• 제목/요약/키워드: Kinetic mechanism

검색결과 719건 처리시간 0.027초

평행사변형 구조를 갖는 매니퓰레이터 동역학의 선형화 및 단순화 설계 (A Design of Linearized and Simplited Arm Dynamics for the Manipulator with a Paralled Drive Mechanism)

  • 최진태;이병룡;정규원
    • 대한기계학회논문집
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    • 제13권5호
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    • pp.855-861
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    • 1989
  • 본 연구에서는 평행 사변형 구조를 갖는 매니퓰레이터의 운동에너지와 포텐셜 에너지를 구하고, 운동 에너지 식에서 매니퓰레이터 관성 모멘트 행렬 (manipulator inertia matrix)를 구한다.

Kinetics and Mechanism for the Reactions of N-Methyl-N-phenylcarbamoyl Chlorides with Benzylamines in Acetonitrile

  • 고한중;이호찬;이해황;이익준
    • Bulletin of the Korean Chemical Society
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    • 제17권8호
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    • pp.712-715
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    • 1996
  • Kinetic studies are carried out on the reactions of N-methyl-N-phenylcarbamoyl chlorides with benzylamines in acetonitrile. The selectivity parameters, ρX (=-0.6~-0.8), ρY (=1.0-1.1), and ρXY (=-0.14), suggest that the reaction proceeds by an SN2 mechanism. Kinetic isotope effects, kH/kD, involving deuterated nucleophiles (XC6H4CH2ND2) are all inverse type (<1.0), and the trends of changes in the magnitude are consistent with those expected for the observed negative sign of ρXY(=∂ρX/∂σY = ∂ρY/∂σX < 0). The relatively low activation enthalpies also support the proposed mechanism.

Mechanistic Studies of the Solvolyses of Cyclohexanesulfonyl Chloride

  • Kang, Suk Jin;Koh, Han Joong
    • 대한화학회지
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    • 제63권4호
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    • pp.233-236
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    • 2019
  • In this study, the solvolysis of cyclohexanesulfonyl chloride (1) was studied by kinetics in ethanol-water, methanol-water, acetone-water, and 2,2,2-trifluoroethanol (TFE)-water binary solvent systems. The rate constants were applied to the extended Grunwald-Winstein equation, to obtain the values of m = 0.41 and l = 0.81. These values suggested $S_N2$ mechanism in which bond formation is more important than bond breaking in the transition state (TS). Relatively small activation enthalpy values (11.6 to $14.8kcal{\cdot}mol^{-1}$), the large negative activation entropy values (-29.7 to $-38.7cal{\cdot}mol^{-1}{\cdot}K^{-1}$) and the solvent kinetic isotope effects (SKIE, 2.29, 2.30), the solvolyses of the cyclohexanesulfonyl chloride (1) proceeds via the $S_N2$ mechanism.

Kinetic Study on Aminolysis of 4-Chloro-2-Nitrophenyl X-Substituted-Benzoates in Acetonitrile and in 80 mol % H2O/20 mol % DMSO: Effect of Medium on Reactivity and Reaction Mechanism

  • Kim, Ha-Ram;Um, Tae-Il;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제35권4호
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    • pp.1128-1132
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    • 2014
  • A kinetic study on aminolysis of 4-chloro-2-nitrophenyl X-substituted-benzoates (6a-i) in MeCN is reported. The Hammett plot for the reactions of 6a-i with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X$ = 1.03 and r = 0.78. The nonlinear Hammett plot is not due to a change in rate-determining step (RDS) but is caused by the resonance stabilization of substrates possessing an electron-donating group in the benzoyl moiety. The Br${\phi}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (6e) with a series of cyclic secondary amines is linear with ${\beta}_{nuc}$ = 0.69, an upper limit for reactions reported to proceed through a concerted mechanism. The aminolysis of 6e in aqueous medium has previously been reported to proceed through a stepwise mechanism with a change in RDS on the basis of a curved Br${\phi}$nsted-type plot. It has been concluded that instability of the zwitterionic tetrahedral intermediate ($T^{\pm}$) in MeCN forces the reaction to proceed through a concerted mechanism. This is further supported by the kinetic result that the amines used in this study are less reactive in MeCN than in $H_2O$, although they are more basic in MeCN over 7 $pK_a$ units.

응집 pH와 응집제 종류에 따른 Al(III)가수분해종 특성변화에 대한 연구 (A Study of Al(III) Hydrolysis Species Characterization under Various Coagulation Condition)

  • 송유경;정철우;손인식
    • 한국물환경학회지
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    • 제22권5호
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    • pp.958-967
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    • 2006
  • The overall objective of this research was to find out the role of rapid mixing conditions in the species of hydrolyzed Al(III) formed by Al(III) coagulants and to evaluate the distribution of hydrolyzed Al(III) species by coagulant dose and coagulation pH. When an Al(III) salt was added to water, monomers, polymers and solid precipitates may form. Different Al(III) coagulants (alum and PSOM) show to have different Al(III) species distribution over a rapid mixing condition. During the rapid mixing period, for alum, formation of dissolved AI(III) (monomer and polymer) increases, but for PSOM, precipitates of $Al(OH)_{3(S)}$ increases rapidly. During the rapid mixing period, for high coagulant dose, Al-ferron reaction increases rapidly. The kinetic constants, Ka and Kb, derived from AI-ferron reaction. The kinetic constants followed very well the defined tendencies for coagulation condition. For pure water, when the rapid mixing time increased, the kinetic constants, Ka and Kb showed lower values. Also, for raw water, when the rapid mixing time increased, the kinetic constants, Ka and Kb showed lower values. At A/D(Adsorption and Destabilization) and sweep condition, both $Al(OH)_{3(S)}$ and dissolved Al(III) (monomer and polymer) exist, concurrent reactions by both mechanism appear to cause simultaneous precipitation.