Effect of Co-precursor Maliec Anhydride on the Thermal Decomposition of Acetyl Ferrocene: A Reaction Kinetic Analysis

2019 ◽  
Vol 9 (1) ◽  
pp. 22-35
Author(s):  
Bratati Das ◽  
Ashis Bhattacharjee
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Reaction Mechanism ◽  
Kinetic Analysis ◽  
Reaction Rate ◽  
Reaction Kinetic ◽  
Step Process ◽  
Probable Reaction Mechanism ◽  
Probable Reaction ◽  
Reaction Atmosphere

Background: Thermal decomposition of iron-bearing organometallic complex acetyl ferrocene, (C5H4COCH3)Fe(C5H5), leads to hematite (α-Fe2O3) nanoparticles. Presence of maliec anhydride, C4H2O3 as co-precursor during thermal decomposition modifies the size of the particles as well as the quantity of the reaction product significantly. Objective: Kinetic analysis of the solid-state thermal reaction of acetyl ferrocene in the presence of varying amount of co-precursor maliec anhydride under inert reaction atmosphere has been studied in order to understand the reaction mechanism involved behind the formation of hematite and the role of co-precursor in the reaction process. For this purpose, reaction kinetic analysis of three mixtures of acetyl ferrocene and maliec anhydride has been carried out. Methods: Thermogravimetry under non-isothermal protocol with multiple heating rates has been employed. The data are analyzed using model-free iso-conversional kinetic techniques to estimate the activation energy of reaction and reaction rate. The most-probable reaction mechanism has been identified by master plot method. The kinetic triplets (activation energy, reaction rate, most probable reaction mechanism function) have been employed to estimate the thermodynamic triplets (ΔS, ΔH and ΔG). Observations: Acetyl Ferrocene (AFc) undergoes thermal decomposition in a four-step process leaving certain residual mass whereas maliec anhydride (MA) undergoes complete mass loss owing to melting followed by evaporation. In contrast, the (AFc1-x-MAx) mixtures undergo thermal decomposition through a two-step process, and the decompositions are completed at much lower temperatures than that in AFc. The estimated activation energy and reaction rate values are found strongly dependent on the extent of conversion as well as on the extent of mixing. Introduction of MA in the solid reaction atmosphere of AFc in one hand reduces the activation energy required by AFc to undergo thermal decomposition and the reaction rate, while on the other hand varies the nature of reaction mechanism involved. Results: The range of reaction rate values estimated for the mixtures indicate that the activated complexes during Step-I of thermal decomposition may be treated as ‘loose’ complex whereas ‘tight’ complex for the Step-II. From the estimated entropy values, thermal process of (AFc1-x-MAx) mixture for Steps I and II may be interpreted as ‘‘slow’’ stage. Conclusion: Variation of Gibb’s free energy with the fraction of maliec anhydride in the mixtures for Step-I and II indicate that the thermal processes of changing the corresponding activated complexes are non-spontaneous at room temperature.

Oscillation system of Belousov-Zhabotinskii type in presence of Cl- ions

1986 ◽  
Vol 51 (12) ◽  
pp. 2693-2701 ◽  
Author(s):  
Marta Mrákavová ◽  
Ľudovít Treindl
Keyword(s):  
Reaction Mechanism ◽  
Ethyl Ester ◽  
Reaction System ◽  
Oscillation System ◽  
Low Concentration ◽  
Redox Catalyst ◽  
Probable Reaction Mechanism ◽  
Oxobutanoic Acid ◽  
Probable Reaction

A modified Belousov-Zhabotinskii oscillation system involving ethyl ester of 3-oxobutanoic acid and Fe(phen)32+ - Fe(phen)33+ as redox catalyst is remarkable in that it shows an oxygen-induced excitability. The oscillating state, involving 4-5 oscillations in the absorbancy of Fe(phen)32+ ions, comes soon to its end but can be restored by shaking the reaction system, thus incresing the transport of oxygen from the air. This phenomenon is not influenced by Cl- ions in a low concentration, but if this is equal to 10-3 mol dm-3 or higher, no oscillations are observed, the increase of the concentration of Fe(phen)32+ ions is autocatalytic in character and can be reproduced several times by shaking or stirring the solution. These phenomena are discussed in terms of a probable reaction mechanism.

scholarly journals Thermogravimetric and Kinetic Analysis of Melon (Citrullus colocynthis L.) Seed Husk Using the Distributed Activation Energy Model

2015 ◽  
Vol 15 (1) ◽  
pp. 77-89 ◽  
Author(s):  
Bemgba Bevan Nyakuma
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Kinetic Analysis ◽  
Biomass Conversion ◽  
Clean Energy ◽  
Frequency Factor ◽  
Energy Model ◽  
Distributed Activation Energy Model ◽  
Solid Biofuel ◽  
Seed Husk

Abstract This study seeks to characterize the thermochemical fuel properties of melon seed husk (MSH) as a potential biomass feedstock for clean energy and power generation. It examined the ultimate analysis, proximate analysis, FTIR spectroscopy and thermal decomposition of MSH. Thermogravimetric (TG) analysis was examined at 5, 10, 20 °C/min from 30-800 °C under nitrogen atmosphere. Subsequently, the Distributed Activation Energy Model (DAEM) was applied to determine the activation energy, E, and frequency factor, A. The results revealed that thermal decomposition of MSH occurs in three (3) stages; drying (30-150 °C), devolatization (150-400 °C) and char degradation (400-800 °C). Kinetic analysis revealed that the E values fluctuated from 145.44-300 kJ/mol (Average E = 193 kJ/mol) while A ranged from 2.64 × 1010 to 9.18 × 1020 min-1 (Average E = 9.18 × 1019 min-1) highlighting the complexity of MSH pyrolysis. The fuel characterization and kinetics of MSH showed it is an environmentally friendly solid biofuel for future thermal biomass conversion.

scholarly journals Thermal and kinetic analysis of pure and contaminated ionic liquid: 1-butyl-2.3-dimethylimidazolium chloride (BDMIMCl)

2016 ◽  
Vol 18 (2) ◽  
pp. 122-125 ◽  
Author(s):  
Ayyaz Muhammad
Keyword(s):  
Activation Energy ◽  
Thermal Stability ◽  
Thermal Decomposition ◽  
Ionic Liquid ◽  
Thermal Degradation ◽  
Kinetic Analysis ◽  
Kinetic Parameters ◽  
Process Design ◽  
Research Work ◽  
Thermal Stability Of

Abstract In this research work, thermal decomposition and kinetic analysis of pure and contaminated imidazolium based ionic liquid (IL) has been investigated. As thermal decomposition and kinetics evaluation plays a pivotal role in effective process design. Therefore, thermal stability of pure 1-butyl-2,3-dimethylimidazolium chloride (BDMIMCl) was found to be higher than the sample of IL with the addition of 20% (wt.) NH4Cl as an impurity. The activation energy of thermal degradation of IL and other kinetic parameters were determined using Coats Redfern method. The activation energy for pure IL was reduced in the presence of NH4Cl as contaminant i.e., from 58.7 kJ/mol to 46.4 kJ/mol.

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 Thermal Decomposition Study of Ferrocene [(C5H5)2Fe]

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Ashis Bhattacharjee ◽  
Amlan Rooj ◽  
Debasis Roy ◽  
Madhusudan Roy
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Heating Rate ◽  
Isoconversional Methods ◽  
Thermal Reaction ◽  
Single Step ◽  
Model Free ◽  
Probable Reaction ◽  
Single Heating ◽  
Made In

A single-step thermal decomposition of ferrocene [(C5H5)2Fe] using nonisothermal thermogravimetry (TG) has been studied using single- as well as multiple-heating rate programs. Both mechanistic and nonmechanistic methods have been used to analyze the TG data to estimate the kinetic parameters for the solid state reaction. Two different isoconversional methods (improved iterative method and model-free method) have been employed to analyze the TG results to find out whether the activation energy of the reaction depends on the extent of decomposition and to predict the most probable reaction mechanism of thermal decomposition as well. A comparison of the activation energy values for the single-step thermal reaction of ferrocene estimated by different methods has been made in this work. An appraisal on the applicability of single-heating rate data for the analysis of single-step thermal decompositions over the recommendations by the International Confederation for Thermal Analysis and Calorimetry (ICTAC) is made to look beyond the choice.

Thermal Stability and Kinetic Analysis of Xanthoceras sorbifolia Polysaccharide

2012 ◽  
Vol 518-523 ◽  
pp. 3904-3907 ◽  
Author(s):  
Quan Cheng Zhou ◽  
Hong Mei Zhang ◽  
De Mao Li
Keyword(s):  
Activation Energy ◽  
Thermal Stability ◽  
Kinetic Model ◽  
Thermal Degradation ◽  
Kinetic Analysis ◽  
Large Scale ◽  
Degradation Process ◽  
Second Step ◽  
Step Process ◽  
Thermal Degradation Process

Pyrolysis and kinetic analysis of Xanthoceras Sorbifolia polysaccharide were evaluated using the TG-DTG/DTA method. The results indicated that its mass loss occured in three-step process . The first step could be attributed to the expulsion of water of crystallization at 25 - 176 °C. The second step corresponded to the large scale degradation of X. Sorbifolia polysaccharide in the temperature range of 179 - 661 °C. The final step was slow degradation of residues. Heating rate had significant effects on the pyrolysis of X. Sorbifolia polysaccharide and nitrogen could improve its stability. A close value of activation energy E of the thermal degradation process has been obtained by FWO, KAS and Popescu methods. The possible kinetic model was estimated to be Jander 5 (g(α)=[1-(1-α)1/3]1/2.

The kinetics of dehydroxylation of kaolinite

Clay Minerals ◽  
1987 ◽  
Vol 22 (4) ◽  
pp. 447-456 ◽  
Author(s):  
S. A. T. Redfern
Keyword(s):  
Activation Energy ◽  
Reaction Mechanism ◽  
Kinetic Analysis ◽  
Rate Constants ◽  
Avrami Equation ◽  
Isothermal Thermogravimetry ◽  
Temperature Range ◽  
Homogeneous Models ◽  
Kinetics Of ◽  
Fraction Method

AbstractThe dehydroxylation of kaolinite has been investigated by isothermal thermogravimetry. Kinetic analysis using the Avrami equation shows that a combination of atomic mechanisms operates throughout the temperature range 734 K to 890 K. An empirical activation energy of 222 kJ mol-1 was calculated from the Arrhenius relationship using rate constants based on diffusion and homogeneous models. The activation energy (Ea) was calculated for a series of degrees of dehydroxylation by the time to a given fraction method, showing an increase in Ea during the early stages of the reaction. The isothermal plots indicate that OH is retained in the final stages of the reaction. The observations are explained in terms of a reaction mechanism in which kaolinite grains dehydroxylate from the edges inwards, parallel to (001).

PHOTO-INITIATED REACTIONS OF THIOLS AND OLEFINS: I. THE THIYL RADICAL CATALYZED ISOMERIZATION OF BUTENE-2 AND 1,2-ETHYLENE-d2

1964 ◽  
Vol 42 (10) ◽  
pp. 2239-2249 ◽  
Author(s):  
D. M. Graham ◽  
R. L. Mieville ◽  
C. Sivertz
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Kinetic Study ◽  
Rate Constants ◽  
Reaction Rate ◽  
Kinetic Studies ◽  
Thiyl Radical ◽  
First Order ◽  
Thiyl Radicals ◽  
Simple Mechanism

Kinetic studies have been made of the isomerization of butene-2 and 1,2-ethylene-d2 catalyzed by thiyl radicals produced from the photolysis of methanethiol. The rate of isomerization was found to be first order with respect to both the olefin and [Formula: see text] concentrations. The lack of influence of pressure on the reaction rate, at pressures above about 4 mm, leads to a simple mechanism in which isomerization is considered to occur as a result of thermal decomposition of the collisionally stabilized adduct radical produced in the reaction [Formula: see text]. The rate constants for this attack step were found to be 2 × 107 and 4.8 × 106 l mole−1 s−1 for butene-2 and ethylene-d2, respectively. In both cases the activation energy for isomerization was found to be close to zero. From a kinetic study of the isomerization of cis-butene-2 in the presence of butadiene-1,3, which acts as a retarder, the attack constant for butadiene at 25 °C was found to be 4.5 × 108 l mole−1 s−1.

The Kinetic Analysis of Thermal Decomposition of PMMA/MMT Nanocomposites

2007 ◽  
Vol 353-358 ◽  
pp. 1366-1369 ◽  
Author(s):  
Kui Chen ◽  
Rui Chen Yang ◽  
S.W. Cheng
Keyword(s):  
Activation Energy ◽  
Thermal Stability ◽  
Thermal Decomposition ◽  
Methyl Methacrylate ◽  
Mass Loss ◽  
Apparent Activation Energy ◽  
Kinetic Analysis ◽  
Decomposition Kinetics ◽  
Ozawa Equation ◽  
Thermal Stability Of

The thermal decomposition kinetics and thermal stability of poly (methyl methacrylate) (PMMA) and PMMA/ montmorillonite (MMT) nanocomposites containing 4 wt% MMT were researched by thermogravimetry (TG). The results show that, because of the barrier behavior of exfoliated MMT layer, the temperature of thermal decomposition of PMMA/ MMT nanocomposites is improved by about 10 °C, and thermal stability is improved by about double. The apparent activation energy of decomposition, calculated by Ozawa equation, of nanocomposites is higher than that of PMMA before 27 % mass loss.

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