CuxFe3-xO4 catalyst and ZnxFe3-xO4 catalyst were synthesized by the air oxidation method with various C(II) and Zn(II) weights. Activated catalysts decomposed carbon dioxide to carbon at 350℃, 380℃, 410℃ and 440℃. The value of carbon dioxide decomposition rate for Cu0.003Fe2.997O4 and Zn0.003Fe2.997O4 catslysts than was better catalysts. The decomposed rate of the catalysts is about 85%~90%. The reaction rate constant(4.00 psi1-α/min) and activation energy(2.62 kcal/mole) of Cu0.003Fe2.997O4 catalyst are better than Zn0.003Fe2.997O4

Diglycidy1 ether of bisphenol A (DEGBA)/4, 4'-methylene dianiline(MDA) 계의 반응속도에 미치는 10 phr의 pheny1 glycidy1 ether(PGE)-acetamide(AcAm)의 영향을 살펴보았다. PGE-AcAm이 첨가됨으로 인해서 승온적 DSC 곡선에서 최대 발열피크의 온도와 피크 시작 온도가 감소하였다. PGE-AcAm의 첨가 여부에 관계없이 전화율 곡선은 s-자 형상이었고, 이는 DGEBA/MDA 계와 DGEBA/MDA/PGE-AcAm 계가 자촉대 반응을 한다는 것을 의미한다. 또한 PGE-AcAm이 10 phr 첨가됨으로 인해서 1.2-1.4배 증가하였는데, 이는 PGE-AcAm의 수산기가 촉매로 작용하기 때문이다.

The rate constants of hydrolysis of N-tert-butyl-α-phenylnitrone and its derivatives have been determined by UV spectrophotometry at 25℃ and a rate equation which can be applied over a wide pH range was obtained. On the basis of rate equations derived and judging from the hydrolysis products obtained and general base and substituent effects, plausible mechanism of hydrolysis in various pH range have been proposed. Below pH 4.5, the hydrolysis was initiated by the protonation and followed by the addition of water to α-carbon. Above pH 10.0, the hydrolysis was proceeded by the addition of hydroxides ion to α-carbon. In the range of 4.5~10.0 the addition of water to nitrone was rate controlling step.

Furfurylidene acetophenone derivatives were synthesis, it was measured that nucleophilic addition made use of UV at a wide pH 1.0~13.0 range in 30% dioxane-H2O solution, 25℃. On the basis of general base catalysis, substitutent effect, confirmation of nucleophilic addition products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It may be concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion: Above pH 10.0. sulfide anion adds to the double bond (Michael type addition), a part having no concern with pH, addition reaction to double bond is initiated by addition of neutral thiourea molecule. From the result of measurement the reaction rate, nucleophilic addition of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect. It found that reaction rate was accelerated by electron attracting group. On the basis of these findings, nucleophilic addition of thiourea for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

The Kinetics velocity for hydrolysis reaction of vanillylidene imine derivatives has been measured by ultra-violet ray spectrophotometer in 20wt% dioxane-H2O at 25℃. It was measured the reaction rate Constant of vanillylidene imine derivatives that can be applied widely following to pH-change at 25℃. Final products that hydrolyzed the vanillylidene imine certified in vanillin and aniline derivative, and the effect of substitution radical that has affected on hydrolysis reaction was largely promoted to reaction rate by electron attrating group in acidity and electron donoring group in basic. From the results of rate constant to hydrolysis reaction, substituent radical effect and final products. It has certified the hydrolysis reaction mechanism of vanillylidene imine derivatives.

Benzoyl styrene derivatives were synthesized by Claisen-Schmidt condensation. It was measured that nucleophilic addition of thiourea for benzoyl styrene made use of ultraviolet spectrophotometery at a wide pH 1.0~13.0 range in 5% dioxane-H2O at 40℃. On the basis of general base catalysis, substitutent effect, and confirmation of addtion reaction product, the nucleophilic addtion kinetics of thiourea for benzoylstyrene derivatives were measured by pH change. It maybe concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion : Above pH 10.0. It was in propotion to concentration of hydroxide ion, a part having no concern with pH was added to the neutral thiourea molecule. From the results of measurement the reaction rate and there findings, nucleophilic addition of thiourea to benzoylstyrene derivative was proposed a fitting mechanism.

The rate constant of Nucleophilic addition of sodium thiophenoxide to nitrone were determined by UV Spectrophotometry and a rate equation which can be applied over wide pH range was obtained. Base on the rate equation, general base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Blow pH 3.0, the reaction was initiated of thiophenol, and in the range of pH 3.0~10.0, proceeded by the competitive addition of thiophenol and thiophenoxide anion. Above the pH 10.0, the reaction proceeded through the addition of a thiophenoxide anion.

The Hydrolysis kinetics of Benzoyl Styrene Derivatives[I]~[IV] was investigated by ultraviolet spectrophotometery in 5% dioxane-H2O at 40℃. The structure of these compounds were ascertained by means of ultraviolet, melting point, IR and NMR spectra. The rate equations which were applied over a wide pH range (pH 1.0~13.0) were obtained. The substituent effects on Benzoyl styrene derivatives[I]~[IV] were studied, and the hydrolysis were facilitated by electron attracting groups. On the basis of the rate equation and substitutent effect and final product, the plausible hydrolysis reaction mechanism was proposed: At pH 1.0~pH 9.0, not relevant to the hydrogenl ion concentration, neutral H2O molecule competitively attacked on the double bond. By contrary. Above pH 9.0, It was proportional to concentration of hydroxidel ion.

본연구는 DSC (dynamic run)의 Barrett method Integral mdthod DGEBA/MDA/MN(malononitrile) DSC DSC pre exponential factor, kinetic parameter 들을 구할 수 있었다.

The rate constants of hydrolysis of α-phenly-N-iso-propylnitrone and its derivatives have been determined by UV spectrophotometry at 25℃ and a rate equation which can be applied over a wide pH range was obtained. On the basis of rate equations derived and judging from the hydrolysis products obtained and general base and substituent effects, plausible mechanism of hydrolysis in various pH range have been proposed. Below pH 4.5, the hydrolysis was initiated by the protonation and followed by the addition of water to α-carbon. Above pH 10.0, the hydrolysis was proceeded by the addition of hydroxide ion to α-carbon. In the range of 4.5~10.0, the addition of water to nitrone was rate controlling step.

The hydrolysis reaction kinetics of 2-thienyl chalcone derivatives [II]~[V] was investigated by ultraviolet spectrophotometery in 20% dioxane-H2O at 25℃ and the structure of these compounds were ascertained by means of ultraviolet, infrared and NMR spectra. The rate equations which were applied over a wide pH range(pH 1.0~13.0) were obtained. The substituent effects on 2-thienyl chalcone derivatives[II]~[V] were studied, and the hydrolysis were facilitated by electron attracting groups. On the basis of the rate equation, substitutent effect and final product, the plausible hydrolysis reaction mechanism was proposed : At pH 1.0~9.0, not relevant to the hydrogen ion concentration, neutral H2O molecule competitvely attacked on the double bond. By contraries, above pH 9.0, it was proportional to concentration of hydroxide ion.

The kinetics of the addition of thiourea to cinnamenylisophorone derivatives(X : H, p-Br, p-CH3 m-CH3, p-OCH3) was investigated using ultraviolet spectrophotometry in 20%(v/v) dioxane-H2O at 25℃. A rate equation which can be applied over wide pH range(pH 1.0~13.0) was obtained. In order to investigate the substituent effects of cinnamenylisophorone derivatives. Hammett constant was plotted. As the result, the rate of uncleophilic addition of thiourea to cinnamenylisophorone derivatives was facilitated by electron donating group. It was found that addition of neutral thiourea which was not dissociated at the pH 1.0~9.0 was proceeded, the reaction was proceeded by addition of dissociated anion of thiourea above the pH 10.0. On the basis of this kinetic study, the reaction mechanism of nucleophilic addition of thiourea was investigated.

에폭시 수지를 개질하기 위하여 반응성 첨가제 Malononitrild(MN)을 Diglycidy1 ether fo vispenol A (CGEBA)/Methylene dianiline(MDA)계를 첨가하여 이 계의 경화 반응속도론과 경화반응메카니즘을 시차주사 열분석(DSC)과 적외선 흡수 분광법을 통해 관찰하였다. 경화반응속도론으로부터 MN으로 개질된 DGEBA/MDA는 완전히 경화를 이루기 위하여 80˚C로 부터 170˚C까지 30˚C간격으로 경화시킨 시료로 반응메카니즘을 고찰한 결과 PA(primary amine)-E(epoxide)그리고 E(epoxide)-OH(hydroxy1 group)반응 이외에 PA(primary amine)-CN(nitrile)과 CN(nitrile)-OH(hydroxy1 group)반응이 일어남을 알았다.

The hydrolysis kinetics of 2-furyl chalcone derivatives [I]~[V] was investigated by ultraviolet spectrophotometery in 30% dioxane-H2O at 25℃ and the structure of these compounds were ascertained by means of ultraviolet, infrared and NMR spectra. The rate equations which were applied over a wide pH range(pH 1.0~12.0) were obtained. The substituent effects on 2-furyl chalcone derivatives [I]~[V] were studied, and the hydrolysis were facilitated by the electron attrecting groups. On the basis of the rate equation, substituent effect, general base effect and final product. the plausible hydrolysis mechaism was proposed: Below pH 4.0, it was only proportional to concentration of hydronium ion, at pH 4.0~9.0, neutral H2O molecule competitively attacked on the double bond. By contrast, above pH 9.0, it was proportional to concentration of hydroxide ion.

The kinetics of the hydrolysis of indolylacrylophenone derivatives(IA) was investigated by ultraviolet spectrophotometry in 30% dioxane-H2O at 25℃ Rate equations were obtained over a wide pH range. On the basis of rate equation, general base catalysis and Hammett's plot, the mechanism of hydrolysis to the (IA) were proposed: Below pH 3.0, the hydrolysis of (IA) was proportional to hydronium ion concentration, between pH 4.0~9.0 neutral water molecule and hydroxide ion were added to carbon-carbon double bond and over pH 10.0 hydrolysis of (IA) was proportional to hydroxide ion concentration.

Diglycidyl ether of bisphenol A (DGEBA)와 경화제로서 4, 4'-methylene dianiline(MDA) 에 반응성 첨가제 succinonitrile(SN)을 첨가한 새로운 계를 Differential Scanning Calorimetry (DSC)로 이용하여 30˚C부터 350˚C의 온도 범위에서 승온적 진행 방범(dynamic run method)으로 얻은 값을 가지고 최대 반응속도에서의 온도에 승온속도가 미치는 영향을 해석 할 수 있는 kissinger식을 적용하여 경화반응 속도론을 연구하였다. SN을 첨가한 DGEBA/MDA계의 활성화에너지 (Ea)와 pre-exponential factor(A) 그리고, SN이 첨가될 때 에폭시와 아민과의 반응속도 상수 k를 구하였다.

The kinetics of the addition of 1-benzylindole-3-(p-substituted) acetophenone derivatives was investigated by ultraviolet spectrophotometery in 30% dioxane -H2O at 25℃. A rate equation which can be applied over wide pH range was obtained. The Substituent effects on 1-benzylindole-3-(p-substituted) acetophenone derivatives were studied, and addition were facilitated by electron attracting groups. On the base of the rate equation, substituent effect, and general base effect the plausible addition mechanism was proposed : Below pH 3.0, only neutral thiourea molecule was added to the carbon-carbon double bond, and in the range of pH 0.0~14.0, netural thiourea molecule and thiourea anion competitively attacted the double bond. By contrast, above pH 10.0, the reaction was dependent upon only the addition of thiourea anion.

The kinetics of hydrolysis of cinnamenylisophorone derivatives (rho-H, rho-Br, P-Cl, rho-OCH3) was investigated using ultraviolet spectrophotometry in 20%(v/v) dicxane-H2O at 25℃. A rate equation which can be applied over wide pH range (pH 1.0~13.0) was obtained. In order to investigate the substituent effects on cinnarnenylisophorone derivatives, Hammett constant was plotted. As the result, the rate of hydrolysis of cinnamenylisophorone derivatives was facilitated by electron donating group. Final products of the hydrolysis were benzaldehyde and isophorone, From the measurement of reaction rate constant according to pH changes, substituent effect, and final products, it was found that the hydrolysis of cinnarnenylisophorone derivatives was initiated by the neutral H2O molecule which does not dissociated at below pH 9.0, and in the range of pH 9.0~11.0 this reaction occurs by H2O or hydroxide ion competitively, but proceeded by the hydroxide ion above pH 11.0. On the basis of this kinetic study, the reaction mechanism of the hydrolysis of cinnamenylisophorone derivatives was proposed.