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Aminolysis of 2,4-Dinitrophenyl and 3,4-Dinitrophenyl 2-Thiophenecarboxylates: Effect of ortho-Nitro Group on Reactivity and Mechanism

  • Seo, Jin-A;Chun, Sun-Mee;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제29권8호
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    • pp.1459-1463
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    • 2008
  • Second-order rate constants (kN) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl 2-thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide at 25.0 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature for the aminolysis of 2. The curved Brønsted-type plot is similar to that reported for the corresponding reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (1). The reactions of 1 and 2 have been suggested to proceed through the same mechanism, i.e., through a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step. Substrate 2 is less reactive than 1 toward weakly basic amines (e.g., $pK_a$ < 10.4) but becomes more reactive as the basicity of amines increases further. Dissection of kN into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but larger $k_1$ than the corresponding reaction of 1. Steric hindrance exerted by the ortho-nitro group has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1.

Characterization of Dielectric Relaxation and Reliability of High-k MIM Capacitor Under Constant Voltage Stress

  • Kwak, Ho-Young;Kwon, Sung-Kyu;Kwon, Hyuk-Min;Sung, Seung-Yong;Lim, Su;Kim, Choul-Young;Lee, Ga-Won;Lee, Hi-Deok
    • JSTS:Journal of Semiconductor Technology and Science
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    • 제14권5호
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    • pp.543-548
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    • 2014
  • In this paper, the dielectric relaxation and reliability of high capacitance density metal-insulator-metal (MIM) capacitors using $Al_2O_3-HfO_2-Al_2O_3$ and $SiO_2-HfO_2-SiO_2$ sandwiched structure under constant voltage stress (CVS) are characterized. These results indicate that although the multilayer MIM capacitor provides high capacitance density and low dissipation factor at room temperature, it induces greater dielectric relaxation level (in ppm). It is also shown that dielectric relaxation increases and leakage current decreases as functions of stress time under CVS, because of the charge trapping effect in the high-k dielectric.

Luminescence Wavelength Control of $CaAlSiN_3:Eu^{2+}$ by Ca-replacing: Computational and Experimental Study

  • Onuma, Hiroaki;Suehiro, Takayuki;Suzuki, Ai;Tsuboi, Hideyuki;Hatakeyama, Nozomu;Endou, Akira;Takaba, Hiromitsu;Kubo, Momoji;Sato, Tsugio;Miyamoto, Akira
    • 한국정보디스플레이학회:학술대회논문집
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    • 한국정보디스플레이학회 2009년도 9th International Meeting on Information Display
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    • pp.290-293
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    • 2009
  • We both theoretically and experimentally investigated the luminescence wavelength control of the $Eu^{2+}$-doped $CaAlSiN_3$ (CASN:$Eu^{2+}$). To modify emission wavelength, Na-doped and Mg-doped CASN:$Eu^{2+}$ (NCASN:$Eu^{2+}$ and MCASN:$Eu^{2+}$) have been studied. According to quantum chemistry calculation result, we synthesized NCASN:$Eu^{2+}$ and MCASN:$Eu^{2+}$. NCASN:$Eu^{2+}$ and MCASN:$Eu^{2+}$ showed shorter emission wavelength than that of CASN:$Eu^{2+}$.

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Pyridinolyses of 2,4-Dinitrophenyl Phenyl Carbonate and 2,4-Dinitrophenyl Benzoate: Effect of Nonleaving Group on Reactivity and Mechanism

  • Um, Ik-Hwan;Son, Min-Ji;Kim, Song-I;Akhtar, Kalsoom
    • Bulletin of the Korean Chemical Society
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    • 제31권7호
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    • pp.1915-1919
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    • 2010
  • Second-order rate constants $(k_N)$ have been measured for reactions of 2,4-dinitrophenyl phenyl carbonate (2) with a series of pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ and compared with the $k_N$ values reported for the corresponding reactions of 2,4-dinitrophenyl benzoate (1) to investigate the effect of nonleaving group on reactivity and mechanism. The reactions of 2 result in larger $k_N$ values than those of 1. The Br${\o}$nsted-type plot for the reactions of 2 exhibits a downward curvature (i.e., ${\beta}2$ = 0.84 and ${\beta}1$ = 0.16), which is typical for reactions reported to proceed through a stepwise mechanism with a change in rate-determining step. The $pK_a$ at the center of the Br${\o}$nsted curvature, defined as $pK_a{^{\circ}}$, has been found to be 8.5 and 9.5 for the reactions of 2 and 1, respectively. Dissection of $k_N$ into the microscopic rate constants (e.g., $k_1$ and $k_2/k_{-1}$ ratio) has revealed that the reactions of 2 result in larger k1 values than those of 1, indicating that PhO behaves as a stronger electron-withdrawing group than Ph. However, the $k_2/k_{-1}$ ratio has been found to be independent of the electronic nature of Ph and PhO.

K2CO3가 흡착된 합성제올라이트 구조체의 소화농도에 관한 연구 (A Study on Extinguishing Concentration of K2CO3-Zeolite Composites)

  • 김승일;신창섭
    • 한국화재소방학회논문지
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    • 제26권4호
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    • pp.42-47
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    • 2012
  • 본 연구에서는 입자크기 및 밀도가 비교적 작고 소화효과에 있어서 부촉매효과를 나타내는 다공성 흡착제인 합성제올라이트에 $K_2CO_3$를 중량비에 따라 흡착시킨 구조체의 소화농도를 측정하였다. 그리고 구조적 특성을 파악하고자 주사전자 현미경(SEM)의 측정 및 X-Ray 회절분석, 열분석 등을 실시하였다. 흡착구조체의 소화농도실험에서 중량비에 관계없이 순수 $K_2CO_3$의 소화농도보다 모두 낮게 나타났다. 그리고, 특히 $K_2CO_3$와 합성제올라이트의 중량비가 7 : 3인 경우는 소화농도가 5.72배 낮게 측정되었고 ABC분말소화약제보다 약 1.1배 낮게 나타났다. SEM 사진 및 XRD 회절패턴분석을 통해 $K_2CO_3$가 합성제올라이트에 흡착되었다는 것을 알 수 있었고, 열분석을 통해 흡착구조체가 순수 $K_2CO_3$보다 소화에 긍정적인 영향을 미쳤을 것이라 추정할 수 있었다.

K2O·CaO·P2O5계 유리의 열적특성과 구조분석 (A Study of Structure and Thermal Properties of K2O·CaO·P2O5 Glasses)

  • 윤영진;윤태민;이용수;강원호
    • 한국세라믹학회지
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    • 제39권2호
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    • pp.194-198
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    • 2002
  • $K_2O{\cdot}CaO{\cdot}P_2O_5$를 기본조성으로 하여 용융법에 의해 유리 형성범위를 정의하고자 하였다. TG-DTA와 DSC를 이용하여 열적 특성을 관찰하고자 하였으며, FT-IR과 Raman Spectroscopy를 이용하여 구조를 분석하였다. $K_2O{\cdot}CaO{\cdot}P_2O_5$의 함량이 증가함에 따라 유리전이온도 및 연화온도는 감소하였다. $K_2O{\cdot}CaO{\cdot}P_2O_5$ 유리의 기본 구조는 이웃한 구조와 상호 결합을 위한 $PO_2$$PO_4^{3-}$ 구조와 유리의 골격구조를 이루는 P-O-P 결합이며, CaO의 함량이 증가함에 따라, 유리내의 P-O-P의 결합력은 점차적으로 증가하였으며, $PO_2$$PO_4^{3-}$의 intensity는 점차적으로 감소하였다.

THE DIMENSION OF THE CONVOLUTION OF BIPARTITE ORDERED SETS

  • Bae, Deok-Rak
    • 대한수학회지
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    • 제36권3호
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    • pp.633-648
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    • 1999
  • In this paper, for any two bipartite ordered sets P and Q, we define the convolution P * Q of P and Q. For dim(P)=s and dim(Q)=t, we prove that s+t-(U+V)-2 dim(P*Q) s+t-(U+V)+2, where U+V is the max-mn integer of the certain realizers. In particular, we also prove that dim(P)=n+k- {{{{ { n+k} over {3 } }}}} for 2 k n<2k and dim(Pn ,k)=n for n 2k, where Pn,k=Sn*Sk is the convolution of two standard ordered sets Sn and Sk.

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Local Moves and Gordian Complexes, II

  • Nakanishi, Yasutaka
    • Kyungpook Mathematical Journal
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    • 제47권3호
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    • pp.329-334
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    • 2007
  • By the works of Levine [2] and Rolfsen [5], [6], it is known that a local move called a crossing-change is strongly related to the Alexander invariant. In this note, we will consider to what degree the relationship is strong. Let K be a knot, and $K^{\times}$ the set of knots obtained from a knot K by a single crossing-change. Let MK be the Alexander invariant of a knot K, and MK the set of the Alexander invariants $\{MK\}_{K{\in}\mathcal{K}}$ for a set of knots $\mathcal{K}$. Our main result is the following: If both $K_1$ and $K_2$ are knots with unknotting number one, then $MK_1=MK_2$ implies $MK_1^{\times}=MK_2^{\times}$. On the other hand, there exists a pair of knots $K_1$ and $K_2$ such that $MK_1=MK_2$ and $MK_1^{\times}{\neq}MK_2^{\times}$. In other words, the Gordian complex is not homogeneous with respect to Alexander invariants.

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