• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2003-2008
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Bulletin of the Korean Chemical Society
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• v.35 no.12
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• pp.3559-3566
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• 2014

Study on the unimolecular reaction for $CH_2FO$ and $CD_2FO$ is carried out. The structures, energy barriers and zero point energy of the three channels in the title unimolecular reactions are computed with the MP2/6-311++G(3df, 3pd) method. RRKM theory is used to calculate the rate constants of canonical case at temperature range of 500-5000 K and microcanonical system at total energy of 19.05-71.68 kcal/mol. The results indicate that the anharmonic effect and isotope effect are very small for the three channels, and the anharmonic rate constants, around $10^9-10^{11}s^{-1}$, are close to the experimental prediction reasonably.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4304-4308
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• 2011

Kinetic studies of the reactions of O,O-dimethyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots for substituent X variations in the nucleophiles are discrete with a break region between 4-Me and H, while the Hammett plots (log $k_2$ vs ${\sigma}_Z$) for substituent Z variations in the leaving groups are linear. The sign of the cross-interaction constant (${\rho}_{XZ}$) is positive for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ (= 2.54) value is observed with the weakly basic nucleophiles compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = 0.17). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a stepwise with a rate-limiting leaving group expulsion from the intermediate involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles.

• Bulletin of the Korean Chemical Society
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• v.3 no.2
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• pp.79-81
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• 1982

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.5 no.4
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• pp.357-362
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• 2000

Stable isotope ratios of oxygen and hydrogen were investigated in southern Yellow Sea in August 1997. Salinity showed good positive correlation with ${\delta}^{18}$O and ${\delta}$. The correlation between ${\delta}^{18}$O and ${\delta}$D is good. From the relationship between these parameters, we obtained two lines of conclusion: 1) seawater of study area I in summer is a mixture of Changjiang Water and modified Kuroshio Water; 2) stable isotopes are very useful tracers in studying property and behavior of water masses in the study area. In case when water masses can not be easily distinguished by T-S analysis, the stable isotopes seem to be powerful tools for this purpose.

• Journal of the Korean Institute of Gas
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• v.9 no.2 s.27
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• pp.22-27
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• 2005

In this study, we analyze computational simulation of cryogenic distillation process to separate $^{13}CH_4$ and $^{12}CH_4$ from LNG by using the cryogenic energy. Used computational simulation program is made Smoker's equation and FUG(Fenske-Underwood-Gilliland)'s method by short-cut method. Generally speaking, the technology of carbon isotope separation is studied by many methods, especially the separation by cryogenic distillation process is commercialized because of many merits.

• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3218-3222
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• 2013

The aminolyses, anilinolysis and pyridinolysis, of bis(2-oxo-3-oxazolidinyl) phosphinic chloride (1) have been kinetically investigated in acetonitrile at 55.0 and $35.0^{\circ}C$, respectively. For the reactions of 1 with substituted anilines and deuterated anilines, a concerted SN2 mechanism is proposed based on the selectivity parameters and activation parameters. The deuterium kinetic isotope effects ($k_H/k_D$) invariably increase from secondary inverse to primary normal as the aniline becomes more basic, rationalized by the transition state variation from a backside to a frontside attack. For the pyridinolysis of 1, the authors propose a stepwise mechanism with a rate-limiting step change from bond breaking for more basic pyridines to bond formation for less basic pyridines based on the selectivity parameters and activation parameters. Biphasic concave upward free energy relationship with X is ascribed to a change in the attacking direction of the nucleophile from a frontside attack with more basic pyridines to a backside attack with less basic pyridines.

• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1797-1802
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• 2007

The kinetics and mechanism of the nucleophilic substitution reactions of diphenyl phosphinic (1) and thiophosphinic (2) chlorides with substituted X-pyridines are investigated kinetically in acetonitrile at 35.0 and 55.0 oC, respectively. A concerted mechanism with backside nucleophilic attack is proposed for the pyridinolysis of 1, on the basis of the linear Bronsted plot with the βX value of 0.68. In the case of the pyridinolysis of 2, the Hammett and Bronsted plots are biphasic concave upwards with the break point at 3- phenyl pyridine. These results indicate a change in mechanism from a concerted SN2(P) process with direct backside nucleophilic attack for less basic nucleophiles (X = 3-CN-3-Ph) to a stepwise process with frontside attack for more basic nucleophiles (X = 4-MeO-3-Ph). Apparent secondary inverse kinetic isotope effects with deuterated pyridine (C5D5N), kH/kD < 1, are observed for the pyridinolysis of 1 and 2.

• Bulletin of the Korean Chemical Society
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• v.26 no.6
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• pp.935-938
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• 2005

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to $\alpha-cyano-\beta$-phenylacrylamides (CPA; $YC_6H_4CH=C(CN)CONH_2$) have been investigated in acetonitrile at 25.0 ${^{\circ}C}$. The rate is first order with respect to BA and CPA and no base catalysis is observed. The addition of BA to CPA occurs in a single step in which the addition of BA to $C_{\beta}$ of CPA and proton transfer from BA to $C_{\alpha}$ of CPA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($\rho_X$) and Bronsted ($\beta_X$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the crossinteraction constant, $\rho_XY$ (= −D0.26), is comparable to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($k_H/k_D\;{\gt}$ 1.0) and relatively low ${\Delta}H^{\neq}$ and large negative ${\Delta}S^{\neq}$ values are also consistent with the mechanism proposed.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4185-4190
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• 2011

The nucleophilic substitution reactions of ethylene phosphorochloridate (1c) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 1c involving a cyclic five-membered ring is four thousand times faster than its acyclic counterpart (1a: diethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}=+30\;cal\;mol^{-1}K^{-1}$ compared to negative value of 1a (${\Delta}S^{\neq}=-45\;cal\;mol^{-1}K^{-1}$) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=27.7\;kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=8.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. The free energy correlations exhibit biphasic concave upwards for substituent X variations in the X-anilines with a break point at X = 3-Me. The deuterium kinetic isotope effects are secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines and primary normal ($k_H/k_D$ > 1) with the weakly basic anilines and rationalized by the TS variation from a dominant backside attack to a dominant frontside attack, respectively. A concerted $S_N2$ mechanism is proposed and the primary normal deuterium kinetic isotope effects are substantiated by a hydrogen bonded, four-center-type TS.