scholarly journals Activation Energy Determination in Case of Independent Complex Kinetic Processes

Processes ◽  
2019 ◽  
Vol 7 (10) ◽  
pp. 738 ◽  
Author(s):  
Luciano ◽  
Svoboda

Theoretically simulated kinetic data were used to evaluate the performance of the most common isoconversional methods of kinetic analysis in complex-process scenarios with two independent overlapping processes exhibiting nucleation-growth kinetics, and further expand the conclusions for the autocatalytic kinetic processes with positive asymmetry. In close-to-real-life situations all the integral isoconversional methods provided practically indistinguishable E-α outcomes. The Friedman and incremental modified Vyazovkin methods results in significant over- and undershoots. However, the combined utilization of the integral and differential isoconversional methods was demonstrated to greatly contribute to the interpretation of the E-α dependences and estimation of E1 and E2—the conceptual evaluation involving positions of inflection points and plateaus is introduced. The influence of the range of applied heating rates q+ on the course of E-α dependences was studied. In this regard, the performance of the isoconversional methods changes significantly with both, the consistence of the shape of the complex kinetic curve and weighted presence of full overlaps of the involved sub-processes.

Energies ◽  
2021 ◽  
Vol 14 (13) ◽  
pp. 3796
Author(s):  
Mudassar Azam ◽  
Asma Ashraf ◽  
Saman Setoodeh Setoodeh Jahromy ◽  
Sajjad Miran ◽  
Nadeem Raza ◽  
...  

In connection to present energy demand and waste management crisis in Pakistan, refuse-derived fuel (RDF) is gaining importance as a potential co-fuel for existing coal fired power plants. This research focuses on the co-combustion of low-quality local coal with RDF as a mean to reduce environmental issues in terms of waste management strategy. The combustion characteristics and kinetics of coal, RDF, and their blends were experimentally investigated in a micro-thermal gravimetric analyzer at four heating rates of 10, 20, 30, and 40 °C/min to ramp the temperature from 25 to 1000 °C. The mass percentages of RDF in the coal blends were 10%, 20%, 30%, and 40%, respectively. The results show that as the RDF in blends increases, the reactivity of the blends increases, resulting in lower ignition temperatures and a shift in peak and burnout temperatures to a lower temperature zone. This indicates that there was certain interaction during the combustion process of coal and RDF. The activation energies of the samples were calculated using kinetic analysis based on Kissinger–Akahira–Sunnose (KAS) and Flynn–Wall–Ozawa (FWO), isoconversional methods. Both of the methods have produced closer results with average activation energy between 95–121 kJ/mol. With a 30% refuse-derived fuel proportion, the average activation energy of blends hit a minimum value of 95 kJ/mol by KAS method and 103 kJ/mol by FWO method.


2017 ◽  
Vol 898 ◽  
pp. 657-665
Author(s):  
Dao Zhang ◽  
Wang Shu Lu ◽  
Xiao Yan Wang ◽  
Sen Yang

The non-isothermal crystallization kinetics of Mg61Zn35Ca4 glassy alloy prepared via melt-spinning were studied by using isoconversion method. The crystalline characterization of Mg61Zn35Ca4 was examined by X-ray diffraction. Different scanning calorimeter was used to investigate the non-isothermal crystallization kinetics at different heating rates (3-60 K/min). The calculated value of Avrami exponent obtained by Matusita method indicated that the crystalline transformation for Mg61Zn35Ca4 is a complex process of nucleation and growth. The Kissinger-Akahira-Sunose method was used to investigate the activation energy. The activation energy of crystallization varies with the extent of crystallization and hence with temperature. The Sestak-Berggren model was used to describe the non-isothermal crystallization kinetics.


2016 ◽  
Vol 78 (8-3) ◽  
Author(s):  
Olagoke Oladokun ◽  
Arshad Ahmad ◽  
Tuan Amran Tuan Abdullah ◽  
Bemgba Bevan Nyakuma ◽  
Syie Luing Wong

This study is the first attempt at investigating the solid state decomposition and the devolatilization kinetics of Imperata cylindrica (lalang) grass termed the “farmer’s nightmare weed” as a potential solid biofuel of the future. Biomass conversion technologies such as pyrolysis and gasification can be utilized for future green energy needs. However an important step in the efficient utilization and process optimizing of biomass conversion processes is understanding the thermal decomposition kinetics of the feedstock. Consequently, thermogravimetric analysis (TGA) of Imperata cylindrica was carried out in the temperature range of 30-1000 °C at four heating rates of 5, 10, 15, and 20 K min-1 using Nitrogen at a flow rate of 20 L min-1 as purge gas. Using the TGA results, the kinetic parameters activation energy (Ea) and pre-exponential frequency factor (ko) of the grass were estimated via the model free or isoconversional methods of Kissinger and Starink. The results obtained for Kissinger model were 151.36 kJ moI-1 and 5.83 x 109 min-1 for activation energy and pre-exponential frequency factor respectively. However, Starink model activation energy and pre-exponential frequency factor were a function of conversion (α) with average values of 159.93 kJ mol-1 and 6.33 x 1022 min-1 respectively. 


2018 ◽  
Vol 28 ◽  
pp. 75-89
Author(s):  
Hamid Reza Javadinejad ◽  
Sayed Ahmad Hosseini ◽  
Mohsen Saboktakin Rizi ◽  
Eiman Aghababaei ◽  
Hossein Naseri

The kinetic study for the synthesis of Fluorapatite has been done using the thermogravimetric technique under non-isothermal conditions and at four heating rates of 5, 10, 15 and 20 °C. Both model free and model-fitting methods were used to investigate kinetic parameters. Calcium oxide, phosphorus pentoxide and calcium fluoride were used as the precursor materials. The activation energy values were calculated through model-fitting and isoconversional methods and were used to predict the reaction model and pre-exponential factor. In this case several techniques were considered such as master plots and compensation effects. The results indicated that the reaction mechanism was chemically controlled with second and third order reaction models in the whole range of conversion which the activation energy varied from 25 to 43 kJ/mol.


2014 ◽  
Vol 881-883 ◽  
pp. 726-733
Author(s):  
Gui Ying Xu ◽  
Jiang Bo Wang ◽  
Ling Ping Guo ◽  
Guo Gang Sun

TG analysis was used to investigate the thermal decomposition of switchgrass, which is a potential gasification feedstock. 10 mg switchgrass sample with the particles between 0.45 and 0.70 mm was linearly heated to 873 K at heating rates of 10, 20, 30 K/min, respectively, under high-purity nitrogen. The Kissinger method and three isoconversional methods including Friedman, Flynn-wall-Ozawa, Vyazovkin and Lenikeocink methods were used to estimate the apparent activation energy of switchgrass. With the three isoconversional methods, it can be concluded that the activation energy increases with increasing conversion. The four model free methods reveal activation energies in the range of 70-460 kJ/mol. These activation energy values provide the basic data for the thermo-chemical utilization of the switchgrass.


2011 ◽  
Vol 65 (6) ◽  
pp. 717-726 ◽  
Author(s):  
Mladjan Popovic ◽  
Jaroslava Budinski-Simendic ◽  
Mirjana Jovicic ◽  
Joszef Mursics ◽  
Milanka Djiporovic-Momcilovic ◽  
...  

Differential scanning calorimetry (DSC) was used to evaluate the curing kinetics of two commercial urea-formaldehyde (UF) adhesives having different formaldehyde to urea (F/U) ratio of 1.112 (UF1) and 1.086 (UF2). DSC measurements were done in dynamic scanning regime with heating rates of 5, 10, 15 and 20?C?min-1 in order to determine the activation energy for each adhesive. Obtained data were analyzed using isoconversional methods with application of Ozawa-Flynn-Wall and Kissinger-Akahira-Sunose kinetic models. In addition, different catalyst levels were tested at the heating rate of 10?C/min. Results showed that the adhesive with higher F/U ratio achieved higher activation energy, while having lower peak temperature of curing reaction. It was also noticed that the increase of catalyst level influenced the increase of reaction enthalpy of the adhesive with lower F/U ratio.


Nanomaterials ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 1990
Author(s):  
Maryam Jouyandeh ◽  
Vahideh Akbari ◽  
Seyed Mohammad Reza Paran ◽  
Sébastien Livi ◽  
Luanda Lins ◽  
...  

We synthesized pristine mica (Mica) and N-octadecyl-N’-octadecyl imidazolium iodide (IM) modified mica (Mica-IM), characterized it, and applied it at 0.1–5.0 wt.% loading to prepare epoxy nanocomposites. Dynamic differential scanning calorimetry (DSC) was carried out for the analysis of the cure potential and kinetics of epoxy/Mica and epoxy/Mica-IM curing reaction with amine curing agents at low loading of 0.1 wt.% to avoid particle aggregation. The dimensionless Cure Index (CI) was used for qualitative analysis of epoxy crosslinking in the presence of Mica and Mica-IM, while qualitative cure behavior and kinetics were studied by using isoconversional methods. The results indicated that both Mica and Mica-IM improved the curability of epoxy system from a Poor to Good state when varying the heating rate in the interval of 5–15 °C min−1. The isoconversional methods suggested a lower activation energy for epoxy nanocomposites with respect to the blank epoxy; thus, Mica and Mica-IM improved crosslinking of epoxy. The higher order of autocatalytic reaction for epoxy/Mica-IM was indicative of the role of liquid crystals in the epoxide ring opening. The glass transition temperature for nanocomposites containing Mica and Mica-IM was also lower than the neat epoxy. This means that nanoparticles participated the reaction because of being reactive, which decelerated segmental motion of the epoxy chains. The kinetics of the thermal decomposition were evaluated for the neat and mica incorporated epoxy nanocomposites epoxy with varying Mica and Mica-IM amounts in the system (0.5, 2.0 and 5.0 wt.%) and heating rates. The epoxy/Mica-IM at 2.0 wt.% of nanoparticle showed the highest thermal stability, featured by the maximum value of activation energy devoted to the assigned system. The kinetics of the network formation and network degradation were correlated to demonstrate how molecular-level transformations can be viewed semi-experimentally.


2019 ◽  
Vol 38 (2) ◽  
pp. 202-212 ◽  
Author(s):  
Ghulam Ali ◽  
Jan Nisar ◽  
Munawar Iqbal ◽  
Afzal Shah ◽  
Mazhar Abbas ◽  
...  

Due to a huge increase in polymer production, a tremendous increase in municipal solid waste is observed. Every year the existing landfills for disposal of waste polymers decrease and the effective recycling techniques for waste polymers are getting more and more important. In this work pyrolysis of waste polystyrene was performed in the presence of a laboratory synthesized copper oxide. The samples were pyrolyzed at different heating rates that is, 5°Cmin−1, 10°Cmin−1, 15°Cmin−1 and 20°Cmin−1 in a thermogravimetric analyzer in inert atmosphere using nitrogen. Thermogravimetric data were interpreted using various model fitting (Coats–Redfern) and model free methods (Ozawa–Flynn–Wall, Kissinger–Akahira–Sunose and Friedman). Thermodynamic parameters for the reaction were also determined. The activation energy calculated applying Coats–Redfern, Ozawa–Flynn–Wall, Kissinger–Akahira–Sunose and Friedman models were found in the ranges 105–148.48 kJmol−1, 99.41–140.52 kJmol−1, 103.67–149.15 kJmol−1 and 99.93–141.25 kJmol−1, respectively. The lowest activation energy for polystyrene degradation in the presence of copper oxide indicates the suitability of catalyst for the decomposition reaction to take place at lower temperature. Moreover, the obtained kinetics and thermodynamic parameters would be very helpful in determining the reaction mechanism of the solid waste in a real system.


2010 ◽  
Vol 638-642 ◽  
pp. 1743-1748
Author(s):  
G.J. Chen ◽  
Y.H. Shih ◽  
Jason S.C. Jang ◽  
S.R. Jian ◽  
P.H. Tsai ◽  
...  

In this study,the (FePt)94-xCu6Nbx (x=0, 2.87, 4.52, 5.67) alloy films were prepared by co-sputtering. The effects of Nb addition content and heat treatment on the microstructure and magnetic properties of the polycrystalline FePtCu films are reported. Our previous experiments showed that the ordering temperature of the (FePt)94Cu6 films reduced to 320 °C, which is much lower than that of the FePt alloy. However, the grain growth after heat treatment limited the practical application in recording media. By adding the Nb content in the (FePt)94Cu6 film, the grain sizes of the films can be adjusted from 50 to 18nm, even for the films annealed at temperature as high as 600°C. DSC traces of as-deposited disorder films at different heating rates, to evaluate the crystallization of the order phase, revealed that the addition of Nb enhanced the activation energy of ordering from 87 kJ/mol to 288 kJ/mol for the (FePt)94-xCu6Nbx (x=0 and 2.87, respectively) films. The reduction of the grain size and the corresponding increase in the activation energy of the Fe-Pt-Cu-Nb films might result from the precipitation of the Nb atoms around the ordering FePt phase. The (FePt)94-xCu6Nbx (x=2.87) film showed a coercive force of 13.4 kOe and the magnetization of 687 emu/cc.


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