• Journal of the Korean Chemical Society
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• v.28 no.3
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• pp.155-162
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• 1984

Kinetic studies for the nucleophilic substitution reactions of para-substituted benzyl bromides and benzyl iodide with anilines were carried out in MeOH-MeCN mixtures at 35.0$^{\circ}$C. Hammett $ {\rho}_N,\;{\rho}_C$, Bronsted $ {\beta}$ and solvatochromic correlation coefficient a, s values were determined in order to clarify the transition state variations caused by changing nucleophiles, substituents, leaving group and solvents. The results of solvatochromic equation showed that ${\pi}^{ast}$effect was a dominant factor for the reaction systems studied. It was shown that the reaction proceeds via the dissociative $S_N$2 mechanism using the potential energy surface model approach. The potential energy surface model approach however failed to account for the transition state variation due to leaving group changes. The quatum mechanical approach showed that kinetic results were consistent with proposed dissociative $S_N$2 mechanism.

• Journal of the Korean Chemical Society
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• v.29 no.1
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• pp.15-22
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• 1985

Kinetic studies of nucleophilic substitution reaction of substituted benzoyl cyanides and benzoyl chlorides with pyridines were conducted at 25$^{\circ}C$ in pure acetone solvent. Results showed that (ⅰ) magnitudes of $_{\rho}_S$, $_{\rho}_N$ and ${\beta}$ associated with a change of substituent in the nucleophile indicate relatively advanced bond-formation in the transition state, (ⅱ) the potential energy surface model is able to predict the reaction mechanism, but it is unable to predict the transition state variation to a more product-like transition state, where bond-formation is much more progressed than bond breaking, upon changing the leaving group to that with better leaving ability (ⅲ) the quantum mechanical model predicted the product-like transition state and slightly better leaving ability of CN- as compared with Cl-.

• Journal of the Korean Chemical Society
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• v.19 no.3
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• pp.156-162
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• 1975

Rates of reactions of methanesulfonyl chloride with various substituted anilines have been measured in methanol. Substituent effects in aniline are found to be linearly correlated with pKa(Bronsted relation with ${\beta}$ = 0.84) and ${\rho}$(Hammett equation with ${\rho}$ = -2.46) respectively. The results are interpreted in terms of degree of bond-formation at the transition state, which was found to have progressed relatively further. The rates for o-methylaniline deviated from the Bronsted plot established by meta and para substituted anilines because of a steric effect of ortho position in aniline. Activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ have also been determined. The enthalpy of activation showed a regular variation in that electron donating substituents in the p-substituted aniline decrease ${\Delta}H^{\neq}$ and increase the negative value of ${\Delta}S^{\neq}$.

• Journal of the Korean Chemical Society
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• v.43 no.4
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• pp.456-460
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• 1999

Rates of 1-adamantyl fluoroformate with substituted pyridines ($3-CH_3,\;4-CH_3,\;H,\;3-Cl,\;3,4-(CH_3)_2,\;3,5-(CH_3)_2$) in methanol have been measured by conductometric method at various temperatures and concentrations. The activation parameters (${\Delta}H^{\neq},\;{\Delta}S^{\neq}$) and Hammett reaction constant (${\rho}$) or Bronsted coefficient (${\beta}$) were evaluated from rate constants. The activation entropies are large and negative, and the activation enthalpies are small and positive. The Hammett reaction constant (${\rho}$) and Bronsted coefficient (${\beta}$) values were -4.15 and 0.63, respectively. From the above results, it may be concluded that this reaction proceeds to a concerted displacement mechanism in methanol.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1579-1582
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• 2009

The reaction rates of 4-X-2,6-dinitrochlorobenzenes (X = $NO_2,\;CN,\;CF_3$) with Y-substituted pyridines (Y = 3-$OCH_3,\;H,\;3-CH_3,\;4-CH_3$) in methanol-acetonitrile mixtures were measured by conductometry at 25 ${^{\circ}C}$. It was observed that the rate constant increased in the order of X = 4-$NO_2\;>\;4-CN\;>\;4-CF_3$ and the rate constant also increased in the order of Y = 4-$CH_3\;>\;3-CH_3\;>\;H\;>\;3-OCH_3$. When the solvent composition was varied, the rate constant increased in order of MeCN > 50% MeOH > MeOH. The electrophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic hydrogen and nitrogen of pyridines in ground state. Based on the transition parameters, ${\rho}_S,\;{\rho}_N,\;{\beta}_Y,\;{\rho}_{XY}$ and solvent effects, the reaction seems to proceed via $S_N$Ar-Ad.E mechanism. We also estimated the isokinetic solvent mixtures (${\rho}_{XY}$ = 0) based on cross-interaction constants, where the substituent effects of the substrate and nucleophile are compensated.

• Journal of the Korea Society of Computer and Information
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• v.16 no.7
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• pp.95-103
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• 2011

The actual utilization of Semantic Web technology which aims to provide more intelligent and automated service for information retrieval over the Web becomes gradually reality. RDF is widely used as the one of standard formats to present and manage the voluminous data on the Web. Efficient query processing on RDF data, therefore, is one of the ongoing research topics. Retrieving resources having a specific association from a given resource is the typical query processing type and several researches for this have done. However the most of previous researches have not fully considered discovering the complex relationship among resources such as returning the association between resources as the query processing result. This paper introduces the indexing and query processing for ${\rho}$-intersect operation which is one of the semantic association retrieval types. It includes an indexing scheme using suffix array and optimal processing approaches for handling ${\rho}$-intersect operation. The experimental evaluations shows that the average execution times for the proposed approach is 3~7 times faster than the previous approach.

• Proceedings of the International Microelectronics And Packaging Society Conference
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• 2002.11a
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• pp.73-77
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• 2002

Characteristics of Cu/Si/Cu ohmic contacts to n-type 4H-SiC were investigated systematically. The ohmic contacts were formed by rf sputtering of multi layer Cu/Si/Cu sputtered sequentially. The annealings were peformed With 2-Step using RTP in vacuum ambient. The specific contact resistivity($\rho$c), sheet resistance(Rs), contact resistance(Rc), transfer length(L$_{T}$) were calculated from resistance(R$_{T}$) versus contact spacing(d) measurements obtained from TLM(transmission line method) structure. Best results were obtained for a sample annealed at vacuum as $\rho$c = 1.0x10$^{-6}$ $\Omega$$\textrm{cm}^2$, Rc = 2$\Omega$ and L$_{T}$ = 1${\mu}{\textrm}{m}$. The physical properties of contacts were examined using XRO and AES. The results showed that copper silicide was formed on SiC and Cu was migrated into SiC.o SiC.

• Journal of the Korean Chemical Society
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• v.28 no.5
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• pp.284-292
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• 1984

This paper aims to predict the substituent and Lewis acid catalysis effect or reactivity on the regioselectivity of (4+2) cycloaddition reaction of the substituted-E-arene-diazocyanides and nitrosobenzenes. Frontier orbital theory (FMO) has been applied to thermal and catalyzed Diels-Alder reaction by means of CNDO/2 and EHT-SPD methods. It has been found that: (1) The above reaction is positive rho(${\rho}$) values in Hammett equation, so it takes normal electron demand reaction, and four-frontier orbitals and Anh methods are identical with experimental major regioisomer.(2) When electron withdrawing radicals are substituted HOMO and LUMO energies of dienophiles are reduced, and the reactivity is increased. (3) The major regioisomer is predicted as B type, as the Lewis acid makes complexes of dienophile, and polaries LUMO coefficients of dienophile in an opposite way. (4) The linear correlation of Hammett is indicated in the graph of stabilized energies(${\Delta}$E) and sigma(${\sigma}$).

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11a
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• pp.197-200
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• 2001

In this letter, we report on the investigation of Ni/Si/Ni Ohmic contacts to n-type 4H-SiC. Ohmic contacts have been formed by a vacuum annealing and N$_2$ gas ambient annealing method at 950$^{\circ}C$ for 10 min. The specific contact resistivity($\rho$$\sub$c/), sheet resistance(R$\sub$S/), contact resistance(R$\sub$S/), transfer length(LT) were calculated from resistance(R$\sub$T/) versus contact spacing(d) measurements obtained from 10 TLM(transmission line method) structures. The resulting average values of vacuum annealing sample were $\rho$$\sub$c/=3.8x10$\^$-5/ Ω$\textrm{cm}^2$ , R$\sub$c/=4.9Ω, R$\sub$T/=9.8Ω and L$\sub$T/=15.5$\mu\textrm{m}$, resulting average values of another sample were $\rho$$\sub$c/=2.29x10$\^$-4/ Ω$\textrm{cm}^2$ , R$\sub$c/=12.9Ω, R$\sub$T/=25.8Ω. The Physical properties of contacts were examined using X-Ray Diffraction and Auger analysis, there was a uniform intermixing of the Si and Ni, migration of Ni into the SiC.

• Journal of the Korean Vacuum Society
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• v.14 no.4
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• pp.195-200
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• 2005

For the longevity of OLEDs, passivation of OLEDs is an important process step since organic materials used in OLEDs are very vulnerable to moisture. In this work, the passivation effect of the plasma polymerized para-xylene (PP$\rho$X) layers was studied. The PPpX layers deposited by PECVD were formed on top of the cathode with various plasma powers of 50 - 90 W. Passivation effect of PP$\rho$X was significantly dependent upon the deposition plasma power of the PP$\rho$X film. The lifetime of OLEDs with the 70 W deposited PP$\rho$X passivation layer was about 5 times longer than that of the control device.