• 제목/요약/키워드: State transition

검색결과 1,893건 처리시간 0.027초

Tetramethyltin과 Iodine의 $S_F2$ 분해반응에 대한 압력의 영향 (The Effect of Pressure on the $S_F2$ Cleavage Reaction of Tetramethyltin with Iodine)

  • 권오천;경진범;이영훈
    • 대한화학회지
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    • 제37권3호
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    • pp.287-293
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    • 1993
  • n-헥산과 아세톤 용매내에서 요오드와 테트라메틸주석간의 전하이동 상호작용을 분광학적 방법으로 연구하였다. 이들의 결과로부터 일시적인 전하이동착물의 흡수 스펙트럼이 관찰되었으며, 흡수 스펙트럼의 후속적인 감소현상이 요오드에 의한 테트라메틸주석의 분해반응임을 알았다.(iododestannylation). 따라서 iododestannylation에 대한 속도상수를 온도 10, 25 및 35$^{\circ}C$, 압력을 1600 bar까지 변화시켜 가면서 측정하였으며, 이때의 반응속도상수는 온도와 압력에 따라 증가함을 알았다. 이 반응속도상수로부터 ${\Delta}V^{\neq}$, ${\Delta}{\beta}^{\neq}$, ${\Delta}H^{\neq}$${\Delta}S^{\neq}$의 값을 얻었으며, 이들 값으로부터 전이상태의 용매구조 변화 및 메카니즘을 규명하였다. 이러한 사실로부터 본 반응은 S$_F$2 메카니즘이 지배적이며 압력이 증가함에 따라 S$_F$2의 성격이 약화됨을 알았다.

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Base-Catalyzed Rearrangement of Some 1,3-Oxathiolane Sulfoxides: Mechanistic Viewpoint of the Sigmatropic and Elimination Reactions

  • Hahn, Hoh-Gyu;Nam, Kee-Dal;Cheon, Seung-Hoon
    • Bulletin of the Korean Chemical Society
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    • 제25권9호
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    • pp.1379-1384
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    • 2004
  • Rearrangements of 1,3-oxathiolane sulfoxides 8 and 9 in the presence of base are described from a mechanistic viewpoint of sigmatropic and elimination reactions. In the presence of triethylamine the (Z)-sulfoxide 8 gave the corresponding thiolsulfinate 10 by way of dimerization of the sulfenic acid intermediate 2 at room temperature while the (E)-sulfoxide 9 was recovered even after refluxing in ethyl acetate by the reversal of the [2,3]-sigmatropic rearrangement of the sulfenic acid 4. Triethylamine promoted the developing charge separation in the transition state of the sigmatropic rearrangement of the (Z)-sulfoxide 8 to facilitate the ring opening to the sulfenic acid 2. The reason for more facile ring opening of the (Z)-sulfoxide 8 in comparison with the corresponding (E)-sulfoxide 9 is attributable to the differences in the reactivity of the hydrogen adjacent to the carbonyl group. Triethylamine was not strong base to deprotonate the carbonyl-activated methylene hydrogen of the (E)-sulfoxide 9 but enough to catalyze the sigmatropic process of the sulfoxides. The sulfenic acid 2 dimerized to the thiolsulfinate 10 while the sulfenic acid 4 proceeded the sigmatropic ring closure. In the presence of strong base such as potassium hydroxide, the elimination reaction was predominant over the sigmatropic rearrangement. In this reaction condition, both sulfoxides 8a and 9a gave a mixture of the disulfide 12, the isomeric disulfide 14, and the sulfinic acid 13. Under the strong alkaline condition an elimination of activated hydrogen from the carbon adjacent to the carbonyl group to furnish the sulfenic acid 2a and the isomeric sulfenic acid 18. The formation of the transient intermediate in the reaction was proven by isolation of the isomeric disulfide 14. The reactive entity was regarded as the sulfenic acid rather than sulfenate anion under these reaction conditions.

Tetramethyltin과 Iodine의 친전자 치환반응에 대한 압력의 영향 (The Effect of Pressure on the Electrophilic Substitution Reaction of Tetramethyltin with Iodine)

  • 권오천;이훈영
    • 대한화학회지
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    • 제37권6호
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    • pp.555-561
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    • 1993
  • 메탄올용매내에서 요오드와 테트라메틸주석 사이의 Iododestannylation에 대한 반응속도를 분광학적 방법으로 연구하였다. 이 결과로부터 일시적인 전하이동착물의 흡수 스펙트럼이 관찰되었으며, 흡수 스펙트럼의 후속적인 감소현상으로 요오드에 의한 테트라메틸주석의 분해반응임을 알았다. 따라서 iododestannylation에 대한 속도상수를 온도 10, 25 및 35$^{\circ}C$ 압력을 1600 bar 까지 변화시켜 가면서 측정하였으며, 이때의 반응속도상수는 온도와 압력에 따라 증가함을 알았다. 이 반응속도상수로부터 ${\Delta}V^\neq,\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}$${\Delta}G^{\neq}$의 값을 구하였다. 활성화 부피와 활성화 압축율계수는 모두 음의 값이며, 활성화 엔탈피는 양의 값을, 활성화 엔트로피는 음의 값을 나타내었다. 이들 값으로부터 전이상태의 용매구조변화 및 메카니즘을 규명하였다. 이러한 사실로부터 본 반응은 $S_E2$ 메카니즘이 지배적이며 압력이 증가함에 따라 $S_E2$의 성격이 약화됨을 알았다

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유연 기판 소재로 응용을 위한 폴리(에틸렌/프로필렌 나프탈레이트)의 치수안정성 연구 (Dimensional Stability of Poly(ethylene/propylene naphthalate) as a Flexible Substrate Application)

  • 김재현;허혜영;정태형;한준희;강호종
    • 폴리머
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    • 제33권4호
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    • pp.371-376
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    • 2009
  • 폴리(에틸렌 나프탈레이트) 공중합체를 합성하기 위하여 에틸렌글리콜과 함께 1,3-프로판디올을 혼합사용하여 폴리(에틸렌/프로필렌 나프탈레이트)를 합성하고 이를 유연 기판 소재로 적용하기 위한 물성을 살펴보았다. NMR 실험 결과, 에틸렌과 프로필렌 segment가 함께 공존하는 폴리(에틸렌/프로필렌 나프탈레이트)가 합성되었음을 확인하였다. 에틸렌과 함께 프로필렌 segment가 존재하는 경우 합성된 폴리에스터의 결정화가 일어나지 않으며 유리전이온도와 열분해온도는 감소함을 알 수 있다. 합성된 폴리(에틸/프로필렌 나프탈레이트)의 주사슬에 에틸렌 보다 상대적으로 긴 프로필렌이 공존함에 따라 주사슬 배향이 어려워 열팽창계수가 감소함에 따라 합성 시 1,3-프로판디올 첨가에 따른 다소간의 내열온도 감소에도 저수축 유연기판 소재로 적용 가능함을 알 수 있었다.

Kinetic Studies on Halogen Exchange of Substituted Benzenesulfonylbromides

  • Kim, Jaerok
    • Nuclear Engineering and Technology
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    • 제5권4호
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    • pp.321-333
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    • 1973
  • 브롬화벤젠썰포닐류 (R-C$_{6}$H$_4$SO$_2$Br, R=p-MeO, p-$CH_3$, p-H, p-NO$_2$등)의 할로겐 교환반응을 무수 아세톤 중에서 행하고 두 온도에서의 반응속도항수를 구함으로써 활성화 파라메타들을 아울러 결정하였다. 친핵자의 강도는 강한 전자흡인 치환기를 가졌거나 약한 전자공여 치환기를 가진 유도체에 대하여는 Cl->I-$\geq$Br-의 순위였으며, 강한 전자공여 치환기의 유도체에 대하여는 I-$\geq$Cl->Br-의 순위임을 보았다. 하메트(Harnmett)점시는 치환기를 가진 염화벤젠쎌포닐류에서와 유사하게 약간 위로 볼록한 특징을 보였는데 이것은 치환기를 가진 염화벤질류의 할로겐 교환반응의 그것이 아래로 오목함을 보이는 것과는 대조적이었다. 한편 브롬화벤젠썰포닐과 브롬화리티움 사이의 할로겐 교환반응 속도를 여러용매에서 측정한 결과 반응속도가 큰 순서는 ($CH_3$)$_2$CO>$CH_3$CN》MeOH이었다. 속도항수와 활성화파라메타들을 염화벤젠쎌포닐류에 대한 것과 비교하였으며 치환기효과, 용매효과 등에서 얻은 결과들을 전이상태의 구조적 특징으로 설명하고 반응기구를 논의하였다.

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CaAl2O4:RE3+(RE = Tb, Dy) 형광체의 발광 특성 (Photoluminescence Properties of CaAl2O4:RE3+(RE = Tb, Dy) Phosphors)

  • 조신호
    • 한국재료학회지
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    • 제26권3호
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    • pp.143-148
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    • 2016
  • $CaAl_2O_4:RE^{3+}$(RE = Tb or Dy) phosphor powders were synthesized with different contents of activator ions $Tb^{3+}$ and $Dy^{3+}$ by using the solid-state reaction method. The effects of the content of activator ions on the crystal structure, morphology, and emission and excitation properties of the resulting phosphor particles were investigated. XRD patterns showed that all the synthesized phosphors had a monoclinic system with a main (220) diffraction peak, irrespective of the content and type of $Tb^{3+}$ and $Dy^{3+}$ ions. For the $Tb^{3+}$-doped $CaAl_2O_4$ phosphor powders, the excitation spectra consisted of one broad band centered at 271 nm in the range of 220-320 nm and several weak peaks; the main emission band showed a strong green band at 552 nm that originated from the $^5D_4{\rightarrow}^7F_5$ transition of $Tb^{3+}$ ions. For the $Dy^{3+}$-doped $CaAl_2O_4$ phosphor, the emission spectra under ultraviolet excitation at 298 nm exhibited one strong yellow band centered at 581 nm and two weak bands at 488 and 672 nm. Concentration-dependent quenching was observed at 0.05 mol of $Tb^{3+}$ and $Dy^{3+}$ contents in the $CaAl_2O_4$ host lattice.

An Analytical Appraisal of Building Information Modelling (BIM) Guidelines to Identify Variations in the Procedures

  • Das, Dakshata;Moon, Sungkon
    • 한국BIM학회 논문집
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    • 제6권3호
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    • pp.1-14
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    • 2016
  • The usage of Building Information Modelling (BIM) in building projects has enabled improvement in project planning, implementation and collaboration process amongst various stakeholders within architecture, engineering and construction (AEC) industry. However, variations exist in the current practices of BIM implementation and coordination process in the industry. These variations result in inconsistent degree of BIM use across the construction industry. This inconsistency gives rise to several managerial and technological challenges such as data interoperability issues and purposeful integration and exchange of information within the BIM components. In order to tackle the issue, it is essential to analyse the different BIM approaches employed by the industry practitioners. BIM guidelines serve as a critical link between the BIM model, and its subsequent execution. They therefore provide the best reflection of BIM application and processes. This research paper aims to address the variations existing in BIM practices across the construction industry. It includes an extensive study of 21 existing, publicly available BIM-based guidelines in order to establish an understanding of the present state of practice and deduce issues and concerns related to them. All guidelines analysed in this paper are first categorised based on authorship and the release date for efficient comparison. The points of similarity and difference between them are thereby realized and outlined. In addition, the transition of project implementation process from traditional methods to BIM technology is also explained. The existence of inconsistencies in the BIM guidelines reviewed in this paper reflects the need of a BIM 'Code Compliance Check'. The Code Compliance Check will serve as a regulatory project guideline that will further improve the potential of BIM by incorporating a consistent BIM modelling methodology for the entire construction industry.

Performance Analysis of Opportunistic Spectrum Access Protocol for Multi-Channel Cognitive Radio Networks

  • Kim, Kyung Jae;Kwak, Kyung Sup;Choi, Bong Dae
    • Journal of Communications and Networks
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    • 제15권1호
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    • pp.77-86
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    • 2013
  • Cognitive radio (CR) has emerged as one of effective methods to enhance the utilization of existing radio spectrum. Main principle of CR is that secondary users (SUs) are allowed to use the spectrum unused by primary users (PUs) without interfering PU's transmissions. In this paper, PUs operate on a slot-by-slot basis and SUs try to exploit the slots unused by PUs. We propose OSA protocols in the single channel and we propose an opportunistic spectrum access (OSA) protocols in the multi-channel cognitive radio networks with one control channel and several licensed channels where a slot is divided into contention phase and transmission phase. A slot is divided into reporting phase, contention phase and transmission phase. The reporting phase plays a role of finding idle channels unused by PUs and the contention phase plays a role of selecting a SU who will send packets in the data transmission phase. One SU is selected by carrier sense multiple access / collision avoidance (CSMA/CA) with request to send / clear to send (RTS/CTS) mechanism on control channel and the SU is allowed to occupy all remaining part of all idle channels during the current slot. For mathematical analysis, first we deal with the single-channel case and we model the proposed OSA media access control (MAC) protocol by three-dimensional discrete time Markov chain (DTMC) whose one-step transition probability matrix has a special structure so as to apply the censored Markov chain method to obtain the steady state distribution.We obtain the throughput and the distribution of access delay. Next we deal with the multi-channel case and obtain the throughput and the distribution of access delay by using results of single-channel case. In numerical results, our mathematical analysis is verified by simulations and we give numerical results on throughput and access delay of the proposed MAC protocol. Finally, we find the maximum allowable number of SUs satisfying the requirements on throughput and access delay.

950℃ 불순물을 포함한 헬륨 환경에서 CVD β-SiC의 산화 (Oxidation of CVD β-SiC in Impurity-Controlled Helium Environment at 950℃)

  • 김대종;김원주;장지은;윤순길;김동진;박지연
    • 한국세라믹학회지
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    • 제48권5호
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    • pp.426-432
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    • 2011
  • The oxidation behavior of CVD ${\beta}$-SiC was investigated for Very High Temperature Gas-Cooled Reactor (VHTR) applications. This study focused on the surface analysis of the oxidized CVD ${\beta}$-SiC to observe the effect of impurity gases on active/passive oxidation. Oxidation test was carried out at $950^{\circ}C$ in the impurity-controlled helium environment that contained $H_2$, $H_2O$, CO, and $CH_4$ in order to simulate VHTR coolant chemistry. For 250 h of exposure to the helium, weight changes were barely measurable when $H_2O$ in the bulk gas was carefully controlled between 0.02 and 0.1 Pa. Surface morphology also did not change based on AFM observation. However, XPS analysis results indicated that a very small amount of $SiO_2$ was formed by the reaction of SiC with $H_2O$ at the initial stage of oxidation when $H_2O$ partial pressure in the CVD ${\beta}$-SiC surface placed on the passive oxidation region. As the oxidation progressed, $H_2O$ consumed and its partial pressure in the surface decreased to the active/passive oxidation transition region. At the steady state, more oxidation did not observable up to 250 h of exposure.

0.8 이상의 전기기계결합계수(k33)를 가지는 고효율 무연 압전 Ba(Ti0.94Zr0.06)O3 단결정 ("Lead-free" Piezoelectric Ba(Ti0.94Zr0.06)O3 Single Crystals with Electromechanical Coupling Factor (k33) Higher Than 0.8)

  • 이종엽;오현택;이호용
    • 한국세라믹학회지
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    • 제51권6호
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    • pp.623-628
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    • 2014
  • Orthorhombic $Ba(Ti_{0.94}Zr_{0.06})O_3$ single crystals are fabricated using the cost-effective solid-state single crystal growth (SSCG) method; their dielectric and piezoelectric properties are also characterized. Measurements show that (001) $Ba(Ti_{0.94}Zr_{0.06})O_3$ single crystals have an electromechanical coupling factor ($k_{33}$) higher than 0.83, piezoelectric charge constant ($d_{33}$) of about 400 [pC/N], and piezoelectric voltage constant ($g_{33}$) higher than 50 [${\times}10^{-3}Vm/N$]. The transition temperature ($T_{OT}$) of the (001) $Ba(Ti_{0.94}Zr_{0.06})O_3$ single crystals between orthorhombic and tetragonal phases is also observed to be about $61^{\circ}C$. Because their electromechanical coupling factor ($k_{33}$) and piezoelectric voltage constant ($g_{33}$) are higher than those of soft PZT ceramics, it is expected that (001) $Ba(Ti_{0.94}Zr_{0.06})O_3$ single crystals can be used as "lead-free" piezoelectric materials in many piezoelectric applications.