高壓下에서의 메틸벤질 클로라이드의 가용매 분해 반응에 대한 연구

權五千,景鎭範,司空烈 漢陽大學校 環境科學硏究所 1983 環境科學論文集 Vol.4 No.-

ρ-메틸벤질 클로라이드의 가용매 분해 반응 속도를 40℃에서 압력을 1∼1200bar로 변화시키고 에탄올-물 혼합용매의 조성이 0.00∼0.40인 에탄올 몰분율의 범위내에서 전기 전도도 법으로 측정하였다. 이 반응의 속도 상수로 부터 활성화 파라미터 ??와 ??를 구한 결과 혼합용매의 몰분율이 0.30부근에서 extremum을 나타내었다. 이러한 현상은 용매 구조의 변화에 의하여 검토되었다. 그리고 전이 상태에서 반응에 관여한 물 분자수를 계산하여 그에 따른 반응메카니즘을 고찰하였다. The rates of solvolysis for p-methylbenzyl chloride have been measured by the electric conductivity method in aqueous ethanol from 0.00 to 0.40 mole fraction of ethanol under various pressures up to 1200bar at 40℃. The activation parameters, ?? and ?? are evaluation from the rate constants. The results indicated that they exhibit an extremum behavior near 0.30 mole fraction of ethanol. This behaviors are discussed in terms of solvent structure variation. And the reaction were discussed in terms of solvent structure variation. And the reaction were discussed from the number of H₂O molecule participated in the transition states.

電解質 溶液의 濃度에 따른 粘度係數와 表面張力에 關한 硏究

司空烈 慶北大學校 1964 論文集 Vol.8 No.-

The viscosity and surface tension of aqueous solutions of electolytes such as KCI, NaI, KI, NaBr, CaBr_2, and LiCl have been measured over a fairly wide range of concentraion variation. To secure more accurate measurement, Ostwald viscometer and differential capillarimeter were made with pyrex glass both of which were utillized by Grinnell Jones and his co-worker. Timing system in our viscometer, unlike ordinary ones currently used, was entirely functioned by electronics system and pulse counter of 510 cycles/sec, thus enabling us to make more accurate time measurement. The results obtained were in good agreement with the Jone's value except extremely dilute range of which were not measured so far. As the experimental data obtained were in good agreement with the Jones' values, Jones-Dole equation for the viscosity of electolytic solutions were deduced. η_r=1+0.0052√c-0.016c+0.008c^2 (KCl at 30℃) η_r=1+0.0220√c-0.129c+0.030c^2 (Kl at 25℃) η_r=1+0.0240√c-0.064c+0.033c^2 (NaI at 25℃) η_r=1-0.054√c+1.23c-2.07c^2 (NaBr at 25℃) η_r=1+0.070√c-0.177c+0.565c^2 (CaBr_2 at 25℃) η_r=1-0.037√c+0.881c-0.610c^2 (LiCl at 25℃) For surface tension the data were in good agreement with Jones' value and M. Dole's equation were in good agreement. But we have made some virial equation like that of viscosity as follows; σ_r=1-0.0048√c+0.0799c-0.063c^2 (KCl at 30℃) σ_r=1-0.0058√c+0.0983c-0.069c^2 (Kl at 25℃) σ_r=1-0.0052√c+0.0703c-0.409c^2 (NaI at 25℃) σ_r=1+0.204√c-0.638c+0.953c^2 (NaBr at 25℃) σ_r=1+2.98√c-8.21c+3.98c^2 (CaBr_2 at 25℃) σ_r=1-0.560√c+4.00c+0.09c^2 (LiCl at 25℃) G. Jones et al have investigated the relation between viscosity and concentration of various electolytic solutions, and passed upon qualitative tendencies, they classified electolytic solutions into two categories. For solutions which belong to the first type, the viscosity at first increase in proportion to concentration until it reaches maximum value, to be followed hereafter the decrease of viscosity. Other solution that may be grouped in latter category show quite different viscosity-concentration relation, the viscosity decreases at first with the increase of concentration and passing the minimum, the viscosity starts to increase. According to our result viscosity and concentration curve prolonged in extremely dilute range of concentraion, most of electrolytic aqueous solution increase the viscosity as concentration increase, but pass the maximum and decrease the viscosity as concentration increase but the concentraion which shows the viscosity manimum is different according to the kind of salts. In concentraion range viscosity of solution increase again and made a oscillation of sin curve. The reason why the effect of viscosity varies with concentraion we have conclude that there are three factors. The presence of a few ions assists the formation of water arrangement around ions, and increase the viscosity. In dilute range, the hydrated ion cut hydrogen bond locally, to attract loose tetrahedral structure closer, thereby resulting the increase of fluidity and have decrease of viscosity. In concentration range, the number of hydrated ions increase (most free water is exhausted), and the formation of large particles cause again the increase of viscosity. Therefore the viscosity and concentration curves of the most electolytic solutions follow oscillation of rough sinusoidal pattern.

MeOH-1,1,2,2-Tetrachloroethane 혼합용매에서 tert-Butyl Halides의 이온화에 미치는 분광용매화변수들의 협동효과

사공열,김시준,주재범,Yeol Sakong,Shi Choon KIm,Jae Bum Choo 대한화학회 1986 대한화학회지 Vol.30 No.3

MeOH-1,1,2,2-tetrachloroethane 혼합용매에서 할로겐화삼차부틸(t-BuCl, t-BuBr, t-BuI)의 가메탄올 분해반응을 속도론적으로 연구하였으며, 이온화에 미치는 용매효과를 고찰하기 위하여 6가지 indicater를 이용한 분광용매화비교법을 적용하였다. 이결과 할로겐화삼차부틸의 가메탄올 분해반응에 미치는 용매화의 작용은 용매의 극상-편극성에 기인되는 상호작용이 주된 것이긴 하지만 halide leaving group의 living ability에 미치는 electrophilic assistance와 t-Butyl 양이온쪽에 대한 nucleophilic assistance도 상당히 작용함을 알 수 있다. 특히 hydrogen bonding에 의한 electrophilic assistance는 basicity가 큰 leaving group일수록 커지며 ($I^-<Br^-<Cl^-$), 탄소 중심일수록 커짐을 밝힐 수 있었다. (t-BuCl<t-BuBr<t-BuI) Kinetic studies for the methanolysis of tert-butyl halides (t-BuCl, t-BuBr, t-BuI) were carried out in MeOH-1,1,2,2-tetrachloroethane mixtures. The solvatochromic comparison method was used with six indicators to analyze solvent effects on the ionizations of tert-butyl halides. It was shown that the cooperative effect of solvent polarity-polarizability was the most important factor influenced on the methanolysis rates of tert-butyl halides, but the electrophilic assistance for halide leaving group and the nucleophilic assistance for tert-butylium ion were considerably influential, too. And it was found that the electrophilic assistance caused by hydrogen bonding and the nucleophilic assistance for carbon center were stronger for more basic leaving group ($I^-<Br^-<Cl^-$) and more polarizable leaving group(t-BuCl<t-BuBr<t-BuI), respectively.

아세톤 溶液內에서의 1-Phenethyl Chloride의 할로겐 交換反應에 관한 速度論的 硏究

司空烈 漢陽大學校 1975 論文集 Vol.9 No.-

Kinetics of halogen exchange reaction of 1-phenethyl chloride using radioisotopic tracer halide ions in acetone have been studied. The rate constant was determined at two temperature and the activation parameters, ?? and ?? were calculated. The reactions were believed to be ?? processes and the orders of relative nucleop- hilicity of halide ions were ??. The reaction rate is slower than that of benzyl chloride. These were interpreted in terms of so1vation effect of halide ions and HSAB principle.

電解質溶液의 粘度係數의 測定과 濃度關係에 對한 考察

사공열,황정의,Sakong, Yull,Hwang, Jung-Eui 대한화학회 1964 대한화학회지 Vol.8 No.1

전해질용액의 점도가 농도의 양수임은 기지의 사실이나 전농도에 걸쳐 잘 맞는 관계식은 아직 발견되지 않았다. 표면장력 역시 이러한 관계가 있으나 완전한 식은 없으며 이들은 모두 용액내의 이온의 상태에 기인하므로 표면장력과 덤도간에도 일정한 관계가 있을 것으로 생각되는 바이다. 순수한 물질에 대한 관계식은 Silverman1)이 Batchinski식 과 MacLeod 식에서 ${\gamma}^{\frac{1}{4}}=\;A/{\eta}$ + B 식을 유도하여 실험오차 범위안에서 일치된다고 했으나 아직 $Jones^{(4)}$들이 측정한 몇가지 염을 제외하고는 거의 모든 염용액의 점도나 표면장력의 정밀한 값은 측정되지 않았음으로 우선 여기서는 몇가기 염용액의 점도를 측정하였고 또 점도계수와 농도관계를 고찰하였다. The viscosities of strong electrolytic solutions, such as KCl, KI and NaI have been measured over a fairy wide range of concentration variation (from 0.00002 to 3.7M). It was hoped that a study of the data in the light of modern theories on solution might reveal new relation between viscosity and surface tension of electrolytic solution. To secure more accurate measurements of viscosity and surface tension of the solutions, Ostwald viscometer was made with pyrex glass and modified the timing system for the transit of the meniscus with a new electronics system and with a pulse counter. As the experimental data obtained were in good agreement with the Jone's values, Jones-Dole equations for the electrolytic solutions were deduced, ${\eta}KCl\;=\;1\;+\;0.0052{\sqrt{c}}\;-\;0.01612c\;+\;0.00808c^2\;at\;30^{\circ}C$ ${\eta}KI\;=\;1\;+\;0.0220{\sqrt{c}}\;-\;0.01290c\;+\;0.02988c^2\;at\;25^{\circ}C$${\eta}Na\; =\;1\;+\;0.0240{\sqrt{c}}\;-\;0.0640c\;+\;0.03268c^2\;at\;25^{\circ}C$Gruneisen effect appeared in the dilute solution, whereas anti-Gruneisen effect was found for the extremely dilute solution. No satisfactory interpretation for the variation of the viscosity with concentration can be found at the present.

이온교환막의 전기화학적 고찰

司空烈 漢陽大學校 基礎科學硏究所 1981 基礎科學論文集 Vol.1 No.-

The permselectivity, ion activity measurement and other electrochemical properties of various ion exchange membrane were studied extensively by previous workers. In the present work, the following investigations have been done for some of cation or anion membranes: 1. The qualitative relation between the change of transference numbers in membrane and concentration of solution. 2. The validity of eq. ?? in univalent system. 3. Concentration potential for measurement of activity and study of pachment paper properties. The cell diagram in this work; Hg|Hg₂Cl₂, sat.KCl||solu. α₁ membrane solu. α₂ || sat. KCl, Hg₂Cl₂|Hg is similar to those adopted by previous workers. From these investigations, the following conclusion has been made: 1. The transference number in ion exchange increase as the concentration of solution decrease, and below 0.002N the number remains almost unchanged. 2. The ratio of ion mobility in membrane was constant whe the concentration of solution was bolow 0.5N. 3. Relaton between ??and ?? was found to be ??. From this equation, it is possible to obtain the activity of various KCl solutions.

E. M. F.法에 依한 活性度係數의 測定과 Ion水和에 對한 考察

사공열,황정의,Sakong, Yell,Hwang, Jung-Euy 대한화학회 1962 대한화학회지 Vol.6 No.2

In this study we have measured the activity coefficients of NaCl in solution by E.M.F. method, depending upon MacInnes' equation at 25 dog. The cell (electrodes) is same as MacInnes' except the cock which was designed by ourselves as figure 1.Additionally, we have calculated the hydration number of NaCl from the activity coefficients using Robinson's equation and ionic hydration number according to our new formula $\frac{n_M{^+}+0.8}{n_A{^-}-0.1}=n_{MA}$, which was mentioned our former thesis.We also have calculated the hydration number of some salts from the ionic hydration number using upper formula and have got reasonable series match with other's value.As the results of our studying, we conclude it as follow;1) Liquid junction potential depend only on the bulk concentration of the both solution.2) The formula $\frac{n_M{^+}+0.8}{{n_A{^-}}-0.1}=n_{MA}$ is reasonable one in deducing to ionic hydration number.3) From upper relation, we can calculate the hydration number of unknown salts from it's ionic hydration numbers.

단분자막을 통하는 물질이동에 관한 속도론적 고찰

사공열 漢陽大學校 1979 論文集 Vol.13 No.-

The absorption rates of methanol, acetone and methlacetate vapor through the monomolecular layers of tetra-, hexa-, and octadecanol on water surface were measured under lower pressure and at room temperature. The initial rates are fitted to the first order kinetics with respect to vapor concentration and the rate determining step is the processing through the monolayer film. The apparent activation energies calculated from the rate constants at different temperatures are shown in table 2. It was found that the appareent activation energies increase linearity with increasng cross sectional area of the permeant molecule.

이성분 혼합용매중에서 활로겐화 삼차부틸의 가메탄올 분해반응에 대한 속도론적 연구

김시준,김진성,유승교,사공열 漢陽大學校 基礎科學硏究所 1989 基礎科學論文集 Vol.8 No.-

메탄올 -1·2-dichloroethane 및 메탄올 - 피리딘 혼합용매의 AN값과 분광용매화변수간의 관계를 규명하기 위해 4가지 지시약을 사용해 UV/??분광기의 흡수파장과 FT-NMR분광기로서 (??)₃PO의 ??-chemical shift를 측정하여 그 값을 다중회귀분석법으로 조정하여 상관관계를 결정하였다. 이 결과 메탄올 -피리딘 혼합용매의 AN값은 용매의 극성-편극성의 기여보다 Et₃PO의 charge separation 안정화에 기여하는 용매의 수소결합 주게능력에 더 민감하며, 이러한 관계는 amphiprotic 이성분 혼합용매의 성질을 이해하는데 매우 중요한 용매효과로 생각된다. The relationship between aceptor unmber(AN) and solvatochromic parameters of binary mixture of MeOH with 1,2-dichloroethane and pyridine was determined by measuring absorption wavelength for four indicators with UV/?? spectrophotometer and ??-chemical shift for triethylphosphine oxide(Et₃PO) with FT-NMR spectrometer, and using multiple linear regression analysis program. The result is that the acceptor number of MeOH-pyridine mixture was more sensitive to solvent hydrogen bond donor ability, which contributed to stabilization for charge separation of Et₃PO, than contribution of solvent polarity-polarizability. This relationship as solvent effect was very important to understanding the property of binary mixture of amphiprotic solvent.

고압하에서의 클로로벤질 클로라이드의 가용매 분해 반응에 대한 연구

權五千,李相哲,司空烈 漢陽大學校 基礎科學硏究所 1983 基礎科學論文集 Vol.2 No.-

p-클로로 벤질 클로라이드의 가용매분해 반응에 대한 압력의 영향을 전기전도법에 의하여 에탄올-물 혼합용매내에서 연구하였다. p-클로로 벤질 클로라이드의 분해에 따르는 용액의 저항변화를 40℃에서 에탄올의 몰분율을 0.00, 0.10, 0.20, 0.30, 0.40. 압력을 1, 200, 400, 800, 1200 bar 의 여러 조건하에서 측정하여 Guggenheim 법에 의해 유사 1 차반응의 속도상수를 구하였다. 이 속도상수로 부터 활성화부피 ??를 구한 결과 각 몰분율에서 음의 값을 나타내었다. 그러므로 가용매분해반응의 전이상태에서 electrostriction 현상이 있음을 알 수 있었다. 그리고 전이상태에서 반응에 관여한 물분자수를 계산한 결과 각 압력하에서 6∼7의 값을 나타내었고, 이 값으로 부터 p-클로로 벤질 클로라이드의 가용매분해 반응은 ?? 반응메카니즘을 갖는다고 고찰하였다. The effect of pressure on the solvolysis of p-Chlorobenzyl chloride has been investigated in ethanol-water mixtures by the conductometric method. The resistances of p-Chlorobenzyl chloride were measured in aqueous ethanol of various mole fraction of ethanol at 40℃ under 1-1200 bars. The rate constants for the solvolysis of p-Chlorobenzyl chloride were calculated by the Guggenheim's method. The activation volumes obtained by the electrostriction in the transition states were calculated from the rate constants. And the reaction mechanisms were discussed from the number of H₂O molecule participated in the transition states.