Polymer Structure and the Compensation Effect of the Diffusion Pre-Exponential Factor and Activation Energy of a Permeating Solute

2007 ◽  
Vol 111 (11) ◽  
pp. 2828-2835 ◽  
Author(s):  
Ju-Meng Zheng ◽  
Jun Qiu ◽  
Luis M. Madeira ◽  
Adélio Mendes
Keyword(s):  
Activation Energy ◽  
Compensation Effect ◽  
Polymer Structure ◽  
Exponential Factor

On the Possibility to Observe a Compensation Effect around the Glass Transition Temperature

2006 ◽  
Vol 514-516 ◽  
pp. 1462-1466
Author(s):  
Rodica M. Neagu ◽  
José N. Marat-Mendes ◽  
Eugen R. Neagu
Keyword(s):  
Activation Energy ◽  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Compensation Effect ◽  
Depolarization Current ◽  
Exponential Factor ◽  
Relaxation Parameters ◽  
Maximum Current ◽  
Thermally Stimulated Depolarization

Compensation has been reported for the relaxation parameters: the activation energy W and the pre-exponential factor τ0, determined from the Thermal Sampling of Thermally Stimulated Depolarization Current technique. Below the glass transition it is assumed that the relaxation time follows an Arrhenius equation. In the vicinity of glass transition temperature an experimental thermogram may be analyzed using the Vogel-Fulcher-Tamman-Hesse (VFTH) or the Williams- Landel -Ferry equation. In this article we use the VFTH relationship to study the compensation effect in the range of glass transition. For an elementary peak obtained by TS there is a relationship between the activation energy W, the temperature of the maximum current Tm, the VFTH temperature, the compensation temperature Tc and the compensation time τ c. We employ this relationship for a basic analysis of the compensation effect in the temperature range around Tg. By numerical simulations, and assuming parameters similar to those measured experimentally, we show that it is possible to observe a compensation point in some well defined conditions

scholarly journals Thermodynamic model and kinetic compensation effect of oil sludge pyrolysis based on thermogravimetric analysis

2020 ◽  
pp. 350-350
Author(s):  
Hui Liu ◽  
Chenglang Xiang ◽  
Jie Mu ◽  
Jieyu Yao ◽  
Dong Ye ◽  
...  
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Compensation Effect ◽  
Thermodynamic Characteristics ◽  
Oil Sludge ◽  
High Heating Rate ◽  
Thermodynamic Models ◽  
Heating Rates ◽  
Kinetic Compensation Effect ◽  
Exponential Factor

Oil sludge (OS) is an organic solid waste in the petrochemical industry and improper treatment of OS will cause environmental pollution. Pyrolysis is an effective way to realize its resource reuse. In order to understand the pyrolysis behavior and thermodynamic characteristics of OS, four OS samples from storage tanks were used as the research object, and pyrolysis experiments were carried out at heating rates of 5, 10, and 15?/min under a nitrogen atmosphere. The kinetic parameters of pyrolysis of OS are calculated by three equal conversion methods (Friedman method (FR), Flynn-Wall-Ozawa method (FWO) and Distributed activation energy model (DAEM)), and the most possible thermodynamic models for the main pyrolysis phase were analyzed and discussed by introducing the Malek method. The results show: High heating rate can promote the pyrolysis of OS; In the pyrolysis stage, the apparent activation energy increases with the increase of the conversion rate. The apparent activation energy calculated by the FR method is more reliable. The average apparent activation energies of the four OS are 221.23, 84.71, 94.67 and 116.56 kJ/mol, respectively. The apparent activation energy and the pre-exponential factor are positively correlated, indicating that there is a kinetic compensation effect in the pyrolysis process. The thermodynamic models of the four OS samples are all three-dimensional diffusion models, but their integral functions are different. The research results can provide theoretical support for the industrialization, harmlessness and resource utilization of OS pyrolysis.

Thermal and kinetic behaviors of corn stover and polyethylene in catalytic co-pyrolysis

BioResources ◽  
2018 ◽  
Vol 13 (2) ◽  
pp. 4102-4117
Author(s):  
Shaoqing Wang ◽  
Xiaona Lin ◽  
Zhihe Li ◽  
Weiming Yi ◽  
Xueyuan Bai
Keyword(s):  
Activation Energy ◽  
Corn Stover ◽  
Compensation Effect ◽  
Kinetic Studies ◽  
Order Reaction ◽  
Kinetic Compensation Effect ◽  
Exponential Factor ◽  
First Order ◽  
Thermogravimetric Data ◽  
Kinetics Of

Thermal decomposition characteristics and kinetics of high-density polyethylene (HDPE), corn stover (CS), and their blended mixture (1:1 w/w ratio) during non-catalytic and catalytic co-pyrolysis were studied via thermogravimetric analysis (TGA). The results indicated synergetic interactions between the biomass and the plastics during co-pyrolysis as measured by weight loss (ΔW); this effect was attributed to radical interactions during co-pyrolysis. The pyrolysis catalysts with higher nickel loadings (5%, 10%, and 15%) appreciably diminished the solid residue. Kinetic studies indicated that the pyrolysis was a first-order reaction based on the fitted thermogravimetric data. The activation energy (E) and pre-exponential factor (A) ranged between 26.13 kJ/mol to 392.67 kJ/mol and between 156.24 min-1 to 9.19 x 1023 min-1, respectively. There was a kinetic compensation effect (KCE) observed among the two kinetic parameters. The activation energy (E) decreased for each pyrolysis stage with the presence of a catalyst. The results indicated that catalytic co-pyrolysis could provide great potential for reducing the pyrolysis energy input.

Microscopic Interpretation of Arrhenius Parameters

2018 ◽  
Author(s):  
Niels Engholm Henriksen ◽  
Flemming Yssing Hansen
Keyword(s):  
Activation Energy ◽  
Transition State ◽  
Transition State Theory ◽  
Average Energy ◽  
Zero Point ◽  
State Theory ◽  
Exponential Factor ◽  
Quantum Tunnelling ◽  
Microscopic Interpretation ◽  
The Difference

This chapter reviews the microscopic interpretation of the pre-exponential factor and the activation energy in rate constant expressions of the Arrhenius form. The pre-exponential factor of apparent unimolecular reactions is, roughly, expected to be of the order of a vibrational frequency, whereas the pre-exponential factor of bimolecular reactions, roughly, is related to the number of collisions per unit time and per unit volume. The activation energy of an elementary reaction can be interpreted as the average energy of the molecules that react minus the average energy of the reactants. Specializing to conventional transition-state theory, the activation energy is related to the classical barrier height of the potential energy surface plus the difference in zero-point energies and average internal energies between the activated complex and the reactants. When quantum tunnelling is included in transition-state theory, the activation energy is reduced, compared to the interpretation given in conventional transition-state theory.

Physicochemical Characterization and Pyrolysis Kinetic Study of Sugarcane Bagasse Using Thermogravimetric Analysis

2016 ◽  
Vol 138 (5) ◽  
Author(s):  
Anil Kumar Varma ◽  
Prasenjit Mondal
Keyword(s):  
Activation Energy ◽  
Sugarcane Bagasse ◽  
Physicochemical Characterization ◽  
Maximum Error ◽  
Proximate Analysis ◽  
Pyrolysis Kinetics ◽  
Exponential Factor ◽  
Physiochemical Properties ◽  
Model Free ◽  
Complex Process

The present study was conducted to investigate the physicochemical properties and pyrolysis kinetics of sugarcane bagasse (SB). The physiochemical properties of SB were determined to examine its potential for pyrolysis. The physiochemical properties such as proximate analysis, ultimate analysis, heating values, lignocellulosic composition, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) of SB were investigated. The pyrolysis experiments were conducted in a nonisothermal thermogravimetric analyzer (TGA) to understand the thermal degradation behavior of SB. The activation energy (Ea) of SB pyrolysis was calculated by model-free Kissinger–Akahira–Sunose (KAS) and Ozawa–Flynn–Wall (OFW) methods. Average values of activation energy determined through KAS and OFW methods are found as 91.64 kJ/mol and 104.43 kJ/mol, respectively. Variation in the activation energy with degree of conversion was observed, which shows that pyrolysis is a complex process composed of several reactions. Coats–Redfern method was used to calculate the pre-exponential factor and reaction order. Conversion of SB due to heat treatment computed by using the kinetic parameters is found to be in good agreement with the experimental conversion data, and the maximum error limit between the experimental and predicted conversions is 8.5% for 5 °C/min, 6.0% for 10 °C/min, and 11.6% for 20 °C/min. The current investigation proves the suitability of SB as a potential feedstock for pyrolysis.

Isotope Exchange of Gaseous Oxygen with Oxide LaMno3+δ Nanograins Boundary

2010 ◽  
Vol 297-301 ◽  
pp. 1301-1305
Author(s):  
Anatoly Yakovlevich Fishman ◽  
Tatiana Eugenievna Kurennykh ◽  
Vladimir Borisovich Vykhodets ◽  
V.B. Vykhodets
Keyword(s):  
Activation Energy ◽  
Exchange Rate ◽  
Isotope Exchange ◽  
Shock Wave Loading ◽  
Wave Loading ◽  
Gaseous Oxygen ◽  
Exponential Factor ◽  
Significant Difference ◽  
Exponential Factors ◽  
Arrhenius Expression

Isotope exchange of oxygen 18О2 with the boundary of nanograins of oxide LaMnO3+ obtained by the method of shock-wave loading was investigated in the temperature range of 400 – 500 °C. It was established that the temperature dependence of the isotope exchange rate is described by the Arrhenius expression, the activation energy and the pre-exponential factor being 1.67 eV and 1.8∙102 cm/s, respectively. Comparison with literature data has shown that for oxide LaMnO3+, a significant difference in activation energies and pre-exponential factors is observed for the isotope exchange rate with a ‘defect-free’ surface and the nanograin boundary. In case of the boundary, these parameters were higher: the activation energy about two times, and the pre-exponential factor, by almost 7 orders of magnitude.

Mechanisms and kinetics of initial pyrolysis and combustion reactions of 1,1-diamino-2,2-dinitroethylene from density functional tight-binding molecular dynamics simulations

2019 ◽  
Vol 97 (11) ◽  
pp. 795-804 ◽  
Author(s):  
Dong Xiang ◽  
Weihua Zhu
Keyword(s):  
Activation Energy ◽  
Molecular Dynamics ◽  
Density Functional ◽  
Tight Binding ◽  
Combustion Process ◽  
Exponential Factor ◽  
Three Stages ◽  
Dynamics Simulations ◽  
Combustion Processes ◽  
Kinetics Of

The density functional tight-binding molecular dynamics approach was used to study the mechanisms and kinetics of initial pyrolysis and combustion reactions of isolated and multi-molecular FOX-7. Based on the thermal cleavage of bridge bonds, the pyrolysis process of FOX-7 can be divided into three stages. However, the combustion process can be divided into five decomposition stages, which is much more complex than the pyrolysis reactions. The vibrations in the mean temperature contain nodes signifying the formation of new products and thereby the transitions between the various stages in the pyrolysis and combustion processes. Activation energy and pre-exponential factor for the pyrolysis and combustion reactions of FOX-7 were obtained from the kinetic analysis. It is found that the activation energy of its pyrolysis and combustion reactions are very low, making both take place fast. Our simulations provide the first atomic-level look at the full dynamics of the complicated pyrolysis and combustion process of FOX-7.

scholarly journals KINETICS OF PALM OIL TRANSESTERIFICATION IN METHANOL WITH POTASSIUM HYDROXIDE AS A CATALYST

2010 ◽  
Vol 8 (2) ◽  
pp. 219-225
Author(s):  
Yoeswono Yoeswono ◽  
Triyono Triyono ◽  
Iqmal Tahir
Keyword(s):  
Activation Energy ◽  
Palm Oil ◽  
Rate Constants ◽  
Potassium Hydroxide ◽  
Catalyst Concentration ◽  
Time Interval ◽  
Pseudo First Order Reaction ◽  
Exponential Factor ◽  
Potassium Methoxide ◽  
First Order

A study on palm oil transesterification to evaluate the effect of some parameters in the reaction on the reaction kinetics has been carried out. Transesterification was started by preparing potassium methoxide from potassium hydroxide and methanol and then mixed it with the palm oil. An aliquot was taken at certain time interval during transesterification and poured into test tube filled with distilled water to stop the reaction immediately. The oil phase that separated from the glycerol phase by centrifugation was analyzed by 1H-NMR spectrometer to determine the percentage of methyl ester conversion. Temperature and catalyst concentration were varied in order to determine the reaction rate constants, activation energies, pre-exponential factors, and effective collisions. The results showed that palm oil transesterification in methanol with 0.5 and 1 % w/w KOH/palm oil catalyst concentration appeared to follow pseudo-first order reaction. The rate constants increase with temperature. After 13 min of reaction, More methyl esters were formed using KOH 1 % than using 0.5 % w/w KOH/palm oil catalyst concentration. The activation energy (Ea) and pre-exponential factor (A) for reaction using 1 % w/w KOH was lower than those using 0.5 % w/w KOH.   Keywords: palm oil, transesterification, catalyst, first order kinetics, activation energy, pre-exponential factor

Grain Boundary Migration and Compensation Effect

2007 ◽  
Vol 550 ◽  
pp. 387-392
Author(s):  
Pavel Lejček
Keyword(s):  
Grain Boundary ◽  
Grain Boundaries ◽  
Compensation Effect ◽  
Activation Enthalpy ◽  
Boundary Migration ◽  
Grain Boundary Migration ◽  
Boundary Motion ◽  
Exponential Factor ◽  
Grain Boundary Motion

Anisotropy of grain boundary motion in a Fe–6at.%Si alloy is represented by a spectrum of values of the activation enthalpy of migration and the pre-exponential factor, depending on the orientation of individual grain boundaries. The general plot of these values exhibits a pronounced linear interdependence called the compensation effect. It is shown that changes of these values, caused by changes of intensive variables, are thermodynamically consistent.

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