Search results for "Activation energy"

Modelling of the cation motions in complex system: case of Na-mordenites

2002

Abstract Semi-empirical inter-atomic potentials and Monte Carlo algorithms are proposed to predict the evolution of the interaction energy between sodium ions and a mordenite type aluminosilicate network as a function of Si/Al ratio. This result is favourably compared with the activation energy barriers for Na + `jumps' responsible for the polarization change, measured by thermally stimulated current (TSC) spectroscopy, for Na-mordenites characterized by Si/Al ratios ranged from 5.5 to 12. Finally, we propose a possible mechanism for the cation motions, which involves activation barriers within the same order of magnitude than those measured by TSC.

Determination of kinetic parameters of redox reactions using CE‐ICP‐MS: A case study for the reduction of Np(V) by hydroxylamine hydrochloride

2018

The rate constants k of the reduction of 5 × 10-5  M Np(V) to Np(IV) by hydroxylamine hydrochloride (HAHCl) in 1 M HCl have been determined by CE-ICP-MS in the temperature range of ϑ = 30-70°C and with varying concentrations of HAHCl from 1 to 7.2 M. The reaction was found to have (pseudo)first order kinetics with respect to HAHCl. The experimental results for k ranged from 0.0029(1) min-1 (ϑ = 40°C, c(HAHCl) = 3 M) to 0.039(7) min-1 (ϑ = 60°C, c(HAHCl) = 7.2 M). The activation energy of the reaction was determined as EA  = (72 ± 10) kJ/mol. These results and a comparison with literature data show that the coupling of CE to ICP-MS provides a powerful analytical tool for the investigation of…

Polaronic relaxation in perovskites

1995

We report a low-temperature loss anomaly in several oxidic perovskites such as ${\mathrm{KTaO}}_{3}$, ${\mathrm{KTaO}}_{3}$:Nb, ${\mathrm{SrTiO}}_{3}$, ${\mathrm{SrTiO}}_{3}$:Ca, ${\mathrm{PbTiO}}_{3}$:La, Cu, and ${\mathrm{BaTiO}}_{3}$:La. We show that this anomaly arises from a low-frequency dielectric relaxation. The activation energy and the relaxation time of this process are nearly the same for all the investigated perovskites disregarding their composition, texture, and ferroelectric properties. We thus ascribe the loss anomaly to the localization of polarons on residual defects. Although the dielectric losses in ${\mathrm{SrTiO}}_{3}$ and ${\mathrm{SrTiO}}_{3}$:Ca are qualitatively …

Mechanism of self-trapped hole motion in corundum crystals

1993

Abstract Atomistic simulations of the self-trapped hole eauilibrium geometry and migration in a pure corundum crystal have been carried out using the semiempirical method of intermedia te neglect of differential overlap and atom-atom potentials, as implemented in the CASCADE code. The activation energies for three different hole-hopping mechanisms are calculated. It is shown that the 60° reorientations of a self-trapped hole and hopping to the nearest O-atom triangle reauire almost the same activation energy, approximately 0.9 eV, which agrees auite well with the experi-mental value for hole migration of 0.7 eV. A new mechanism of small-polaron motion is suggested.

Dielectric investigation of lead‐free perovskite strontium titanate with 25% bismuth ceramics

2009

In this work lead-free 0.75SrTiO3-0.25BiTiO3 ceramics have been investigated in broad frequency range. Obtained results showed pronounced dispersion below room temperature typical for the dipolar glasses. The calculated relaxation time distribution function broadens toward longest relaxation times part on cooling. The obtained most probable relaxation time diverges according to the Vogel-Fulcher relationship with the following parameters: dipole activation energy EA=2123 K, glassy state temperature T0=52.7 K, shortest relaxation time, referring to dipole relaxations at very high temperatures, τ0=2.1·10–14 s. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Annealing of Radiation Defects in X-Irradiated LiBaF3

2002

AbstractResults of application of the glow rate technique GRT for analysis of the activation energy of thermostimulated annealing of X-ray created F-type color centers in LiBaF3 crystals, pure and containing hetero-valence oxygen centers are presented. It is shown that depending on impurity composition in crystal two alternative mechanisms are involved in annealing of color centers. It is proposed that either the anion vacancy governed migration of F- centers resulting in recombination with complementary defects, or the thermal delocalization of radiation created fluorine (Fi) interstitials captured by anti-structure defects followed by recombination with all kinds of complementary F- type …

Kinetics of correlated annealing of radiation defects in alkali halide crystals

1992

Abstract Kinetics of the correlated annealing of pairs of neutral (F-H) Frenkel defects in the KBr crystal is treated theoretically, taking into account defect diffusion, and annihilation at short distances stimulated by an elastic interaction. It is shown that an elastic interaction affects the annealing kinetics and the survival probability of close geminate detects considerably. The widespread description of the correlated annealing in terms of a first-order reaction fails for close defects yielding effective energies which in fact differ essentially from an activation energy of diffusion. Ea, even if it is corrected by an interaction energy. The effect of the initial distribution of def…

On structural phase transitions inn-butylammonium chloroantimonate(III) and chlorobismuthate(III) crystals: x-ray, differential scanning calorimetry,…

1997

Numerous structural phase transitions are detected in new crystals of the n-butylammonium compounds: , and by means of differential scanning calorimetry, dilatometric and dielectric dispersion (1 kHz - 1 MHz) studies. For the transitions the basic thermodynamic data are determined. Interesting dielectric properties are found in a metastable form of the crystals. Debye-like dispersion of the electric permittivity between 30 and 800 MHz is observed around the 310 K phase transition for this crystal. The activation energy of the reorientation of the n-butylammonium cations is found to be 16 kJ . The structure of ( form) has been refined to R = 0.0439 and shows isolated units and two non-equiva…

1H NMR, DSC, dielectric, and dilatometric studies of phase transitions and molecular dynamics in N (C2H5)4SbCl4

1994

The results of dielectric, dilatometric, 1H NMR, and DSC studies on N(C2H5)4SbCl4 crystals are presented. The title compound undergoes two phase transitions at Tc1 = 272 K reversible of first order and at Tc2 = 393 K irreversible. The values of transition entropies and enthalpies are compared with those of other tetraethylammonium halogenoantimonates and bismuthates (III). The spin-lattice relaxation times and the values of the second moments of the 1H NMR line for the N(C2H5)4SbCl4 crystal are measured in the temperature range of 70 to 400 K. Two minima of T1 are observed. They are attributed to CH3 group reorientations. The activation energies for the processes are determined.

1986

The molecular order and mobility of two liquid-crystalline polyacrylates with phenyl benzoate moieties as mesogenic side groups and (CH2)m spacers (m = 2 and m = 6) were investigated by pulsed 2H NMR. The mesogenic side groups were isotopically labelled at the terminal phenylene ring. In the glassy state the orientational distribution function was characterized from the angular dependence of the 2H NMR line shape of samples macroscopically ordered in their nematic phase by the 8,4 T magnetic field of an NMR spectrometer. It was found to be Gaussian with widths of ± 18,5° and ± 10,5° for the m = 2 frozen nematic and m = 6 frozen smectic system, respectively. The phenylene rings undergo 180° …