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.

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.

MeOH-DMSO 혼합용매중에서 tert-butyl halide의 이온화에 미치는 용매효과

사공열,김시준,김진성,이본수,Yeol Sakong,Shi Choon Kim,Jin Sung Kim,Bon Su Lee 대한화학회 1985 대한화학회지 Vol.29 No.1

MeOH-DMSO 혼합용매중에서 t-butyl halide의 가메탄올 분해반응 속도상수 및 활성화 파라미터를 전기전도도법으로 측정하였고, Taft의 분광용매화 변수인 용매의 극성-편극성(${\pi}^{\ast}$), 수소결합주기산도(${\alpha}$) 및 수소결합 받기염기도(${\beta}$)를 분광법에 의해서 5가지의 지시약을 이용하여 측정계산하였다. 분광용매화변수와 반응속도상수로부터 얻은 활성화파라미터를 써서 용매의 부피조성비에 따른 가용매분해반응의 속도상수 변화를 논의한 결과, t-butyl halide의 이온화에 용매의 ${\pi}^{\ast}$, ${\alpha}$ 및 ${\beta}$가 협동적으로 기여했고, 또한 이탈기와 혼합용매사이의 이온-쌍극자 작용과 수소결합주기-받기 작용과 같은 독특한 상호작용이 전이상태의 안정화에 미치는 가장 중요한 용매효과 인자들임을 밝혔다. Rate constants and activation parameters for the methanolysis of t-butyl halide (t-BuCl, t-BuBr, t-BuI) in various MeOH-DMSO mixtures were measured by conductometric method. Taft's solvatochromic parameters, such as polarity-polarizability(SPP's), ${\pi}^{\ast}$, hydrogen bond donor (HBD) acidity, ${\alpha}$, and hydrogen bond acceptor (HBA) basicity, ${\beta}$ of the solvents, were determined by the so called solvatochromic method using five indicators. The variation of methanolysis rate with the solvent composition was discussed on the basis of the activation parameters and the correlation of the rates with the solvatochromic parameters. It is concluded that the polarity-polarizability, HBD acidity and HBA basicity of the mixtures had an effect on the ionization of t-butyl halide cooperatively, also that the specific interaction between the leaving groups and the solvents, such as ion-dipole and hydrogen bond acceptor-donor interaction, is the most important factor of solvent effects on the stabilization of transition states.

ISOPIESTIC法에 依한 活性度係數의 測定과 ION水和數의 硏究

司空烈,黃正儀 慶北大學校 1960 論文集 Vol.4 No.-

It is important to know the activity coefficients in the study of a solution, and the phenomena of solvation in the electrolytic solution especially. Hence, we have measured the activity coefficients by the isopiestic method and calculited the ratio of the hydration numbers of the solutes in dilute electrolytic solution. Robinson and Sinclair have derived the following equation from the activity coefficients and molalities of the two isopiestic solutions If we know y1, m1 amd ms, we can calculate y2, which is the active coefficient of the unknown solution. The activity coefficient for the reference solution is y1. Here, we selected KCI solution as a reference solution and measured the activity coefficients for alkalihalides, and calculated the hydration numbers by the formula propose by Robinson and Stockes, in which we used the weight values as the Debye-Huckel constants, and a value of 0.7 as the correction term. The numerical values are some what different from Robinson's but their mumerical order is the same. It is more reasonable to speak of the hydration ratio rather then the hydration number, because hydrated water and free water are not exactly distinct. In addition, it is useful to think of the ionic hydration ratio, which compose the hydration ratio,

몇가지 電解質溶液의 表面張力에 관한 硏究

사공열,황정의,손무용,Sakong, Yull,Hwang, Jung-Euy,Son, Moo-Yong 대한화학회 1964 대한화학회지 Vol.8 No.1

Relative surface tensions of aqueous solutions of KCl, KI and NaI have been measured at 25$^{circ}C$(30$^{circ}C$ for KCl) over a concentration range of 0.0001 to 3M solution. It was observed that there was a minimum in the surface tension-concentration curve for the extremely dilute solutions. Appearance of the minimum has been reported for the other salt solutions so far reported. At moderate and high concentration, these three salts increase the surface tension of water almost linearly as concentration increased, and behaved as a typical "capillary inactive substance", whereas they acted as a capillary active substance in very dilute solutions. Since the Onsager-Samaras equation for the surface tension as a function did not agree with the experimental data, the following empirical equations for the whole concentration range used were obtained. ${\sigma}_r\;=\;1\;+\;0.00072{\sqrt{c}}\;-\;0.0011c\;+\;0.023c^2\; for\;KCl\;at\;30^{\circ}C$ ${\sigma}_r\;=\;1\;+\;0.0077{\sqrt{c}}\;-\;0.0015c\;+\;0.024c^2\;for\;KI\;at\;25^{\circ}C$ ${\sigma}_r\;=\;1\;+\;0.00011{\sqrt{c}}\;-\;0.0090c\;+\;0.077c^2\;for\;NaI\;at\;25^{\circ}C$