• 제목/요약/키워드: charge transfer complex

검색결과 159건 처리시간 0.033초

N,N-Dimethylaniline과 Iodine간의 반응에 있어서 Charge Transfer Complex의 영향 (The Effects of Charge Transfer Complex on the Reaction of N,N-dimethylaniline and Iodine)

  • 권오윤;백우현;김응렬
    • 대한화학회지
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    • 제36권2호
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    • pp.191-196
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    • 1992
  • $CHCl_3,\;CHCl_3 : CH_2Cl_2$(1:1) 및 $CH_2Cl_2$ 용매 중에서 N,N-dimethylaniline(N,N-DMA)과 iodine간의 반응을 전도도법을 이용하여 속도론적으로 조사하였다. 유사 1차반응 속도상수($k_{obs}$) 및 2차반응 속도상수($k_{obs}$/[N,N-DMA])가 N,N-DMA 농도 의존성을 보였다. 실험적으로 구한 2차반응 속도상수는 N,N-DMA 농도 증가와 더불어 증가하였다. 이러한 결과를 반응 중간 생성물로서 charge tranfer complex의 생성에 기인하는 것으로 보고, 반응 scheme의 설정과 속도상수식의 유도로부터 complex 생성에 따른 평형상수와 변환에 따른 활성화 파라미터를 계산하였다. 평형상수는 용매의 유전상수의 증가와 더불어 감소하였으며, 1.9${\sim}$4.2$M^{-1}$의 값을 보였다. 또한 변환의 빠르기는 용매의 극성에 크게 의존하였으며, ${\Delta}H^{\neq}$값은 6.3-12.6kJ/mol, ${\Delta}S^{\neq}$값은 약 -234J/mol K의 큰 음의 값을 나타내었다.

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분자간 전하이동형 기능성 색소의 합성과 물성 (Syntheses and Characteristics of Intermolecular Charge-Transfer Complex Dyes)

  • Kim, Sung Hoon;Lee, Soon Nam;Lim, Yong Jin
    • 한국염색가공학회지
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    • 제4권1호
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    • pp.21-25
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    • 1992
  • The charge-transfer(CT) complexes derived from various donors and acceptors were evaluated as coloring matter. Dyes absorbing light in the region from the visible to the near-infrared wavelengths were synthesized. In order to determine the molar ratio of the donor to the acceptor in the CT complex in the solution, the continuous variational method was applied to each system. A 1:1 correspondence between the donor and the acceptor molecules in the CT complex in the solution is established. Color development properties in paper were examined. The longer the exposure time at constant temperature, the deeper the strength of color in paper. The strength of color at high temperature was decreased, because sublimed CT dyes in paper were migrated out side of paper.

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Quercetin과 (+)-Catechin의 카드뮴(II)에 대한 착물반응 (Complexation Studies for Cadmium (II) with Quercetin and (+)-Catechin)

  • 이정호;신선우;백승화
    • 약학회지
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    • 제53권6호
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    • pp.342-350
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    • 2009
  • The interaction of cadmium (II) ion with quercetin and (+)-catechin was investigated in aqueous solution at various pH. The flavonoid/cadmium stochiometries for cadmium (II) binding to quercetin and (+)-catechin have been determined by UV-vis spectroscopy. 1 : 1 Cd (II)-Flavonoid complex had a maximum absorbance and showed the bathochromic shift of the long-wavelength band of the UV-vis spectra in the alkaline pH, that occurs upon complexation, due to a ligandto-metal charge transfer. These results suggest that Cd (II)-flavonoid complex has the optimal condition of chelation in 0.2 M $NH_3$ - 0.2 M $NH_4Cl$ (pH 8.0) solution.

고압하의 전하이동착물에 대한 물성론적 연구. 사염화탄소 용액내에서의 헥사메틸벤젠과 1,3,5-트리니트로벤젠과의 전하이동착물 생성에 대한 압력과 온도의 영향 (The Physicochemical Properties on the Organic, Charge Transfer Complexes under High Pressure)

  • 권오천;김명자
    • 대한화학회지
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    • 제32권6호
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    • pp.513-519
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    • 1988
  • 헥사메틸벤젠과 1,3,5-트리니트로벤젠과의 사이에 전하이동착물의 안정도에 미치는 압력과 온도의 영향을 사염화탄소용액내에서 분광광도법으로 연구하였다. 압력은 1, 200, 500, 1000, 1400 bar. 온도는 25, 40, $50^{\circ}C$사이에서 측정하였다. 착물의 평형상수는 압력 및 온도 증가와 더불어 증가 또는 감소하고 흡수계수는 대체로 증가함을 알았다. 이들 각 평형상수로부터 착물형성에 따른 부피, 엔탈피, 자유에너지 및 엔트로피 변화량을 구하였다. 도한 압력 증가에 의한 red-shift, 온도 증가에 의한 blue-shift 현상 및 압력 변화에 의한 진동자세기의 관계를 열역학함수와 관계지어 설명하였다.

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EXCITED-STATE TWISTED INTRAMOLECLILAR CHARGE TRANSFER OF p-N,N-DIMETHYLAMINOBENZOIC ACID IN AQUEOUS CYCLODEXTRIN SOLUTIONS: TIME-RESOLVED FLUORESCENCE STUDY

  • Kim, Yong-Hee;Cho, Dae-Won;Yoon, Min-Joong
    • Journal of Photoscience
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    • 제3권3호
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    • pp.153-158
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    • 1996
  • The effects of $\alpha$- and $\beta$-cyclodextrins (CD) on the twisted intramolecular charge transfer (TICT) behavior of p-N,N'-dimethylaminobenzoic acid (DMABA) in buffered aqueous solution have been investigated by examining formation and decay behaviors of the TICT-typical dual fluorescence. The ratio of the TICT emission to the normal emission (I$_a$/I$_b$) increases linearly $\alpha$-CD concentration increases, while in the presence of $\beta$-CD it shows nonlinear dependences on the CD concentration. The analysis of the CD-dependent changes of the I$_a$/I$_b$ and absorption spectra demonstrates formation of 1:1 inclusion complexes between DMABA and CDs. The decay time of the normal emission (ca. 700 ps) is little affected by the formation of $\alpha$-CD inclusion complex, whereas it increases upto ca. 1.6 ns upon formation of $\beta$-CD inclusion complex. The TICT emission for the $\beta$-CD inclusion complex exhibits two decay components while it shows a single component for the $\alpha$-CD inclusion complex, indicating formation of one or two types of inclusion complex in the presence of $\alpha$-CD or $\beta$-CD, respectively. These results are attributed to the CD cavity size dependence on patterns of complexation between CDs and DMABA. The CD size dependences of the TICT fluorescence properties with the orientation of the guest molecule demonstrate that the specific hydrogen bonding between the carboxylic acid group and water plays an important role in the excited-state TICT.

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Reaction of $FeC_5H_5^+$ Ion with Neutral Ferrocene: The Dependence of Reaction Pathways on Its Internal Energy

  • 김병주;소훈영
    • Bulletin of the Korean Chemical Society
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    • 제20권10호
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    • pp.1181-1185
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    • 1999
  • The reaction of FeC5H5+ ion with ferrocene molecule is investigated using FT-ICR mass spectrometry. FeC5H5+ ions are generated by dissociative ionization of ferrocenes using an electron beam. The reaction gives rise to the formation of the adduct ion, Fe2(C5H5)3+, in competition with charge transfer reaction leading to the formation of ferrocene molecular ion, Fe(C5H5)2+·. The branching ratio of the adduct ion increases as the internal energy of the reactant ion decreases and correspondingly the branching ratio for the charge transfer reaction product decreases. The observed rate of the addition reaction channel is slower than that of the charge transfer reaction. The observation of the stable adduct ions in the low-pressure ICR cell is attributed to the radiative cooling of the activated ion-molecule complex. The mechanism of the reaction is presented to account for the observed experimental results.

The Study on the Physicochemical Properties of Fluid under High Pressure (Ⅱ). The Effect of Pressure and Temperature on the Hexamethyl Benzene-Iodine Charge Transfer Complex in n-Hexane

  • 권오천;김정림
    • Bulletin of the Korean Chemical Society
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    • 제6권4호
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    • pp.186-191
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    • 1985
  • The effect of pressure and temperature on the stabilities of the charge transfer complexes of hexamethyl benzene with iodine in n-hexane has been investigated by UV-spectrophotometric measurements. In this experiment the absorption spectra of mixed solutions of hexamethyl benzene and iodine in n-hexane were measured at 25, 40 and $60^{\circ}C$ under 1,200, 600, 1200 and 1600 bar. The equilibrium constant of the complex formation was increased with pressure while being decreased with temperature raising. Changes of volume, enthalpy, free energy and entropy for the formation of the complexes were obtained from the equilibrium constants. The red shift at higher pressure, the blue shift at higher temperature and the relation between pressure and oscillator strength were discussed by means of thermodynamic functions. In comparison with the results in the previous studies, it can be seen that the pressure dependence of oscillator strength has a extremum behavior in durene as the variation of ${\Delta}H$ or ${\Delta}S$ with the number of methyl groups of polymethyl benzene near atmospheric pressure in the previous study. The shift or deformation of the potential in the ground state and in the excited state of the complexes formed between polymethyl benzene and iodine was considered from the correlation between the differences of the electron transfer energies and the differences of free energies of the complex formation for the pressure variation.

Intepretation of Faradaic Impedance for Corrosion Monitoring

  • Itagaki, M.;Taya, A.;Imamura, M.;Saruwatari, R.;Watanabe, K.
    • Corrosion Science and Technology
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    • 제3권1호
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    • pp.1-5
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    • 2004
  • A polarization resistance is generally used to estimate the corrosion rate in the corrosion monitoring by an electrochemical impedance method. When the Faradaic impedance has a time constant due to the reaction intermediate, the electrochemical impedance describes more than one loop on the complex plane. For example, the electrochemical impedance of iron in acidic solution shows capacitive and inductive loops on the complex plane. In this case, the charge transfer resistance and the polarization resistance are determined at middle and low frequency ranges, respectively. Which should be selected for corrosion resistance in corrosion monitoring, the charge transfer resistance or the polarization resistance'? In the present paper, the above-mentioned question is examined theoretically and experimentally.

파라퀴논 유도체와의 전하이동착물 형성을 이용한 에녹사신 정량 (The Determination of Enoxacin with p-Quinone Derivatives)

  • 이지연;김동오;남수자;정문모;허문회;안문규
    • 약학회지
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    • 제43권4호
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    • pp.437-441
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    • 1999
  • Enoxacin[1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-\piperazinyl)-1,8-naphthyridine-3-carboxylic acid, ENX] is a new quinolone antibacterial agent. The method is based on the highly colored charge-transfer complex formation of this drug as a $\pi$-electron donor with 7,7,8,8-tetracyanoquinodimethane(TCNQ) or chloranil(CL) as $\pi$-acceptors. The colored products were measured spectrophotometrically at 842 nm and 552 nm for TCNQ and CL, respectively. The different experimental conditions are optimized. The linearities for TCNQ and CL were $1.6{\;}\mu\textrm{g}/mL~32{\;}\mu\textrm{g}/mL$ and $6.4{\;}\mu\textrm{g}/mL~160{\;}\mu\textrm{g}/mL$, respectively and colors were produced in non-aqueous media. This report describes a simple and ra\pid method for the analysis of enoxacin.

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