• Journal of the Korean Chemical Society
• /
• v.13 no.4
• /
• pp.289-296
• /
• 1969

The rate constants for the addition reaction of ethylmercaptan to ethylcinnamate has been measured by iodometry and for the proposed reaction mechanism a rate equation which can be applied over wide pH range was derived. From this rate equation, one may conclude that the reaction is started by addition of ethylmercaptan molecule below pH 3. However, above pH 7, this addition reaction is proceeded by the ethylmercaptide ion. At pH 3-7, the complex addition reaction mechanism can also be revealed by this rate equation.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.11
• /
• pp.2183-2188
• /
• 2008

• Journal of the Korean Chemical Society
• /
• v.12 no.3
• /
• pp.106-113
• /
• 1968

The rate-constants of the nucleophilic addition reaction of n-butylmercaptan to 3,4-methylenedioxy-${\beta}$-nitrostyrene were determined at various acidic pH and a rate equation which can be applied over wide pH range was obtained. From this equation, one may conclude that this reaction is started by addition of mercaptan molecule below pH 3, while above pH 6, the overall rate of addition is almost only depend upon the concentration of nitrostyrene and the mercaptide ion. At pH 3∼6, the complex mechanism of this addition reaction can also be fully explained by the rate equation.

• Bulletin of the Korean Chemical Society
• /
• v.17 no.10
• /
• pp.939-943
• /
• 1996

Reactions that proceed within mixed acetylene-methanol and ethylene-methanol cluster ions were studied using an electron-impact time-of-flight mass spectrometer. When acetylene and methanol seeded in helium are expanded and ionized by electron impact, the ion abundance ratio, [CH3OH+]/[CH2OH+] shows a propensity to increase as the acetylene/methanol mixing ratio increases, indicating that the initially ionized acetylene ion transfers its charge to adjacent methanol molecules within the clusters. Investigations on the relative cluster ion intensity distributions of [CH3OH2+]/[CH3OH+] and [(CH3OH)2H+]/[CH3OH·CH2OH+] under various experimental conditions suggest that hydrogen-atom abstraction reaction of acetylene molecule with CH3OH ion is responsible for the effective formation of CH2OH ion. In ethylene/methanol clusters, the intensity ratio of [CH3OH2]/[CH3OH] increases linearly as the relative concentration of methanol decreases. The prominent ion intensities of (CH3OH)mH over (CH3OH)m-1CH2OH ions (m=1, 2, and 3) at all mixing ratios are also interpreted as a consequence of hydrogen atom transfer reaction between C2H4 and CH3OH to produce the protonated methanol cluster ions.

• Journal of the Korean Chemical Society
• /
• v.56 no.1
• /
• pp.14-19
• /
• 2012

We investigate the doublet and quartet potential energy surfaces associated with the gas-phase reaction between $Ti^+$ and $CF_3COCH_3$ for two plausible reaction pathways, $TiF_2^+$ and $TiO^+$ formation pathways by using the density functional theory (DFT) method. The molecular structures of intermediates and transition states involved in these reaction pathways are optimized at the DFT level by using the PBE0 functional. All transition states are identified by using the intrinsic reaction coordinate (IRC) method, and the resulting reaction coordinates describe how $Ti^+$ activates $CF_3COCH_3$ and produces $TiF_2^+$ and $TiO^+$ as products. On the basis of presented results, we propose the most favorable reaction pathway in the reaction between $Ti^+$ and $CF_3COCH_3$.

• Journal of the Korean Chemical Society
• /
• v.19 no.2
• /
• pp.123-129
• /
• 1975

The rate constants of the hydrolysis of phenylvinylsulfone were determined by ultraviolet spectrophotometry at various pH and a rate equation which can be applied over wide pH range was obtained. The reaction mechanism of hydrolysis of phenylvinylsulfone and especially the catalytic contribution of hydroxide ion which did not study carefully before in acidic media, can be fully explained by the rate equation obtained. The rate equation reveals that: below pH 7, the reaction is initiated by the addition of water molecule to phenylvinylsulfone. At above pH 9, the overall rate constant is only dependent upon the concentration of hydroxide ion.

• Journal of the Korean Chemical Society
• /
• v.18 no.6
• /
• pp.423-429
• /
• 1974

The rate constant of the addition of hydrogen cyanide to $ ${\alpha}$-cyano-\beta-piperonylacrylic$ acid (CPA) were determined by UV spectrophotometry at various pH and a rate equation which can be applied over wide pH range was obtained. From this equation, one may conclude that below pH 3 the reaction is started by the addition of hydrogen cyanide molecule to CPA, however, at pH 6~8, hydrogen cyanide is added to $ {\alpha}$-cyano-$ {\beta}$-piperonyl acrylate anion. From pH 3 to 6, these two reaction are competitive. Above pH 9, the reaction is proceeded by the addition of cyanide ion to $ {\alpha}$-cyano-$ {\beta}$-piperonyl acrylate ion. From pH 3 to 9, the complex reaction mechanism can also be fully explained by the rate equation obtained.

• Journal of the Korean Chemical Society
• /
• v.16 no.4
• /
• pp.232-240
• /
• 1972

The rate constants for the addition reaction of n-butylmercaptan to ethylacrylate have been measured by iodometry and for the proposed reaction mechanism a rate equation which can be applied over wide pH range was derived. From this rate equation, one may conclude that the reaction is started by addition of n-butylmercaptan molecule below pH 4. However, above pH 7, this addition reaction is proceeded by the n-butylmercaptide ions. At pH 4-7, the complex addition reaction mechanism can also be revealed by this rate equation.

• Analytical Science and Technology
• /
• v.9 no.1
• /
• pp.1-12
• /
• 1996

The thermally labile compounds with hydroxyl group generate the [${MNH_4}^+$] ion, [$MH^+$] and [$MH^+-OH$] ion by ion-molecule reaction in LC/TSP/MS. But these ions create the trouble in the estimation of molecular weight of an unknown compound because the margin of [${MNH_4}^+$] ion and [$MH^+$] ion is same to that of [$MH^+$] ion and [$MH^+-OH$] ion. If it is compensated for the results by using of the $CF_3COOD+NH_4OH$ LC eluent, the molecular weight of analyte will be able to be confirmed. And this study was tried to recognize whether the fragment ions of thermally labile compound are generated by electron impact or by thermal degradation in ion source.

• Journal of the Korean Chemical Society
• /
• v.26 no.6
• /
• pp.407-413
• /
• 1982

The rate constants of the nucleophilic addition of cysteine to 3,4-methylenedioxyphenylmethylene malononitrile were determined by UV Spectrophotometry and a rate equation which can be applied over wide pH range was obtained. On the basis of rate equation, it may be concluded that the rate constants were dependent upon only the concentration of hydroxide ion above pH 9.0, however, below pH 6.0, the reaction were initiated by the addition of neutral cysteine molecule to carbon-carbon double bond and at pH 7.0~9.0, the addition of a neutral cysteine molecule and it's anion occurred competitively.