• The Korean Journal of Food And Nutrition
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• v.10 no.1
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• pp.6-13
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• 1997

Reactivity and reaction mechanism for the photosensitized generation of hydroxyl radical by various coumarin derivatives are investigated by means of ESR and laser flash photolysis methods. The nine kinds of coumarin derivatives show to be proceeded through the OH·radical generation mechanism, however 1-ethyl-3-nitro-1-nitrosoguanidine decomposes and produces the carbene intermediate before OH·radical generation reaction occurs. The nine coumarin derivatives show the signals, which are corresponded to DMPO-OH spin adducts. NaN3, EtOH and HCOONa act as a strong photosensitizer to quench OH·radical. The decay rate constants of the hydrated electrons in the case of added N2O show higher than added K3Fe(CN)6.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.164-167
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• 1989

The rate for the aquation of $trans-[Cr(tmd)_2FX]^+(X=F^-,\;Cl^-)$ ion in aqueous acidic solution has been measured by spectrophotometric method at various temperatures and pressures. The rate constants are increased with increasing temperatures and pressures. The values of activation entropy are 5.2 eu for $trans-[Cr(tmd)_2F_2]^+$ and -16.62 eu for $trans-[Cr(tmd)_2FCl]^+$ ions. Activation volumes have all negative values and lie in the limited range $-3∼-2\;cm^3mol^{-1}$ for $trans-[Cr(tmd)_2F_2]^+$ and $-8∼-7\;cm^3mol^{-1} for $trans-[Cr(tmd)_2FCl]^+$ ion. From the above results, we may deduce that the mechanism for the aquation of $trans-[Cr(tmd)_2F_2]^+$ and $trans-[Cr(tmd)_2FCl]^+$ ions is interchange-associative mechanism and dissociative mechanism respectively.

• Applied Chemistry for Engineering
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• v.20 no.2
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• pp.159-164
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• 2009

Monomers of oxetane high explosives were theoretically examined in terms of reactivity, reaction mechanism and process of polymerization substituted by azido $(-CH_2N_3)$, nitrato $(-CH_2ONO_2)$ and hydrazino $(-CH_2N_2H_3)$ which belong to the 5th class hazardous materials and have explosiveness under acid catalyst using MINDO/3, MNDO, and AMI methods for formal charge, heat of formation, and energy level. Nucleophilicity and base of oxetane high explosives could be explained by negative charge size of oxetane oxygen atom and reactivity of oxetane in the growth stage of polymerization under acid catalyzer could be expected to be governed by positive charge size of axial carbon atom and low LUMO energy of electrophile. It could be estimated that carbenium ion was more beneficial in the conversion process of oxetane high explosives than that of stabilization energy (13.90~31.02 kcal/mole) of oxonium ion. In addition, concentration of oxonium ion and carbenium ion in equilibrium state influenced mechanism and it was also estimated that $S_N1$ mechanism reacts faster than that of $S_N2$ in prepolymer growth stage considering quick equilibrium based on form and calculation of polymerization under acid catalyzer.

• Nuclear Engineering and Technology
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• v.11 no.2
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• pp.119-126
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• 1979

The reaction of 4,4'-dihydroxydiphenl methane (4,4'-DPM) with glycidyl methacrylate (GMA) catalyzed by triethylbenzyl ammonium chloride (TEBAC) has been studied for the purpose of synthesis of electron beam curable prepolymer. The reaction was in good agreement with third-order kinetics. according to -d[GMA]/dt=k[TEBAC][DPM][GMA] and the apparent activation energy was about 33.4kca1/mole. However, the reaction rates were increased if tile reaction proceeded after the mixtures exposed to air for 24 hrs at room temperature. The effects of the catalyst and the difference in the reactivity between 2.2'-DPM to GMA were discussed. The plausible reaction mechanism was proposed on basis of experimental data obtained.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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• pp.47.2-47.2
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• 2011

광전환 효율 20% (AM1.5G) 이상의 고효율 화합물 박막태양전지의 광흡수층으로 많은 관심을 받고 있는 $Cu(In,Ga)Se_2$ (CIGS) 태양전지의 광흡수층은 다양한 공정에 의해 제조가 가능하다. 현재 고효율 CIGS 셀 생성을 위해 널리 사용되고 있는 CIGS 흡수층 성장공정은 "co-evaporation (동시증발법)"과 2-step 공정이라 불리는 "precursorselenization(전구체-셀렌화)" 방법이다. 동시증발법은 개별원소 Cu, In, Ga, Se들을 고진공 분위기에서 고온(550~600$^{\circ}C$) 기판위에 증착하는 방법으로 소면적에서 가장 좋은 효율(~20%)을 보이는 공정이다. 하지만, 고온, 고진공 공정조건과 대면적 증착시 온도 및 조성 불균일 등의 문제점 등으로 상용화에 어려움이 있다. 전구체-셀렌화 공정은 1단계에서 다양한 방식(예: 스퍼터링, 전기도금, 프린팅 등) 방식으로 CuGaIn 전구체를 증착하고, 2단계에서 고온(550~600$^{\circ}C$)하에 H2Se gas 혹은 Se vapor와 반응시켜 CIGS를 생성한다. 일본의 Showa Shell와 Honda Soltec 등에 의해 이미 상업화 되었듯이, 저비용 대면적으로 상업화 가능성이 높은 공정으로 평가되고 있다. 하지만, 2단계에서 사용되는 H2Se 및 Se vapor의 유독성, 기상 Se과 금속전구체 간의 느린 셀렌화 반응속도, 셀렌화반응 후 생성된 CIGS 박막 두께방향으로의 Ga 불균일 분포, 생성된 CIGS/Mo 계면 접착력 저하 등의 문제점들이 개선, 해결되어야만 상업화에 성공할 수 있을 것이다. 본 연구에서는 Se layer가 코팅된 금속전구체의 셀렌화 반응메카니즘을 in-situ high-temperature XRD를 이용하여 연구하였다. 금속전구체는 스퍼터링, 스프레이 등 다양한 방법으로 제조되었고, 반응메카니즘 연구결과를 바탕으로 Se 코팅된 금속전구체를 이용한 급속열처리 공정의 최적화를 시도하였다.

• Journal of the Korean Chemical Society
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• v.40 no.1
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• pp.11-19
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• 1996

The cationic polymerization of energetic substituted oxetanes which have pendant energetic group such as azido and nitrato are investigated theoretically, using semiempirical HF/3-21G, MINDO/3, MNDO and AM1 method. The stereo- and electronic structure of binary molecular complex composed of energetic substituted oxetane and boron trifluoride can be explain by molecular orbital theory. The reactivity of propagation in the copolymerization of oxetanes can be presented by the positive charge on carbon(C2) atom of oxetane and energy level of the lowest unoccupied molecular orbital(LUMO) of propagating species of oxetanes. The reactivity ratios for copolymerization of oxetanes are a random copolymer-zation which is agree with MO calculated and experimental results. The relative equlibrium concentration of cyclic oxonium and open carbenium ions is found to be a major determinant of mechanism, owing to the rapid equilibrium of these cation forms and the expectation based on calculation that in the prepolymer propagation step, SN1 mechanism will be at least as fast as that for SN2 mechanism.

• Applied Chemistry for Engineering
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• v.21 no.3
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• pp.278-283
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• 2010

The cationic polymerization of oxolane high explosives which have pendant explosive groups such as azido, nitrato and hydrazino is investigated theoretically using the semiempirical MINDO/3, MNDO and AM1 methods. The nucleophilicity and basicity of oxolane high explosives can be explained by the negative charge on oxygen atom of oxolane. The reactivity of propagation in the polymerization of oxolane can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxolane. The reaction of the oxolane high explosives in oxonium ion form to the open chain carbenium ion form is expected by computational stability energy (17.950~30.197 kcal/mol) of the oxonium ion and carbenium ion favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium ion and carbenium ion is found to be a major determinant of mechanism, owing to the rapid equilibrium of these catoinic forms. Based on calculation, in the prepolymer propagation step, $S_N1$ mechanism will be at least as fast as that for $S_N2$ mechanism.

• Applied Chemistry for Engineering
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• v.4 no.3
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• pp.549-557
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• 1993

In the conversion of ethanol over heteropoly acids, we have studied catalytic reactivity, reaction mechanism, effect of organic bases added to reactant, and relation between acid strength of ion-exchanged catalysts and catalytic activities. The conversion of ethanol proceeded in the pseudoliquid phase of heteropoly acid. Due to this novel behavior, area increased by supporting with $SiO_2$. The reaction mechanism of ethylene production was different from that of ether production, and various partially substituted Al salts of 12-tungstophosphoric acid showed different catalytic activities.

• Journal of the Korean Chemical Society
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• v.21 no.4
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• pp.262-269
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• 1977

The solvolysis of 1-naphthalene-and 2-naphthalenesulfonyl chlorides in acetone-water mixtures have been studied by means of conductometry. The solvent effect and mechanism have been discussed in terms of variation in solvent composition and activation parameters. The reaction was predominantly $S_N2$ type, but bond breaking increased with the increase of water content. The rate constant for 1-naphthyl compound was smaller than that of 2-naphthyl compound due to the ground state stabilization effect and peri-hydrogen effect, and the latter effect was similar to that in ethanol-water mixtures.

• Journal of the Korean Chemical Society
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• v.48 no.5
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• pp.461-466
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• 2004

Kinetics for the nucleophiles have been studied under high vacuum and high pressures in various temperatures. Pseudo-first order rate constants, second order rate constants, thermodynamic parameters and Hammett ${\rho}$-values are determined. The values of ${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq}\;and\;{\Delta}S^{\neq}$are all negative. The Hammett r-values are negative for the nucleophile (${\rho}$x) over the pressure range studied. The results of kinetic studies for pressure and nucleophilet show that these reactions proceed in typical $S_N2$ reaction mechanism and change of mechanism.