18 resultados para apparent activation energy


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6 x 8cm(2) electrochromic devices (ECDs) with the configuration K-glass/EC-layer/electrotype/ion-storage (IS) layer/K-glass, have been assembled using Nb2O5:Mo EC layers, a (CeO2)(0.81)-TiO2 IS-layer and a new gelatin electrolyte containing Li+ ions. The structure of the electrolyte is X-ray amorphous. Its ionic conductivity passed by a maximum of 1.5 x 10(-5) S/CM for a lithium concentration of 0.3g/15ml. The value increases with temperature and follows an Arrhenius law with an activation energy of 49.5 kJ/mol. All solid-state devices show a reversible gray coloration, a long-term stability of more than 25,000 switching cycles (+/- 2.0 V/90 s), a transmission change at 550 nm between 60% (bleached state) and 40% (colored state) corresponding to a change of the optical density (Delta OD = 0. 15) with a coloration efficiency increasing from 10cm(2)/C (initial cycle) to 23cm(2)/C (25,000th cycle). (c) 2007 Elsevier B.V. All rights reserved.

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Freestanding castor oil-based polyurethane (PU) film was obtained using spin-coating method. The effect of polyol content was analysed by means of thermally stimulated depolarisation current and AC dielectric measurements techniques. Two relaxation peaks were observed in the temperature range of -40 to 60 degrees C for PU with different polyol contents. The presence of polyol excess provides a shift to lower temperature of the a relaxation and the decrease in the activation energy of the transition in this region might be attributed to the plasticising effect of the polyol. The peak at higher temperature is due to the Maxwell-Wagner-Sillars relaxation, which also shifts in the low temperature direction as the polyol content is increased.

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B3LYP/6-31 + G(d) calculations were employed to investigate the mechanism of the transesterification reaction between a model monoglyceride and the methoxide and ethoxide anions. The gas-phase results reveal that both reactions have essentially the same activation energy (5.9 kcal mol(-1)) for decomposition of the key tetrahedral intermediate. Solvent effects were included by means of both microsolvation and the polarizable continuum solvation model CPCM. Both solvent approaches reduce the activation energy, however, only the microsolvation model is able to introduce some differentiation between methanol and ethanol, yielding a lower activation energy for decomposition of the tetrahedral intermediate in the reaction with methanol (1.1 kcal mol(-1)) than for the corresponding reaction with ethanol (2.8 kcal mol(-1)), in line with experimental evidences. Analysis of the individual energy components within the CPCM approach reveals that electrostatic interactions are the main contribution to stabilization of the transition state. (C) 2009 Elsevier Ltd. All rights reserved.