• Bulletin of the Korean Chemical Society
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• 제25권8호
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• pp.1231-1237
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• 2004

Rate constants for photolytic reactions of p-substituted 2-diazopropiophenones were determined in acetonitrile. The reactions show a comparatively low value of activation energy and activation enthalpy to alkylcarbenes or other arylcarbenes. The transition state corresponds to the step of a new carbonyl bond formation. The high negative ρ -values are shown in Hammett plots. The kinetics results and EPR spectrum are in accord with a phenomenon that occurs in interconversion between singlet and triplet carbenes.

• 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.

• 대한화학회지
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• 제63권4호
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• pp.233-236
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• 2019

In this study, the solvolysis of cyclohexanesulfonyl chloride (1) was studied by kinetics in ethanol-water, methanol-water, acetone-water, and 2,2,2-trifluoroethanol (TFE)-water binary solvent systems. The rate constants were applied to the extended Grunwald-Winstein equation, to obtain the values of m = 0.41 and l = 0.81. These values suggested $S_N2$ mechanism in which bond formation is more important than bond breaking in the transition state (TS). Relatively small activation enthalpy values (11.6 to $14.8kcal{\cdot}mol^{-1}$), the large negative activation entropy values (-29.7 to $-38.7cal{\cdot}mol^{-1}{\cdot}K^{-1}$) and the solvent kinetic isotope effects (SKIE, 2.29, 2.30), the solvolyses of the cyclohexanesulfonyl chloride (1) proceeds via the $S_N2$ mechanism.

• Journal of Mechanical Science and Technology
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• 제16권1호
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• pp.94-101
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• 2002

Convection-dominated melting in a rectangular cavity is analyzed numerically with particular attention to the multi-cellular flows in the melt. At the earlier stage of the melting, the melt region is quite similar to a cavity with high aspect rati71, where the multi-cellular natural convection appears. Numerical results show that the formation and evolution of the multiple flow cells in the melt region is approximately similar to t]tat of a single-phase flow in a tall cavity with the same aspect ratio; however, the continuous change of the melt region due to the melting affects the detailed process. Also, numerical aspects for the prediction of the detailed flow structure in the melt are discussed.

• 대한화학회지
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• 제35권2호
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• pp.135-141
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• 1991

N,N'-oxalylbis(salicylaldehyde hydrazone) (OBSH)과 Zn (II), Cd (II) 및 Pb(II) 이온들과의 착물 형성에 따르는 안정도상수를 DMSO 용액에서 폴라로그래피법으로 측정하였다. 안정도상수의 크기는 Cd(II) < Zn(II) < pb(II) 이온의 순서로 증가하였으며, 모든 중금속이온들의 OBSH 리간드와 매우 안정한 착물을 형성하였다. 안정도상수를 여러 온도에서 측정하여 엔탈피 및 엔트로피 변화를 구한 결과, 착물의 안정도에 많은 기여를 하고 있음을 알았다.

• 한국응용과학기술학회지
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• 제6권1호
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• pp.67-73
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• 1989

The adsorptions of 2-(dimethylalkylammonio)propanoates with straight chain alkyl group having from 12 to 16 carbon atoms on the liquid-air interface were decreased while lowering the surface tensions at critical micelle concentrations. In micellization, the standard free energy changes per methylene in alkyl group were found to make same contribution to the micelle formation of corresponding C-alkylcarboxybetaines, and the standard enthalpy and entropy changes were studied within the range of temperature from 30 to $50^{\circ}C$.

• 한국식품과학회지
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• 제32권3호
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• pp.500-506
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• 2000

시차주사열량계(differential scanning calorimetry, DSC)를 사용하여 분석한 결과 밀전분으로 부터 분리한 아밀로펙틴은 밀전분의 노화특성과 일치된 특성을 나타내었다. 수분함량 8%의 아밀로펙틴과 SSL을 10 : 1의 중량 비율(w/w)로 혼합하여 DSC로 1차 가열과 냉각 후 2차 가열한 결과 $55{\sim}70^{\circ}C$의 온도범위에서 용융 peak를 나타낸 반면 SSL은 $40{\sim}55^{\circ}C$의 온도범위에서 용융 peak를 나타내어 서로 다른 융점을 나타내었다. 또한 아밀로펙틴과 SSL의 혼합물은 가열과 냉각을 반복함에 따라 결정질의 아밀로펙틴 g당 용융 peak의 엔탈피값이 증가되는 결과를 보였다. 전체 수분함량 50%에서 밀전분과 밀전분으로 부터 분리한 아밀로오스와 아밀로펙틴 각각에 대해 SSL을 5 : 1의 중량비율로 혼합하여 DSC로 1차와 2차 가열한 결과 SSL의 용융 peak 이외에 SSL과 아밀로펙틴의 결합물로 판단되는 $60-70^{\circ}C$ 범위의 가역적인 용융 peak가 관찰되었다. SSL과 아밀로펙틴 결합물은 V 도형의 아밀로오스와 지방 결합물과 차이가 있는 결정질을 나타내는 X-ray diffraction angle$(2{\theta})$ 값을 나타내었다. 전체수분함량 60%에서 SSL은 밀전분의 호화 엔탈피값을 감소시켰으며 아밀로오스와 지방결합물의 용융 엔탈피값을 증가시켰다. 동일한 전체수분함량에서 밀전분과 아밀로펙틴에 대해 SSL을 20 : 1과 10 : 1의 비율로 혼합한 겔의 저장실험은 SSL을 포함한 시료가 SSL을 포함하지 않은 시료보다 노화에 대해 억제효과를 나타내었다.

• 한국응용과학기술학회지
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• 제36권2호
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• pp.407-416
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• 2019

아닐린 수용액에서의 암모늄형 양이온성 계성면활성제 (DTAB, TTAB 및 CTAB)의 미셀화에 대한 임계미셀농도(CMC)값을 UV-Vis법으로 측정하였다. 290K ~ 314K 사이에서 측정된 양이온성 계면활성제의 CMC값의 변화로부터 미셀화에 대한 Gibbs 자유에너지(${\Delta}G^0$)값을 구하고, 이 값으로부터 엔탈피(${\Delta}H^0$)와 엔트로피(${\Delta}S^0$)를 계산하고 분석하였다. 또한 n-부탄올 및 염화나트륨의 농도 변화가 미셀화에 미치는 영향을 열역학적 함수를 이용하여 비교 분석하였다. 실험한 온도 구간 및 첨가제의 농도 범위 내에서 측정된 모든 ${\Delta}G^0$ 값은 음의 값을 나타냈었으며, 엔탈피(${\Delta}H^0$) 변화값은 모두 음의 값을 그리고 엔트로피(${\Delta}S^0$) 변화값은 모두 양의 값을 나타내었다. 아닐린 수용액에서 양이온성 계면활성제의 미셀화는 자발적 발열반응이며, 열역학적 값들로부터 계산된 등구조온도에 의하면 이들 계면활성제의 미셀화는 엔탈피(${\Delta}H^0$)와 엔트로피(${\Delta}S^0$)가 거의 동일하게 기여하고 있음을 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제28권6호
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• pp.1021-1030
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• 2007

The effects of the creamide III (CER3) and cholesterol (CHOL) on the structure of a non-hydrous distearoyl phosphatidylcholine (DSPC)-based lamellar liquid crystal (LC) hydrated by only propylene glycol (PG) without water were investigated by differential scanning calorimetry (DSC), X-ray diffractions (XRDs), and polarized microscope (PM). As soon as CER3 was incorporated into the lamellar phase, the characteristic LPP was appeared as well as the characteristic SPP, and the formation of separated CER3 crystalline phase was observed depending upon the increase of CER3 content by XRDs. Also, by DSC, it was shown that the increase of CER3 made the monotectic thermal transition be changed to the eutectic thermal transition which indicates the formation of separated CER3 crystalline phases and the main transition temperatures (Tc1) to be gradually decreased and the enthalpy change (ΔH) to be linearly increased. Incorporating CHOL, the formation of LPP and SPP showed almost similar behaviors to CER3, but incorporating small amounts of CHOL showed the characteristic peaks of CHOL which meant the existence of crystalline CHOL phase due to the immiscibility of CHOL with DSPC swollen by PG differently from CER3, and increasing CHOL made the intensity of the 1st order diffraction for LPP weakened as well as the intensities of the characteristic diffractions for DSPC. Also, in the results of DSC, it showed more complex thermal behaviors having several Tc than CER3 due to its bulky chemical structure. In the present study, the inducement of CER3 and CHOL as other lipids present in human stratum corneum (SC) into a non-hydrous lamellar phase is discussed in terms of the influence on their structural and thermal transition.

• Journal of Nuclear Fuel Cycle and Waste Technology
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• 제1권1호
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• pp.65-73
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• 2013

Temperature-dependent hydrolysis behaviors of aqueous U(VI) species were investigated with time-resolved laser fluorescence spectroscopy (TRLFS) in the temperature range from 15 to $75^{\circ}C$. The formation of four different U(VI) hydrolysis species was measured at pHs from 1 to 7. The predominant presence of $UO{_2}^{2+}$, $(UO_2)_2(OH){_2}^{2+}$, $(UO_2)_3(OH){_5}^+$, and $(UO_2)_3(OH){_7}^-$ species were identified based on the spectroscopic properties such as fluorescence wavelengths and fluorescence lifetimes. With an increasing temperature, a remarkable decrement in the fluorescence lifetime for all U(VI) hydrolysis species was observed, representing the dynamic quenching behavior. Furthermore, the increase in the fluorescence intensity of the further hydrolyzed U(VI) species was clearly observed at an elevated temperature, showing stronger hydrolysis reactions with increasing temperatures. The formation constants of the U(VI) hydrolysis species were calculated to be $log\;K{^0}_{2,2}=-4.0{\pm}0.6$ for $(UO_2)_2(OH){_2}^{2+}$, $log\;K{^0}_{3,5}=-15.0{\pm}0.3$ for $(UO_2)_3(OH){_5}^+$, and $log\;K{^0}_{3,7}=-27.7{\pm}0.7$ for $(UO_2)_3(OH){_7}^-$ at $25^{\circ}C$ and I = 0 M. The specific ion interaction theory (SIT) was applied for the extrapolation of the formation constants to infinitely diluted solution. The results of temperature-dependent hydrolysis behavior in terms of the U(VI) fluorescence were compared and validated with those obtained using computational methods (DQUANT and constant enthalpy equation). Both results matched well with each other. The reaction enthalpies and entropies that are vital for the computational methods were determined by a combination of the van't Hoff equation and the Gibbs free energy equation. The temperature-dependent hydrolysis reaction of the U(VI) species indicates the transition of a major U(VI) species by means of geothermal gradient and decay heat from the radioactive isotopes, representing the necessity of deeper consideration in the safety assessment of geologic repository.