• Bulletin of the Korean Chemical Society
• /
• 제23권10호
• /
• pp.1463-1482
• /
• 2002

Partially doped Aurivillius phases SrBi2N$b_{2-x}M_xO_9$ (M=Cr and Mo) were successfully synthesized and characterized. The extent of the substitution was limited at ~20 mole % because of the size differences between $Nb^{5+}$ and $Cr^{6+}$, and between $Nb^{5+}$ and $Mo^{6+}$. When the amount of substitution exceeded ~20 mole%, the phases began to collapse and the second phases were made. The dielectric constants of substituted compounds were enlarged nevertheless Cr or Mo is substituted. The increment is bigger in the Mo substituted compound than in the Cr doped one although the Nb(Cr)$O_6$ octahedra could be more strongly distorted than the Nb(Mo)$O_6$ octahedra since the ionic size difference between $Nb^{5+}$ and of $Cr^{6+}$ is much bigger than that between $Nb^{5+}$ and $Mo^{6+}$. Consequently, the dielectric constant of the substituted Aurivillius phase $Bi_2$A_{n-1}B_{n-x}M_xO_{3n+1}$$ depends on the extent of distortion of the B$O_6$ octahedra and more strongly on the polarizability of the metal.

• 한국조명전기설비학회지:조명전기설비
• /
• 제5권1호
• /
• pp.31-39
• /
• 1991

편광유지 광섬유의 한 종류인 저 복굴절 광섬유의 고유복굴절 및 자기광학 효과에 의한 편광 특성을 이론적으로 해석하고 실험하였다. 일반 단일모드 광섬유에 비해 편광유지 특성이 양호하게 나타났으며, 실험결과 본 실험에 사용된 광섬유(길이: 68.28cm, 163.72cm, 139.52cm)의 편광도는 0.818이상으로 특정되었다. 입력 편광각에 대한 출력 편광각의 변화는 $9^{\circ}$이하로 측정되었다. 자계 측정 실험결과 10kAT까지의 자계 강도를 선형적으로 측정할 수 있었으며 최대 오차는 4kTA에서 1.95%였다.

• Bulletin of the Korean Chemical Society
• /
• 제30권7호
• /
• pp.1452-1458
• /
• 2009

The change in the electronic absorption and emission energy of 7-aminocoumarin derivatives in binary solvent mixtures has been studied. The electronic transition energy along with the Stokes' shift is correlated with the orientation polarizability of the solvent as well as the empirical solvent polarity parameters $E_T$ (30). It is observed that the emission peak shift traces the change of $E_T$ (30) value very closely in binary solvent mixtures. The emission transition more strongly depends on the solvent polarity than the absorption, which indicates the dipole moment gets larger on excitation. From the dependence of the Stokes’ shift of 7-aminocoumarins with the solvent polarity parameters and the ground state dipole moment obtained by the semi-empirical calculations, the excited state dipole moment was estimated. The fluorescence lifetime change of 7-aminocoumarins in binary solvent mixtures was measured and the results are explained in terms of molecular conformation and solvent polarity. The study indicates the empirical solvent polarity $E_T$ (30) is a good measure of microscopic solvent polarity and it probes in general the non-specific solvent interactions.

• 전자공학회논문지A
• /
• 제31A권8호
• /
• pp.7-15
• /
• 1994

In this paper, the directional coupler for Ku-band, which is designed is of the crossguide type with a coupling value of about 3-dB. The apertures chosen for this design are crosses. We used polynomial approximations of rounded end slot to obtain the electric and magnetic polarizability of crossed-slot and compared the results with Cohn's experimental results. The optimized dimensions and positions of the cross aperture are obtained by a trial-and-error reiteration of the program. This paper presents the measurement results for the designed coupler. The very flat coupling shows a total variation of only 29.80$\pm$0.04dB for the design frequency ranges of 12.25GHz-12.75GHz. The measured minimum directivity is 25dB. The aperture attenuation for the finite diaphragm thickness is about 2dB pr 0.5mm, which is in agreement with the theoretical value. The transmission loss and input return loss at center frequency are 0.0564dB and 48.16dB respectively. We obtained the measured minimum directivity of the coupler. Whose apertures are both circles is better than that containing holes in the performance of directivity.

• 공학논문집
• /
• 제6권2호
• /
• pp.85-98
• /
• 2004

The adsorption equilibrium data for the binary gas mixture system from the pure gas adsorption data of carbon dioxide and ethylene on ZSM-5 prepared were predicted. The binary gas mixture adsorption data have been examined against predicted values by two models-the vacancy solution model(VSM) and the statistical thermodynamic model(STM), using parameters obtained from the single component isotherm. The binary gas mixture data for the carbon dioxide-ethylene system were obtained for cation exchanged forms of ZSM-5 for the gas phase carbon dioxide mole fraction of 0.752 at $37^{\circ}C$ and 1 atm. The experimental adsorption phase diagrams were obtained for carbon dioxide-ethylene on sodium form ZSM-5 synthesized. The single component adsorption isotherms for carbon dioxide and ethylene were also obtained for this zeolite. The single component data were used to obtain parameters derived in two models. These parameters were, in turn, used to predict the binary mixture isotherms for this zeolite. Both the vacancy solution and the statistical thermodynamic models give satisfactory predictions of adsorption phase diagrams for the binary gas mixtures of carbon dioxide and ethylene on sodium exchanged ZSM-5. Also the correlation between the experimental data and the predicted values is generally in good agreement. The system appears to show ideal behavior with a relatively constant separation factor. The slight increase in adsorption capacity with an increase in ionic radius is due, in part, to the higher polarizability associated with larger cations.

• Bulletin of the Korean Chemical Society
• /
• 제20권8호
• /
• pp.948-952
• /
• 1999

Electrophilic substitutions on β-position of 2,5-dimethyl pyrrole have been investigated theoretically. The electron donating methyl groups enrich electron densities on C-3, C-4 positions and π* interactions with methyl groups substituted on C-2 and C-5 positions pushed up the HOMO level of the pyrroles consequently induce rapid substitutions on C-3, C-4 sites. Substitution of phenylsulfonyl group on nitrogen stabilized LUMO levels through weak π bonding interactions. Unexpected deoxidation reaction underwent on the sulfonyl group substituted at C-3 position. The structures were solved by X-ray crystallography. Meanwhile, gas phase HF/6-31G* and density functional method (B3LYP/6-31G*) calculations gave favorable energies for 1-phenylsulfinyl pyrrole (6) over 3-phenylsulfinyl pyrrole (5) by 3.6-4.7 kcal/mol which is contrary to the experimental result. However the methods involve the effects of molecular polarizability and solvent, molecular dynamics (MD) and ab-initio self consistent reaction field (SCRF) calculations showed same trend as experiments. According to MD calculations, compound 5 is more stable than compound 6 by 4.15 kcal/mol and the SCRF, HF/6-31G* calculations gave more stable energy value for structure 5 than 6 by 0.03 kcal/mol.

• Bulletin of the Korean Chemical Society
• /
• 제12권5호
• /
• pp.510-514
• /
• 1991

Second-order rate constants have been determined spectrophotometrically for reactions of S-p-nitrophenyl substituted thiobenzoates with various phenoxide ions and S-aryl substituted thiobenzoates with $HO^-$ ion. Thiol esters have been found to be more reactive than the corresponding oxygen esters toward phenoxide ions. The high reactivity of thiol esters relative to oxygen esters becomes insignificant as the basicity of the nucleophile increases. Furthermore, the highly basic $HO^-$ ion is less reactive toward thiol esters than oxygen esters. The significant dependence of the reactivity of thiol esters on the basicity of nucleophiles has been attributed to the nature of the HSAB principle. The present kinetic study has also revealed that the reactivity of thiol esters compared to oxygen esters is not so pronounced as expected based on the enhanced nucleofugicity of thiol esters. However, the effects of substituents in the nucleophile and in the acyl moiety of the substrate on rate appear to be significant. These kinetic results have led to a conclusion that the present reactions proceed via a rate-determining formation of a tetrahedral intermediate followed by a fast breakdown of it. The magnitude of the ${\beta}$ values shows no tendency either to increase or to decrease with the intrinsic reactivity of the reagents. The constancy of ${\beta}$ values in the present system is suggestive that the RSP should have limited applicability.

• Bulletin of the Korean Chemical Society
• /
• 제17권4호
• /
• pp.353-357
• /
• 1996

Second-order rate constants have been measured spectrophotometrically for the reaction of 2,4-dinitrophenyl X-substituted benzenesulfonates with Z-substituted phenoxides in absolute ethanol at 25.0±0.1 ℃. The nucleophilic substitution reaction gives both S-O bond and C-O bond cleavage products. The extent of S-O bond cleavage increases significantly with increasing electron withdrawing ability of the sulfonyl substitutent X, while that of the C-O bond cleavage is independent on the electronic effect of the substituent. On the contratry, the effect of the substituent Z in the nucleophilic phenoxide is more significant for the C-O bond cleavage than for the S-O bond cleavage. Aminolyses of 2,4-dinitrophenyl benzenesulfonate (1) with various 1°, 2° and 3°amines have revealed that steric effect is little important. The extent of S-O bond cleavage increases with increasing the basicity of the amines, but decreases with increasing the basicity of the nucleophilic aryloxides, indicating that the HSAB principle is not always operative. Besides, reactant and solvent polarizability effect has also been found to be an important factor in some cases but not always to influence the reaction site.

• Bulletin of the Korean Chemical Society
• /
• 제26권12호
• /
• pp.2007-2016
• /
• 2005

An artificial neural network (ANN) is successfully presented for prediction acidity constant (pKa) of various benzoic acids and phenols with diverse chemical structures using a nonlinear quantitative structure-property relationship. A three-layered feed forward ANN with back-propagation of error was generated using six molecular descriptors appearing in the multi-parameter linear regression (MLR) model. The polarizability term $(\pi_1)$, most positive charge of acidic hydrogen atom $(q^+)$, molecular weight (MW), most negative charge of the acidic oxygen atom $(q^-)$, the hydrogen-bond accepting ability $(\epsilon_B)$ and partial charge weighted topological electronic (PCWTE) descriptors are inputs and its output is pKa. It was found that properly selected and trained neural network with 205 compounds could fairly represent dependence of the acidity constant on molecular descriptors. For evaluation of the predictive power of the generated ANN, an optimized network was applied for prediction pKa values of 37 compounds in the prediction set, which were not used in the optimization procedure. Squared correlation coefficient $(R^2)$ and root mean square error (RMSE) of 0.9147 and 0.9388 for prediction set by the MLR model should be compared with the values of 0.9939 and 0.2575 by the ANN model. These improvements are due to the fact that acidity constant of benzoic acids and phenols in water shows nonlinear correlations with the molecular descriptors.

• Elastomers and Composites
• /
• 제43권4호
• /
• pp.230-240
• /
• 2008

분산중합법에 의해 무기물을 포함하는 고분자 미립자를 합성하기 위해 styrene과 n-butyl methacrylate가 알루미나와 함께 중합되었다. Styrene과 n-butylmethacrylate의 무게 비는 3:1이었고, 입자안정제는 poly(N-vinyl pyrrolidon), 중합 개시제로는 2,2'-azobis(isobutyronitrile)를 사용하여 개시제의 농도, 분산매의 종류, 분산매의 혼합 용해도 상수 (${\delta}_{mix}$), 커플링제의 종류와 농도에 따른 입자경을 조사하였다. 개시제의 농도가 증가함에 따라 입자경이 소폭 상승하였고 분산매의 극성이 증가할수록 입경이 증가하였고, 분산매로서, 이소프로판올과 이온교환수를 조성비에 따라 사용한 경우, $[{\delta}_{mix}]^{-4.01}\;{\propto}$ 평균 입자경과 $[{\delta]_{mix}]^{-0.83}\;{\propto}$ 입경 분포의 관계를 얻을 수 있었다. 커플링제의 종류와 농도변화에 따른 입자경 및 입자경 분포는 뚜렷한 차이가 없었다.