• Journal of the Korean Chemical Society
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• v.32 no.2
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• pp.94-102
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• 1988

A quantitative description of the principle of least motion is suggested. The reaction path function of electronic variables, its norm and the reaction path average energy, which are unique for a given reaction path on a potential energy surface of a reacting system, are defined and their characteristics are discussed. It is postulated that the norm of the function and the average energy can be used as a criterion for identification of the preferred path of a unimolecular isomerization reaction. For a molecule with a certain symmetry, the preferred path, with which Woodward-Hoffmann rule agrees, is immediately identified without laborious computation.

• Journal of the Korean Chemical Society
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• v.32 no.2
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• pp.103-112
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• 1988

For two possible paths of thermal ring opening reactions, the approximate reaction path functions, their norms and the approximate reaction path average energies are computed and compared. Illustrated examples clearly justify the postulate that the path with larger norm and lower average energy has lower barrier height than the other.

• Journal of the Korean Society of Marine Environment & Safety
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• v.23 no.6
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• pp.661-668
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• 2017

The purpose of this study is to analyze the chemical reaction pathway for explosion accident of mixed cargo. The analysis used a structural scenario using event-tree analysis. Structural scenarios were constructed by estimating various chemical reaction paths in the content of the mixed cargo accident recorded in the written verdict. The analytical method was applied to three kinds of analysis: chemical analysis based on chemical theory, quantitative analysis using chemical reaction formula, and probabilistic analysis through questionnaire. As a result of analysis, the main pathway of the accident occurred in three ways: the path of explosion due to the reaction of concentrated sulfuric acid with water, the path of explosion due to the reaction of metal and mixed acid, and the path of explosion by synthesizing with special substances. This result is similar to the path recorded in the validation, and it leads to thar the proposed path analysis method is valid. The proposed method is expected to be applicable to chemical reaction path estimation of various chemical accidents.

• Economic and Environmental Geology
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• v.35 no.1
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• pp.13-23
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• 2002

The chemical compositions of groundwaters from the granite areas mainly belong to Ca-HC0$_{3}$ and Na-HC0$_{3}$type, and some of these belong to Ca-(CI+S0$_{4}$) and Na-(CI+S0$_{4}$) type. Spring waters and groundwaters from anorthosite areas belong to Ca-HC03 and Na-HC03 type, respectively. The result of reaction path modeling shows that the chemical compositions of aqueous solution reacted with granite evolve from initial Ca-CI type, via CaHC0$_{3}$ type, to Na-HC0$_{3}$ type. The result of rain water-anorthosite interaction is similar to evolution path of granite reaction and both of these results agree well with the field data. In the reaction path modeling of rain watergranite/anorthosite reaction, as a reaction is progressing, the activity of hydrogen ion decreases (pH increases). The concentrations of cations are controlled by the dissolution of rock-forming minerals and precipitation and re-dissolution of secondary minerals according to the pH. The continuous addition of granite causes the formation of secondary minerals in the following sequence; gibbsite plus hematite, Mn-oxide, kaolinite, silica, chlorite, muscovite (a proxy for illite here), calcite, laumontite, prehnite, and finally analcime. In the anorthosite reaction, the order of precipitation of secondary minerals is the same as with granite reaction except that there is no silica precipitation and paragonite precipitates instead of analcime. The silica and kaolinite are predominant minerals in the granite and anorthosite reactions, respectively. Total quantities of secondary minerals in the anorthosite reaction are more abundant than those in the granite reaction.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.29 no.5 s.236
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• pp.617-624
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• 2005

An analysis of the effects of $CO_{2}$ on fundamental combustion characteristics was performed in Oxygen enriched condition by comparing the laminar burning velocities, flame structures, fuel oxidation paths. Fictitious $CO_{2}$ was introduced to discriminate the chemical reaction effects of $CO_{2}$ from the thermal effects. PREMIX code was utilized to evaluate the laminar burning velocities. OPPDIF code was utilized to investigate the flame structure and fuel oxidation path variation. The contributions of thermal effects on laminar burning velocities are dominant at lowly oxygen-enriched condition but those of chemical reaction effects become dominant at highly oxygen-enriched condition. Chemical reaction effects caused the additional flame temperature decrease besides thermal effects and oxygen-leakage increase in non-premixed flame. Specific fuel oxidation path and CO production path is enhanced in spite of overall decrement of fuel consumption rate by chemical reaction effects of$CO_{2}$.

• Economic and Environmental Geology
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• v.33 no.5
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• pp.405-415
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• 2000

This study was carried out to understand the formation of acid mine drainage (AMD) by pyrophyllite (so-called Napseok)-rainwater interaction (weathering), dispersion patterns of heavy metals, and patterns of mixing with non-polluted water in the Tongnae pyrophyllite mine. Based on the mass balance and reaction path modeling, using both the geochemistry of water and occurrence of the secondary minerals (weathering products), the geochemical evolution of AMD was simulated by computer code of SOLVEQ and CHILLER. It shows that the pH of stream water is from 6.2 to 7.3 upstream of the Tongnae mine. Close to the mine, the pH decreases to 2. Despite being diluted with non-polluted tributaries, the acidity of mine drainage water maintains as far as downstream. The results of modeling of water-rock interaction show that the activity of hydrogen ion increases (pH decreases), the goncentration of ${HCO_3}^-$ decreases associated with increasing $H^+$ activity, as the reaction is processing. The concentration of ${SO_4}^{2-}$first increases minutely, but later increases rapidly as pH drops below 4.3. The concentrations of cations and heavy metals are controlled by the dissolution of reactants and re-dissolution of derived species (weathering products) according to the pH. The continuous adding of reactive minerals, namely the progressively larger degrees of water-rock interaction, causes the formation of secondary minerals in the following sequence; goethite, then Mn-oxides, then boehmite, then kaolinite, then Ca-nontronite, then Mgnontronite, and finally chalcedony. The results of reaction path modeling agree well with the field data, and offer useful information on the geochemical evolution of AMD. The results of reaction path modeling on the formation of AMD offer useful information for the estimation and the appraisal of pollution caused by water-rock interaction as geological environments. And also, the ones can be used as data for the choice of appropriate remediation technique for AMD.

• Proceeding of EDISON Challenge
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• 2015.03a
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• pp.6-13
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• 2015

이 연구는 초기 지구의 대기 환경에서 유기화합물(glycine)이 합성되는 실험(Urey-Miller 실험)에서의 반응 경로를 Deterministic한 방법의 중간체 sampling 방법으로 반응 네트워크를 구성하고 Yen's알고리즘으로 네트워크 내의 최단경로를 제시함으로써 반응물과 생성물이 결정되어 있을 때 최소한의 화학적 직관만을 이용하여 제시하는 것이 목표이다. 이 연구 결과는 2014년도 Nature Chemistry에 발표된 다른 방법론을 적용하여 제시된 Urey-Miller reaction path와 비교해 어떠한 반응이 상대적으로 더 타당한 경로를 제시했을지 알아보았다. 이 연구에서 나온 reaction path에서의 중간체들에 대해 GAMESS를 이용한 B3LYP/6-31g(d,p) DFT계산을 수행하였다. 결과를 분석해보면서 어떤 부분이 부족하며 이 연구에 적용한 방법론을 어떻게 발전시켜나가야 더 나은 결과를 얻을 수 있을지를 함께 고려해 보았다.

• Bulletin of the Korean Chemical Society
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• v.10 no.3
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• pp.262-269
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• 1989

The gas phase thermal decomposition of 1-bromo-3-chloropropane in the presence of radical inhibitor was studied by using the conventional static system. The mechanism of unimolecular elimination channel is shown below. [...] In this scheme, the total molecular dissociation rate constant, ($k_1\;+\;k_2$), for the decomposition of $BrCH_2CH_2CH_2Cl$ was determined by pyrolyzing the $BrCH_2CH_2CH_2Cl$ in the temperature range of $380-420^{\circ}C$ and in the pressure range of 10∼100 torr. To obtain $k_3\;and\;k_4,\;and\;to\;obtain\;k_1\;and\;k_2$ independently, the thermal decompositions of allyl chloride and allyl bromide were also studied. The Arrhenius parameters for each step are as follows; $log\;A_{\infty}\;=\;14.20(sec^{-1}),\;E_a$ = 56.10(kcal/mol) for reaction path 1; $log\;A_{\infty}\;=\;12.54(sec^{-1}),\;E_a$ = 49.75(kcal/mol) for reaction path 2; $log\;A_{\infty}\;=\;13.41(sec^{-1}),\;E_a$ = 50.04(kcal/mol) for reaction path 3; $log\;A_{\infty}\;=\;12.43(sec^{-1}),\;E_a$ = 52.78(kcal/mol) for reaction path 4; Finally, the experimentally observed pressure dependence of the rate constants in each step is compared with the theoretically predicted values that are obtained by the RRKM calculations.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3591-3596
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• 2013

The enantioselective aza-Morita Baylis Hillman reaction of nitroalkene and N-tosylimine catalyzed by thiourea-tertiary amine has been investigated using density functional theory. Enantioselectivity is dominated by the cooperative effect of non-covalent and weak covalent interactions imposed by different units of catalyst. As Lewis base, the tertiary amine unit activates nitroalkene via weak covalent bond. The weak covalent interaction orients the reaction in a major path with smaller variations of this bond. The aromatic ring unit activates N-tosylimine via ${\pi}-{\pi}$ stacking. The non-covalent interaction selects the major path with smaller changes of the efficient packing areas. Thiourea unit donates more compact H-bonded network for species of the major path. The calculated ee value in xylene solution phase (97.6%) is much higher than that in N,N-Dimethylformamide (27.2%). Our conclusion is also supported by NBO analysis.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.692-698
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• 1991

The reaction path Smoluchowski equation approach developed in a recent work to calculate the rate constant for a diffusive multidimensional barrier crossing process is extended to incorporate the configuration-dependent diffusion matrix. The resulting formalism is then applied to the investigation of stilbene photoisomerization dynamics. Adapting a model two-dimensional potential and a model diffusion matrix proposed by Agmon and Kosloff [J. Phys. Chem.,91 (1987) 1988], we derive an eigenvalue equlation for the relaxation rate constant of the stilbene photoisomerization. This eigenvalue equation is solved numerically by using the finite element method. The advantages and limitations of the present method are discussed.