• Title/Summary/Keyword: Rate Determining Step

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Theoretical Analysis on Bifurcation Behavior of Catalytic Surface Reaction on Nonadiabatic Stagnation Plane (비단열 정체면에서 촉매 표면반응의 천이 거동에 대한 이론적 해석)

  • Lee, Su- Ryong
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.28 no.6
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    • pp.697-704
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    • 2004
  • Bifurcation behavior of ignition and extinction of catalytic reaction is theoretically investigated in a stagnation-point flow. Considering that reaction takes place only on the catalytic surface, where conductive heat losses are allowed to occur, activation energy asymptotics with a overall one-step Arrhenius-type catalytic reaction is employed. For the cases with and without the limiting reactant consumption, the analysis provides explicit expressions, which indicate the possibility of multiple steady-state solution branches. The difference between the solutions with and without reactant consumption is in the existence of an upper solution branch, and the neglect of reactant consumption is inappropriate for determining extinction conditions. For larger values of reactant consumption, the solution response is all monotone, suggesting that multiple solutions are not possible. It is shown that bifurcation Damkohler numbers increase (decrease) with increasing of conductive heat loss (gain) on the catalytic surface, which means that smaller (larger) values of the strain rate allow the surface reaction to tolerate larger heat losses (gains). Lewis number of the limiting reactant can also significantly affect bifurcation behavior in a similar way to the effect of heat loss.

Nucleophilic Substitution Reactions of Aryl Thiophene-2-carbodithioates with Pyridines in Acetonitrile

  • Oh, Hyuck-Keun;Lee, Jae-Myon
    • Bulletin of the Korean Chemical Society
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    • v.25 no.2
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    • pp.203-206
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    • 2004
  • The kinetics of reactions between Z-aryl thiophene-2-carbodithioates and X-pyridines in acetonitrile at 60.0 $^{\circ}C$ have been investigated. The Bronsted plots obtained for the pyridinolysis of aryl thiophene-2-carbodithioates are curved, with the center of curvature at $pK_a$ ~ 5.2 ($pK_a^{\circ}$). The Bronsted plots for these nucleophilic reactions show a change in slope from a large ( ${\beta}_X{\cong}$0.78-0.87) to a small ( ${\beta}_X{\cong}$0.33-0.35) value, which can be attributed to a change in the rate-determining step from breakdown to formation of a zwitterionic tetrahedral intermediate in the reaction path as the basicity of the pyridine nucleophile increases. A clear-cut change in the crossinteraction constants, ${\rho}_{XZ}$, from +0.92 to -0.23 supports the proposed mechanistic change. The breakpoint at $pK_a$ = 5.2 for R = thiophene ring in the present work is in agreement with those for the pyridinolysis of R = Me and 2-furyl, and attests to the insignificant effects of acyl group, R, on the breakpoint.

Determining Appropriate Production Conditions in Cellular Manufacturing Systems (셀생산(生産)의 효율적(效率的)인 운용(運用)을 위한 시뮤레이션 연구(硏究))

  • Song, Sang-Jae;Choi, Jung-Hee
    • Journal of Korean Institute of Industrial Engineers
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    • v.19 no.2
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    • pp.23-34
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    • 1993
  • Although there are numerous studies that address the problem of optimal machine grouping and part family classification for cellular manufacturing, little research has been reported that studies the conditions where cellular manufacturing is appropriate. This paper, in order to evaluate and compare the job shop with the GT cellular shop, the performance of those shops were simulated by using SIMAN. We tested the effect of independent variables including changes of product demands, intercell flow level, group setup time, processing time variability, variety of material handling systems, and job properties (ratio of processing time and material handling time). And also performance measures (dependent variables), such as machine utilization, mean flow time, average waiting time, and throughput rate, are discussed. Job shop model and GT cellular shop written in SIMAN simulation language were used in this study. These systems have sixteen machines which are aggregated as five machine stations using the macro feature of SIMAN. The results of this research help to better understand the effect of production factors on the performance of cellular manufacturing systems and to identify some of the necessary conditions required to make these systems perform better than traditional job shops. Therefore, this research represents one more step towards the characterization of shops which may benefit from cellular manufacturing.

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A Dynamic Placement Mechanism of Service Function Chaining Based on Software-defined Networking

  • Liu, Yicen;Lu, Yu;Chen, Xingkai;Li, Xi;Qiao, Wenxin;Chen, Liyun
    • KSII Transactions on Internet and Information Systems (TIIS)
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    • v.12 no.10
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    • pp.4640-4661
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    • 2018
  • To cope with the explosive growth of Internet services, Service Function Chaining (SFC) based on Software-defined Networking (SDN) is an emerging and promising technology that has been suggested to meet this challenge. Determining the placement of Virtual Network Functions (VNFs) and routing paths that optimize the network utilization and resource consumption is a challenging problem, particularly without violating service level agreements (SLAs). This problem is called the optimal SFC placement problem and an Integer Linear Programming (ILP) formulation is provided. A greedy heuristic solution is also provided based on an improved two-step mapping algorithm. The obtained experimental results show that the proposed algorithm can automatically place VNFs at the optimal locations and find the optimal routing paths for each online request. This algorithm can increase the average request acceptance rate by about 17.6% and provide more than 20-fold reduction of the computational complexity compared to the Greedy algorithm. The feasibility of this approach is demonstrated via NetFPGA-10G prototype implementation.

Correlation of the Rates of Solvolysis of 1- and 2-Naphthyl Chloroformates Using the Extended Grunwald-Winstein Equation

  • Moon, Doo-Hwan;Seong, Mi-Hye;Kyong, Jin-Burm;Lee, Ye-Lin;Lee, Yong-Woo
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2413-2417
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    • 2011
  • The specific rates of solvolysis of 1- naphthyl chloroformate (1-NaphOCOCl, 1) and 2-naphthyl chloroformate (2-NaphOCOCl, 2) have been determined in a wide range of solvents at 2.0 and 10.0$^{\circ}C$. These give a satisfactory correlation over the full range of solvents when the extended (two-term) Grunwald-Winstein equation is applied. The sensitivities (l and m-values) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) are similar to those reported previously for solvolysis of phenyl chloroformate, which has been suggested to proceed through an addition-elimination mechanism with the addition step being rate determining. For four representative solvents, studies were made at several temperatures and activation parameters determined. These observations were also compared with those previously reported for phenyl chloroformates and naphthoyl chlorides.

The α-Effect in SNAr Reaction of 1-Fluoro-2,4-dinitrobenzene with Hydrazine: Ground-State Destabilization versus Transition-State Stabilization

  • Cho, Hyo-Jin;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2371-2374
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    • 2014
  • A kinetic study is reported on SNAr reaction of 1-fluoro-2,4-dinitrobenzene with a series of primary amines including hydrazine in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{obsd}$ vs. [amine] are linear and pass through the origin, indicating that general-base catalysis by a second amine molecule is absent. The Br${\o}$nsted-type plot exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.46 when hydrazine is excluded from the correlation. The reaction has been suggested to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs after the rate-determining step (RDS). Hydrazine is ca. 10 times more reactive than similarly basic glycylglycine (i.e., the ${\alpha}$-effect). A five-membered cyclic intermediate has been suggested for the reaction with hydrazine, in which intramolecular H-bonding interactions would facilitate expulsion of the leaving group. However, the enhanced leaving-group ability is not responsible for the ${\alpha}$-effect shown by hydrazine because expulsion of the leaving group occurs after RDS. Destabilization of the ground-state of hydrazine through the electronic repulsion between the nonbonding electron pairs is responsible for the ${\alpha}$-effect found in the current $S_NAr$ reaction.

Kinetic Study on Aminolysis of 4-Nitrophenyl Nicotinate and Isonicotinate: Factors Influencing Reactivity and Reaction Mechanism

  • Kim, Min-Young;Shin, Minah;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2443-2447
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    • 2014
  • A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate (7) and 4-nitrophenyl isonicotinate (8) with a series of cyclic secondary amines in $H_2O$ containing 20 mol % DMSO at $25.0^{\circ}C$. The Br${\o}$nsted-type plots for the reactions of 7 and 8 are linear with ${\beta}_{nuc}=0.90$ and 0.92, respectively, indicating that the reactions proceed through a stepwise mechanism with expulsion of the leaving group occurring in the rate-determining step. Comparison of the reactivity of 7 and 8 with that of 4-nitrophenyl benzoate (2a) and 4-nitrophenyl picolinate (6) has revealed that their reactivity toward the amines increases in the order 2a < 7 < 8 < 6, although the reactions of these substrates proceed through the same mechanism. Factors that control reactivity and reaction mechanism have been discussed in detail (e.g., inductive and field effects, H-bonding interaction, solvent effect, etc.).

Oxygen Reduction Mechanism and Electrode Properties of (La,Sr)$MnO_3$-YSZ Composite Cathode for Solid Oxide Fuel Cell (Part I: Oxygen Reduction Mechanism) (고체산화물 연료전지용 (La,Sr)$MnO_3$-YSZ 복합체 양극의 산소환원 반응기구 및 전극 특성 (Part I: 산소환원 반응기구))

  • 김재동;김구대;이기태
    • Journal of the Korean Ceramic Society
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    • v.38 no.1
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    • pp.84-92
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    • 2001
  • (La,Sr)MnO$_3$(LSM)-YSZ 복합체 양극의 산소환원 반응기구에 대해 고찰하였다. YSZ를 첨가함에 따라 복합체 양극의 ohmic 저항이 증가하고, 분극 저항은 YSZ를 40 wt%~50 wt% 혼합하였을 때 최소값을 나타내었다. 또한 LSM-YSZ 복합체 양극의 산소환원 반응기구는 1가 산소이온의 표면확산과 산소이온전달반응에 의해서 지배됨을 알 수 있었다. 임피던스 분석 결과에 따르면 고주파수 영역에서 나타나는 반원은 산소이온전달반응으로 산소분압 의존성이 거의 없고, YSZ가 40 wt% 첨가되었을 때 최소값을 나타내었다. 중간주파수 영역에서 나타나는 반원은 1가 산소이온의 표면확산반응으로 산소분압 의존성은 약 1/4이고, YSZ가 40~50 wt% 첨가되었을 때 최소값을 나타냈다. 한편, 저주파수 영역에 나타나는 반원은 가스확산반응으로 산소분압 의존성이 1이고, 온도에 따른 의존성이 거의 없었다.

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Detection and Recognition of Overlapped Circular Objects based a Signature Representation Scheme (Signature 기반의 겹쳐진 원형 물체 검출 및 인식 기법)

  • Park, Sang-Bum;Hahn, Hern-Soo;Han, Young-Joon
    • Journal of Institute of Control, Robotics and Systems
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    • v.14 no.1
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    • pp.54-61
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    • 2008
  • This paper proposes a new algorithm for detecting and recognizing overlapped objects among a stack of arbitrarily located objects using a signature representation scheme. The proposed algorithm consists of two processes of detecting overlap of objects and of determining the boundary between overlapping objects. To determine overlap of objects, in the first step, the edge image of object region is extracted and those areas in the object region are considered as the object areas if an area is surrounded by a closed edge. For each object, its signature image is constructed by measuring the distances of those edge points from the center of the object, along the angle axis, which are located at every angle with reference to the center of the object. When an object is not overlapped, its features which consist of the positions and angles of outstanding points in the signature are searched in the database to find its corresponding model. When an object is overlapped, its features are partially matched with those object models among which the best matching model is selected as the corresponding model. The boundary among the overlapping objects is determined by projecting the signature to the original image. The performance of the proposed algorithm has been tested with the task of picking the top or non-overlapped object from a stack of arbitrarily located objects. In the experiment, a recognition rate of 98% has been achieved.

Assembly of Laccase over Platinum Oxide Surface and Application as an Amperometric Biosensor

  • Quan, De;Kim, You-sung;Yoon, Kyung-Byung;Shin, Woon-sup
    • Bulletin of the Korean Chemical Society
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    • v.23 no.3
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    • pp.385-390
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    • 2002
  • Laccase could be successfully assembled on an amine-derivatized platinum electrode by glutaraldehyde coupling. The enzyme layer formed on the surface does not communicate electron directly with the electrode, but the enzymatic activity of the surf ace could be followed by electrochemical detection of enzymatically oxidized products. The well-known laccase substrates, ABTS (2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)) and PPD (p-phenylenediamine) were used. ABTS can be detected down to 0.5 ${\mu}M$ with linear response up to 15 ${\mu}M$ and current sensitivity of 75 nA/ ${\mu}M.$ PPD showed better response with detection limit of 0.05 ${\mu}M$, linear response up to 20 ${\mu}M$, and current sensitivity of 340 nA/ ${\mu}M$ with the same electrode. The sensor responses fit well to the Michaelis-Menten equation and apparent $K_M$ values are 0.16 mM for ABTS and 0.055 mM for PPD, which show the enzymatic reaction is the rate-determining step. The laccase electrode we developed is very stable and more than 80% of initial activity was still maintained after 2 months of uses.