• Title/Summary/Keyword: Reaction rate equation

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Investigation on the Relationship between Mass Transfer and Reaction within the Washcoat of Monolith Type Micro-scale Catalytic Combustor (모노리스 타입 마이크로 촉매 연소기의 담층 내부 물질전달 및 반응 관계에 관한 연구)

  • Lee, Gwang Goo;Suzuki, Yuji
    • Journal of the Korean Society of Combustion
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    • v.20 no.2
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    • pp.46-53
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    • 2015
  • The relationship between mass transfer and reaction within the washcoat is investigated in a monolith type micro-scale Pt-catalytic combustor. Nondimensionalized balance equation of butane is applied in a simplified washcoat geometry having the shape of slab. Both Thiele modulus and effectiveness factor are considered to compare reaction rate and diffusion rate according to the operation temperature and the diameter of alumina nano-pores. The effect of reaction becomes stronger as the temperature increases, while the effect of diffusion becomes relatively dominant as the diameter of nano-pores increases. From the analysis of butane distribution within the washcoat, design criterion for the thickness of washcoat is discussed.

Study of the Curing Reaction Rate of a Glass Fiber Reinforced Bisphenol-A (BPA) Epoxy Prepreg by Differential Scanning Calorimetry (DSC) (Differential Scanning Calorimetry (DSC)를 이용한 유리섬유 Bisphenol-A(BPA)계 에폭시 프리프레그의 경화 반응 속도 연구)

  • Kwon, Hyeon-Jin;Park, Hee-Jung;Lee, Eun-Ju;Ku, Sang-Min;Kim, Seon-Hong;Lee, Kee-Yoon
    • Composites Research
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    • v.31 no.1
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    • pp.30-36
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    • 2018
  • The curing behavior of glass fiber reinforced epoxy prepregs based on Bisphenol-A (BPA) was studied by differential scanning calorimetry (DSC). The total heat of reaction(${\Delta}H_{total}=280.3J/g$) was determined based on the results of the dynamic heating scanning experiments. Isothermal experiments were carried out at $110{\sim}130^{\circ}C$, and it was observed that the maximum conversion and the maximum reaction rate were increased as temperature increased. Also Kamal equation was applied to analyze autocatalytic reaction of epoxy prepregs. The higher temperatures, the greater reaction rate constants ($k_1$, $k_2$). Theoretical values were calculated by these reaction rate constants and compared with experimental values. And it was confirmed that they were in reasonable agreement. At the beginning of the reaction, the experimental data and theoretical prediction were shown the same tendency, but at the end of reaction, the experimental data were smaller than theoretical predicted values due to reaction rates controlled by diffusion.

Cure Reactions of Epoxy/Anhydride/(Polyamide Copolymer) Blends

  • Youngson Choe;Kim, Wonho
    • Macromolecular Research
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    • v.10 no.5
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    • pp.259-265
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    • 2002
  • The cure kinetics of blends of epoxy (DGEBA, diglycidyl ether of bisphenol A)/anhydride resin with polyamide copolymer, poly(dimmer acid-co-alkyl polyamine), were studied using differential scanning calorimetry (DSC) under isothermal condition. On increasing the amount of polyamide copolymer in the blends, the reaction rate was increased and the final cure conversion was decreased. Lower values of final cure conversions in the epoxy/(polyamide copolymer) blends indicate that polyamide hinders the cure reaction between the epoxy and the curing agent. The value of the reaction order, m, for the initial autocatalytic reaction was not affected by blending polyamide copolymer with epoxy resin, and the value was approximately 1.3, whereas the reaction order, n, for the general n-th order of reaction was increased by increasing the amount of polyamide copolymer in the blends, and the value increased from 1.6 to 4.0. A diffusion-controlled reaction was observed as the cure conversion increased and the rate equation was successfully analyzed by incorporating the diffusion control term for the epoxy/anhydride/(polyamide copolymer) blends. Complete miscibility was observed in the uncured blends of epoxy/(polyamide copolymer) up to 120 $^{\circ}C$, but phase separations occurred in the early stages of the curing process at higher temperatures than 120 "C. During the curing process, the cure reaction involving the functional group in polyamide copolymer was detected on a DSC thermogram.gram.

Numerical modeling of underwater explosion phenomena (수중 폭발현상에 대한 전산해석)

  • Lee Jaimin;Kuk Jeong-Hyun;Choi Kyung Young;Cho Yong Soo;Song So-young
    • 한국전산유체공학회:학술대회논문집
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    • 1998.05a
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    • pp.1-14
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    • 1998
  • Underwater explosion properties for TNT, an ideal explosive, and DXD-04, a nonideal explosive, were numerically modeled with a one-dimensional Lagrangian hydrodynamic code. The equation of state parameters for detonation products for TNT and DXD-04 were obtained from the BKW code, assuming complete reaction. Burn of TNT was modeled by using the Chapman-Jouguet(CJ) volume burn technique, a programmed-burn technique, assuming instantaneous detonation reaction. Burn of DXD-04 was modeled by using the same technique and by using the reaction rate calibrated from two-dimensional steady-state detonation experiments. The calculations for TNT reproduced the experimental peak pressure of the shock wave propagating through water with an error of $3.0\%$ and the experimental oscillation period of the bubble formed of detonation products with an error of $2.3\%$. For DXD-04, the CJ volume burn technique could not reproduce the experimental observations. When the reaction rate calibrated from two-dimensional steady-state detonation experimental data, the calculated peak pressure was slightly higher by $7.3\%$ than the experimental data, but the calculated shock profile was in good agreement. The bubble period was reproduced with an error of $1.8\%$. These results demonstrated that underwater explosion properties for an ideal explosive can be predicted by using a programmed burn technique, and that, however, those for a nonideal explosive can be predicted only when a well-calibrated reaction rate is used.

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Oxidation of Chloroethenes by Heat-Activated Persulfate (과황산의 열적활성화 및 염소계용제의 산화분해)

  • Zhang, Hailong;Kwon, Hee-Won;Choi, Jeong-Hak;Kim, Young-Hun
    • Journal of Environmental Science International
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    • v.26 no.11
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    • pp.1201-1208
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    • 2017
  • Oxidative degradation of chlorinated ethenes was carried out using heat-activated persulfate. The activation rate of persulfate was dependent on the temperature and the activation reaction rate could be explained based on the Arrhenius equation. The activation energy of persulfate was 19.3 kcal/mol under the assumption that the reaction between the sulfate radical and tricholoroethene (TCE) is very fast. Activation could be achieved at a moderate temperature, so that the adverse effects due to high temperature in the soil environment were mitigated. The reaction rate of TCE was directly proportional to the concentration of persulfate, indicating that the remediation rate can be controlled by the concentration of the injected persulfate. The solution was acidized after the oxidation, and this was dependent on the oxidation temperature. The consumption rate of persulfate was high in the presence of the target organic, but the self-decomposition rate became very low as the target was completely removed.

Solvolysis Reaction Kinetics, Rates and Mechanism for Phenyl N-Phenyl Phosphoramidochloridate

  • Choi, Hojune;Yang, Kiyull;Koh, Han Joong;Koo, In Sun
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2465-2470
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    • 2014
  • The rate constants of solvolysis of phenyl N-phenyl phosphoramidochloridate (PhNHPO(Cl)OPh, Target Compound-TC1) have been determined by a conductivity method. The solvolysis rate constants of TC1 are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and YCl solvent ionizing scale, and sensitivity values of $0.85{\pm}0.14$ and $0.53{\pm}0.04$ for l and m, respectively. These l and m values were similar to those obtained previously for the complex chemical substances dimethyl thiophosphorochloridate; N,N,N',N'-tetramethyldiamidophosphorochloridate; 2-phenyl-2-ketoethyl tosylate; diphenyl thiophosphinyl chloride; and 9-fluorenyl chloroformate. As with the five previously studied solvolyses, an $S_N2$ pathway is proposed for the solvolyses of TC1. For four representative solvents, the rate constants were measured at several temperatures, and activation parameters (${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$) were estimated. These activation parameters are also in line with the values expected for an $S_N2$ reaction.

Kinetic Studies on the Oxidation Reaction of Malonic Acid by Ceric Ion (세륨(Ⅳ)에 의한 말론산의 산화반응에 관한 반응속도론적 연구)

  • Kim, Wang Gi
    • Journal of the Korean Chemical Society
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    • v.38 no.10
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    • pp.705-709
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    • 1994
  • The kinetics of the oxidation reaction of malonic acid by ceric ion in 1 M sulfuric acid solution at $20^{\circ}C$ have been investigated by spectrophotometric method. The reaction rate at a large excess of malonic acid was found to be pseudo-first order. The observed pseudo-first order rate constants, $k_{obs}$, are dependent on the concentration of malonic acid, [MA], of which relationship has been found to be $k_{obs}$ = (0.592[MA])/(1+14.5[MA]$^2$). A mechanism for the reaction has been suggested on the basis of the above rate equation. The rate determining step may be the electron transfer reaction between enolate type malonate anion, which is formed by the acid dissociation reaction of malonic acid, and Ce(IV). The rate depression in the range of high concentration of MA has been explained by the formation of 1 : 2 chelate between Ce(IV) and malonate. According to the mechanism, the pH dependence of the rate, which was studied by Sengupta et al., has also been explained.

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Oxidation Study on the Fabrication of Fe-36Ni Oxide Powder from Its Scrap

  • Yun, Jung Yeul;Park, Man Ho;Yang, Sangsun;Lee, Dong-Won;Wang, Jei-Pil
    • Journal of Powder Materials
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    • v.20 no.1
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    • pp.48-52
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    • 2013
  • A study of oxidation kinetic of Fe-36Ni alloy has been investigated using thermogravimetric apparatus (TGA) in an attempt to define the basic mechanism over a range of temperature of 400 to $1000^{\circ}C$ and finally to fabricate its powder. The oxidation rate was increased with increasing temperature and oxidation behavior of the alloy followed a parabolic rate law at elevated temperature. Temperature dependence of the reaction rate was determined with Arrhenius-type equation and activation energy was calculated to be 106.49 kJ/mol. Based on the kinetic data and micro-structure examination, oxidation mechanism was revealed that iron ions and electrons might migrate outward along grain boundaries and oxygen anion diffused inward through a spinel structure, $(Ni,Fe)_3O_4$.

Photocure Reactions of Photoreactive Prepolymers with Cinnamate Groups

  • Kim, Whan-Gun
    • Bulletin of the Korean Chemical Society
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    • v.32 no.3
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    • pp.993-999
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    • 2011
  • The photoreactive prepolymers with multifunctional cinnamate and bisphenol Atype cinnamate groups that could perform photodimerization without photoinitiators were synthesized by the reaction of t-cinnamic acids (CAs) and epoxy resins. Their photocure reaction rates and the extent of reaction conversion were measured with Fourier transform infrared spectroscopy, and these increased with the intensity of UVirradiation. The experimental data of these reaction rates showed the characteristics of nth-order kinetics reaction, and all kinetic constants of each photoreactive polymer with this equation were summarized. Although the GTR-1800-HCA and KWG1-EP-HCA with hydroxyl group substituted cinnamate showed lower reaction conversion rates and rate constant than GTR-1800-CA and KWG1-EP-CAwith an unsubstituted cinnamate group, GTR-1800-MCAand KWG1-EP-MCAwith methoxy group substituted cinnamate showed similar and higher reaction conversion rates than the former, respectively. These results were explained in terms of segmental mobility for photopolymerization by molecular interactions.

Kinetics and Mechanism of the Hydrolysis of ${\alpha}$-Cyano-${\beta}$-piperonylacrylic Acid (${\alpha}$-Cyano-${\beta}$-Piperonylacrylic Acid의 가수분해 메카니즘과 그의 반응속도론적 연구)

  • Tae Rin Kim;Kwang Il Lee
    • Journal of the Korean Chemical Society
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    • v.17 no.4
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    • pp.269-274
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    • 1973
  • The rate constants of the hydrolysis of ${\alpha}$-Cyano-${\beta}$-piperonylacrylic acid were determined by Ultraviolet spectrophotometry at various pH and a rate equation which can be applied over wide pH range was obtained. The reaction mechanism of hydrolysis of ${\alpha}$-Cyano-${\beta}$-piperonylic acid and especially the catalytic contribution of hydroxide ion which not studied carefully before in acidic media, can be fully explained by the rate equation obtained. The rate equation reveals that; below pH 4.0, the reaction is initiated by the addition of water molecule to ${\alpha}$-Cyano-${\beta}$-piperonyl acrylic acid. At pH $5.0{\sim}7.5$, ${\alpha}$-Cyano-${\beta}$-piperonylacrylic acid compete with ${\alpha}$-Cyano-${\beta}$-piperonyl acrylate ion in adding of water. At pH 8.0, water is the only nucleophile for ${\alpha}$-Cyano-${\beta}$-piperonylacrylate ion, however, above pH 12.0, hydroxide ion is an addendum and the accepter is ${\alpha}$-Cyano-${\beta}$-piperonylacrylate ion.

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