• Title/Summary/Keyword: Kinetic decomposition

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Oxygen Potential Gradient Induced Degradation of Oxides

  • Martin, Manfred
    • Journal of the Korean Ceramic Society
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    • v.49 no.1
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    • pp.29-36
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    • 2012
  • In many applications of functional oxides originally homogeneous materials are exposed to gradients in the chemical potential of oxygen. Prominent examples are solid oxide fuel cells (SOFCs) or oxygen permeation membranes (OPMs). Other thermodynamic potential gradients are gradients of electrical potential, temperature or uni-axial pressure. The applied gradients act as generalized thermodynamic forces and induce directed fluxes of the mobile components. These fluxes may lead to three basic degradation phenomena of the materials, which are kinetic demixing, kinetic decomposition, and morphological instabilities.

COMBUSTION KINETICS OF POLYETHYLENE TEREPHTHALATE

  • Oh, Sea-Cheon;Lee, Dong-Gyu;Kwak, Hyun;Bae, Seong-Youl
    • Environmental Engineering Research
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    • v.11 no.5
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    • pp.250-256
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    • 2006
  • The combustion kinetics of poly(ethylene terephthalate) (PET) was studied by the dynamic model which accounts for the thermal decomposition of polymer at any time. The kinetic analysis was performed by a conventional nonisothermal thermogravimetric (TG) technique at several heating rates between 10 and 40 K/min in air atmosphere. The thermal decomposition of PET in air atmosphere was found to be a complex process composed of at least two stages for which kinetic values can be calculated. The combustion kinetic analysis of PET gave apparent activation energy for the first stage of $257.3{\sim}269.9\;kJ/mol$, with a value of $140.5{\sim}213.8\;kJ/mol$ for the second stage. To verify the effectiveness of the kinetic analysis method used in this work, the kinetic analysis results were compared with those of various analytical methods. The kinetic parameters were also compared with values of the pyrolysis of PET in nitrogen atmosphere.

A Kinetic Study of Thermal-Oxidative Decomposition of Waste Polyurethane (폐폴리우레탄의 열적 산화분해에 대한 속도론적 연구)

  • Jun, Hyun Chul;Oh, Sea Cheon;Lee, Hae Pyeong;Kim, Hee Taik
    • Applied Chemistry for Engineering
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    • v.17 no.3
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    • pp.296-302
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    • 2006
  • The kinetics of the thermal-oxidative decomposition of waste polyurethane (PU) according to oxygen concentration has been studied using a non-isothermal thermogravimetric technique at several heating rates from 10 to $50^{\circ}C/min$. A kinetic model accounting for the effects of the oxygen concentration by the differential and integral method based on Arrhenius equation was proposed to describe the thermal-oxidative decomposition of waste PU. To obtain the information on the kinetic parameters such as activation energy, reaction order, and pre-exponential factor, the thermogravimetric analysis curves and its derivatives have been analyzed using the kinetic analysis method proposed in this work. From this work, it was found that reaction orders for oxygen concentration had a negative sign, and activation energy decreased as the oxygen concentration increased. It was also found that the kinetic parameters obtained from the integral method using the single heating rate experiments varied with heating rates. Therefore, it is thought that the differential method using the multiple heating rate experiments more effectively represents the thermal-oxidative decomposition of waste polyurethane.

Kinetics on the Thermal Decomposition of Cellulose (셀룰로오스의 열분해 반응속도론)

  • 최승찬;박영수
    • Journal of the Korean Society of Tobacco Science
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    • v.5 no.2
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    • pp.55-62
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    • 1983
  • Four of non- isothermal methods evaluating kinetics have been studied by using differential scanning calorimetry (DSC) and thermogravimetry (TG) and applied for kinetics of the thermal decomposition of cellulose. It is concluded that the heating evolution methods with DSC and approximative methods with TC can lead to satisfactory kinetic analysis. Results calculating the reacting order and the activation energy of cellulose decomposition were 1/2 order and 42kcaB/mol, respectively.

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Kinetics of Pyrolysis Degradation of Cured Phenol Resin (SC-1008) (I). (경화된 페놀 수지 (SC-1008)의 열분해 반응에 관한 연구(I).)

  • 김연철;강희철;예병한;배주찬
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 1996.11a
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    • pp.137-144
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    • 1996
  • The kinetic coefficients far decomposition of the cured phenol resin (SC-1008) using a modified Arrhenius relationship have been determined from thermogavimetric analyses (TGA). The kinetic parameters were determined by multiple heating rate technique developed by Freideman and Henderson. Weight loss (decomposition) and weight loss rate (decomposition rate)were measured and recorded for three heating rates; $5^{\circ}C$/min ,$10^{\circ}C$/min, and $20^{\circ}C$/min. Relatively good agreement was obtained between measured and calculated decomposition as a function of temperature. By separating the reaction, the reaction order and pre exponential factor become empirical parameters which provide a "best fit" of the data. However, this method yields an extremely accurate reproduction of the thermograms over a wide range of heating rates. This is the desired result for kinetic parameters used in thermal models.al models.

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Influence of Oxidation Inhibitor on Carbon-Carbon Composites : 8. Studies on Thermal Decomposition Mechanism and Thermal Stability of Composites Impregnated with TEOS (산화억제제를 첨가한 탄소/탄소 복합재료의 물성에 관한 연구 : 8. TEOS를 함유한 복합재료의 열분해 메카니즘 및 열안정성 연구)

  • 박수진;서민강;이재락
    • Polymer(Korea)
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    • v.25 no.6
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    • pp.866-875
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    • 2001
  • In this work, thermal decomposition mechanism based on kinetic parameters and thermal stability of carbon fiber-reinforced carbon matrix composites (C/C composites), have been studied under high temperature oxidative conditions with addition of tetra-ethylorthosilicate (TEOS) as an oxidation inhibitor. Thermogravimetric analysis (TGA) was executed to evaluate the thermal decomposition mechanism and thermal stability of C/C composites in the temperature range of 30 ~ $850^{\circ}C$. As a result, the kinetic parameters of the composites impregnated with TEOS, i.e., activation energy for thermal decomposition ($E_d$), order of reaction (n) , and pre-exponential factor (A) were evaluated as 136 kJ/mol, 0, and 2.3$\times$$10^9s^{-1}$, respectively. Especially, the IPDT and $E_d$ of C/C composites impregnated with TEOS were improved largely compared with the composites impregnated without TEOS, due to the formation of $SiO_2$ on composite surfaces, resulting in interrupting the oxygen attack to carbon active site in the composites.

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Thermal Decomposition Kinetics of ZPP as a Primary Charge of Initiators (착화기용 ZPP의 열분해 특성)

  • Kim, Junhyung;Seo, Taeseok;Ko, Seungwon;Ryu, Byungtae
    • Journal of the Korean Society of Propulsion Engineers
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    • v.19 no.5
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    • pp.15-21
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    • 2015
  • The thermal decomposition characteristics of the ZPP(Zirconium/Potassium perchlorate), widely used as a primary charge of initiators, were investigated by differential scanning calorimetry(DSC). The DSC results with different heating rates were elaborated with AKTS-Thermokinetics software for the determination of the kinetic parameters of the thermal decomposition of ZPP. There was good agreement between the experimental and the simulation curves, based on the determined kinetic parameters, which indicates the validity of the kinetic description of the thermal decomposition process of ZPP.

Crystal Structure and Thermal Decomposition Studies on Cobalt (II) Complex of 4-Chloro-2-((E)-(Isopropylimino)methyl)phenol (4-Chloro-2-((E)-(Isopropylimino)methyl)phenol 코발트(II) 착물에 대한 결정 구조 및 열분해 연구)

  • Pu, Xiao-Hua
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.341-345
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    • 2011
  • The Schiff base cobalt(II) complex, bis[4-chloro-2-((E)-(isopropylimino) methyl) phenol]cobalt(II), has been prepared and characterized by single-crystal X-ray diffraction analyses. The phenomenological, kinetic and mechanistic aspects of the cobalt (II) complex have been studied by TG/DTG techniques. On the basis of the experimental data, the kinetic parameters such as activation energy, pre-exponential factor and entropy of activation were computed, and then the most probable mechanism function was estimated as $g({\alpha})={\alpha}^2$ 2. Hence the rate controlling process at all stages of decomposition is onedimensional diffusion (Parabolic model).

Kinetic Analysis for the Catalytic Pyrolysis of Polyethylene Terephthalate Over Cost Effective Natural Catalysts

  • Pyo, Sumin;Hakimian, Hanie;Kim, Young-Min;Yoo, Kyung-Seun;Park, Young-Kwon
    • Applied Chemistry for Engineering
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    • v.32 no.6
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    • pp.706-710
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    • 2021
  • In the current research, thermal and catalytic thermogravimetric (TG) analysis of polyethylene terephthalate (PET) over natural zeolite (NZ), olivine, bentonite, HZSM-5, and HAl-MCM-41 were investigated using a TG analyzer and model-free kinetic analysis. Catalytic TG analysis of PET was carried out at multi-heating rates, 10, 20, 30, and 40 ℃/min, under nitrogen atmosphere. Apparent activation energy (Ea) values for the thermal and catalytic pyrolysis of PET were calculated using Flynn-Wall-Ozawa method. Although natural catalysts, NZ, olivine, and bentonite, could not lead the higher PET decomposition efficiency than synthetic zeolites, HZSM-5 and HAl-MCM-41, maximum decomposition temperatures on the differential TG (DTG) curves for the catalytic pyrolysis of PET, 436 ℃ over olivine, 435 ℃ over bentonite, and 434 ℃ over NZ, at 10 ℃/min, were definitely lower than non-catalytic pyrolysis. Calculated Ea values for the catalytic pyrolysis of PET over natural catalysts, 177 kJ/mol over olivine, 168 kJ/mol over bentonite, and 171 kJ/mol over NZ, were also not lower than those over synthetic zeolites, however, those were also much lower than the thermal decomposition, suggesting their feasibility as the proper and cost-effective catalysts on the pyrolysis of PET.

Determination of Hydroperoxyl/superoxide Anion Radical (HO2·/O2·-) Concentration in the Decomposition of Ozone Using a Kinetic Method

  • Kwon, Bum-Gun;Lee, Jai H.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1785-1790
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    • 2006
  • A novel kinetic method for determination of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ in ozone decomposition in water is described. In this study, potential interferences of $O_3$ and the hydroxyl radicals, $^{\cdot}OH_{(O3)}$, are suppressed by $HSO_3{^-}/SO_3{^{2-}}$. $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ formed in ozone decomposition reduces $Fe^{3+}$-EDTA into $Fe^{2+}$-EDTA and subsequently the well-known Fenton-like (FL) reaction of $H_2O_2$ and $Fe^{2+}$-EDTA produces the hydroxyl radicals, $^{\cdot}OH_{(FL)}$. Benzoic acid (BA) scavenges $^{\cdot}OH_{(FL)}$ to produce OHBA, which are analyzed by fluorescence detection (${\lambda}_{ex}=320nm$ and ${\lambda}_{ex}=400nm$). The concentration of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ in ozone decomposition has been determined by the novel kinetic method using the experimentally determined half-life ($t_{1/2}$). The steady-state concentration of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ is proportional to the $O_3$ concentration at a given pH. However, the steady-state concentration of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ in ozone decomposition is inversely proportional to pH values. This pH dependence is due to significant loss of $O_2{^{{\cdot}-}}$ by $O_3$ at higher pH conditions. The steady-state concentrations of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ are in the range of $2.49({\pm}0.10){\times}10^{-9}M(pH=4.17){\sim}3.01({\pm}0.07){\times}10^{-10}M(pH=7.59)$ at $[O_3]_o=60{\mu}M$.