Search results for "equation"

Application of SQMFF Vibrational Calculations to Transition States:  DFT and ab Initio Study of the Kinetics of Methyl Azide and Ethyl Azide Thermoly…

1998

DFT including nonlocal corrections and ab initio calculations at MP2 and MP4 levels of theory have been performed in order to provide information concerning the mechanism of the rate limiting step of the thermal decomposition of methyl azide and ethyl azide. The chemically interesting points of the ground-state potential energy surface have been fully optimized, and a detailed normal-mode analysis for the reagents and the transition states is presented. The well-established scaled quantum mechanical force field method has been used to obtain reliable vibrational frequencies for these molecular structures. The force fields of transition states have been modified by using the scale factors co…

Determination of the glass transition temperature of poly(cyclohexyl acrylate) from oxygen permeability measurements

1993

Abstract The glass transition temperature ( T g ) of poly(cyclohexyl acrylate) (PCA) has been obtained from measurements of the oxygen permeability ( P = 0.60 barrers, T g = 23.5 ± 2.0°C) using a potentiostatic electrochemical sensor, and from the oxygen diffusion coefficient ( D = 0.12 × 10 −8 cm 2 s −1 , T g = 24.0 ± 1.8°C) by the time-lag method. A T g of 25 ± 1°C was found by differential scanning calorimetry and a T g of 25.0 ± 3.5°C was obtained from the specific volume by dilatometry. The fractional free volume ( v f ) at T g is 0.020 ± 0.002, which is slightly below (∼ 20%) most glassy polymers. A linear correlation has been observed between ln D and the reciprocal of v f , which su…

Methyl vinyl ketone+OH and methacrolein+OH oxidation reactions: a master equation analysis of the pressure- and temperature-dependent rate constants.

2006

High-level electronic structure calculations and master equation analyses were carried out to obtain the pressure- and temperature-dependent rate constants of the methyl vinyl ketone+OH and methacrolein+OH reactions. The balance between the OH addition reactions at the high-pressure limit, the OH addition reactions in the fall-off region, and the pressure-independent hydrogen abstractions involved in these multiwell and multichannel systems, has been shown to be crucial to understand the pressure and temperature dependence of each global reaction. In particular, the fall-off region of the OH addition reactions contributes to the inverse temperature dependence of the rate constants in the Ar…

(Bounded) Traveling combustion fronts with degenerate kinetics

2022

Abstract We consider the propagation of a flame front in a solid periodic medium. It is governed by an equation of Hamilton–Jacobi type, whose front’s velocity depends on the temperature via a nonlinear degenerate kinetic rate. The temperature solves a free boundary problem subject to boundary conditions depending on the front’s velocity itself. We show the existence of nonplanar traveling wave solutions which are bounded and global. Previous results by the same authors (cf. Alibaud and Namah, 2017) were obtained for essentially positively lower bounded kinetics or eventually which have some very weak degeneracy. Here we consider very general degenerate kinetics, including for the first tim…

Anomalies in the temperature dependence of the 1.2-? absorption of liquid water

1975

The weakly absorbed 1.2-μ combination band of water was accurately studied as a function of temperature, in both its profile and first derivative, to obtain information on the bulk properties of liquid water. Arrhenius plots of integrated component intensity ratios showed well aligned experimental points, except for a neatly defined break occurring in the 30 to 40°C temperature interval for pure water A similar break, shifted by some 18°C towards lower temperature, was found in the case of 1M NaClO4 aqueous solutions. The breaks are tentatively assumed to result from abrupt though subtle changes involving low-frequency modes. This tentative, assumption appears independent of specific models…

1989

The reaction kinetics for the group transfer polymerization (GTP) of tert-butyl methacrylate (TBMA) using a silyl ketene acetal initiator and a nucleophilic catalyst are investigated. The reaction is shown to be of first order in both monomer and catalyst concentrations. The “livingness” of this system appears to be influenced by the reaction temperature. At temperatures above −20°C, deactivation is observed, with its severity increasing with increasing temperature. This deactivation is attributed to a depletion of catalyst by side reactions. It was demonstrated that reactivation is made possible by the addition of more catalyst. This result is in contrast to the anionic polymerization of T…

Synthesis and structural and ionic conductivity studies of Na2ZrSi4O11

1996

The compound Na 2 ZrSi 4 O 1 1 has been prepared both by solid state synthesis and by the sol-gel technique via alkoxides. The structure of Na 2 ZrSi 4 O 11 was investigated by the Rietveld method using X-ray diffractometer data. The powder diffraction data show evidence for a triclinic distortion of the basic monoclinic structure. The ionic conductivity has been determined in the temperature interval 130-560°C using a.c. impedance measurements. The Na + ion mobility is limited, with E a =1.04 eV and σ(300°C)= 2-9 10 7 S/cm. Samples with Ta partially substituted for Zr, according to the formula Na 2-x (Zr 1-x Ta x )Si 4 O 11 with x ≤0.2, showed the same evidence for a triclinic distortion. …

Diffusion of oxygen in nickel: A variable charge molecular dynamics study

2010

Abstract Variable charge molecular dynamics have been performed to study the diffusion mechanisms of oxygen atoms (O) in nickel (Ni) in the temperature range 950 K–1600 K. It is observed that oxygen does not diffuse via jumps of oxygen through interstitial sites but via a vacancy diffusion mechanism. The oxygen diffusivity can be well described by an Arrhenius law over the temperature range considered. The oxygen diffusion coefficient has been analysed and indicates a value of E a = 1.99 eV for the activation energy and D 0 = 39.2 cm 2 s − 1 for the pre-exponential factor. Our numerical results were compared with a compilation of experimental and theoretical studies, and exhibit a good agre…

Role of vitreous matrix on the optical activity of Ge-doped silica

2003

Abstract We report an experimental study on the relationship between the optical activity of Ge-oxygen deficient centers and dynamic properties and conformational heterogeneity of vitreous matrix in silica. We focus our attention on the absorption band at ∼5.2 eV (B 2β ) and on the two related emissions at ∼4.2 eV (α E ) and at ∼3.1 eV (β). From the temperature dependence of B 2β band we estimate a mean energy value of 26 meV for local vibrational modes coupled to the electronic transition, suggesting that the chromophore and its surrounding have access to low frequency dynamics. From the thermal behavior of the two emissions we distinguish the two competitive relaxation processes from the …

Space charge and induced dipole relaxation in solid electrolytes

1996

The space charge relaxation and induced dipole relaxation in solid electrolytes is discussed. The di-electric responses of these relaxations gives a satisfactory fit to the universal conductivity behaviours in the frequency range from DC to infrared.