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Preexponential Factor (preexponential + factor)
Selected AbstractsDesorption kinetics of model polar stratospheric cloud films measured using Fourier Transform Infrared Spectroscopy and Temperature-Programmed DesorptionINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2001Birgit G. Koehler This study combines Fourier transform infrared (FTIR) spectroscopy and temperature-programmed desorption to examine the evaporation kinetics of thin films of crystalline nitric acid hydrates, solid amorphous H2O/HNO3 mixtures, H2O,ice, ice coated with HCl, and solid HNO3. IR spectroscopy measured the thickness of each film as it evaporated, either at constant temperature or during a linear temperature ramp (temperature-programmed infrared, TPIR). Simultaneously, a mass spectrometer measured the rate of evaporation directly by monitoring the evolution of the molecules into the gas phase (temperature-programmed desorption, TPD). Both TPIR and TPD data provide a measurement of the desorption rate and yield the activation energy and preexponential factor for desorption. TPD measurements have the advantage of producing many data points but are subject to interference from experimental difficulties such as uneven heating from the edge of a sample and sample-support as well as pumping-speed limitations. TPIR experiments give clean but fewer data points. Evaporation occurred between 170 and 215 K for the various films. Ice evaporates with an activation energy of 12.9 ± 1 kcal/mol and a preexponential factor of 1 × 1032±1.5 molec/cm2 s, in good agreement with the literature. The beta form of nitric acid trihydrate, ,,NAT, has an Edes of 15.6 ± 2 kcal/mol with log A = 34.3 ± 2.3; the alpha form of nitric acid trihydrate, ,,NAT, is around 17.7 ± 3 kcal/mol with log A = 37.2 ± 4. For nitric acid dihydrate, NAD, Edes is 17.3 ± 2 kcal/mol with log A = 35.9 ± 2.6; for nitric acid monohydrate, NAM, Edes is 13 ± 3 kcal/mol with log A = 31.4 ± 3. The ,,NAT converts to ,,NAT during evaporation, and the amorphous solid H2O/HNO3 mixtures crystallize during evaporation. The barrier to evaporation for pure nitric acid is 14.6 ± 3 kcal/mol with log A = 34.4 ± 3. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 295,309, 2001 [source] Synthesis, characterization, and kinetic of thermal degradation of oligo-2-[(4-bromophenylimino)methyl]phenol and oligomer-metal complexesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2009smet Kaya Abstract Oligo-2-[(4-bromophenylimino)methyl]phenol (OBPIMP) was synthesized from the oxidative polycondensation reaction of 2-[(4-bromophenylimino)methyl]phenol (BPIMP) with air and NaOCl oxidants in an aqueous alkaline medium between 50 and 90°C. The yield of OBPIMP was found to be 67 and 88% for air and NaOCl oxidants, respectively. Their structures were confirmed by elemental and spectral such as IR, ultraviolet,visible spectrophotometer (UV,vis), 1H-NMR, and 13C-NMR analyses. The characterization was made by TG-DTA, size exclusion chromatography, and solubility tests. The resulting complexes were characterized by electronic and IR spectral measurements, elemental analysis, AAS, and thermal studies. According to TG analyses, the weight losses of OBPIMP, and oligomer-metal complexes with Co+2, Ni+2, and Cu+2 ions were found to be 93.04%, 59.80%, 74.23%, and 59.30%, respectively, at 1000°C. Kinetic and thermodynamic parameters of these compounds investigated by Coats-Redfern, MacCallum-Tanner, and van Krevelen methods. The values of the apparent activation energies of thermal decomposition (Ea), the reaction order (n), preexponential factor (A), the entropy change (,S*), enthalpy change (,H*), and free energy change (,G*) obtained by earlier-mentioned methods were all good in agreement with each other. It was found that the thermal stabilities of the complexes follow the order Cu(II) > Co(II) > Ni(II). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Electrical Properties of Gadolinium,Europium Zirconate CeramicsJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 4 2010Xiao-Liang Xia (Gd1,xEux)2Zr2O7 (0,x,1.0) ceramics are prepared via a solid-state reaction process at 1973 K for 10 h in air. (Gd1,xEux)2Zr2O7 (0.2,x,1.0) ceramics exhibit an ordered pyrochlore-type structure; however, Gd2Zr2O7 has a disordered defect fluorite-type structure. Raman spectroscopy analysis indicates that the degree of structural ordering increases with the increase of Eu content. The electrical properties of (Gd1,xEux)2Zr2O7 ceramics are investigated using complex impedance spectroscopy over a frequency range of 0.1 Hz to 20 MHz from 623 to 923 K. Electrical conductivity obeys the Arrhenius equation. Both the activation energy and the preexponential factor for grain conductivity decrease with increasing europium content from Gd2Zr2O7 (x=0) to Eu2Zr2O7 (x=1.0). The measured electrical conductivity of (Gd1,xEux)2Zr2O7 ceramics increases with increasing Eu content and temperature. Electrical conductivity of the pyrochlore-type materials is higher than that of the defect fluorite-type material in (Gd1,xEux)2Zr2O7 solid solution systems. The electrical conductivity of (Gd0.4Eu0.6)2Zr2O7 is almost independent of oxygen partial pressure from 1.0 × 10,4 to 1.0 atm. The high ionic transference number of (Gd0.4Eu0.6)2Zr2O7 ceramic at different temperatures proves that conduction is purely ionic with negligible electronic contribution. [source] Catalytic cracking, dehydrogenation, and aromatization of isobutane over Ga/HZSM-5 and Zn/HZSM-5 at low pressuresINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2002Yanping Sun Isobutane cracking, dehydrogenation, and aromatization over Ga/HZSM-5 and Zn/HZSM-5 has been investigated in a Knudsen cell reactor and the kinetics of the primary reaction steps for isobutene and propene formation have been accurately determined. Although cracking is the dominant reaction channel, with propene and methane being primary products, methane formation is significantly less than propene formation. This indicates that a proportion of the cracking proceeds via Lewis acid attack at CC bonds, and not just via alkanium ion formation at Bronsted acid sites. This is particularly apparent over Zn/HZSM-5. Intrinsic rate constants for cracking, calculated from the rate of propene formation, are and for dehydrogenation, calculated from the rate of isobutene formation, are Large preexponential factors for cracking and dehydrogenation over Ga/HZSM-5 indicate that either the coverage of active sites is significantly less than the coverage of exposed sites or the intrinsic reaction step involves a large entropy change between reactant and transition state. For Zn/HZSM-5 the small preexponential factors suggest either small entropy changes during activation, perhaps initiated by Lewis acid sites, or a steady-state distribution of active and exposed sites is rapidly reached. Differences in intrinsic activation energies may reflect the ratio of Lewis and Bronsted acid sites on the respective catalyst surfaces. Aromatization is more prolific over Ga/HZSM-5 than over Zn/HZSM-5 under the low-pressure conditions. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 467,480, 2002 [source] | ||||||||||