• 멤브레인
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• 제13권3호
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• pp.154-161
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• 2003

본 연구에서는 소수성 PTFE (Polytetrafluoroethylene) 분리막의 산소동위원소 분리특성을 확인하기 위해 물의 온도에 따른 수증기의 막 투과특성을 Air Cap Membrane Distillation (AGMD)과 Vacuum Enhanced Membrane Distillation (VEMD) 방법을 이용하여 각각 측정하였다. 투과된 수증기는 트랩에서 수거하여 투과플럭스 (permeation flux)를 측정하였고$ H_2^{16}O$와 $H_2^{18}O$의 성분비는 다이오드 레이저 흡수분광법을 이용하여 측정하였다. 분리막을 투과한 수증기에서 무거운 산소동위원소의 성분비가 감소함을 확인하였고 분리계수는 실험 조건에 따라 1.004~1.01로 측정되었다. 또한 분리막의 기공에 있는 공기가 산소동위원소의 분리에 미치는 영향을 확인하였고 기공내 공기가 없을 때 동위원소 분리계수가 증가함을 관찰하였다.

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

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3274-3278
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• 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
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• 제32권9호
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• pp.3245-3250
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• 2011

The nucleophilic substitution reactions of diisopropyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.71-0.95) with maximum magnitude at X = H.A concerted mechanism involving predominant backside nucleophilic attack is proposed on the basis of the secondary inverse DKIEs.

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4403-4407
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• 2011

The nucleophilic substitution reactions of dipropyl chlorothiophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal ($k_H/k_D$ = 1.11-1.35). A concerted mechanism involving predominant frontside nucleophilic attack is proposed on the basis of the primary normal DKIEs and selectivity parameters. Hydrogen bonded, four-center-type transition state is proposed. The steric effects of the two ligands on the anilinolysis rates of various substrates are discussed.

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

• Bulletin of the Korean Chemical Society
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• 제12권1호
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• pp.101-103
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• 1991

The kinetic isotope effects (KIE) are determined for the reactions of benzyl benzenesulfonates (BBS), ethyl benzenesulfonates (EBS) and phenacyl benzensulfonates (PAB) with deuterated benzylamine nucleophiles. The inverse secondary ${\alpha}$-deuterium KIE observed were somewhat smaller than those for the corresponding reactions with aniline nucleophiles. The primary $KIE_s$ obtained with PAB were slightly greater than those for the corresponding reactions with anilines, which suggested that the inverse secondary KIE is decreased due to a relatively earlier transition state for bond-making with little change in the hydrogen bonding strength to the carbonyl oxygen.

• Bulletin of the Korean Chemical Society
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• 제11권5호
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• pp.435-438
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• 1990

Primary and secondary ${\alpha}$-deuterium kinetic isotope effects are determined with deuterated aniline nucleophiles in the nucleophilic substitution reactions of benzyl benzenesulfonates and 1-phenylethyl benzenesulfonates in acetonitrile at 30.0^{\circ}C. The $k_H/k_D$ values support our previous conclusions regarding the transition state structures proposed for the two reactions based on the cross-interaction constants ${\rho}_{ij}$; the former is a typical $S_N2$ reaction whereas in the latter the four-center transition state may be involved.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.4095-4098
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• 2011

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