• 제목/요약/키워드: Formation free energy

검색결과 233건 처리시간 0.026초

벤젠과 요오드 사이의 전하이동착물에 대한 압력과 온도의 영향 (The Effect of Pressure and Temperature on the Benzene-Iodine Charge Transfer Complex in n-Hexane)

  • 권오천;김정림
    • 대한화학회지
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    • 제27권2호
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    • pp.102-110
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    • 1983
  • 벤젠과 요오드 사이의 전하이동착물의 안정도에 미치는 압력과 온도의 영향을 n-헥산 용매내에서 자외선 분광 광도법으로 연구하였다. 압력은 1에서 1600 bar, 온도는 25, 40, $60^{\circ}C$에서 측정하였다. 착물 형성에 대한 평형상수는 압력이 증가함에 따라 증가하고, 온도가 상승함에 따라 감소하였으며 착물의 흡수계수는 압력 및 온도와 함께 같이 증가함을 알았다. 이들 각 평형상수로 부터 착물 형성에 따른 부피, 엔탈피, 자유에너지 및 엔트로피 변화양을 구하였다. 또한 압력의 증가에 의한 red-shift, 온도의 상승에 의한 blue-shift 현상 및 압력 변화에 의한 진동자 세기의 관계를 열역학 함수와 관계지워 설명하였다.

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Kinetics and Mechanism of the Pyridinolysis of S-Aryl Phenyl Phosphonochloridothioates in Acetonitrile

  • Adhikary, Keshab Kumar;Lumbiny, Bilkis Jahan;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권10호
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    • pp.3743-3747
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    • 2011
  • Kinetic studies on the reactions of Y-S-aryl phenyl phosphonochloridothioates with X-pyridines have been carried out in MeCN at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H. The Hammett plots for substituent Y variations in the substrates are biphasic concave upwards with a break point at Y = H, and the sign of ${\rho}_Y$ is changed from unusual negative (${\rho}_Y$ < 0) with the weaker electrophiles to positive (${\rho}_Y$ > 0) with the stronger electrophiles. The stepwise mechanism is proposed on the basis of the ${\rho}_X$, ${\beta}_X$, and ${\rho}_{XY}$ values as follows: a ratelimiting leaving group departure from the intermediate involving a frontside attack and product-like TS for the stronger nucleophiles and weaker electrophiles; a rate-limiting leaving group departure from the intermediate involving a backside attack and product-like TS for the weaker nucleophiles and electrophiles; a rate-limiting bond formation involving a frontside attack for the stronger nucleophiles and electrophiles; a rate-limiting bond formation involving a backside attack for the weaker nucleophiles and stronger electrophiles. The substituent effects of X and Y on the pyridinolysis mechanisms of $R_1R_2P$(=S)Cl-type substrates are discussed.

ON THE IMPORTANCE OF USING APPROPRIATE SPECTRAL MODELS TO DERIVE PHYSICAL PROPERTIES OF GALAXIES

  • PACIFICI, CAMILLA;DA CUNHA, ELISABETE;CHARLOT, STEPHANE;YI, SUKYOUNG
    • 천문학논총
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    • 제30권2호
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    • pp.535-537
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    • 2015
  • Interpreting ultraviolet-to-infrared (UV-to-IR) observations of galaxies in terms of constraints on physical parameters-such as stellar mass ($M_{\ast}$) and star formation rate (SFR)-requires spectral synthesis modelling. We investigate how increasing the level of sophistication of the standard simplifying assumptions of such models can improve estimates of galaxy physical parameters. To achieve this, we compile a sample of 1048 galaxies at redshifts 0.7 < z < 2.8 with accurate photometry at rest-frame UV to near-IR wavelengths from the 3D-HST Survey. We compare the spectral energy distributions of these galaxies with those from different model spectral libraries to derive estimates of the physical parameters. We find that spectral libraries including sophisticated descriptions of galaxy star formation histories (SFHs) and prescriptions for attenuation by dust and nebular emission provide a much better representation of the observations than 'classical' spectral libraries, in which galaxy SFHs are assumed to be exponentially declining functions of time, associated with a simple prescription for dust attenuation free of nebular emission. As a result, for the galaxies in our sample, $M_{\ast}$ derived using classical spectral libraries tends to be systematically overestimated and SFRs systematically underestimated relative to the values derived adopting a more realistic spectral library. We conclude that the sophisticated approach considered here is required to reliably interpret fundamental diagnostics of galaxy evolution.

톨루엔과 요오드 사이의 전하이동착물에 대한 압력의 영향 (I) (The Effect of Pressures on the Formation of Charge Transfer Complexes of Toluene with Iodine (I))

  • 권오천
    • 대한화학회지
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    • 제19권2호
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    • pp.73-84
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    • 1975
  • 톨루엔과 요오드 사이의 전하이동착물의 안정도에 미치는 압력과 온도의 영향을 n-헥산용액에서 자외선 분광광도법으로 연구하였다. 압력은 1에서 1,200bar, 온도는 $25^{\circ}C$에서 $60^{\circ}C 사이에서 측정하였다. 착물의 평형상수는 압력 및 온도의 증가와 더불어 증가 및 감소하고 흡수계는 대체로 증가함을 알았다. 이들 각 평형정수로부터 착물 형성에 따른 부피, 엔탈피, 자유에너지 및 엔트로피 변화 양을 구하였다. 또한 압력의 증가에 의한 blue-shift현상 및 압력 변화에 의한 진동자 세기와의 관계를 열역학적 함수와 관계지워 설명하였다

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Spatial mapping of screened electrostatic potential and superconductivity by scanning tunneling microscopy/spectroscopy

  • Hasegawa, Yukio;Ono, Masanori;Nishio, Takahiro;Eguchi, Toyoaki
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2009년도 제38회 동계학술대회 초록집
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    • pp.12-12
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    • 2010
  • By using scanning tunneling microscopy/spectroscopy (STM/S), we can make images of various physical properties in nanometer-scale spatial resolutions. Here, I demonstrate imaging of two electron-correlated subjects; screening and superconductivity by STM/S. The electrostatic potential around a charge is described with the Coulomb potential. When the charge is located in a metal, the potential is modified because of the free electrons in the host. The potential modification, called screening, is one of the fundamental phenomena in the condensed matter physics. Using low-temperature STM we have developed a method to measure electrostatic potential in high spatial and energy resolutions, and observed the potential around external charges screened by two-dimensional surface electronic states. Characteristic potential decay and the Friedel oscillation were clearly observed around the charges [1]. Superconductivity of nano-size materials, whose dimensions are comparable with the coherence length, is quite different from their bulk. We investigated superconductivity of ultra-thin Pb islands by directly measuring the superconducting gaps using STM. The obtained tunneling spectra exhibit a variation of zero bias conductance (ZBC) with a magnetic field, and spatial mappings of ZBC revealed the vortex formation [2]. Size dependence of the vortex formation will be discussed at the presentation.

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The Study on the Physicochemical Properties of Fluid under High Pressure (1). Effects of Pressure and Temperature on the Pentamethyl Benzene-Iodine Charge Transfer Complex in n-HexaneⅠ

  • Kim, Jeong-Rim;Kwun, Oh-Cheun
    • Bulletin of the Korean Chemical Society
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    • 제6권2호
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    • pp.74-79
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    • 1985
  • The stabilities of the charge transfer complexes of pentamethyl benzene with iodine in n-hexane have been investigated by UV-spectrophotometric measurements at 25, 40 and 60$^{\circ}C$ up to 1600 bars. 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 have been discussed by means of thermodynamic functions. In comparison with the results in the previous studies, the absolute values of ${\Delta}$V at each temperature were increased with the number of methyl groups of polymethyl benzene. However, it can be seen that both ${\Delta}$H and ${\Delta}$S show extreme behaviors in durene near atmospheric pressure but they are negatively increased with the number of methyl groups near 1600 bar. This order of the thermodynamic parameters may be a measure of the relative basicities of polymethyl benzenes toward iodine under each pressure, and these phenomena are explained in terms of a positive inductive effect and a steric hindrance effect of the polymethyl benzene molecule.

DETECTION OF PHYSIOLOGICAL PROCESSES IN WHEAT BY NIR

  • Salgo, A.;Gergely, Sz.;Scholz, E.
    • 한국근적외분광분석학회:학술대회논문집
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    • 한국근적외분광분석학회 2001년도 NIR-2001
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    • pp.1158-1158
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    • 2001
  • Fast and dynamic biochemical, enzymatic and morphological changes occur during the so-called generative development and during the vegetative processes in seeds. The most characteristic biochemical and compositional changes of this period are the formation and decline of storage components or their precursors, the change of their degree in polymerization and an extensive change in water content. The aim of the present study was to detect the maturation processes in seed nondestructively and to verify the applicability of near infrared spectroscopic methods in the measurement of physiological, chemical and biochemical changes in wheat seed. The amount and variation of different water “species” has been changed intensively during maturation. Characteristic changes of three water absorption bands (1920, 1420 and 1150 nm) during maturation were analysed. It was concluded that the free/bound transition of water molecules could be followed sensitively in different region of NIR spectra. Kinetic changes of carbohydrate reserves were characteristic during maturation. An intensive formation and decline of carbohydrate reserves were observed during early stage of maturation (0 -13 days, high energy demand). An accelerated formation of storage carbohydrates (starch) was detected in the second phase of maturation. Five characteristic absorption bands were analysed which were sensitive indicators the changes of carbohydrates occurred during maturation. Precursors of protein synthesis and the synthesis of reserve proteins and their kinetic changes during maturation were followed from NIR spectra qualitative and qualitatively. Dynamic formation of amino acids and the changes of N forms were detected by spectroscopic, chromatographic and by capillary electrophoresis methods. Calibration equations were developed and validated in order to measure the optimal maturation time protein and moisture content of developing wheat seeds. The spectroscopic methods are offering chance and measurement potential in order to detect fine details of physiological processes. The spectra have many hidden details, which can help to understand the biochemical background of processes.

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Thermodynamic Analyses of the Constitutive Splicing Pathway for Ovomucoid Pre-mRNA

  • Ro-Choi, Tae Suk;Choi, Yong Chun
    • Molecules and Cells
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    • 제27권6호
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    • pp.657-665
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    • 2009
  • The ovomucoid pre-mRNA has been folded into mini-hairpins adaptable for the RNA recognition motif (RRM) protein binding. The number of mini-hairpins were 372 for pre-mRNA and 83-86 for mature mRNA. The spatial arrangements are, in average, 16 nucleotides per mini-hairpin which includes 7 nt in the stem, 5.6 nt in the loop and 3.7 nt in the inter-hairpin spacer. The constitutive splicing system of ovomucoid-pre-mRNA is characterized by preferred order of intron removal of 5/6 > 7/4 > 2/1 > 3. The 5' splice sites (5'SS), branch point sequences (BPS) and 3' splice sites (3'SS) were identified and free energies involved have been estimated in 7 splice sites. Thermodynamic barriers for splice sites from the least (|lowest| -Kcal) were 5, 4, 7, 6, 2, 1, and 3; i.e., -18.7 Kcal, -20.2 Kcal, -21.0 Kcal, -24.0 Kcal, - 25.4 Kcal, -26.4 Kcal and -28.2 Kcal respectively. These are parallel to the kinetic data of splicing order reported in the literature. As a result, the preferred order of intron removals can be described by a consideration of free energy changes involved in the spliceosomal assembly pathway. This finding is consistent with the validity of hnRNP formation mechanisms in previous reports.

울릉분지 서부에서의 탄화수소 생성 및 지표 (Hydrocarbon generation and indicator in the western Ulleung Basin)

  • 류병재;김지훈;이영주;;;김일수
    • 한국신재생에너지학회:학술대회논문집
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    • 한국신재생에너지학회 2007년도 춘계학술대회
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    • pp.507-510
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    • 2007
  • Piston cores retrieved from the western Ulleung Basin, East Sea were analyzed to examine the potential for hydrocarbon generation and to determine the hydrocarbon indicators. 2D multi-channel reflection seismic and Chirp data were also investigated for mapping and characterizing the geophysical hydrocarbon indicators such as BSR (bottom simulating reflector), blank zone, pock-mark etc. High organic carbon contents and sedimentation rates that suggest good condition for hydrocarbon generation. High pressure and low temperature condition, and high residual hydrocarbon concentrations are favor the formation of natural gas hydrate. In the piston cores, cracks generally oriented to bedding may indicate the gas expansion. The seismic data show several BSRs that are associated with natural gas hydrates and underlying free gas. A number of vertical to sub-vertical blank zones were well identified in the seismic sections. They often show the seismic pull-up structures, probably indicating the presence of high velocity hydrates. Numerous pockmarks were also observed in the Chirp profiles. They may indicate the presence of free gas below the hydrate stability zone as well.

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Composite Materials with MWCNTs and Conducting Polymer Nanorods and their Application as Supercapacitors

  • Liua, Lichun;Yoo, Sang-Hoon;Park, Sung-Ho
    • Journal of Electrochemical Science and Technology
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    • 제1권1호
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    • pp.25-30
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    • 2010
  • This study demonstrated the synthesis of high-surface-area metal-free carbonaceous electrodes (CE) from anodic aluminum oxide (AAO) templates, and their application as supercapacitors. Multi-walled Carbon nanotubes (MWCNTs) were interwoven into a porous network sheet that was attached to one side of AAO template through a vacuum filtration of the homogeneously dispersed MWCNT toluene solution. Subsequently, the conducting polymer was electrochemically grown into the porous MWCNT network and nanochannels of AAO, leading to the formation of a carbonaceous metal-free film electrode with a high surface area in the given geometrical surface area. Typical conducting polymers such as polypyrrole (PPY) and poly(3,4-ethylenedioxythiophene) (PEDOT) were examined as model systems, and the resulting electrodes were investigated as supercapacitors (SCs). These SCs exhibited stable, high capacitances, with values as high as 554 F/g, 1.08 F/$cm^2$ for PPY and 237 F/g, 0.98 F/$cm^2$ for PEDOT, that were normalized by both the mass and geometric area.