• 대한전기학회:학술대회논문집
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• 대한전기학회 1988년도 전기.전자공학 학술대회 논문집
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• pp.799-801
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• 1988

This paper was studied on the effects of Ca-La-Nb substitution and Zr/Ti ratio variation to Pb(Zr, Ti)$O_3$ system on structural, electrical, optical and sound level characteristics in order to develope the piezoelectric and electrooptic ceramic devices. Also the specimens were prepared by the two stage sintering technique. The molecular formular was X($CaO{\cdot}1/4La_{2}O_{3}{\cdot}1/4Nb_{2}O_{5}){\cdot}(1-X)Pb(Zr_{Y}Ti_{1-Y})O_{3}$(x=100X, y=100Y), and the variation of x was $6{\sim}12$, y was 60${\sim}$49 and second stage sintering time was 20${\sim}$40 hours. The experimental results obtained from this study are as follows : 1. The density was decreased, the grain size was increased according to increase of Ca-La-Nb substitution. 2. The crystal structure was rhombohedral in composition 6/60/40, and the crystal structure was tetragonal and cubic according to increase of Ca-La-Nb substitution. 3. The Ca substitution of PZT system enhanced the sintering property. The Pb site vacancy resulting from the substitution of La-Nb increased the dielectrical constant, the piezoelectric charge constant, the dielectric loss and decreased the coercive field. 4. The resistivity of PZT system which has the P type conduction mechanism increased according to substitution of La-Nb because of the substituent acting as donor. 5. The PZT ceramics varied from ferroelectric substance according to increase of Ca-La-Nb substituent. The coercive field and saturation remanent polarization decreased, and at last straight line according to increase of La-Nb substitution. 6. The amount of Ca-La-Nb substitution to improve the light transmittance of speciment was 10 mol%, the Zr/Ti ratio was 49/51, and the second stage sintering time was 40 hours. 7. According to Ca-La-Nb substitution, the specimens was to be transparent. The 7.5/51/49 specimen was suitable for transparent sound vibrator because it had 58% light transmittance (thick 0.2[mm], wave length 700[mm]) and 48% electromechanical coupling factor.

• 대한화학회지
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• 제35권3호
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• pp.196-203
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• 1991

25$^{\circ}$C 때 벤조산과 메타 및 파라위치에 할로겐(F, Cl, Br)이 치환된 $pK_a$값을 메탄올-물 혼합용매(0∼80% 메탄올) 중에서 Fuoss-Kraus 식에 근거한 전도도법과 Gelb의 전도도법을 이용하여 결정하였다. 할로겐 치환기에 따른 벤조산의 $pK_a$ 변화를 전자받게 유도효과와 전자주게 공명효과로 복합시킨 치환기 상수(${\sigma}_1$ 및 ${\sigma}_R$)로써 논의하였다. ${\sigma}_1$가 $D^{-1}$에 대하여 양(+)의 기울기를 갖는 직선성을 보인 반면 ${\sigma}_R$은 $D^{-1}$에 대하여 음(-)의 기울기를 갖는 직선성을 보이고 있는데, 이를 field effect의 유전상수 의존성과 할로겐 치환기의 ${\pi}$-고립쌍 전자와 이온화 중심간의 through-space ${\pi}$-상호작용으로 해석하였다.

• 한국응용과학기술학회지
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• 제8권2호
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• pp.161-167
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• 1991

The kinetics of hydrolysis of cinnamenylisophorone derivatives (${rho}-H,\;{rho}-Br,\;P-Cl,\;{rho}-OCH_3$) was investigated using ultraviolet spectrophotometry in 20%(v/v) dicxane-$H_2O$ at 25$^{\circ}C$. A rate equation which can be applied over wide pH range (pH $1.0{\sim}13.0$) was obtained. In order to investigate the substituent effects on cinnarnenylisophorone derivatives, Hammett constant was plotted. As the result, the rate of hydrolysis of cinnamenylisophorone derivatives was facilitated by electron donating group. Final products of the hydrolysis were benzaldehyde and isophorone, From the measurement of reaction rate constant according to pH changes, substituent effect, and final products, it was found that the hydrolysis of cinnarnenylisophorone derivatives was initiated by the neutral $H_2O$ molecule which does not dissociated at below pH 9.0, and in the range of pH $9.0{\sim}11.0$ this reaction occurs by $H_2O$ or hydroxide ion competitively, but proceeded by the hydroxide ion above pH 11.0. On the basis of this kinetic study, the reaction mechanism of the hydrolysis of cinnamenylisophorone derivatives was proposed.

• Elastomers and Composites
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• 제12권1호
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• pp.27-32
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• 1977

The kinetics of azo-coupling reaction of N-acetyl-H-acid (1-acetamino-8-hydroxynaphthalene-3, 6-disulfonic acid) with several heterocyclic diasonium compounds such as diazotiged 3-aminopyridine, 3-aminoquinoline, 8-aminoauinoline and aniline was studied. It was found that reactions proceeded at remarkably different rate. Reaction rate was in increasing order; 3-aminopyridine, 3-aminoquinoline, 8-aminoauinoline and aniline. And the activation energies were 9.62, 10.10, 10.39, 10.70 Kcal/mole, respectively. Especially, the rate constant of 3-aminopyridine was 100 times larger than that of benzene diasonium compound even in strong acidity. Hammett plot was also made of the rate constants obtained against the heterocyclic substituent constants reported in the literature. A good linear relationship was obtained and the reaction constant of N-acetyl H-acid was calculated to be 3.14.

• 한국응용과학기술학회지
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• 제12권2호
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• pp.145-150
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• 1995

The Kinetics velocity for hydrolysis reaction of vanillylidene imine derivatives has been measured by ultra-violet ray spectrophotometer in 20wt% $dioxane-H_2O$ at $25^{\circ}C$. It was measured the reaction rate Constant of vanillylidene imine derivatives that can be applied widely following to pH-change at $25^{\circ}C$. Final products that hydrolyzed the vanillylidene imine certified in vanillin and aniline derivative, and the effect of substitution radical that has affected on hydrolysis reaction was largely promoted to reaction rate by electron attrating group in acidity and electron donoring group in basic. From the results of rate constant to hydrolysis reaction, substituent radical effect and final products. It has certified the hydrolysis reaction mechanism of vanillylidene imine derivatives.

• 한국응용과학기술학회지
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• 제37권2호
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• pp.250-259
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• 2020

가용화현상에 있어서 유기물(피가용화물)과 계면활성제와의 상호관계를 조사하고자 UV-Vis 법을 이용하여 가용화상수(K_s)값을 구하였다. 유기물의 para-위치에 알킬치환기가 도입된 4-alkylanilines과 양이온계면활제인 소수기 길이가 서로 다른 DTAB, TTAB, CTAB를 이용하여 유기물과 계면활성제간의 소수성 상호작용에 따른 가용화 상수값과 그에 따른 열역학함수들을 다양한 온도에서 구하여 서로 비교하였다. 그 결과 유기물에서 알킬치환기에 의한 소수성효과는 탄소사슬의 길이가 증가할수록 일정한 비율로 증가하였고, 또한 계면활성제에서 소수기의 길이효과도 일정한 비율로 증가하였다. 그런데 이러한 소수성 효과는 유기물에서 알킬치환기에 의한 효과가 계면활성제에서 소수기의 효과 보다 더 크게 나타났다. 또한 계산된 열역학 함수값들의 결과들로부터 유기물의 소수성이 증가할수록 그리고 계면활성제의 소수성이 증가할수록 유기물은 미셀내부의 더 깊은 곳으로 가용화됨을 알 수 있었다. 등구조온도는 실험 조건 범위 내에서 큰 차이를 보이지 않았으며, 최대값과 최소값의 차이가 1K미만으로 차이가 거의 없는 것으로 나타났다.

• 산업기술연구
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• 제39권1호
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• pp.41-45
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• 2019

Hydrogen sulfide ($H_2S$) is mainly produced along with methane and hydrocarbons in many gas fields as well as hydrodesulfurization processes of crude oils containing sulfur compounds and the emission of $H_2S$ has a considerable effect on both environmental problem and human health aspects due to formation of, e.g. acid rain and smog. In recent years, ionic liquids (ILs) have been proposed as the most promising solvents for $CO_2$ and hazardous pollutants capture, such as $H_2S$ and sulfur dioxide ($SO_2$). In this work, we demonstrate the use of the predictive COSMO-SAC model for the prediction of Henry's law constant of $H_2S$ in ILs. Furthermore, the method is used to screen for potential IL candidates for $H_2S$ capture from a set of 2,624 ILs formed from 82 cations and 32 anions. The effects of cation on the Henry's law constant of $H_2S$ such as (i) the variation of the alkyl chain length on cation, (ii) the substituent of methyl group ($-CH_3$) for H in C(2) position and (iii) the change of ring structure for cation family are clearly predicted by COSMO-SAC model.

• 대한화학회지
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• 제29권6호
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• pp.565-574
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• 1985

MeOH-MeCN 혼합용매계에서 4-치환-2,6-이니트로염화벤젠과 아닐린 치환제 사이의 친핵성 치환반응속도를 전기 전도법에 의해 측정하였다. 기질의 고리에 있는 치환기의 치환기변화에 따른 속도상수의 크기순서는 4-$NO_2{\gg}4-CN {\gg}$4-$CF_3$이었고, 아닐린 고리에 있는 치환기에 의한 속도상수의 크기는 p-O$CH_3 {\gg}p- CH_3{\gg}H {\gg}p-Cl{\gg}m-NO_2$ 순서였다. MeOH함량이 많은 용매에서 속도상수가 MeCN 함량이 많은 용매속에서의 속도상수보다 컸다. MeOH-MeCN 혼합용매계와 친핵체 변화에 대한 속도론적 연구로 볼 때 Cl의 이탈단계가 속도결정단계로 보여졌다. MeOH에 의한 친전자적 촉매작용은 알코올의 수소와 이탈기 염소원자 사이의 전이상태에서 수소결합 형성으로 이루어지고 친핵성 촉매작용은 전이상태에서 알코올의 산소와 아민의 수소사이의 수소결합에 의한 것으로 생각 되었다. 모든 이의 사실로 보아 본 반응은 제 2단계가 속도결정단계인 $S_N$Ar메카니즘으로 진행됨을 알 수 있고 이와 같은 메카니즘은 PES모형으로도 설명할 수 있다.

• Applied Biological Chemistry
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• 제38권6호
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• pp.570-576
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• 1995

새로운 16종의 ortho 이치환 benzenesulfonyl urea계 제초성 화합물인 N-2-(1-hydroxy-2-fluoroethyl)-6-치환(X)-benzenesulfonyl-N'-4,6-dimethoxypyrimidinyl-2-yl urea 유도체들을 합성하고 벼(Orysa sativa L.)를 위시하여 논 잡초인 강피(Echninochloa orizola) 및 올챙이고랭이(Scirpus juncoides)를 대상으로 측정된 제초활성값$(pI_{50})$과 ortho-치환기{X)들의 변화에 따른 물리-화학적 파라미터와 가수분해 반응 속도상수로 부터 구조-활성 관계(SAR)를 검토하였다. 잡초들의 제초활성에 미치는 물리-화학적 파라미터의 영향은 입체상수가 음의값$(Es,\;L_1,$ 및 $B_4<0)$이고 반응 속도상수는 양의 값(logk>0)으로 ortho-치환기에 의한 입체효과보다 반응속도 상수에 의존적이었다. 초종간의 선택성은 나타나지 않았으나, 강피>볍씨>올챙이고랭이>벼 3엽기의 순으로 halogen(2 및 5), methyl(15) 및 비(H)치환체(1) 등이 가장 큰 제초활성을 보였다. Ortho-치환기(X)는 전자를 밀수록 제초활성이 증가되었고 수용액 중에서 잔류성은 단축되었으며 pH 6.0의 $45^{\circ}C$에서 반감기(T1/2)는 14시간${sim}$58일 범위였다. 그리고 가수분해와 제초활성 반응이 유사한 경로로 진행될 것임을 예상 할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제29권6호
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• pp.1195-1198
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• 2008

Kinetic studies of the additions of benzylamines to a noncyclic dicarbonyl group activated olefin, methyl $\alpha$-acetyl-$\beta$ -phenylacrylates (MAP), in acetonitrile at 30.0 ${^{\circ}C}$ are reported. The rates are lower than those for the cyclic dicarbonyl group activated olefins. The addition occurs in a single step with concurrent formation of the $C_\alpha$ -N and $C_\beta$ -H bonds through a four-center hydrogen bonded transition state. The kinetic isotope effects ($k_H/k_D$ > 1.0) measured with deuterated benzylamines ($XC_6H_4CH_2ND_2$) increase with a stronger electron acceptor substituent ($\delta\sigma$ X > 0) which is the same trend as those found for other dicarbonyl group activated series (1-4). The sign and magnitude of the cross-interaction constant, ρXY, is comparable to those for the normal bond formation processes in the $S_N2$ and addition reactions. The relatively low ${\Delta}H^\neq$ and large negative ${\Delta}S^\neq$ values are also consistent with the mechanism proposed.