• 제목/요약/키워드: Third-order rate constant

검색결과 21건 처리시간 0.03초

Modeling of an elastomer constitutive relation

  • Sung, Dan-Keun
    • 제어로봇시스템학회:학술대회논문집
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    • 제어로봇시스템학회 1988년도 한국자동제어학술회의논문집(국제학술편); 한국전력공사연수원, 서울; 21-22 Oct. 1988
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    • pp.1018-1021
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    • 1988
  • This study is concerned with modeling an elastomer constitutive relation by utilizing the truncated Volterra series. Actual experimental data from the Instron Tester are obtained for combined input, i.e. constant strain rate followed by a constant strain input. These data are then estimated for step inputs and utilized for the truncated Volterra series models. One second order and one third order truncated Volterra series models have been employed to estimated the force-displacement relation which is one of the prominent properities to characterize the viscoelastic material. The third order Volterra series model has better results, compared with those of the second order Volterra series model.

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Kinetic Studies on Bromine-Exchange Reactions of Antimony Tribromide with $\alpha$-Phenyl-n-butyl and $\alpha$-Phenyl-i-butyl Bromides in Nitrobenzene$^\dag$

  • Rhyu, Sok-Hwan;Choi, Sang-Up
    • Bulletin of the Korean Chemical Society
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    • 제8권5호
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    • pp.408-414
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    • 1987
  • The rate of bromine-exchange reaction between antimony tribromide and ${\alpha}-phenyl-n-butyl$ bromide in nitrobenzene has been determined, using antimony tribromide labelled with Br-82. The results indicate that the exchange reaction follows the first-order kinetics with respect to the organic bromide, and either the second- or first-order kinetics with respect to antimony tribromide depending on its concentration. The third-order rate constant obtained was 7.50 ${\times}10^{-2}l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. Similar study on the bromine-exchange reaction between antimony tribromide and ${\alpha}$-phenyl-i-butyl bromide has also been carried out. The results of the study show the same kinetic orders as the ones observed with $\alpha$-phenyl-n-butyl bromide. The third-order rate constant observed was 2.40 ${\times} 10^{-2} l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. The activation energy, the enthalpy of activation and the entropy of activation for the two exchange reactions mentioned above have been determined. The reaction mechanisms for the exchange reactions are discussed.

기체 상태에서의 오존과 아황산가스의 반응연구 (The Kinetics Study of Ozone with Sulfur Dioxide in the Gas Phase)

  • 권영식
    • 대한화학회지
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    • 제35권2호
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    • pp.111-118
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    • 1991
  • 기체 상태의 오존(0.5 torr)과 이산화황간의 반응속도를 연구하였다. 이산화황은 7∼22 torr 의 압력범위에서 90∼155$^{\circ}$C의 온도영역에서 반응시켰다. 오존과 이산화황의 반응속도는 이산화탄소와의 반응보다 빨리 진행되었다. 오존과 이산화황의 반응속도식은 -d(O$_3 )/dt = k _0 (SO _2 )(M)(O _3)+2k _1(SO_2 )(O _3$)였다. 이 속도식의 첫 항은 3분자 반응으로 낮은 온도에서 우세하게 진행되었으며, 속도상수 k$_0 =(9.35{\pm}8.6){\times}10^9e^{-(11.05{\pm}2.04)kcal/RT}(M^{-2}s^{-1}$)이다. 속도식의 두번째 항은 2분자 열분해 반응으로부터 유도된 주된 반응으로 속도상수 k$_1=(1.53{\pm}1.5){\times}10^{11}e^{-22.7 kcal/RT}$이다. 전 반응차수는 주로 2차 반응이며 3차 반응과 복합반응으로 진행되었다.

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고무의 힘-변위 관계를 나타내는 모델링에의 볼테라 급수의 응용 (Application of Volterra Series to Modeling an Elastomer Force-Displacement Relation)

  • 성단근
    • 대한전자공학회논문지
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    • 제26권6호
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    • pp.71-78
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    • 1989
  • 비선형 시스템의 입출력 관계는 볼테라 급수로 나타낼 수 있으며 그것은 볼테라 커널에 의해 규명될 수 있다. 본 연구는 소수의 볼테라 급수항을 사용하여 계단 입력에 의한 고무의 힘-변위 관계를 모델링하는데 관한 것이다. 무한의 기울기를 가진 계단 입력을 가하여 얻어진 실험결과에서 일정한 압축시의 계단입력에 대한 결과를 예측한다. 비스코일레스틱 재료를 나타내는 현저한 특징중의 하나인 힘-변위 관계를 모델링하기 위해 2차와 3차 볼테라 급수 모델을 사용한다. 3차 볼테라 급수 모델이 2차 볼테라 급수 모델의 결과에 비해 더 좋은 결과가 얻어지고 있다.

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Kinetics of the Bromine-Exchange Reaction of Gallium Bromide with i-Butyl Bromide in 1,2,4,-Trichlorobenzene and in Nitrobenzene

  • Kwun, Oh-Cheun;Kim, Young-Cheul;Choi, Sang-Up
    • Bulletin of the Korean Chemical Society
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    • 제2권4호
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    • pp.138-141
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    • 1981
  • The rate of the bromine-exchange reaction between gallium bromide and i-butyl bromide in 1,2,4-trichlorobenzene or nitrobenzene was measured at 19, 25 and $40^{\circ}C$, using i-butyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to i-butyl bromide. The third-order rate constant determined at $19{\circ}C$ was $3.28{\times}10^{-2}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in 1,2,4-trichlorobenzene and $9.25{\times}10^{-3}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in nitrobenzene. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined.

Kinetics of the Bromine-Exchange Reaction of Gallium Bromide with n-Propyl Bromide in 1,2,4-Trichlorobenzene and in Nitrobenzene

  • Kwun, Oh-Cheun;Kim, Young-Cheul;Choi ,Sang-Up
    • Bulletin of the Korean Chemical Society
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    • 제2권3호
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    • pp.86-89
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    • 1981
  • The rate of the bromine-exchange reaction between gallium bromide and n-propyl bromide in 1,2,4-trichlorobenzene and in nitrobenzene was measured at 19, 25 and $40^{\circ}C$, using n-propyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to n-propyl bromide. The third-order rate constant determined at $19^{\circ}C$ is $2.9{\times} 10^{-2}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in 1,2,4-trichlorobenzene and $4.5{\times}10^{-3}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$. in nitrobenzene. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined. Reaction mechanism for the bromine exchange of n-propyl bromide seemed to be similar to those observed in earlier studies with other alkyl bromides.

Product-Rate Correlations for Solvolyses of 2,4-Dimethoxybenzenesulfonyl Chloride

  • Kim, Soo Ryeon;Choi, Hojune;Park, Jong Keun;Koo, In Sun;Koh, Han Joong
    • Bulletin of the Korean Chemical Society
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    • 제35권1호
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    • pp.51-56
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    • 2014
  • The solvolysis rate constants of 2,4-dimethoxybenzenesulfonyl chloride (1) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $0.93{\pm}0.14$ and $0.65{\pm}0.06$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.4 to $14.6kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -15.5 to -$32.3kcal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effects (SKIE) were 1.74 to 1.86, which is also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The values of product selectivity (S) for solvolyses of 1 in alcohol/water mixtures was 0.57 to 6.5, which is also consistent with the proposed bimolecular reaction mechanism. Third-order rate constants, $k_{ww}$ and $k_{aa}$, were calculated from the rate constants ($k_{obs}$), together with $k_{aw}$ and $k_{wa}$ calculated from the intercept and slope of the plot of 1/S vs. [water]/[alcohol]. The calculated rate constants, $k_{calc}$ ($k_{ww}$, $k_{aw}$, $k_{wa}$ and $k_{aa}$), are in satisfactory agreement with the experimental values, supporting the stoichiometric solvation effect analysis.

황의 친핵성 치환반응 (제11보). 염화나프탈렌술포닐과 아닐린과의 반응 (Nucleophilic Displacement at Sulfur Center (XI). Reaction of Naphthalenesulfonyl Chlorides with Anilines)

  • 이익춘;엄태섭;이억석
    • 대한화학회지
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    • 제22권5호
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    • pp.281-288
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    • 1978
  • 1-염화 및 2-염화나프탈렌술포닐과 아닐린과의 반응에서 그 반응의 유사 일차 반응속도상수($k_{obs}$)를 구하고 또한 2차 반응속도 상수 $k_2$및 3차반응 촉매속도상수 $k_3$$k_{obs}$로 부터 구하였다. 1-염화나프탈렌술포닐과의 반응에서는 Peri-hydrogen 효과가 관측되었다. 또한 Brensted 그림표에서는 큰 값의 ${\beta}$와 Hammett 그림표의 기울기로부터 크 음의 ${\rho}$값을 얻었다. 따라서 이 반응의 메카니즘은 매우 낮은 활성화파라미터의 값을 갖는 결과로$S_AN$반응메카니즘과 잘 일치되지만 associative$S_N2$메카니즘으로도 동일하게 잘 설명될 수 있었다.

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니트로벤젠 용액내에서의 브롬화갈륨과 브롬화이소프로필의 브롬 교환 반응 (Kinetics of the Bromine-Exchange Reaction of Gallium Bromide with Isopropyl Bromide in Nitrobenzene)

  • 최상업
    • 대한화학회지
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    • 제14권1호
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    • pp.85-89
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    • 1970
  • 방사성 브롬으로 표시한 브롬화이소프로필을 사용하여 니트로벤젠 용액내에서 브롬화칼륨과 브롬과이소프로필 사이에 일어나는 브롬교환반응의 속도를 19$^{\circ},\;25^{\circ}$및 40$^{\circ}C$에서 측정하였다. 본 실험의 결과는 이 브롬교환반응이 브롬화갈륨에 관하여 2차 반응이고 브롬화이소프로필에 관하여 1차 반응임을 보여준다. 19$^{\circ}C$에서의 반응속도 상수 값이 $k_3=3.2{\times}10^{-2}l^2{\cdot}mole^{-2}sec^{-1}$임을 알았다. 그리고 반응속도상수와 온도와의 관계로부터 이 교환반응에 대한 활성화에너지, 활성화엔탈피 및 활성화엔트로피 값을 계산하였다.

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국내외 우수 여자선수 100m 허들동작의 운동학적 비교 분석 (The Kinematic Analysis and Comparison of Foreign and Domestic 100m Elite Woman's Hurdling Techniques)

  • 류재균;여홍철;장재관
    • 한국운동역학회지
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    • 제17권4호
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    • pp.157-167
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    • 2007
  • The purpose of this study was to analyze kinematic techniques in the woman's 100m hurdle. In order to find the kinematic parameters, a 3-D video system for kinematic analysis-kwon3d 3.1(Kwon3D Motion Analysis Program Version 3.1)-was used. Eight JVC video cameras(GR-HD1KR) were used to film the performance of Lee Yeon-Kyoung at a frame rate of 60fields/s. The kinematic characteristics from the first hurdle to last hurdle were analyzed at the clearing hurdle spots such as distance, velocities, heights and angles. The real-life three-dimensional coordinates of 20 body landmarks during each phases were collected using a Direct Linear Transformation procedure. After analyzing the kinematic variables in the 100m hurdle run, the following conclusion were obtained; Lee Yeon-Kyoung had to maintain constant stride lengths between hurdles and increase takeoff distance before clearance and shorter landing distance after clearance. She also had to hit the correct takeoff point in front of the hurdle and extend the lead leg at the moment of landing in order to minimize the loss of velocity. She had to sprint between hurdles as fast as possible over 8m/s and run powerful first stride and shortened third stride preparing for the following hurdle clearances.