• 제목/요약/키워드: chemical mechanism

검색결과 3,263건 처리시간 0.025초

Very Efficient Nucleophilic Aromatic Fluorination Reaction in Molten Salts: A Mechanistic Study

  • Jang, Sung-Woo;Park, Sung-Woo;Lee, Byoung-Se;Chi, Dae-Yoon;Song, Choong-Eui;Lee, Sung-Yul
    • Bulletin of the Korean Chemical Society
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    • 제33권3호
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    • pp.881-884
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    • 2012
  • We report a quantum chemical study of an extremely efficient nucleophilic aromatic fluorination in molten salts. We describe that the mechanism involves solvent anion interacting with the ion pair nucleophile $M^+F^-$(M = Na, K, Rb, Cs) to accelerate the reaction. We show that our proposed mechanism may well explain the excellent efficiency of molten salts for SNAr reactions, the relative efficacy of the metal cations, and also the observed large difference in rate constants in two molten salts $(n-C_4H_9)_4N^+\;CX_3SO_3^-$, (X=H, F) with slightly different sidechain ($-CH_3$ vs. $-CF_3$).

Ti$Cl_4$에 의한 Trioxane의 양이온 중합에 있어서 개시 반응기구 (The Initiation Mechanism in the Polymerization of Trioxane with Titanium Tetrachloride)

  • 한만정
    • 대한화학회지
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    • 제22권6호
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    • pp.423-430
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    • 1978
  • 트리옥산을 니트로벤젠 용매중에서 Ti$Cl_4$로서 중합시킬때 개시 반응기구를 연구하였다. 중합반응속도를 측정한결과 미량의 물이나 메탄올을 첨가하면 반응속도가 급격히 감소하였으며 중합을 개시하는 데는 조촉매로서 다른 물질이 필요 없음이 알려졌다. 유전상수 측정결과에 의하면 중합과정중 양성이온이 생기지 않으며 중합제나 개시제 용액의 전기전도도를 측정한 결과 개시 반응은 니트로벤젠 용매중에서 개시제가 동종간 주고 받기반응에 의하여 생긴 Ti$Cl_3^+$ 양이온에 의하여 일어난다는 것이 판명되었다.

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3중화염의 구조에 미치는 연료종류에 관한 수치해석 (Numerical Analysis on the Triple Flame Structure with Different Kinds of Fuel)

  • 최낙정
    • Journal of Advanced Marine Engineering and Technology
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    • 제23권1호
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    • pp.88-95
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    • 1999
  • This study investigates the effects of different kind fuels on the flame structure by using the numerical simulation in triple flame made by a co-flowing fuels-air stream based on the elementary chemical reaction mechanism. Methane and Hydrogen were used as fuel for this study. In order to interpret the result of the study on numerical simulation Skeletal chemistry is employe as the elementary chemical reaction mechanism for methane Gutheil's as an offset ele-mentary chemical reaction mechanism for hydrogen. The result of this study is as follows. In com-parison between the apparent burning velocity change of triple flame and the one-dimensional pre-mixed flame hydrogen fuel flame is higher than methane fuel flame. The flame thrusts out for-ward in the down stream of the boundary between air-fuel mixture and air stream and a part of the flow is bent and forks out in this protruding flame so that a triple flame is originated.

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Kinetics and Mechanism of the Hydrolysis of N-(Benzenesulfonyl) benzimidoyl Chlorides

  • Kim, Tae-Rin;Kwon, Hyo-Shik
    • Bulletin of the Korean Chemical Society
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    • 제9권3호
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    • pp.157-160
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    • 1988
  • The rates of hydrolysis of N-(benzenesulfonyl) benzimidoyl chlorides (p-H, $p-CH_3,\;p-CH_3,\;p-NO_2\;and m-NO_2$) have been measured by UV spectrometry in 60% methanol-water at $25^{\circ}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 7.00, the substituent effect on the hydrolysis rate of N-(benzenesulfonyl) benzimidoyl chloride was found to conform to the Hammett ${\sigma}$ constant with ${\rho}$ = -0.91, whereas above pH 9.00, with ${\rho}$ = 0.94. On the basis of the rate equation obtained and the effect of solvent, substituents and salt, the following reaction mechanism were proposed; below pH 7.00, the hydrolysis of N-(benzenesulfonyl) benzimidoyl chloride proceeds by $S_N1$ mechanism, however, above pH 9.00, the hydrolysis is initiated by the attack of the hydroxide ion and in the range of pH 7.00-9.00, these two reactions occur competitively.

산 수용액내에서 [Co(en)2(CO3)]+의 아쿠아 반응속도와 반응메커니즘 (Kinetics and Mechanism for aquation of [Co(en)2(CO3)]+ in [H+] aqueous solution)

  • 이철재;김동엽
    • 한국산업융합학회 논문집
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    • 제8권3호
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    • pp.155-160
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    • 2005
  • Kinetic studies were carried out for aquation of carbonatobis(ethylenediamine)cobalt(III) complexes in [H+] aqueous solution by UV/VIS-spectrophotometry. The rate law that in deduced from rate data is $rate=k_H{^+}[H^+]^{1.4}$ {$[Co(en)_2(CO_3)]^+$}1.0 where $k_H{^+}$ is the rate constant considering acidic catalyst, $H^+$ ion whose value is $0.241l{\cdot}mol^{-1}{\cdot}sec^{-1}$. The values of activation parameters Ea, ${\Delta}H^{\ast}$ and ${\Delta}S^{\ast}$ were $15.33Kcal{\cdot}mol^{-1}$, $14.52Kcal{\cdot}mol^{-1}$ and -57.49 e.u. respectively. On the basis of kinetic data and the observed activation parameters, we have proposed the mechanism that proceeds with two step protonations. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation. It has been seen that our modified mechanism for Harris's proton freequilibrium one prefer to the his concerted mechanism, and more the last product substitute $H_2O$ for $OH^-$ the Harris's mechanism in the acidity range 2 < pH < 5.

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