• Title/Summary/Keyword: Kinetic decomposition

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PREPARATION OF POLY(ETHYLENE-CO-VINYL ALCOHOL) MEMBRANE VIA THERMALLY INDUCED PHASE SEPARATION

  • Matsuyama, Hideto;Shang, Mengxian;Teramoto, Masaaki
    • Proceedings of the Membrane Society of Korea Conference
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    • 2004.05a
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    • pp.74-77
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    • 2004
  • Porous membranes were prepared via thermally induced phase separation (TIPS) of (ethylene-co-vinyl alcohol) (EVOH)/glycerol mixtures. The liquid-liquid (L-L) phase boundaries are shifted to higher temperature when the ethylene contents in EVOH increase. Moreover, the kinetic study proved that the growth of droplets formed by the general liquid-liquid (L-L) phase separation obeyed a power-law scaling relationship in the later stage of spinodal decomposition (SD). A new phase separation mechanism was presented, in which the L-L phase separation could be resulted from the crystallization. The hollow fiber membranes were prepared. The membranes showed asymmetric structures with skin layer near the outer surface, the larger pores just below the skin layer and the smaller pores near the inner surface. The effect of ethylene content (EC) in EVOH, cooling water bath temperature and take-up speed on membrane performance was investigated.

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Geometries and Energies of S$_N$2 Transition States$^\dag$

  • Lee, Ik-Choon;Kim, Chan-Kyung;Song, Chang-Hyun
    • Bulletin of the Korean Chemical Society
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    • v.7 no.5
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    • pp.391-395
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    • 1986
  • MNDO calculations were carried out to determine reactant complexes and transition states of the $S_N2$ reactions of $CH_3X\;+\;Y^-\;{\to}\;CH_3Y\;+\;X^-$ where X = F, Cl, CN and Y = CN, OH, F, Cl. The leaving group ability was found to vary inversely with the activation barrier, which in turn was mainly ascribable to the deformation energies accompanied with bond stretching of C-X bond and inversion of $CH_3$ group. The nucleophilicity was shown to be in the order $Cl^->F^->OH^->CN^-$ but the effect on the activation barrier was relatively small compared with that of the leaving group. The bond breaking and bond formation indices and energy decomposition analysis showed that the TS for the reaction of $CH_3$Cl occurs in the early stage of the reaction coordinate relative to that of $CH_3$F. It has been shown that the potential energy surface (PES) diagrams approach can only accommodate thermodynamic effects but fails to correlate intrinsic kinetic effects on the TS structure.

A Gas Phaes Kinetic Study of the Energy Transfer by using the High Power CO$_2$ Laser. (II). Decomposition of $BrCH_2CH_2CH_2CH_2Cl$

  • Lee, Yong-Sik;Kim, Yang-Sik;Jeoung, Sae-Chae;Choo, Kwang-Yul
    • Bulletin of the Korean Chemical Society
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    • v.9 no.3
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    • pp.161-164
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    • 1988
  • Infrared multiphoton decompositions (IRMPD) of $BrCH_2CH_2CH_2CH_2Cl$ were studied by using the pulsed $CO_2$laser. At 0.3 J laser energy the experimentally observed product ratios could be reasonably explained by the RRKM calculation with initial excitation energy of ca. 80 Kcal/mol. The pressure dependence of product yields led us to conclude that the collisional deactivation by the inert gas decreased the yield of low energy dissociation channel more significantly.

High energy laser heating and ignition study

  • Lee, K.C.;Kim, K.H.;Yoh, J.J.
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2008.03a
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    • pp.525-530
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    • 2008
  • We present a model for simulating high energy laser heating and ignition of confined energetic materials. The model considers effect of ablation of steel plate with long laser pulses and continuous lasers of several kilowatts and the thermal response of well-characterized high explosives for ignition. Since there is enough time for the thermal wave to propagate into the target and to create a region of hot spot in the high explosives, electron thermal diffusion of ultra-short(femto- and pico-second) lasing is ignored; instead, heat diffusion of absorbed laser energy in the solid target is modeled with thermal decomposition kinetic models of high explosives are used. Numerically simulated pulsed-laser heating of solid target and thermal explosion of cyclotrimethylenetrinitramine(RDX), triaminotrinitrobenzene(TATB), and octahydrotetranitrotetrazine(HMX) are compared to experimental results. The experimental and numerical results are in good agreement.

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A Study of Nitrous Oxide Decomposition using Calcium Oxide (Calcium Oxide를 이용한 N2O 분해에 관한 CO2의 영향 연구)

  • Paek, Jin-Young;Park, Yeong-Sung;Shun, Dowon;Bae, Dal-Hee
    • Korean Chemical Engineering Research
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    • v.40 no.6
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    • pp.746-751
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    • 2002
  • Fluidized bed combustion is a coal combustion technology that can reduce both SOx and NOx emission; SOx is removed by limestone that is fed into the combustion chamber and the NOx is reduced by low temperature combustion in a fluidized bed combustor and air stepping, but $N_2O$ generation is quite high. $N_2O$ is not only a greenhouse gas but also an agent of ozone destruction in the stratosphere. The calcium oxide(CaO) is known to be a catalyst of $N_2O$ decomposition. This study of $N_2O$ decomposition reaction in fixed bed reactor packed over CaO bed has been conducted. Effects of parameters such as concentration of inlet $N_2O$ gas, reaction temperature, CaO bed height and effect of $CO_2$, NO, $O_2$ gas on the decomposition reaction have been investigated. As a result of the experiment, it has been shown that $N_2O$ decomposition reaction increased with the increasing fixed bed temperature. While conversion of the reaction was decreased with increasing $CO_2$ concentration. Also, under the present of NO, the conversion of $N_2O$ decomposition is decreased. From the result of kinetic study gained the heterogeneous reaction rate on $N_2O$ decomposition. In the case of $N_2O$ decomposition over CaO, heterogeneous reaction rate is. $\frac{d[N_2O]}{dt}=\frac{3.86{\times}10^9{\exp}(-15841/R)K_{N_2O}[N_2O]}{(1+K_{N_2O}[N_2O]+K_{CO_2}[CO_2])}$. In this study, it is found that the calcium oxide is a good catalyst of $N_2O$ decomposition.

Pyrolysis Characteristics of the Mixture of Waste Fishing Net and Waste Ship Lubricating Oil (폐어망과 선박용 폐윤활유 혼합물의 열분해반응 특성 연구)

  • Kim, Seung-Soo;Kim, Young-Sik
    • Applied Chemistry for Engineering
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    • v.19 no.5
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    • pp.568-573
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    • 2008
  • Kinetic tests on pyrolysis of waste fishing net [WFN; nylon-6], waste ship lubricating oil [WSLO] and their mixture were carried out by thermogravimetric analysis (TGA) with heating rate of 0.5, 1.0, and $2.0^{\circ}C/min$. Pyrolysis of waste fishing net started at $300^{\circ}C$, and the main region of decomposition temperature was between 360 and $440^{\circ}C$ at each heating rate. Decomposition temperature of the mixture of WFN and WSLO was lower than that of WFN and WSLO, and the shape of thermogravimetic graph of mixture was different as well. The corresponding kinetic parameters including activation energy and pre-exponential factor were determined by differential method over the degree of conversions. The values of activation energies for the mixture of WFN and WSLO were between 98 and 427 kJ/mol as the conversion increased from 5% to 95%. Tubing reactor was used to analysis of pyrolyzed oil at $440^{\circ}C$ for 80 min. The selectivity of specific hydrocarbons was not detected and the carbon number distribution of the pyrolyzed oil was below $C_{22}$.

Research on Pyrolysis Properties of Waste Plastic Films (폐플라스틱 필름의 열분해특성에 대한 연구)

  • Kim, Young-Min;Lee, Boram;Han, Tae Uk;Kim, Seungdo;Yu, Tae-U;Bang, Byoung Yeol;Kim, Joug-Su;Park, Young-Kwon
    • Applied Chemistry for Engineering
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    • v.28 no.1
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    • pp.23-28
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    • 2017
  • Pyrolysis characteristics of waste plastic films were investigated by using a thermogravimetric analysis and pyrolyzer-gas chromatography/mass spectrometry. Thermogravimetric analysis results revealed that the pyrolysis of waste plastic films can be divided into two distinct reactions; (1) the decomposition reaction of starch at between 200 and $370^{\circ}C$ and (2) that of other plastic polymers such as PS, PP, PE at between 370 and $510^{\circ}C$. The kinetic analysis results obtained by using the revised Ozawa method indicated that the apparent activation energy of the pyrolysis reaction of waste plastic films was also changed dramatically according to the different decomposition reactions of two major waste plastic film components. Py-GC/MS results also revealed that the typical pyrolyzates of each polymer in waste plastic films were levoglucosan (starch), terephthalic acid (PET), styrene monomer, dimer, and trimer (PS), methylated alkenes (PP), and triplet peaks (PE) composed of alkadiene/alkene/alkane. The phthalate, used as a polymer additive, was also detected on the pyrogram of waste plastic films mixture.

In-situ Fourier Transform Infrared Spectroscopic Study during Thermolysis of Trimethylaluminum and its Adduct (Trimethylaluminum (TMA), $NH_3$ 및 TMA :$NH_3$Adduct의 열분해 반응에 대한 in-situ FTIR 분광학적 연구)

  • Hyang Sook Kim;Seong Han Kim;Jin Soo Hwang;Joong Gill Choi;Paul Joe Chong
    • Journal of the Korean Chemical Society
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    • v.37 no.12
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    • pp.995-1002
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    • 1993
  • The thermal decomposition of trimethylaluminum (TMA) with ammonia has been investigated by in-situ Fourier transform infrared spectroscopy. The spectroscopic reaction cell, which permits heating interna lly up to 1100$^{\circ}C$, consists of stainless-steel hexagonal-port chamber containing two NaCl windows installed in parallel. In this work, the stoichiometric reaction between TMA and $NH_3$ is found to be completed immediately after mixing. FTIR spectra observed in the range of temperature 25∼1100$^{\circ}C$ show that TMA and TMA : $NH_3$ adduct decompose into methane as a predominant product around 500$^{\circ}C$. The assignments of the IR bands due to the gaseous TMA, $NH_3$ and TMA : $NH_3$ adduct are attempted on the basis of the published data. Furthermore, the decomposition of TMA can be described as a first-order reaction. Kinetic data about the decompositon of TMA and TMA : $NH_3$adduct will also be discussed.

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A Study on Formation and Thermal Decomposition Kinetics of PU Elastomers by Dynamic DSC and TGA Analysis (Dynamic DSC 및 TGA 열분석을 이용한 PU Elastomer의 중합반응 및 열분해 반응 Kinetics에 관한 연구)

  • Yoon, Soo-Koong;Ahn, Won-Sool
    • Elastomers and Composites
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    • v.42 no.1
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    • pp.47-54
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    • 2007
  • Reaction kinetics of polyurethane elastomers (PU) were studied using dynamic DSC and TGA for three PU samples of general purpose (Sample A), high temperature cross-likable CASE purpose with MOCA (Sample B), and RT cross-likable CASE purpose grade (Sample C). From DSC results, sample with MOCA(Sample B) showed lower shift of peak temperature, while showing broader thermograms than those of general purpose grade (Sample A). On the other hand, RT cross-linkable PU grade (Sample C) showed an interesting double mode reaction patterns, i.e., a lower temperature reaction at about $70\;^{\circ}C$, and a higher temperature reaction in the range of $140{\sim}170\;^{\circ}C$, indicating that it requires 2-step reaction process in order to complete the reaction. Once the cross-linking reaction completed, however, TGA results showed that all the samples would be considered to have similar chemical structures, showing similar decomposition processes. Sample C, especially, had showed decomposition properties of both Sample A and Sample B. Formation activation energies calculated from Kissinger method showed 10.39, 65.85, 36.52(Low $T_p$) and 18.21(High $T_p$) kcal/mol, while decomposition activation energies were 31.94, 30.84, 24.16 kcal/mol, respectively.

Effect of Precipitation Temperature and Solution pH on the Precipitation of Ammonium Metavanadate (침전온도 및 수용액 pH가 암모늄메타바나데이트 침전반응에 미치는 영향)

  • Heo, Seo-Jin;Kim, Rina;Chung, Kyeong Woo;Jeon, Ho-Seok;Kim, Chul-Joo;Yoon, Ho-Sung
    • Resources Recycling
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    • v.30 no.6
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    • pp.3-11
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    • 2021
  • In this study, the effect of the solubility of ammonium metavanadate and the decomposition ratio of ammonium ions on a precipitation reaction-the precipitation of ammonium metavanadate by adding ammonium chloride to a sodium vanadate solution-was investigated. As the precipitation temperature and pH increased, the decomposition ratio of ammonium ions increased, and the decomposition ratio was greater than 81% at 45 ℃ and pH 9.3. This was approximately four times higher than that at pH 8. The result of the precipitation reaction, in view of these two factors that significantly influence the precipitation reaction, was that the precipitation yield increased as the temperature increased. However, the effect of temperature was not significant above 35 ℃. A kinetic study of the precipitation reaction revealed that the activation energy of the reaction was 42.3 kJ/mol. Therefore, considering the solubility of ammonium metavanadate, the lower the temperature, the better the vanadium recovery yield. Additionally, considering the decomposition of ammonium ions, the lower the pH of the aqueous solution, the more advantageous. However, at pH 8 or less, sodium polyvanadate is precipitated and the purity of vanadium oxide may reduce.