Search results for "Arrhenius"
showing 10 items of 99 documents
Plastic yielding of glass in high-pressure torsion apparatus
2018
International audience; Hardness measurements performed at room temperature have demonstrated that glass can flow under elevated pressure, whereas the effect of high pressure on glass rheology remains poorly quantified. Here, we applied a high-pressure torsion (HPT) apparatus to deform SCHOTT SF6 â glass and attempted to quantify the effect of pressure and temperature on the shear deformation of glass subjected to pressures from 0.3 GPa to 7 GPa and temperatures from 25 ℃ to 496 ℃. Results show that the plastic yield deformation was occurring during the HPT experiments on the SF6 glass at elevated temperature from 350 ℃ to 496 ℃. The yield stress of SF6 glass decreases with increasing tempe…
Thermokinetic Investigation of the Drying Conditions on Amorphous Calcium Phosphate
2017
The present work investigated dried calcium phosphate powders which still retain an amorphous or poorly crystalline structure under a variety of conditions. In previous studies, freeze-drying was found to be the optimum drying condition. However, several publications, as well as our previous studies, have shown that calcium phosphate amorphous, or a poorly crystalline structure, can retain their structure even if the samples are dried immediately after synthesis up to 200°C. In our study, we used the thermokinetic studies FTIR and XRD and showed that the samples are amorphous, or poorly crystalline, but were unable to answer the questions: Is there a difference between the differently dried…
Stability of vacuolar betaxanthin pigments in juices from Moroccan yellow Opuntia ficus indica fruits
2008
Pigment stability of yellow juices prepared from Moroccan cactus pear (Opuntia ficus indica) was determined as a function of temperature and pH. The experiments were carried out at temperatures ranging from 80 to 100 °C with juices at pH 3.5, 5 and 6.5. The degree of pigment retention decreased when the temperature increased. The degradation constant rates were determined for thermal degradation rates of pseudo-first order. The Arrhenius plot obtained for the degradation of betaxanthin from the yellow fruits was not linear. Regardless of the temperature treatment, the lowest degradation was obtained for pH 5. Where some stabilizers were tested for the protection of pigments, the results sho…
Correlation spectroscopy in molten and supercooled antimony trichloride.
1990
Correlation spectroscopy measurements performed on molten and supercooled antimony trichloride with the homodyne technique show correlation functions that have a nonexponential behavior. Two well-defined distributions of correlation times can be observed in different temporal regions. This behavior is discussed in terms of a structural relaxation of clusters dynamically formed by intermolecular and interchain bonds. The Arrhenius plot of these correlation times shows a linear behavior with the same activation energy for both. In contrast, the activation energy of shear viscosity has a different value, showing that the processes determining the temperature behavior of \ensuremath{\tau} and $…
Rational enantioselective design of chiral heterobimetallic single-chain magnets: synthesis, crystal structures and magnetic properties of oxamato-br…
2011
A new series of neutral oxamato-bridged M(II)Cu(II) chiral chains of general formula [MCuL(x)(S)(m)(H(2)O)(n)]·aS·bH(2)O [L(1)=(M)-1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (1a) and Co (1b); L(2)=(P)-1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (2a) and Co (2b)] and the analogous racemic chains of formula [MCuL(3)(S)(m)(H(2)O)(n)]·aS·bH(2)O [L(3)=1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (3a) and Co (3b)] have been prepared by reaction of the corresponding dianionic oxamatocopper(II) complex [Cu(L(x))](2-) with Mn(2+) or Co(2+) cations in either dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). Solid circular dichroism (CD) spectra of the bimetallic chain compounds were reco…
Coligand Effects on the Field-Induced Double Slow Magnetic Relaxation in Six-Coordinate Cobalt(II) Single-Ion Magnets (SIMs) with Positive Magnetic A…
2019
Two mononuclear cobalt(II) compounds of formula [Co(dmphen)2(OOCPh)]ClO4·1/2H2O·1/2CH3OH (1) and [Co(dmbipy)2(OOCPh)]ClO4 (2) (dmphen = 2,9-dimethyl-1,10-phenanthroline, dmbipy = 6,6'-dimethyl-2,2'-bipyridine and HOOCPh = benzoic acid) are prepared and magnetostructurally investigated. Each cobalt(II) ion is six-coordinate with a distorted octahedral CoN4O2 environment. The complex cations are interlinked leading to supramolecular chains (1) and pairs (2) that grow along the crystallographic c-axis with racemic mixtures of (Δ,Λ)-Co units. FIRMS allowed us to directly measure the zero-field splitting between the two lowest Kramers doublets, which led to axial anisotropy values of 58.3 cm-1 ≤…
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…