• Bulletin of the Korean Chemical Society
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• 제33권1호
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• pp.270-274
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• 2012

The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1c) with X-pyridines are investigated kinetically in acetonitrile at $-25.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 1c with a cyclic five-membered ring is $2.70{\times}10^5$ times faster than its acyclic counterpart (1a: phenyl ethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}$ = +26 eu) compared to negative value of 1a (${\Delta}S^{\neq}$= -24 eu) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=20.5kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=12.7kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed on the basis of greater selectivity parameters (${\rho}_X$ = -1.99 and ${\beta}_X$ = 0.41) with the strongly basic pyridines compared to those (${\rho}_X$ = -0.42 and ${\beta}_X$ = 0.07) with the weakly basic pyridines.

• 한국세라믹학회지
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• 제12권1호
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• pp.16-22
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• 1975

The network structure of a glass is known to be cracked by a chemical reaction, diffusion, and ion exchange of alkali ion, formed at the crack tip of the glass surface, when water is present on the glass surface. Since the durability of glass is reduced, due to the fatigue phenomenon mentioned above, pollution problem of glass goods, especially bottle glass, is becoming acute gradually. A static fatigue phenomenon was studied thermodynamically in this paper, and a mechanism of static fatigue, a quality control, and a method of preventing pollution for the main local glass goods were also investigated. The PH of reacted solution and the quantity of extracted alkali were measured at different conditions such as temperature, reacting time, particle size of a crushed glass sample, and the nature of reacting solution. The enthalpy change was calculated from the Arrhenius equation. The results are given below; 1) The absolute value of enthalpy change for the bottle glass was found to be higher than the for the flat glass. 2) The fatigue phenomenon of a glass was more sensitive to the temperature than to the reacting time. 3) The durability of glass in acid solution is stronger than in alkaline solution. 4) The substance which cracks the network structure of glas is considered the hydroxyl ion.

• 대한화학회지
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• 제14권1호
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• pp.85-89
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• 1970

방사성 브롬으로 표시한 브롬화이소프로필을 사용하여 니트로벤젠 용액내에서 브롬화칼륨과 브롬과이소프로필 사이에 일어나는 브롬교환반응의 속도를 19$^{\circ},\;25^{\circ}$및 40$^{\circ}C$에서 측정하였다. 본 실험의 결과는 이 브롬교환반응이 브롬화갈륨에 관하여 2차 반응이고 브롬화이소프로필에 관하여 1차 반응임을 보여준다. 19$^{\circ}C$에서의 반응속도 상수 값이 $k_3=3.2{\times}10^{-2}l^2{\cdot}mole^{-2}sec^{-1}$임을 알았다. 그리고 반응속도상수와 온도와의 관계로부터 이 교환반응에 대한 활성화에너지, 활성화엔탈피 및 활성화엔트로피 값을 계산하였다.

• Bulletin of the Korean Chemical Society
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• 제8권5호
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• pp.408-414
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• 1987

The rate of bromine-exchange reaction between antimony tribromide and ${\alpha}-phenyl-n-butyl$ bromide in nitrobenzene has been determined, using antimony tribromide labelled with Br-82. The results indicate that the exchange reaction follows the first-order kinetics with respect to the organic bromide, and either the second- or first-order kinetics with respect to antimony tribromide depending on its concentration. The third-order rate constant obtained was 7.50 ${\times}10^{-2}l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. Similar study on the bromine-exchange reaction between antimony tribromide and ${\alpha}$-phenyl-i-butyl bromide has also been carried out. The results of the study show the same kinetic orders as the ones observed with $\alpha$-phenyl-n-butyl bromide. The third-order rate constant observed was 2.40 ${\times} 10^{-2} l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. The activation energy, the enthalpy of activation and the entropy of activation for the two exchange reactions mentioned above have been determined. The reaction mechanisms for the exchange reactions are discussed.

• 한국수소및신에너지학회논문집
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• 제13권4호
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• pp.270-278
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• 2002

Mg and Mg alloys are attractive hydrogen storage materials because of their lightweight and high absorption capacity. Their range of applications could be further extended if their hydrogenation properties and degradation behavior could be improved, The main emphasis of this study was to find an economic manufacturing method for Mg-Ti-Ni-H systems, and to investigate their hydrogenation properties, In order to examine hydrogenation behavior, a Sieverts type automatic pressure-composition-isotherm(PCI) apparatus was used and the experiments were performed at 423, 473, 523, 573, 623 and 673K. The results of thermogravimetric analysis(TGA) reveal that the absorbed hydrogen contents are around 2.5 wt% for ($Mg_9Ti_1$)-10 wt% Ni. With increased Ni content, the absorbed hydrogen content decreases to 1.7 wt%, whereas the dehydriding starting temperatures are lowered by some 70-100K. The results of PCI on ($Mg_9Ti_1$)-20 wt% Ni show that its hydrogen capacity is around 5.3 wt% and its reversible capacity and plateau pressure are also excellent at 523K and 573K. In addition, the reaction enthalpy, $\Delta$HD.plateau, is $30.6{\pm}5.7kJ/molH_2$.

• 분석과학
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• 제11권2호
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• pp.92-95
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• 1998

변형된 two-bulb pyrex관을 사용하여 K-SGICs(인조흑연 층간화합물)를 합성하였다. 흑연과 칼륨을 반응시키기 위하여 two-bulb관내에 압력을 $10^{-3}$ torr로 유지하여 주었다. 변형된 방법에 의하여 얻어진 K-SGICs는 유동 파라핀 내에서 $25{\sim}1400^{\circ}C$ 사이에서 열처리하여 deintercalation을 시켰다. K-SGICs의 온도 의존성과 열적 안정성을 DSC 분석기에 의하여 특성화하였다. K-SGIC의 엔탈피와 엔트로피 형성은 여러 온도에 의존하는 열역학적 발열반응과 deintercalation을 확인하여 계산하였다. 칼륨이온의 deintercalation 반응이 얼어나는 동안 K-SGICs 의 구조변이와 열적 안정성을 XRD에 의하여 확인하였다.

• Journal of the Korean Wood Science and Technology
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• 제38권5호
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• pp.414-420
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• 2010

The effect of polymeric diphenyl methane-4,4-diisocyanate (pMDI) or 1,6-hexamethylene diisocyanate (HDI) in the UMF resin was discussed for improvement of the dry and wet shear strengths of plywood manufactured from high moisture content veneers. The curing behavior of UMF resin by pMDI or HDI content was examined by DSC and TGA, and its adhesion performance was evaluated by dry and wet shear strength tests of plywood. With the increase of pMDI content in the UMF resin, the curing temperature, reaction enthalpy (${\Delta}H$), and thermal stability consistently increased. With the increase of HDI content in the UMF resin, however, the curing temperature and reaction enthalpy (${\Delta}H$) decreased consistently and the thermal stability slightly increased in the range of 200 to $400^{\circ}C$ but decreased beyond $400^{\circ}C$. Also, the dry tensile shear strength increased up to the pMDI content of 5% and then decreased with its further addition but the wet tensile shear strength showed slight tendency to increase with the increase of pMDI content in the UMF resin. As the HDI content increased, however, the dry and wet tensile shear strengths of plywood consistently increased.

• Bulletin of the Korean Chemical Society
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• 제8권1호
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• pp.31-39
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• 1987

By using a complete rate constant($k_e$) which treats a solvent (water) as a reactant, and a conventional rate constant($k_c$), which ignores the solvent in describing the rate, the parameters ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were introduced. These quantities represent the volume change, the enthalpy change, and the entropy change accompanying the electrostriction which occurs when solvent molecules condense on the activated complex. The authors measured the rates of the solvolysis of benzoyl chloride in water-acetone mixtures at $15^{\circ}$ to $30^{\circ}C$ and 1 bar to 2500 bars. Applying the authors' theory to the experimental results, the parameters, ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were evaluated, and it was found that they are all negative, indicating that water dipoles condense on the activated complex. They also proposed the following equations: ${\Delta}H^{\neq}_c\;=\;{\Delta}H^{\neq}_e\;+\;{\Delta}H^{\neq}_s\;and\; {\Delta}S^{\neq}_c\;=\;{\Delta}S^{\neq}_e\;+{\Delta}S^{\neq}_s\;,\;where\;{\Delta}H^{\neq}_c\;and\;{\Delta}H^{\neq}_c\;and\;{\Delta}S^{\neq}_s $are the activation enthalpy change and the activation entropy change for the conventional reaction rate, respectively, and ${\Delta}H^{\neq}_e$ and ${\Delta}S^{\neq}_e$ are the corresponding quantities for the complete reaction rate. The authors proposed that for the $SN_1$ type, all the quantities, ${\Delta}V^{\neq}_s,\;{\Delta}S^{\neq}_s\;,{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ are comparatively large, and for the $SN_2$ type, these quantities are smaller than for the $SN_1$ type, and occasionally the case ${\Delta}S^{\neq}_e$ < 0 occurs. Using these criteria, the authors concluded that at high temperature, high pressure and for a high water content solvent, the SN_1$ type mechanism predominates whereas in the reversed case the $SN_2$M type predominates.

• 한국수소및신에너지학회논문집
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• 제5권2호
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• pp.65-71
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• 1994

Electrochemical and thermodynamic properties of $MmNi_5$ and the related alloys for nickel-metal hydride battery(Ni-MH) were studied in terms of the equilibrium hydrogen pressure. $MmNi_5$ alloy with high equilibrium hydrogen pressure(10~20atm at room temperature), which is usually difficult to charge, was substituted for Al in part. Partial substitution of Al made not only the equilibrium pressure to be reduced remarkably, but also the enthalpy change depending on the formation of metal hydride to be agreed to the value in gas phase reaction and electrochemical reaction. Besides the composition of Al which can be given the maximum discharge capacity was turned out to be between the 0.5~1.0 atoms of Al.

• Bulletin of the Korean Chemical Society
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• 제23권5호
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• pp.715-720
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• 2002

Kinetic studies of the reaction of Z-aryl cyclobutanecarboxylates with X-pyridines in acetonitrile at $55.0^{\circ}C$ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterion ic tetrahedral intermediate, T $\pm$ . These mechanistic conclusions are drawn based on (i) the large magnitude of ${\rho}X$ and $\rhoZ$, (ⅱ) the positive sign of ${\rho}XZ$ and the larger magnitude of $\rhoXZ$ than normal SN2 processes, (ⅲ) a small positive enthalpy of activation, ${\Delta}H{\neq}$, and a large negative, ${\Delta}S{\neq}$, and lastly (iv) adherence to the reactivity-selectivity principle (RSP) in all cases.