• 제목/요약/키워드: Correlation constants

검색결과 214건 처리시간 0.027초

A New Substituent Constant $σ^{c+}4_s$;a Fit for π-Participation in Modified Hammett-Brown Equation

  • 조정호;신정휴
    • Bulletin of the Korean Chemical Society
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    • 제17권4호
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    • pp.347-348
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    • 1996
  • A set of substituent constants, σc+, has been widely used comparing the stability of carbocation in super acid condition. Plotting of 13C chemical shifts of cationic carbon (Δδc+) against σc+ constants yields an excellent correlation with a good correlation coefficient (r=0.999) for a cyclopentyl cation system. But these σc+ constants show poor linearity in norbornenyl cations that well known to show homoallylic stabilization in a cationic condition. We calculated the new substituent constant, σc+π, and found that the new substituent constants give an excellent correlation in π- and πσ-participating cation systems.

Determination of the Frumkin and Temkin Adsorption Isotherms of Hydrogen at Nickel/Acidic and Alkaline Aqueous Solution Interfaces Using the Phase-Shift Method and Correlation Constants

  • Chun, Jang-H.
    • 전기화학회지
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    • 제15권1호
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    • pp.54-66
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    • 2012
  • The phase-shift method and correlation constants, which are unique electrochemical impedance spectroscopy techniques for studying the linear relationship between the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) vs. potential (E) behavior for the optimum intermediate frequency ($f_o$) and the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. E behavior, are proposed and verified to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and the related electrode kinetic and thermodynamic parameters. At Ni/0.5 M $H_2SO_4$ and 0.1M LiOH aqueous solution interfaces, the Frumkin and Temkin adsorption isotherms (${\theta}$ vs. E) of H for the cathodic hydrogen ($H_2$) evolution, interaction parameters (g), equilibrium constants (K), standard Gibbs energies (${\Delta}G^0_{\theta}$) of H adsorption, and rates of change (r) of ${\Delta}G^0_{\theta}$ with ${\theta}$ have been determined using the phase-shift method and correlation constants. A lateral repulsive interaction (g>0) between the adsorbed H species appears. The value of K in the alkaline aqueous solution is much greater than that in the acidic aqueous solution.

The New Substituent Constants in the Excited States

  • Shim Sang Chul;Park Joon Won;Ham Hie Seok
    • Bulletin of the Korean Chemical Society
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    • 제3권1호
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    • pp.13-18
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    • 1982
  • The new substituent constants $({\sigma}^{\ast})$ are calculated from the acidity constants $(pK^{\ast})$ of phenol derivatives in the excited state ($^1L_b$). These substituent constant are applied to the Hammett equations and found good correlation with $pK^{\ast}$ of 2,6-di-tert-butyl phenol, benzamide, nitroaniline, thiophenol, azobenzene, and benzoic acid derivatives. The correlation was much better than that of ground state substituent constants such as ${\sigma},\;{\sigma}^+$, and ${\sigma}^-$. From these results, the new substituent constants $({\sigma}^{\ast})$are proposed to be used for the linear free energy relationship in the $^1({\pi},{\pi}^{\ast})$ excited states of phenyl compounds.

Determination of Adsorption Isotherms of Hydrogen on Zirconium in Sulfuric Acid Solution Using the Phase-Shift Method and Correlation Constants

  • Chun, Jang-H.;Chun, Jin-Y.
    • 전기화학회지
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    • 제12권1호
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    • pp.26-33
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    • 2009
  • The phase-shift method and correlation constants, i.e., the unique electrochemical impedance spectroscopy (EIS) techniques for studying the linear relationship between the behavior ($-{\varphi}$ vs. E) of the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) for the optimum intermediate frequency and that ($\theta$ vs. E) of the fractional surface coverage ($0{\leq}{\theta}{\leq}1$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at noble metal (alloy)/aqueous solution interfaces. At a Zr/0.2 M ${H_2}{SO_4}$ aqueous solution interface, the Frumkin and Temkin adsorption isotherms ($\theta$ vs. E), equilibrium constants (K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ for the Frumkin and K = $1.401{\times}10^{-16}\exp(8.1{\theta})mol^{-1}$ for the Temkin adsorption isotherm), interaction parameters (g = 3.5 for the Frumkin and g = 8.1 for the Temkin adsorption isotherm), rates of change of the standard free energy (r = $8.7\;kJ\;mol^{-1}$ for g = 3.5 and r = $20\;kJ\;mol^{-1}$ for g = 8.1) of H with $\theta$, and standard free energies ($96.13{\leq}{\Delta}G^0_{\theta}{\leq}104.8\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ and $0{\leq}{\theta}{\leq}1$ and ($94.44<{\Delta}G^0_{\theta}<106.5\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-16}\exp(-8.1{\theta})mol^{-1}$ and $0.2<{\theta}<0.8$) of H are determined using the phase-shift method and correlation constants. At 0.2 < $\theta$ < 0.8, the Temkin adsorption isotherm correlating with the Frumkin adsorption isotherm, and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are probably the most accurate, useful, and effective ways to determine the adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at highly corrosion-resistant metal/aqueous solution interfaces.

회귀항수에 의한 치아크기의 추정에 관한 연구 (A STUDY ON ESTIMATING TOOTH SIZE WITH REGRESSION CONSTANTS)

  • 남동석
    • 대한치과교정학회지
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    • 제11권1호
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    • pp.31-34
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    • 1981
  • A study of a sample of 81 Korean adolescents was taken to determine the degree of correlation between mandibular anterior teeth size and the size of the canines and premolars. The correlation between the total mesiodistal width of the mandibular permanent incisors and that of maxillary or mandibular canine and first and second premolars was found to be 0.53 and 0.58, respectively. Further , regression constants were determined in an attempt to estimate the buccal segments from the mandibular incisors.

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Determination of Adsorption Isotherms of Hydroxide ata Platinum Electrode Interface Using the Phase-Shift Method and Correlation Constants

  • Chun, Jin-Y.;Chun, Jang-H.
    • 전기화학회지
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    • 제10권3호
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    • pp.219-228
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    • 2007
  • The phase-shift method and correlation constants, i.e., the electrochemical impedance spectroscopy (EIS) techniques for studying linear relationships between the behaviors (${\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and those (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}{\theta}{\geq}0$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at noble and transition-metal/aqueous solution interfaces. At the Pt/0.1 MKOH aqueous solution interface, the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=5.6{\times}10^{-10}\;mol^{-1}\;at\;0{\leq}{\theta}<0.81$, $K=5.6{\times}10^{-9}{\exp}(-4.6{\theta})\;mol^{-1}\;at\;0.2<{\theta}<0.8$, and $K=5.6{\times}10^{-10}{\exp}(-12{\theta})\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$, interaction parameters (g = 4.6 for the Temkin and g = 12 for the Frumkin adsorption isotherm), rates of change of the standard free energy ($r=11.4\;kJ\;mol^{-1}$ for g=4.6 and $r=29.8\;kJ\;mol^{-1}$ for g=12), and standard free energies (${\Delta}G_{ads}^0=52.8\;kJ\;mol^{-1}\;at\;0{\leq}{\theta}<0.81,\;49.4<{\Delta}G_{\theta}^0<56.2\;kJ\;mol^{-1}\;at\;0.2<{\theta}<0.8$ and $80.1<{\Delta}_{\theta}^0{\leq}82.5\;kJ\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$) of OH for the anodic $O_2$ evolution reaction (OER) are also determined using the phase-shift method and correlation constants. The adsorption of OH transits from the Langmuir to the Frumkin adsorption isotherm (${\theta}\;vs.E$), and vice versa, depending on the electrode potential (E) or the fractional surface coverage (${\theta}$). At the intermediate values of ${\theta}$, i.e., $0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms and related electrode kinetic and thermodynamic parameters. They are useful and effective ways to study the adsorptions of intermediates (H, OH) for the sequential reactions (HER, OER) at the interfaces.

강원도에 분포하는 화강토의 다짐특성 및 토질정수의 상관관계에 관한 연구 (A Study on Correlations between Compaction Properties and Soil Constants of Granite Soil in the Kangwon Province)

  • 유남재;박병수;홍영길
    • 산업기술연구
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    • 제18권
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    • pp.77-86
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    • 1998
  • This study is to provide the useful data for the design and construction of the geotechnical engineering works by collecting and analyzing the soil properties of granite soil in the Kangwon Province. Data base was obtained from 92 field sites in the Kangwon province divided into 15 areas based on administration district. Total numbers of data were 478. Correlations between soil constants, especially compaction properties, were obtained by performing statistical analysis. Analyzed results were as follows. 1. Most of granite soil consists of SM and GM based on United Soil Classification System. 2. Mean gravity of granite soil is 2.65 3. High correlations between optimum moisture content and the maximum dry density, plasticity index and liquid limit are obtained. 4. Analyzed results between other soil constants show relatively low correlation. However, they show consistent trends matchable to geotechnical engineering senses.

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Review on the Determination of Frumkin, Langmuir, and Temkin Adsorption Isotherms at Electrode/Solution Interfaces Using the Phase-Shift Method and Correlation Constants

  • Chun, Jinyoung;Chun, Jang H.
    • Korean Chemical Engineering Research
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    • 제54권6호
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    • pp.734-745
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    • 2016
  • This review article described the electrochemical Frumkin, Langmuir, and Temkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) and deuterium (OPD D) for the cathodic $H_2$ and $D_2$ evolution reactions (HER, DER) at Pt, Ir, Pt-Ir alloy, Pd, Au, and Re/normal ($H_2O$) and heavy water ($D_2O$) solution interfaces. The Frumkin, Langmuir, and Temkin adsorption isotherms of intermediates (OPD H, OPD D, etc.) for sequential reactions (HER, DER, etc.) at electrode/solution interfaces are determined using the phase-shift method and correlation constants, which have been suggested and developed by Chun et al. The basic procedure of the phase-shift method, the Frumkin, Langmuir, and Temkin adsorption isotherms of OPD H and OPD D and related electrode kinetic and thermodynamic parameters, i.e., the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. potential (E) behavior (${\theta}$ vs. E), equilibrium constant (K), interaction parameter (g), standard Gibbs energy (${\Delta}G_{\theta}{^{\circ}}$) of adsorption, and rate (r) of change of ${\Delta}G_{\theta}{^{\circ}}$ with ${\theta}$ ($0{\leq}{\theta}{\leq}1$), at the interfaces are briefly interpreted and summarized. The phase-shift method and correlation constants are useful and effective techniques to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and related electrode kinetic and thermodynamic parameters (${\theta}$ vs. E, K, g, ${\Delta}G_{\theta}{^{\circ}}$, r) at electrode/solution interfaces.

프랙탈 차원을 이용한 해저 퇴적환경 분석 적용성 검토 (A Review of the Applicability of The Fractal Dimension of Grain Size Distribution for a Analysis of Submarine Sedimentary Environments)

  • 노수각;손영환;봉태호;박재성
    • 한국농공학회논문집
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    • 제53권6호
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    • pp.43-50
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    • 2011
  • The fractal method has recently been applied to a model for determining soil grain size distribution. The objective of this study is to review the applicability of the fractal method for a analysis of submarine sedimentary environments by comparing fractal constants with grain size statistical analysis for the soil samples of Pohang (PH) and Namhae (NH). The y-interception of log (grain size)-log (passing) equation was also used because grain size distribution couldn't be expressed with fractal dimension only. The result of comparison between fractal constants (dimension, y-interception) and grain size statistical indices, the fractal dimension was directly proportional to the mean and the sorting. And the y-interception showed high correlation with the mean. The fractal dimension and y-interception didn't show significant correlation with the skewness and the kurtosis. Thus regression equations between fractal constants and two statistical indices (mean, sorting) were derived. All classifications of the mean and the sorting could be determined using the regression equation based on the fractal dimension and y-interception. Therefore, fractal constants could be used as an alternative index representing the sedimentary environments instead of the mean and sorting.

Twisted Yarn 복합재료의 탄성계수 예측모델 (Elastic Model of Twisted Yarn Composites)

  • 변준형;이상관;엄문광
    • 한국복합재료학회:학술대회논문집
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    • 한국복합재료학회 2002년도 춘계학술발표대회 논문집
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    • pp.57-60
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    • 2002
  • The stiffness model has been proposed to predict elastic constants of twisted yarn composites. The model is based upon the unit cell structure, the coordinate transformation, and the volume averaging of compliance constants for constituent materials. For the correlation of analytic results with experiments, composite samples of various yarn twist angle were tested. The samples were fabricated by the RTM process using glass yarns and epoxy resin. The correlations of elastic constants showed relatively good agreements. The model provides the predictions of the three-dimensional engineering constants, which are valuable input data for the analytic characterization of textile composites made of twisted yarn.

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