An innovative reaction model determination methodology in solid state kinetics based on variable activation energy

2014 ◽  
Vol 585 ◽  
pp. 25-35 ◽  
Author(s):  
Muhammad Azeem Arshad ◽  
Abdel-Karim Maaroufi
Keyword(s):  
Activation Energy ◽  
Solid State ◽  
Reaction Model ◽  
Solid State Kinetics ◽  
Model Determination ◽  
Variable Activation Energy

Evaluation of Kinetic Parameter Calculation Methods for Non-Isothermal Experiments in Case of Varying Activation Energy in Solid-State Transformations / Neizotermisko Eksperimentu Kinētisko Parametru Noteikšanas Metožu Izvērtēšana Mainīgas Aktivācijas Enerģijas Gadījumā Cietfāžu Pārvērtībām

2012 ◽  
Vol 51 (3) ◽  
pp. 209-227 ◽  
Author(s):  
A. Bērziņš ◽  
A. Actiņš
Keyword(s):  
Activation Energy ◽  
Solid State ◽  
Kinetic Model ◽  
Kinetic Models ◽  
Frequency Factor ◽  
Conversion Degree ◽  
Model Free ◽  
Determination Methods ◽  
Model Determination ◽  
Energy Determination

Simulations of solid-state transformation kinetics were carried out calculating temperature and conversion degree for non-isothermal experiments with different heating rates. Simulations were divided in two parts: with constant and with variable activation energy. Simulations were analyzed with widely used model-based and model-free activation energy determination methods, frequency factor and kinetic model determination methods. Much of the attention was devoted to the calculation of kinetic models and frequency factors, as a more difficult and less developed step. For simulations where activation energy did not change all activation energy determination methods were found to give correct results. However, much attention should be devoted to frequency factor determination, because incorrect results would lead to problems in determination of kinetic models. For simulations where activation energy changes, correct activation energy can be determined only by differential methods or integral methods using numerical integration over small intervals. Isokinetic relationship coefficients b and c were more accurately determined with the average linear integral method. Correct kinetic model determination was possible only when coefficients b and c were accurate, and only by analyzing results of all available methods.

Effect of CeO2 on the reaction kinetics for the formation of Sr0.5Ba0.5CexNb2O6+δ

2003 ◽  
Vol 18 (11) ◽  
pp. 2594-2599 ◽  
Author(s):  
Jyh-Tzong Shiue ◽  
Tsang-Tse Fang
Keyword(s):  
Activation Energy ◽  
Kinetic Equation ◽  
Solid State ◽  
Empirical Model ◽  
Reaction Model ◽  
Heating Rates ◽  
Strontium Barium ◽  
Isothermal Reaction ◽  
Nonisothermal Kinetic ◽  
Different Temperatures

The solid-state reaction of SrNb2O6, BaNb2O6, and CeO2 to form Sr0.5Ba0.5CexNb2O6+δ at different temperatures and heating rates was investigated. A nonisothermal kinetic empirical model was used to evaluate the activation energy and rate constant of Sr0.5Ba0.5CexNb2O6+δ. The values of the activation energy evaluated from the slopes are 762, 800, and 844 kJ/mol, respectively, for S50, 1CeS50, and 2CeS50, which increase with the increase in Ce doping. The order of reaction was found to decrease with the increase of the Ce doping. A kinetic equation was developed based on the parameters evaluated from the nonisothermal reaction model, which was successfully used to predict the isothermal reaction of Ce-doped strontium barium niobate.

Gas Cell Infrared and Attenuated Total Reflection Infrared Spectroscopic Studies for Organic–Inorganic Interactions in Adsorption of Fulvic Acid on the Goethite Surface Generating Carbon Dioxide

2021 ◽  
pp. 000370282199121
Author(s):  
Yuki Nakaya ◽  
Satoru Nakashima ◽  
Takahiro Otsuka
Keyword(s):  
Carbon Dioxide ◽  
Activation Energy ◽  
Fulvic Acid ◽  
Spectroscopic Studies ◽  
Reaction Model ◽  
Total Reflection ◽  
Attenuated Total Reflection ◽  
Gas Cell ◽  
Rate Determining Step ◽  
Ir Spectroscopic

The generation of carbon dioxide (CO2) from Nordic fulvic acid (FA) solution in the presence of goethite (α-FeOOH) was observed in FA–goethite interaction experiments at 25–80 ℃. CO2 generation processes observed by gas cell infrared (IR) spectroscopy indicated two steps: the zeroth order slower CO2 generation from FA solution commonly occurring in the heating experiments of the FA in the presence and absence of goethite (activation energy: 16–19 kJ mol–1), and the first order faster CO2 generation from FA solution with goethite (activation energy: 14 kJ mol–1). This CO2 generation from FA is possibly related to redox reactions between FA and goethite. In situ attenuated total reflection infrared (ATR-IR) spectroscopic measurements indicated rapid increases with time in IR bands due to COOH and COO– of FA on the goethite surface. These are considered to be due to adsorption of FA on the goethite surface possibly driven by electrostatic attraction between the positively charged goethite surface and negatively charged deprotonated carboxylates (COO–) in FA. Changes in concentration of the FA adsorbed on the goethite surface were well reproduced by the second order reaction model giving an activation energy around 13 kJ mol–1. This process was faster than the CO2 generation and was not its rate-determining step. The CO2 generation from FA solution with goethite is faster than the experimental thermal decoloration of stable structures of Nordic FA in our previous report possibly due to partial degradations of redox-sensitive labile structures in FA.

scholarly journals Gas-phase detonation propagation in mixture composition gradients

2012 ◽  
Vol 370 (1960) ◽  
pp. 567-596 ◽  
Author(s):  
D. A. Kessler ◽  
V. N. Gamezo ◽  
E. S. Oran
Keyword(s):  
Activation Energy ◽  
Reaction Model ◽  
Single Step ◽  
Mixture Composition ◽  
Composition Gradient ◽  
Detonation Properties ◽  
High Activation ◽  
Zone Structure ◽  
Detonation Cell ◽  
High Activation Energy

The propagation of detonations through several fuel–air mixtures with spatially varying fuel concentrations is examined numerically. The detonations propagate through two-dimensional channels, inside of which the gradient of mixture composition is oriented normal to the direction of propagation. The simulations are performed using a two-component, single-step reaction model calibrated so that one-dimensional detonation properties of model low- and high-activation-energy mixtures are similar to those observed in a typical hydrocarbon–air mixture. In the low-activation-energy mixture, the reaction zone structure is complex, consisting of curved fuel-lean and fuel-rich detonations near the line of stoichiometry that transition to decoupled shocks and turbulent deflagrations near the channel walls where the mixture is extremely fuel-lean or fuel-rich. Reactants that are not consumed by the leading detonation combine downstream and burn in a diffusion flame. Detonation cells produced by the unstable reaction front vary in size across the channel, growing larger away from the line of stoichiometry. As the size of the channel decreases relative to the size of a detonation cell, the effect of the mixture composition gradient is lessened and cells of similar sizes form. In the high-activation-energy mixture, detonations propagate more slowly as the magnitude of the mixture composition gradient is increased and can be quenched in a large enough gradient.

A kinetic study of mechanochemical halogen bond formation by in situ31P solid-state NMR spectroscopy

2017 ◽  
Vol 53 (71) ◽  
pp. 9930-9933 ◽  
Author(s):  
Yijue Xu ◽  
Lysiane Champion ◽  
Bulat Gabidullin ◽  
David L. Bryce
Keyword(s):  
Activation Energy ◽  
Solid State ◽  
Nmr Spectroscopy ◽  
Kinetic Study ◽  
Solid State Nmr ◽  
Halogen Bond ◽  
Bond Formation ◽  
Nmr Studies ◽  
Solid State Nmr Spectroscopy

In situ 31P solid-state NMR studies of mechanochemical halogen bond formation provide insights into the cocrystallisation process and an estimate of the activation energy.

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