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Experimental Data. (experimental + data)
Kinds of Experimental Data. Selected AbstractsCorrelation of Density Pedestal Width and Neutral Penetration LengthCONTRIBUTIONS TO PLASMA PHYSICS, Issue 1-3 2004X. Q. Xu Abstract Pedestal studies in DIII-D and MAST find good correlation between the width of the H-mode density barrier and the neutral penetration length [1, 2]. These results suggest that the width may be set by the combined effects of neutrals and plasma transport. This paper is a report on fluid simulations of boundary plasma using the BOUT code[3] with a neutral source added. Thus both neutral and plasma physics are treated. The plasma transport is self-consistently driven by boundary turbulence due to the resistive X-point mode, while neutrals are described by a simple analytic model. The plasma profiles are evolved on the same time scale as the turbulence for the given heat source from the core plasma and particle source from the neutrals. For prescribed neutral profiles, we find the formation of a density pedestal inside the separatrix in the L-mode even though the calculated plasma diffusion coefficients are almost radially constant and without the formation of a temperature pedestal. These results support the hypothesis that particle fueling can provide the dominant control for the size of the H-mode density barrier. The width of the density barrier decreases as the pedestal density increases which is also consistent with experimental data. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Blob Transport in the Tokamak Scrape-off-LayerCONTRIBUTIONS TO PLASMA PHYSICS, Issue 1-3 2004D. A. D'Ippolito Abstract Recent experimental evidence suggests the importance of fast radial plasma transport in the scrape-off-layer (SOL) of tokamaks. The outward transport appears to be convective rather than diffusive, extends into the far SOL, and can produce significant recycling from the main-chamber walls, partially bypassing the divertor. A plausible theoretical mechanism to explain this phenomenon is the radial transport of "blobs" of locally dense plasma created by turbulent processes. A related process is the inward transport of "holes" of reduced density plasma, which provides a mechanism for rapid inward transport of impurities. The blob model is also consistent with the spatial and temporal intermittency and the non-Gaussian statistics observed in the SOL plasma. This paper reviews the present status of blob theory, including analytic models and simulations, and discusses the preliminary comparisons of the blob model with experimental data. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Application of mean-separation-works method to protein crystal nucleationCRYSTAL RESEARCH AND TECHNOLOGY, Issue 3 2008Christo N. Nanev Abstract Using mean-separation-works method of Stranski and Kaischew calculations of nucleus form and energy barrier for its formation are performed for globular protein crystals. This is done on the basis of a simple model suggested for crystal nucleation of such proteins. The prerequisite for the model is the fact that strict selection of definite sticky patches on protein molecule surface is obligatory for forming crystal lattices. The calculation results are in agreement with experimental data. (© 2008 WILEY -VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Receptor versus Counterion: Capability of N,N, -Bis(2-aminobenzyl)-diazacrowns for Giving Endo- and/or Exocyclic Coordination of ZnIIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2007Lea Vaiana Abstract The structure of ZnII complexes with receptors L1 and L2[L1 = N,N, -bis(2-aminobenzyl)-1,10-diaza-15-crown-5 and L2 = N,N, -bis(2-aminobenzyl)-4,13-diaza-18-crown-6] was studied both in the solid state and in acetonitrile solution. Both receptors form mononuclear ZnII complexes in this solvent, while no evidence for the formation of dinuclear complexes was obtained. This is in contrast with previous investigations that demonstrated the formation of dinuclear complexes of L2 with first-row transition metals such as NiII, CoII and CuII. Compounds of formula [Zn(L1)](ClO4)2 (1), [Zn(L1)](NO3)2·2CH3CN (2), [Zn(L2)](ClO4)2 (3) and [Zn(L2)(NO3)2] (4) were isolated and structurally characterised by X-ray diffraction analyses. L1 forms seven-coordinate ZnII complexes in the presence of both nitrate and perchlorate anions, as a consequence of the good fit between the macrocyclic cavity and the ionic radius of the metal ion. The ZnII ion is deeply buried into the receptor cavity and the anions are forced to remain out of the metal coordination sphere. The cation [Zn(L1)]2+ present in 1 and 2 is one of the very few examples of seven-coordinate Zn complexes. Receptor L2 provides a very rare example of a macrocyclic receptor allowing endocyclic and exocyclic coordination on the same guest cation, depending on the nature of the anion present. Thus, in 3 the ZnII ion is endocyclically coordinated, placed inside the crown hole coordinated to four donor atoms of the ligand in a distorted tetrahedral environment, whereas in 4, the presence of a strongly coordinating anion such as nitrate results in an exocyclic coordination of ZnII, which is directly bound only to the two primarily amine groups of L2 and two nitrate ligands. Spectrophotometric titrations of [Zn(L2)]2+ with tetrabutylammonium nitrate in acetonitrile solution demonstrate the stepwise formation of 1:1 and 1:2 adducts with this anion in acetonitrile solution. The [Zn(L1)]2+, [Zn(L2)]2+ and [Zn(L2)(NO3)2] systems were characterised by means of DFT calculations (B3LYP model). The calculated geometries show an excellent agreement with the experimental structures obtained from X-ray diffraction analyses. Calculated binding energies of the macrocyclic ligands to ZnII are also consistent with the experimental data.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Stereoselective Hydrolysis of Quaternary Quinuclidinium Benzoates Catalyzed by ButyrylcholinesteraseEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 2 2003Ines Primoz Abstract Four chiral, quaternary, N -methyl and N -benzyl derivatives of (R)- and (S)-quinuclidin-3-yl benzoates were synthesized and studied as substrates of horse serum butyrylcholinesterase (BChE). The kcat for the substrates decreased in the order (R)- N -methyl > (R)- N -benzyl (2.3-fold slower) >> (S)- N -methyl (70.5-fold slower reaction), while for the (S)- N -benzyl ester inhibition of the enzyme was observed. The kinetics of inhibition (Ka = 3.3 ,M) indicated that binding to the catalytic site of BChE occurred. From the ratio of the kcat/KM values of both enantiomers an enantiomeric excess of 95% was calculated for N -methyl derivatives. Thus, BChE is suitable as a biocatalyst for the resolution of racemic quaternary quinuclidinium esters. In order to explain the experimental data, combined quantum chemical (HF/3,21G*) and semiempirical (PM3) calculations within the ONIOM scheme of the stable species in the acylation step were performed. Geometry optimizations were carried out for all benzoate esters for an assumed active site model of BChE. It was confirmed that hydrolysis is affected to an appreciable extent by a proper geometrical orientation of substrates at the choline subsite. The energies of the optimized systems were in good agreement with the experimental data. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Regioselective formation of a 2,3-oxaphosphabicyclo[2.2.2]octene 3-oxide in Baeyer,Villiger type oxidation; a dual pathway for its fragmentationHETEROATOM CHEMISTRY, Issue 5 2006Stefan Jankowski The O-insertion reaction of a 7-phos- phanorbornene (3) unsubstituted on the double- bond gave the corresponding 2,3-oxaphosphabicyclo- [2.2.2]octene oxide (4a) in a regioselective manner that was useful in the fragmentation-related phosphonylation of alcohols. Both the UV-light mediated and the thermoinduced phosponylation accomplished on the bridged P-heterocycle (4a) were found to be sensitive toward steric factors, suggesting that beside the well-known elimination,addition reaction path taking place via metaphosphonate (11), a competitive novel addition--elimination route involving an intermediate with a pentacoordinated P-atom (12) is also present. This was confirmed by the kinetic consideration of our experimental data. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:369,375, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20213 [source] Syntheses and spectroscopic investigation of some cyclophosphazanes: Analysis of pseudo-triplet splittingHETEROATOM CHEMISTRY, Issue 4 2006Khodayar Gholivand Some new phosphoramidates, 1,3, and the corresponding cyclophosphazanes, 4,6, with formula Cl2P(p -NHC6H4CH3) 1, Cl2P(O)(p -NHC6H4NO2) 2, (CH3)2NP(O)Cl(p -NHC6H4CH3)3, [ClP(p -NC6H4CH3)]24, [ClP(O)(p -NC6H4NO2)]25, and [(CH3)2NP(O)(p -NC6H4CH3)]26 were synthesized and characterized by 1H, 13C, 31P NMR, IR, mass spectroscopy, and elemental analysis. A pseudo-triplet signal was observed in the 1H NMR spectrum of molecule 6 for the N(CH3)2 protons. The A6A, 6X2 spin system was suggested for the pseudo-triplet pattern of 3JPNCH coupling in this molecule. Ab initio calculations were performed at the HF and B3LYP levels of theory with 6-311G** standard basis set on the geometry of compound 6. Also, the NMR chemical shift calculations were done to compare the computed results with the experimental ones. The calculated results are in good agreement with experimental data. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:337,343, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20229 [source] Ab initio chemical kinetics for the NH2 + HNOx reactions, part II: Kinetics and mechanism for NH2 + HONOINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 11 2009Shucheng Xu The kinetics and mechanism for the reaction of NH2 with HONO have been investigated by ab initio calculations with rate constant prediction. The potential energy surface of this reaction has been computed by single-point calculations at the CCSD(T)/6-311+G(3df, 2p) level based on geometries optimized at the CCSD/6-311++G(d, p) level. The reaction producing the primary products, NH3 + NO2, takes place via precomplexes, H2N,,,c -HONO or H2N,,,t -HONO with binding energies, 5.0 or 5.9 kcal/mol, respectively. The rate constants for the major reaction channels in the temperature range of 300,3000 K are predicted by variational transition state theory or Rice,Ramsperger,Kassel,Marcus theory depending on the mechanism involved. The total rate constant can be represented by ktotal = 1.69 × 10,20 × T2.34 exp(1612/T) cm3 molecule,1 s,1 at T = 300,650 K and 8.04 × 10,22 × T3.36 exp(2303/T) cm3 molecule,1 s,1 at T = 650,3000 K. The branching ratios of the major channels are predicted: k1 + k3 producing NH3 + NO2 accounts for 1.00,0.98 in the temperature range 300,3000 K and k2 producing OH + H2NNO accounts for 0.02 at T > 2500 K. The predicted rate constant for the reverse reaction, NH3 + NO2 , NH2 + HONO represented by 8.00 × 10,26 × T4.25 exp(,11,560/T) cm3 molecule,1 s,1, is in good agreement with the experimental data. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 678,688, 2009 [source] Kinetics and mechanism of the hydrolytic disproportionation of iodineINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 11 2004Krisztina Seb, k-Nagy Kinetics of the hydrolytic disproportionation of I2 was studied by UV,VIS spectrophotometry at 298 K and at the ionic strength 0.2 M (NaClO4) in buffered solutions in the pH range 8.91,10.50 at different initial iodide concentrations. The characterization of this reaction is fundamental for modeling oscillatory and front reactions in the presence of iodine as reactant or intermediate as well as for drinking water treatment. A matrix rank analysis confirmed three absorbing species in the beginning of the reaction, whereas later assumption of two species is enough to describe the experimental data in the visible part of the spectrum. A reaction mechanism was proposed for disproportionation by using fitting/simulation with a multipurpose program package ZiTa, by simultaneous evaluation of 17,906 points in 79 experimental curves. A parameter set was suggested, which was obtained by absolute, relative, and orthogonal fittings of the experimental data. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 596,602, 2004 [source] Crystal structure and theoretical calculations of Julocrotine, a natural product with antileishmanial activity,,INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2008Rafael Y. O. Moreira Abstract Julocrotine, N -(2,6-dioxo-1-phenethyl-piperidin-3-yl)-2-methyl-butyramide, is a potent antiproliferative agent against the promastigote and amastigote forms of Leishmania amazonensis (L.). In this work, the crystal structure of Julocrotine was solved by X-ray diffraction, and its geometrical parameters were compared with theoretical calculations at the B3LYP and HF level of theory. IR and NMR spectra also have been obtained and compared with theoretical calculations. IR absorptions calculated with the B3LYP level of theory employed together with the 6-311G+(d,p) basis set, are close to those observed experimentally. Theoretical NMR calculations show little deviation from experimental results. The results show that the theory is in accordance with the experimental data. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Comparative study of electrostatic solvent response by RISM and PCM methods,INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2007S. Chiodo Abstract The solvent response on the solute is calculated by the reference interaction site model (RISM) and by the polarizable continuum model (PCM) methods. The linearized RISM technique is developed to treat free energies of atomic and polyatomic ions in water. An empirical repulsive bridge is used for the RISM calculations. The solvent electrostatic potential is approximated by a linear dependence on the solute atomic charges. For a series of monovalent polyatomic cations and anions, the method provides free energies deviating by few percent from the experimental data. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Gas-phase acidity of proline from density functional computationsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2001T. Marino Abstract Density functional computations using the B3LYP hybrid potential coupled with the extended 6-311++G** basis set were performed to evaluate gas-phase acidity of proline ,-amino acid. The computed value of gas-phase acidity is 1403.8 kJ/mol in good agreement with the experimental counterpart (1395.0±13.8 kJ/mol) and is referred to the deprotonated species deriving from the first relative minimum of neutral proline characterized by the exo ring conformation with the carboxyl group in cis position. The most stable neutral proline isomer gives rise to a species for which the gas-phase acidity value (1384.5 kJ/mol) is also close to the experimental data. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 264,268, 2001 [source] A physics-based model of DC and microwave characteristics of GaN/AlGaN HEMTsINTERNATIONAL JOURNAL OF RF AND MICROWAVE COMPUTER-AIDED ENGINEERING, Issue 3 2007Jonathan C. Sippel Abstract A physics-based model of AlGaN/GaN High Electron Mobility Transistor (HEMT) is developed for the analysis of DC and microwave characteristics. Large- and small-signal parameters are calculated for a given device dimensions and operating conditions. Spontaneous and piezoelectric polarizations at the heterointerface and finite effective width of the 2DEG gas have been incorporated in the analysis. The model predicts a maximum drain current of 523 mA/mm and transconductance of 138 mS/mm for a 1 ,m × 75 ,m device, which are in agreement with the experimental data. © 2007 Wiley Periodicals, Inc. Int J RF and Microwave CAE, 2007. [source] Ionic conductivity of solid polymer electrolytes for dye-sensitized solar cellsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010Joo Wan Kim Abstract We developed an ionic conductivity model of solid polymer electrolytes for dye-sensitized solar cells (DSSCs) based on the Nernst,Einstein equation in which the diffusion coefficient is derived from the molecular thermodynamic model. We introduced concentration-dependence of the diffusion coefficient into the model, and the diffusion coefficient was expressed by differentiating the chemical potential by concentration. The ionic conductivities of polymer electrolytes (PEO/LiI/I2 system) were investigated at various temperatures and compositions. We prepared a set of PEO in which an EO : LiI mole ratio of 10 : 1 was kept constant for PEO·LiI·(I2)n compositions with n = 0.02, 0.05, 0.1, 0.15, 0.2, and 0.3 (mole ratio of LiI : I2). The ionic conductivities of the electrolytes were measured using a stainless steel/polymer-electrolyte/stainless steel sandwich-type electrode structure using alternating current impedance analysis. The values calculated using the proposed model agree well with experimental data. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Closed loop folding units from structural alignments: Experimental foldons revisitedJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 15 2010Sree V. Chintapalli Abstract Nonoverlapping closed loops of around 25,35 amino acids formed via nonlocal interactions at the loop ends have been proposed as an important unit of protein structure. This hypothesis is significant as such short loops can fold quickly and so would not be bound by the Leventhal paradox, giving insight into the possible nature of the funnel in protein folding. Previously, these closed loops have been identified either by sequence analysis (conservation and autocorrelation) or studies of the geometry of individual proteins. Given the potential significance of the closed loop hypothesis, we have explored a new strategy for determining closed loops from the insertions identified by the structural alignment of proteins sharing the same overall fold. We determined the locations of the closed loops in 37 pairs of proteins and obtained excellent agreement with previously published closed loops. The relevance of NMR structures to closed loop determination is briefly discussed. For cytochrome c, cytochrome b562 and triosephophate isomerase, independent folding units have been determined on the basis of hydrogen exchange experiments and misincorporation proton-alkyl exchange experiments. The correspondence between these experimentally derived foldons and the theoretically derived closed loops indicates that the closed loop hypothesis may provide a useful framework for analyzing such experimental data. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] Theoretical and kinetic study of the H + C2H5CN reactionJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2010Jingyu Sun Abstract The reaction of H radical with C2H5CN has been studied using various quantum chemistry methods. The geometries were optimized at the B3LYP/6-311+G(d,p) and B3LYP/6-311++G(2d,2p) levels. The single-point energies were calculated using G3 and BMC-CCSD methods based on B3LYP/6-311++G(2d,2p) geometries. Four mechanisms were investigated, namely, hydrogen abstraction, C-addition/elimination, N-addition/elimination and substitution. The kinetics of this reaction were studied using the transition state theory and multichannel Rice-Ramsperger-Kassel-Marcus methodologies over a wide temperature range of 200,3000 K. The calculated results indicate that C-addition/elimination channel is the most feasible over the whole temperature range. The deactivation of initial adduct C2H5CHN is dominant at lower temperature with bath gas H2 of 760 Torr; whereas C2H5+HCN is the dominant product at higher temperature. Our calculated rate constants are in good agreement with the available experimental data. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] Theoretical study of ribonucleotide reductase mechanism-based inhibition by 2,-azido-2,-deoxyribonucleoside 5,-diphosphatesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 2 2004Susana Pereira Abstract 2,-Azido-2,-deoxyribonucleoside 5,-diphosphates are mechanism-based inhibitors of Ribonucleotide Reductase. Considerable effort has been made to elucidate their mechanism of inhibition, which is still controversial and not fully understood. Previous studies have detected the formation of a radical intermediate when the inhibitors interact with the enzyme, and several authors have proposed possible structures for this radical. We have conducted a theoretical study of the possible reactions involved, which allowed us to identify the structure of the new radical among the several proposals. A new reactional path is also proposed that is the most kinetically favored to yield this radical and ultimately inactivate the enzyme. The energetic involved in this mechanism, both for radical formation and radical decay, as well as the calculated Hyperfine Coupling Constants for the radical intermediate, are in agreement with the correspondent experimental values. This mechanistic alternative is fully coherent with remaining experimental data. © 2003 Wiley Periodicals, Inc. J Comput Chem 25: 227,237, 2004 [source] About the calculation of exchange coupling constants in polynuclear transition metal complexesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 8 2003Eliseo Ruiz Abstract The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H · · · He and CH2 · · · He units to compare with Hartree,Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 982,989, 2003 [source] The effect of column diameter and bed height on minimum fluidization velocityAICHE JOURNAL, Issue 9 2010Akhil Rao Abstract Experiments show that the minimum fluidization velocity of particles increases as the diameter of the fluidization column is reduced, or if the height of the bed is increased. These trends are shown to be due to the influence of the wall. A new, semicorrelated model is proposed, which incorporates Janssen's wall effects in the calculation of the minimum fluidization velocity. The wall friction opposes not only the bed weight but also the drag force acting on the particles during fluidization. The enhanced wall friction leads to an increase in the minimum fluidization velocity. The model predictions compare favorably to existing correlations and experimental data. © 2010 American Institute of Chemical Engineers AIChE J, 2010 [source] Experimental and numerical research for fluidization behaviors in a gas,solid acoustic fluidized bedAICHE JOURNAL, Issue 7 2010Changqing Cao Abstract The effects of sound assistance on fluidization behaviors were systematically investigated in a gas,solid acoustic fluidized bed. A model modified from Syamlal,O'Brien drag model was established. The original solid momentum equation was developed and an acoustic model was also proposed. The radial particle volume fraction, axial root-mean-square of bed pressure drop, granular temperature, and particle velocity in gas,solid acoustic fluidized bed were simulated using computational fluid dynamics (CFD) code Fluent 6.2. The results showed that radial particle volume fraction increased using modified drag model compared with that using the original one. Radial particle volume fraction was revealed as a parabolic concentration profile. Axial particle volume fraction decreased with the increasing bed height. The granular temperature increased with increasing sound pressure level. It showed that simulation values using CFD code Fluent 6.2 were in agreement with the experimental data. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] Estimation of an effective water diffusion coefficient during infrared-convective drying of a polymer solutionAICHE JOURNAL, Issue 9 2009N. Allanic Abstract This article deals with the drying of an aqueous solution of polyvinyl alcohol mixed with a plasticizer. A heating combining forced convection and short-infrared radiation was investigated. A one-dimensional model taking into account the shrinkage of the product was developed to get the temperature and moisture content evolutions during the drying. The water diffusion coefficient was estimated by an inverse method. A sensitivity analysis and numerical tests showed the relevance of using an objective function taking both mass and temperature measurements into account for the estimation procedure. This estimation was performed on several convective and infrared-convective experimental drying kinetics. The model predictions fit well mass and temperature experimental data. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Molecular simulation of ammonia absorption in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N])AICHE JOURNAL, Issue 9 2009Wei Shi Isotherms for ammonia absorption in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) are computed at temperatures ranging from 298 K to 348 K using osmotic ensemble Monte Carlo simulations. The results agree well with previous experimental measurements. Activity coefficients vary from 0.5 to 0.8, indicating negative deviations from Raoult's Law. The computed enthalpy of mixing ranges from ,2 to ,11 kJ/mol. Computed partial molar volumes are on the order of 25,30 cm3/mol. Energy and radial distribution analyses indicate that ammonia interacts more strongly with the cation than the anion, in contrast to observations made of other gases in ionic liquids such as CO2. The reason for this behavior is that ammonia forms a strong hydrogen bond with the ring hydrogen atoms of the cation. The simulations predict that strategies aimed at changing the solubility of ammonia should focus on altering the hydrogen bond donating ability of the cation, and that altering the anion will have more modest effects. It is shown that this hypothesis is consistent with available experimental data. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Kinetics of the thermal dissociation of ZnO exposed to concentrated solar irradiation using a solar-driven thermogravimeter in the 1800,2100 K rangeAICHE JOURNAL, Issue 6 2009Lothar O. Schunk Abstract The two-step H2O-splitting thermochemical cycle based on the Zn/ZnO redox reactions is considered for solar H2 production, comprising the endothermal dissociation of ZnO followed by the exothermal hydrolysis of Zn. A solar-driven thermogravimeter, in which a packed-bed of ZnO particles is directly exposed to concentrated solar radiation at a peak solar concentration ratio of 2400 suns while its weight loss is continuously monitored, was applied to measure the thermal dissociation rate in a set-up closely approximating the heat and mass transfer characteristics of solar reactors. Isothermal thermogravimetric runs were performed in the range 1834,2109 K and fitted to a zero-order Arrhenius rate law with apparent activation energy 361 ± 53 kJ mol,1 K,1 and frequency factor 14.03 × 106 ± 2.73 × 106 kg m,2 s,1. Application of L,vov's kinetic expression for solid decomposition along with a convective mass transport correlation yielded kinetic parameters in close agreement with those derived from experimental data. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Distributed midpoint chain scission in ultrasonic degradation of polymersAICHE JOURNAL, Issue 9 2004G. Sivalingam Abstract The ultrasonic degradation of poly(bisphenol A carbonate), poly(,-caprolactone), and poly(vinyl acetate) was investigated with various solvents such as benzene, monochlorobenzene, and dichlorobenzene. The time evolution of molecular weight was determined using gel permeation chromatography. A limiting molecular weight was observed for all the systems and was a function of solvent properties. The degradation rates increased with increase in viscosity and decrease in vapor pressure. The polydispersity reached a maximum before reaching a constant value at longer times. The experimental data indicate that the breakage of the polymer is around midpoint, with a distribution rather than an ideal midpoint scission. A continuous distribution model with a stoichiometric kernel based on Lorentzian probability distribution function was developed to satisfactorily model the experimental data. © 2004 American Institute of Chemical Engineers AIChE J, 50: 2258,2265, 2004 [source] Measurement and prediction of the ultrafiltration of whey proteinAICHE JOURNAL, Issue 7 2004M. Davey Abstract Ultrafiltration of proteins and other compressible material is characterized by a significant transmembrane pressure and is often limited by the formation of a fouling layer. This study examines the compressive rheology of such fouling layers. A model is proposed that can be used to predict the performance of filtration processes where there is significant pressure drop across the clean membrane and the filtration rate is limited by fouling during the filtration cycle. The information required for the model can in principle be obtained from simple centrifuge tests and the clean membrane pressure drop. The model can be used to optimize the cycle times, pressures, and other operating parameters of the ultrafiltration process. The model was tested on the ultrafiltration of whey protein concentrate and shown to describe the experimental data. © 2004 American Institute of Chemical Engineers AIChE J, 50: 1431,1437, 2004 [source] Parametric and temperature-sensitivity study of resonance frequency of microstrip antennas using spectral-domain methodMICROWAVE AND OPTICAL TECHNOLOGY LETTERS, Issue 4 2001Ashutosh Kedar Abstract In the present paper, a study is carried out to visualize the effects of various design parameters, including temperature, on the resonant frequency of a microstrip patch antenna. The analysis is carried out using the spectral-domain method with efficient evaluation of infinite 2-D reaction integrals improving the rate of convergence. Some of the numerical results are compared with the experimental data. © 2001 John Wiley & Sons, Inc. Microwave Opt Technol Lett 30: 276,280, 2001. [source] Reliability of computational scienceNUMERICAL METHODS FOR PARTIAL DIFFERENTIAL EQUATIONS, Issue 4 2007I. Babu Abstract Today's computers allow us to simulate large, complex physical problems. Many times the mathematical models describing such problems are based on a relatively small amount of available information such as experimental measurements. The question arises whether the computed data could be used as the basis for decision in critical engineering, economic, and medicine applications. The representative list of engineering accidents occurred in the past years and their reasons illustrate the question. The paper describes a general framework for verification and validation (V&V) which deals with this question. The framework is then applied to an illustrative engineering problem, in which the basis for decision is a specific quantity of interest, namely the probability that the quantity does not exceed a given value. The V&V framework is applied and explained in detail. The result of the analysis is the computation of the failure probability as well as a quantification of the confidence in the computation, depending on the amount of available experimental data. © 2007 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 23: 753,784, 2007 [source] Simulation of electronic density of states and optical properties of PbB4O7 by first-principles DFT methodPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 2 2009Hui Wang Abstract First-principles calculations based on the density functional theory and the generalized gradient approximation were carried out to systematically investigate the electronic structure and linear optical properties of lead tetraborate (PbB4O7; PTB) single crystals. An indirect band gap of 4.34 eV is obtained. The valence band top is at the X-point and the conduction band is at the ,-point. The calculated total and partial densities of states indicate that the top valence band is constructed from O 2p states and the low conduction band mainly consists of Pb 6p states. The optical absorption spectra show several prominent structures but with very small directional anisotropy. PTB crystals have a higher refractive index but a small birefringence. The calculated frequency-dependent refractive index is in good agreement with experimental data. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Magnetic properties of DyFe2Si2 studied with a two-ion model for rare-earth antiferromagnetsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 2 2009Z.-S. Liu Abstract A two-ion model for rare-earth antiferromagnets is proposed and utilized to investigate the magnetic properties of DyFe2Si2 in this work. The theoretical magnetization curves obtained with the model show good agreements with experimental data. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Theoretical studies of the spin Hamiltonian parameters and the local structure for the orthorhombic V4+ in CaYAlO4PHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 6 2008Chuan-Ji Fu Abstract The spin Hamiltonian parameters (g -factors and the hyperfine structure constants) and the local structure for the orthorhombic V4+ in CaYAlO4 are theoretically studied from the perturbation formulas of these parameters for a 3d1 ion in orthorhombically distorted octahedra. Based on the present studies, this center is explicitly assigned to V4+ occupying the Al3+ site, associated with one next-nearest-neighbor Mg2+ replacing the host Al3+ (i.e. MgAl) in the ab -plane due to the charge compensation. Since the effective charge of the compensator is negative (,e), the ligand O2, intervening in the impurity V4+ and the MgAl would undergo a small displacement (,0.08 Å) towards the central ion because of the electrostatic repulsion. The local structure of this center can be described as elongation of the oxygen octahedron along the c- axis and the slight orthorhombic distortion in the perpendicular direction. The theoretical spin Hamiltonian parameters and the optical transitions based on the above local structure show reasonable agreement with the experimental data. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] | |||||||||||||||||||