• Bulletin of the Korean Chemical Society
• /
• 제15권3호
• /
• pp.183-186
• /
• 1994

• Bulletin of the Korean Chemical Society
• /
• 제22권2호
• /
• pp.244-246
• /
• 2001

• Bulletin of the Korean Chemical Society
• /
• 제14권3호
• /
• pp.319-320
• /
• 1993

• Bulletin of the Korean Chemical Society
• /
• 제13권3호
• /
• pp.339-341
• /
• 1992

• Bulletin of the Korean Chemical Society
• /
• 제32권6호
• /
• pp.1851-1858
• /
• 2011

Details of the double-bond isomerization of 1-hexene over H-ZSM-5 were clarified using density functional theory. It is found that the reaction proceeds by a mechanism which involves the Br${\o}$nsted acid part of the zeolite solely. According to this mechanism, 1-hexene is first physically adsorbed on the acidic site, and then, the acidic proton transfers to one carbon atom of the double bond, while the other carbon atom of the double bond bonds with the Br${\o}$nsted host oxygen, yielding a stable alkoxy intermediate. Thereafter, the Br${\o}$nsted host oxygen abstracts a hydrogen atom from the $C_6H_{13}$ fragment and the C-O bond is broken, restoring the acidic site and yielding trans-2-hexene. The calculated activation barrier is 12.65 kcal/mol, which is in good agreement with the experimental value. These results well explain the energetic aspects during the course of double-bond isomerization and extend the understanding of the nature of the zeolite active sites.

• 한국독성학회:학술대회논문집
• /
• 한국독성학회 2003년도 추계학술대회
• /
• pp.24-25
• /
• 2003

Genotoxicity plays an important role for the safety evaluation of chemicals. When the carcinogenicity is evident on a chemical, the threshold can be estimated only when genotoxic mechanism does not operate for carcinogenesis otherwise threshold cannot be set. Without genotoxic mechanism- non-genotoxic carcinogen-threshold can be estimated but with genotoxic mechanism-genotoxic- carcinogen-it cannot be estimated.(omitted)

• Bulletin of the Korean Chemical Society
• /
• 제32권5호
• /
• pp.1539-1542
• /
• 2011

The aminolysis of O-methyl S-aryl thiocarbonates with benzylamines are studied in acetonitrile at -45.0$^{\circ}C$. The ${\beta}_X$(${\beta}_{nuc}$) values are in the range 0.62-0.80 with a negative cross-interaction constant, ${\rho}_{XZ}$ = -0.42, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles ($XC_6H_4CH_2ND_2$) are large, $k_H/k_D$ = 1.29-1.75, suggesting that the N-H(D) bond is partially broken in the transition state by forming a hydrogen-bonded four-center cyclic structure. The concerted mechanism is enforced by the strong push provided by the MeO group which enhances the nucleofugalities of both benzylamine and arenethiolate from the putative zwitterionic tetrahedral intermediate.

• 한국정밀공학회:학술대회논문집
• /
• 한국정밀공학회 2004년도 추계학술대회 논문집
• /
• pp.925-928
• /
• 2004

The application of focused ion beam (FIB) technology in micro/nano machining has become increasingly popular. Its use in micro/nano machining has advantages over contemporary photolithography or other micro/nano machining technologies such as small feature resolution, the ability to process without masks and being accommodating for a variety of materials and geometries. This paper was carried out some experiments and verifications of mechanism on FIB-CVD using SMI8800 made by Seiko. FIB-CVD has in fact proved to be commercially useful for repair processes because the beam can be focused down to 0.05$\mu\textrm{m}$ dimensions and below and because the same tool can be used to sputter off material with sub-micrometer precision simply by turning off the gas ambient. Recently the chemical vapour deposition induced ion beam has been required more deposition rate and accurate pattern because of trying to manufacture many micro and nano parts. Therefore this paper suggested the optimization parameters and discussed some mechanism of chemical vapour deposition induced ion beam on FIB-CVD for simple pattern.

• Journal of Mechanical Science and Technology
• /
• 제16권1호
• /
• pp.102-108
• /
• 2002

Numerical simulations of 1, 2 dichloroethane(EDC) pyrolyisis are conducted to understand the process in the production of the vinyl chloride monomer (VCM) and by-products. A chemical kinetic mechanism Is developed, with the adopted scheme involving 44 gas-phase species and 260 elementary forward and backward reactions. Detailed sensitivity analyses and the rates of production analysis are performed on each of the reactions and the various species, respectively. The concentrations of EDC, VCM, and HCI predicted by this mechanism are in good agreement with those deduced from experiments of commercial and laboratory scale. The mechanism is found to accurately predict the EDC yield an(1 the production of by-products by varying the ranges of pyrolysis temperature, residence time, and pressure which impact on the pyrolysis of 1, 2 dichloroethane. The influence of reactions related to H atom on the relative sensitivity of EDC becomes important as the residence time increases. The pyrolysis of EDC mainly occurs through C$_2$H$_4$Cl$_2$+Cl=CH$_2$CICHI+HCI.

• Bulletin of the Korean Chemical Society
• /
• 제32권1호
• /
• pp.137-140
• /
• 2011

The aminolysis reactions of phenyl N-benzyl thiocarbamate with benzylamines in acetonitrile at $50.0^{\circ}C$ are investigated. The reactions are first order in both the amine and the substrate. Under amine excess, pseudo-first coefficient ($k_{obs}$) are obtained, plot of $k_{obs}$ vs free amine concentration are linear. The signs of ${\rho}_{XZ}$ (< 0) are consistent with concerted mechanism. Moreover, the variations of $\rho_X$ and $\rho_Z$ with respect to the sustituent in the substrate and large ${\rho}_{XZ}$ value indicate that the reactions proceed concerted mechanism. The normal kinetic isotope effects ($k_H/k_D$ = 1.3 ~ 1.5) involving deuterated benzylamine nucleophiles suggest a hydrogen-bonded, four-centered-type transition state. The activation parameters, ${\Delta}H^\ddagger$ and ${\Delta}S^\ddagger$, are consistent with this transition state structure.