• Bulletin of the Korean Chemical Society
• /
• 제30권12호
• /
• pp.2909-2912
• /
• 2009

The amines studied in this study are less reactive toward ethyl propiolate (3) in MeCN than in H$_2$O although they are 7 to 9 pK$_a$ units more basic in the aprotic solvent. The reactivity of morpholine and deuterated morpholine toward 3 is found to be identical, indicating that proton transfer occurs after rate-determining step (RDS). The fact that kinetic isotope effect is absent excludes a stepwise mechanism in which proton transfer occurs in RDS as well as a concerted mechanism in which nucleophilic attack and proton transfer occur concertedly through a 4-membered cyclic transition state (TS). Thus, the reactions have been concluded to proceed through a stepwise mechanism in which proton transfer occurs after RDS. Brønsted-type plots are linear with small ${\beta}_{nuc}$ values, i.e., ${\beta}_{nuc}$ = 0.29 in H$_2$O and ${\beta}_{nuc}$ = 0.51 in MeCN, indicating that bond formation is not advanced significantly in RDS. The small ${\beta}_{nuc}$ value also supports the conclusion drawn from the study of kinetic isotope effect.

• Bulletin of the Korean Chemical Society
• /
• 제33권10호
• /
• pp.3274-3278
• /
• 2012

The kinetic studies on the reactions of phenyl N-phenyl phosphoramidochloridate (8) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $60.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are huge secondary inverse ($k_H/k_D$ = 0.52-0.69). A concerted mechanism is proposed with a backside attack transition state (TS) on the basis of the secondary inverse DKIEs and the variation trends of the $k_H/k_D$ values with X. The degree of bond formation in the TS is really extensive taking into account the very small values of the DKIEs. The steric effects of the two ligands on the rates are extensively discussed for the aminolyses of the chlorophosphate-type substrates on the basis of the Taft equation.

• Bulletin of the Korean Chemical Society
• /
• 제34권10호
• /
• pp.2989-2994
• /
• 2013

The solvolysis rate constants of 3,4- (1) and 3,5-dimethoxybenzoyl (2) chlorides were measured in various pure and binary solvents at $25.0^{\circ}C$, and studied by application of the extended Grunwald-Winstein (G-W) equation, kinetic solvent isotope effect in methanolysis and activation parameters. The solvolysis of 1 was interpreted as the unimolecular pathway due to a predominant resonance effect from para-methoxy substituent like 4-methoxybenzoyl chloride (3), while that of 2 was evaluated as the dual mechanism, with unimolecular or bimolecular reaction pathway according to the character of solvent systems (high electrophilic/nucleophilic) chosen, caused by the inductive effect by two meta-methoxy substituents, no resonance one. In the solvolyses of 1 and 2 with two $-OCH_3$ groups, the resonance effect of para-methoxy substituent is more important to decide the mechanism than the inductive effect with other corresponding evidences.

• Bulletin of the Korean Chemical Society
• /
• 제34권4호
• /
• pp.1096-1100
• /
• 2013

The kinetic studies on the reactions of O-methyl (1), O-propyl (3) and O-isopropyl (4) phenyl phosphonochloridothioates with substituted anilines and deuterated anilines have been carried out in acetonitrile at $55.0^{\circ}C$. A concerted $S_N2$ mechanism is proposed for the anilinolyses of 1, 3 and 4. The anilinolysis rates of the phosphonochloridothioates are predominantly dependent upon the steric effects over the inductive effects of the two ligands. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal with 1 and 3, while secondary inverse with 4. Primary normal and secondary inverse DKIEs are rationalized by frontside and backside nucleophilic attack transition state, respectively. The DKIEs of the phosphonochloridothioates do not have any consistent correlations with the two ligands.

• International Journal of Automotive Technology
• /
• 제7권4호
• /
• pp.501-508
• /
• 2006

The effect of chemical additives, such as dimethyl ether(DME), ethanol, carbon disulfide on the soot formation were examined numerically. ill this study, the Frenklach soot mechanism was used as a base mechanism to predict the soot formation in the ethane flame. The combination of Westbrook's DME mechanism, Marinov's ethanol mechanism, and chemical kinetic mechanism for hydrogen sulfide and carbon disulfide flames was made with the base mechanism because the DME, ethanol, $CS_2$ additives are added into the ethane fuel. CHEMKIN code was used as a numerical analysis software to simulate the effect of chemical additives on reduction of the polycyclic aromatic hydrocarbons(PAH's) which are soot precursors. From the numerical results it is observed that addition of DME, ethanol and $CS_2$ into ethane fuel can reduce PAH species significantly. That means theses additives can reduce soot formation significantly. Results also strongly suggest suppression of soot formation by these additives to be mainly a chemical effect. Hand OH radicals may be the key species to the reduction of PAH species for additives.

• Bulletin of the Korean Chemical Society
• /
• 제27권2호
• /
• pp.224-230
• /
• 2006

Escherichia coli transcription termination factor Rho catalyzes the unwinding of RNA/DNA duplex in reactions that are coupled to ATP binding and hydrolysis. We report here the kinetic mechanism of presteady state ATP binding and hydrolysis by the Rho-RNA complex. Presteady state chemical quenched-flow technique under multiple turnover condition was used to probe the kinetics of ATP binding and hydrolysis by the Rho-RNA complex. The quenched-flow presteady state kinetics of ATP hydrolysis studies show that three ATPs are bound to the Rho-RNA complex with a rate of $4.4\;{\times}\;10^5M^{-1}s^{-1}$, which are subsequently hydrolyzed at a rate of $88s^{-1}$ and released during the initiation process. Global fit of the presteady state ATP hydrolysis kinetic data suggests that a rapid-equilibrium binding of ATP to Rho-RNA complex occurs prior to the first turnover and the chemistry step is not reversible. The initial burst of three ATPs hydrolysis was proposed to be involved in the initialization step that accompanies proper complex formation of Rho-RNA. Based on these results a kinetic model for initiation process for Rho-RNA complex was proposed relating the mechanism of ATP binding and hydrolysis by Rho to the structural transitions of Rho-RNA complex to reach the steady state phase, which is implicated during translocation along the RNA.

• 한국자동차공학회논문집
• /
• 제16권6호
• /
• pp.74-80
• /
• 2008

A combustion of CAI engine is purely dominated by fuel chemical reactions. In order to simulate the combustion of CAI engine, it should be considered the effect of fuel components and chemical kinetics. So it needs enormous computational power. To overcome this problem reduced problem of needing massive computational power, chemical kinetic mechanism and multi-zone method is proposed here in this paper. A reduced chemical kinetic mechanism for a gasoline surrogate was used in this study for a CAI combustion. This gasoline surrogate was modeled as a blend of iso-octane, n-heptane, and toluene. For the analysis of CAI combustion, a multi-zone method as combustion model for a CAI engine was developed and incorporated into the computational fluid dynamics code, STAR-CD, for computing efficiency. This coupled multi-zone model can calculate 3 dimensional computational fluid dynamics and multi-zoned chemical reaction simultaneously in one time step. In other words, every computational cell interacts with the adjacent cells during the chemical reaction process. It can enhance the reality of multi-zone model. A greatly time-saving and yet still relatively accurate CAI combustion simulation model based on the above mentioned two efficient methodologies, is thus proposed.

• Bulletin of the Korean Chemical Society
• /
• 제30권8호
• /
• pp.1887-1890
• /
• 2009

• Bulletin of the Korean Chemical Society
• /
• 제31권6호
• /
• pp.1793-1796
• /
• 2010

• Bulletin of the Korean Chemical Society
• /
• 제31권6호
• /
• pp.1785-1788
• /
• 2010