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Activation Enthalpy (activation + enthalpy)
Selected AbstractsOxygen Grain-Boundary Diffusion in Polycrystalline Mullite CeramicsJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 12 2004Peter Fielitz Oxygen tracer diffusivities of low- and high-alumina mullite ceramics (72 wt% Al2O3, 28 wt% SiO2 and 78 wt% Al2O3, 22 wt% SiO2, respectively) were determined. Gas/solid exchange experiments were conducted in an atmosphere enriched in the rare stable isotope 18O, and the resulting 18O isotope depth distributions were analyzed using SIMS depth profiling. The investigation showed that grain-boundary diffusivities for both mullite ceramics were several orders of magnitude higher than mullite volume diffusivity. Activation enthalpies of oxygen diffusion were 363 ± 25 kJ/mol for the low-alumina and 548 ± 46 kJ/mol for the high-alumina materials. Because the glassy grain-boundary films were not identified, the differences between the low- and high-alumina materials might be explained by different impurity concentrations in the grain boundaries of the two materials. [source] Magnetic properties of Fe76X2B22 (X=Cr,Zr,Nb) amorphous alloysPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 1 2003A. Chrobak Abstract The paper contains experimental results referring to optimization of soft magnetic properties and crystallization in the Fe76X2B22 (X=Cr,Zr,Nb) amorphous alloys. We have used measurement of thermomagnetic balance, magnetic permeability, coercive field and also HREM and X-ray diffraction techniques. It was shown that Zr and Nb alloying additions cause a slowing down of diffusion processes and an increase of the annealing for 1 hour optimization temperature of about 50 and 100 K, respectively. Activation enthalpies of the crystallization process were determined as: 2.0 eV (X=Cr), 2.6 eV (X=Zr) and 4.4 eV (X=Nb). [source] The mechanism of alkaline hydrolysis of amides: a comparative computational and experimental study of the hydrolysis of N -methylacetamide, N -methylbenzamide, and acetanilideJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 6 2009Diana Cheshmedzhieva Abstract Theoretical computations and experimental kinetic measurements were applied in studying the mechanistic pathways for the alkaline hydrolysis of three secondary amides: N -methylbenzamide, N -methylacetamide, and acetanilide. Electronic structure methods at the HF/6-31+G(d,p) and B3LYP/6-31+G(d,p) levels of theory are employed. The energies of the stationary points along the reaction coordinate were further refined via single point computations at the MP2/6-31+G(d,p) and MP2/6-311++G(2d,2p) levels of theory. The role of water in the reaction mechanisms is examined. The theoretical results show that in the cases of N -methylbenzamide and N -methylacetamide the process is catalyzed by an ancillary water molecule. The influence of water is further assessed by predicting its role as bulk solvent. The alkaline hydrolysis process in aqueous solution is characterized by two distinct free energy barriers: the formation of a tetrahedral adduct and its breaking to products. The results show that the rate-determining stage of the process is associated with the second transition state. The entropy terms evaluated from theoretical computations referring to gas-phase processes are significantly overestimated. The activation barriers for the alkaline hydrolysis of N -methylbenzamide and acetanilide were experimentally determined. Quite satisfactory agreement between experimental values and computed activation enthalpies was obtained. Copyright © 2008 John Wiley & Sons, Ltd. [source] Mechanism and dynamics of organic reactions: 1,2-H shift in methylchlorocarbene,JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 8 2002Elfi Kraka Abstract The unified reaction valley approach (URVA) was used to investigate the mechanism of the rearrangement of methylchlorocarbene to chloroethene [reaction(1)] in the gas phase with special emphasis on the role of H tunneling. The reaction valley of (1) was explored using different methods (HF, MP2 and DFT/B3LYP) and different basis sets [6,31G(d), 6,31G(d,p) and cc-pVTZ]. Results were analyzed characterizing normal modes, reaction path vector and curvature vector in terms of generalized adiabatic modes associated with internal parameters that are used to describe the reaction complex. For reaction (1), H tunneling plays a significant role even at room temperature, but does not explain the strongly curved Arrhenius correlations observed experimentally. The probability of H tunneling can be directly related to the curvature of the reaction path and the associated curvature couplings. The reaction is preceeded in the forward and reverse direction by energy-consuming conformational changes that prepare the reactant for the actual 1,2-H shift, which requires only little energy. The effective energy needed for CH bond breaking is just 6,kcal,mol,1 for (1). The gas-phase and the solution-phase mechanisms of (1) differ considerably, which is reflected by the activation enthalpies: 11.4 (gas, calculated) and 4.3,kcal,mol,1 (solution, measured). Stabilizing interactions with solvent molecules take place in the latter case and reduce the importance of H tunneling. The non-linearity of the measured Arrhenius correlations most likely results from bimolecular reactions of the carbene becoming more important at lower temperatures. Copyright © 2002 John Wiley & Sons, Ltd. [source] H/D exchange reactions;CHEMPHYSCHEM, Issue 6 2003sigma-bond metathesis; The mechanism of the H/D exchange reaction in alkane/hydrogen mixtures on silica-supported zirconium hydride was investigated by a modelling study using density functional theory (DFT) calculations. The electronic activation enthalpy (,H) for the CH bond activation step (TS3) was calculated to be around 92 kJ,mol,1, whereas it would be 258 kJ,mol,1for a direct exchange process (TS1, also called the kite TS). These data clearly speak in favour of the former as a mechanism for CH bond scrambling. Moreover, the calculated enthalpy of activation (,H) for H/D exchange in H2/D2mixtures (TS2) is 33.5 kJ,mol,1, which shows that this reaction is much faster than the H/D scrambling in alkane/H2mixtures, as shown experimentally. Additionally, the calculated activation entropies (For TS1,4,,S ranges between ,129 and ,174 J,mol,1,K,1) are very negative. Although the calculated activation entropies are also in full agreement with experimental data (,S=,113 J,mol,1,K,1), overall, the calculated activation enthalpies are much higher than the experimental ones. This suggests that the actual catalyst is probably more electrophilic than the model chosen for the calculations. [source] Structures and Thermodynamics of the Sulfuranes SF3CN and SF2(CN)2 as well as of the Persulfurane SF4(CN)2 , An ab initio MO Study by the G3(MP2) MethodEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2003Yana Steudel Abstract At the G3(MP2) level of theory the trans isomer 1a of the hypothetical molecule SF4(CN)2 is more stable than the cis isomer 1b by 8 kJ·mol,1. The isomerization of 1a to 1b requires an activation enthalpy of 319 kJ·mol,1 at 298 K. The decomposition of trans -SF4(CN)2 to SF2(CN)2 and F2 is endothermic (,Ho298 = 395 kJ·mol,1) but the elimination of FCN from trans -SF4(CN)2 is exothermic by ,7 kJ·mol,1. The elimination of (CN)2 from cis -SF4(CN)2 is exothermic by ,137 kJ·mol,1. The activation enthalpies for the latter two reactions were calculated as 251 and 311 kJ·mol,1, respectively. Thus, SF4(CN)2 should be a thermally stable compound. In the sulfuranes SF3CN and SF2(CN)2 the CN ligands prefer the equatorial positions; mutual exchange of an axial F atom by an equatorial CN group requires a reaction enthalpy of 51 kJ·mol,1 [SF3CN] or 58 kJ·mol,1 [SF2(CN)2]. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Lewis Acid Induced [2+2] Cycloadditions of Silyl Enol Ethers with ,,,-Unsaturated Esters: A DFT AnalysisEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2005Manuel Arnó Abstract The Lewis acid (LA) induced cycloaddition of trimethysilyl vinyl ether with methyl acrylate has been studied by DFT methods at the B3LYP/6-31G* level. In the absence of an LA, a [4+2] cycloaddition between the silyl enol ether and methyl acrylate in the s-cis conformation takes place through an asynchronous, concerted bond-formation process. This cycloaddition presents a large activation enthalpy of 21.1 kcal,mol,1. Coordination of the LA AlCl3 to the carbonyl oxygen atom of methyl acrylate yields a change of molecular mechanism from a concerted to a two-step mechanism and produces a drastic reduction of the activation energy. This stepwise mechanism is initialized by the nucleophilic attack of the enol ether at the ,-position of methyl acrylate in a Michael-type addition. The very low activation energy (7.1 kcal,mol,1)associated with this nucleophilic attack can be related to the increase of the electrophilicity of the LA-coordinated ,,,-unsaturated ester, which favors the cycloaddition through a polar process. The subsequent ring-closure allows the formation of the corresponding [2+2] and [4+2] cycloadducts. While the [4+2] cycloadduct is formed by kinetic control, the [2+2] cycloadducts are formed by thermodynamic control. The energetic results provide an explanation for the conversion of [4+2] cycloadducts into the thermodynamically more stable [2+2] ones. The cis/trans ratio found for the catalytic [2+2] process is in agreement with the experimental outcome. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Experimental dehydration kinetics of serpentinite using pore volumometryJOURNAL OF METAMORPHIC GEOLOGY, Issue 4 2007S. LLANA-FÚNEZ Abstract A series of dehydration experiments was carried out on both intact rock and cold-pressed powdered samples of serpentinite at temperatures in the range 535,610 °C, 100,170 °C above the onset of the breakdown temperature of 435 °C. Pore water pressures near 120 MPa were servo-controlled using a pore volumometer that also allowed dehydration reaction progress to be monitored through measurement of the amount of evolved water. Effective hydrostatic confining pressures were varied between 0 and 113 MPa. The reaction rate of intact specimens of initially near-zero porosity was constant up to 50,80% reaction progress at any given temperature, but decreased progressively as transformation approached completion. Water expulsion rates were not substantially affected by elevation of effective pressures that remained insufficient to cause major pore collapse. An Arrhenius relation links reaction rate to temperature with an activation enthalpy of 429 ± 201 and 521 ± 52 kJ mol,1 for powdered and intact specimens, respectively. Microstructural study of intact specimens showed extensive nucleation beginning at pre-existing cracks, veins and grain boundaries, and progressing into the interior of the lizardite grains. Extrapolation of these data towards equilibrium temperature provides an upper bound on the kinetics of this reaction in nature. [source] Secondary Ion Mass Spectroscopy Study of Oxygen-18 Tracer Diffusion in 2/1-Mullite Single CrystalsJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 12 2001Peter Fielitz Oxygen 18O tracer diffusion in Czochralski-grown mullite single crystals is investigated along [010] and [001]. Oxygen diffusion coefficients range between ,5 × 10,20 m2/s (1250°C) and ,9 × 10,18 m2/s (1525°C). The data does not show any significant anisotropy. The values of the activation enthalpy (4.5 eV) and of the activation entropy ((3.4 ± 1.6)kB, where kB is the Boltzmann constant) suggest that the atomic transport occurs via thermally activated vacancies. [source] Oxygen diffusion in YSZ single crystals at relatively low temperaturesPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 2 2003Ralf Röwer Abstract The 18O tracer experiments were carried out on two cubic YSZ single crystals at temperatures of TD = 423 K and TD = 473 K. The diffusion profiles were determined by the SIMS technique. The diffusion coefficients, the surface exchange coefficients and the activation enthalpy are discussed together with earlier data at higher temperatures. The present oxygen diffusion data demonstrate that the same diffusion process is operating over a wide temperature range. (© 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] In-vitro antimicrobial, thermal and spectral studies of mixed ligand Cu(II) heterochelates of clioquinol and coumarin derivativesAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 4 2010G. J. Kharadi Abstract The mixed-ligand heterochelates of Cu(II) with 5-chloro-7-iodo-8-hydroxyquinoline (clioquinol) and various uninegative bidentate ligands were prepared. The structure of mixed-ligand heterochelates was investigated using spectral, physicochemical, elemental analysis and thermal studies. The FAB-mass spectrum of [Cu(A2)(CQ)(H2O)2].2H2O has been carried out. Magnetic moment and reflectance spectral studies reveal that an octahedral geometry has been assigned to all the prepared heterochelates. The kinetic parameters such as order of reaction (n), the energy of activation (Ea), the pre-exponential factor (A), the activation entropy (,S#), the activation enthalpy (,H#) and the free energy of activation (,G#) have been reported. The ligands, metal salts, heterochelates, control and standard drug were tested for their in-vitro antibacterial activity against Escherichia coli, Pseudomonas aeruginosa, Serratia marcescens and Bacillus substilis. The metal complexes exhibit good activity against bacterial strains compared with parental compounds, and moderate compared with the standard drug (clioquinol). Copyright © 2010 John Wiley & Sons, Ltd. [source] Novel drug-based Fe(III) heterochelates: synthetic, spectroscopic, thermal and in-vitro antibacterial significanceAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 2 2010D.H. Jani Abstract A series of novel heterochelates of the type [Fe(An)(L)(H2O)2],mH2O [where H2An = 4,4,-(arylmethylene)bis(3-methyl-1-phenyl-4,5-dihydro-1H-pyrazol-5-ol); aryl = 4-nitrophenyl, m = 1 (H2A1); 4-chlorophenyl, m = 2 (H2A2); phenyl, m = 2 (H2A3); 4-hydroxyphenyl, m = 2 (H2A4); 4-methoxyphenyl, m = 2 (H2A5); 4-hydroxy-3-methoxyphenyl, m = 1.5 (H2A6); 2-nitrophenyl, m = 1.5 (H2A7); 3-nitrophenyl, m = 0.5 (H2A8); p -tolyl, m = 1 (H2A9) and HL = 1-cyclopropyl-6-fluoro-4-oxo-7-(piperazin-1-yl)-1,4-dihydroquinoline-3-carboxylic acid] were investigated. They were characterized by elemental analysis (FT-IR, 1H- & 13C-NMR, and electronic) spectra, magnetic measurements and thermal studies. The FAB-mass spectrum of [Fe(A3)(L)(H2O)2],2H2O was determined. Magnetic moment and reflectance spectral studies revealed that an octahedral geometry could be assigned to all the prepared heterochelates. Ligands (H2An) and their heterochelates were screened for their in-vitro antibacterial activity against Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Serratia marcescens bacterial strains. The kinetic parameters such as order of reaction (n), the energy of activation (Ea), the pre-exponential factor (A), the activation entropy (,S#), the activation enthalpy (,H#) and the free energy of activation (,G#) are reported. Copyright © 2009 John Wiley & Sons, Ltd. [source] Antibacterial, spectral and thermal aspects of drug based-Cu(II) mixed ligand complexesAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 10 2009G. J. Kharadi Abstract The antibiotic agent clioquinol is well known for its drug design and coordinating ability towards metal ions. Copper(II) mixed-ligand complexes of clioquinol with various uninegative bidentate ligands were prepared. The structure of the synthesized complexes was characterized using elemental analyses, infrared spectra, 1H-NMR spectra, electronic spectra, magnetic measurements, FAB mass spectrum and thermo gravimetric analyses. The kinetic parameters such as order of reaction (n) and the energy of activation (Ea) are reported using the Freeman,Carroll method. The pre-exponential factor (A), the activation entropy (,S#), the activation enthalpy (,H#) and the free energy of activation (,G#) were calculated. Complexes were also screened for their in vitro antibacterial activity against a range of Gram-positive and Gram-negative bacteria in order to set the precursors for anti-tumourigenic agent. Copyright © 2009 John Wiley & Sons, Ltd. [source] Thermal Behavior and Non-isothermal Decomposition Reaction Kinetics of NEPE Propellant with Ammonium DinitramideCHINESE JOURNAL OF CHEMISTRY, Issue 5 2010Weiqiang Pang Abstract Thermal decomposition behavior and non-isothermal decomposition reaction kinetics of nitrate ester plasticized polyether NEPE propellant containing ammonium dinitramide (ADN), which is one of the most important high energetic materials, were investigated by DSC, TG and DTG at 0.1 MPa. The results show that there are four exothermic peaks on DTG curves and four mass loss stages on TG curves at a heating rate of 2.5 K·min,1 under 0.1 MPa, and nitric ester evaporates and decomposes in the first stage, ADN decomposes in the second stage, nitrocellulose and cyclotrimethylenetrinitramine (RDX) decompose in the third stage, and ammonium perchlorate decomposes in the fourth stage. It was also found that the thermal decomposition processes of the NEPE propellant with ADN mainly have two mass loss stages with an increase in the heating rate, that is the result of the decomposition heats of the first two processes overlap each other and the mass content of ammonium perchlorate is very little which is not displayed in the fourth stage at the heating rate of 5, 10, and 20 K·min,1 probably. It was to be found that the exothermal peak temperatures increased with an increase in the heating rate. The reaction mechanism was random nucleation and then growth, and the process can be classified as chemical reaction. The kinetic equations of the main exothermal decomposition reaction can be expressed as: d,/dt=1012.77(3/2)(1,,)[,ln(1,,)]1/3 e,1.723×104/T. The critical temperatures of the thermal explosion (Tbe and Tbp) obtained from the onset temperature (Te) and the peak temperature (Tp) on the condition of ,,0 are 461.41 and 458.02 K, respectively. Activation entropy (,S,), activation enthalpy (,H,), and Gibbs free energy (,G,) of the decomposition reaction are ,7.02 J·mol,1·K,1, 126.19 kJ·mol,1, and 129.31 kJ·mol,1, respectively. [source] | |||||||||||||