• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1729-1733
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• 2012

The solvolysis rate constants of 2,2,2-trichloroethyl chloroformate ($Cl_3CCH_2OCOCl$, $\mathbf{3}$) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $1.28{\pm}0.06$ and $0.46{\pm}0.03$ for $l$ and $m$, respectively. The activation enthalpies (${\Delta}H^{\neq}$) are 10.1 to 12.8 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) are -27.8 to -36.8 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect ($k_{MeOH}/k_{MeOD}$) of 2.39 is also in accord with $S_N2$ mechanism probably assisted by general-base catalysis.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.65-70
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• 2002

We have evaluated the specific hydroxyl group-solvent and carbonyl group-solvent interactions by using an Alltima C18 stationary phase and by measuring the retention data of carefully selected solutes in 60/40, 70/30, and 80/20(v/v%) acetonitrile/water eluents at 25, 30, 35, 40, 45, and 50 oC. The selected solutes are phenol, acetophenone, alkylbenznes(benzene to hexylbenznene), 4 positional isomers of phenylbutanol, 5-phenyl-1-pentanol, 3 positional isomers of alkylarylketone derived from butylbenzene, and 1-phenyl-2-hexanone. The magnitudes of hydroxyl group-acetonitrile/water specific interaction enthalpies are larger than those of carbonyl group-acetonitrile/water specific interaction enthalpies in general while the magnitudes of carbonyl group-methanol/water specific interaction enthalpies are larger than those of hydroxyl group-methanol/water specific interactions. We observed clear discrepancies in functional group-solvent specific interaction among positional isomers. The variation trends of solute transfer enthalpies and entropies with mobile phase composition in the acetonitrile/water system are much different from those in the methanol/water system. The well-known pocket formation of acetonitrile in aqueous acetonitrile mixtures has proven to be useful to explain such phenomena.

• Bulletin of the Korean Chemical Society
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• v.31 no.7
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• pp.1963-1967
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• 2010

The rates of solvolysis of 4-morpholinecarbonyl chloride (MPC) have measured at $35.0^{\circ}C$ in water, $D_2O$, $CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol, and 2,2,2-trifluoroethanol. An extended (two-term) Grunwald-Winstein equation correlation gave sensitivities towards changes in solvent nucleophilicity and solvent ionizing power as expected for a dissociative $S_N2$ and/or $S_N1$(ionization) pathway. For nine solvents specific rates were determined at two additional temperatures and higher enthalpies and smaller negative entropies of activation were observed, consistent with the typical dissociative $S_N2$ or $S_N1$(ionization) pathway. The solvent deuterium isotope effect values for the hydrolysis of MPC of $k_{H_2O}/k_{D_2O}$ = 1.27 and for the methanolysis of MPC of $k_{MeOH}/k_{MeOD}$ = 1.22 are typical magnitudes of the $S_N1$ or ionization mechanism.

• Bulletin of the Korean Chemical Society
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• v.32 no.4
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• pp.1268-1272
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• 2011

The specific rates of solvolysis of phenyl fluorothionoformate (PhOCSF, 1) have been determined in 22 pure and binary solvents at $10.0^{\circ}C$. The extended Grunwald-Winstein equation has been applied to the specific rates of solvolysis of 1 over the full range of solvents. The sensitivities (l = $1.32{\pm}0.13$ and m = $0.39{\pm}0.08$) toward the changes in solvent nucleophilicity and solvent ionizing power, and the $k_F/k_{Cl}$ values are similar to those previously observed for solvolyses of acyl haloformate esters, consistent with the addition step of an additionelimination pathway being rate-determining. The large negative values for the entropies of activation are consistent with the bimolecular nature of the proposed rate-determining step. The results are compared with those reported earlier for phenyl chloroformate and chlorothionoformate esters and mechanistic conclusions are drawn.

• Journal of the Korean Graphic Arts Communication Society
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• v.14 no.1
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• pp.47-54
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• 1996

Deuterium NMR studies have been carried out for two kinds of main- chain dimer liquid crystals $\alpha$.$\omega$-bis[(4,4`-cyanobipheny0oxy] alkane (CBA-n, n=9,100.The H-NMR spectra were recorded on a JEOP JNM-GSX-500 spectrometer by using deuterium labelled CBA-n at various temperatures. The RIS analysis of the NMR spectra was performed so as to elucidate the conformational characteristics of the spacer in the nematic phase. Following the previous treatment, the single-ordering-matrix model was adopted, in which the molecular axis was defined parallel to the line connecting the centers of the terminal mesogenic cores. Conformer fractions of the spacer were estimated by simulation so as to reproduce the observed NMR profile. The conformational entropy changes at both CN and NI interphases were estimated on the basis of the nematic conformations taken from the conformation map as well as those derived from the simulation. In these calculations the spacer was assumed th by in the all-trans conformation and in the random coil stats in the crystal and isotropic phases respectively. The esimated conformational entropy change values were then compared with the corresponding constant-volume entropies obtained from PVT measurements. The correspondence between both entropy values was found to be quite good in consideration of the uncertainties involved in both experiment and calculations.

• Journal of the Korean Applied Science and Technology
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• v.10 no.1
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• pp.67-74
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• 1993

1, 2-Isopropylidene glycerol produced by ketalyzation of glycerol with aceton was esterified with long chain fatty acids in the presence of a Mucor miehei lipase to obtain 1, 2-isopropylidene 3-long chain acyl glycerol. To determine optimal conditions for the esterification reaction, esterification was proceeded as a reversible second-order reaction in various parameters that are enzyme/substrate ratio 0.096g/g at reaction temperatures ranged from $25^{\circ}C$ to $70^{\circ}C$. The order of reaction rate of fatty acids were lauric acid, myristic acid, oleic acid, and stearic acid. The range of their activation energies were from 7.8 to 11.4 (kcal/mol) and that of entropies of activation which have negative values were from 42.8 to 52.5(e.u.).

• Journal of the Korean Society for information Management
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• v.16 no.4
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• pp.95-107
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• 1999

Various approaches have been made for dividing images in content-based image retrieval. One of them defined five regions for images and conducted a series of experiments. A major assumption of the experiment is that the center regions of images are very important. It is based on the observation that meaningful objects are usually located in the center region of images. From this point of view, we tried to test if the assumptions is objectively valid by calculating and comparing PIM(Picture Information Measure) entropies of image regions proposed by S.K Chang. The experimental results showed that there were statistical PIM differences between the center and other regions.

• Journal of the Korean Chemical Society
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• v.41 no.6
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• pp.299-303
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• 1997

The rate constants($k_{OH}$) for the alkaline hydrolysis of the 4-substituted phenyl ethyl benzylphosphonates were determined in various buffer solutions by UV(Vis spectrophotometer. The activation entropies of the title reactions show negative values and this result is not consistent with a dissociative mechanism (EA) for which a positive or slightly negative value of the entropy of activation should be expected. An associative mechanism(AE) is favorable because the negligible negative charge is generated on the leaving group in the rate determining step from a good Hammett relationship(ρ=1.89). By the results of a kinetic study, we conclude that a dissociative mechanism is not proceeded in the title reactions.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2263-2270
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• 2014

Solvolysis rate constants of 2-phenylethyl-(2-$PhCH_2CH_2OCOCl$, 1) and 2,2-diphenylethyl chloroformate (2,2-$Ph_2CHCH_2OCOCl$, 2), together with the previously studied solvolyses of ${\alpha}$- and ${\beta}$-substituted chloroformate ester derivatives, are reported in pure and binary solvents at $40.0^{\circ}C$. The linear free energy relationship (LFER) and sensitivities (l and m) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) of the solvolytic reactions are analyzed using the Grunwald-Winstein equation. The kinetic solvent isotope effects (KSIEs) in methanol and activation parameter values in various solvents are investigated for 1 and 2. These results support well the bimolecular pathway with same aspects. Furthermore, the small negative values of the entropies of activation of solvolysis of 1 and 2 in the highly ionizing aqueous fluoroalcohols are consistent with the ionization character of the rate-determining step, and the KSIE values of 1.78 and 2.10 in methanol-d indicate that one molecule of solvent acts as a nucleophile and the other acts as a general-base catalyst. It is found that the ${\beta}$-substituents in alkyl chloroformate are not the important factor to decide the solvolysis reaction pathway.

• Journal of the Korean Society for Library and Information Science
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• v.6
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• pp.87-103
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• 1979

Information storage and retrieval is a part of general communication process. In the Shannon's information theory, information contained in a message is a measure of -uncertainty about information source and the amount of information is measured by entropy. Indexing is a process of reducing entropy of information source since document collection is divided into many smaller groups according to the subjects documents deal with. Significant concepts contained in every document are mapped into the set of all sets of index terms. Thus index itself is formed by paired sets of index terms and documents. Without indexing the entropy of document collection consisting of N documents is $log_2\;N$, whereas the average entropy of smaller groups $(W_1,\;W_2,...W_m)$ is as small $(as\;(\sum\limits^m_{i=1}\;H(W_i))/m$. Retrieval efficiency is a measure of information system's performance, which is largely affected by goodness of index. If all and only documents evaluated relevant to user's query can be retrieved, the information system is said $100\%$ efficient. Document file W may be potentially classified into two sets of relevant documents and non-relevant documents to a specific query. After retrieval, the document file W' is reclassified into four sets of relevant-retrieved, relevant-not retrieved, non-relevant-retrieved and non-relevant-not retrieved. It is shown in the paper that the difference in two entropies of document file Wand document file W' is a proper measure of retrieval efficiency.