• Title/Summary/Keyword: entropies

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The Characteristics of PET Micro Fiber Fabrics Decomposed dy Sodium Ethylene glycol Solution (Sodium ethylene glycolate 용액에 의한 PET 극세사 직물의 분해 특성)

  • Bae, Jung-Sook;Cho, Yong-Suk
    • Journal of the Korean Home Economics Association
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    • v.36 no.8
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    • pp.95-104
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    • 1998
  • PET microfiber fabric dissociation reactions by ethylene glycol (EG) catalayzed by the corresponding EG anions were examined to provide an empirical basis for the improvement of a PET microfiber fabrics. The alkoxide ions, monosodium ethylene glycolate in ethylene glycol solution(MSEG-EG) are prepared by the reaction between NaH and the EG respectively. The dissociation reactions were carried out until the sample PET microfiber fabrics dissociate up to 80%. Temperature used ranged 100~$160^{\circ}C$. The kinetic behaviors of the dissociated PET microfiber fabrics were examined. The results are as follows : 1. In all cases, it was found that the PET-alkoxide dissociation rate constants increased exponentially with increasing temperature. The activation energies (Ea) of the reactions were 23.31kcal/mol in PET-EG system respectively. The calculated enthalpies of the activated [PET-EG] complexes from the corresponding Ea values were 22.53 ~ 22.61 kcal/mol, and the entropies were -19.03 ~ -19.24 kcal/mol/k respectively. 2. The kinetic behavior of the PET-alkoxide dissociation reactions examined was explained by the transition state theory. PET-alkoxide transition state is believed to be formed during the ester interchange mechanism between PET and MSEG-EG in the course of the PET dissociation reactions.

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Transient State Theory of Significant Liquid Structure Applied to A Binary Mixture of Benzene and Carbon Tetrachloride (이성분 액체 혼합물 ($C_6H_6-CCl_4$)의 통계열역학적 연구)

  • Choi, Dong-Sik;Ahn, Woon-Sun;Kim, Kak-Choong;Chang, Sei-Hun
    • Journal of the Korean Chemical Society
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    • v.11 no.4
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    • pp.143-149
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    • 1967
  • The Transient State Theory of Significant Liquid Structure is applied to a binary liquid solution of benzene and carbon tetrachloride, which gives slightly positive deviation from Raoults law. The partition function for the solution is derived according to the proposed theory. The various thermodynamic properties such as total and partial vapor pressures, molar volumes, entropies of mixing, and compressibilities are calculated at three different temperatures, 298.15^{\circ}K$, 313.15^{\circ}K$ and 343.1515^{\circ}K$. The calculated values agree satisfactorily with experimental data.

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Correlation of the Rates of Solvolysis of Isopropyl Fluoroformate Using the Extended Grunwald-Winstein Equation

  • Lee, So-Hee;Rhu, Chan-Joo;Kyong, Jin-Burm;Kim, Dong-Kook;Dennis N. Kevill
    • Bulletin of the Korean Chemical Society
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    • v.28 no.4
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    • pp.657-661
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    • 2007
  • The specific rates of solvolysis of isopropyl fluoroformate are well correlated using the extended Grunwald-Winstein equation, with a sensitivity (l ) to changes in solvent nucleophilicity (NT) and a sensitivity (m) to changes in solvent ionizing power (YCl). The sensitivities (l = 1.59 ± 0.16 and m = 0.80 ± 0.06) toward changes in solvent nucleophilicity and solvent ionizing power, and the kF/kCl values are very similar to those for solvolyses of n-octyl fluoroformate, suggesting that the addition step of an addition-elimination mechanism is rate-determining. For methanolysis, a solvent deuterium isotope effect of 2.53 is compatible with the incorporation of general-base catalysis into the substitution process. The large negative values for the entropies of activation are consistent with the bimolecular nature of the proposed rate-determining step. These observations are also compared with those previously reported for the corresponding chloroformate and fluoroformate esters.

Significant Liquid Structure of Binary Mixture, $C_6H_6-C_2H_4Cl_2$ (이성분 액체 혼합물의 통계열역학적 연구)

  • Ahn, Woon-Sun;Pak, Hyung-Suk;Chang, Sei-Hun
    • Journal of the Korean Chemical Society
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    • v.9 no.4
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    • pp.215-221
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    • 1965
  • The significant liquid structure theory is extended to binary mixture, benzene-ethylenechloride system. The partition function, applicable throughout the temperature range in which Raoult's law is satisfied is derived. The thermodynamic quantities such as total and partial pressures, molar volumes and mixing entropies are calculated from the partition function at the temperatures $293.15^{\circ},\;323.14^{\circ}\;and\;357.15^{\circ}K.$ The theoretical values, thus calculated, are found to agree with the experimental data in the literatures.

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Anomaly Detection Method Using Entropy of Network Traffic Distributions (네트워크 트래픽 분포 엔트로피를 이용한 비정상행위 탐지 방법)

  • Kang Koo-Hong;Oh Jin-Tae;Jang Jong-Soo
    • The KIPS Transactions:PartC
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    • v.13C no.3 s.106
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    • pp.283-294
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    • 2006
  • Hostile network traffic is often different from normal traffic in ways that can be distinguished without knowing the exact nature of the attack. In this paper, we propose a new anomaly detection method using inbound network traffic distributions. For this purpose, we first characterize the traffic of a real campus network by the distributions of IP protocols, packet length, destination IP/port addresses, TTL value, TCP SYN packet, and fragment packet. And then we introduce the concept of entropy to transform the obtained baseline traffic distributions into manageable values. Finally, we can detect the anomalies by the difference of entropies between the current and baseline distributions. In particular, we apply the well-known denial-of-service attacks to a real campus network and show the experimental results.

Kinetic Studies of the Solvolyses of 2,2,2-Trichloro-1,1-Dimethylethyl Chloroformate

  • Koh, Han-Joong;Kang, Suk-Jin;Kevill, Dennis N.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.835-839
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    • 2010
  • The rate constants of solvolyses of 2,2,2-trichloro-1,1-dimethylethyl chloroformate ($\underline{I}$) in 33 solvents can be well correlated using the extended Grunwald-Winstein equation, with incorporation of the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivities towards changes in the scale having values of $1.42\;{\pm}\;0.09$ for l and $0.39\;{\pm}\;0.05$ for m, respectively. The activation enthalpies are ${\Delta}H^{\neq}\;=\;12.3$ to $14.5\;kcal{\cdot}mol^{-1}$ and the activation entropies are -28.2 to $-35.5\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$, consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.14 in MeOH/MeOD is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

Rate and Product Studies on the Solvolyses of Allyl Chloroformate

  • Koh, Han Joong;Kang, Suk Jin
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4117-4121
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    • 2012
  • The solvolysis rate constants of allyl chloroformate ($CH_2=CHCH_2OCOCl$, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with the sensitivity values of $0.93{\pm}0.05$ and $0.41{\pm}0.02$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.5 to 13.4 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -34.4 to -37.3 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.16 was also in accord with the $S_N2$ mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.

Chandra Archival Survey of Galaxy Clusters: X-ray Point Sources in Cool-core and Non-cool-core Clusters

  • Kim, Minsun;Kim, Eunhyeuk
    • The Bulletin of The Korean Astronomical Society
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    • v.37 no.2
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    • pp.78.1-78.1
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    • 2012
  • We have studied the physical properties of X-ray point sources in galaxy clusters using ~600 Chandra archival observations. The goal of this study is to investigate the density environmental effects on the physical properties of X-ray point sources by comparing the properties of X-ray point sources in galaxy clusters to those in typical blank fields. In this presentation, we show the nature of X-ray point sources which are expected to be related with galaxy clusters with different core properties. Using ~60 galaxy clusters observed with Chandra, we investigate the physical properties of X-ray point sources in cool-core and non-cool-core clusters. The cool-core clusters are known to have short central cooling time, and are characterized by low central entropy, systematic central temperature drops, and a brightest cluster galaxy at the X-ray peak. While the non-cool-core clusters have longer central cooling time, and are characterized by large central entropies and flat or centrally rising temperature profile. We show that how central core properties of galaxy clusters affect on the physical properties of X-ray point sources.

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Dehydrogenation of Ethylalcohol Catalyzed by Alcoholdehydrogenase Under High Pressure

  • Jee Jong-Gi;Shin Jin-Young;Hwang Jung-Ui
    • Bulletin of the Korean Chemical Society
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    • v.10 no.1
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    • pp.50-57
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    • 1989
  • A pressure effect of the dehydrogenation of ethylalcohol catalyzed by alcoholdehydrogenase was observed in Tris-HCl buffer, pH 8.8 from $25^{\circ}C$ to $35^{\circ}C$ under high pressure system by using our new theory. The theory makes it possible for us to obtain all rate and equilibrium constants for each step of all enzymatic reaction with a single intermediate. We had enthalpy and volume profiles of the dehydrogenation to suggest a detail and reasonable mechanism of the reaction. In these profiles, both enthalpy and entropy of the reaction are positive and their values decrease with enhancing pressure. It means that the first step is endothermic reaction, and its strength decrease with elevating pressure. At the same time, all activation entropies have large negative values, which prove that not only a ternary complex has a more ordered structure at transition state, but also water molecules make a iceberg close by the activated complex. In addition to this fact, the first and second step equilibrium states are controlled by enthalpy. The first step kinetic state is controlled by enthalpy but the second step kinetic state is controlled by entropy.

Rate-Product Correlations for the Solvolysis of 5-Nitro-2-Furoyl Chloride

  • Choi, Ho-June;Koh, Han-Joong;Ali, Dildar;Yang, Ki-Yull;Koo, In-Sun
    • Bulletin of the Korean Chemical Society
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    • v.33 no.10
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    • pp.3293-3297
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    • 2012
  • The solvolysis rate constants of 5-nitro-2-furoyl chloride (5-$NO_2(C_4H_2O)$-2-COCl, 1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and YCl solvent ionizing scale, with sensitivity values of $1.20{\pm}0.05$ and $0.37{\pm}0.02$ for l and m, respectively. The activation enthalpies (${\Delta}H^{\neq}$) were 5.63 to $13.0kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -25.9 to $-43.4cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.65 was also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The product selectivity (S) for solvolysis of 1 in alcohol/water mixtures was 1.2 to 11, which is also consistent with the proposed bimolecular reaction mechanism.