The decomposition of some RDX and HMX based materials in the one-dimensional time to explosion apparatus. Part 1. Time to explosion and apparent activation energy

A One-Dimensional Time to Explosion (ODTX) apparatus has been used to study the times to explosion of a number of compositions based on RDX and HMX over a range of contact temperatures. The times to explosion at any given temperature tend to increase from RDX to HMX and with the proportion of HMX in the composition. Thermal ignition theory has been applied to time to explosion data to calculate kinetic parameters. The apparent activation energy for all of the compositions lay between 127 kJ mol−1 and 146 kJ mol−1. There were big differences in the pre-exponential factor and this controlled the time to explosion rather than the activation energy for the process.

Electrocatalytic effect of Pb and Sn adatoms on the oxidation of 1-propanol on platinized platinum electrodes: Determination of the apparent activation energy

The electrocatalytic oxidation of 1-propanol was investigated on platinum electrodes modified by submonolayers of Pb and Sn in acid media. An increase of oxidation rates observed for both Pb and Sn, and the influence of theta values was investigated. The values of the apparent activation energy evaluated from the Arrhenius plots concerning the electrochemical oxidation of 1-propanol on modified platinzed platinum electrodes, reveal a significant decrease in the presence of upd Sn and Ph adatoms. A decrease from 56 to 26 U mol(-1) in the presence of Sn. and from 78 to 25 U mol(-1) for Ph adatoms are some illustrative values which reflect the promoting effect of the upd adatoms.

Correlation Between Apparent Activation Energy and NOx emission of renewable diesel from sugar cane, biodiesel, fossil diesel and their blends

Biofuels and their blends with fossil fuel are important energy resources, which production and application have been largely increased internationally. This study focus on the development of a correlation between apparent activation energy (Ea) and NOx emission of the thermal decomposition of three pure fuels: farnasane (renewable diesel from sugar cane), biodiesel and fossil diesel and their blends. Apparent Activation energy was determined by using thermogravimetry and Model-Free Kinetics. NOx emission was obtained from the European Stationary Cycle (ESC) with OM 926LA CONAMA P7/Euro 5 engine. Results showed that there is a linear correlation between apparent activation energy and NOx emission with R2 of 0,9667 considering pure fuels and their blends which is given as: NOx = 2,2514Ea - 96,309. The average absolute error of this correlation is 2.96% with respect to the measured NOx value. The main advantage of this correlation is its capability to predict NOx emission when either a new pure fuel or a blend of fuels is proposed to use in enginees.

Using apparent activation energy as a reactivity criterion for biomass pyrolysis

The reactivity of chemically isolated lignocellulosic blocks, namely, α-cellulose, holocellulose, and lignin, has been rationalized on the basis of the dependence of the effective activation energy (Eα) upon conversion (α) determined via the popular isoconversional kinetic analysis, Friedman’s method. First of all, a detailed procedure for the thermogravimetric data preparation, kinetic calculation, and uncertainty estimation was implemented. Resulting Eα dependencies obtained for the slow pyrolysis of the extractive-free Eucalyptus grandis isolated α-cellulose and holocellulose remained constant for 0.05 < α < 0.80 and equal to 173 ± 10, 208 ± 11, and 197 ± 118 kJ/mol, thus confirming the single-step nature of pyrolysis. On the other hand, large and significant variations in Eα with α from 174 ± 10 to 322 ± 11 kJ/mol in the region of 0.05 and 0.79 were obtained for the Klason lignin and reported for the first time. The non-monotonic nature of weight loss at low and high conversions had a direct consequence on the confidence levels of Eα. The new experimental and calculation guidelines applied led to more accurate estimates of Eα values than those reported earlier. The increasing Eα dependency trend confirms that lignin is converted into a thermally more stable carbonaceous material.

Strength development of mortars containing ground granulated blast-furnace slag: Effect of curing temperature and determination of apparent activation energies

The strength development of mortars containing ground granulated blast-furnace slag (ggbs) and portland cement was investigated. Variables were the level of ggbs in the binder, water-binder ratio and curing temperature. All mortars gain strength more rapidly at higher temperatures and have a lower calculated ultimate strength. The early age strength is much more sensitive to temperature for higher levels of ground granulated blast-furnace slag. The calculated ultimate strength is affected to a similar degree for all ggbs levels and water-binder ratios, with only the curing temperature having a significant effect. Apparent activation energies were determined according to ASTM C1074 and were found to vary approximately linearly with ggbs level from 34 kJ/mol for portland cement mortars to around 60 kJ/mol for mortars containing 70% ggbs. The water-binder ratio appears to have little or no effect oil the apparent activation energy. (c) 2005 Elsevier Ltd. All rights reserved.

SO2 Saturation of the Room Temperature Ionic Liquid [C(2)mim][NTf2] Much Reduces the Activation Energy for Diffusion

The physical effect of high concentrations of reversibly dissolved SO2 on [C(2)mim][NTf2] was examined using cyclic voltammetry, chronoamperometry, and ESR spectroscopy. Cyclic voltammetry of the oxidation of solutions of ferrocene, N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), and chloride in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethanesufonyl)imide ([C(2)mim][NTf2]) reveals an increase in limiting current of each species corresponding to the addition of increasing concentrations of sulfur dioxide. Quantitative chronoamperometry reveals an increase in each species' diffusion coefficient with SO2 concentration. When chronoamperometric data were obtained for ferrocene in [C(2)mim][NTf2] at a range of temperatures, the translational diffusion activation energy (29.0 +/- 0.5 kJ mol(-1)) was found to be in good agreement with previous studies. Adding SO2 results in apparent near-activationless translational diffusion. A significant decrease in the activation energy of rotational diffusion with the SO2 saturation of a 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) solution in [C(2)mim][NTf2] (29.9 +/- 2.0 to 7.7 +/- 5.3 kJ mol(-1)) was observed using electron spin resonance (ESR) spectroscopy. The reversible physical absorption Of SO2 by [C(2)mim][NTf2] should have no adverse effect on the ability of that ionic liquid to be employed as a solvent in an electrochemical gas sensor, and it is possible that the SO2-mediated reduction of RTIL viscosity could have intrinsic utility.

Determination of diffusion parameters and activation energy of diffusion in V3Si phase with A15 crystal structure

Diffusion such is the integrated diffusion coefficient of the phase, the tracer diffusion coefficient of species at different temperatures and the activation energy for diffusion, are determined in V3Si phase with A15 crystal structure. The tracer diffusion coefficient of Si Was found to be negligible compared to the tracer diffusion coefficient of V. The calculated diffusion parameters will help to validate the theoretical analysis of defect structure of the phase, which plays an important role in the superconductivity.

New temperature fluctuation method for direct determination of thermal activation energy of deep levels in semiconductors

A new method is suggested where the thermal activation energy is measured directly and not as a slope of an Arrhenius plot. The sample temperature T is allowed to fluctuate about a temperature T0. The reverse-biased sample diode is repeatedly pulsed towards zero bias and the transient capacitance C1 at time t1 is measured The activation energy is obtained by monitoring the fluctuations in C1 and T. The method has been used to measure the activation energy of the gold acceptor level in silicon.

Graphical method to include temperature variation of activation energy in Hall data analysis

A graphical method is presented for Hall data analysis, including the temperature variation of activation energy due to screening. This method removes the discrepancies noted in the analysis of recently reported Hall data on Si(In).

Fractional power dependence of rate on activation energy for reactions with very low internal barriers

The dynamics of reactions with low internal barriers are studied both analytically and numerically for two different models. Exact expressions for the average rate,kI, are obtained by solving the associated first passage time problems. Both the average rate constant, kI, and the numerically calculated long-time rate constant, kL, show a fractional power law dependence on the barrier height for very low barriers. The crossover of the reaction dynamics from low to high barrier is investigated.

Interdiffusion and activation energy in Ti3Au phase with A15 crystal structure

The knowledge of diffusion parameters, such as integrated diffusion coefficient and the activation energy for diffusion is important to understand the growth rate of the product phase and the atomic mechanism of diffusion. These parameters are determined in Ti3Au phase with A15 crystal structure. The calculated diffusion parameters will help in validating the theoretical analysis on defect structure of the phase.

Correlation between conductivity or diffusivity and activation energy in amorphous solids

There exist many investigations of ionic transport in a variety of glasses. These studies exhibit strong correlation between ionic conductivity and activation energy: Typically, it is found that higher conductivity is associated with lower activation energies and vice versa. Although there are explanations for this at a phenomenological level, there is no consistent physical picture to explain the correlation between conductivity and activation energy. We have carried out molecular dynamics simulation as a function of the size of the impurity atom or diffusant (both neutral and charged) in a host amorphous matrix. We find that there is a maximum in self-diffusivity as a function of the size of the impurity atom suggesting that there is an appropriate size for which the diffusivity is maximum. The activation energy is found to be the lowest for this size of the impurity. A similar maximum has been previously found in other condensed phases, such as confined fluids and dense liquids, and has its origin in the levitation effect. The implications of this result for understanding ionic conductivity in glasses are discussed. Our results suggest that there is a relation between microscopic structure of the amorphous solid, diffusivity or conductivity, and activation energy. The nature of this relationship is discussed in terms of the levitation parameter showing that diffusivity is maximum when the size of the neck or doorway radius is comparable with the size of the diffusant. Our computational results here are in excellent agreement with independent experimental results of Nascimento et al. [Braz. J. Phys. 35, 626 (2005)] that structural features of the glass are important in determining the ionic conductivity.