• Title/Summary/Keyword: log-concave

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Bayesian Estimation of k-Population Weibull Distribution Under Ordered Scale Parameters (순서를 갖는 척도모수들의 사전정보 하에 k-모집단 와이블분포의 베이지안 모수추정)

  • 손영숙;김성욱
    • The Korean Journal of Applied Statistics
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    • v.16 no.2
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    • pp.273-282
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    • 2003
  • The problem of estimating the parameters of k-population Weibull distributions is discussed under the prior of ordered scale parameters. Parameters are estimated by the Gibbs sampling method. Since the conditional posterior distribution of the shape parameter in the Gibbs sampler is not log-concave, the shape parameter is generated by the adaptive rejection sampling. Finally, we applied this estimation methodology to the data discussed in Nelson (1970).

Kinetics and Mechanism of the Benzylaminolysis of O,O-Diphenyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1625-1629
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    • 2011
  • Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.

Characteristic of Raindrop Size Distribution Using Two-dimensional Video Disdrometer Data in Daegu, Korea (2차원 광학 우적계 자료를 이용한 대구지역 우적크기분포 특성 분석)

  • Bang, Wonbae;Kwon, Soohyun;Lee, GyuWon
    • Journal of the Korean earth science society
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    • v.38 no.7
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    • pp.511-521
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    • 2017
  • This study analyzes Two-dimensional video disdrometer (2DVD) data while summer 2011-2012 in Daegu region and compares with Marshall and Palmer (MP) distribution to find out statistical characteristics and characteristics variability about drop size distribution (DSD) of Daegu region. As the characterize DSD of Daegu region, this study uses single moment parameters such as rainfall intensity (R), reflectivity factor (Z) and double moment parameters such as generalized characteristics number concentration ($N{_0}^{\prime}$) and generalized characteristics diameter ($D{_m}^{\prime}$). Also, this study makes an assumption that DSD function can be expressed as general gamma distribution. The results of analysis show that DSD of Daegu region has ${\log}_{10}N{_0}^{\prime}=2.37$, $D{_m}^{\prime}=1.04mm$, and c =2.37, ${\mu}=0.39$ on average. When the assumption of MP distribution is used, these figures then end up with the different characteristics; ${\log}_{10}N{_0}^{\prime}=2.27$, $D{_m}^{\prime}=0.9mm$, c =1, ${\mu}=1$ on average. The differences indicate liquid water content (LWC) of Daegu distribution is generally larger than MP distribution at equal Z. Second, DSD shape of Daegu distribution is concave upward. Other important facts are the characteristics of Daegu distribution change when Z changes. DSD shape of Daegu region changes concave downward (c =2.05~2.55, ${\mu}=0.33{\sim}0.77$) to cubic function-like shape (c =3.0, ${\mu}=-0.13{\sim}-0.33$) at Z > 45 dBZ. 35 dBZ ${\leq}$ Z > 45 dBZ group of Daegu distribution has characteristics similar to maritime cluster of diverse climate DSD study. However, Z > 45 dBZ group of Daegu distribution has a difference from the cluster.

Nucleophilic Substitution Reactions of α-Bromoacetanilides with Benzylamines

  • Adhikary, Keshab Kumar;Kim, Chan-Kyung;Lee, Bon-Su;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.29 no.1
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    • pp.191-196
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    • 2008
  • Kinetic studies of the reactions of a-bromoacetanilides [YC6H4NHC(=O)CH2Br] with substituted benzylamines (XC6H4CH2NH2) have been carried out in dimethyl sulfoxide at 35.0 oC. The Hammett plots for substituent (Y) variations in the substrate (log kN vs. sY) are biphasic concave upwards/downwards with breaks at Y = 4-Cl (sY = 0.23). The Hammett coefficients rY and the cross-interaction constant rXY (= +0.16) are positive for sY 0.23, while the rY values are positive/negative [rY > 0 for X = (4-MeO and 4-Me) and rY < 0 for X = (H, 4-Cl and 3-Cl)] and the rXY (= -1.51) value is negative for sY ³ 0.23. Based on these and other results, the benzylaminolyses of a-bromoacetanilides are proposed to proceed through rate-limiting expulsion of the bromide leaving group from a zwitterionic tetrahedral intermediate, T, with a bridged transition state for s Y 0.23, while the reaction proceeds through concerted mechanism with an enolate-like TS in which the nucleophile attacks the a-carbon for s Y ³ 0.23.

Pyridinolysis of O,O-Diphenyl S-Phenyl Phosphorothiolates in Acetonitrile

  • Adhikary, Keshab Kumar;Lumbiny, Bilkis Jahan;Kim, Chan-Kyung;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.29 no.4
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    • pp.851-855
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    • 2008
  • The reactions of O,O-diphenyl Z-S-phenyl phosphorothiolates with X-pyridines have been studied kinetically in acetonitrile at $35.0{^{\circ}C}$. The Hammett plots for substituent (Z) variations in the leaving group (log $k_2$ vs. $\sigma$ Z) are biphasic concave downwards with breaks at Z = H. The large magnitudes of ${\rho}X(\rho_{nuc})$, ${\beta}X(\rho_{nuc})$, and the cross-interaction constant, $\rho$XZ, suggest frontside nucleophilic attack toward the leaving group. The sign reversal of $\rho$Z from positive in $\sigma$ Z $\leq$ 0 to negative in $\sigma$ Z $\geq$ 0 is interpreted as the change in mechanism from concerted to stepwise with rate-limiting expulsion of the leaving group. The anomalous negative sign of $\rho$ Z for leaving groups with electron-withdrawing substituents is interpreted as the intramolecular ligand exchange process of the leaving group from the equatorial position in the intermediate to the apical position in the TS.

Distribution of Electrically Conductive Sedimentary Layer in Jeju Island Derived from Magnetotelluric Measurements (MT 탐사자료를 이용한 제주도 지역의 전도성 퇴적층 분포 연구)

  • Lee, Choon-Ki;Lee, Heuisoon;Oh, Seokhoon;Chung, Hojoon;Song, Yoonho;Lee, Tae Jong
    • Geophysics and Geophysical Exploration
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    • v.17 no.1
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    • pp.28-33
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    • 2014
  • We investigate the spatial distribution of highly conductive layer using the one-dimensional inversions of the new magnetotelluric (MT) measurements obtained at the mid-mountain (400 ~ 900 m in elevation) western area of Jeju Island and the previous MT data over Jeju Island, Korea. The conductive layer indicates the sedimentary layer comprised of Seoguipo Fomation and U Formation. There is a definite positive correlation between the top of conductive layer and the earth surface in elevation. On the contrary, the bottom of conductive layer has a negative correlation with the surface elevation. In other words, the conductive layer has a shape of convex lens, which is thickest in the central part. The basement beneath the conductive layer could be concave in the central part of Jeju Island. A kriging considering the correlation between the layer boundary and the surface elevation provides a reliable geoelectric structure model of Jeju Island. However, further studies, i.e. three-dimensional modeling and interpretation integrated with other geophysical or logging data, are required to reveal the possible presence of three-dimensional conductive body near the subsurface vent of Mt. Halla and the causes of the bias in the depths of layer estimated from MT and core log data.