• Title/Summary/Keyword: order of reaction

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The Development of the Short Mechanism for Premixed Dimethyl Ether-Air Flames (Dimethyl Ether-Air 예혼합화염의 축소 반응 메카니즘 개발)

  • Lee, Ki Yong;Lee, Su Gak
    • 한국연소학회:학술대회논문집
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    • 2012.11a
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    • pp.211-214
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    • 2012
  • A short reaction mechanism was developed in order to predict the flame phenomena in premixed Dimethyl Ether-Air flame with the methods of SEM-CM(Simulation Error Minimization Connectivity Method), sensitivity analysis, and the rate of production analysis. It consisted of 31 species including nitrogen as inert gas and 177 elementary reactions. The flame structures obtained using a detailed reaction mechanism and the short reaction mechanism were compared with various equivalence ratios and pressure, and the results were in good agreement. Therefore, the short reaction mechanism would be used to aim at studying the development of a reduced reaction mechanism.

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Silicon Melt Infiltration of Reaction-Bonded Silicon Carbide (반응소결 탄화규소에서 실리콘의 침윤향상)

  • 신현익;김주선;이종호;김긍호;송휴섭;이해원
    • Journal of the Korean Ceramic Society
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    • v.39 no.7
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    • pp.693-698
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    • 2002
  • Reaction-Bonded Silicon Carbide (RBSC) Ceramics were fabricated which satisfies the maximum packing density of silicon carbide skeleton in the green compacts. Such a high packing density induced incomplete infiltration during reaction-sintering; forms linear void around the interface of large alpha silicon carbide powders. During reaction-sintering, the limited extraction and entrapped gas induced by residue oxide was considered to be a reason of linear void formation. In order to improve infiltration behavior in the highly packed preform, the pre-treatment methods for residue oxide removal were proposed.

Accelerating Effect of Neutral Salts on Alkaline Hydrolysis of Poly(ethylene terephthalate) (I) - Cationic Effect - (중성염의 폴리에틸렌 텔레프탈레이트의 알칼리 가수분해 촉진효과에 관한 연구(I) - 양이온의 영향 -)

  • Do, Sung-Guk;Cho, Hwan
    • Textile Coloration and Finishing
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    • v.6 no.1
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    • pp.33-43
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    • 1994
  • In the present work, to clarify the mechanism of the neutral salt effect on the alkaline hydrolysis of PET, many salts with different cations like LiCl, NaCl, KCl, CsCl were added to the aqueous alkaline solutions. Then PET was hydrolyzed with aqueous solutions of many salts in alkali metal hydroxides under various conditions. Some conclusions obtained from the experimental results were summarized as follows. The reaction rate of the alkaline hydrolysis of PET was increased by the addition of neutral salts and In k was increased nearly linearly with the square root of ionic strength of reaction medium. This fact suggested that the ionic strength effect by Debye-Huckel and Bronsted theory was exerted on the reaction. The specific salt effect was also observed. The reaction rate was increased with the increase in the electrophilicity of cations of neutral salts, i. e., in the order of $Cs^+$/ < $K^+$/ $a^+$/ $i^$^+$. It was considered that the reaction rate was increased in the order of C $s^+$. < $K^+$. $a^+$. $i^+$. because the lowering effect of the cations on the negative charge of PET surface was increased with the electrophilicity of cations. It was thought that $E_{a}$ was increased because the cations of neutral salts decreased the negative charge of PET surface. It, however, was inferred from the increase in ${\Delta}$S* and the decrease in the ${\Delta}$G* that the cations of neutral salts associated with PET increased the collision frequency between carbonyl carbon and OH- ion and then accelerated the reaction rate.te.

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Application of Horizontal Subgrade Reaction Modulus to Bridge Abutment Design after Soil Improvement (연약지반 개량후 교대구간 수평지반반력계수 적용 사례)

  • Kim, Kyung-Tae;Park, See-Boum;Kim, Chang-Hyun;Lee, Jong-Bum;Yoon, Yea-Won
    • Proceedings of the Korean Geotechical Society Conference
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    • 2006.03a
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    • pp.1228-1236
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    • 2006
  • In soft ground, There are many case that Bridge Abutment is constructed after soil improvement in order to reduce the Negative Friction and prevent from Lateral Soil movements of Bridge Abutment. That section of Horizontal Subgrade Reaction $Modulus(K_h)$ derivation has much important mean due to Horizontal Stability of Abutment. It is come from behavior of Pile and Soil within depth of $1/\beta$. After Soil Improvement, however, If Bridge Abutment was construction, It's not impossible to carry out Field Investigation After Ground of Improved at design stage. Therefore, It's not able to derivate Horizontal Subgrade Reaction $Modulus(K_h)$. Therefore, in this case of study compare with Field Construction Test Data in order to derivation of Horizontal Subgrade Reaction $Modulus(K_h)$ and Reliability in terms of ground of Bridge Abutment by Sand Compaction Pile(SCP) during design of The 2nd Bridge Connection Road of Incheon International Airport. In this paper determine, Soil Property(The rate of strength increase, $c_u$ so on) and Horizontal Subgrade Reaction $Modulus(K_h)$ after soil improvement at design stage.

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Effect of Alkali Metal Ions on Alkaline Ethanolysis of 2-Pyridyl and 4-Pyridyl Benzoates in Anhydrous Ethanol

  • Lee, Jae-In;Kang, Ji-Sun;Kim, Song-I;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2929-2933
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    • 2010
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured for nucleophilic substitution reactions of 2-pyridyl benzoate 5 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol. The plots of $k_{obsd}$ vs. $[EtOM]_o$ are curved upwardly but linear in the excess presence of 18-crown-6-ether (18C6) with significant decreased $k_{obsd}$ values in the reaction with EtOK. The $k_{obsd}$ value for the reaction of 5 with a given EtONa concentration decreases steeply upon addition of 15-crown-5-ether (15C5) to the reaction medium up to ca. [15C5]/$[EtONa]_o$ = 1, and remains nearly constant thereafter, indicating that $M^+$ ions catalyze the reaction in the absence of the complexing agents. Dissection $k_{obsd}$ into $k_{EtO^-}$- and $k_{EtOM}$, i.e., the second-order rate constants for the reaction with the dissociated $EtO^-$ and the ion-paired EtOM, respectively has revealed that ion-paired EtOM is 3.2 - 4.6 times more reactive than dissociated $EtO^-$. It has been concluded that $M^+$ ions increase the electrophilicity of the reaction center through a 6-membered cyclic transition state. This idea has been examined from the corresponding reactions of 4-pyridyl benzoate 6, which cannot form such a 6-membered cyclic transition state.

Metal Ion Catalysis in Nucleophilic Substitution Reaction of 4-Nitrophenyl Picolinate with Alkali Metal Ethoxides in Anhydrous Ethanol

  • Hong, Yeon-Ju;Kim, Song-I;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.9
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    • pp.2483-2487
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    • 2010
  • Pseudo-first-order rate constants ($k_{obsd}$) were measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl picolinate (6) with alkali metal ethoxides (EtOM, $M^+\;=\;K^+$, $Na^+$ and $Li^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] exhibits upward curvature regardless of the nature of $M^+$ ions. However, the plot for the reaction of 6 with EtOK is linear with significantly decreased $k_{obsd}$ values when 18-crown-6-ether (18C6, a complexing agent for $K^+$ ion) is added in the reaction medium. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that ion-paired EtOM is 3~17 times more reactive than dissociated $EtO^-$. The reaction has been proposed to proceed through a 5-membered cyclic transition state, in which $M^+$ ion increases the electrophilicity of the reaction site. Interestingly, $Na^+$ ion exhibits the largest catalytic effect. The presence of a nitrogen atom in the pyridine moiety of 6 has been suggested to be responsible for the high $Na^+$ ion selectivity.

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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Mathematical Modeling of Self-propagating High Temperature Synthesis of Molybdenum- Tungstenb Disilicide (이규화 몰리브덴-텅스텐의 자전 고온 합성 반응 모델링)

  • Yeon, Sun-Hwa;Jang, Dae-Gyu;Lee, Cheol-Gyeong
    • Korean Journal of Materials Research
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    • v.11 no.3
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    • pp.164-170
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    • 2001
  • The Self-propagating High-temperature Synthesis (SHS) for synthesizing ($Mo_{1-z}$ , $W_{z}$)$Si_2$was conducted experimentally with the mole fraction of Tungsten(W) from z=0.0 to z=0.5. The temperature profile was measured according to the reaction time through the thermocouple that was equipped into the center of these samples. When the reaction front is propagated around the thermocouple, the highest temperature appears and we regard this temperature as the adiabatic temperature. We found out by experimental results that the reaction velocity is in the range of 2.14~1.35mm/sec and the adiabatic temperature is in the range of 1883~1507K for the six samples. The reaction velocity and the adiabatic temperature were inclined to decrease with an increasing of the mole fraction of Tungsten (W). The SHS modeling is presented in order to predict the temperature profiles and these results are compared with the experimental results. It is predicted that in case of increasing the initial temperature of these six samples, the reaction temperature increased and that the sample of z=0.5 needs the preheating up to 800~900K in order to become reaction temperature 1900K.

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A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using 2,4'-Bipyridinium Dichromate (2,4'-Bipyridinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응과 반응속도에 관한 연구)

  • Kim, Young Sik;Park, Young Cho
    • Applied Chemistry for Engineering
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    • v.22 no.6
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    • pp.718-722
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    • 2011
  • 2,4'-Bipyridinium dichromate [$(C_{10}H_8N_2H)_2Cr_2O_7$] was synthesized by the reaction of 2,4'-bipyridinie with chromium trioxide in $H_2O$. The structure was characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase in the order of the dielectric constant (${\varepsilon}$), in the order : cyclohexene < chloroform < acetone < N,N'-dimethylformamide. In the presence of hydrochloric acid, 2,4'-bipyridinium dichromate effectively oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant (${\rho}$) was -0.65 at 303 K. The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

A Reaction Kinetic for Selective Catalytic Reduction of NOx with NH3 over Manganese Oxide (NMO, MnO2, Mn2O3) at Low Temperature (망간산화물(NMO, MnO2, Mn2O3)을 이용한 저온에서의 NH3-SCR의 반응속도 연구)

  • Kim, Min Su;Hong, Sung Chang
    • Clean Technology
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    • v.24 no.4
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    • pp.307-314
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    • 2018
  • In this study, NMO (Natural Manganese Ore), $MnO_2$, and $Mn_2O_3$ catalysts were used in the selective catalytic reduction process to remove nitrogen oxides (NOx) using $NH_3$ as a reducing agent at low temperatures in the presence of oxygen. In the case of the NMO (Natural Manganese Ore), it was confirmed that the conversion of nitrogen oxides in the stability test did not change even after 100 hours at 423 K. The Kinetics experiments were carried out within the range where heat and mass transfer were not factors. From a steady-state Kinetics study, it was found that the low-temperature SCR reaction was zero order with the respect to $NH_3$ and 0.41 ~ 0.57 order with the respect to NO and 0.13 ~ 0.26 order with the respect to $O_2$. As temperature increases, the reaction order decreases as a result of $NH_3$ and oxygen concentration. It was confirmed that the reaction between the $NH_3$ dissociated and adsorbedon the catalyst surface and the gaseous nitrogen monoxide (E-R model) and the reaction with the adsorbed nitrogen monoxide (L-H model) occur.