Kinetic Analysis of the Thermal Decomposition of Polymer-Bonded Explosive Based on PETN: Model-Fitting Method and Isoconversional Method

This work investigates kinetics and thermal decomposition behaviors of pentaerythritol tetranitrate (PETN) and two polymer-bonded explosive (PBX) samples created from PETN (named as PBX-PN-85 and PBX-PP-85) using the vacuum stability test (VST) and thermogravimetry (TG/DTG) techniques. Both model-free (isoconversional) and model-fitting methods were applied to determine the kinetic parameters of the thermal decomposition. It was found that kinetic parameters obtained by the modified Kissinger–Akahira–Sunose method (using non-isothermal TG/DTG data) were close to those obtained by the isoconversional and model-fitting methods that use isothermal VST data. The activation energy values of thermal decomposition reactions were 125.6–137.1, 137.3–144.9, and 143.9–152.4 kJ·mol−1 for PBX-PN-85, PETN, and PBX-PP-85, respectively. The results demonstrate the negative effect of the nitrocellulose-based binder in reducing the thermal stability of single PETN, while the polystyrene-based binder seemingly shows no adverse influence on the thermal decomposition of PETN in our presented PBX compositions.

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Determination of Kinetic Parameters for the Thermal Decomposition of Parthenium hysterophorus

Environmental and Climate Technologies ◽

10.1515/rtuect-2018-0001 ◽

2018 ◽

Vol 22 (1) ◽

pp. 5-21 ◽

Cited By ~ 19

Author(s):

Alok Dhaundiyal ◽

Suraj B. Singh ◽

Muammel M. Hanon ◽

Rekha Rawat

Keyword(s):

Thermal Decomposition ◽

Kinetic Parameters ◽

Model Fitting ◽

Frequency Factor ◽

Heating Rates ◽

Model Free ◽

Higher Temperature ◽

Good Agreement ◽

Maximum Weight Loss

Abstract A kinetic study of pyrolysis process of Parthenium hysterophorous is carried out by using thermogravimetric analysis (TGA) equipment. The present study investigates the thermal degradation and determination of the kinetic parameters such as activation E and the frequency factor A using model-free methods given by Flynn Wall and Ozawa (FWO), Kissinger-Akahira-Sonuse (KAS) and Kissinger, and model-fitting (Coats Redfern). The results derived from thermal decomposition process demarcate decomposition of Parthenium hysterophorous among the three main stages, such as dehydration, active and passive pyrolysis. It is shown through DTG thermograms that the increase in the heating rate caused temperature peaks at maximum weight loss rate to shift towards higher temperature regime. The results are compared with Coats Redfern (Integral method) and experimental results have shown that values of kinetic parameters obtained from model-free methods are in good agreement. Whereas the results obtained through Coats Redfern model at different heating rates are not promising, however, the diffusion models provided the good fitting with the experimental data.

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Thermal decomposition and their kinetics of mercury(ii) perchlorate complex with 4-aminopyridine and water

Letters in Applied NanoBioScience ◽

10.33263/lianbs83.649653 ◽

2019 ◽

Vol 8 (3) ◽

pp. 649-653

Keyword(s):

Activation Energy ◽

Thermal Decomposition ◽

Rapid Heating ◽

Model Fitting ◽

Isoconversional Method ◽

Molecular Formula ◽

Isothermal Tg ◽

Different Temperatures ◽

Kinetics Of ◽

Perchlorate Complex

Copper perchlorate complex with 4-aminopyridine and water has been prepared with molecular formula [Hg2(C5H6N2)3(ClO4)4].2H2O. It has been characterised by elemental analysis, thermogravimetry, and IR spectroscopic data. Thermal behaviours have been studied by thermogravimetry (TG) in static air and simultaneous thermogravimetry-derivative thermogravimetry analysis (TG-DTG) in flowing nitrogen atmosphere. Complex decomposes in four steps (less resolved). Difference in decomposition under air and inert atmosphere has been also discussed. Kinetics of thermal decomposition has been investigated using isothermal TG data recorded at five different temperatures applying model-fitting as well as isoconversional method on these data. Model-fitting methods have yielded a single value of activation energy whereas isoconversional method has given different values of activation energy for each extent of conversion, α. Response of synthesized complex towards rapid heating has been investigated by recording explosion delay time (DE) at five different temperatures and using these data kinetics of explosion has been analysed. Activation energy for explosion has been also calculated.

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Kinetics of Thermolysis of Nickel(II) Perchlorate Complex with n-Propylamine

Indian Journal of Materials Science ◽

10.1155/2014/787306 ◽

2014 ◽

Vol 2014 ◽

pp. 1-5 ◽

Cited By ~ 1

Author(s):

Chandra Prakash Singh ◽

Abhishek Singh

Keyword(s):

Model Fitting ◽

Isoconversional Method ◽

Nitrogen Atmosphere ◽

Molecular Formula ◽

Fast Heating ◽

Isothermal Tg ◽

Model Free ◽

Different Temperatures ◽

Explosion Delay ◽

Kinetics Of

Complex of nickel perchlorate with n-propylamine has been synthesised with molecular formula [Ni(n-pa)3(ClO4)(H2O)]ClO4. It has been characterised by elemental analysis, thermogravimetry, UV-VIS, and IR spectroscopic data. Thermal properties have been investigated by thermogravimetry (TG) in static air and by simultaneous thermogravimetry-derivative thermogravimetry-differential thermal analysis (TG-DTG-DTA) in flowing nitrogen atmosphere. Kinetics of thermolysis has been analysed applying model-fitting and model-free isoconversional method on isothermal TG data recorded at five different temperatures. To observe the response of complex towards fast heating, explosion delay time has been recorded at various temperatures and kinetics of explosion has been studied using these data.

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Synthesis, characterization and thermal decomposition of ethyl-2’-amino-5’-cyano-6’-(1H-indole-3yl)-2-oxospiro[indoline-3,4’-pyran]-3’-carboxylate under non‐isothermal condition in nitrogen atmosphere

European Journal of Chemistry ◽

10.5155/eurjchem.10.1.72-81.1812 ◽

2019 ◽

Vol 10 (1) ◽

pp. 72-81

Author(s):

Ganesan Nalini ◽

Natesan Jayachandramani ◽

Radhakrishnan Suresh ◽

Prakasam Thirumurugan ◽

Venugopal Thanikachalam ◽

...

Keyword(s):

Thermal Decomposition ◽

Kinetic Parameters ◽

Model Fitting ◽

Isothermal Condition ◽

Nitrogen Atmosphere ◽

Single Step ◽

Heating Rates ◽

Model Free ◽

Ft Ir ◽

Step Mechanism

A new compound, spiro-oxindole derivative compound namely ethyl-2ʹ-amino-5ʹ-cyano-6ʹ-(1H-indole-3yl)-2-oxospiro[indoline-3,4ʹ-pyran]-3ʹ-carboxylate (EACIOIPC) has been synthesized and characterized by microanalysis, FT-IR, mass spectrum and NMR (1H and 13C) techniques. The thermal decomposition of the compound was studied by thermogravimetric analysis under dynamic nitrogen atmosphere at different heating rates of 10, 15, 20 and 30 K/min. The kinetic parameters were calculated using model-free (Friedman’s, Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) methods) and model-fitting (Coats and Redfern (CR)) methods. The decomposition process of EACIOIPC followed a single step mechanism as evidenced from the data. Existence of compensation effect is noticed for the decomposition of EACIOIPC. Invariant kinetic parameters are consistent with the average values obtained by Friedman and KAS in conversional methods.

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Kinetics of thermal degradation of wood biomass

Chemical Papers ◽

10.2478/s11696-014-0622-y ◽

2014 ◽

Vol 68 (12) ◽

Cited By ~ 4

Author(s):

Ivan Hrablay ◽

Ľudovít Jelemenský

Keyword(s):

Kinetic Parameters ◽

13C Nmr ◽

Model Fitting ◽

Isoconversional Method ◽

Experimental Results ◽

Pyrolysis Kinetics ◽

Exponential Factor ◽

Model Free ◽

Fitting Method ◽

Kinetics Of

AbstractPyrolysis kinetics of a hardwood representative, beech (Fagus sylvatica), was investigated by two different kinetic approaches: model-free isoconversional method and model-fitting method. The model-free isoconversional method was used for the determination of apparent kinetic parameters, i.e. the activation energy and pre-exponential factor. The model fitting method was used for the optimization of kinetic parameters of the reaction pathways of three selected reaction mechanisms: one-step, two-step, and three-step one. In both approaches, thermo-gravimetric data were used at five heating rates: 2°C min−1, 5°C min−1, 10°C min−1, 15°C min−1 and 20°C min−1. As the most suitable mechanism, the three-step mechanism containing the intermediate degradation step was chosen. This selection was supported by experimental results from the 13C NMR analysis of solid residues prepared at the key temperatures within the range of 230–500°C. The progress of mass fraction values of each component in this mechanism was simulated. Conclusions from the simulation were confronted with experimental results from the 13C NMR.

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Consecutive reactions in the thermal decomposition of phenylalkyldiazirines

Canadian Journal of Chemistry ◽

10.1139/v77-505 ◽

1977 ◽

Vol 55 (20) ◽

pp. 3596-3601 ◽

Cited By ~ 13

Author(s):

Michael T. H. Liu ◽

Barry M. Jennings

Keyword(s):

Thermal Decomposition ◽

Kinetic Parameters ◽

Diazo Compounds ◽

First Order ◽

Temperature Range ◽

Decomposition Reactions ◽

Consecutive Reactions ◽

Rate Processes ◽

Subsequent Decomposition

The thermal decomposition of phenyl-n-butyldiazirine and of phenylmethyldiazirine in DMSO and in HOAc have been investigated over the temperature range 80–130 °C. The intermediate diazo compounds, 1-phenyl-1-diazopentane and 1-phenyldiazoethane respectively have been detected and isolated. The decomposition of phenyl-n-butyldiazirine and the subsequent decomposition of its product, 1-phenyl-1-diazopentane, are an illustration of consecutive reactions. The kinetic parameters for the isomerization and decomposition reactions have been determined. The isomerization of phenylmethyldiazirine to 1-phenyldiazoethane is first order and probably unimolecular but the kinetics for the subsequent reactions of 1-phenyldiazoethane are complicated by several competing rate processes.

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