susceptibility of the austenitic phase to deformation-induced martensite formation is strongly affected by the temperature of loading and the stability of austenite, which itself depends on the chemical composition. A key element in this regard is carbon which stabilizes the austenitic phase. It is shown in this study that the carbon concentration can be analysed systematically and reproducible by means of annealing treatments, if the parameters of these treatments are carefully defined on the basis of advanced theoretical thermodynamic and kinetic considerations. First results on the effect of carbon concentration and temperature of fatigue testing on the austenite/martensite transformation are presented, in order to illustrate the significance of these parameters on the martensite formation rate.

  12. COMBINED THEORETICAL AND EXPERIMENTAL INVESTIGATION OF MECHANISMS AND KINETICS OF VAPOR-PHASE MERCURY UPTAKE BY CARBONACOUES SURFACES

    Energy Technology Data Exchange (ETDEWEB)

    Radisav D. Vidic

    2002-05-01

    The first part of this study evaluated the application of a versatile optical technique to study the adsorption and desorption of model adsorbates representative of volatile polar (acetone) and non-polar (propane) organic compounds on a model carbonaceous surface under ultra high vacuum (UHV) conditions. The results showed the strong correlation between optical differential reflectance (ODR) and adsorbate coverage determined by temperature programmed desorption (TPD). ODR technique was proved to be a powerful tool to investigate surface adsorption and desorption from UHV to high pressure conditions. The effects of chemical functionality and surface morphology on the adsorption/desorption behavior of acetone, propane and mercury were investigated for two model carbonaceous surfaces, namely air-cleaved highly oriented pyrolytic graphite (HOPG) and plasma-oxidized HOPG. They can be removed by thermal treatment (> 500 K). The presence of these groups almost completely suppresses propane adsorption at 90K and removal of these groups leads to dramatic increase in adsorption capacity. The amount of acetone adsorbed is independent of surface heat treatment and depends only on total exposure. The effects of morphological heterogeneity is evident for plasma-oxidized HOPG as this substrate provides greater surface area, as well as higher energy binding sites. Mercury adsorption at 100 K on HOPG surfaces with and without chemical functionalities and topological heterogeneity created by plasma oxidation occurs through physisorption. The removal of chemical functionalities from HOPG surface enhances mercury physisorption. Plasma oxidation of HOPG provides additional surface area for mercury adsorption. Mercury adsorption by activated carbon at atmospheric pressure occurs through two distinct mechanisms, physisorption below 348 K and chemisorption above 348 K. No significant impact of oxygen functionalities was observed in the chemisorption region. The key findings of this study

  13. Theoretical study of ferroelectric nanoparticles using phase reconstructed electron microscopy

    DEFF Research Database (Denmark)

    Phatak, C.; Petford-Long, A. K.; Beleggia, Marco

    2014-01-01

    Ferroelectric nanostructures are important for a variety of applications in electronic and electro-optical devices, including nonvolatile memories and thin-film capacitors. These applications involve stability and switching of polarization using external stimuli, such as electric fields. We present...... a theoretical model describing how the shape of a nanoparticle affects its polarization in the absence of screening charges, and quantify the electron-optical phase shift for detecting ferroelectric signals with phase-sensitive techniques in a transmission electron microscope. We provide an example phase shift...

  14. Energy landscape and diffusion kinetics of lithiated silicon: A kinetic activation-relaxation technique study

    Science.gov (United States)

    Trochet, Mickaël; Mousseau, Normand

    2017-10-01

    With large specific and volumetric capacity, lithiated silicon is an excellent anode for lithium-ion batteries. Its application is challenged today, however, by the formation of an amorphous a -LixSi phase associated with a large volume change that occurs at relatively low Li concentration and remains only very partly understood at the microscopic level. In this paper, we characterize the full energy landscape associated with the onset of Li insertion in crystalline Si as a first step for understanding the lithiation process. We identify the diffusion mechanisms and migration energies for one to ten Li atoms in a Si crystal as well as the average lifetime of small lithium aggregates, using the kinetic activation-relaxation technique (kART), an off-lattice kinetic Monte-Carlo method with on-the-fly catalog building capabilities coupled to a newly developed force field (ReaxFF) used as potential based on ab initio results. We show that the short lifetimes of the bound states (from meV to ten meV) mean that Li atoms move in the interstitial sublattice with little interactions, explaining how high Li concentration in Si can be reached.

  15. Protonation of caffeine: A theoretical and experimental study

    Energy Technology Data Exchange (ETDEWEB)

    Bahrami, Hamed [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of); Tabrizchi, Mahmoud, E-mail: m-tabriz@cc.iut.ac.ir [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of); Farrokhpour, Hossein [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of)

    2013-03-29

    Highlights: ► Protonation of caffeine was examined by ion mobility spectrometry equipped with two ionization sources. ► Experimental and theoretical evidence was collected to assign the observed peaks to caffeine related ionic species. ► A new concept of “internal proton affinity”, the protonation tendency for each atom in a molecule, was defined. - Abstract: Protonation of caffeine was examined by ion mobility spectrometry equipped with two ionization sources, corona discharge (CD) and UV photoionization. Three peaks were observed in ion mobility spectrum by simultaneously running the two ionization sources. Experimental and theoretical evidence was collected to link the observed peaks to caffeine related ionic species. One peak was attributed to the M{sup +} ion while the other two were assigned to different protonated isomers of caffeine. In the case of CD ionization source, it was observed that different sites of caffeine compete for protonation and their relative intensities, depends on the sample concentration as well as the nature of the reactant ions. The new concept of “internal proton affinity” (IPA) was defined to express the tendency of holding the added proton for each atom in a molecule.

  16. Catalytic deactivation on methane steam reforming catalysts. 2. Kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Agnelli, M.E.; Ponzi, E.N.; Yeramian, A.A.

    1987-08-01

    The kinetics of methane steam reforming reaction over an alumina-supported nickel catalyst was investigated at a temperature range of 640-740/sup 0/C in a flow reactor at atmospheric pressure. The experiments were performed varying the inlet concentration of methane, hydrogen, and water. A kinetic scheme of the Houghen-Watson type was satisfactorily proposed assuming the dissociative adsorption of CH/sub 4/ as the rate-limiting step, but this kinetic scheme can be easily replaced by a first-order kinetics (r/sub CH/4/sub / = kapparho/sub CH/4/sub /) for engineering purposes. Catalyst activation with H/sub 2/ and N/sub 2/ mixtures or with the reactant mixture results in the same extent of reaction.

  17. Kinetic energy budget studies of areas of convection

    Science.gov (United States)

    Fuelberg, H. E.

    1979-01-01

    Synoptic-scale kinetic energy budgets are being computed for three cases when large areas of intense convection occurred over the Central United States. Major energy activity occurs in the storm areas.

  18. DEFLUORIDATION OF DRINKING WATER BY ELECTROCOAGULATION/ELECTROFLOTATION: KINETIC STUDY

    OpenAIRE

    Mounir Bennajah; Mostafa Maalmi; Yassine Darmane; Mohammed Ebn Touhami

    2010-01-01

    A variable order kinetic (VOK) model derived from the langmuir-freundlish equation was applied to determine the kinetics of fluoride removal reaction by electrocoagulation (EC). Synthetic solutions were employed to elucidate the effects of the initial fluoride concentration, the applied current and the initial acidity on the simulation results of the model. The proposed model successfully describes the fluoride removal in Airlift reactor in comparison with the experimental results. In this st...

  19. An improved pyrite pretreatment protocol for kinetic and isotopic studies

    Science.gov (United States)

    Mirzoyan, Natella; Kamyshny, Alexey; Halevy, Itay

    2014-05-01

    An improved pyrite pretreatment protocol for kinetic and isotopic studies Natella Mirzoyan1, Alexey Kamyshny Jr.2, Itay Halevy1 1Earth and Planetary Sciences, Weizmann Institute of Science, Rehovot 76100, Israel 2Geological and Environmental Sciences, Ben-Gurion University of the Negev, Beer Sheva 84105, Israel Pyrite is one of the most abundant and widespread of the sulfide minerals with a central role in biogeochemical cycles of iron and sulfur. Due to its diverse roles in the natural and anthropogenic sulfur cycle, pyrite has been extensively studied in various experimental investigations of the kinetics of its dissolution and oxidation, the isotopic fractionations associated with these reactions, and the microbiological processes involved. Pretreatment of pyrite for removal of oxidation impurities to prevent experimental artifacts and inaccuracies is often practiced. While numerous pyrite-cleaning methods have been used in experiments, a common pyrite pretreatment method, often used to investigate pyrite chemistry by the isotopic fractionations associated with it, includes several rinses by HCl, acetone and deionized water. Elemental sulfur (S0) is a common product of incomplete pyrite oxidation. Removal of S0 is desirable to avoid experimental biases associated with its participation in pyrite transformations, but is more complicated than the removal of sulfate. Although rinsing with an organic solvent is in part aimed at removing S0, to the best of our knowledge, the extraction efficiency of S0 in existing protocols has not been assessed. We have developed and tested a new protocol for elemental sulfur removal from the surface of pyrite by ultrasonication with warm acetone. Our data demonstrate the presence of large fractions of S0 on untreated pyrite particle surfaces, of which only approximately 60% was removed by the commonly used pretreatment method. The new protocol described here was found to be more efficient at S0 removal than the commonly used method

  20. Theoretical Advanced Study Institute in Elementary Particle Physics

    CERN Document Server

    2017-01-01

    The program will consist of a pedagogical series of lectures and seminars. Lectures will be given over a four-week period, three or four lectures per day, Monday through Friday. The audience will be composed primarily of advanced theoretical graduate students. Experimentalists with a strong background in theory are also encouraged to apply. Some post-doctoral fellows will be admitted, but preference will be given to applicants who will not have received their Ph.D. before 2017. The minimum background needed to get full benefit of TASI is a knowledge of quantum field theory (including RGEs) and familiarity with the Standard Model. Some familiarity with SUSY would be helpful. We hope to provide some subsidy, but students will need partial support from other sources. Rooms, meals, and access to all facilities will be provided at reasonable rates in beautifully located dormitories at the University of Colorado.

  1. Theoretical Advanced Study Institute in Elementary Particle Physics

    CERN Document Server

    2006-01-01

    This book contains write-ups of lectures from a summer school for advanced graduate students in elementary particle physics. In the first lecture, Scott Willenbrock gives an overview of the standard model of particle physics. This is followed by reviews of specific areas of standard model physics: precision electroweak analysis by James Wells, quantum chromodynamics and jets by George Sterman, and heavy quark effective field by Matthias Neubert. Developments in neutrino physics are discussed by André de Gouvea and the theory behind the Higgs boson is addressed by Laura Reina. Collider phenomenology from both experimental and theoretical perspectives are highlighted by Heidi Schellman and Tao Han. A brief survey of dynamical electroweak symmetry breaking is provided by R Sekhar Chivukula and Elizabeth H Simmons. Martin Schmaltz covers the recent proposals for “little” Higgs theories. Markus Luty describes what is needed to make supersymmetric theories realistic by breaking supersymmetry. There is an entir...

  2. Theoretical studies of the physics of the solar atmosphere

    Science.gov (United States)

    Hollweg, Joseph V.

    1992-01-01

    Significant advances in our theoretical basis for understanding several physical processes related to dynamical phenomena on the sun were achieved. We have advanced a new model for spicules and fibrils. We have provided a simple physical view of resonance absorption of MHD surface waves; this allowed an approximate mathematical procedure for obtaining a wealth of new analytical results which we applied to coronal heating and p-mode absorption at magnetic regions. We provided the first comprehensive models for the heating and acceleration of the transition region, corona, and solar wind. We provided a new view of viscosity under coronal conditions. We provided new insights into Alfven wave propagation in the solar atmosphere. And recently we have begun work in a new direction: parametric instabilities of Alfven waves.

  3. Theoretical study on a solar collector loop during stagnation

    DEFF Research Database (Denmark)

    Chen, Ziqian; Dragsted, Janne; Furbo, Simon

    A mathematical model simulating the stagnation behavior of a pressurized solar collector loop with solar collectors with a good emptying behavior is developed. Based on the pre-pressure of the expansion vessel, the system filling pressure of the solar collector loop and the design of the solar...... collector loop, the mass of the fluid flowing into the pressurized expansion vessel and the pressures at the top part and at the bottom part of the solar collector loop during stagnation for the solar collector loop are calculated. The theoretically calculated results are compared with experimental results....... There is a good agreement between calculations and measurements. The developed simulation model is therefore suitable to determine the behavior of solar collector loops during stagnation....

  4. Theoretical and numerical studies on morphological transitions in crack growth

    CERN Document Server

    Mühle, V

    1999-01-01

    This paper investigates the formation of crack patterns in stationary and transient temperature fields analytically with linear elastic fracture mechanics and numerically with the finite elements method (FEM). In particular, we consider the experimental situation of a narrow thin strip of hot glass slowly lowered into cold water, with temperature difference and velocity as variable parameters. The parameter regions of no crack, one straight crack and one oscillating crack are determined. The type of phase transition related to the borderline between straight and oscillating crack is characterized. The theoretical results are compared with those of other Similar investigations and comparisons are done for the propagation of multiple cracks. Quenching of a wide thin strip leads to a hierarchy of cracks whose scaling properties are analyzed. Without any fitting, theory and experiment agree surprisingly well.

  5. Benchmark Study of Density Cumulant Functional Theory: Thermochemistry and Kinetics.

    Science.gov (United States)

    Copan, Andreas V; Sokolov, Alexander Yu; Schaefer, Henry F

    2014-06-10

    We present an extensive benchmark study of density cumulant functional theory (DCFT) for thermochemistry and kinetics of closed- and open-shell molecules. The performance of DCFT methods (DC-06, DC-12, ODC-06, and ODC-12) is compared to that of coupled-electron pair methods (CEPA0 and OCEPA0) and coupled-cluster theory (CCSD and CCSD(T)) for the description of noncovalent interactions (A24 database), barrier heights of hydrogen-transfer reactions (HTBH38), radical stabilization energies (RSE30), adiabatic ionization energies (AIE), and covalent bond stretching in diatomic molecules. Our results indicate that out of four DCFT methods the ODC-12 method is the most reliable and accurate DCFT formulation to date. Compared to CCSD, ODC-12 shows superior results for all benchmark tests employed in our study. With respect to coupled-pair theories, ODC-12 outperforms CEPA0 and shows similar accuracy to the orbital-optimized CEPA0 variant (OCEPA0) for systems at equilibrium geometries. For covalent bond stretching, ODC-12 is found to be more reliable than OCEPA0. For the RSE30 and AIE data sets, ODC-12 shows competitive performance with CCSD(T). In addition to benchmark results, we report new reference values for the RSE30 data set computed using coupled cluster theory with up to perturbative quadruple excitations.

  6. Theoretical study to investigate the impact of plasma parameters on the catalyst nanoparticle growth

    Science.gov (United States)

    Gupta, R.; Sharma, S. C.; Gupta, N.

    2017-05-01

    The plasma kinetics based model is adopted to elucidate the effect of plasma parameters on the nucleation and growth mechanism of catalyst nanoparticle. The present model considers the plasma processing of thin catalyst film, power equalization at the film surface, flux and kinetics of plasma species (electrons, ions, and neutrals). In our investigation, it is found that catalyst nanoparticle diameter decreases with increase in ion number density in plasma. Moreover, it is also found that catalyst film thickness significantly affect the catalyst nanoparticle size i.e., catalyst nanoparticle diameter increases with catalyst film thickness. In addition, it is observed that the substrate temperature increases during the plasma processing and finally achieve saturation. Our theoretical results are in good agreement with the experimental results.

  7. Modeling Exoplanetary Atmospheres using BART, TEA, and Drift-RHD; Theoretical studies and Observational Implications

    Science.gov (United States)

    Dobbs-Dixon, Ian

    numerous published papers, further work is needed to couple them self-consistently. Our theoretical studies focus on a number of objectives. We will start by incorporating our kinetic, non-equilibrium cloud model within BART, allowing us to obtain a consistent solution for cloud characteristics. We will further test simple parameterizations against the full solution to explore the reliability of simpler models. Utilizing Drift-RHD, we will explore the role of horizontal advection on cloud distribution, investigate the validity of 1D retrievals by comparing them to selfconsistently generated 3D models, and develop a retrieval framework for wavelengthdependent phase-curves. TEA will be enhanced with additional databases and the inclusion of condensates, providing realistic initial cloudy-model for retrievals. To explore the importance of equilibrium chemistry and exclude non-plausible chemical compositions (often the outcome of many retrieval approaches) we will relax the assumption of non-equilibrium chemistry by utilizing an analytical chemical equilibrium approach in BART. To address observations, our OBS suit for generating synthetic observations will be adapted to interface with our models, allowing us to both compare to existing observations and make predictions for future observations. With these tools, we are particularly well suited to understand discriminants between classes of models and identifying which particular set of observations could most readily distinguish cloud constituents and temperature features. The proposed research is directly relevant to the Planetary Science and Astrophysics goals through furthering our understanding of compositions, dynamics, energetics, and chemical behaviors of exoplanetary atmospheres. In addition, to maximize NASA's investment and encourage open access, we have and will continue to make all of our codes public and available to the community throughout the course of the research.

  8. Theoretical Kinetics Analysis for $\\dot{H}$ Atom Addition to 1,3-Butadiene and Related Reactions on the $\\dot{C}$4H7 Potential Energy Surface

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yang [National Univ. of Ireland, Galway (Ireland). Combustion Chemistry Centre; Klippenstein, Stephen J. [Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Zhou, Chong-Wen [Beihang Univ., Beihang (China). School of Energy and Power Engineering; Curran, Henry J. [National Univ. of Ireland, Galway (Ireland). Combustion Chemistry Centre

    2017-09-29

    The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of poly-unsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution towards soot formation. Based on our previous work on propene and the butene isomers (1-, 2- and isobutene), it was found that the reaction kinetics of H-atom addition to the C=C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations and flame speed measurements. In this study, the rate constants and thermodynamic properties for $\\dot{H}$-atom addition to 1,3-butadiene and related reactions on the $\\dot{C}$4H7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero point energies, single point energies, rate constants, barrier heights and thermochemistry are systematically compared among the two quantum chemical methods. 1-methylallyl ($\\dot{C}$4H71-3) and 3-buten-1- yl ($\\dot{C}$4H71-4) radicals and C2H4 + $\\dot{C}$2H3 are found to be the most important channels and reactivity promoting products, respectively. We calculated that terminal addition is dominant (> 80%) compared to internal $\\dot{H}$-atom addition at all temperatures in the range 298 – 2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C4H6 + $\\dot{H}$ → products and C2H4 + $\\dot{C}$2H3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C4 species the

  9. KINETIC MODELS STUDY OF HYDRODESULPHURIZATION VACUUM DISTILLATE REACTION

    Directory of Open Access Journals (Sweden)

    AbdulMunem A. Karim

    2013-05-01

    Full Text Available    This study deals with  kinetics of hydrodesulphurization (HDS reaction of vacuum gas oil (611-833 K which was distillated from Kirkuk crude oil and which was obtained by blending the fractions, light vacuum gas oil (611 - 650 K, medium vacuum gas oil (650-690 K, heavy vacuum gas oil (690-727 K and very heavy vacuum gas oil (727-833 K.   The vacuum gas oil was hydrotreated on a commercial cobalt-molybdenum alumina catalyst presulfied at specified conditions in a laboratory trickle bed reactor. The reaction temperature range (583-643 K,liquid hourly space velocity range (1.5-3.75 h-1 and hydrogen pressure was kept constant at 3.5 MPa with hydrogen to oil ratio about 250 lt/lt.           The conversion results for desulphurization reaction appeared to obey the second order reaction. According to this model, the rate constants for desulphurization reaction were determined. Finally, the apparent activation energy (Ea, enthalpy of activation ( H* and entropy ( S* were calculated based on the values of rate constant (k2 and were equal 80.3792 KJ/mole, 75.2974 KJ/mole and 197.493 J/mole, respectively.

  10. Kinetic Study of Nonequilibrium Plasma-Assisted Methane Steam Reforming

    Directory of Open Access Journals (Sweden)

    Hongtao Zheng

    2014-01-01

    Full Text Available To develop a detailed reaction mechanism for plasma-assisted methane steam reforming, a comprehensive numerical and experimental study of effect laws on methane conversion and products yield is performed at different steam to methane molar ratio (S/C, residence time s, and reaction temperatures. A CHEMKIN-PRO software with sensitivity analysis module and path flux analysis module was used for simulations. A set of comparisons show that the developed reaction mechanism can accurately predict methane conversion and the trend of products yield in different operating conditions. Using the developed reaction mechanism in plasma-assisted kinetic model, the reaction path flux analysis was carried out. The result shows that CH3 recombination is the limiting reaction for CO production and O is the critical species for CO production. Adding 40 wt.% Ni/SiO2 in discharge region has significantly promoted the yield of H2, CO, or CO2 in dielectric packed bed (DPB reactor. Plasma catalytic hybrid reforming experiment verifies the reaction path flux analysis tentatively.

  11. Detailed kinetic modeling study of n-pentanol oxidation

    KAUST Repository

    Heufer, Karl Alexander

    2012-10-18

    To help overcome the world\\'s dependence upon fossil fuels, suitable biofuels are promising alternatives that can be used in the transportation sector. Recent research on internal combustion engines shows that short alcoholic fuels (e.g., ethanol or n-butanol) have reduced pollutant emissions and increased knock resistance compared to fossil fuels. Although higher molecular weight alcohols (e.g., n-pentanol and n-hexanol) exhibit higher reactivity that lowers their knock resistance, they are suitable for diesel engines or advanced engine concepts, such as homogeneous charge compression ignition (HCCI), where higher reactivity at lower temperatures is necessary for engine operation. The present study presents a detailed kinetic model for n-pentanol based on modeling rules previously presented for n-butanol. This approach was initially validated using quantum chemistry calculations to verify the most stable n-pentanol conformation and to obtain C-H and C-C bond dissociation energies. The proposed model has been validated against ignition delay time data, speciation data from a jet-stirred reactor, and laminar flame velocity measurements. Overall, the model shows good agreement with the experiments and permits a detailed discussion of the differences between alcohols and alkanes. © 2012 American Chemical Society.

  12. Studies on drying kinetics of olive foot cake

    Directory of Open Access Journals (Sweden)

    Hamlat, M. S.

    2002-06-01

    Full Text Available The olive foot cake is a very important by-product of olive oil industry since it can contain until 12 % of oil which can be extracted using solvent. The used solvent is often immiscible with water. This is the reason why its effect is limited by the moisture of olive foot cake making its drying imperative. In this paper, we present the behaviour of olive foot cake subjected to convective drying. The experimental results show that the drying rate versus moisture presents only one period of decreasing rate. The influence of the main parameters on drying kinetics is studied.El orujo es un importante subproducto de la industria del aceite de oliva ya que puede contener hasta el 12 % del aceite, el cual puede ser extraído usando un disolvente apropiado. El uso del disolvente es a menudo inmiscible con el agua. Esta es la razón por la que su efecto está limitado por la humedad del orujo, haciendo su secado imperativo. En este artículo se presenta el comportamiento del orujo sometido a un secado por convección. Los resultados experimentales mostraron que la velocidad de secado frente a la humedad, presenta un solo período de disminución de dicha velocidad. Se ha estudiado la influencia de los principales parámetros sobre la cinética de secado.

  13. Kinetic study of the convective drying of spearmint

    Directory of Open Access Journals (Sweden)

    Mourad Ayadi

    2014-01-01

    Full Text Available This work presents the kinetic study of the convective drying of Tunisian spearmint in two manners. The traditional protocol which consists in carrying out drying experimental tests at constant temperatures 40–45–50–55 °C and a new protocol which consists in carrying out these tests at variable temperatures in an increasing and decreasing way between 40 °C and 55 °C. All the experimental drying curves show only a falling drying rate period. The main factor in controlling this rate is found to be the drying air temperature. The mode at variable temperatures in an increasing way is more performant and more efficient than the mode at decreasing way or at constant temperature. These experimental curves are fitted to a number of mathematical models. The Midilli–Kucuk drying model is found as the best model which suitably follows the drying curves of spearmint. The characteristic drying curve of spearmint is determined and compared with the modes at variable temperatures. Those at constant temperature and increasing temperature are very close with a correlation coefficient (R2 of 0.8 and Chi-square (χ2 of 0.014, whereas the decreasing mode is a little distant due to the problem of rehumidification at the drying end. Initial moisture has a great influence on a characteristic drying curve.

  14. Kinetic study of seawater reverse osmosis membrane fouling

    KAUST Repository

    Khan, Muhammad

    2013-10-01

    Reverse osmosis (RO) membrane fouling is not a static state but a dynamic phenomenon. The investigation of fouling kinetics and dynamics of change in the composition of the foulant mass is essential to elucidate the mechanism of fouling and foulant-foulant interactions. The aim of this work was to study at a lab scale the fouling process with an emphasis on the changes in the relative composition of foulant material as a function of operating time. Fouled membrane samples were collected at 8 h, and 1, 2, and 4 weeks on a lab-scale RO unit operated in recirculation mode. Foulant characterization was performed by CLSM, AFM, ATR-FTIR, pyrolysis GC-MS, and ICP-MS techniques. Moreover, measurement of active biomass and analysis of microbial diversity were performed by ATP analysis and DNA extraction, followed by pyro-sequencing, respectively. A progressive increase in the abundance of almost all the foulant species was observed, but their relative proportion changed over the age of the fouling layer. Microbial population in all the membrane samples was dominated by specific groups/species belonging to Proteobacteria and Actinobacteria phyla; however, similar to abiotic foulant, their relative abundance also changed with the biofilm age. © 2013 American Chemical Society.

  15. Biological conversion of synthesis gas. Mass transfer/kinetic studies

    Energy Technology Data Exchange (ETDEWEB)

    Klasson, K.T.; Basu, R.; Johnson, E.R.; Clausen, E.C.; Gaddy, J.L.

    1992-03-01

    Mass transfer and kinetic studies were carried out for the Rhodospirillum rubrum and Chlorobium thiosulfatophilum bacterial systems. R. rubrum is a photosynthetic anaerobic bacterium which catalyzes the biological water gas shift reaction: CO + H{sub 2}0 {yields} CO{sub 2} + H{sub 2}. C. thiosulfatophilum is also a H{sub 2}S and COS to elemental sulfur. The growth of R. rubrum may be satisfactorily carried out at 25{degree} and 30{degree}C, while CO uptake and thus the conversion of CO best occurs at temperatures of either 30{degree}, 32{degree} or 34{degree}C. The rate of conversion of COs and H{sub 2}O to CO{sub 2} and H{sub 2}S may be modeled by a first order rate expression. The rate constant at 30{degree}C was found to be 0.243 h{sup {minus}1}. The growth of C. thiosulfatophilum may be modeled in terms of incoming light intensity using a Monod equation: {mu} = {sub 351} + I{sub o}/{sup 0.152}I{sub o}. Comparisons of the growth of R. rubrum and C. thiosulfatophilum shows that the specific growth rate of C. thiosulfatophilum is much higher at a given light intensity.

  16. Kinetic study of ultrasonic antisolvent crystallization of sirolimus

    Energy Technology Data Exchange (ETDEWEB)

    Gandhi, P.J. [Chemical Engineering Department, S. V. National Institute of Technology, Surat 395007, Gujarat (India); Concept Medical Research Pvt. Ltd., Ground Floor, Narayan Darshan, Nr. Rupam Cinema, Salabatpura, Surat 395003, Gujarat (India); Murthy, Z.V.P.

    2010-03-15

    Sirolimus, generally used in organ transplantation, is derived from bacterium Streptomyces hygroscopicus. Mass transfer controlled ultrasonic antisolvent method was used for determining the precipitation kinetics of sirolimus. The effect of temperature was determined on the particles size, percentage recovery, critical radius of nucleus, mass transfer coefficient, etc. for sirolimus dissolved in methanol and antisolvent water using ultrasonic treatment. The study was done using classical nucleation theory, which can also be applied to precipitation processes. Experiments were carried out at various temperatures; viz: 45, 50, 60 and 70 C and the percentage recoveries of sirolimus were found to be 90.74, 91.5, 92.64 and 93.61%, respectively, for initial amount of 8 mg dissolved in 1 mL of solvent and further introduced into 12 mL of HPLC water. The final average diameters of crystals observed for the temperatures were 1371, 1287, 1063 and 863 nm, respectively. The systems were found to be mass transfer controlling and that the mass diffusivities were found to be about 3.97 x 10{sup -9}, 4.00 x 10{sup -9}, 3.01 x 10{sup -9} and 1.92 x 10{sup -9} m{sup 2}/s, respectively. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  17. Novel tannin-based adsorbent in removing cationic dye (Methylene Blue) from aqueous solution. Kinetics and equilibrium studies.

    Science.gov (United States)

    Sánchez-Martín, J; González-Velasco, M; Beltrán-Heredia, J; Gragera-Carvajal, J; Salguero-Fernández, J

    2010-02-15

    Natural tannin-based adsorbent has been prepared on the basis of the gelification of Quebracho bark extract. The resulting product, Quebracho Tannin Gel (QTG) was tested as cationic dye adsorbent with Methylene Blue (MB). Kinetics of adsorption process were studied out and a period of 15 days was determined for reaching equilibrium. The influences of pH and temperature were evaluated. As pH or temperature raise q capacity of QTG increases. Theoretical modelization of dye-QTG adsorption was carried out by multiparametric adjustment according to Langmuir's hypothesis. Values of the k(l1), k(l2) and activation energies were calculated.

  18. Electrochemical and theoretical complexation studies for Zn and Cu with individual polyphenols

    Energy Technology Data Exchange (ETDEWEB)

    Esparza, I. [Departamento de Quimica y Edafologia, Universidad de Navarra, c/ Irunlarrea s/n, 31080 Pamplona, Navarra (Spain); Salinas, I. [Departamento de Quimica y Edafologia, Universidad de Navarra, c/ Irunlarrea s/n, 31080 Pamplona, Navarra (Spain); Santamaria, C. [Departamento de Quimica y Edafologia, Universidad de Navarra, c/ Irunlarrea s/n, 31080 Pamplona, Navarra (Spain); Garcia-Mina, J.M. [INABONOS, Poligono Arazuri, 31160 Orcoyen, Navarra (Spain); Fernandez, J.M. [Departamento de Quimica y Edafologia, Universidad de Navarra, c/ Irunlarrea s/n, 31080 Pamplona, Navarra (Spain)]. E-mail: jmfdez@unav.es

    2005-07-06

    Zn and Cu interactions with three selected flavonoids (catechin, quercetin and rutin) have been electrochemically monitored. It has been shown that catechin takes one atom of metal per molecule; quercetin takes two atoms, and rutin is able to take up to three atoms. Not all ligands bind metals equally strong, and weakly bonded metals can be distinguished. Zn shows a sluggish kinetics and, at the same time, the highest conditional formation constants. The method could be applied to a real sample. Theoretical models are proposed for the most favourable compounds.

  19. Theoretical study on photorecombination of C V ion

    Science.gov (United States)

    Ma, Kun; Xie, Lu-You; Zhang, Deng-Hong; Dong, Chen-Zhong

    2015-07-01

    The partial and total photorecombination cross sections of the ground-state C V ion in the KLL and KLM resonant energy regions were calculated in detail by using the Dirac atomic R-matrix code based on a fully relativistic R-matrix method. Meanwhile, the principal resonant lines in each photorecombination channel have been classified according to the calculated transition energies and probabilities from the KLL and KLM resonant states to the 1s2nl (n = 2, 3 and l = s,p,d) final states. The validity of these calculations is assessed by comparison with previously published experimental and theoretical data. The good agreement between the present calculated results and those obtained using different approaches confirms the accuracy of the present results. In addition, it is found that the damping effect can be neglected for the KLL resonant, but not for the KLM resonant. Project supported by the National Natural Science Foundation of China (Grant Nos. 11274254, U1332206, and U1331122) and the International Scientific and Technological Cooperative Project of Gansu Province, China (Grant No. 1104WCGA186).

  20. A Theoretical Study of Remobilizing Surfactant Retarded Fluid Particle Interfaces

    Science.gov (United States)

    Wang, Yanping; Papageorgiou, Dimitri; Maldarelli, Charles

    1996-01-01

    Microgravity processes must rely on mechanisms other than bouyancy to move bubbles or droplets from one region to another in a continuous liquid phase. One suggested method is thermocapillary migration in which a temperature gradient is applied to the continuous phase. When a fluid particle contacts this gradient, one pole of the particle becomes warmer than the opposing pole. The interfacial tension between the drop or bubble phase and the continuous phase usually decreases with temperature. Thus the cooler pole is of higher interfacial tension than the warmer pole, and the interface is tugged in the direction of the cooler end. This thermocapillary or thermally induced Marangoni surface stress causes a fluid streaming in the continuous phase from which develops a viscous shear traction and pressure gradient which together propel the particle in the direction of the warmer fluid. In this paper, we provide a theoretical basis for remobilizing surfactant retarded fluid particle interfaces in an effort to make viable the use of thermocapillary migrations for the management of bubbles and drops in microgravity,

  1. Theoretical and Experimental Studies of Elementary Particle Physics

    Energy Technology Data Exchange (ETDEWEB)

    Evans, Harold G [Indiana University; Kostelecky, V Alan [Indiana University; Musser, James A [Indiana University

    2013-07-29

    The elementary particle physics research program at Indiana University spans a broad range of the most interesting topics in this fundamental field, including important contributions to each of the frontiers identified in the recent report of HEPAP's Particle Physics Prioritization Panel: the Energy Frontier, the Intensity Frontier, and the Cosmic Frontier. Experimentally, we contribute to knowledge at the Energy Frontier through our work on the D0 and ATLAS collaborations. We work at the Intensity Frontier on the MINOS and NOvA experiments and participate in R&D for LBNE. We are also very active on the theoretical side of each of these areas with internationally recognized efforts in phenomenology both in and beyond the Standard Model and in lattice QCD. Finally, although not part of this grant, members of the Indiana University particle physics group have strong involvement in several astrophysics projects at the Cosmic Frontier. Our research efforts are divided into three task areas. The Task A group works on D0 and ATLAS; Task B is our theory group; and Task C contains our MINOS, NOvA, and LBNE (LArTPC) research. Each task includes contributions from faculty, senior scientists, postdocs, graduate and undergraduate students, engineers, technicians, and administrative personnel. This work was supported by DOE Grant DE-FG02-91ER40661. In the following, we describe progress made in the research of each task during the final period of the grant, from November 1, 2009 to April 30, 2013.

  2. Solid-state stability studies of faropenem based on chromatography, spectroscopy and theoretical analysis.

    Science.gov (United States)

    Cielecka-Piontek, Judyta; Lewandowska, Kornelia; Barszcz, Bolesław; Czartek, Aleksandra

    2014-01-01

    The purpose of this study was to investigate the stability of faropenem in solid state. The kinetic and thermodynamic parameters of degradation of faropenem were studied using an RP-HPLC method while the changes of spectral properties were investigated using derivative UV and FT-IR. Quantum-chemical calculations, based on the density functional theory, were carried out to support the estimation of the intra-ring stresses of faropenem and for theoretical interpretation of the spectra. The degradation of faropenem was a first-order reaction depending on the substrate concentration at an increased relative humidity and in dry air. The dependence ln k = f(1/T) became the ln k = (2.03 ± 3.22) × 10(4)-(9761 ± 3052)(1/T) in dry air and ln k = (1.25 ± 0.22) × 10(5)-(9004 ± 3479)(1/T ) at 90.0% RH. The thermodynamic parameters Ea, ΔH(≠a), and ΔS(≠a) of the degradation of faropenem were calculated. The dependence ln k = f(RH%) assumed the form ln k = (7.58 ± 1.88) × 10(-2) (RH%) - (5.90 ± 3.90) × 10(-8). Stability studies of faropenem showed that the fusion of β-lactam and thiazolidine rings reduces the intra-ring stress, leading to a lower susceptibility to degradation in dry air and at increased RH.

  3. Kinetic Studies on Ni-YSZ Composite Electrodes

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Sudireddy, Bhaskar Reddy; Hjelm, Johan

    2015-01-01

    AC and DC techniques were applied to investigate the electrochemical reaction kinetics of porous composite Ni/8-mol% yttria-stabilized zirconia (Ni/8YSZ) solid oxide cell (SOC) electrodes using a novel pseudo-3-electrode cell geometry. From OCV impedance spectra an activation energy Ea of 1.13 e......V, prefactor yan of 3.7·105·T, hydrogen and steam partial pressure dependencies a and b respectively of -0.07 and 0.22 were determined. DC current density vs. overpotential curves compared with those predicted using the determined kinetic parameters. Apparent Butler-Volmer charge transfer coefficients α were...... branch and the need for different α values for each branch suggests that a simple BV model of the measured electrode kinetics is insufficient and/or different reaction mechanisms might be occurring in anodic vs cathodic polarization....

  4. Nonlinear optical properties of organic materials: A theoretical study

    Science.gov (United States)

    Cardelino, Beatriz H.

    1991-01-01

    Replacement of electronic switching circuits in computing and telecommunication systems with purely optical devices offers the potential for extremely high throughput and compact information processing systems. The potential application of organic materials containing molecules with large nonresonant nonlinear effects in this area have triggered intensive research during the last decade. Interest on this area was due to two facts: (1) that many organic materials show nonlinearities that are orders of magnitude larger than those of conventional inorganic materials such as lithium niobate and potassium dihydrogen phosphate; and (2) that organic materials show much flexibility in terms of molecular designs. Some of the desirable characteristics that these materials should have are that they be transparent to the frequency of the incident laser and its second or third harmonic, that they have a high damage threshold, and, in the case of second-order effects, that their crystal structure or molecular orientation be accentric. Since polymeric assemblages can enhance the nonlinear response of organic molecules severalfold, efforts have been directed toward the synthesis of thin films with interpenetrating lattices of electroactive molecules. The goal of this theoretical investigation is to predict the magnitude of the molecular polarizabilities of organic molecules that could be incorporated into films. These calculations are intended to become a powerful tool to assist material scientists in screening for the best candidates for optical applications. The procedure that was developed for the present calculations is based on the static-field approach, and is a modification to the method developed by Dewar and Stewart, 1984 for calculating molecular linear polarizabilities.

  5. Theoretical study on fulvic acid structure, conformation and aggregation

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez-Puebla, R.A. [Department of Applied Chemistry, Public University of Navarra, Campus Arrosadia, E-31006 Pamplona (Spain); Valenzuela-Calahorro, C. [Department of Inorganic Chemistry, Faculty of Pharmacy, University of Granada, E-18071 Granada (Spain); Garrido, J.J. [Department of Applied Chemistry, Public University of Navarra, Campus Arrosadia, E-31006 Pamplona (Spain)]. E-mail: j.garrido@unavarra.es

    2006-04-01

    The ubiquitous presence of humic substances (HS), combined with their ability to provide multiple sites for chemical reaction, makes them relevant to numerous biogeochemical processes such as mineral weathering, nutrient bioavailability, and contaminant transport. The reactivity of HS depends on their functional group chemistry and microstructure, which are in turn influenced by the composition of the surrounding media. In order to help towards an understanding of structure conformations and aggregation process of HS in soils and waters and to get a better knowledge of these kinds of materials, a fulvic acid (FA) has been modelled as a function of its ionic state under different conditions. Our proposed theoretical model based on the Temple-Northeastern-Birmingham (TNB) monomer fits well with experimental observations on the solubility (dipolar moment) and electronic and vibrational spectra of FAs. The presence of water molecules has a great stabilization effect on the electrostatic energy; this effect is greater as ionized rate increases. In vacuum, the non-ionized aggregated species are more stable than monomers because of the increase in their interaction due to H-bonding and non-bonding forces. When the molecules are ionized, no aggregation process takes place. In solution, the FA concentration is a critical factor for the aggregation. The system containing two FA molecules probably did not form aggregates because its equivalent concentration was too low. When the concentration was increased, the system gave rise to the formation of aggregates. The ionic state is another critical factor in the aggregation process. The ionized FA has a higher electric negative charge, which increases the energetic barriers and inhibits the approximation of FA caused by the Brownian movement.

  6. Theoretical Studies of Spectroscopic Line Mixing in Remote Sensing Applications

    Science.gov (United States)

    Ma, Q.; Boulet, C.; Tipping, R. H.

    2015-01-01

    The phenomenon of collisional transfer of intensity due to line mixing has an increasing importance for atmospheric monitoring. From a theoretical point of view, all relevant information about the collisional processes is contained in the relaxation matrix where the diagonal elements give half-widths and shifts, and the off-diagonal elements correspond to line interferences. For simple systems such as those consisting of diatom-atom or diatom-diatom, accurate fully quantum calculations based on interaction potentials are feasible. However, fully quantum calculations become unrealistic for more complex systems. On the other hand, the semi-classical Robert-Bonamy (RB) formalism, which has been widely used to calculate half-widths and shifts for decades, fails in calculating the off-diagonal matrix elements. As a result, in order to simulate atmospheric spectra where the effects from line mixing are important, semi-empirical fitting or scaling laws such as the ECS (Energy-Corrected Sudden) and IOS (Infinite-Order Sudden) models are commonly used. Recently, while scrutinizing the development of the RB formalism, we have found that these authors applied the isolated line approximation in their evaluating matrix elements of the Liouville scattering operator given in exponential form. Since the criterion of this assumption is so stringent, it is not valid for many systems of interest in atmospheric applications. Furthermore, it is this assumption that blocks the possibility to calculate the whole relaxation matrix at all. By eliminating this unjustified application, and accurately evaluating matrix elements of the exponential operators, we have developed a more capable formalism. With this new formalism, we are now able not only to reduce uncertainties for calculated half-widths and shifts, but also to remove a once insurmountable obstacle to calculate the whole relaxation matrix. This implies that we can address the line mixing with the semi-classical theory based on

  7. Theoretical studies on the reaction pathways of electronically excited DAAF

    Energy Technology Data Exchange (ETDEWEB)

    Quenneville, Jason M [Los Alamos National Laboratory; Moore, David S [Los Alamos National Laboratory

    2009-01-01

    an explosive compound. Here we describe high level quantum chemistry calculations aimed at mapping the electronic states involved in excitation of 3,3{prime}-Diamino-4,4{prime}-azoxyfurazan (DAAF) with 400-nm light. DAAF is a high-nitrogen high explosive that is of interest for its relative insensitivity to shock compression. The goal of the theoretical work described here is to determine the competing pathways for radiative and non-radiative electronic state quenching in an effort to help guide spectroscopic experiments being conducted in tandem.

  8. Theoretical Studies of Spectroscopic Line Mixing in Remote Sensing Applications

    Science.gov (United States)

    Ma, Q.

    2015-12-01

    The phenomenon of collisional transfer of intensity due to line mixing has an increasing importance for atmospheric monitoring. From a theoretical point of view, all relevant information about the collisional processes is contained in the relaxation matrix where the diagonal elements give half-widths and shifts, and the off-diagonal elements correspond to line interferences. For simple systems such as those consisting of diatom-atom or diatom-diatom, accurate fully quantum calculations based on interaction potentials are feasible. However, fully quantum calculations become unrealistic for more complex systems. On the other hand, the semi-classical Robert-Bonamy (RB) formalism, which has been widely used to calculate half-widths and shifts for decades, fails in calculating the off-diagonal matrix elements. As a result, in order to simulate atmospheric spectra where the effects from line mixing are important, semi-empirical fitting or scaling laws such as the ECS and IOS models are commonly used. Recently, while scrutinizing the development of the RB formalism, we have found that these authors applied the isolated line approximation in their evaluating matrix elements of the Liouville scattering operator given in exponential form. Since the criterion of this assumption is so stringent, it is not valid for many systems of interest in atmospheric applications. Furthermore, it is this assumption that blocks the possibility to calculate the whole relaxation matrix at all. By eliminating this unjustified application, and accurately evaluating matrix elements of the exponential operators, we have developed a more capable formalism. With this new formalism, we are now able not only to reduce uncertainties for calculated half-widths and shifts, but also to remove a once insurmountable obstacle to calculate the whole relaxation matrix. This implies that we can address the line mixing with the semi-classical theory based on interaction potentials between molecular absorber and

  9. Kinetic Studies of Colour and Phenol Removal from Wastewater ...

    African Journals Online (AJOL)

    ... blue (MB) and phenol adsorptions. Intra-particle diffusion kinetic plots did not pass through the origin, indicating that intra-particle diffusion was not the only rate controlling mechanism. The results showed that mango seed shell activated carbon (MSSAC) is more effective for adsorption of colour than phenol in wastewater.

  10. Kinetic studies of biogas generated from water hyacinth ( Eichhornia ...

    African Journals Online (AJOL)

    Abstract. This research work investigated the operational process of production of biogas by the leaves, stem and their mixtures of the water hyacinth (Eichhornia crassipes), during anaerobic digestion for a period of eight weeks, using locally constructed ... Keywords: Kinetic models, biomass, biogas, Water hyacinth, energy ...

  11. Isothermal, kinetic and thermodynamic studies on basic dye sorption ...

    African Journals Online (AJOL)

    In this paper, a new cation sorbent, which bore carboxyl and hydroxyl groups of tartaric acid (TA) derived from esterified wheat straw (EWS), was originally prepared by solid phase thermochemistry method. The isotherm, kinetics and thermodynamics of basic dye sorptions from aqueous solution onto EWS were investigated ...

  12. Kinetic study of sphingomyelin hydrolysis for ceramide production

    DEFF Research Database (Denmark)

    Zhang, Long; Hellgren, Lars; Xu, Xuebing

    2008-01-01

    in cosmetic and pharmaceutical industries such as in hair and skin care products. The enzymatic hydrolysis of sphingomyelin has been proved to be a feasible method to produce ceramide. The kinetic performance of sphingomyelin hydrolysis in the optimal two-phase (water:organic solvent) reaction system...

  13. An Undergraduate Laboratory Exercise for Studying Kinetics of Batch Crystallization

    Science.gov (United States)

    Louhi­-Kultanen, Marjatta; Han, Bing; Nurkka, Annikka; Hatakka, Henry

    2015-01-01

    The present work describes an undergraduate laboratory exercise for improving understanding of fundamental phenomena in cooling crystallization. The exercise of nucleation and crystal growth kinetics supports learning of theories and models presented in lectures and calculation exercises. The teaching methodology incorporates precepts the…

  14. KINETIC STUDY OF LIQUID-PHASE ADSORPTIVE REMOVAL OF ...

    African Journals Online (AJOL)

    2006-10-25

    Ciencias Exactas, Nacional Universidad de La Plata, 16 Surcural 1900, La Plata Argentina. (Received October 25, 2006; revised April 10, 2007). ABSTRACT. The kinetic sorption of five metal ions - Al3+, Cr6+, Zn2+, Ag+ and Mn2+ - from aqueous solution onto almond tree leaves (ATL) waste in single component system ...

  15. Kinetic Studies on State of the Art Solid Oxide Cells

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Graves, Christopher R.; Mogensen, Mogens Bjerg

    2016-01-01

    Electrochemical reaction kinetics at the electrodes of Solid Oxide Cells (SOCs) were investigated at 700 °C for two cells with different fuel electrode microstructures as well as on a third cell with a reduced active electrode area. Three fuel mixtures were investigated – hydrogen/steam and refor...

  16. Kinetics Study of Balanites Aegyptiaca Oil Transesterification for the ...

    African Journals Online (AJOL)

    User-PC

    moles/sec. for the transesterification process at the prescribed temperatures. ... process didn't proceed in accordance with the Arrhenius equation. ..... Process standardization and kinetics of ethanol driven biodiesel production by transesterification of ricebran oil. Int. J. Ind. Chem. 7 (2016) 121. 4. Atadashi,I. Aroua, M. Abdul, ...

  17. Penicillin Hydrolysis: A Kinetic Study of a Multistep, Multiproduct Reaction.

    Science.gov (United States)

    McCarrick, Thomas A.; McLafferty, Fred W.

    1984-01-01

    Background, procedures used, and typical results are provided for an experiment in which students carry out the necessary measurements on the acid-catalysis of penicillin in two hours. By applying kinetic theory to the data obtained, the reaction pathways for the hydrolysis of potassium benzyl penicillin are elucidated. (JN)

  18. Kinetic, Equilibrium and thermodynamic studies on the biosorption ...

    African Journals Online (AJOL)

    The kinetics, equilibrium and thermodynamics of the biosorption of Cd (II) from aqueous solution by the leaf biomass of Calotropis procera popularly known in western Nigeria as 'bom bom'and genrally known as Sodom apple were investigated at different experimental conditions. Optimum conditions of pH, contact time, ...

  19. Kinetic study on anaerobic oxidation of methane coupled to denitrification.

    Science.gov (United States)

    Yu, Hou; Kashima, Hiroyuki; Regan, John M; Hussain, Abid; Elbeshbishy, Elsayed; Lee, Hyung-Sool

    2017-09-01

    Monod kinetic parameters provide information required for kinetic analysis of anaerobic oxidation of methane coupled to denitrification (AOM-D). This information is critical for engineering AOM-D processes in wastewater treatment facilities. We first experimentally determined Monod kinetic parameters for an AOM-D enriched culture and obtained the following values: maximum specific growth rate (μmax) 0.121/d, maximum substrate-utilization rate (qmax) 28.8mmol CH4/g cells-d, half maximum-rate substrate concentration (Ks) 83μΜ CH4, growth yield (Y) 4.76gcells/mol CH4, decay coefficient (b) 0.031/d, and threshold substrate concentration (Smin) 28.8μM CH4. Clone library analysis of 16S rRNA and mcrA gene fragments suggested that AOM-D reactions might have occurred via the syntrophic interaction between denitrifying bacteria (e.g., Ignavibacterium, Acidovorax, and Pseudomonas spp.) and hydrogenotrophic methanogens (Methanobacterium spp.), supporting reverse methanogenesis-dependent AOM-D in our culture. High μmax and qmax, and low Ks for the AOM-D enrichment imply that AOM-D could play a significant role in mitigating atmospheric methane efflux. In addition, these high kinetic features suggest that engineered AOM-D systems may provide a sustainable alternative to nitrogen removal in wastewater treatment. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Aqueous chlorination of carbamazepine: kinetic study and transformation product identification.

    Science.gov (United States)

    Soufan, M; Deborde, M; Delmont, A; Legube, B

    2013-09-15

    Carbamazepine reactivity and fate during chlorination was investigated in this study. From a kinetic standpoint, a third-order reaction (first-order relative to the CBZ concentration and second-order relative to the free chlorine concentration) was observed at neutral and slightly acidic pH, whereas a second-order reaction (first order relative to the CBZ concentration and first order relative to the free chlorine concentration) was noted under alkaline conditions. In order to gain insight into the observed pH-dependence of the reaction order, elementary reactions (i.e. reactions of Cl2, Cl2O, HOCl with CBZ and of ClO(-) with CBZ or of HOCl with the ionized form of CBZ) were highlighted and second order rate constants of each of them were calculated. Close correlations between the experimental and modeled values were obtained under these conditions. Cl2 and Cl2O were the main chlorination agents at neutral and acidic pH. These results indicate that, for a 1 mg/L free chlorine concentration and 1-10 mg/L chloride concentration at pH 7, halflives about 52-69 days can be expected. A low reactivity of chlorine with CBZ could thus occur under the chlorination steps used during water treatment. From a mechanistic viewpoint, several transformation products were observed during carbamazepine chlorination. As previously described for the chlorination of polynuclear aromatic or unsaturated compounds, we proposed monohydroxylated, epoxide, diols or chlorinated alcohol derivatives of CBZ for the chemical structures of these degradation products. Most of these compounds seem to accumulate in solution in the presence of excess chlorine. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. A study on equilibrium and kinetics of ion exchange of alkaline earth ...

    Indian Academy of Sciences (India)

    A study on equilibrium and kinetics of ion exchange of alkaline earth metals using an inorganic cation exchanger - zirconium titanium phosphate ... Further, various kinetic parameters like self-diffusion coefficient (0), energy of activation () and entropy of activation (*) have been evaluated under conditions favouring a ...

  2. Nickel and cobalt sorption on anaerobic granular sludges: kinetic and equilibrium studies

    NARCIS (Netherlands)

    Hullebusch, van E.D.; Zandvoort, M.H.; Lens, P.N.L.

    2004-01-01

    The kinetics and equilibria of sorption of the divalent metal ions cobalt and nickel onto anaerobic granular sludge are described. Single component and binary equimolar systems were studied at different pH values (pH 6, 7 and 8). The kinetic modelling of metal sorption by anaerobic granular sludge

  3. Oxidation of L-cystine by chromium(VI) - a kinetic study | Kumar ...

    African Journals Online (AJOL)

    The kinetics of the title reaction was studied spectrophotometrically in HClO4 medium at 380 nm. The data suggested that the order with respect to cystine is fractional, whereas chromium(VI) follows first order kinetics. The reaction was second order in [H+]. Cysteic acid was found to be the main product of oxidation.

  4. Novel swirl-flow reactor for kinetic studies of semiconductor photocatalysis

    NARCIS (Netherlands)

    Ray, A.K; Beenackers, A.A C M

    1997-01-01

    A new two-phase swirl-flow monolithic-type reactor was designed to study the kinetics of heterogeneous photocatalytic processes on immobilized semiconductor catalysts. True kinetic rate constants for destruction of a textile dye were measured as a function of wavelength of light intensity and angle

  5. A study on the effect of particle size on coal flotation kinetics using fuzzy logic

    Energy Technology Data Exchange (ETDEWEB)

    Abkhoshk, E.; Kor, M.; Rezai, B. [Shahrood University of Technology, Shahrood (Iran)

    2010-07-15

    This paper investigates the effect of particle size on the flotation kinetics of coal in a batch flotation cell. The relationship between flotation kinetics constant and theoretical flotation recovery with particle size was estimated with nonlinear equations. Analysis of variance shows that varying of particle size is statistically significant on kinetics constant with approximately 96.5% confidence level; however it is not significant on maximum theoretical flotation recovery (RI) in 95% confidence level. Using fuzzy logic method, a multi-input/single-output (MISO) fuzzy model with two input variables: particle size and time and one output variable: cumulative recovery was established to predict the effect of particle size on the flotation kinetics of coal in a batch flotation cell. Application of fuzzy model shows that the results of model fits well to the result of batch flotation and the fuzzy model can be applied to predict cumulative recovery of different coal particle size. The correlation coefficient (R{sup 2}) values of the proposed fuzzy model were 0.986. 0.993, 0.983, 0.977 and 0.972 for 37.5 {mu}m, 112.5 {mu}m, 225 {mu}m, 400 {mu}m and 625 {mu}m average particle sizes, respectively.

  6. Theoretical and Policy Implications of Case Study Findings About Federal Efforts to Improve Public Schools

    Science.gov (United States)

    Gross, Neal

    1977-01-01

    Impediments to educational change were identified in six case studies of major innovative efforts in school systems. Their theoretical and policy implications are examined. The findings suggest the need for a reformulation of the theoretical scheme most frequently used to account for the fate of organizational innovations: overcoming resistance to…

  7. Theoretical study of diaquamalonatozinc(II) single crystal for ...

    Indian Academy of Sciences (India)

    MITESH CHAKRABORTY

    2017-11-28

    Nov 28, 2017 ... and rare earth ion complexes doped in the host contain- ... Studies of the relaxation behaviour in complexes due to ZFS .... From the EPR experimental study of DAMZ single crystal with posi- tive sign of axial ZFS D and rhombic ZFS E, the dopant. Mn(II) is expected to exhibit compressed octahedron.

  8. Theoretical study on the structural effect of some organic ...

    African Journals Online (AJOL)

    A quantitative structure property relationship (QSPR) analysis of some organic compounds (imines or Schiff bases) is studied. The corrosion inhibition efficiencies of these imines have been studied by using AM1 (Austin model 1) Hamiltonian SCF-MO method and QSPR analysis. One of the most promising semiempirical ...

  9. Study of metastatic kinetics in metastatic melanoma treated with B-RAF inhibitors: Introducing mathematical modelling of kinetics into the therapeutic decision.

    Directory of Open Access Journals (Sweden)

    Niklas Hartung

    Full Text Available Evolution of metastatic melanoma (MM under B-RAF inhibitors (BRAFi is unpredictable, but anticipation is crucial for therapeutic decision. Kinetics changes in metastatic growth are driven by molecular and immune events, and thus we hypothesized that they convey relevant information for decision making.We used a retrospective cohort of 37 MM patients treated by BRAFi only with at least 2 close CT-scans available before BRAFi, as a model to study kinetics of metastatic growth before, under and after BRAFi. All metastases (mets were individually measured at each CT-scan. From these measurements, different measures of growth kinetics of each met and total tumor volume were computed at different time points. A historical cohort permitted to build a reference model for the expected spontaneous disease kinetics without BRAFi. All variables were included in Cox and multistate regression models for survival, to select best candidates for predicting overall survival.Before starting BRAFi, fast kinetics and moreover a wide range of kinetics (fast and slow growing mets in a same patient were pejorative markers. At the first assessment after BRAFi introduction, high heterogeneity of kinetics predicted short survival, and added independent information over RECIST progression in multivariate analysis. Metastatic growth rates after BRAFi discontinuation was usually not faster than before BRAFi introduction, but they were often more heterogeneous than before.Monitoring kinetics of different mets before and under BRAFi by repeated CT-scan provides information for predictive mathematical modelling. Disease kinetics deserves more interest.

  10. Theoretical and Experimental Studies of Magneto-Rayleigh-Taylor Instabilities

    Energy Technology Data Exchange (ETDEWEB)

    Lau, Yue Ying [University of Michigan, Ann Arbor, MI (United States); Gilgenbach, Ronald [University of Michigan, Ann Arbor, MI (United States)

    2013-07-07

    Magneto-Rayleigh-Taylor instability (MRT) is important to magnetized target fusion, wire-array z-pinches, and equation-of-state studies using flyer plates or isentropic compression. It is also important to the study of the crab nebula. The investigators performed MRT experiments on thin foils, driven by the mega-ampere linear transformer driver (LTD) facility completed in their laboratory. This is the first 1-MA LTD in the USA. Initial experiments on the seeding of MRT were performed. Also completed was an analytic study of MRT for a finite plasma slab with arbitrary magnetic fields tangential to the interfaces. The effects of magnetic shear and feedthrough were analyzed.

  11. A study of the Sabatier-methanation reaction kinetics

    Science.gov (United States)

    Verostko, C. E.; Forsythe, R. K.

    1974-01-01

    The kinetics of the Sabatier methanation reaction, the reduction of carbon dioxide with hydrogen to methane and water, was investigated for 58 percent nickel on kieselguhr catalyst and 20 percent ruthenium on alumina catalyst. Differential rate data from an experimental program were correlated with a power function rate equation both for forward and reverse reactions. The kinetic parameters of activation energy, frequency rate constant and reaction order were determined for the rate equation. The values of these parameters were obtained from an Arrhenius plot of the experimental differential rate data. Also the carbon monoxide side reaction effect was measured and included in the correlation of parameters. The reaction was found to fit the rate equation experimentally within the temperature range 421 K, where the reaction effectively begins, the 800 K where the reaction rate drops and departs from the rate equation form.

  12. Using motion planning to study RNA folding kinetics.

    Science.gov (United States)

    Tang, Xinyu; Kirkpatrick, Bonnie; Thomas, Shawna; Song, Guang; Amato, Nancy M

    2005-01-01

    We propose a novel, motion planning based approach to approximately map the energy landscape of an RNA molecule. A key feature of our method is that it provides a sparse map that captures the main features of the energy landscape which can be analyzed to compute folding kinetics. Our method is based on probabilistic roadmap motion planners that we have previously successfully applied to protein folding. In this paper, we provide evidence that this approach is also well suited to RNA. We compute population kinetics and transition rates on our roadmaps using the master equation for a few moderately sized RNA and show that our results compare favorably with results of other existing methods.

  13. Kinetic Studies on Ni-YSZ Composite Electrodes

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Hjelm, Johan; Graves, Christopher R.

    2015-01-01

    transfer at the reaction sites gas conversion at the flow fields, and ohmic drop across the electrolyte. Since these processes occur in both electrodes and some of them with overlapping characteristic frequencies, it is particularly challenging to isolate and characterize a particular mechanism....... Furthermore, when polarized, the cell heats up due to joule heating of the electrolyte but also the electrodes either heat or cool due to exothermic oxidation or endothermic reduction of gaseous reactant species. Kinetic investigation of SOC electrodes independent of the above effects thus requires......). The curve at 700°C shows that for a current density of 100 mA/cm2 in cathodic polarization, an overpotential of ca. 150 mV is required, compared with 100 mV in anodic polarization. This reflects asymmetry2–6in the kinetics of hydrogen oxidation and steam reduction. By recording current density vs...

  14. Kinetic studies of alkaline phosphatase extracted from rabbit (Lepus ...

    African Journals Online (AJOL)

    user

    Double reciprocal plot of ALP assay in the presence of inhibitor NaH2PO4 ( ) and the control ( ) analysis. [I]: concentration of inhibitor = 0.67 mM. Table 2. Kinetic constants of alkaline phosphatase extracted from L. townsendii liver. Km (mM ). Ki (mM). Vmax (µM/min-1). 0.5 ± 0.25. 0.9 ± 0.33. 20 ± 0.63. Values are Mean ± S.D ...

  15. Kinetic Studies of Biological Interactions By Affinity Chromatography

    OpenAIRE

    Schiel, John E.; Hage, David S.

    2009-01-01

    The rates at which biological interactions occur can provide important information on the mechanism and behavior of such processes in living systems. This review will discuss how affinity chromatography can be used as a tool to examine the kinetics of biological interactions. This approach, referred to here as biointeraction chromatography, uses a column with an immobilized binding agent to examine the association or dissociation of this agent with other compounds. The use of HPLC-based affin...

  16. A kinetic modeling study of phosphate adsorption onto Phoenix dactylifera L. date palm fibers in batch mode

    Directory of Open Access Journals (Sweden)

    Khalifa Riahi

    2017-01-01

    Full Text Available The removal of phosphates from aqueous solutions by adsorption onto date palm fibers (DPF has been studied in batch mode. The aim of this study was to understand the mechanisms that govern phosphate sorption and find an appropriate model for the kinetics of removal. In order to investigate the mechanism of sorption and potential rate controlling steps, pseudo first-order, pseudo second-order, intra-particle diffusion and the Elovich equations have been used to test experimental data. Kinetic analysis of the four models has been carried out for initial phosphate concentration in the range of 30–110 mg/L. The rate constants for the four models have been determined and the correlation coefficients have been calculated in order to assess which model provides the best fit predicted data with experimental results. Seven statistical functions were used to estimate the error deviations between experimental and theoretically predicted kinetic adsorption values, including the average relative error deviation (ARED, Marquardt’s percent standard error deviation (MPSED, the hybrid fractional error function (HYBRID, the sum of the squares of the errors (SSE and three alternative statistical functions, including the Chi-square test, the F-test and Student’s T-test. The results showed that, both Elovich equation and pseudo second-order equation provide the best fit to experimental data for different initial phosphate concentrations.

  17. Differences in kinetic variables between injured and noninjured novice runners : A prospective cohort study

    NARCIS (Netherlands)

    Bredeweg, Steef W.; Kluitenberg, Bas; Bessem, Bram; Buist, Ida

    Objectives: This prospective study examined differences in kinetic variables between injured and noninjured novice female and male runners and their potential contribution to RRIs. Design: A prospective cohort study. Methods: At baseline vertical ground reaction forces were assessed with an

  18. Experimental and Theoretical Studies in Hydrogen-Bonding Organocatalysis

    Directory of Open Access Journals (Sweden)

    Matej Žabka

    2015-08-01

    Full Text Available Chiral thioureas and squaramides are among the most prominent hydrogen-bond bifunctional organocatalysts now extensively used for various transformations, including aldol, Michael, Mannich and Diels-Alder reactions. More importantly, the experimental and computational study of the mode of activation has begun to attract considerable attention. Various experimental, spectroscopic and calculation methods are now frequently used, often as an integrated approach, to establish the reaction mechanism, the mode of activation or explain the stereochemical outcome of the reaction. This article comprises several case studies, sorted according to the method used in their study. The aim of this review is to give the investigators an overview of the methods currently utilized for mechanistic investigations in hydrogen-bonding organocatalysis.

  19. Integrated Experimental and Theoretical Studies of Stem Cells.

    Science.gov (United States)

    Sladitschek, Hanna L; Neveu, Pierre A

    2017-01-01

    Stem cells have to balance self-renewal and differentiation. The dynamic nature of these fate decisions has made stem cell study by traditional methods particularly challenging. Here we highlight recent advances in the field that draw on combining quantitative experiments and modeling to illuminate the biology of stem cells both in vitro and in vivo. Recent studies have shown that seemingly complex processes such as the fate decision-making of stem cells or the self-organization of developing tissues obey remarkably simple mathematical models. Negative feedback loops appear to stabilize cellular states hereby ensuring robust fate decision-making and reproducible outcomes. Stochastic fate decisions can account for the great variability observed in biological systems. The study of stem cells is hampered by the necessity to track the fate of a cell's progeny over time. Confronting experiments with simple predictive models has allowed to circumvent this problem and gain insights from stem cell heterogeneity in vitro to organ morphogenesis.

  20. TEBPP: Theoretical and Experimental study of Beam-Plasma-Physics

    Science.gov (United States)

    Anderson, H. R.; Bernstein, W.; Linson, L. M.; Papadopoulos, K.; Kellogg, P. J.; Szuszczewicz, E. P.; Hallinan, T. J.; Leinbach, H.

    1980-01-01

    The interaction of an electron beam (0 to 10 keV, 0 to 1.5 Amp) with the plasma and neutral atmospheres at 200 to 400 km altitude is studied with emphasis on applications to near Earth and cosmical plasmas. The interaction occurs in four space time regions: (1) near electron gun, beam coming into equilibrium with medium; (2) equilibrium propagation in ionosphere; (3) ahead of beam pulse, temporal and spatial precursors; (4) behind a beam pulse. While region 2 is of the greatest interest, it is essential to study Region 1 because it determines the characteristics of the beam as it enters 2 through 4.

  1. A Theoretical Study of Subsurface Drainage Model Simulation of ...

    African Journals Online (AJOL)

    A three-dimensional variable-density groundwater flow model, the SEAWAT model, was used to assess the influence of subsurface drain spacing, evapotranspiration and irrigation water quality on salt concentration at the base of the root zone, leaching and drainage in salt affected irrigated land. The study was carried out ...

  2. Theoretical studies of the dynamics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, A.F. [Argonne National Laboratory, IL (United States)

    1993-12-01

    Recent research effort has focussed on several reactions pertinent to combustion. The formation of the formyl radical from atomic hydrogen and carbon monoxide, recombination of alkyl radicals and halo-alkyl radicals with halogen atoms, and the thermal dissociation of hydrogen cyanide and acetylene have been studied by modeling. In addition, the inelastic collisions of NCO with helium have been investigated.

  3. Theoretical Study of Spin Crossover in 30 Iron Complexes

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2016-01-01

    Spin crossover was studied in 30 iron complexes using density functional theory to quantify the direction and magnitude of dispersion, relativistic effects, zero-point energies, and vibrational entropy. Remarkably consistent entropy−enthalpy compensation was identified. Zero-point energies favor ...

  4. Theoretical Study of Physiochemical Properties of Insulin-like ...

    African Journals Online (AJOL)

    The computational approach to studying structural changes in a wide range of physical and biological problems, the empirical force fields, have great difficulty in simulating folding of Insulin-like Growth Factor 1 (IGF-1). In an effort to understand the conformational preferences that may be attributed to stereoelectronic effects, ...

  5. A theoretical parametric study of Water Flooding | Ohirhian | Journal ...

    African Journals Online (AJOL)

    A multidimensional mathematical model derived by combining equation of continuity and Darcy's law and solved using the strongly implicit procedure (SIP) has been used to study the effects of permeability distribution, shape of the relative permeability and capillary pressure curves, ratio of water to oil viscosity, and amount ...

  6. Synthesis, experimental and theoretical studies of two cocrystals in 1 ...

    Indian Academy of Sciences (India)

    (API) and electronic industry.11–20 Also, several theo- retical studies have been performed on these structural molecules.21–26. In this paper research, we report the synthesis and characterization of two novel cocrystals, [(DABTZ). ∗For correspondence. (bpo)] (1) and [(DABTZ) (bpa)] (2) by elemental and thermal analysis ...

  7. A Correlational Study of Students' Theoretical and Practical

    African Journals Online (AJOL)

    Galadanci & Mukhtar

    Scores in Computer Applications Courses in Bayero University Kano. A CORRELATIONAL STUDY OF STUDENTS ... students of Computer Science with Economics in Bayero. University, Kano, Nigeria, in year 1 and ... School Certificate (WASC) examinations showed little correlation between the performance of students in ...

  8. Theoretical study of the catalytic desulfurization mechanism of ...

    African Journals Online (AJOL)

    The desulfurization process of compounds implicates two steps. The first step is the adsorption process on the catalytic site and the second, the breaking of the carbon-heteroatom bond leading to the heteroatom elimination. The adsorption process of thiiren have been studied and published in previous works. The results ...

  9. Platinum and palladium on carbon nanotubes : Experimental and theoretical studies

    NARCIS (Netherlands)

    Adjizian, J. J.; De Marco, P.; Suarez-Martinez, I.; El Mel, A. A.; Snyders, R.; Gengler, R. Y. N.; Rudolf, P.; Ke, X.; Van Tendeloo, G.; Bittencourt, C.; Ewels, C. P.

    2013-01-01

    Pristine and oxygen plasma functionalised carbon nanotubes (CNTs) were studied after the evaporation of Pt and Pd atoms. High resolution transmission electron microscopy shows the formation of metal nanoparticles at the CNT surface. Oxygen functional groups grafted by the plasma functionalization

  10. Theoretical study of the mechanism of proton transfer in tautomeric ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 113; Issue 4 ... Proton transfers; tautomerism; dissociative process; direct proton transfer. Abstract. Semiempirical SCF-MO studies of tautomerism in alloxan preclude the possibility of direct proton transfer in the gas phase due to the strain in the four-centred transition ...

  11. Is it really theoretical? A review of sampling in grounded theory studies in nursing journals.

    Science.gov (United States)

    McCrae, Niall; Purssell, Edward

    2016-10-01

    Grounded theory is a distinct method of qualitative research, where core features are theoretical sampling and constant comparative analysis. However, inconsistent application of these activities has been observed in published studies. This review assessed the use of theoretical sampling in grounded theory studies in nursing journals. An adapted systematic review was conducted. Three leading nursing journals (2010-2014) were searched for studies stating grounded theory as the method. Sampling was assessed using a concise rating tool. A high proportion (86%) of the 134 articles described an iterative process of data collection and analysis. However, half of the studies did not demonstrate theoretical sampling, with many studies declaring or indicating a purposive sampling approach throughout. Specific reporting guidelines for grounded theory studies should be developed to ensure that study reports describe an iterative process of fieldwork and theoretical development. © 2016 John Wiley & Sons Ltd.

  12. EXPERIMENTAL AND THEORETICAL STUDIES OF REGIONAL SEISMIC SAFETY (BAIKAL REGION

    Directory of Open Access Journals (Sweden)

    Yu. А. Berzhinsky

    2015-09-01

    Full Text Available  The article reviews problems of regional seismic safety and current programs aimed at earthquake proofing of buildings, houses, facilities and life-support systems. It describes the main scientific methodological principles for certification of buildings and facilities located in earthquake-prone regions. With reference to case studies of Angarsk, Shelekhov and Baikalsk and data on Ulaan Baatar (jointly studied with ICAG of the Academy of Sciences of Mongolia, examples of the certification method application in practice are described. Special attention is given to monitoring of the technical status of bearing-wall apartment buildings and houses built in 1960s and 1970s. Cooperation between the Laboratory of Earthquake-Proof Construction and leading scientific research institutes of Russia is reviewed specifically within the framework of the Federal Seismic Safety Program and participation of the Laboratory in development of the national standard titled GOST R Earthquake Intensity Scale.  

  13. Quantum Chemical and Kinetic Study on Polychlorinated Naphthalene Formation from 3-Chlorophenol Precursor

    Directory of Open Access Journals (Sweden)

    Fei Xu

    2015-08-01

    Full Text Available Polychlorinated naphthalenes (PCNs are the smallest chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs and are often called dioxin-like compounds. Chlorophenols (CPs are important precursors of PCN formation. In this paper, mechanistic and kinetic studies on the homogeneous gas-phase formation mechanism of PCNs from 3-CP precursor were investigated theoretically by using the density functional theory (DFT method and canonical variational transition-state theory (CVT with small curvature tunneling contribution (SCT. The reaction priority of different PCN formation pathways were disscussed. The rate constants of crucial elementary steps were deduced over a wide temperature range of 600−1200 K. The mechanisms were compared with the experimental observation and our previous works on the PCN formation from 2-CP and 4-CP. This study shows that pathways ended with Cl elimination are favored over those ended with H elimination from the 3-CP precursor. The formation potential of MCN is larger than that of DCN. The chlorine substitution pattern of monochlorophenols has a significant effect on isomer patterns and formation potential of PCN products. The results can be input into the environmental PCN controlling and prediction models as detailed parameters, which can be used to confirm the formation routes of PCNs, reduce PCN emission and establish PCN controlling strategies.

  14. Generation, structure and reactivity of arynes: A theoretical study

    Indian Academy of Sciences (India)

    For case 4c, the electron-donating resonance effect of Z makes the p-carbon more negative than the m-one thereby leading to preferential attack of the nucleophile at the m-position. In the 3,4-pyridyne case of 4d, the p-carbon is activated towards nucleophilic attack, resulting in a p-substituted product. 1.5 Scope of this study.

  15. Theoretical Study on Nano-Catalyst Burn Rate

    Science.gov (United States)

    2014-11-26

    adsorption energy of 4.98 eV) is associated with formation NH3 and HClO4 molecules as shown in Figure 4. Thus, from the cluster calculations, it...Following the adsorption process of AP on anatase TiO2 (001) surface as well as on TiO2 clusters, the formation of NH3 and HClO4 molecules was studied

  16. Theoretical and conformational studies of a series of cannabinoids

    Science.gov (United States)

    Da Silva, Albérico B. F.; Trsic, Milan

    1995-11-01

    The MNDO semi-empirical method is applied to the study of a series of cannabinoids with the aim of providing an improved understanding of the structure-activity relationship (SAR). The conformation of some groups that seem important in the biological activity (psychoactivity) of these compounds is characterized. Some electronic properties, such as atomic net charges and HOMO and LUMO energies, are correlated with the psychoactive effect.

  17. The Case Study Approach: Some Theoretical, Methodological and Applied Considerations

    Science.gov (United States)

    2013-06-01

    studies have a long history of use and account for a large portion of articles and books in various disciplines, such as psychology , sociology...photographs, videotapes, projective techniques and psychological testing, life histories and the like (Stake 1995; Tellis 1997; Yin 2009). Hence, case...Choudrie (2007) examined the behaviours of employees including understanding of the humanistic elements such as meta-abilities (i.e. cognitive skills

  18. Theoretical Study of the Charge-Transfer State Separation within Marcus Theory

    DEFF Research Database (Denmark)

    Volpi, Riccardo; Nassau, Racine; Nørby, Morten Steen

    2016-01-01

    We study, within Marcus theory, the possibility of the charge-transfer (CT) state splitting at organic interfaces and a subsequent transport of the free charge carriers to the electrodes. As a case study we analyze model anthracene-C60 interfaces. Kinetic Monte Carlo (KMC) simulations on the cold...

  19. Theoretical and experimental study of fiber-optic fluorescence immunosensors

    Science.gov (United States)

    Cao, He

    This dissertation investigates the optical detection of antigens (in this case, food pathogens such as Salmonella) with fiber-optic immunosensors. The major techniques used for this optical detection include: (1)Linking the antigens to some physical tracers that can be optically detected; (2)Collecting and transmitting the optical signal to an optical detector. From an optical point of view, the problem is a nonimaging-optics problem to collect a fluorescent signal from an extended Lambertian source and deliver it to an optical detection system with maximum energy transfer and distinct wavelength separation. A raytrace model of the optical detection system was used for numerical simulations to analyze and optimize the optical design. The result leads to an improvement of the optical detection. Related physical problems such as magnetic focusing effect, fluorescence detection, and wavelength separation have also been studied in detail. With the adoption of a single-step immunomagnetic assay, experimental studies have been conducted for the detection of Salmonella, with a dual- fiber optical probe and tapered tubular waveguide probes. The test results have shown that the detection system gives detection limit of approximately 106 CFU/ml with dual-fiber optical probes, and 105 CFU/ml with improved tubular waveguide probes. The system developed for this research project is designed as a cost-effective portable instrument that may be used for field-testing. Rapid and on-site detection, low cost instrumentation and a reusable optical probe have been emphasized throughout the study.

  20. Role of hot electron transport in scintillators: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Huihui [SZU-NUS Collaborative Innovation Center for Optoelectronic Science and Technology, Key Lab. of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen Univ. (China); Li, Qi [Physical Sciences Division, IBM TJ Watson Research Center, Yorktown Heights, NY (United States); Department of Computer Science, University of Illinois at Urbana-Champaign, Urbana, IL (United States); Lu, Xinfu; Williams, R.T. [Department of Physics, Wake Forest University, Winston Salem, NC (United States); Qian, Yiyang [College of Engineering and Applied Science, Nanjing University (China); Wu, Yuntao [Scintillation Materials Research Center, University of Tennessee, Knoxville, TN (United States)

    2016-10-15

    Despite recent intensive study on scintillators, several fundamental questions on scintillator properties are still unknown. In this work, we use ab-initio calculations to determine the energy dependent group velocity of the hot electrons from the electronic structures of several typical scintillators. Based on the calculated group velocities and optical phonon frequencies, a Monte-Carlo simulation of hot electron transport in scintillators is carried out to calculate the thermalization time and diffusion range in selected scintillators. Our simulations provide physical insights on a recent trend of improved proportionality and light yield from mixed halide scintillators. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. Theoretical studies of photoassociation in ultracold metastable helium

    Energy Technology Data Exchange (ETDEWEB)

    Cocks, D G; Whittingham, I B, E-mail: daniel.cocks@jcu.edu.a, E-mail: ian.whittingham@jcu.edu.a [School of Mathematics, Physics and Information Technology, James Cook University, Townsville, 4811 (Australia)

    2009-09-01

    Line shifts and line shapes for photoassociation of spin-polarised metastable helium to long-range vibrational states in the J = 1,0{sup +}{sub u} potential dissociating to the 2s{sup 3}S{sub 1} + 2p {sup 3}P{sub 0} limit are studied using a nonperturbative multichannel calculation valid for arbitrary laser intensities. Asymptotically-free dressed states of the laser plus matter system are used to obtain the S-matrix elements required to generate the photoassociation profiles. Issues associated with the very shallow nature of the potentials that support the excited states are investigated.

  2. Biological and Theoretical Studies of Adaptive Networks: The Conditioned Response.

    Science.gov (United States)

    1992-06-30

    suggest experimental tests and provide direction for physiological studies. 14 SU~la TIPO ~IS- NIJUMS Of PAGIS 17. @1d-ftA ITY CLASSIPtCATICON...sessions of CI retraining, we allowed enough 60 Hz shock , at an interstimulus interval of 500 ins. The post-operative retraining for recovery of...followed 200 msec later by the US, giving a nominal CS-US interval of 350 msec. The US was a mild eye shock , and the CR was extension of the

  3. Hydrogen Bonding and Vibrational Spectroscopy: A Theoretical Study

    Science.gov (United States)

    Chaban, Galina M.

    2005-01-01

    Effects of hydrogen bonding on vibrational spectra are studied for several hydrogen-bonded complexes, in which hydrogen bonding ranges from weak (25 kcal/mol). The systems studied include complexes of inorganic acids and salts with water and ammonia, as well as complexes of several organic molecules (nitriles and amino acids) with water. Since anharmonic effects are very strong in hydrogen-bonded systems, anharmonic vibrational frequencies and infrared intensities are computed using the correlation-corrected vibrational self-consistent field (CC-VSCF) method with ab initio potential surfaces at the MP2 and CCSD(T) levels. The most common spectral effects induced by hydrogen bonding are red shifts of stretching vibrational frequencies ranging from approx.200/cm to over 2000/cm and significant increases of infrared intensities for those bonds that participate in hydrogen bonding. However, some systems (e.g. nitrile-water complexes) exhibit shifts in the opposite direction (to the blue) upon formation of hydrogen bonds.

  4. Experimental and theoretical studies of vertical annular liquid jets

    Science.gov (United States)

    Chigier, Norman; Ramos, J. I.; Kihm, K. D.

    1988-05-01

    The objectives of this study are to determine the stability, dynamics, and convergence of vertical annular liquid jets as a function of the initial radius, sheet thickness, and velocity. The influence of variation of Froude, Reynolds, and Weber numbers and geometry on convergence and stability are examined. An implicit finite-difference scheme is developed for solution of the steady-state and time-dependent axisymmetric Navier-Stokes equations. In collaboration with Westinghouse, a cylindrical film chemical reactor will be designed for control of reactions such as reduction of zirconium. Annular liquid curtains have been formed with an initial curtain radius of 50 mm and initial sheet thicknesses of 0.5 and 1.0 mm. Three Froude numbers have been studied: 1.27, 4.27, and 8.87 with variation of the liquid flow rate. Pressure within the curtains has been varied progressively from 0 to 3 Pa. Several flow regimes were found: (1) non-pressurized, (2) pressurized, (3) oscillating, and (4) punctured. Curtain shape and convergence length were determined for each condition by photography. Axial mean velocity in the liquid curtain was measured by Laser Doppler Anemometry along the length of the curtain. The variation of liquid film thickness with axial distance was determined.

  5. Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

    Directory of Open Access Journals (Sweden)

    Javier Morales

    Full Text Available Detection of singlet oxygen emission, λ(max = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T, and the reactive reaction rate constant, k(r, for the reaction between singlet oxygen and several flavonoids. Values of k(T determined in deuterated water, ranging from 2.4×10(7 M(-1 s(-1 to 13.4×10(7 M(-1 s(-1, for rutin and morin, respectively, and the values measured for k(r, ranging from 2.8×10(5 M(-1 s(-1 to 65.7×10(5 M(-1 s(-1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

  6. Experimental and Theoretical Studies of Wetting and Multilayer Adsorption

    Science.gov (United States)

    Moldover, M. R.; Schmidt, J. W.; Cahn, J. W.; Kayser, R. F.

    1985-01-01

    The recent work with partially miscible binary liquid mixtures has established that the structure of the liquid-vapor interface can undergo a first-order phase transition from incomplete to complete wetting of the vapor as the temperature is raised. A discontinuity in the change of interfacial tension as a function of temperature at the phase transition has been predicted to occur in many systems and to play an important role in the growth of uniform composites from alloy melts at monotectic points. These measurements are the first to establish the order of the transition. Studies of capillary rise in SF6 in a unique interferometer have led to the first measurements of the thickness of wetting layers (or equivalently, multilayer adsorbed films) on a solid surface near a liquid-vapor critical point. Instabilities in wetting layers were observed. A theory for the instabilities is being developed and will be checked by both static and dynamic optical experiments. The effect of gravity on the apparent thickness of interfaces (as measured by ellipsometry) is under study.

  7. Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

    Science.gov (United States)

    Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

    2014-05-22

    Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P < 10 Torr with the high pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

  8. Experimental and theoretical study of delayed ettringite damage in concrete

    Science.gov (United States)

    Ramadan, Elsaid Osman

    2000-12-01

    An experimental study is conducted to investigate the effect of a range of parameters on concrete expansion and premature deterioration associated with delayed ettringite formation (DEF). These parameters were identified from a comprehensive literature review; they include concrete curing conditions and cement chemistry. Specifically, the study investigated the effect of potassium and magnesium contents as well as the effect of water and steam curing conditions on concrete damage associated with DEF. An accelerated test method for DEF was evaluated and modifications are suggested. Concrete specimens were prepared with varying amounts of potassium and magnesium and subjected to different curing conditions. To accelerate any potential expansion, a beat cycle was employed. The change in length of the specimens was monitored for the duration of the study. Specimens were analyzed using the scanning electron microscope, x-ray dispersive analysis, and x-ray diffraction to determine the mechanism responsible for deterioration. Computed tomography x-ray was also employed as a non-destructive method for examining the internal crack patterns associated with expansion. The expansion data is fitted using the Kohnogorov-Avrami-Johenson-Mehl (KAJM) equation. This theory makes it possible to identify individual expansion processes and to identify the contribution of different expansion mechanisms. All concretes showed expansion following the beat cycle. Subjecting concrete to the heat cycle has a primary role in accelerating expansion. The age at which concrete is subjected to the beat cycle as well as the sample dimensions have a profound effect on the resulting expansion. The use of the concrete prisms as suggested in the modified test method offers a better alternative to cores suggested by Duggan. Increasing the potassium content has a deleterious effect on concrete expansion and premature deterioration and is also associated with dramatic reduction in compressive strength

  9. Theoretical study of the crossover into hydrodynamic regime in graphene

    Science.gov (United States)

    Ho, Derek; Yudhistira, Indra; Hu, Ben Yu-Kuang; Adam, Shaffique

    Experiments on graphene have recently succeeded in entering the hydrodynamic regime, as demonstrated by successful observations of strong violation of Wiedemann-Franz law, the Gurzhi effect and electronic Poiseuille flow. It is known that electronic systems enter the hydrodynamic regime when electron-electron scattering dominates over electron-impurity and electron-phonon scattering. However, a quantitative study of this transition from the Fermi liquid to hydrodynamic regime is still lacking. In view of this, we quantitatively analyze the electron-electron, electron-impurity and electron-phonon scattering rates as a function of temperature, charge doping and disorder (charge puddle) strength. This yields a quantitative understanding of the onset of hydrodynamic electronic behavior in graphene samples. This work is supported by the National Research Foundation of Singapore under its Fellowship program (NRF-NRFF2012-01) and by the Singapore Ministry of Education and Yale-NUS College through Grant No. R-607-265-01312.

  10. Exergy performance of different space heating systems: A theoretical study

    DEFF Research Database (Denmark)

    Kazanci, Ongun Berk; Shukuya, Masanori; Olesen, Bjarne W.

    2016-01-01

    , the effects of floor covering resistance on the whole system performance were studied using two heat sources; a natural gas fired condensing boiler and an air-source heat pump. The heating systems were also compared in terms of auxiliary exergy use for pumps and fans. The low temperature floor heating system...... performed better than other systems in terms of exergy demand. The use of boiler as a heat source for a low-exergy floor heating system creates a mismatch in the exergy supply and demand. Although an air-source heat pump could be a better heat source, this depends on the origin of the electricity supplied...... the performance of the floor heating and the whole system. The exergy input to auxiliary components plays a significant role in the overall exergy performance of systems, and its effects become even more significant for low temperature heating systems....

  11. Theoretical study of short pile effect in tunnel excavation

    Science.gov (United States)

    Tian, Xiao-yan; Liu, Jing; Gao, Xiao-mei; Li, Yuan

    2017-09-01

    The Misaki Sato Go ideal elastoplastic model is adopted and the two stage analysis theory is used to study the effect of tunnel excavation on short pile effect in this paper. In the first stage, the free field vertical displacement of the soil at the corresponding pile location is obtained by using empirical formula. In the second stage, the displacement is applied to the corresponding pile location. The equilibrium condition of micro physical differential equation settlement of piles. Then through logical deduction and the boundary condition expressions of the settlement calculation, obtain the pile side friction resistance and axial force of the week. Finally, an engineering example is used to analyze the influence of the change of main parameters on their effects.

  12. Theoretical study on interactions between lignocellulose components and ionic liquids

    Science.gov (United States)

    Wang, J.; Zhuang, W. C.; Shi, X. Q.; Cao, W. L.

    2017-09-01

    Interactions between lignocellulose and ionic liquids have been studied by designed lignocellulose components models, and their complexes with 1-butyl-3-methylimidazolium chloride. All the structures were optimized by DFT methods and hydrogen bonds within lignocelluloses components, and their complexes with 1-butyl-3-methylimidazolium chloride were investigated by AIM calculations. Our calculated results demonstrate that when dissolved in ionic liquids, the stable intermolecular hydrogen bonds and weak π-stacking interactions between ionic liquids and lignocelluloses components reduce the energy of complex systems, which are advantageous for lignocelluloses components dissolution in ionic liquids. Moreover, there are deformation accrued for both lignocelluloses components and ionic liquids, which may be a prerequisite for lignocelluloses components dissolution in ionic liquids.

  13. Theoretical study of solar light reflectance from vertical snow surfaces

    Directory of Open Access Journals (Sweden)

    O. V. Nikolaeva

    2013-04-01

    Full Text Available The influence of horizontal and vertical inhomogeneity of snow surfaces on solar light reflectance is studied using the radiative transfer theory (RTT. We compared 1-D RTT and 2-D RTT and found that large errors are produced if the 1-D RTT is used for the calculation of the snow reflection function (and, therefore, also in the retrievals of the snow grain radii in 2-D measurement geometries. Such 2-D geometries are common in the procedures for the determination of the effective snow grain radii using near-infrared photography and spectroscopy of vertical snow walls. In particular, we have considered three cases for the numerical calculations: (1 the case with no black film; (2 the case with a black film at the pit's bottom; (3 the case with a black film at the pit's bottom and also at one of the vertical snow walls.

  14. Theoretical study on the reactivity of sulfate species with hydrocarbons

    Science.gov (United States)

    Ma, Q.; Ellis, G.S.; Amrani, A.; Zhang, T.; Tang, Y.

    2008-01-01

    The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions SO42 - are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of SO42 - is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions (HSO4-) and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive. Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of HSO4- relative to SO42 -. However, in formation waters typically encountered in petroleum reservoirs, the concentration of HSO4- is likely to be significantly lower than the levels

  15. A theoretical and experimental study of a novel refrigerant compressor

    Science.gov (United States)

    Eames, I. W.

    A refrigerant compressor concept was envisaged consisting of a small scale centrifugal compressor driven by a high frequency induction motor on a common shaft with an impeller supported in aerodynamic bearings. The combination of state-of-the-art compressor, bearing and motor technologies potentially provides refrigerator designers with improved system performance and better compressor reliability with significant reductions in weight and physical size at reduced capital and running costs. A detailed description of the prototype compressor unit is included. The concept is compared with conventional compressor systems, and key areas of research requiring detailed investigation are identified. The following are described and/or evaluated: (1) the results of a literature survey into performance of centrifugal compressors; (2) the electric motor; (3) an investigation into the design of the drive shaft and bearing assemblies; (4) external and internal sources of machine vibration; (5) the manufacture of the prototype compressor unit; (6) testing of the compressor unit; (7) development problems encountered during testing; and (8) a computer simulation study of the behavior of a refrigeration system incorporating the prototype compressor. Aspects of the manufacture considered include surface finishes, tolerancing, heat treatments, and balancing processes.

  16. Theoretical Framework of the filmed Interview in Communication Studies

    Directory of Open Access Journals (Sweden)

    LEBTAHI Yannick

    2016-07-01

    Full Text Available In the Social Sciences today, there are a variety of ways to approach the various areas of investigation and a wide range of observational methods. Depending on academic background and research interests, researchers explore and emphasize certain approaches and categorizations at the expense of others in the implementation of their audiovisual investigations. These observations lead us to first question the definition of image in its connection to the object of research and its status and, secondly, to identify the diversity of current practices and uses. Indeed, the status of an image changes according to the media used and the contexts of reception. The circulation of images promotes exchange and connection between the various groups of actors. If we awkwardly accompany images, we risk unwittingly betraying their original meaning. Furthermore, there is the possibility of conflicts or unintended distortions linked to the activities of projection and identification. Our goal will be to propose a methodological framework and establish an initial model for all researchers in Communication Studies using the audiovisual method. Finally, the researcher accepts not only to properly conduct his research, but also to present an audiovisual project taking into account from the start advantages, constraints, issues of influence and scientific impact.

  17. A theoretical study on vomitoxin and its tautomers

    Energy Technology Data Exchange (ETDEWEB)

    Tuerker, Lemi [Middle East Technical University, Department of Chemistry, 06531 Ankara (Turkey)], E-mail: lturker@metu.edu.tr; Guemues, Selcuk [Middle East Technical University, Department of Chemistry, 06531 Ankara (Turkey); Yuezuencue Yil Universitesi, Kimya Boeluemue, 65080 Kampues, Van (Turkey)

    2009-04-15

    In the present work, the structural and electronic properties of vomitoxin (deoxynivalenol, a mycotoxin) and all of its possible tautomers have been investigated by the application of B3LYP/6-31G(d,p) type quantum chemical calculations. According to the results of the calculations, tautomer V{sub 4} has been found to be the most stable one among all the structures both in the gas and aqueous phases. The calculations also indicated that, vomitoxin and V{sub 2} possess the deepest and the highest lying HOMO levels, respectively. Hence, V{sub 2} is to be more susceptible to oxidations than the others. On the other hand, V{sub 5}(S) and vomitoxin have the lowest and the next lowest LUMO energies, respectively. Whereas, V{sub 1} and V{sub 2} possess quite highly lying (within the group) LUMO energy levels which result in comparatively unfavorable reduction potentials. Some important geometrical and physicochemical properties and the calculated IR spectra of the systems have also been reported in the study.

  18. Theoretical study of bismuth-doped cadmium telluride

    Science.gov (United States)

    Menendez-Proupin, E.; Rios-Gonzalez, J. A.; Pena, J. L.

    Cadmium telluride heavily doped with bismuth has been proposed as an absorber with an intermediate band for solar cells. Increase in the photocurrent has been shown recently, although the overall cell efficiency has not improved. In this work, we study the electronic structure and the formation energies of the defects associated to bismuth impurities. We have performed electronic structure calculations within generalized density functional theory, using the exchange-correlation functional HSE(w) , where the range-separation parameter w has been tuned to reproduce the CdTe bandgap. Improving upon previous reports, we have included the spin-orbit interaction, which modifies the structure of the valence band and the energy levels of bismuth. We have found that interstitial Bi (Bii) tends to occupy Cd vacancies, cadmium substitution (BiCd) creates single donor level, while tellurium substitution (BiTe) is a shallow single acceptor. We investigate the interaction between these point defects and how can they be combined to create a partially filled intermediate band. Supported by FONDECYT Grant 1130437, CONACYT-SENER SUSTENTABILIDAD ENERGETICA/project CeMIE-Sol PY-207450/25 and PY-207450/26. JARG acknowledges CONACYT fellowship for research visit. Powered@NLHPC (ECM-02).

  19. Theoretical Study of the Rovibronic States of CaO

    Science.gov (United States)

    Khalil, H.; Le Quéré, F.; Brites, V.; Léonard, C.

    2012-01-01

    The spin-rovibronic energy levels of CaO, which result from the couplings of X1Σ +, a3Π, A'1Π, b3Σ +, and A1Σ + low-lying electronic states, are determined from wave packet time propagations and Prony analysis. The electronic potentials were taken from our previous study [Chem. Phys., 386, 50 (2011)]. The spin-orbit and L^ coupling functions were determined by CASSCF and MRCI calculations. The effects of spin-orbit coupling on vibrational levels were analyzed in the Ω = 0 +, 0 -, 1 coupling schemes. All spin-vibronic energy levels associated with the a3Π, A'1Π, b3Σ +, and A1Σ + states were determined up to 16 000 cm -1 above the electronic ground-state minimum. The results obtained from the spin-orbit coupling functions are in remarkable agreement with the experimental data extracted using a deperturbation procedure. The final energies calculated for J = 2 and J = 25 are used to compare the experimental observations concerning the X1Σ +- A1Σ + transition.

  20. Theoretical study of the relativistic molecular rotational g-tensor

    Energy Technology Data Exchange (ETDEWEB)

    Aucar, I. Agustín, E-mail: agustin.aucar@conicet.gov.ar; Gomez, Sergio S., E-mail: ssgomez@exa.unne.edu.ar [Institute for Modeling and Technological Innovation, IMIT (CONICET-UNNE) and Faculty of Exact and Natural Sciences, Northeastern University of Argentina, Avenida Libertad 5400, W3404AAS Corrientes (Argentina); Giribet, Claudia G.; Ruiz de Azúa, Martín C. [Physics Department, Faculty of Exact and Natural Sciences, University of Buenos Aires and IFIBA CONICET, Ciudad Universitaria, Pab. I, 1428 Buenos Aires (Argentina)

    2014-11-21

    An original formulation of the relativistic molecular rotational g-tensor valid for heavy atom containing compounds is presented. In such formulation, the relevant terms of a molecular Hamiltonian for non-relativistic nuclei and relativistic electrons in the laboratory system are considered. Terms linear and bilinear in the nuclear rotation angular momentum and an external uniform magnetic field are considered within first and second order (relativistic) perturbation theory to obtain the rotational g-tensor. Relativistic effects are further analyzed by carrying out the linear response within the elimination of the small component expansion. Quantitative results for model systems HX (X=F, Cl, Br, I), XF (X=Cl, Br, I), and YH{sup +} (Y=Ne, Ar, Kr, Xe, Rn) are obtained both at the RPA and density functional theory levels of approximation. Relativistic effects are shown to be small for this molecular property. The relation between the rotational g-tensor and susceptibility tensor which is valid in the non-relativistic theory does not hold within the relativistic framework, and differences between both molecular parameters are analyzed for the model systems under study. It is found that the non-relativistic relation remains valid within 2% even for the heavy HI, IF, and XeH{sup +} systems. Only for the sixth-row Rn atom a significant deviation of this relation is found.

  1. Theoretical study on the constricted flow phenomena in arteries

    Science.gov (United States)

    Sen, S.; Chakravarty, S.

    2012-12-01

    The present study is dealt with the constricted flow characteristics of blood in arteries by making use of an appropriate mathematical model. The constricted artery experiences the generated wall shear stress due to flow disturbances in the presence of constriction. The disturbed flow in the stenosed arterial segment causes malfunction of the cardiovascular system leading to serious health problems in the form of heart attack and stroke. The flowing blood contained in the stenosed artery is considered to be non-Newtonian while the flow is treated to be two-dimensional. The present pursuit also accounts for the motion of the arterial wall and its effect on local fluid mechanics. The flow analysis applies the time-dependent, two-dimensional incompressible nonlinear Navier-Stokes equations for non-Newtonian fluid representing blood. An extensive quantitative analysis presented at the end of the paper based on large scale numerical computations of the quantities of major physiological significance enables one to estimate the constricted flow characteristics in the arterial system under consideration which deviates significantly from that of normal physiological flow conditions.

  2. Kinetic and Thermodynamic Studies of Charge-Transfer Complex ...

    African Journals Online (AJOL)

    NICOLAAS

    the donor in the two solvents was estimated and compared with the theoretical values. KEYWORDS. Charge-transfer complex ... drug-receptor binding mechanisms,7 in solar energy storage 8,9 and in surface chemistry10 as well as in many ..... dyes-sensitized solar cells, Renew. Energ., 2010, 35, 1724–1728. 10 S.M. ...

  3. Electrochemical degradation, kinetics & performance studies of solid oxide fuel cells

    Science.gov (United States)

    Das, Debanjan

    Linear and Non-linear electrochemical characterization techniques and equivalent circuit modelling were carried out on miniature and sub-commercial Solid Oxide Fuel Cell (SOFC) stacks as an in-situ diagnostic approach to evaluate and analyze their performance under the presence of simulated alternative fuel conditions. The main focus of the study was to track the change in cell behavior and response live, as the cell was generating power. Electrochemical Impedance Spectroscopy (EIS) was the most important linear AC technique used for the study. The distinct effects of inorganic components usually present in hydrocarbon fuel reformates on SOFC behavior have been determined, allowing identification of possible "fingerprint" impedance behavior corresponding to specific fuel conditions and reaction mechanisms. Critical electrochemical processes and degradation mechanisms which might affect cell performance were identified and quantified. Sulfur and siloxane cause the most prominent degradation and the associated electrochemical cell parameters such as Gerisher and Warburg elements are applied respectively for better understanding of the degradation processes. Electrochemical Frequency Modulation (EFM) was applied for kinetic studies in SOFCs for the very first time for estimating the exchange current density and transfer coefficients. EFM is a non-linear in-situ electrochemical technique conceptually different from EIS and is used extensively in corrosion work, but rarely used on fuel cells till now. EFM is based on exploring information obtained from non-linear higher harmonic contributions from potential perturbations of electrochemical systems, otherwise not obtained by EIS. The baseline fuel used was 3 % humidified hydrogen with a 5-cell SOFC sub-commercial planar stack to perform the analysis. Traditional methods such as EIS and Tafel analysis were carried out at similar operating conditions to verify and correlate with the EFM data and ensure the validity of the

  4. Theoretical Study of Amplitude Modulation Application during Radio Frequency Electrocoagulation

    Directory of Open Access Journals (Sweden)

    V. A. Karpuhin

    2015-01-01

    Full Text Available This article concerns the investigation results of influence of the amplitude-modulated acting signal parameters on the thermoelectric characteristics of biological tissues for a specified geometry of the working electrode section during RF mono-polar electrocoagulation. The geometric model ‘electrode - a biological tissue’ was suggested to study the distribution of power and temperature fields in biological tissue during mono-polar coagulation. The model of biological tissue is represented as a cylinder and the needle electrode is an ellipsoid immersed in the biological tissue. The heat and quasi-electrostatics equations are used as a mathematical model. These equations are solved in Comsol Multiphysics environment.As a result, we have got the following findings: the technique of calculating parameters of the PAM acting signal which has a fixed carrier frequency for the needle electrode of a specified geometry and the immersion depth in biological tissues is suggested. Parameters of PAM signal are determined for this electrode geometry. These parameters provide a 60 ... 80°C heating range of biological tissues near the working part of the tool for different amplitudes of acting signal during RF coagulation. It has been found out that both the temperature and the relaxation frequency of biological tissue depend on exposure time for the needle electrode of a specified geometry and immersion depth of the working part of tool into biological tissue.It is shown that the relaxation frequency of the biological tissue, subjected to the radiofrequency pulses, linearly depends on its heating temperature and can be used as a numerical criterion for maintaining the specified temperature conditions. It is found that the relaxation frequency of the biological tissue depends on the contact area of the tool working part and biological tissues. To reduce this dependence it is necessary to provide automatic current control of the output action.

  5. Theoretical studies in nuclear reactions and nuclear structure. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    1992-05-01

    Research in the Maryland Nuclear Theory Group focusses on problems in four basic areas of current relevance. Hadrons in nuclear matter; the structure of hadrons; relativistic nuclear physics and heavy ion dynamics and related processes. The section on hadrons in nuclear matter groups together research items which are aimed at exploring ways in which the properties of nucleons and the mesons which play a role in the nuclear force are modified in the nuclear medium. A very interesting result has been the finding that QCD sum rules supply a new insight into the decrease of the nucleon`s mass in the nuclear medium. The quark condensate, which characterizes spontaneous chiral symmetry breaking of the late QCD vacuum, decreases in nuclear matter and this is responsible for the decrease of the nucleon`s mass. The section on the structure of hadrons contains progress reports on our research aimed at understanding the structure of the nucleon. Widely different approaches are being studied, e.g., lattice gauge calculations, QCD sum rules, quark-meson models with confinement and other hedgehog models. A major goal of this type of research is to develop appropriate links between nuclear physics and QCD. The section on relativistic nuclear physics represents our continuing interest in developing an appropriate relativistic framework for nuclear dynamics. A Lorentz-invariant description of the nuclear force suggests a similar decrease of the nucleon`s mass in the nuclear medium as has been found from QCD sum rules. Work in progress extends previous successes in elastic scattering to inelastic scattering of protons by nuclei. The section on heavy ion dynamics and related processes reports on research into the e{sup +}e{sup {minus}} problem and heavy ion dynamics.

  6. Theoretical studies in nuclear reactions and nuclear structure

    Energy Technology Data Exchange (ETDEWEB)

    1992-05-01

    Research in the Maryland Nuclear Theory Group focusses on problems in four basic areas of current relevance. Hadrons in nuclear matter; the structure of hadrons; relativistic nuclear physics and heavy ion dynamics and related processes. The section on hadrons in nuclear matter groups together research items which are aimed at exploring ways in which the properties of nucleons and the mesons which play a role in the nuclear force are modified in the nuclear medium. A very interesting result has been the finding that QCD sum rules supply a new insight into the decrease of the nucleon's mass in the nuclear medium. The quark condensate, which characterizes spontaneous chiral symmetry breaking of the late QCD vacuum, decreases in nuclear matter and this is responsible for the decrease of the nucleon's mass. The section on the structure of hadrons contains progress reports on our research aimed at understanding the structure of the nucleon. Widely different approaches are being studied, e.g., lattice gauge calculations, QCD sum rules, quark-meson models with confinement and other hedgehog models. A major goal of this type of research is to develop appropriate links between nuclear physics and QCD. The section on relativistic nuclear physics represents our continuing interest in developing an appropriate relativistic framework for nuclear dynamics. A Lorentz-invariant description of the nuclear force suggests a similar decrease of the nucleon's mass in the nuclear medium as has been found from QCD sum rules. Work in progress extends previous successes in elastic scattering to inelastic scattering of protons by nuclei. The section on heavy ion dynamics and related processes reports on research into the e{sup +}e{sup {minus}} problem and heavy ion dynamics.

  7. Theoretical study of ultraviolet induced photodissociation dynamics of sulfuric acid

    Energy Technology Data Exchange (ETDEWEB)

    Murakami, Tatsuhiro; Ohta, Ayumi; Suzuki, Tomoya; Ikeda, Kumiko [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan); Danielache, Sebastian O. [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan); Earth-Life Science Institute (ELSI), Tokyo Institute of Technology (Japan); Department of Environmental Science and Techonology, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Yoohama 226-8502 (Japan); Nanbu, Shinkoh, E-mail: shinkoh.nanbu@sophia.ac.jp [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan)

    2015-05-01

    Highlights: • Photodissociation dynamics of H{sub 2}SO{sub 4} at low-lying electronically excited states were investigated. • Photochemical processes were simulated by on-the-fly ab initio MD. • Sulfuric acid after the excitation to the S{sub 1} state dissociated to HSO{sub 4}(1{sup 2}A″) + H({sup 2}S). • Sulfuric acid after the excitation to the S{sub 2} state dissociated to HSO{sub 4}(2{sup 2}A″) + H({sup 2}S). • The energy region of the UV spectra where NMD fractionation may occur is predicted. - Abstract: Photodissociation dynamics of sulfuric acid after excitation to the first and second excited states (S{sub 1} and S{sub 2}) were studied by an on-the-fly ab initio molecular dynamics simulations based on the Zhu–Nakamura version of the trajectory surface hopping (ZN-TSH). Forces acting on the nuclear motion were computed on-the-fly by CASSCF method with Dunning’s augmented cc-pVDZ basis set. It was newly found that the parent molecule dissociated into two reaction-channels (i) HSO{sub 4}(1{sup 2}A″) + H({sup 2}S) by S{sub 1}-excitation, and (ii) HSO{sub 4}(2{sup 2}A″) + H({sup 2}S) by S{sub 2}-excitation. The direct dissociation dynamics yield products different from the SO{sub 2} + 2OH fragments often presented in the literature. Both channels result in the same product and differs only in the electronic state of the HSO{sub 4} fragment{sub .} The trajectories running on S{sub 2} do not hop with S{sub 0} and a nonadiabatic transition happens at the S{sub 2}–S{sub 1} conical intersection located at a longer OH bond-length than the S{sub 1}–S{sub 0} intersection producing an electronic excited state (2{sup 2}A″) of HSO{sub 4} product.

  8. Centrifugation. A theoretical study of oxygen enrichment by centrifugation

    Energy Technology Data Exchange (ETDEWEB)

    Kierkegaard, P.; Raetz, E.

    1998-12-01

    In the present paper we first investigate what happens if we fill a cylinder with air, close it and rotate it. The results show that no matter which peripheral speed is used, it is not possible by means of the radial separation effect alone, to enrich the oxygen concentration from the previous 21% to more then 23.3%, which is of no practical value. In case of a too low enrichment in one centrifuge, the wanted material from this centrifuge can be used as an input for a second centrifuge and so on, in this way forming a cascade of centrifuges. Oxygen will be enriched in each step, until the desired concentration is reached. Cascading was the technology in the very beginning by enrichment plants for uraniumhexaflouride, used for atomic weapons and nuclear power plants. In this study we try to avoid cascading by aiming for higher separation factors. Therefore, we next investigate the possibilities of using a countercurrent centrifuge where in principle the enriched gas is subjected to several centrifugation in the same centrifuge. The calculations show, that in this way it is possible to produce nearly a 100% pure oxygen (polluted with some heavier molecules like argon) in one machine. Our third step was to calculate the amount of oxygen produced per hour. Using a countercurrent centrifuge of the Zippe type, 100 cm high and 20 cm in diameter, it is or will be possible in the near future to produce 17 g enriched air per hour enriched to 50% oxygen. That corresponds to processing 1 m{sup 3} atmospherical air in the period of approximately 24 hours. This is not very impressive. Our fourth step was to estimate the amount of power used for producing this amount of oxygen. A rough, but complicated, estimate shows that the power consumption at the production level will be about the double of the consumption used today. The overall conclusion is, that centrifugation as a production method for oxygen (or nitrogen) will not be competitive with the currently used method in the

  9. A Theoretical and Experimental Study of DNA Self-assembly

    Science.gov (United States)

    Chandran, Harish

    The control of matter and phenomena at the nanoscale is fast becoming one of the most important challenges of the 21st century with wide-ranging applications from energy and health care to computing and material science. Conventional top-down approaches to nanotechnology, having served us well for long, are reaching their inherent limitations. Meanwhile, bottom-up methods such as self-assembly are emerging as viable alternatives for nanoscale fabrication and manipulation. A particularly successful bottom up technique is DNA self-assembly where a set of carefully designed DNA strands form a nanoscale object as a consequence of specific, local interactions among the different components, without external direction. The final product of the self-assembly process might be a static nanostructure or a dynamic nanodevice that performs a specific function. Over the past two decades, DNA self-assembly has produced stunning nanoscale objects such as 2D and 3D lattices, polyhedra and addressable arbitrary shaped substrates, and a myriad of nanoscale devices such as molecular tweezers, computational circuits, biosensors and molecular assembly lines. In this dissertation we study multiple problems in the theory, simulations and experiments of DNA self-assembly. We extend the Turing-universal mathematical framework of self-assembly known as the Tile Assembly Model by incorporating randomization during the assembly process. This allows us to reduce the tile complexity of linear assemblies. We develop multiple techniques to build linear assemblies of expected length N using far fewer tile types than previously possible. We abstract the fundamental properties of DNA and develop a biochemical system, which we call meta-DNA, based entirely on strands of DNA as the only component molecule. We further develop various enzyme-free protocols to manipulate meta-DNA systems and provide strand level details along with abstract notations for these mechanisms. We simulate DNA circuits by

  10. A study of spin isomer conversion kinetics in supercritical fluid hydrogen for cyrogenic fuel storage technologies

    Science.gov (United States)

    Matthews, Manyalibo J.; Petitpas, Guillaume; Aceves, Salvador M.

    2011-08-01

    A detailed kinetic study of para-ortho hydrogen conversion under supercritical conditions using rotational Raman scattering is presented. Isochoric measurements of initially low ortho concentrations over temperatures 32 hydrogen fuel tank dormancy performance for hydrogen-power vehicles.

  11. Kinetic study of oil extraction from olive foot cake

    Directory of Open Access Journals (Sweden)

    Lamrous, O.

    2006-06-01

    Full Text Available The kinetics of oil extraction from olive foot cake can be explained by a model based on two stages. The first step corresponds to a simple washing of the oil from the particle surface. In the second step, the extraction is controlled by two mechanisms: slow diffusion from broken cells and very slow diffusion from intact cells.The kinetic coefficients of this mathematical model are calculated using the experimental results obtained from hexane and commercial ethyl alcohol for different particle sizes.La cinética de extracción de aceite de orujo puede ser explicada por un modelo basado en dos etapas. La primera etapa corresponde a un simple lavado del aceite de la superficie de las partículas. En la segunda etapa, la extracción esta controlada por dos mecanismos: difusión lenta desde las células rotas y difusión muy lenta desde las células intactas.Los coeficientes cinéticas de este modelo matemático se calculan usando los resultados experimentales obtenidos con hexano y alcohol etílico comercial para diferentes tamaños de partícula.

  12. Stable isotope studies of nicotine kinetics and bioavailability

    Energy Technology Data Exchange (ETDEWEB)

    Benowitz, N.L.; Jacob, P. 3d.; Denaro, C.; Jenkins, R. (Univ. of California, San Francisco (USA))

    1991-03-01

    The stable isotope-labeled compound 3',3'-dideuteronicotine was used to investigate the disposition kinetics of nicotine in smokers, the systemic absorption of nicotine from cigarette smoke, and the bioavailability of nicotine ingested as oral capsules. Blood levels of labeled nicotine could be measured for 9 hours after a 30-minute intravenous infusion. Analysis of disposition kinetics in 10 healthy men revealed a multiexponential decline after the end of an infusion, with an elimination half-life averaging 203 minutes. This half-life was longer than that previously reported, indicating the presence of a shallow elimination phase. Plasma clearance averaged 14.6 ml/min/kg. The average intake of nicotine per cigarette was 2.29 mg. A cigarette smoke-monitoring system that directly measured particulate matter in smoke was evaluated in these subjects. Total particulate matter, number of puffs on the cigarette, total puff volume, and time of puffing correlated with the intake of nicotine from smoking. The oral bioavailability of nicotine averaged 44%. This bioavailability is higher than expected based on the systemic clearance of nicotine and suggests that there may be significant extrahepatic metabolism of nicotine.

  13. Theoretical Study on the Flow of Refilling Stage in a Safety Injection Tank

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jun Sang [Halla Univ. Daejeon (Korea, Republic of)

    2017-10-15

    In this study, a theoretical analysis was performed to the flow of refilling stage in a safety injection tank, which is the core cooling system of nuclear power plant in an emergency. A theoretical model was proposed with a nonlinear governing equation defining on the flow of the refilling process of the coolant. Utilizing the Taylor-series expansion, the 1st - order approximation flow equation was obtained, along with its analytic solution of closed type, which could predict accurately the variations of free surface height and flow rate of the coolant. The availability of theoretical result was confirmed by comparing with previous experimental results.

  14. A comprehensive theoretical and experimental study of coplanar waveguide shunt stubs

    Science.gov (United States)

    Dib, Nihad I.; Ponchak, George E.; Katehi, Linda P. B.

    1993-01-01

    A comprehensive theoretical and experimental study of straight and bent coplanar waveguide (CPW) shunt stubs is presented. In the theoretical analysis, the CPW is assumed to be inside a cavity, while, the experiments are performed on open structures. A hybrid technique was developed to analyze the CPW discontinuities which proved to be accurate since the theoretical and experimental results agree very well. The effect of the cavity resonances on the behavior of the stubs with and without air-bridges is investigated. In addition, the encountered radiation loss due to the discontinuities is evaluated experimentally.

  15. Twisted amides: X-ray crystallographic and theoretical study of two acylated glycolurils with aromatic substituents

    Science.gov (United States)

    Matta, Chérif F.; Cow, Christopher N.; Harrison, Paul H. M.

    2003-11-01

    X-ray crystallography and theoretical analysis were applied to explore the molecular basis for the efficient and selective Claisen-like condensations of diacylglycolurils. The crystal structures of 1-acetyl-6-benzoyl-3,4,7,8-tetramethylglycoluril ( 4b), and of 1-(3'-oxo-3'-phenylpropionyl)-3,4,7,8-tetramethylglycoluril ( 5b), the product of base-promoted intramolecular condensation of 4b, were obtained by X-ray diffraction. The acetyl (Ac) group in 4b is essentially coplanar with the attached tetrahydroimidazolone ring of the glycoluril core ( τ=7°), while the benzoyl (Bz) group is twisted by τ=45° relative to a plane through the ring to which it is bonded. Product 5b contains a flat amide ( τ=7°). Ab initio energy optimizations of the experimental structures for 4b and 5b give optimized geometries which are not dramatically altered, suggesting that crystal packing effects are small. An atoms-in-molecules study of the delocalization of the Fermi hole reveals that electrons in the Bz CO group of 4b are delocalized into the phenyl ring as well as into the urea moiety of the glycoluril core. This effect stabilizes the Bz over the Ac carbonyl group, and accounts for selective twisting of the Bz group. The Laplacian of the electron density reveals a non-bonded valence shell charge concentration at O of the Ac group, corresponding to a lone-pair region, aligned with a charge depletion in the valence shell of the Bz CO carbon [∠(C15-O16⋯C18)=113°]. The angle of approach [∠(O16⋯C18O19)] is 100°, equal to the angle for ideal nucleophilic attack on a carbonyl group. Oxygen atom O16 is thus poised to attack C18; only the O16⋯C18 distance (3.248 Å) seems to prevent reaction. These results suggest that the same distance restraint may prevent O-acylation in the enolate intermediate 6b derived from 4b. By contrast, the transition state for C-acylation, leading from 6b towards product 5b requires a different geometry, which may explain the

  16. Extraction of astaxanthin from giant tiger (Panaeus monodon) shrimp waste using palm oil: studies of extraction kinetics and thermodynamic.

    Science.gov (United States)

    Handayani, Akdes Dewi; Sutrisno; Indraswati, Nani; Ismadji, Suryadi

    2008-07-01

    Study of extraction of astaxanthin from giant tiger (Panaeus monodon) shrimp waste using palm oil was conducted to determine the extraction kinetics and thermodynamic parameters. Two extraction models were proposed: mass transfer kinetic model and reaction kinetic model. It was found that both of mass transfer and reaction kinetic control the extraction of astaxanthin from shrimp waste using palm oil. The thermodynamic parameters of extraction were also obtained in this study.

  17. An in-depth analysis of theoretical frameworks for the study of care coordination

    Directory of Open Access Journals (Sweden)

    Sabine Van Houdt

    2013-06-01

    Full Text Available Introduction: Complex chronic conditions often require long-term care from various healthcare professionals. Thus, maintaining quality care requires care coordination. Concepts for the study of care coordination require clarification to develop, study and evaluate coordination strategies. In 2007, the Agency for Healthcare Research and Quality defined care coordination and proposed five theoretical frameworks for exploring care coordination. This study aimed to update current theoretical frameworks and clarify key concepts related to care coordination. Methods: We performed a literature review to update existing theoretical frameworks. An in-depth analysis of these theoretical frameworks was conducted to formulate key concepts related to care coordination.Results: Our literature review found seven previously unidentified theoretical frameworks for studying care coordination. The in-depth analysis identified fourteen key concepts that the theoretical frameworks addressed. These were ‘external factors’, ‘structure’, ‘tasks characteristics’, ‘cultural factors’, ‘knowledge and technology’, ‘need for coordination’, ‘administrative operational processes’, ‘exchange of information’, ‘goals’, ‘roles’, ‘quality of relationship’, ‘patient outcome’, ‘team outcome’, and ‘(interorganizational outcome’.Conclusion: These 14 interrelated key concepts provide a base to develop or choose a framework for studying care coordination. The relational coordination theory and the multi-level framework are interesting as these are the most comprehensive.

  18. [Nursing practice based on theoretical models: a qualitative study of nurses' perception].

    Science.gov (United States)

    Amaducci, Giovanna; Iemmi, Marina; Prandi, Marzia; Saffioti, Angelina; Carpanoni, Marika; Mecugni, Daniela

    2013-01-01

    Many faculty argue that theory and theorizing are closely related to the clinical practice, that the disciplinary knowledge grows, more relevantly, from the specific care context in which it takes place and, moreover, that knowledge does not proceed only by the application of general principles of the grand theories to specific cases. Every nurse, in fact, have  a mental model, of what may or may not be aware, that motivate and substantiate every action and choice of career. The study describes what the nursing theoretical model is; the mental model and the tacit  knowledge underlying it. It identifies the explicit theoretical model of the professional group that rapresents nursing partecipants, aspects of continuity with the theoretical model proposed by this degree course in Nursing.. Methods Four focus groups were made which were attended by a total of 22 nurses, rapresentatives of almost every Unit of Reggio Emilia Hospital's. We argue that the theoretical nursing model of each professional group is the result of tacit knowledge, which help to define the personal mental model, and the theoretical model, which explicitly underlying theoretical content learned applied consciously and reverted to / from nursing practice. Reasoning on the use of theory in practice has allowed us to give visibility to a theoretical model explicitly nursing authentically oriented to the needs of the person, in all its complexity in specific contexts.

  19. Ignition characteristics of 2-methyltetrahydrofuran: An experimental and kinetic study

    KAUST Repository

    Tripathi, Rupali

    2016-10-15

    The present paper elucidates oxidation behavior of 2-methyltetrahydrofuran (2-MTHF), a novel second-generation biofuel. New experimental data sets for 2-MTHF including ignition delay time measurements in two different combustion reactors, i.e. rapid compression machine and high-pressure shock tube, are presented. Measurements for 2-MTHF/oxidizer/diluent mixtures were performed in the temperature range of . 639-1413 K, at pressures of 10, 20, and 40 bar, and at three different equivalence ratios of 0.5, 1.0, and 2.0. A detailed chemical kinetic model describing both low-and high-temperature chemistry of 2-MTHF was developed and validated against new ignition delay measurements and already existing flame species profiles and ignition delay measurements. The mechanism provides satisfactory agreement with the experimental data. For identifying key reactions at various combustion conditions and to attain a better understanding of the combustion behavior, reaction path and sensitivity analyses were performed.

  20. An experimental study on dissolution kinetics of paraffin waste form

    Energy Technology Data Exchange (ETDEWEB)

    Kim, J. Y.; Jung, C. H. [Seoul National Univ., Seoul (Korea, Republic of); Choi, H. J.; Kim, C. R. [KNETEC, Taejon (Korea, Republic of)

    1999-10-01

    Ninety-day's leaching test of paraffin waste form with boric acid, cobalt, strontium and cesium was performed. In case that the mixing weight ratio of waste form between boric acid and paraffin was 78/22, which had been adopted in the concentrate waste drying system(CWDS) of domestic nuclear power plants, the cumulative fraction leached(CFL) of boric acid was about 55% after ninety days and the CFLs of cobalt, strontium and cesium were almost same value of 63%. The compressive strengths of waste form before and after the leaching test exhibited 4.53 MPa (666 psi) and 1.38 MPa(203 psi), respectively. The CFL of paraffin waste form was well expressed by diffusion-controlled dissolution model such as Jander kinetics. The cross-sectional area of specimen after the test showed that this unreacted shrinking core model can be applied to the mechanistic analysis of paraffin waste form.

  1. Alkaline assisted thermal oil recovery: Kinetic and displacement studies

    Energy Technology Data Exchange (ETDEWEB)

    Saneie, S.; Yortsos, Y.C.

    1993-06-01

    This report deals with two major issues of chemical assisted flooding - the interaction of caustic, one of the proposed additives to steam flood, with the reservoir rock, and the displacement of oil by a chemical flood at elevated temperatures. A mathematical model simulating the kinetics of silica dissolution and hydroxyl ion consumption in a typical alkaline flooding environment is first developed. The model is based on the premise that dissolution occurs via hydrolysis of active sites through the formation of an intermediate complex, which is in equilibrium with the silicic acid in solution. Both static (batch) and dynamic (core flood) processes are simulated to examine the sensitivity of caustic consumption and silica dissolution to process parameters, and to determine rates of propagation of pH values. The model presented provides a quantitative description of the quartz-alkali interaction in terms of pH, salinity, ion exchange properties, temperature and contact time, which are of significant importance in the design of soluble silicate flooding processes. The modeling of an adiabatic hot waterflood assisted by the simultaneous injection of a chemical additive is next presented. The model is also applicable to the hot alkaline flooding under conditions of negligible adsorption of the generated anionic surfactant and of hydroxide adsorption being Langmuirian. The theory of generalized simple waves (coherence ) is used to develop solutions for the temperature, concentration, and oil saturation profiles, as well as the oil recovery curves. It is shown that, for Langmuir adsorption kinetics, the chemical resides in the heated region of the reservoir if its injection concentration is below a critical value, and in the unheated region if its concentration exceeds this critical value. Results for a chemical slug injection in a tertiary recovery process indicate recovery performance is maximized when chemical resides in the heated region of the reservior.

  2. Implementing atomic force microscopy (AFM) for studying kinetics of gold nanoparticle's growth

    DEFF Research Database (Denmark)

    Georgiev, P.; Bojinova, A.; Kostova, B.

    2013-01-01

    In a novel experimental approach Atomic Force Microscopy (AFM) was applied as a tool for studying the kinetics of gold nanoparticle growth. The gold nanoparticles were obtained by classical Turkevich citrate synthesis at two different temperatures. From the analysis of AFM images during the synth......In a novel experimental approach Atomic Force Microscopy (AFM) was applied as a tool for studying the kinetics of gold nanoparticle growth. The gold nanoparticles were obtained by classical Turkevich citrate synthesis at two different temperatures. From the analysis of AFM images during...... approach. We also compared AFM experimental data with Dynamic Light Scattering (DLS) and with Transmission Electron Microscopy (TEM) data. The experimental data from all the applied methods were fitted with two step Finke-Watzky kinetics model and the corresponding kinetics constants were obtained...

  3. Flow-Based Systems for Rapid and High-Precision Enzyme Kinetics Studies

    Directory of Open Access Journals (Sweden)

    Supaporn Kradtap Hartwell

    2012-01-01

    Full Text Available Enzyme kinetics studies normally focus on the initial rate of enzymatic reaction. However, the manual operation of steps of the conventional enzyme kinetics method has some drawbacks. Errors can result from the imprecise time control and time necessary for manual changing the reaction cuvettes into and out of the detector. By using the automatic flow-based analytical systems, enzyme kinetics studies can be carried out at real-time initial rate avoiding the potential errors inherent in manual operation. Flow-based systems have been developed to provide rapid, low-volume, and high-precision analyses that effectively replace the many tedious and high volume requirements of conventional wet chemistry analyses. This article presents various arrangements of flow-based techniques and their potential use in future enzyme kinetics applications.

  4. Theoretical study of the C-H bond dissociation energy of acetylene

    Science.gov (United States)

    Taylor, Peter R.; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1990-01-01

    The authors present a theoretical study of the convergence of the C-H bond dissociation energy (D sub o) of acetylene with respect to both the one- and n-particle spaces. Their best estimate for D sub o of 130.1 plus or minus 1.0 kcal/mole is slightly below previous theoretical estimates, but substantially above the value determined using Stark anticrossing spectroscopy that is asserted to be an upper bound.

  5. Experimental Studies and Modeling of the Drying Kinetics of Multicomponent Polymer Films.

    Science.gov (United States)

    Velaga, Sitaram P; Nikjoo, Dariush; Vuddanda, Parameswara R

    2018-01-01

    The process of drying thin polymer films is an important operation that influences the film structure and solid state, and the stability of the product. The purpose of this work was to study and model the drying kinetics of multicomponent films based on two polymers: hydroxypropyl methylcellulose (HPMC, amorphous) and polyvinyl alcohol (PVA, semicrystalline). The isothermal drying kinetics of the films at different temperatures (40, 60, and 80°C) were studied using thermo-gravimetric analysis (TGA) and convection oven methods. Solid-state characterization tools used in the study included polarization and hot-stage microscopy, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The drying kinetics of HPMC and PVA films in the TGA apparatus and convection oven were comparable. The three-parameter (W max, τ, n) Hill equation successfully modeled the experimental drying kinetics. The time factor τ in the Hill equation nicely explained two drying phases in the films. Solid-state phase changes occurring in the films during dehydration had a bearing on the drying kinetics and mechanisms. TGA can be used as a simple tool to determine the end points in drying processes using ovens or tunnels. The three-parameter Hill equation explained the drying kinetics and diffusion mechanisms of the solvent through the polymer films for the first time. This study advances our understanding of film drying, in particular for pharmaceutically relevant thin films.

  6. Study on Austenitization Kinetics of SA508 Gr.3 Steel Based on Isoconversional Method

    OpenAIRE

    Xiaomeng Luo; Lizhan Han; Jianfeng Gu

    2015-01-01

    The austenitization kinetics of SA508 Gr.3 steel during heating was studied using the isoconversional method combined with continuous thermal dilatometric tests for the first time. The model-free austenitization kinetics was built and the effective activation energy as a function of transformed austenite fraction was determined without transformation models. Then, the corresponding regression validation was carried out. The time-temperature-austenitization (TTA) diagram of SA508 Gr.3 steel, w...

  7. Toward a Theoretical Framework for Studying Climate Change Policies: Insights from the Case Study of Singapore

    Directory of Open Access Journals (Sweden)

    Ai Sian Ng

    2017-07-01

    Full Text Available The world decided in December 2015 to take actions to reduce global warming. To contribute toward this goal, this research examines possible policy levers for inclusion in the climate change ratification plan. A case study of the measures taken by the Republic of Singapore, a low-lying 719.2 km2 island without natural resources in Asia, is conducted. Being vulnerable to climate change impact and yet having to balance her people’s needs and economic progress with limited resources, the measures taken by this small country could offer policy insights for small states and states without access to alternative energy sources. This research analyzes the online policy documents posted by eleven organizations to answer the main research question of identifying policy levers as theoretical constructs to form a framework that can be used to study climate change policies. A qualitative data analysis software, QSR NVivo 10, is used to classify the proposed nodes developed by the researchers using a system perspective integrating the insights from the key international climate change frameworks with the theoretical concepts from the model of pro-environmental behavior. The findings can offer insights toward developing a new contextual influence framework, which can help strengthen policy development and outcome measurement.

  8. Kinetic study of brilliant green adsorption from aqueous solution onto white rice husk ash.

    Science.gov (United States)

    Tavlieva, Mariana P; Genieva, Svetlana D; Georgieva, Velyana G; Vlaev, Lyubomir T

    2013-11-01

    The present research was focused on the study of adsorption kinetics of brilliant green (BG) onto white rice husk ash from aqueous solutions. The research was performed in the temperature interval 290-320 K in 10° steps and in the concentration range of 3-100 mg L(-1). Batch studies were conducted in order to determine the optimal adsorbent dose, and the time required to reach the adsorption equilibrium at each temperature. The effect of the initial concentration of brilliant green was studied (pH not adjusted), as well as the effect of temperature. The maximum adsorption capacity of the WRHA for BG at 320 K was determined to be 85.56 mg g(-1). The adsorption kinetic data were analyzed employing several kinetic models: pseudo-first-order equation, pseudo-second-order equation, Elovichequation, Banghman's equation, Diffusion-chemisorption model, and Boyd kinetic expression. It was established that the adsorption process obeyed the pseudo-second-order kinetic model. Based on the rate constants obtained by this kinetic model using Arrhenius and Eyring equations, the activation parameters were determined, namely the activation energy (50.04 kJ mol(-1)), the change of entropy (-318.31 J mol(-1) K(-1)), enthalpy (-47.50 kJ mol(-1)), and Gibbs free energy (range 44.81-54.36 kJ mol(-1)) for the formation of activated complex from the reagents. Copyright © 2013 Elsevier Inc. All rights reserved.

  9. Theoretical and analyzed data related to thermal degradation kinetics of poly (L-lactic acid/chitosan-grafted-oligo L-lactic acid (PLA/CH-g-OLLA bionanocomposite films

    Directory of Open Access Journals (Sweden)

    Akhilesh Kumar Pal

    2017-02-01

    Full Text Available The theoretical and analyzed data incorporated in this article are related to the recently published research article entitled “Thermal degradation behaviour of nanoamphiphilic chitosan dispersed poly (lactic acid bionanocomposite films” (http://dx.doi.org/10.1016/j.ijbiomac.2016.11.024 (A.K. Pal, V. Katiyar, 2016 [1]. Supplementary information and data (both raw and analyzed are related to thermal degradation kinetics and explains various model fitting and is conversional methods, which are used in this research work to enhance the knowledge about degradation behaviour of PLA/CH-g-OLLA bionanocomposite system. Non-isothermal degradation kinetics of such polymeric system was proposed using Kissinger, Kissinger–Akahira–Sunose, Flynn–Wall–Ozawa and Augis and Bennett models to estimate the activation energies (Ea and R2 values.

  10. Time resolved spectroscopic investigation of SiD2 + D2: kinetic study

    Science.gov (United States)

    Al-Rubaiey, Najem A.; Walsh, Robin

    2017-03-01

    Silylenes (silanediyls) have made an important impact on organosilicon chemistry even if it is of more recent foundation than carbenes in organic chemistry and much less complete. These species are highly reactive intermediates. They play a central role in the chemical vapour deposition (CVD) of various silicon-containing thin films which have a technological importance in microelectronics as well as in the dry etching processes of silicon wafers. Spectroscopic methods have been developed to observe these species, a necessary pre-requisite to their direct monitoring. In this work, deuterated phenylsilane precursor, PhSiD3 was chosen for SiD2 because its analogue phenylsilane, PhSiH3 proved to be a good precursor for SiH2 and the high quality decay signals observed revealed that SiD2 be readily detected from PhSiD3 and that if other decomposition pathways (e.g. PhSiD + D2) are occurring, they do not effect measurements of the rate constants for SiD2. The absorption spectrum of SiD2 formed from the flash photolysis of a mixture of PhSiD3 and SF6 at 193nm were found in the region 17384-17391 cm-1 with strong band at 17387.07 cm-1. This single rotational line of pQ1 was chosen to monitor SiD2 removal. Time-resolved studies of SiD2 have been carried out to obtain rate constants for its bimolecular reactions with D2. The reactions were studied over the pressure range 5-100 Torr (in SF6 bath gas) at four temperatures in the range 298-498K. Single decay from 10 photolysis laser shots were averaged and found to give reasonable first-order kinetics fits. Second order kinetics were obtained by pressure dependence of the pseudo first order decay constants and substance D2 pressures within experimental error. The reaction was found to be weakly pressure dependent at all temperatures, consistent with a third-body mediated association process. In addition, SiH2+ H2 reaction is approximately ca. 60% faster than SiD2+D2 reaction. Theoretical extrapolations (using Lindemann

  11. Time resolved spectroscopic investigation of SiD2 + D2: kinetic study

    Directory of Open Access Journals (Sweden)

    Al-Rubaiey Najem A.

    2017-01-01

    Full Text Available Silylenes (silanediyls have made an important impact on organosilicon chemistry even if it is of more recent foundation than carbenes in organic chemistry and much less complete. These species are highly reactive intermediates. They play a central role in the chemical vapour deposition (CVD of various silicon-containing thin films which have a technological importance in microelectronics as well as in the dry etching processes of silicon wafers. Spectroscopic methods have been developed to observe these species, a necessary pre-requisite to their direct monitoring. In this work, deuterated phenylsilane precursor, PhSiD3 was chosen for SiD2 because its analogue phenylsilane, PhSiH3 proved to be a good precursor for SiH2 and the high quality decay signals observed revealed that SiD2 be readily detected from PhSiD3 and that if other decomposition pathways (e.g. PhSiD + D2 are occurring, they do not effect measurements of the rate constants for SiD2. The absorption spectrum of SiD2 formed from the flash photolysis of a mixture of PhSiD3 and SF6 at 193nm were found in the region 17384-17391 cm-1 with strong band at 17387.07 cm-1. This single rotational line of pQ1 was chosen to monitor SiD2 removal. Time-resolved studies of SiD2 have been carried out to obtain rate constants for its bimolecular reactions with D2. The reactions were studied over the pressure range 5-100 Torr (in SF6 bath gas at four temperatures in the range 298-498K. Single decay from 10 photolysis laser shots were averaged and found to give reasonable first-order kinetics fits. Second order kinetics were obtained by pressure dependence of the pseudo first order decay constants and substance D2 pressures within experimental error. The reaction was found to be weakly pressure dependent at all temperatures, consistent with a third-body mediated association process. In addition, SiH2+ H2 reaction is approximately ca. 60% faster than SiD2+D2 reaction. Theoretical extrapolations (using

  12. Thermogravimetric analysis and kinetic study of formation of lithium titanate by solid state route

    Energy Technology Data Exchange (ETDEWEB)

    Sonak, Sagar; Jain, Uttam [Fusion Reactor Materials Section, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Sahu, Ashok Kumar [Glass and advanced Materials Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Kumar, Sanjay; Krishnamurthy, Nagaiyar [Fusion Reactor Materials Section, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

    2015-02-15

    The kinetics of formation of lithium titanate from the solid state reaction of lithium carbonate and titanium oxide was studied using non-isothermal thermogravimetric technique. Thermogravimetric data for the reaction of lithium carbonate and titanium oxide was obtained at various heating rates. The methods such as Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose were used to estimate the kinetic parameters from the obtained thermogravimetric data. The average activation energy for the formation of lithium titanate by solid state route was found to be 243 kJ/mol K. The reaction mechanism was determined by the method given by Malek. It was found that the three dimensional diffusion model best describes the reaction kinetics. A kinetic equation describing the reaction is proposed and reaction mechanism is discussed.

  13. Thermogravimetric analysis and kinetic study of formation of lithium titanate by solid state route

    Science.gov (United States)

    Sonak, Sagar; Jain, Uttam; Sahu, Ashok Kumar; Kumar, Sanjay; Krishnamurthy, Nagaiyar

    2015-02-01

    The kinetics of formation of lithium titanate from the solid state reaction of lithium carbonate and titanium oxide was studied using non-isothermal thermogravimetric technique. Thermogravimetric data for the reaction of lithium carbonate and titanium oxide was obtained at various heating rates. The methods such as Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose were used to estimate the kinetic parameters from the obtained thermogravimetric data. The average activation energy for the formation of lithium titanate by solid state route was found to be 243 kJ/mol K. The reaction mechanism was determined by the method given by Malek. It was found that the three dimensional diffusion model best describes the reaction kinetics. A kinetic equation describing the reaction is proposed and reaction mechanism is discussed.

  14. SOLAR WATER DISINFECTION IN NORTHEAST BRAZIL: KINETICS OF THE PROCESS AND THE STUDY FOR THE DEVELOPMENT OF A PILOT PLANT

    Directory of Open Access Journals (Sweden)

    LORNA FALCÃO FÉLIX

    2009-09-01

    Full Text Available An experimental and numerical study of decontamination efficiency was carried through to evaluate the application of solar energy in water treatment in Northeast Brazil. The methodology used was the one proposed by Solar Water Disinfection (SODIS. Contaminated water samples were collected at the community of Robalo, Sergipe State, Brazil, which is characterized by poverty, social exclusion and a high incidence of waterborne diseases. The method used for pre- and post-disinfection microbiological analyses was the Colilert® QuantiTray (IDEXX one. The results show that the efficiency of the disinfection process reached 80 to 100%, however a post-treatment increase in colony counts was observed in some samples. The experimental results were treated numerically, to give disinfection kinetics, thus allowing theoretical and experimental data to be compared. This study further presents considerations for the development of an experimental pilot plant for water disinfection using SODIS.

  15. Theoretical investigation on the kinetics and mechanisms of hydroxyl radical-induced transformation of parabens and its consequences for toxicity: Influence of alkyl-chain length.

    Science.gov (United States)

    Gao, Yanpeng; Ji, Yuemeng; Li, Guiying; An, Taicheng

    2016-03-15

    As emerging organic contaminants (EOCs), the ubiquitous presence of preservative parabens in water causes a serious environmental concern. Hydroxyl radical ((•)OH) is a strong oxidant that can degrade EOCs through photochemistry in surface water environments as well as in advanced oxidation processes (AOPs). To better understand the degradation mechanisms, kinetics, and products toxicity of the preservative parabens in aquatic environments and AOPs, the (•)OH-initiated degradation reactions of the four parabens were investigated systematically using a computational approach. The four studied parabens with increase of alkyl-chain length were methylparaben (MPB), ethylparaben (EPB), propylparaben (PPB), and dibutylparaben (BPB). Results showed that the four parabens can be initially attacked by (•)OH through (•)OH-addition and H-abstraction routes. The (•)OH-addition route was more important for the degradation of shorter alkyl-chain parabens like MPB and EPB, while the H-abstraction route was predominant for the degradation of parabens with longer alkyl-chain for example PPB and BPB. In assessing the aquatic toxicity of parabens and their degradation products using the model calculations, the products of the (•)OH-addition route were found to be more toxic to green algae than original parabens. Although all degradation products were less toxic to daphnia and fish than corresponding parental parabens, they could be still harmful to these aquatic organisms. Furthermore, as alkyl-chain length increased, the ecotoxicity of parabens and their degradation products was found to be also increased. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Kinetic studies of clavulanic acid recovery by ion exchange chromatography.

    Science.gov (United States)

    Barboza, M; Almeida, R M; Hokka, C O

    2001-01-01

    Clavulanic acid (CA) is a beta-lactamase inhibitor produced by strains of Streptomyces clavuligerus. Nowadays, the combination of CA with amoxycillin is the most successful example of the use of a beta-lactam antibiotic sensitive to beta-lactamases together with an inhibitor of these enzymes. Clavulanic acid is purified from fermentation broth by a series of steps consisting mainly of two-phase separation processes such as liquid-liquid extraction, adsorption or ion-exchange chromatography, among others. Amberlite IRA 400, a strong anion-exchange resin, has a very high adsorption capacity for CA (Mayer et al. 1997). This resin can be pre-treated with NaCl (chloride cycle), to remove selectively only those anions, which are able to displace chloride from the resin or with NaOH (hydroxyl cycle), to remove all species of anions. In order to decide the best operating conditions for CA recovery by ion-exchange resins and then to construct a model of this separation process, batch experiments were conducted using Amberlite IRA 400 in the chloride cycle. These runs were carried out in a 200 ml stirred tank, at two different initial solution pH, 6.2 and 4.0; the temperature was maintained at 10 degrees C and 20 degrees C during adsorption and 30 degrees C during the desorption step. It was possible, on the basis of these batch results, to model the separation process, including the adsorption kinetics, equilibrium data and mass transfer limitations.

  17. Kinetic studies of amylase and biomass production by Calvatia gigantea

    Energy Technology Data Exchange (ETDEWEB)

    Kekos, D.; Macris, B.J.

    1987-01-01

    Production of alpha-amylase (alpha-4, glucan 4-glucanohydrolase, EC 3.2.1.1) by microorganisms has been practiced for many years in small and large scale operations and the literature on this enzyme is voluminous. Aspergillus niger and Aspergillus oryzae have been reported as the main fungal species used for commercial production of the enzyme. On the other hand, large volumes of low-cost agricultural products such as acorn (the perisperm-free dry seed contains approximately 60% starch) are wasted in many countries and provide a challenge to biotechnology to efficiently utilize these rich sources of starch for the production of high added value products like enzymes. C. gigantea is an edible puffball excreting high levels of alpha-amylase when cultivated on different sources of starch containing elevated quantities of toxic tannic compounds. This fungus has been employed for the production of microbial protein from wastes and acorns containing high levels of toxic tannic compounds. The same fungus was also reported to grow on both hydrolyzable and condensed tannins as sole carbon sources. The present work was undertaken to investigate certain kinetic characteristics of alpha-amylase and biomass production by C. gigantea grown on soluble and acorn starch in a lab fermenter. (Refs. 18).

  18. MicroScale Thermophoresis (MST) for studying actin polymerization kinetics.

    Science.gov (United States)

    Topf, Andrea; Franz, Peter; Tsiavaliaris, Georgios

    2017-10-01

    Here, we present a MicroScale Thermophoresis (MST)-based assay for in vitro assessment of actin polymerization. By monitoring the thermophoretic behavior of ATTO488-labeled actin in a temperature gradient over time, we could follow polymerization in real time and resolve its three characteristic phases: nucleation, elongation, and steady-state equilibration. Titration experiments allowed us to evaluate the effects of actin-binding proteins (ABPs) on polymerization, including DNase I-induced inhibition and mDia2FH1FH2 (mDia2)-assisted acceleration of nucleation. The corresponding rates of actin filament elongation were quantitatively determined, yielding values in good agreement with those obtained using the pyrene-actin polymerization assay. Finally, we measured the effect of myosin on actin polymerization, circumventing the problems of fluorescence quenching and signal disturbance that occur with other techniques. MST is a simple and valuable research tool for investigating actin kinetics covering a wide range of molecular interactions, with low protein consumption.

  19. A kinetic study on the development of porosity in porcelain stoneware tile sintering

    Directory of Open Access Journals (Sweden)

    Jazayeri, S. H.

    2007-02-01

    Full Text Available The aim of this work is to develop a mathematical model to study the mechanism of elimination of total porosity as a function of soaking time using the Navier-Stokes. Then, parameters of the model such as kinetic constants and apparent activation energy are calculated on the basis of experimental data for a standard porcelain stoneware tile composition. The theoretical data calculated from the model are in good agreement with the experimental data. Using the model developed, it is possible to estimate the best soaking time to obtain minimum total porosity at a given firing temperature . The effects of nepheline on sintering process of porcelain stoneware tile is investigated. It was found that when the nepheline syenite content of the starting mix was increased to 10%, the constant kp of the kinetic equation also increased. The results showed that addition of nepheline to composition of porcelain stoneware bodies was influenced remarkably suitable soaking time to obtain the minimum total porosity and increased shrinkage and bulk density while total and closed porosity fall down.

    El propósito de este trabajo es desarrollar un modelo matemático tipo Navier-Stokes para estudiar el mecanismo de eliminación de la porosidad en función del tiempo de maduración en cocción. Los parámetros del modelo tales como las constantes cinéticas y la energía de activación aparente se calcularon a partir de datos experimentales para una composición de gres porcelánico estándar. Los datos teóricos obtenidos a partir del modelo están en buena concordancia con los datos experimentales. Se investigaron los efectos de la nefelina en el gres porcelánico, encontrado que cuando se aumenta el contenido hasta un 10%, la constante de la ecuación cinética kp aumenta. Empleando el modelo desarrollado, es posible estimar el tiempo de maduración en cocción para obtener la porosidad mínima (se alcanza la eliminación de la porosidad debido a la presi

  20. Study of the semi-theoretical relation of the hydraulic jump evolving ...

    African Journals Online (AJOL)

    This study has for objective to study the theoretical relation of the hydraulic jump by sill, evolving in an U-shaped channel, with a rough bed. Functional relations, in non-dimensional form, relating the jump characteristics, seeming the effect of the bed's roughness, are obtained. A comparative study with the hydraulic jump in ...

  1. Validation of a Theoretical Model of Diagnostic Classroom Assessment: A Mixed Methods Study

    Science.gov (United States)

    Koh, Nancy

    2012-01-01

    The purpose of the study was to validate a theoretical model of diagnostic, formative classroom assessment called, "Proximal Assessment for Learner Diagnosis" (PALD). To achieve its purpose, the study employed a two-stage, mixed-methods design. The study utilized multiple data sources from 11 elementary level mathematics teachers who…

  2. Experimental and Chemical Kinetic Modeling Study of Dimethylcyclohexane Oxidation and Pyrolysis

    KAUST Repository

    Eldeeb, Mazen A.

    2016-08-30

    A combined experimental and chemical kinetic modeling study of the high-temperature ignition and pyrolysis of 1,3-dimethylcyclohexane (13DMCH) is presented. Ignition delay times are measured behind reflected shock waves over a temperature range of 1049–1544 K and pressures of 3.0–12 atm. Pyrolysis is investigated at average pressures of 4.0 atm at temperatures of 1238, 1302, and 1406 K. By means of mid-infrared direct laser absorption at 3.39 μm, fuel concentration time histories are measured under ignition and pyrolytic conditions. A detailed chemical kinetic model for 13DMCH combustion is developed. Ignition measurements show that the ignition delay times of 13DMCH are longer than those of its isomer, ethylcyclohexane. The proposed chemical kinetic model predicts reasonably well the effects of equivalence ratio and pressure, with overall good agreement between predicted and measured ignition delay times, except at low dilution levels and high pressures. Simulated fuel concentration profiles agree reasonably well with the measured profiles, and both highlight the influence of pyrolysis on the overall ignition kinetics at high temperatures. Sensitivity and reaction pathway analyses provide further insight into the kinetic processes controlling ignition and pyrolysis. The work contributes toward improved understanding and modeling of the oxidation and pyrolysis kinetics of cycloalkanes.

  3. Kinetics of corneal epithelium turnover in vivo. Studies of lovastatin

    Energy Technology Data Exchange (ETDEWEB)

    Cenedella, R.J.; Fleschner, C.R. (Kirksville College of Osteopathic Medicine, MO (USA))

    1990-10-01

    The authors developed a direct chemical approach for estimating the rate of turnover of the corneal epithelium in vivo. The method was used to examine the effects of lovastatin, a potent inhibitor of cholesterol biosynthesis, on proliferation and turnover of the epithelium. Corneal DNA was labeled by pulse injection (IP) of the rat with 3H-thymidine, and 3H-labeled DNA was recovered from peripheral and central corneas over the next 15 days. Only the epithelium became labeled, and the loss of label by cell desquamation began 3 days after injection. The loss of 3H-DNA from the cornea (peripheral plus central region) followed first-order kinetics. The half-life of the disappearance was about 3 days. The peripheral cornea became more highly labeled than the central cornea and began to lose 3H-DNA before the central cornea. These observations support the possibility of a higher mitotic rate in the peripheral region and the centripetal movement of a population of peripheral epithelial cells in the normal cornea. The half-lives of the disappearance of 3H-DNA from peripheral and central corneas measured between days 5 and 15 postinjection were identical, both at 3 days. Complete turnover of the corneal epithelium would, therefore, require about 2 weeks (4-5 half-lives). Treatment of the rat with lovastatin had no obvious effects upon the proliferation or turnover of the corneal epithelium. Although lovastatin inhibited corneal 3-hydroxy-3-methylglutaryl coenzyme A reductase, the key regulatory enzyme of cholesterol synthesis, the cornea compensated by induction of this enzyme so that there was no net inhibition of cholesterol synthesis in the cornea.

  4. Effect of patulin on the kinetic properties of the enzyme aldolase studied in rat liver.

    Science.gov (United States)

    Sakthisekaran, D; Shanmugasundaram, E R

    1990-01-01

    The toxic nature of the secondary metabolite has been studied in rats. Changes in the concentration of a few key enzymes in carbohydrate metabolism have also been studied. In this, liver aldolase concentration was found to be significantly lowered. Since aldolase is one of the important bifunctional enzymes of glycolysis, it has been isolated and purified and studied on its kinetic properties were made. The kinetic studies did not show any significant variations in the properties of liver aldolase of normal and patulin treated animals. These results suggest that most probably, patulin toxicosis inhibits the biosynthesis of liver aldolase.

  5. Medication competency of nurses according to theoretical and drug calculation online exams: A descriptive correlational study.

    Science.gov (United States)

    Sneck, Sami; Saarnio, Reetta; Isola, Arja; Boigu, Risto

    2016-01-01

    Medication administration is an important task of registered nurses. According to previous studies, nurses lack theoretical knowledge and drug calculation skills and knowledge-based mistakes do occur in clinical practice. Finnish health care organizations started to develop a systematic verification processes for medication competence at the end of the last decade. No studies have yet been made of nurses' theoretical knowledge and drug calculation skills according to these online exams. The aim of this study was to describe the medication competence of Finnish nurses according to theoretical and drug calculation exams. A descriptive correlation design was adopted. Participants and settings All nurses who participated in the online exam in three Finnish hospitals between 1.1.2009 and 31.05.2014 were selected to the study (n=2479). Quantitative methods like Pearson's chi-squared tests, analysis of variance (ANOVA) with post hoc Tukey tests and Pearson's correlation coefficient were used to test the existence of relationships between dependent and independent variables. The majority of nurses mastered the theoretical knowledge needed in medication administration, but 5% of the nurses struggled with passing the drug calculation exam. Theoretical knowledge and drug calculation skills were better in acute care units than in the other units and younger nurses achieved better results in both exams than their older colleagues. The differences found in this study were statistically significant, but not high. Nevertheless, even the tiniest deficiency in theoretical knowledge and drug calculation skills should be focused on. It is important to identify the nurses who struggle in the exams and to plan targeted educational interventions for supporting them. The next step is to study if verification of medication competence has an effect on patient safety. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Theoretical Explanation for Success of Deep-Level-Learning Study Tours

    Science.gov (United States)

    Bergsteiner, Harald; Avery, Gayle C.

    2008-01-01

    Study tours can help internationalize curricula and prepare students for global workplaces. We examine benefits of tours providing deep-level learning experiences rather than industrial tourism using five main theoretical frameworks to highlight the diverse learning benefits associated with intensive study tours in particular. Relevant theoretical…

  7. Curriculum, Curriculum Development, Curriculum Studies? Problematising Theoretical Ambiguities in Doctoral Theses in the Education Field

    Science.gov (United States)

    du Preez, Petro; Simmonds, Shan

    2014-01-01

    Theoretical ambiguities in curriculum studies result in conceptual mayhem. Accordingly, they hinder the development of the complicated conversation on curriculum as a verb. This article aims to contribute to reconceptualizing curriculum studies as a dynamic social practice that aspires to thinking and acting with intelligences and sensitivity so…

  8. The generation of charge carriers in semi conductors – A theoretical study

    CSIR Research Space (South Africa)

    Kiarii, EM

    2017-04-01

    Full Text Available , vol. 678: 167-176 The generation of charge carriers in semi conductors – A theoretical study Kiarii EM Govender, Krishna K Ndungu PG Govender PG ABSTRACT: A systematic study of electronic and optical properties of titanium dioxide under...

  9. Theoretical study of loss compensation in long-range dielectric loaded surface plasmon polariton waveguides

    NARCIS (Netherlands)

    García Blanco, Sonia Maria; Pollnau, Markus; Bozhevolnyi, Sergey I.

    In this paper, a theoretical study of loss compensation in long-range dielectric loaded surface plasmon waveguides (LR-DLSPPs) is presented. Although extendable to other gain materials, rare-earth doped double tungstates are used as gain material in this work. Two different structures are studied

  10. Theoretical modelling of semiconductor surfaces microscopic studies of electrons and photons

    CERN Document Server

    Srivastava, G P

    1999-01-01

    The state-of-the-art theoretical studies of ground state properties, electronic states and atomic vibrations for bulk semiconductors and their surfaces by the application of the pseudopotential method are discussed. Studies of bulk and surface phonon modes have been extended by the application of the phenomenological bond charge model. The coverage of the material, especially of the rapidly growing and technologically important topics of surface reconstruction and chemisorption, is up-to-date and beyond what is currently available in book form. Although theoretical in nature, the book provides

  11. Theoretical studies on the new system of neutron flux measurement in the nuclear reactor

    CERN Document Server

    Wan Jun Sheng; Zhao Zhu Min; Chen Li Xin; Jing Chun Yuan; Wang Dao Hua

    2002-01-01

    The neutron measurement system based on the Nuclear Pumped Laser (NPL) techniques was explored in this work utilizing the relationship between the neutron flux and the NPL laser power. Following the studies on the mechanism of the NPL, the laser intrinsic efficiency and the energy deposition efficiency in the laser cell of this system were theoretically studied in detail. A laser pumping mechanism was proposed. The variation of sensitivity with working time and the response function on neutron flux was discussed. The feasibility of this neutron measurement system was demonstrated theoretically

  12. Theoretical/Computational Studies of High-Temperature Superconductivity from Quantum Magnetism

    Science.gov (United States)

    2016-06-09

    AFRL-AFOSR-VA-TR-2016-0204 Theoretical/Computational Studies of High-Temperature Superconductivity from Quantum Magnetism Jose Rodriguez CALIFORNIA...TITLE AND SUBTITLE Theoretical/Computational Studies of High-Temperature Superconductivity from Quantum Magnetism 5a.  CONTRACT NUMBER 5b.  GRANT...SUBJECT TERMS quantum magnetism , HTS, superconductivity 16.  SECURITY CLASSIFICATION OF: 17.  LIMITATION OF       ABSTRACT UU 18.  NUMBER        OF

  13. Mechanism and Kinetics Study for Photocatalytic Oxidation Degradation: A Case Study for Phenoxyacetic Acid Organic Pollutant

    Directory of Open Access Journals (Sweden)

    Kian Mun Lee

    2015-01-01

    Full Text Available Photocatalysis is a rapidly expanding technology for wastewater treatment, including a wide range of organic pollutants. Thus, understanding the kinetics and mechanism of the photocatalytic oxidation (PCO for degradation of phenoxyacetic acid (PAA is an indispensable component of risk assessment. In this study, we demonstrated that the central composite design (CCD coupled with response surface methodology (RSM was successfully employed to probe the kinetics and mechanism of PCO degradation for PAA using an efficient zinc oxide (ZnO photocatalyst. In our current case study, four independent factors such as ZnO dosage, initial concentration of PAA, solution pH, and reaction time on the PCO degradation for PAA were examined in detail. Based on our results obtained from RSM analyses, an efficient pathway leading to the high degradation rate (>90% was applying 0.4 g/L of ZnO dosage with 16 mg/L of concentration of PAA at pH 6.73 for 40 minutes. The experimental results were fitted well with the derived response model with R2 = 0.9922. This study offers a cost-effective way for probing our global environmental water pollution issue.

  14. EFFICIENCY OF ISO 9001 IN PORTUGAL: A QUALITATIVE STUDY FROM A HOLISTIC THEORETICAL PERSPECTIVE

    Directory of Open Access Journals (Sweden)

    Alcina Dias

    2013-03-01

    Full Text Available The purpose of this paper is to analy se the efficiency of ISO 9001 from a holistic theoretical approach where the Contingency theory, the Institutional theory and the Resources-Based View are integrated. The study was carried out in companies of different sectors of activity in Portugal, based on a qualitative methodology (interviews. The fact of the interviews having been undertaken under an ISO 9001 structure made it easier for companies to grasp the issues under investigation. An ISO 9001 characterisation was carried out on a theoretical framework approach and findings point out efficiency gains and revealed that the absence of ISO 9001 would work as a competitive disadvantage. The contribution of this research aims to reinforce the state of art as concerns the theoretical scope of analysis of these issues enriched by the case study achievement.

  15. Theoretical and experimental study of passive spatiotemporal shaping of picosecond laser pulses

    Directory of Open Access Journals (Sweden)

    A. K. Sharma

    2009-03-01

    Full Text Available We report the results of theoretical and experimental studies on passive spatiotemporal shaping of cw mode-locked picosecond laser pulses for driving the photocathode of a high-brightness, high-current energy recovery linear accelerator. The temporal pulse shape is modified using birefringent crystals, while a refractive optical system is used to generate a flattop spatial beam profile. An optical transport system is designed and implemented to deliver the flattop pulse onto a photocathode sited 9 m away from the shapers. The alignment tolerances on the beam shaper and the temporal pulse stacker have been studied both theoretically and experimentally. The experimental results agree well with theoretical simulations.

  16. Study of trapping effect on ion-acoustic solitary waves based on a fully kinetic simulation approach

    Science.gov (United States)

    Hosseini Jenab, S. M.; Spanier, F.

    2016-10-01

    A fully kinetic simulation approach, treating each plasma component based on the Vlasov equation, is adopted to study the disintegration of an initial density perturbation into a number of ion-acoustic solitary waves (IASWs) in the presence of the trapping effect of electrons. The nonlinear fluid theory developed by Schamel [Plasma Phys. 13, 491 (1971); J. Plasma Phys. 7, 1 (1972); Plasma Phys. 14, 905 (1972); J. Plasma Phys. 9, 377 (1973); Phys. Scr. 20, 306 (1979)] has identified three separate regimes of ion-acoustic solitary waves based on the trapping parameter. Here, the disintegration process and the resulting self-consistent IASWs are studied in a wide range of trapping parameters covering all the three regimes continuously. The dependency of features such as the time of disintegration, the number, speed, and size of IASWs on the trapping parameter are focused upon. It is shown that an increase in this parameter slows down the propagation of IASWs while decreases their sizes in the phase space. These features of IASWs tend to saturate for large values of trapping parameters. The disintegration time shows a more complicated behavior than what was predicted by the theoretical approach. Also for the case of trapping parameters bigger than one, propagation of IASWs is observed in contrast with the theoretical predictions. The kinetic simulation results unveil a smooth and well-defined dependency of solitary waves' features on the trapping parameter, showing the possibility of bridging all the three regimes. Finally, it is shown that for β around zero, the electron phase space structure of the accompanying vortex stays symmetric. The effect of the electron-to-ion temperature ratio on the disintegration and the propagation of IASWs are considered as a benchmarking test of the simulation code (in the nonlinear regime).

  17. Hydration energies of zinc(II): threshold collision-induced dissociation experiments and theoretical studies.

    Science.gov (United States)

    Cooper, Theresa E; Carl, D R; Armentrout, P B

    2009-12-10

    The first experimentally determined sequential bond dissociation energies of Zn(2+)(H(2)O)(n) complexes, where n = 6-10, are measured using threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer coupled with an electrospray ionization source. Kinetic energy dependent cross sections are obtained and analyzed to yield 0 K threshold measurements for the loss of one and two water ligands after accounting for multiple collisions, kinetic shifts, and energy distributions. The threshold measurements are then converted from 0 to 298 K values to give the hydration energies for sequentially losing one water from each parent complex. Theoretical geometry optimizations and single-point energy calculations are performed using several levels of theory for comparison to experiment. Although different levels of theory disagree on the ground-state conformation of most complexes examined here leading to potential ambiguities in the final thermochemical values, calculations at the MP2(full) level provide the best agreement with experiment. On this basis, the present experiments are most consistent with the inner solvent shell of Zn(2+) being five waters, except for Zn(2+)(H(2)O)(6) where all waters bind directly to the metal ion. The charge separation process, Zn(2+)(H(2)O)(n) --> ZnOH(+)(H(2)O)(m) + H(+)(H(2)O)(n-m-1), which is in competition with the loss of water from the parent complex, is also observed for n = 6-8. These processes are analyzed in detail in the following paper.

  18. Kinetics adsorption study of the ethidium bromide by graphene oxide as adsorbent from aqueous matrices

    Science.gov (United States)

    Rajabi, M.; Moradi, O.; Zare, K.

    2017-01-01

    In this study of ethidium bromide, adsorption from aqueous matrices by graphene oxide as adsorbent was investigated. Influencing parameters in the adsorption study included contact time, temperature, and pH. The optimum time was selected 17 min, and the best value of pH was determined at 8. All adsorption experiments were performed at 298 K temperature. The maximum wavelength of ethidium bromide was 475 nm. The Elovich, four types of the pseudo-second-order, the pseudo-first-order, and intra-particle diffusion kinetic adsorption models were used for kinetic study, and the results show that adsorption of ethidium bromide on graphene oxide surface best complied with type (I) of the pseudo-second-order kinetic model.

  19. Experimental and theoretical study using DFT method for the competitive adsorption of two cationic dyes from wastewaters

    Energy Technology Data Exchange (ETDEWEB)

    Regti, Abdelmajid [Equipe de Chimie Analytique & Environnement, Faculté Poly-disciplinaire, Université Cadi Ayyad, BP 4162, 46000 Safi (Morocco); Instituto de Ciencia Molecular/ICMol, Universidad de Valencia, C/. Catedrático José Beltrán, 2, 46980 Paterna, Valencia (Spain); Ayouchia, Hicham Ben El [Equipe de Chimie Moléculaire, Matériaux et Modélisation, Faculté Poly-disciplinaire, Université Cadi Ayyad, BP 4162, 46000 Safi (Morocco); Instituto de Ciencia Molecular/ICMol, Universidad de Valencia, C/. Catedrático José Beltrán, 2, 46980 Paterna, Valencia (Spain); Laamari, My Rachid [Equipe de Chimie Analytique & Environnement, Faculté Poly-disciplinaire, Université Cadi Ayyad, BP 4162, 46000 Safi (Morocco); Instituto de Ciencia Molecular/ICMol, Universidad de Valencia, C/. Catedrático José Beltrán, 2, 46980 Paterna, Valencia (Spain); Stiriba, Salah Eddine; Anane, Hafid [Equipe de Chimie Moléculaire, Matériaux et Modélisation, Faculté Poly-disciplinaire, Université Cadi Ayyad, BP 4162, 46000 Safi (Morocco); Instituto de Ciencia Molecular/ICMol, Universidad de Valencia, C/. Catedrático José Beltrán, 2, 46980 Paterna, Valencia (Spain); and others

    2016-12-30

    Highlights: • The adsorption efficiency increases with increasing pH, thus more negatively charged surface was available. • Monolayer adsorption and homogeneous adsorbent surface. • The experimental and theoretical data are in good agreement showing that MB has ability to accept electrons allowing more adsorption than BY28 dye. - Abstract: The adsorption of cationic dyes, Basic Yellow (BY28) and Methylene Blue (MB) on a new activated carbon from medlar species were studied in both single and binary system. Some experimental parameters, namely, pH, amount of adsorbent and contact time are studied. Quantum chemical results indicate that the adsorption efficiency was directly related to the dye electrophilicity power. Some theorical parameters were calculated and proved that MB is more electrophilic than BY28, than greatest interaction with surface sites. Kinetic study showed that the adsorption follows the pseudo-second-order model and Freundlich was the best model to describe the phenomenon in the single and binary system. According to the local reactivity results using Parr functions, the sulphur and nitrogen atoms will be the main adsorption sites.

  20. Adsorption kinetic and desorption studies of Cd2+ on Multi-Carboxylic-Functionalized Silica Gel

    Science.gov (United States)

    Li, Min; Wei, Jian; Meng, Xiaojing; Wu, Zhuqiang; Liang, Xiuke

    2018-01-01

    In the present study, the adsorption behavior of cadmium (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of contact time on adsorption capacity of cadmium (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. And the adsorption mechanism of the process was studied by intra-particle and film diffusion, it was found out that the adsorption rate was governed primarily by film diffusion to the adsorption onto the SG-MCF. In addition, column experiments were conducted to assess the effects initial inlet concentration and the flow rate on breakthrough time and adsorption capacity ascertaining the practical applicability of the adsorbent. The results suggest that the total amount of adsorbed cadmium (II) ion increased with declined flow rate and increased the inlet concentration. The adsorption-desorption experiment confirmed that adsorption capacity of cadmium (II) ion didn’t present an obvious decrease after five cycles.

  1. Adsorption kinetic and desorption studies of Cu2+ on Multi-Carboxylic-Functionalized Silica Gel

    Science.gov (United States)

    Li, Min; Meng, Xiaojing; Liu, Yushuang; Hu, Xinju; Liang, Xiuke

    2018-01-01

    In the present study, the adsorption behavior of copper (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of contact time on adsorption capacity of copper (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. And the adsorption mechanism of the process was studied by intra-particle and film diffusion, it was found out that the adsorption rate was governed primarily by film diffusion to the adsorption onto the SG-MCF. In addition, column experiments were conducted to assess the effects initial inlet concentration and the flow rate on breakthrough time and adsorption capacity ascertaining the practical applicability of the adsorbent. The results suggest that the total amount of adsorbed copper (II) ion increased with declined flow rate and increased the inlet concentration. The adsorption-desorption experiment confirmed that adsorption capacity of copper (II) ion didn’t present an obvious decrease after five cycles.

  2. Immobilized Kluyveromyces marxianus cells in carboxymethyl cellulose for production of ethanol from cheese whey: experimental and kinetic studies.

    Science.gov (United States)

    Roohina, Fatemeh; Mohammadi, Maedeh; Najafpour, Ghasem D

    2016-09-01

    Cheese whey fermentation to ethanol using immobilized Kluyveromyces marxianus cells was investigated in batch and continuous operation. In batch fermentation, the yeast cells were immobilized in carboxymethyl cellulose (CMC) polymer and also synthesized graft copolymer of CMC with N-vinyl-2-pyrrolidone, denoted as CMC-g-PVP, and the efficiency of the two developed cell entrapped beads for lactose fermentation to ethanol was examined. The yeast cells immobilized in CMC-g-PVP performed slightly better than CMC with ethanol production yields of 0.52 and 0.49 g ethanol/g lactose, respectively. The effect of supplementation of cheese whey with lactose (42, 70, 100 and 150 g/l) on fermentative performance of K. marxianus immobilized in CMC beads was considered and the results were used for kinetic studies. The first order reaction model was suitable to describe the kinetics of substrate utilization and modified Gompertz model was quite successful to predict the ethanol production. For continuous ethanol fermentation, a packed-bed immobilized cell reactor (ICR) was operated at several hydraulic retention times; HRTs of 11, 15 and 30 h. At the HRT of 30 h, the ethanol production yield using CMC beads was 0.49 g/g which implies that 91.07 % of the theoretical yield was achieved.

  3. [Efficacy analysis and theoretical study on Chinese herbal properties of Açaí (Euterpe oleracea)].

    Science.gov (United States)

    Zhang, Jian-jun; Chen, Shao-hong; Zhu, Ying-li; Wang, Chun; Wang, Jing-xia; Wang, Lin-yuan; Gao, Xue-min

    2015-06-01

    Açaí (Euterpe oleracea) emerged as a source of herb has a long history in South America, which was approved by the Ministry of Health used in China and it has been introduced planting in Guangdong and Taiwan. This article summarized applied history of Açaí and its present status in China. Did theoretical study on the Chinese herbal properties of Açaí based on the Chinese traditional philosophical culture to analysis the function and symptom preliminary, combining with used for medical recordation, chemical component, biological activity. It is aiming at establishing the theoretical foundation for the application under the guidance of TCM theory.

  4. Theoretical study of band alignment in nano-porous ZnO interacting with substituted Phthalocyanines

    OpenAIRE

    Wahnón Benarroch, Perla; Palacios Clemente, Pablo

    2011-01-01

    The aim of this work is the theoretical study of the band alignment between the two components of a hybrid organic-inorganic solar-cell. The working organic molecules are metal tetra-sulphonated phthalocyanines (M-Pc) and the inorganic material is nano-porous ZnO growth in the 001 direction. The theoretical calculations are being made using the density functional theory (DFT) using a GGA functional with the SIESTA code, which projects electron wave functions and density onto a real space grid...

  5. Theoretical and experimental study of dissolution of inhomogeneities formed during spinodal decomposition in polymer mixtures

    Science.gov (United States)

    Akcasu, A. Ziya; Bahar, I.; Erman, B.; Feng, Y.; Han, C. C.

    1992-10-01

    Dissolution (mixing or melting) of inhomogeneities formed during spinodal decomposition in binary polymer mixtures is studied both experimentally and theoretically. The details of the dissolution experiment with time-resolved light scattering on polystyrene/poly(vinylmethylether) are presented. The theoretical approach differs from that of Langer, Bar-on, and Miller in the way the fluctuations are treated in the nonlinear theory, and in the details of the calculations arising from the chain connectivity (polymer effect). The effect of mode coupling arising from nonlinearity on the relaxation rate is discussed. It is found both experimentally and theoretically that the wave number corresponding to peak intensity decreases in time asymptotically following a t-0.5 power law.

  6. Red/blue shifting hydrogen bonds in acetonitrile-dimethyl sulphoxide solutions: FTIR and theoretical studies

    Science.gov (United States)

    Kannan, P. P.; Karthick, N. K.; Mahendraprabu, A.; Shanmugam, R.; Elangovan, A.; Arivazhagan, G.

    2017-07-01

    FTIR spectra of neat acetonitrile (AN), dimethyl sulphoxide (DMSO) and their binary solutions at various mole fractions have been recorded at room temperature. Theoretical calculations have also been carried out on acetonitrile (monomer, dimer), dimethyl sulphoxide (monomer, dimer) and AN - DMSO complex molecules. 1:2 (AN:DMSO) and 2:1 complexation through the red shifting (AN) C - H ⋯ O = S(DMSO) and blue shifting (DMSO) C - H ⋯ N ≡ C(AN) hydrogen bonds has been identified. The experimental and theoretical studies favour the presence of both the monomer and dimer in liquid AN, but only closed dimers in DMSO. The dipole-dipole interactions existed in AN and DMSO dimers disappear in the complex molecules. Partial π bond between S and O atoms, and three lone pair of electrons on oxygen atom of DMSO have been noticed theoretically.

  7. Kinetic step-growth polymerization: A dissipative particle dynamics simulation study.

    Science.gov (United States)

    Xu, Dan; Ni, Chun-Yan; Zhu, You-Liang; Lu, Zhong-Yuan; Xue, Yao-Hong; Liu, Hong

    2018-01-14

    Kinetic step-growth polymerization is studied by dissipative particle dynamics coupled with our previously developed reaction algorithm on a coarse-grained level. The simulation result proves that this step-growth polymerization obeys the second-order reaction kinetics. We apply this algorithm to study the step-growth polymerization using the subunits with different flexibilities or within confinement. Good agreement of the number fraction distributions with the Flory distribution is obtained, implying that this algorithm is reasonable to describe such a kind of step-growth polymerization. This algorithm can further supply a convenient platform for simulating typical step-growth polymerization in reactive polymer systems.

  8. Biosorption of lead contaminated wastewater using cattails (Typha angustifolia) leaves: kinetic studies

    OpenAIRE

    YEN LING SHARAIN-LIEW; Joseph, Collin G.; SIEW-ENG HOW

    2011-01-01

    In this work, dried leaves of Typha angustifolia (TA), also known as the common cattail, were used as an adsorbent in kinetic studies of Pb(II) adsorption from synthetic aqueous solutions. Batch adsorption studies with dried TA leaves were conducted and they were able to adsorb Pb(II) from 100 mL of a 25 mg L-1 Pb(II) solution effectively with the optimized dosage of 0.6 g. Adsorption equilibrium was achieved within 8 h with an effective removal of 86.04 %. Adsorption kinetics was further eva...

  9. Copper adsorption on magnetite-loaded chitosan microspheres: A kinetic and equilibrium study

    Energy Technology Data Exchange (ETDEWEB)

    Podzus, P.E., E-mail: ppodzus@gmail.com [Grupo de Aplicaciones de Materiales Biocompatibles, Departamento de Quimica, Facultad de Ingenieria, Universidad de Buenos Aires, Paseo Colon 850, C1063ACV Buenos Aires (Argentina); Debandi, M.V. [Grupo de Aplicaciones de Materiales Biocompatibles, Departamento de Quimica, Facultad de Ingenieria, Universidad de Buenos Aires, Paseo Colon 850, C1063ACV Buenos Aires (Argentina); Daraio, M.E., E-mail: medit@fi.uba.ar [Grupo de Aplicaciones de Materiales Biocompatibles, Departamento de Quimica, Facultad de Ingenieria, Universidad de Buenos Aires, Paseo Colon 850, C1063ACV Buenos Aires (Argentina)

    2012-08-15

    A composite of Fe{sub 3}O{sub 4} nanoparticles and the biopolymer chitosan, chemically crosslinked, was prepared as microspheres and used to adsorb copper ions, which were chosen as a model of contaminant metal in water. The adsorption of copper on the magnetic microspheres was studied in a batch process, with different aqueous solutions of Cu (II) at concentrations ranging from 40 to 1100 ppm. Kinetic and equilibrium aspects of the adsorption process were studied. The time-dependent Cu (II) adsorption data were well described by a pseudo-second-order kinetic model. It was found that the equilibrium data follow the Langmuir isotherm, with a maximum adsorption capacity of around 500 mg Cu/g chitosan. The used microspheres were removed and after desorption the material was able to be reused as an adsorbent. The prepared microspheres proved efficient in the removal of copper ions through an adsorption process whose kinetic and equilibrium characteristics were analyzed.

  10. Inactivation disinfection property of Moringa Oleifera seed extract: optimization and kinetic studies

    Science.gov (United States)

    Idris, M. A.; Jami, M. S.; Hammed, A. M.

    2017-05-01

    This paper presents the statistical optimization study of disinfection inactivation parameters of defatted Moringa oleifera seed extract on Pseudomonas aeruginosa bacterial cells. Three level factorial design was used to estimate the optimum range and the kinetics of the inactivation process was also carried. The inactivation process involved comparing different disinfection models of Chicks-Watson, Collins-Selleck and Homs models. The results from analysis of variance (ANOVA) of the statistical optimization process revealed that only contact time was significant. The optimum disinfection range of the seed extract was 125 mg/L, 30 minutes and 120rpm agitation. At the optimum dose, the inactivation kinetics followed the Collin-Selleck model with coefficient of determination (R2) of 0.6320. This study is the first of its kind in determining the inactivation kinetics of pseudomonas aeruginosa using the defatted seed extract.

  11. A study of the non-isothermal crystallization kinetic of Zn10Se90 glass

    Science.gov (United States)

    Abdel-Rahim, M. A.; Hafiz, M. M.; Abdel-Latief, A. Y.; Abd-Elnaiem, Alaa M.; Alwany, A. Elwhab. B.

    2015-06-01

    The glass transition and the crystallization kinetics of Zn10Se90 glass by differential thermal analysis (DTA) technique under non-isothermal conduction were studied. The effective activation energies of the glass transition and the crystallization have been evaluated on the basses of the Kissinger and Matusita et al. approximations. Kinetic parameters of the crystallization process are significantly influenced by the heating rate. We have compared the experimental DTA with the calculated data curves for Zn10Se90 system using the Johanson-Mehl-Avrami (JMA) and Sestak-Berggren SB( M, N) models. Simulation results indicated that the SB( M, N) model is more suitable for describing the crystallization kinetics for the studied composition. Furthermore, the crystalline phases of annealed Zn10Se90 were characterized by X-ray diffraction. The surface morphology of the annealed samples was examined using scanning electron microscopy.

  12. Growth of polyphenyls via ion-molecule reactions: An experimental and theoretical mechanistic study

    Energy Technology Data Exchange (ETDEWEB)

    Aysina, Julia; Tosi, Paolo; Ascenzi, Daniela [Dipartimento di Fisica, Universita di Trento, Via Sommarive 14, I-38123 Povo, Trento (Italy); Maranzana, Andrea; Tonachini, Glauco [Dipartimento di Chimica, Universita di Torino, Corso Massimo D' Azeglio 48, I-10125 Torino (Italy)

    2013-05-28

    The reactivity of biphenylium cations C{sub 12}H{sub 9}{sup +} with benzene C{sub 6}H{sub 6} is investigated in a joint experimental and theoretical approach. Experiments are performed by using a triple quadruple mass spectrometer equipped with an atmospheric pressure chemical ion source to generate C{sub 12}H{sub 9}{sup +} via dissociative ionization of various isomers of the neutral precursor hydroxybiphenyl (C{sub 12}H{sub 10}O). C-C coupling reactions leading to hydrocarbon growth are observed. The most abundant ionic products are C{sub 18}H{sub 15}{sup +}, C{sub 18}H{sub 13}{sup +}, C{sub 17}H{sub 12}{sup +}, and C{sub 8}H{sub 7}{sup +}. The dependence of product ion yields on the kinetic energy of reagent ions, as well as further experiments performed using partial isotopic labelling of reagents, support the idea that the reaction proceeds via a long lived association product, presumably the covalently bound protonated terphenyl C{sub 18}H{sub 15}{sup +}. Its formation is found to be exothermic and barrierless and, therefore, might occur under the low pressure and temperature conditions typical of planetary atmospheres and the interstellar medium. Theoretical calculations have focussed on the channel leading to C{sub 8}H{sub 7}{sup +} plus C{sub 10}H{sub 8}, identifying, as the most probable fragments, the phenylethen-1-ylium cation and naphthalene, thus suggesting that the pathway leading to them might be of particular interest for the synthesis of polycyclic aromatic hydrocarbons. Both experiments and theory agree in finding this channel exoergic but hampered by small barriers of 2.7 and 3.7 kcal mol{sup -1} on the singlet potential energy surface.

  13. Theoretical and experimental study of the transport of granular materials by inclined vibratory conveyors

    NARCIS (Netherlands)

    Sloot, E.M.; Sloot, E.M.; Kruyt, Nicolaas P.

    1996-01-01

    A theoretical and experimental study was made of the conveying speed with which granular materials are transported by vibratory conveyors. The basic assumption made is that the layer of granular material can be considered as a point mass. The theory incorporates rest, slide, and flight phases of the

  14. Theoretical study, and infrared and Raman spectra of copper(II) chelated complex with dibenzoylmethane

    DEFF Research Database (Denmark)

    Nekoei, A.-R.; Vakili, M.; Hakimi-Tabar, M.

    2014-01-01

    There are some discrepancies in both the vibrational assignments and in the metal-ligand (M-L) bond strengths predicted in the previous studies on the copper (II) chelated complex of dibenzoylmethane, Cu(dbm)2. Also, there is a lack of theoretical structure, Raman spectrum and full vibrational as...

  15. Using Mathematics, Mathematical Applications, Mathematical Modelling, and Mathematical Literacy: A Theoretical Study

    Science.gov (United States)

    Mumcu, Hayal Yavuz

    2016-01-01

    The purpose of this theoretical study is to explore the relationships between the concepts of using mathematics in the daily life, mathematical applications, mathematical modelling, and mathematical literacy. As these concepts are generally taken as independent concepts in the related literature, they are confused with each other and it becomes…

  16. Theoretical Study of Dipolar Relaxation of Coupled Nuclear Spins at Variable Magnetic Field

    NARCIS (Netherlands)

    Pravdivtsev, A.N.; Ivanov, K.L.; Kaptein, R.|info:eu-repo/dai/nl/074334603; Yurkovskaya, A.V.

    2013-01-01

    A theoretical study was made of magnetic field-dependent dipolar relaxation in two- and three-spin systems. The results for the nuclear magnetic relaxation dispersion (NMRD) curves were compared with those for the simpler model of fluctuating local fields. For both models it was found that at low

  17. Theoretical study of the ground state of (EDO-TTF)(2)PF6

    NARCIS (Netherlands)

    Linker, Gerrit-Jan; van Duijnen, Piet Th.; van Loosdrecht, Paul H.M.; Broer, Ria

    2015-01-01

    In this paper we present a theoretical study of the nature of the ground state of the (EDO-TTF)(2)PF6 charge transfer salt by using ab initio quantum chemical theory for clusters in vacuum, for embedded clusters and for the periodic system. Exemplary for other organic charge transfer systems, we

  18. Theoretical study of two-element array of equilateral triangular patch ...

    Indian Academy of Sciences (India)

    The radiation characteristics of a two-element array of equilateral triangular patch microstrip antenna on a ferrite substrate are studied theoretically by considering the presence of bias magnetic field in the direction of propagation of electromagnetic waves. It is found that the natural modes of propagation in the direction of ...

  19. A theoretical framework to study variations in workplace violence experienced by emergency responders

    NARCIS (Netherlands)

    L. van Reemst (Lisa)

    2016-01-01

    markdownabstractEmergency responders are often sent to the front line and are often confronted with aggression and violence in interaction with citizens. According to previous studies, some professionals experience more workplace violence than others. In this article, the theoretical framework to

  20. A Theoretical Framework to Study Variations in Workplace Violence Experienced by Emergency Responders

    NARCIS (Netherlands)

    L. van Reemst (Lisa)

    2016-01-01

    textabstractEmergency responders are often sent to the front line and are often confronted with aggression and violence in inter- action with citizens. According to previous studies, some professionals experience more workplace violence than others. In this article, the theoretical framework to

  1. [Habermas and Paulo Freire: theoretical referrals for the study on communication in nursing].

    Science.gov (United States)

    Larocca, Liliana Muller; Mazza, Verônica de Azevedo

    2003-08-01

    The present work has the objective of introducing the ideas of Jürgen Habermas and Paulo Freire about the dialogue as a fundamental human phenomenon, data on their trajectories of life, ideological approaches when locating the human being through history and their relevance as theoretical referrals for the study on communication in the process of the nurse's work.

  2. Interaction between adrenaline and dibenzo-18-crown-6: Electrochemical, nuclear magnetic resonance, and theoretical study

    Science.gov (United States)

    Yu, Zhang-Yu; Liu, Tao; Wang, Xue-Liang

    2014-12-01

    The interaction between adrenaline (Ad) and dibenzo-18-crown-6 (DB18C6) was studied by cyclic voltammetry, nuclear magnetic resonance spectroscopy, and the theoretical calculations, respectively. The results show that DB18C6 will affect the electron transfer properties of Ad. DB18C6 can form stable supramolecular complexes with Ad through ion-dipole and hydrogen bond interactions.

  3. Theoretical and experimental study of high-Q resonant modes in terahertz optical systems

    NARCIS (Netherlands)

    Jellema, Willem; Withington, S.; Trappe, Neil; Murphy, J. A.; Wild, Wolfgang

    2004-01-01

    The existence of multiple reflections in terahertz optical system causes numerous problems in applications ranging from astronomical to medical instrumentation. We have performed a detailed theoretical study, using waveguide and free-space modal matching, of the high-Q modes that appear on THz

  4. Electronic structure of copper phthalocyanine : An experimental and theoretical study of occupied and unoccupied levels

    NARCIS (Netherlands)

    Evangelista, Fabrizio; Carravetta, Vincenzo; Stefani, Giovanni; Jansik, Branislav; Alagia, Michele; Stranges, Stefano; Ruocco, Alessandro

    2007-01-01

    An experimental and theoretical study of the electronic structure of copper phthalocyanine (CuPc) molecule is presented. We performed x-ray photoemission spectroscopy (XPS) and photoabsorption [x-ray absorption near-edge structure (XANES)] gas phase experiments and we compared the results with

  5. Substituent effif ects on hydrogen bonding in Watson-Crick base pairs. A theoretical study

    NARCIS (Netherlands)

    Fonseca Guerra, C.; van der Wijst, T.; Bickelhaupt, F.M.

    2005-01-01

    We have theoretically analyzed Watson-Crick AT and GC base pairs in which purine C8 and/or pyrimidine C6 positions carry a substituent X = H, F, Cl or Br, using the generalized gradient approximation (GGA) of density functional theory at BP86/TZ2P. The purpose is to study the effects on structure

  6. Experimental and theoretical NMR study of 4-(1-pyrrolidinyl)piperidine

    African Journals Online (AJOL)

    4-pypp) have been studied experimentally and theoretically using nuclear magnetic resonance (NMR) spectroscopy. 1H, 13C, 15N, DEPT, COSY and HETCOR NMR spectra of 4-pypp (C9H18N2) have been reported. Solvent effects on ...

  7. Computational study on decomposition kinetics of CH3CFClO radical

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 5. Computational study on decomposition kinetics of CH3CFClO radical ... The present study deals with the decomposition of haloalkoxy radical (CH3CFClO) formed from 1,1-dichloro-1-fluoroethane (HCFC-141b) in the atmosphere. The sudy is performed ...

  8. Kinetic and equilibrium study for the sorption of Pb(II) ions from ...

    African Journals Online (AJOL)

    This paper reports the kinetic and equilibrium studies of Eichhornia crassipes root biomass as a biosorbent for Pb(II) ions from aqueous system. Batch adsorption studies were carried out to examine the influence of various parameters such as the pH, contact time, adsorbent dose, initial metal ion concentration, temperature ...

  9. A calorimetric study of solute effects on the kinetic stability of a-amylase

    DEFF Research Database (Denmark)

    Olsen, Søren Nymand; Andersen, Kim Bruno; Øgendal, Lars Holm

    2009-01-01

    In this study we evaluated the applications of isothermal titration calorimetry (ITC) to Study solute effects on the kinetics of irreversible protein denaturation. More specifically, denaturation of Bacillus Halmapalus alpha-amylase (BHA) was initiated by addition of EDTA to the calorimetric cell...

  10. A new study of the kinetics of curd production in the process of cheese manufacture.

    Science.gov (United States)

    Muñoz, Susana Vargas; Torres, Maykel González; Guerrero, Francisco Quintanilla; Talavera, Rogelio Rodríguez

    2017-11-01

    We studied the role played by temperature and rennet concentration in the coagulation process for cheese manufacture and the evaluation of their kinetics. We concluded that temperature is the main factor that determines the kinetics. The rennet concentration was unimportant probably due to the fast action of the enzyme chymosin. The Dynamic light scattering technique allowed measuring the aggregate's size and their formation kinetics. The volume fraction of solids was determined from viscosity measurements, showing profiles that are in agreement with the size profiles. The results indicate that the formation of the aggregates for rennet cheese is strongly dependent on temperature and rennet concentration. The results revealed that at 35·5 °C the volume fraction of solids has the maximum slope, indicating that at this temperature the curd is formed rapidly. The optimal temperature throughout the process was established. Second-order kinetics were obtained for the process. We observed a quadratic dependence between the rennet volume and the volume fraction of solids (curd), thereby indicating that the kinetics of the curd production should be of order two.

  11. Study of Curing Kinetics and Thermal Degradation of UV Curable Epoxy Acrylate Resin

    Directory of Open Access Journals (Sweden)

    Amrita Sharma

    2008-01-01

    Full Text Available Blends of epoxy acrylate resins (acid values 3, 6.5 & 10 mg KOH/gm Solid with monofunctional monomers (ethoxylated phenol monoacrylate were prepared by physical mixing, having weight ratio 50:50. These blends were cured by using UV radiations in presence of photo initiator (Darocure 1173. The thermal degradation kinetics of these resin blends were studied, using thermo gravimetric analysis in nitrogen atmosphere at a heating rate of 10°C/min. by applying Coats-Red fern equation. According to the analysis, all the coating films degrade in two steps. In the first step of degradation kinetics, R2M follows 1.75 order (n=1.75 and all other coating films follow second order (n=2 kinetics. In second step, R2M & R3M follow half order (n=0.5 kinetics and R1M follow first order (n=1 degradation kinetics. Order of the reaction is obtained on the basis of best fit analysis, and all the parameters were confirmed by regression analysis. From the reaction order, value of activation energy (E and pre exponential factor (Z were calculated by the slop and intercept of the plot between X and Y, respectively.

  12. A High Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

    KAUST Repository

    Alquaity, Awad B. S.

    2015-05-15

    Unimolecular dissociation of 1,3,5-trioxane was investigated experimentally and theoretically over a wide range of conditions. Experiments were performed behind reflected shock waves over the temperature range of 775-1082 K and pressures near 900 Torr using a high-repetition rate time of flight mass spectrometer (TOF-MS) coupled to a shock tube (ST). Reaction products were identified directly, and it was found that formaldehyde is the sole product of 1,3,5-trioxane dissociation. Reaction rate coefficients were extracted by the best fit to the experimentally measured concentration-time histories. Additionally, high-level quantum chemical and RRKM calculations were employed to study the falloff behavior of 1,3,5-trioxane dissociation. Molecular geometries and frequencies of all species were obtained at the B3LYP/cc-pVTZ, MP2/cc-pVTZ, and MP2/aug-cc-pVDZ levels of theory, whereas the single-point energies of the stationary points were calculated using coupled cluster with single and double excitations including the perturbative treatment of triple excitation (CCSD(T)) level of theory. It was found that the dissociation occurs via a concerted mechanism requiring an energy barrier of 48.3 kcal/mol to be overcome. The new experimental data and theoretical calculations serve as a validation and extension of kinetic data published earlier by other groups. Calculated values for the pressure limiting rate coefficient can be expressed as log10 k∞ (s-1) = [15.84 - (49.54 (kcal/mol)/2.3RT)] (500-1400 K). © 2015 American Chemical Society.

  13. Kinetic Monte Carlo studies of the reaction kinetics of crystal defects that diffuse one-dimensionally with occasional transverse migration

    DEFF Research Database (Denmark)

    Heinisch, H.L.; Trinkaus, H.; Singh, Bachu Narain

    2007-01-01

    and confirmed by kinetic Monte Carlo (KMC) simulations. Here we report on KMC simulations investigating a different transition from 1D to 3D diffusion of 1D gliding loops for which their 1D migration is interrupted by occasional 2D migration due to conservative climb by dislocation core diffusion within a plane......The reaction kinetics of the various species of mobile defects in irradiated materials are crucially dependent on the dimensionality of their migration. Sink strengths for one-dimensionally (1D) gliding interstitial loops undergoing occasional direction changes have been described analytically...... transverse to their 1D glide direction. Their transition from 1D to 3D kinetics is significantly different from that due to direction changes. The KMC results are compared to an analytical description of this diffusion mode in the form of a master curve relating the 1D normalized sink strength...

  14. Kinetic Monte Carlo studies of the reaction kinetics of crystal defects that diffuse one-dimensionally with occasional transverse migration

    Science.gov (United States)

    Heinisch, H. L.; Trinkaus, H.; Singh, B. N.

    2007-08-01

    The reaction kinetics of the various species of mobile defects in irradiated materials are crucially dependent on the dimensionality of their migration. Sink strengths for one-dimensionally (1D) gliding interstitial loops undergoing occasional direction changes have been described analytically and confirmed by kinetic Monte Carlo (KMC) simulations. Here we report on KMC simulations investigating a different transition from 1D to 3D diffusion of 1D gliding loops for which their 1D migration is interrupted by occasional 2D migration due to conservative climb by dislocation core diffusion within a plane transverse to their 1D glide direction. Their transition from 1D to 3D kinetics is significantly different from that due to direction changes. The KMC results are compared to an analytical description of this diffusion mode in the form of a master curve relating the 1D normalized sink strength to the frequency of disturbance of 1D migration.

  15. Computational and theoretical study of the wave-particle interaction of protons and waves

    Directory of Open Access Journals (Sweden)

    P. S. Moya

    2012-09-01

    Full Text Available We study the wave-particle interaction and the evolution of electromagnetic waves propagating through a plasma composed of electrons and protons, using two approaches. First, a quasilinear kinetic theory has been developed to study the energy transfer between waves and particles, with the subsequent acceleration and heating of protons. Second, a one-dimensional hybrid numerical simulation has been performed, with and without including an expanding-box model that emulates the spherical expansion of the solar wind, to investigate the fully nonlinear evolution of this wave-particle interaction. Numerical results of both approaches show that there is an anisotropic evolution of proton temperature.

  16. Computational and theoretical study of the wave-particle interaction of protons and waves

    Energy Technology Data Exchange (ETDEWEB)

    Moya, P.S.; Munoz, V. [Chile Univ., Santiago (Chile). Dept. de Fisica; Vinas, A.F. [NASA Goddard Space Flight Center, Greenbelt, MD (United States). Heliophysics Science Div.; Valdivia, J.A. [Chile Univ., Santiago (Chile). Dept. de Fisica; Centro para el Desarrollo de la Nanociencia y Nanotecnologia, CEDENNA (Chile); CEIBA complejidad, Bogota (Colombia)

    2012-11-01

    We study the wave-particle interaction and the evolution of electromagnetic waves propagating through a plasma composed of electrons and protons, using two approaches. First, a quasilinear kinetic theory has been developed to study the energy transfer between waves and particles, with the subsequent acceleration and heating of protons. Second, a one-dimensional hybrid numerical simulation has been performed, with and without including an expanding-box model that emulates the spherical expansion of the solar wind, to investigate the fully nonlinear evolution of this wave-particle interaction. Numerical results of both approaches show that there is an anisotropic evolution of proton temperature. (orig.)

  17. Spectroscopic and theoretical studies of ThCl and ThCl.

    Science.gov (United States)

    VanGundy, Robert A; Bartlett, Joshua H; Heaven, Michael C; Battey, Samuel R; Peterson, Kirk A

    2017-02-07

    The electronic structures of ThCl and ThCl+ have been examined using laser induced fluorescence and two-photon ionization techniques. Rotationally resolved spectra, combined with the predictions from relativistic electronic structure calculations, show that the ground state of the neutral molecule is Th+(7s26d)Cl-, X2Δ3/2. Dispersed fluorescence spectra for ThCl revealed the ground state vibrational levels v = 0-10 and low energy electronic states that also originate from the atomic ion 7s26d configuration. Pulsed field ionization-zero kinetic energy photoelectron spectroscopy established an ionization energy (IE) for ThCl of 51 344(5) cm-1, and the ThCl+ vibrational term energies of the v = 1-3 levels. The zero-point level of the first electronically excited state was found at 949(2) cm-1. Comparisons with high-level theoretical results indicate that the ground and excited states are Th2+(7s6d)Cl- X3Δ1 and Th2+(7s2)Cl- Σ+1, respectively. Relativistic coupled cluster composite thermochemistry calculations yielded an IE within 1.2 kcal/mol of experiment and a bond dissociation energy (118.3 kcal/mol) in perfect agreement with previous experiments.

  18. Spectroscopic and theoretical studies of ThCl and ThCl+

    Science.gov (United States)

    VanGundy, Robert A.; Bartlett, Joshua H.; Heaven, Michael C.; Battey, Samuel R.; Peterson, Kirk A.

    2017-02-01

    The electronic structures of ThCl and ThCl+ have been examined using laser induced fluorescence and two-photon ionization techniques. Rotationally resolved spectra, combined with the predictions from relativistic electronic structure calculations, show that the ground state of the neutral molecule is Th+(7s26d)Cl-, X2Δ3 /2 . Dispersed fluorescence spectra for ThCl revealed the ground state vibrational levels v = 0-10 and low energy electronic states that also originate from the atomic ion 7s26d configuration. Pulsed field ionization—zero kinetic energy photoelectron spectroscopy established an ionization energy (IE) for ThCl of 51 344(5) cm-1, and the ThCl+ vibrational term energies of the v = 1-3 levels. The zero-point level of the first electronically excited state was found at 949(2) cm-1. Comparisons with high-level theoretical results indicate that the ground and excited states are Th2+(7s6d)Cl- X3Δ1 and Th2+(7s2)Cl- +1Σ, respectively. Relativistic coupled cluster composite thermochemistry calculations yielded an IE within 1.2 kcal/mol of experiment and a bond dissociation energy (118.3 kcal/mol) in perfect agreement with previous experiments.

  19. Theoretical study on the gas phase reaction of acrylonitrile with a hydroxyl radical.

    Science.gov (United States)

    Sun, Jingyu; Wang, Rongshun; Wang, Baoshan

    2011-10-06

    The mechanism and kinetics of the reaction of acrylonitrile (CH(2)=CHCN) with hydroxyl (OH) has been investigated theoretically. This reaction is revealed to be one of the most significant loss processes of acrylonitrile. BHandHLYP and M05-2X methods are employed to obtain initial geometries. The reaction mechanism conforms that OH addition to C[double bond, length as m-dash]C double bond or C atom of -CN group to form the chemically activated adducts, 1-IM1(HOCH(2)=CHCN), 2-IM1(CH(2)=HOCHCN), and 3-IM1(CH(2)=CHCOHN) via low barriers, and direct hydrogen abstraction paths may also occur. Temperature- and pressure-dependent rate constants have been evaluated using the Rice-Ramsperger-Kassel-Marcus theory. The calculated rate constants are in good agreement with the experimental data. At atmospheric pressure with N(2) as bath gas, 1-IM1(OHCH(2)=CHCN) formed by collisional stabilization is the major product in the temperature range of 200-1200 K. The production of CH(2)CCN and CHCHCN via hydrogen abstractions becomes dominant at high temperatures (1200-3000 K).

  20. Theoretical consideration of drug distribution kinetics in a noneliminating organ: comparison between a "homogeneous (well-stirred)" model and "nonhomogeneous (tube)" model.

    Science.gov (United States)

    Terasaki, T; Sugiyama, Y; Iga, T; Sawada, Y; Hanano, M

    1985-06-01

    Drug distribution kinetics in a noneliminating organ or tissue has been mathematically examined. The homogeneous (well-stirred) model regards the noneliminating organ or tissue as a homogeneous compartment in which the drug is equilibrated with that in the blood leaving the organ or tissue. The nonhomogeneous (tube) model views the noneliminating organ or tissue as comprising a number of parallel cylindrical tubes containing binding sites distributed homogeneously along these tubes. These two models are examined, considering the pseudo-distribution equilibrium phase after bolus injection and a linear binding condition. Although both models predict a similar tissue distribution under a variety of conditions, significant differences exist in the predictions of various pharmacokinetic parameters as a function of the drug distribution, such as blood flow, organ volume, slope of the terminal phase, and the tissue-to-blood partition coefficients. The predictability and limitations of these two models are explored. Distribution characteristics of the two models are also examined for adriamycin, actinomycin D, tetrachlorobiphenyl, hexachlorobiphenyl, digoxin, and ethoxybenzamide; no difference is observed. It is concluded that the assumption of a homogeneous (well-stirred) compartment is suitable for describing the drug distribution kinetics of these drugs.

  1. Impact of contamination with long-lived radionuclides on PET kinetics modelling in multitracer studies

    DEFF Research Database (Denmark)

    Jødal, Lars; Hansen, Søren B.; Jensen, Svend B.

    2016-01-01

    Introduction: An important issue in multitracer studies is the separation of signals from the different radiotracers. This is especially the case when an early tracer has a long physical half-life and kinetic modelling has to be performed, because the early tracer can confer a long...... of subsequent PET tracers. Blood sample counts were corrected by recounting the samples a few days later. A more optimal choice of energy window was also explored. The effect of correction versus noncorrection was investigated using a two-tissue kinetic model with irreversible uptake (K1, k2, k3). Results: K1...... counting of blood samples can lead to a contaminating background not observed in PET imaging and this background can affect kinetic modelling. If the contaminating tracer has a much longer half-life than the foreground tracer, then the problem can be solved by late recounting of the samples....

  2. Study on Austenitization Kinetics of SA508 Gr.3 Steel Based on Isoconversional Method

    Directory of Open Access Journals (Sweden)

    Xiaomeng Luo

    2015-12-01

    Full Text Available The austenitization kinetics of SA508 Gr.3 steel during heating was studied using the isoconversional method combined with continuous thermal dilatometric tests for the first time. The model-free austenitization kinetics was built and the effective activation energy as a function of transformed austenite fraction was determined without transformation models. Then, the corresponding regression validation was carried out. The time-temperature-austenitization (TTA diagram of SA508 Gr.3 steel, which is very difficult to be obtained using experiment measures, was constructed. Finally, the austenitization kinetics in a more realistic case, i.e., under non-constant heating rates, was predicted, which is found to agree well with the experimental results.

  3. MCNP5 study on kinetics parameters of coupled fast-thermal system HERBE

    Directory of Open Access Journals (Sweden)

    Pešić Milan P.

    2011-01-01

    Full Text Available New validation of the well-known Monte Carlo code MCNP5 against measured criticality and kinetics data for the coupled fast-thermal HERBE System at the Reactor B critical assembly is shown in this paper. Results of earlier calculations of these criticality and kinetics parameters, done by combination of transport and diffusion codes using two-dimension geometry model are compared to results of new calculations carried out by the MCNP5 code in three-dimension geometry. Satisfactory agreements in comparison of new results with experimental data, in spite complex heterogeneous composition of the HERBE core, are achieved confirming that MCNP5 code could apply successfully to study on HERBE kinetics parameters after uncertainties in impurities in material compositions and positions of fuel elements in fast zone were removed.

  4. Thermal Stability and Kinetic Study of Fluvoxamine Stability in Binary Samples with Lactose

    Directory of Open Access Journals (Sweden)

    Faranak Ghaderi

    2017-04-01

    Full Text Available Purpose: In the present study the incompatibility of FLM (fluvoxamine with lactose in solid state mixtures was investigated. The compatibility was evaluated using different physicochemical methods such as differential scanning calorimetry (DSC, Fourier-transform infrared (FTIR spectroscopy and mass spectrometry. Methods: Non-Isothermally stressed physical mixtures were used to calculate the solid–state kinetic parameters. Different thermal models such as Friedman, Flynn–Wall–Ozawa (FWO and Kissinger–Akahira–Sunose (KAS were used for the characterization of the drug-excipient interaction. Results: Overall, the incompatibility of FLM with lactose as a reducing carbohydrate was successfully evaluated and the activation energy of this interaction was calculated. Conclusion: In this research the lactose and FLM Maillard interaction was proved using physicochemical techniques including DSC and FTIR. It was shown that DSC- based kinetic analysis provides fast and versatile kinetic comparison of Arrhenius activation energies for different pharmaceutical samples.

  5. Kinetic Study of Acetone-Butanol-Ethanol Fermentation in Continuous Culture.

    Science.gov (United States)

    Buehler, Edward A; Mesbah, Ali

    2016-01-01

    Acetone-butanol-ethanol (ABE) fermentation by clostridia has shown promise for industrial-scale production of biobutanol. However, the continuous ABE fermentation suffers from low product yield, titer, and productivity. Systems analysis of the continuous ABE fermentation will offer insights into its metabolic pathway as well as into optimal fermentation design and operation. For the ABE fermentation in continuous Clostridium acetobutylicum culture, this paper presents a kinetic model that includes the effects of key metabolic intermediates and enzymes as well as culture pH, product inhibition, and glucose inhibition. The kinetic model is used for elucidating the behavior of the ABE fermentation under the conditions that are most relevant to continuous cultures. To this end, dynamic sensitivity analysis is performed to systematically investigate the effects of culture conditions, reaction kinetics, and enzymes on the dynamics of the ABE production pathway. The analysis provides guidance for future metabolic engineering and fermentation optimization studies.

  6. Adsorption of methyl orange from aqueous solution onto PMMA nanofiber: Kinetics study

    Science.gov (United States)

    Zulfikar, Muhammad Ali; Bahri, Afdal; Setiyanto, Henry; Nasir, Muhammad

    2017-07-01

    The potential of polymethyl methacrylate (PMMA) nanofiber prepared by the electrospinning technique for the methyl orange (MO) adsorption from aqueous solution was investigated. In this study, the adsorption experiments were carried out to investigate the effect of temperatures in a batch system. From experiment it can be seen that the MO adsorption using PMMA nanofiber increased with increasing temperature. The kinetic data of MO were analyzed by pseudo-first-order and pseudo-second-order kinetic models. It was found that the amount of MO adsorbed increase with increasing temperature. Kinetics parameters data indicated that the MO adsorption onto PMMA nanofiber was found to follow both pseudo first and second-order rate equations.

  7. A multiscale numerical study into the cascade of kinetic energy leading to severe local storms

    Science.gov (United States)

    Paine, D. A.; Kaplan, M. L.

    1977-01-01

    The cascade of kinetic energy from macro- through mesoscales is studied on the basis of a nested grid system used to solve a set of nonlinear differential equations. The kinetic energy cascade and the concentration of vorticity through the hydrodynamic spectrum provide a means for predicting the location and intensity of severe weather from large-scale data sets. A mechanism described by the surface pressure tendency equation proves to be important in explaining how initial middle-tropospheric mass-momentum imbalances alter the low-level pressure field.

  8. Theoretical spectroscopic study of the conjugate microcystin-LR-europium cryptate

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Julio G.; Dutra, Jose Diogo L.; Costa Junior, Nivan B. da; Freire, Ricardo O., E-mail: rfreire@ufs.br [Universidade Federal de Sergipe (UFS), Sao Cristovao, SE (Brazil). Departamento de Quimica; Alves Junior, Severino; Sa, Gilberto F. de [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Departamento de Quimica Fundamental

    2013-02-15

    In this work, theoretical tools were used to study spectroscopic properties of the conjugate microcystin-LR-europium cryptate. The Sparkle/AM1 model was applied to predict the geometry of the system and the INDO/S-CIS model was used to calculate the excited state energies. Based on the Judd-Ofelt theory, the intensity parameters were predicted and a theoretical model based on the theory of the 4f-4f transitions was applied to calculate energy transfer and backtransfer rates, radiative and non-radiative decay rates, quantum efficiency and quantum yield. A detailed study of the luminescent properties of the conjugate Microcystin-LR-europium cryptate was carried out. The results show that the theoretical quantum yield of luminescence of 23% is in good agreement with the experimental value published. This fact suggests that this theoretical protocol can be used to design new systems in order to improve their luminescence properties. The results suggest that this luminescent system may be a good conjugate for using in assay ELISA for detection by luminescence of the Microcystin-LR in water. (author)

  9. Sorption of basic dyes onto granulated pillared clays: thermodynamic and kinetic studies.

    Science.gov (United States)

    Cheknane, B; Zermane, F; Baudu, M; Bouras, O; Basly, J P

    2012-09-01

    Effect of the granulation process onto the thermodynamic and kinetic sorption parameters of two basic dyes (Basic Yellow 28-BY 28 and Basic Green 4-BG 4) was evaluated in the present work. The charge surface properties of the surfactant-modified aluminium-pillared clay (CTAB-Al-Mont-PILC) particles were not modified, and the isoelectric point remains constant after high shear wet granulation. The Gibbs free energy of both BY 28 and BG 4 sorption was negative and decreased with the granulation; the endothermic nature of the sorption process was confirmed by the positive values of ΔH°. Adsorption kinetics of the two dyes, studied at pH 6 and 150 mg L(-1), follow the pseudo-first order kinetic model with observed rate constants of 2.5-4.2×10(-2) min(-1). The intraparticle diffusion model, proposed by Weber and Morris, was applied, and the intraparticle plots revealed three distinct sections representing external mass transfer, intraparticle diffusion and adsorption/desorption equilibrium. Diffusion coefficients, calculated from the Boyd kinetic equation, increased with the granulation and the particle size. Pseudo-first order kinetic constants, intraparticle diffusion rate constants and diffusion coefficients were determined for two other initial concentrations (50 and 100 mg L(-1)) and include in a statistical study to evaluate the impact of granulation and initial concentration on the kinetic parameters. Kruskal-Wallis tests, Spearman's rank order correlation and factor analysis revealed a correlation between (i) the diffusion coefficients and granulation, and between (ii) the intraparticle diffusion rate constants and initial concentration. Copyright © 2012 Elsevier Inc. All rights reserved.

  10. Theoretical study on the rate constants for the C2H5 + HBr --> C2H6 + Br reaction.

    Science.gov (United States)

    Sheng, Li; Li, Ze-Sheng; Liu, Jing-Yao; Xiao, Jing-Fa; Sun, Chia-Chung

    2004-02-01

    The reaction C(2)H(5) + HBr --> C(2)H(6) + Br has been theoretically studied over the temperature range from 200 to 1400 K. The electronic structure information is calculated at the BHLYP/6-311+G(d,p) and QCISD/6-31+G(d) levels. With the aid of intrinsic reaction coordinate theory, the minimum energy paths (MEPs) are obtained at the both levels, and the energies along the MEP are further refined by performing the single-point calculations at the PMP4(SDTQ)/6-311+G(3df,2p)//BHLYP and QCISD(T)/6-311++G(2df,2pd)//QCISD levels. The calculated ICVT/SCT rate constants are in good agreement with available experimental values, and the calculate results further indicate that the C(2)H(5) + HBr reaction has negative temperature dependence at T 850 K. The current work predicts that the kinetic isotope effect for the title reaction is inverse in the temperature range from 200 to 482 K, i.e., k(HBr)/k(DBr) < 1. Copyright 2003 Wiley Periodicals, Inc.

  11. Curriculum, curriculum development, curriculum studies? Problematising theoretical ambiguities in doctoral theses in the education field

    Directory of Open Access Journals (Sweden)

    Petro du Preez

    2014-06-01

    Full Text Available Theoretical ambiguities in curriculum studies result in conceptual mayhem. Accordingly, they hinder the development of the complicated conversation on curriculum as a verb. This article aims to contribute to reconceptualizing curriculum studies as a dynamic social practice that aspires to thinking and acting with intelligences and sensitivity so as to understand oneself and others. It also raises awareness that equating all forms of research on curriculum with curriculum studies dilutes the scope of the conversation. This exploration asks two key questions: What is the nature of doctoral theses in the field of education's theoretical contributions to nuances of curriculum (curriculum, curriculum development, and curriculum studies? In what ways do these theses perpetuate or even add to current ambiguities in the discipline of curriculum studies? The exploration of these two questions draws on a critical meta-study of 511 theses completed in South African universities (2005-2012 conducted using a three level process. It appears that the main detractions of these theses are that some of them see curriculum studies as a dumping ground and others make no theoretical contribution to the discipline. The article concludes by suggesting ways which would encourage the intellectual advancement of curriculum studies through rigorous disciplinarity.

  12. Kinetic modelling and thermodynamic studies on purification of ...

    African Journals Online (AJOL)

    user

    adsorption mechanism might be a chemisorption process; thermodynamic studies showed that this process is spontaneous and endothermic. These results are very important in optimization of this purification process. Keywords: Polyvinylpyrrolidone (PVP), adsorption, activated carbon, resin, modelling. 1. Introduction.

  13. Chemical kinetics modeling

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Pitz, W.J. [Lawrence Livermore National Laboratory, CA (United States)

    1993-12-01

    This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.

  14. You Are What You Eat: Mass spectrometry in paediatric kinetic studies using stable isotopes

    NARCIS (Netherlands)

    H. Schierbeek (Henk)

    2009-01-01

    textabstractAn overview will be presented about applications of stable isotopes in paediatric research. Mass spectrometry has proven to be an essential tool for unravelling kinetic studies in a large range of different research disciplines related to intestinal diseases, obesities, severe cerebral

  15. Stability and kinetic studies of supported ionic liquid phase catalysts for hydroformylation of propene

    DEFF Research Database (Denmark)

    Riisager, Anders; Fehrmann, Rasmus; Haumann, Marco

    2005-01-01

    Supported ionic liquid phase (SILP) catalysts have been studied with regard to their long-term stability in the continuous gas-phase hydroformylation of propene. Kinetic data have been acquired by variation of temperature, pressure, syngas composition, substrate concentration, and residence time...

  16. 1 H NMR-Based Kinetic-Mechanistic Study of the Intramolecular ...

    African Journals Online (AJOL)

    A 1H NMR study of the acid-catalyzed, intramolecular trans-esterification between isomeric 2-exo-3-exo-dihydroxybornane monoacrylate esters has afforded insights into the reaction mechanism and permitted the determination of kinetic and thermodynamic parameters for the pseudo-first-order processes. KEYWORDS ...

  17. Kinetic modelling in food science : a case study on chlorophyll degradation in olives

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2000-01-01

    This paper critically reviews the use of kinetics in modelling (bio)chemical changes in foods. Multiresponse modelling (taking more reactants and products of the reaction under study into consideration in the modelling process) is advocated as opposed to uniresponse modelling (in which only one

  18. Dissolution kinetics of volatile organic compound vapors in water : An integrated experimental and computational study

    NARCIS (Netherlands)

    G. Mahmoodlu, Mojtaba; Pontedeiro, Elizabeth M.; Pérez Guerrero, Jesús S.; Raoof, Amir; Hassanizadeh, S. Majid; van Genuchten, Martinus Th

    In this study we performed batch experiments to investigate the dissolution kinetics of trichloroethylene (TCE) and toluene vapors in water at room temperature and atmospheric pressure. The batch systems consisted of a water reservoir and a connected headspace, the latter containing a small glass

  19. The renneting of milk : a kinetic study of the enzymic and aggregation reactions

    NARCIS (Netherlands)

    Hooydonk, van A.C.M.

    1987-01-01

    The rennet-induced clotting of milk was studied under various conditions. The kinetics of the enzymic and aggregation reactions was analysed separately and, where possible, related to the physico-chemical properties of the casein micelle and its environment.

    The effects of important

  20. Field ionization kinetic and electron impact studies of gas phase transition states - The cyclic bromonium ion

    Science.gov (United States)

    Green, M. M.; Giguere, R. J.; Falick, A. M.; Aberth, W.; Burlingame, A. L.

    1978-01-01

    Cis- and trans-isomers of 4-t-butylcyclohexyl bromide were studied to determine the mechanism of cyclic bromonium ion formation. The field ionization kinetic and electron impact data indicate that the formation of the cyclic structure occurs simultaneously with loss of the neutral fragment. The data also show that little or no gas-phase cis-trans isomerization occurs.