Decomposition kinetics of cobalt complexes of phenoxy radicals studied by EPR method

1980 ◽  
Vol 45 (2) ◽  
pp. 464-474 ◽  
Author(s):  
Ladislav Omelka ◽  
Alexander Tkáč
Keyword(s):  
Activation Energy ◽  
Room Temperature ◽  
Effective Activation Energy ◽  
Decomposition Kinetics ◽  
Peroxy Radicals ◽  
Substitution Reactions ◽  
Phenoxy Radicals ◽  
Increasing Temperature ◽  
Kinetics Of ◽  
Homolytic Substitution

In bimolecular homolytic substitution reactions type SH2 between coordinated peroxy radicals [Co(III)]RO2 and partially hindered bisphenol 4,4'-thiobis-(3-methyl-6-tert-butylphenol) (an antioxidant with commercial name Santonox R) in non-polar medium at room temperature an equilibrium is established between free and Co(III)-coordinated phenoxy radicals. Increasing temperature shifts the equilibrium in favour of the decomplexed free radicals. The complexation-decomplexation process of phenoxy radicals is practically reversible up to 90°C. Polar coordinating solvents (methanol, H2O, diethyl ether, tetrahydrofurane) displace irreversibly the radicals from the complexes. From their decomposition kinetics at various temperatures activation energy of decomplexation by methanol has been determined (110 ± 8 kJ mol-1). The displaced free partially hindered phenoxy radicals are not sufficiently stable and undergo subsequent radical transformations (dimerization, intramolecular and intermolecular H-transfer) with effective activation energy about 67 kJ mol-1.

scholarly journals Kinetic analysis of oil palm empty fruit bunch (OPEFB) pellets as feedstock for pyrolysis

2015 ◽  
Author(s):  
Bemgba Bevan Nyakuma
Keyword(s):  
Activation Energy ◽  
Oil Palm ◽  
Room Temperature ◽  
Energy Requirement ◽  
Inert Atmosphere ◽  
Decomposition Kinetics ◽  
The Other ◽  
Empty Fruit Bunch ◽  
Heating Rates ◽  
Kinetics Of

The thermal behaviour and decomposition kinetics of pelletized oil palm empty fruit bunch (OPEFB) was investigated in this study using thermogravimetric analysis (TGA). The OPEFB pellets were heated from room temperature to 1000 ºC at different heating rates; 5, 10 and 20 °C min-1 under inert atmosphere. Thermal degradation occurred in three steps; drying, devolatization and char decomposition. Subsequently, the Popescu method was applied to the TG/DTG data to determine the kinetic parameters of the OPEFB pellets. The activation energy, E, for different degrees of conversion, α = 0.05 to 0.7 are 36.60 kJ/mol to 233.90 kJ/mol with high correlation R2 values. In addition, the drying and decomposition of lignin reactions displayed lower E values compared to the devolatization characterized by high E value of 233 kJ/mol at α = 0.2. This indicates that the devolatization process is slower and requires higher energy requirement to reach completion than the other stages of thermal decomposition of the fuel under inert atmosphere. Keywords: decomposition, kinetics, oil palm, empty fruit bunch, pyrolysis.

scholarly journals Kinetic analysis of oil palm empty fruit bunch (OPEFB) pellets as feedstock for pyrolysis

2015 ◽  
Author(s):  
Bemgba Bevan Nyakuma
Keyword(s):  
Activation Energy ◽  
Oil Palm ◽  
Room Temperature ◽  
Energy Requirement ◽  
Inert Atmosphere ◽  
Decomposition Kinetics ◽  
The Other ◽  
Empty Fruit Bunch ◽  
Heating Rates ◽  
Kinetics Of

The thermal behaviour and decomposition kinetics of pelletized oil palm empty fruit bunch (OPEFB) was investigated in this study using thermogravimetric analysis (TGA). The OPEFB pellets were heated from room temperature to 1000 ºC at different heating rates; 5, 10 and 20 °C min-1 under inert atmosphere. Thermal degradation occurred in three steps; drying, devolatization and char decomposition. Subsequently, the Popescu method was applied to the TG/DTG data to determine the kinetic parameters of the OPEFB pellets. The activation energy, E, for different degrees of conversion, α = 0.05 to 0.7 are 36.60 kJ/mol to 233.90 kJ/mol with high correlation R2 values. In addition, the drying and decomposition of lignin reactions displayed lower E values compared to the devolatization characterized by high E value of 233 kJ/mol at α = 0.2. This indicates that the devolatization process is slower and requires higher energy requirement to reach completion than the other stages of thermal decomposition of the fuel under inert atmosphere. Keywords: decomposition, kinetics, oil palm, empty fruit bunch, pyrolysis.

scholarly journals Фотополимеризация в слоях фуллерена молекулярного донорно-акцепторного комплекса \Pt(nPr-=SUB=-2-=/SUB=-dtc)-=SUB=-2-=/SUB=-\·(C-=SUB=-60-=/SUB=-)-=SUB=-2-=/SUB=-

2018 ◽  
Vol 60 (10) ◽  
pp. 2057
Author(s):  
К.П. Мелетов
Keyword(s):  
Activation Energy ◽  
Raman Spectra ◽  
Room Temperature ◽  
Thermal Destruction ◽  
Arrhenius Equation ◽  
Fullerene Complexes ◽  
Donor Acceptor ◽  
Increasing Temperature ◽  
Kinetics Of ◽  
532 Nm

AbstractWe measured Raman spectra in crystals of molecular donor–acceptor fullerene complexes { Me ( n Pr_2 dtc )_2} · (C_60)_2 ( Me = Ni, Cu, Pt). In the spectra of the {Pt( n Pr_2 dtc )_2} · (C_60)_2 complex under prolonged irradiation with a laser with λ = 532 nm, characteristic changes in the photopolymerization of fullerene are observed, associated with the splitting of degenerate phonon Hg modes and softening of Ag modes of the C_60 molecule. The kinetics of photopolymerization under conditions of weak irradiation at room temperature is studied. It was found that thermal destruction of the photopolymer with increasing temperature leads to a decrease in its concentration in the final photopolymerization product. The kinetics of thermal destruction is described by the Arrhenius equation, with the activation energy E _A of (0.68 ± 0.03) eV; the dimers are destructed to a concentration of 1% within 15 min at ~114°C.

On the use of Ozawa/Flynn/Wall method to determine aging activation energy for elastomers

2021 ◽  
pp. 009524432110203
Author(s):  
Sudhir Bafna
Keyword(s):  
Mechanical Properties ◽  
Activation Energy ◽  
Weight Loss ◽  
Oxygen Consumption ◽  
Dwell Time ◽  
Room Temperature ◽  
Elevated Temperatures ◽  
Degradation Mechanism ◽  
Kinetics Of ◽  
Wall Method

It is often necessary to assess the effect of aging at room temperature over years/decades for hardware containing elastomeric components such as oring seals or shock isolators. In order to determine this effect, accelerated oven aging at elevated temperatures is pursued. When doing so, it is vital that the degradation mechanism still be representative of that prevalent at room temperature. This places an upper limit on the elevated oven temperature, which in turn, increases the dwell time in the oven. As a result, the oven dwell time can run into months, if not years, something that is not realistically feasible due to resource/schedule constraints in industry. Measuring activation energy (Ea) of elastomer aging by test methods such as tensile strength or elongation, compression set, modulus, oxygen consumption, etc. is expensive and time consuming. Use of kinetics of weight loss by ThermoGravimetric Analysis (TGA) using the Ozawa/Flynn/Wall method per ASTM E1641 is an attractive option (especially due to the availability of commercial instrumentation with software to make the required measurements and calculations) and is widely used. There is no fundamental scientific reason why the kinetics of weight loss at elevated temperatures should correlate to the kinetics of loss of mechanical properties over years/decades at room temperature. Ea obtained by high temperature weight loss is almost always significantly higher than that obtained by measurements of mechanical properties or oxygen consumption over extended periods at much lower temperatures. In this paper, data on five different elastomer types (butyl, nitrile, EPDM, polychloroprene and fluorocarbon) are presented to prove that point. Thus, use of Ea determined by weight loss by TGA tends to give unrealistically high values, which in turn, will lead to incorrectly high predictions of storage life at room temperature.

Thermal Decomposition Kinetics of RDX with Distributed Activation Energy Model

2013 ◽  
Vol 641-642 ◽  
pp. 144-147 ◽  
Author(s):  
Ming Hua Chen ◽  
Tao Zhang ◽  
Wen Ping Chang ◽  
Xiao Biao Jia
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Energy Model ◽  
Decomposition Kinetics ◽  
Thermal Decomposition Kinetics ◽  
Distributed Activation Energy Model ◽  
Thermogravimetric Analyzer ◽  
Decomposition Stage ◽  
Decomposition Processes ◽  
Kinetics Of

The thermal decomposition kinetics of RDX at different rates was studied by thermogravimetric analyzer(TG) and the activation energy of RDX was calculated by distributed activation energy model. It is shown that the thermal decomposition processes of RDX were divided into three stages according to the TG curves, they are molten stage, thermal decomposition stage and eng stage. The activation energies of RDX are all between 124.34 and 181.48KJ•mol-1 in the thermal decomposition stage of non-monotonously increasing. The activation energy of RDX is 139.98 KJ•mol-1 in the molten stage, and the thermal decomposition stage is167.24KJ•mol-1.

Thermal Decomposition Kinetics of Flame Retardant Polybutylene Terephthalate Matrix Composites

2019 ◽  
Vol 956 ◽  
pp. 181-191
Author(s):  
Jian Lin Xu ◽  
Bing Xue Ma ◽  
Cheng Hu Kang ◽  
Cheng Cheng Xu ◽  
Zhou Chen ◽  
...  
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Flame Retardant ◽  
Mass Loss Rate ◽  
Decomposition Reaction ◽  
Decomposition Kinetics ◽  
Thermal Decomposition Kinetics ◽  
Heating Rates ◽  
Polybutylene Terephthalate ◽  
Kinetics Of

The thermal decomposition kinetics of polybutylene terephthalate (PBT) and flame-retardant PBT (FR-PBT) were investigated by thermogravimetric analysis at various heating rates. The kinetic parameters were determined by using Kissinger, Flynn-Wall-Ozawa and Friedman methods. The y (α) and z (α) master plots were used to identify the thermal decomposition model. The results show that the rate of residual carbon of FR-PBT is higher than that of PBT and the maximum mass loss rate of FR-PBT is lower than that of PBT. The values of activation energy of PBT (208.71 kJ/mol) and FR-PBT (244.78 kJ/mol) calculated by Kissinger method were higher than those of PBT (PBT: 195.54 kJ/mol) and FR-PBT (FR-PBT: 196.00 kJ/mol) calculated by Flynn-Wall-Ozawa method and those of PBT and FR-PBT (PBT: 199.10 kJ/mol, FR-PBT: 206.03 kJ/mol) calculated by Friedman methods. There is a common thing that the values of activation energy of FR-PBT are higher than that of PBT in different methods. The thermal decomposition reaction models of the PBT and FR-PBT can be described by Avarami-Erofeyev model (A1).

scholarly journals Kinetics of carbothermic reduction of synthetic chromite

2014 ◽  
Vol 50 (1) ◽  
pp. 15-21 ◽  
Author(s):  
Y. Wang ◽  
L. Wang ◽  
J. Yu ◽  
K.C. Chou
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Reduction Process ◽  
X Ray Diffraction ◽  
X Ray ◽  
Chromite Ore ◽  
Current Reduction ◽  
Increasing Temperature ◽  
Isothermal Mode ◽  
Kinetics Of

In order to optimize the current reduction process of chromite, a good knowledge of reduction mechanism involved is required. The basic component in chromite ore is FeCr2O4, thus, kinetic investigation of synthetic FeCr2O4 with different amount of carbon were carried out in the temperature range of 1473K to 1673K under both isothermal and non-isothermal mode. The iron can be easily reduced compared with chromium. And higher reduction degree of chromite can be achieved by increasing temperature and carbon content. With the supporting of X-ray Diffraction and Scanning Electron Microscope methods, the formation of metallic products followed the sequence: Fe-C alloy, (Fe,Cr)7C3and Fe-Cr-C alloy. Kinetics analysis showed that the first stage was controlled by nucleation with an apparent activation energy of 120kJ/mol, while the chromium reduction was controlled by crystallochemical transformation with an apparent activation energy of 288kJ/mol.

Characteristics and thermal decomposition kinetics of wood-SiO2 composites derived by the sol-gel process

Holzforschung ◽  
2017 ◽  
Vol 71 (3) ◽  
pp. 233-240 ◽  
Author(s):  
Ke-Chang Hung ◽  
Jyh-Horng Wu
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Apparent Activation Energy ◽  
Sol Gel ◽  
Weight Percent Gain ◽  
Weight Percent ◽  
Decomposition Kinetics ◽  
Thermal Decomposition Kinetics ◽  
Sol Gel Process ◽  
Kinetics Of

Abstract Wood-SiO2 composites (WSiO2Cs) were prepared by means of the sol-gel process with methyltrimethoxysilane (MTMOS) as a reagent, and the physical properties, structure and thermal decomposition kinetics of the composites has been evaluated. The dimensional stability of the WSiO2Cs was better than that of unmodified wood, especially in terms of the weight percent gain (WPG), which achieved values up to 30%. The 29Si-NMR spectra show two different siloxane peaks (T2 and T3), which supports the theory about the formation of MTMOS network structures. Thermal decomposition experiments were also carried out in a TG analyzer under a nitrogen atmosphere. The apparent activation energy was determined according to the iso-conversional methods of Friedman, Flynn-Wall-Ozawa, modified Coats-Redfern, and Starink. The apparent activation energy between 10 and 70% conversion is 147–172, 170–291, 189–251, and 192–248 kJ mol−1 for wood and WSiO2Cs with WPGs of 10, 20, and 30%, respectively. However, the reaction order between 10 and 70% conversion calculated by the Avrami theory was 0.50–0.56, 0.35–0.45, 0.33–0.44, and 0.28–0.48. These results indicate that the dimensional and thermal stability of the wood could be effectively enhanced by MTMOS treatment.

scholarly journals Modelling of Thermal Decomposition Kinetics of Proteins, Carbohydrates and Lipids Using Scenedesmus microalgae thermal Data

2020 ◽  
Vol 32 (11) ◽  
pp. 2921-2926
Author(s):  
BOTHWELL NYONI ◽  
PHUTI TSIPA ◽  
SIFUNDO DUMA ◽  
SHAKA SHABANGU ◽  
SHANGANYANE HLANGOTHI
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Bulk Material ◽  
Decomposition Kinetics ◽  
Second Order ◽  
Thermal Decomposition Kinetics ◽  
Heating Rates ◽  
High Heating ◽  
The Individual ◽  
Kinetics Of

In present work, the thermal decomposition behaviour and kinetics of proteins, carbohydrates and lipids is studied by use of models derived from mass-loss data obtained from thermogravimetric analysis of Scenedesmus microalgae. The experimental results together with known decomposition temperature range values obtained from various literature were used in a deconvolution technique to model the thermal decomposition of proteins, carbohydrates and lipids. The models fitted well (R2 > 0.99) and revealed that the proteins have the highest reactivity followed by lipids and carbohydrates. Generally, the decomposition kinetics fitted well with the Coats-Redfern first and second order kinetics as evidenced by the high coefficients of determination (R2 > 0.9). For the experimental conditions used in this work (i.e. high heating rates), the thermal decomposition of protein follows second order kinetics with an activation energy in the range of 225.3-255.6 kJ/mol. The thermal decomposition of carbohydrate also follows second order kinetics with an activation energy in the range of 87.2-101.1 kJ/mol. The thermal decomposition of lipid follows first order kinetics with an activation energy in the range of 45-64.8 kJ/ mol. This work shows that the thermal decomposition kinetics of proteins, carbohydrates and lipids can be performed without the need of experimentally isolating the individual components from the bulk material. Furthermore, it was shown that at high heating rates, the decomposition temperatures of the individual components overlap resulting in some interactions that have a synergistic effect on the thermal reactivity of carbohydrates and lipids.

scholarly journals INFLUENCE OF TEMPERATURE AND PH ON THE DECOMPOSITION KINETICS OF PERACETIC ACID IN AQUEOUS SOLUTIONS

2014 ◽  
Vol 44 (3) ◽  
pp. 195-201
Author(s):  
L. KUNIGK ◽  
S. P. GALIZIA ◽  
R.T. K. SHIKISHIMA ◽  
R. GEDRAITE ◽  
C. H. JURKIEWICZ
Keyword(s):  
Activation Energy ◽  
Aqueous Solutions ◽  
Peracetic Acid ◽  
Food Industry ◽  
Decomposition Kinetics ◽  
Order Reaction ◽  
Influence Of Temperature ◽  
First Order ◽  
All Solutions ◽  
Kinetics Of

Peracetic acid (PAA) is a strong oxidant used by the food industry as a sanitizer, in medical area as a disinfectant and by the textiles and paper industries as a bleacher. Its decomposition rate is an important parameter in these applications. The main purpose of this paper is to study the decomposition kinetics of PAA between 25 and 45 °C in solutions with pH 3.11, 5.0 and 7.0. The decomposition of PAA is a first-order reaction for all solutions and temperatures studied. The rate constants were between 2.08·10-3 and 9.44·10-3 h-1 (pH 3.11), between 2.61·10-3 and 16.69·10-3 h-1 (pH 5.0) and between 7.50·10-3 and 47.63·10-3 h-1 (pH 7.0). The activation energy of PAA decomposition in aqueous solutions are 58.36 and 72.89 kJ·mol-1 when pH was 3.11 and 5.0, respectively.

Sign in / Sign up

Export Citation Format

Share Document