Search | Korea Science

Jang, Sung-Woo;Park, Sung-Woo;Lee, Byoung-Se;Chi, Dae-Yoon;Song, Choong-Eui;Lee, Sung-Yul
- Bulletin of the Korean Chemical Society
- /
- v.33 no.3
- /
- pp.881-884
- /
- 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. $-CF_3$).
https://doi.org/10.5012/bkcs.2012.33.3.881 인용 PDF KSCI

Han Man Jung
- Journal of the Korean Chemical Society
- /
- v.22 no.6
- /
- pp.423-430
- /
- 1978
The initiation mechanism of trioxane polymerization catalyzed by Ti$Cl_4$ in nitrobenzene was investigated. The kinetic studies revealed that the rate of polymerization was drastically decreased by the addition of a minute amount of water or methanol. A third substance as cocatalyst was not required for the polymerization. Measurements of dielectric constants gave no evidence for the zwitterionic mechanism of the polymerization. The electric conductivity measurements of polymerization system and the initiator solution showed that the initiation was started by Ti$Cl_3^+$ cation, formed by a disproportionation of the initiator in nitrobenzene.
PDF

최낙정
- Journal of Advanced Marine Engineering and Technology
- /
- v.23 no.1
- /
- pp.88-95
- /
- 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.
PDF

Kim, Tae-Rin;Kwon, Hyo-Shik
- Bulletin of the Korean Chemical Society
- /
- v.9 no.3
- /
- pp.157-160
- /
- 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.
https://doi.org/10.5012/bkcs.1988.9.3.157 인용 PDF

Lee, Chul-Je;Kim, Dong-Yeub
- Journal of the Korean Society of Industry Convergence
- /
- v.8 no.3
- /
- pp.155-160
- /
- 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.
PDF