Thermal decomposition of un-irradiated and γ-ray irradiated holmium acetate tetrahydrate. Part 1: kinetics of nonisothermal dehydration of un-irradiated and γ-ray irradiated Ho(CH3COO)3⋅4H2O

2018 ◽  
Vol 106 (9) ◽  
pp. 775-785 ◽  
Author(s):  
Norhan Farghly Rashwan ◽  
Hossam Wahid ◽  
AbdelRahman AbdelMonem Dahy ◽  
Refaat Mohamed Mahfouz
Keyword(s):  
Thermal Decomposition ◽  
Absorbed Dose ◽  
Isoconversional Methods ◽  
Reaction Model ◽  
Host Lattice ◽  
Isothermal Kinetics ◽  
Conversion Degree ◽  
Acetate Tetrahydrate ◽  
Heating Rates ◽  
Γ Ray

Abstract Nonisothermal dehydration of un-irradiated and γ-ray irradiated holmium acetate tetrahydrate with 103 kGy total γ-ray dose absorbed was studied in air atmosphere. The thermal decomposition experiments were conducted at heating rates of (5, 7.5 and 10°C/min). The results showed that for un-irradiated material, the dehydration process proceeds in two decomposition steps with the elimination of 3.0 and 1.0 moles of H2O, respectively. The apparent activation energy, Ea, as given by both linear and nonlinear isoconversional methods showed dependence upon the conversion degree, α, in the range of 0.2–0.75 for the two dehydration steps. In the first dehydration step, the Ea decreases from 228.0 kJ/mol at the beginning of the decomposition to ≈64.0 kJ/mol at the end of the process. In the second dehydration step, the Ea increases from 42.0 to 72.0 kJ/mol by progressively increasing in α. Compared with solid state reaction models, the two reactions are best described by diffusion (D4) and nucleation (A3) models for the first and second dehydration steps, respectively. The results derived from nonisothermal data present a reliable prediction of isothermal kinetics. Straight lines and reduced time plots methods were applied for the determination of the kinetic triplet [Ea, ln A, and reaction model f(α)] from predicted isothermal data. For γ-ray irradiated samples of Ho(CH3COO)3⋅4H2O with 103 kGy total absorbed dose, the dehydration proceeds in two overlapped steps controlled by D3 model. X-ray data showed phase transformation from monoclinic (SG P2/m) to tetragonal phase (SG P4/mmm) by the elimination of water content from the entire structure of Ho(CH3COO)3⋅4H2O. γ-Ray irradiation effects on the thermal decomposition of Ho(CH3COO)3⋅4H2O were evaluated and discussed based on the formation of trapped electrons, point defects, cation and anion vacancies and cluster imperfections in the host lattice of Ho(CH3COO)3⋅4H2O.

Kinetics of nonisothermal dehydration of unirradiated and γ-ray irradiated neodymium (III) acetate hydrate

2019 ◽  
Vol 107 (2) ◽  
pp. 165-178
Author(s):  
Noura Mossaed Saleh ◽  
Ghada Adel Mahmoud ◽  
AbdelRahman AbdelMonem Dahy ◽  
Soliman Abdel-Fadeel Soliman ◽  
Refaat Mohamed Mahfouz
Keyword(s):  
Absorbed Dose ◽  
Isoconversional Methods ◽  
Gas Diffusion ◽  
Conversion Degree ◽  
Monoclinic System ◽  
Air Atmosphere ◽  
Dehydration Reactions ◽  
Γ Ray ◽  
Acetate Hydrate ◽  
Kinetics Of

Abstract Kinetics of dehydration of unirradiated and γ-ray irradiated neodymium (III) acetate hydrate with 103 kGy total γ-ray dose absorbed in air atmosphere were studied by isoconversional nonisothermal method. The dehydration proceeds in two steps with the elimination of 0.8 and 0.4 mol of H2O, respectively. This result indicates that the investigated neodymium (III) acetate hydrate contains 1.2 mol of crystalline water in its structure. The dehydration reactions are best described by nucleation (A2 model) and gas diffusion (D4 model) for unirradiated and γ-ray irradiated samples, respectively. Analysis of the kinetic data using linear and nonlinear isoconversional methods showed that the apparent activation energy, Ea (kJ/mol) is dependent on the conversion degree, α, of the dehydration process. The Ea−α plots for both unirradiated and γ-ray irradiated neodymium (III) acetate hydrate showed that the dehydration is a complex process and contains multistep reactions. The results showed that γ-ray irradiation has a significant effect on the kinetics and thermodynamic parameters of the dehydration reaction. Powder X-ray diffraction showed that neodymium (III) acetate hydrate has a monoclinic system (SG P2/m) and no phase transformation was detected by γ-ray irradiation up to 103 kGy absorbed dose. The system maintains the same crystal structure before and after dehydration.

Global Reaction Model to Describe the Kinetics of Catalytic Pyrolysis of Coffee Grounds Waste

2017 ◽  
Vol 899 ◽  
pp. 173-178 ◽  
Author(s):  
Ronydes Batista Jr. ◽  
Bruna Sene Alves Araújo ◽  
Pedro Ivo Brandão e Melo Franco ◽  
Beatriz Cristina Silvério ◽  
Sandra Cristina Danta ◽  
...  
Keyword(s):  
Thermal Decomposition ◽  
Large Scale ◽  
Catalytic Pyrolysis ◽  
Petroleum Products ◽  
Reaction Model ◽  
Heating Rates ◽  
Coffee Grounds ◽  
One Step ◽  
Global Reaction ◽  
The One

In view of the constant search for new sources of renewable energy, the particulate agro-industrial waste reuse emerges as an advantageous alternative. However, despite the advantages of using the biomass as an energy source, there is still strong resistance as the large-scale replacement of petroleum products due to the lack of scientifically proven efficient conversion technologies. In this context, the pyrolysis is presented as one of the most widely used thermal decomposition processes. The knowledge of aspects of chemical kinetics, thermodynamics these will, heat and mass transfer, are so important, since influence the quality of the product. This paper presents a kinetic study of slow pyrolysis of coffee grounds waste from dynamic thermogravimetric experiments (TG), using different powder catalysts. The primary thermal decomposition was described by the one-step reaction model, which considers a single global reaction. The kinetic parameters were estimated using nonlinear regression and the differential evolution method. The coffee ground waste was dried at 105°C for 24 hours. The sample in nature was analyzed at different heating rates, being 10, 15, 20, 30 and 50 K/min. In the catalytic pyrolysis, about 5% (w/w) of catalyst were added to the sample, at a heating rate of 30 K/min. The results show that the one-step model does not accurately represent the data of weight loss (TG) and its derivative (DTG), but can do an estimative of the activation energy reaction, and can show the differences caused by the catalysts. Although no one can say anything about the products formed with the addition of the catalyst, it would be necessary to micro-pyrolysis analysis, we can say the influence of the catalyst in the samples, based on the data obtained in thermogravimetric tests.

scholarly journals Kinetic Analysis of the Thermal Degradation of Recycled Acrylonitrile-Butadiene-Styrene by non-Isothermal Thermogravimetry

Polymers ◽  
2019 ◽  
Vol 11 (2) ◽  
pp. 281 ◽  
Author(s):  
Rafael Balart ◽  
David Garcia-Sanoguera ◽  
Luis Quiles-Carrillo ◽  
Nestor Montanes ◽  
Sergio Torres-Giner
Keyword(s):  
Thermal Degradation ◽  
Kinetic Analysis ◽  
Acrylonitrile Butadiene Styrene ◽  
Isoconversional Methods ◽  
Reaction Model ◽  
Integral Model ◽  
Heating Rates ◽  
Exponential Factor ◽  
Model Free ◽  
Butadiene Styrene

This work presents an in-depth kinetic study of the thermal degradation of recycled acrylonitrile-butadiene-styrene (ABS) polymer. Non-isothermal thermogravimetric analysis (TGA) data in nitrogen atmosphere at different heating rates comprised between 2 and 30 K min−1 were used to obtain the apparent activation energy (Ea) of the thermal degradation process of ABS by isoconversional (differential and integral) model-free methods. Among others, the differential Friedman method was used. Regarding integral methods, several methods with different approximations of the temperature integral were used, which gave different accuracies in Ea. In particular, the Flynn-Wall-Ozawa (FWO), the Kissinger-Akahira-Sunose (KAS), and the Starink methods were used. The results obtained by these methods were compared to the Kissinger method based on peak temperature (Tm) measurements at the maximum degradation rate. Combined Kinetic Analysis (CKA) was also carried out by using a modified expression derived from the general Sestak-Berggren equation with excellent results compared with the previous methods. Isoconversional methods revealed negligible variation of Ea with the conversion. Furthermore, the reaction model was assessed by calculating the characteristic and functions and comparing them with some master plots, resulting in a nth order reaction model with n = 1.4950, which allowed calculating the pre-exponential factor (A) of the Arrhenius constant. The results showed that Ea of the thermal degradation of ABS was 163.3 kJ mol−1, while ln A was 27.5410 (A in min−1). The predicted values obtained by integration of the general kinetic expression with the calculated kinetic triplet were in full agreement with the experimental data, thus giving evidence of the accuracy of the obtained kinetic parameters.

scholarly journals Determination of the Kinetics and Thermodynamic Parameters of Lignocellulosic Biomass Subjected to the Torrefaction Process

Materials ◽  
2021 ◽  
Vol 14 (24) ◽  
pp. 7877
Author(s):  
Maja Ivanovski ◽  
Aleksandra Petrovic ◽  
Irena Ban ◽  
Darko Goricanec ◽  
Danijela Urbancl
Keyword(s):  
Carbon Content ◽  
Isoconversional Methods ◽  
Conversion Degree ◽  
Heating Rates ◽  
Miscanthus X Giganteus ◽  
Main Method ◽  
Air Atmosphere ◽  
Solid Biofuels ◽  
Lignocellulosic Feedstocks

The torrefaction process upgrades biomass characteristics and produces solid biofuels that are coal-like in their properties. Kinetics analysis is important for the determination of the appropriate torrefaction condition to obtain the best utilization possible. In this study, the kinetics (Friedman (FR) and Kissinger–Akahira–Sunose (KAS) isoconversional methods of two final products of lignocellulosic feedstocks, miscanthus (Miscanthus x giganteus) and hops waste (Humulus Lupulus), were studied under different heating rates (10, 15, and 20 °C/min) using thermogravimetry (TGA) under air atmosphere as the main method to investigate. The results of proximate and ultimate analysis showed an increase in HHV values, carbon content, and fixed carbon content, followed by a decrease in the VM and O/C ratios for both torrefied biomasses, respectively. FTIR spectra confirmed the chemical changes during the torrefaction process, and they corresponded to the TGA results. The average Eα for torrefied miscanthus increased with the conversion degree for both models (25–254 kJ/mol for FR and 47–239 kJ/mol for the KAS model). The same trend was noticed for the torrefied hops waste samples; the values were within the range of 14–224 kJ/mol and 60–221 kJ/mol for the FR and KAS models, respectively. Overall, the Ea values for the torrefied biomass were much higher than for raw biomass, which was due to the different compositions of the torrefied material. Therefore, it can be concluded that both torrefied products can be used as a potential biofuel source.

Kinetic Studies on the Thermal Synthesis of Fluorapatite: Model Free and Model-Fitting Methods

2018 ◽  
Vol 28 ◽  
pp. 75-89
Author(s):  
Hamid Reza Javadinejad ◽  
Sayed Ahmad Hosseini ◽  
Mohsen Saboktakin Rizi ◽  
Eiman Aghababaei ◽  
Hossein Naseri
Keyword(s):  
Activation Energy ◽  
Model Fitting ◽  
Kinetic Studies ◽  
Isoconversional Methods ◽  
Reaction Model ◽  
Heating Rates ◽  
Thermal Synthesis ◽  
Exponential Factor ◽  
Model Free ◽  
Master Plots

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.

Decomposition Kinetics of Switchgrass: Estimating Activation Energy

2014 ◽  
Vol 881-883 ◽  
pp. 726-733
Author(s):  
Gui Ying Xu ◽  
Jiang Bo Wang ◽  
Ling Ping Guo ◽  
Guo Gang Sun
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Apparent Activation Energy ◽  
High Purity ◽  
Isoconversional Methods ◽  
Decomposition Kinetics ◽  
Heating Rates ◽  
Model Free ◽  
Chemical Utilization ◽  
Kinetics Of

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.

scholarly journals Application of a New Statistical Model for the Description of Solid Fuel Decomposition in the Analysis of Artemisia apiacea Pyrolysis

Energies ◽  
2021 ◽  
Vol 14 (18) ◽  
pp. 5789
Author(s):  
Tianbao Gu ◽  
Torsten Berning ◽  
Chungen Yin
Keyword(s):  
Experimental Data ◽  
Reaction Mechanism ◽  
Statistical Model ◽  
Solid Fuel ◽  
Conversion Rate ◽  
Reaction Model ◽  
Thermochemical Conversion ◽  
Conversion Degree ◽  
Heating Rates ◽  
Artemisia Apiacea

Pyrolysis, one of the key thermochemical conversion technologies, is very promising to obtain char, oil and combustible gases from solid fuels. Kinetic modeling is a crucial method for the prediction of the solid conversion rate and analysis of the pyrolysis process. We recently developed a new statistical model for the universal description of solid fuel decomposition, which shows great potential in studying solid fuel pyrolysis. This paper demonstrates three essential applications of this new model in the analysis of Artemisia apiacea pyrolysis, i.e., identification of the conversion rate peak position, determination of the reaction mechanism, and evaluation of the kinetics. The results of the first application show a very good agreement with the experimental data. From the second application, the 3D diffusion-Jander reaction model is considered as the most suitable reaction mechanism for the description of Artemisia stem pyrolysis. The third application evaluates the kinetics of Artemisia stem pyrolysis. The evaluated kinetics vary with the conversion degree and heating rates, in which the activation energies and pre-exponential factors (i.e., lnA vs. Ea) show a linear relationship, regardless of the conversion and heating rates. Moreover, the prediction of the conversion rate using the obtained kinetics shows an excellent fit with the experimental data.

scholarly journals Thermal decomposition of a molecular material {N(n-C4H9)4[FeIIFeIII(C2O4)3]}∞ leading to ferrite: A reaction kinetics study

2013 ◽  
Vol 78 (4) ◽  
pp. 523-536 ◽  
Author(s):  
Ashis Bhattacharjee ◽  
Debasis Roy ◽  
Madhusudan Roy ◽  
Arunabha Adhikari
Keyword(s):  
Thermal Decomposition ◽  
Isoconversional Methods ◽  
Reaction Pathways ◽  
Heating Rates ◽  
Model Free ◽  
Molecular Precursor ◽  
Probable Reaction Mechanism ◽  
Mechanism Of Thermal Decomposition ◽  
Rate Of Reaction ◽  
Probable Reaction

A multi-step thermal decomposition of a molecular precursor, {N(n-C4H9)4[FeIIFeIII(C2O4)3}? has been studied using non-isothermal thermogravimetry (TG) measurements in the temperature range 300 to ~800 K at multiple heating rates (5, 10 and 20 K min-1). The thermal decomposition of the oxalate-based complex proceeds stepwise through a series of intermediate reactions. Two different isoconversional methods, namely, improved iterative method and model-free method are employed to evaluate the kinetic parameters: activation energy and rate of reaction, and the most probable reaction mechanism of thermal decomposition is also determined. The different reaction pathways leading to different steps in the TG profile have also been explored which are supplemented by earlier experimental observations of the present authors.

scholarly journals Thermo-kinetics of Forest Waste Using Model-Free Methods

2019 ◽  
Vol 24 (1) ◽  
pp. 1-31 ◽  
Author(s):  
Alok Dhaundiyal ◽  
Abdulrahman Th Mohammad ◽  
Toth Laszlo
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Parameters ◽  
Frequency Factor ◽  
Isoconversional Methods ◽  
Pine Needles ◽  
Kissinger Method ◽  
Heating Rates ◽  
Pinus Roxburghii ◽  
Kinetics Parameters ◽  
Model Free

Thermal behaviour of pine needles (Pinus Roxburghii) is examined through a thermogravimetry technique. The dried samples of pine needles undergo the non isothermal decomposition at temperature range of 308 - 1173 K. The heating rates used for experimental purposes are: 5 °C min-1, 10 °C min-1 and 15 °C min-1. Kinetic parameters of thermal decomposition reactions of pine needles are obtained through the model-free schemes. The estimated values of activation energy and frequency factor derived from Kissinger method are 132.77 kJ mol-1 and 13.15 x107 min-1, respectively. Furthermore, the averaged values of the same kinetics parameters retrieved from the isoconversional methods are 82.38 kJ mol-1 and 74.833 kJ mol-1, 25.42 x1013 min-1 and 13.449 x1010 min-1, respectively. Instead of the Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira Sunrose (KAS) schemes, the kinetic parameters derived from the Kissinger method are relatively promising for the thermal decomposition process, since the kinetic parameters are highly affected by intermediate stages and overlapping of the concurrent reaction occurred during pyrolysis.

Non-Isothermal Decomposition Kinetic of Polypropylene/Hydrotalcite Composite

2019 ◽  
Vol 19 (11) ◽  
pp. 7493-7501 ◽  
Author(s):  
Sheng Xu ◽  
Min Zhang ◽  
Siyu Li ◽  
Moyu Yi ◽  
Shigen Shen ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Thermal Decomposition ◽  
Nitrogen Atmosphere ◽  
Heating Rates ◽  
Decomposition Reactions ◽  
Kinetic And Thermodynamic Parameters ◽  
Málek Method ◽  
Boundary Reaction ◽  
Phase Boundary Reaction ◽  
Thermal Stability Of

P3O5-10 pillared Mg/Al hydrotalcite (HTs) as a functional fire-retarding filler was successfully prepared by impregnation-reconstruction, where the HTs was used to prepare polypropylene (PP) and HTs composite (PP/HTs). Thermal decomposition was crucial for correctly identifying the thermal behavior for the PP/HTs, and studied using thermogravimetry (TG) at different heating rates. Based on single TG curves and Málek method, as well as 41 mechanism functions, the thermal decompositions of the PP/HTs composite and PP in nitrogen atmosphere were studied under non-isothermal conditions. The mechanism functions of the thermal decomposition reactions for the PP/HTs composite and PP were separately “chemical reaction F3” and “phase boundary reaction R2,” which were also in good agreement with corresponding experimental data. It was found that the addition of the HTs increased the apparent activation energy Ea of the PP/HTs comparing to the PP, which improved the thermal stability of the polypropylene. A difference in the set of kinetic and thermodynamic parameters was also observed between the PP/HTs and PP, particularly with respect to lower ΔS≠ value assigned to higher thermal stability of the PP/HTs composite.

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